U.S. DEPARTMENT OF COMMERCE
                         National Technical Information Service

                         PB-251 441
A  Study  of  Flame
Retardants  for
Textiles
Auerbach Associates, Inc.
Prepared For
Environmental Protection Agency
February 1976

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A-560/1-76-004
      ENVIRONMENTAL PROTECTION AGENCY
          OFFICE OF TOXIC SUBSTANCES
            WASHINGTON, D.C. 20460

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' TECHNICAL REPORT DAT A
(Plane read tottiucttoru on the reverse before completing} ^ ^ 	
1. REPORT NO.
EPA-560/ 1-76-004
2.
4. TITLE AND SUBTITLE
A STUDY OF FLAME RETARDANTS FOR TEXTILES
7. AUTHOR(SI
Thomas J. McGeehan and Jerome T. Maddock
9. PERFORMING ORGANIZATION NAME ANO ADDRESS
Auerbach Associates, Inc.
121 North Broad Street
Philadelphia, Pennsylvania 19107
12. SPONSORING AGENCY NAME ANO ADDRESS
Office of Toxic Substances
Environmental Protection Agency
Washington, D.C. 20460
nrezsTOi
8. REPORT DATE
February 1976
8. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
AUER-2200-TR-4
10. PROGRAM ELEMENT NO.
2LA328
11. CONTRACT/CHANT NO.
68-01-2209 ' •*
13. TYPE OF REPORT AND PERIOD COVERED
Final
14. SPONSORING AGENCY CODE
16. SUPPLEMENTARY NOTES
Supercedes AUER-2200-TR-1 , EPA-560/1 -76-001, (Preliminary Report)
i
16. ABSTRACT
As part of a program for identifying potential environmental hazards
associated with various branchs of technology, a review of the literature
on flame retardants for textiles has been prepared. Covering the periods
1954-74, more than 500 primary documents and consultations with experts
have been digested and cited. Chemicals and chemical treatments which
are being used or have been proposed for producing flame retardant textiles
are listed and discussed. Particular attention is given to toxicological
data, to observations of health effects and to studies of environmental
fates and effects of the materials which are used. The report is divided
into major sections in which classes of natural and man-made textiles are
considered separately. Several chemicals are identified as having their
major application as flame retardants for textiles. These include certain
halogenated monomers, halogenated phosphate esters, and formaldehyde
derivatives of phosphorus and nitrogen compounds. The need for further
studies of the fate and effects of these compounds is indicated.
17.
a. i -DESCRIPTORS
Flame Retardants
Textiles
18. DISTRIBUTION STATEMENT
Release Unlimited
KEY WORDS AND DOCUMENT ANALYSIS
b.lDENTIFIERS/OPCN ENDED TERMS C. COSATI Field/Group
-Environmental Fate 06/F,J,P,T
-Environmental Effects 07/A,B,CX
11/E
#>
19. SECURITY CLASS (This Report}' " "" 2if.'V3l^O^ASSS ""*!'1*
Unclassified
20. SECURITY CLASS (This page)
Unclassified
EPA Form 1*20-1 (t-7J)

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r
   EPA-560/1-76-004
                              A STUDY OF FLAME RETARDANTS
                                     FOR TEXTILES


                                     Final  Report
                              Contract Number 68-01-2209



                                    Project Officer
                                  Irving J. Gruntfest

                              Office of Toxic Substances
                            Environmental Protection Agency
                                Washington, D.C.   20460
                                      Prepared by
                            Environmental Protection Agency
                              Office of Toxic Substances
                                   Washington, D.C.
                                     February 1976                                .

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                               ACKNOWLEDGMENTS

          This study was conducted by the Information Storage and Retrieval
r.roup of AUERBACH Associates, Inc. under the administration of Herbert B. Landau,
Principal Consultant.

          We are indebted to Professor Fred Fortess of the Philadelphia College
of Textiles and Science for his invaluable guidance and assistance in both
tasks of the project.  Through Dr. Fortess' efforts we were able to check the
judgements represented in this report with many renowned flame retardancy
experts in industry, government and academia.

          Helpful consultation in Task II was provided on toxicological impli-
cations of flame retardant compounds, potential degradation products and
interactions with commonly occurring chemical and biological agents by Dr.
Frederic Reidere of National Medical Services, Inc.

          Technical supervision was provided for the EPA Office of Toxic
Substances by Dr. Farley Fisher in Task I and Dr. Irving Gruntfest in Task II.

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                            TABLE OF CONTENTS
 PARAGRAPH                           TITUK                                PACE


                          SECTION I.  INTRODUCTION


 L.I            METHODOLOGY	       1-2

 I.L.I          Search Scope	       1-4
 1.L.2          Time Frame	       1-5
 1.1.3          Study Resources	       1-6

 1.2            FLAME RETARDANTS FOR TEXTILES:   AN OVERVIEW.	       1-7

 1.2.1          Terminology	       1-9
 L.2.2          Flame Retardance and Product End Use	       1-11
 1.2.3          Mechanism of Flame Retardance	       1-13

 1.3            ORGANIZATION OF THE REPORT	       1-16


                    SECTION II.  SUMMARY AND CONCLUSIONS


 2.1            STUDY OVERVIEW	       2-1

 2.1.1          Study Duration	       2-1
 2.1.2          Study Objective	       2-1
 2.1.3          Study Methodology	,	       2-3

 2 .2            FINDINGS, CONCLUSIONS AND RECOMMENDATIONS	       2-3

2.2.1          Nondurable Treatments	       2-3
 2.2.2          Durable Treatments	       2-4
 2.2.3          Man-Made Textiles	       2-5


                     SECTION III.  NONDURABLE TREATMENTS


 3.1            NONDURABLE FORMULATIONS	       3-2

 3.2            PHYSICAL PROPERTIES	       3-2

 3.3            ECONOMIC CONSIDERATIONS	       3-5

 3.3.L          Producers and Production	       3-7
 3.3.2          Principal Markets and Uses	       3-9
 3.3.3          Transportation	       3-13

 3.4            ENVIRONMENTAL IMPLICATIONS	       3-13

 3.4.1          Contamination	       3-13
 3.4.2          Biology and Toxicity	       3-15

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                            TABLE OF CONTENTS (CON-MNUEO)
     *AHAGHAPH                            TITLE                                 PAGE
 3.5            SUMMARY AND CONCLUSIONS	        3-16


                SECTION IV.  DURABLE AND SEMIDURABLE TREATMENTS


 4.1            SEMIDURABLE AND DURABLE FORMULATIONS	        4-2

 4.1.1          Semidurable Flame Retardant Treatments	        4-2
,4.1.2          Durable Flame Retardant Treatments	        4-4

 4.2            PHYSICAL PROPERTIES	        4-5

'4.2.1          Physical Characteristics of Semidurable Treatments.i        4-5
 4.2.2          Physical Characteristics of Durable Treatments	        4-6

 4.3            ECONOMIC CONSIDERATIONS	        4-9

 4.3.1          Producers	        4-9
 4.3.2          Principal Markets and Uses	        4-11
 4.3.3          Transportation	        4-16

 4.4            ENVIRONMENTAL IMPLICATIONS	        4-16

 4.4.1          Contamination	        4-17
 4.4.2          Biology and Toxicity	        4-20

 4.5            SUMMARY AND CONCLUSIONS	        4-23


                         SECTION V.   MAN-MADE TEXTILES

 5.1            STRUCTURES AND PROPERTIES	        5-3

 5.1.1          Halogenated Polymers	        5-4
 5.1.2          Organophosphorus Coreactivesj Additives and
                Finishes	        5-4
 5.1.. '3          Aratnids	        5-7
 5.1.4          Ot:her High Temperature Synthetic Organic Fibers	        5-7
 5.1.5          Physical Properties	        5-9

 5.2            PRODUCTION	        5-13

 5.2.1          Producers	        5-13
 5.2.2          Uses	        5_21
 5.2.3          Current Handling Practices	        5-26

 5.3            ENVIRONMENTAL EFFECTS	        5-27

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                           TABLE OF CONTENTS (CONTINUED)
   PARAGRAPH                           TITLE                                PAGE
5.3.1          Chemistry Involved	       5-28
5.3.2          Biology Involved	       5-29
5.3.3          Biodegradation	„	       5-29
5.3.4          Radiation and Thermal Decomposition	       5-30
5.3.5          Bioaccumulation	       5-32
5.3.6'          Environmental Transport	       5-33
5.3.7          Unreacted Monomers	       5-34
5.3.8          Waste Treatment Problems	       5-35

5.4            TOXICITY	-...	       5-36

5.4.1          Toxicology Studies of Tris (2,3 Dibromopropyl) Phos-
               phate	       5-37
5.4.2          Human Toxicity	       5-38
5.4.3          Toxicity to Birds and Mammals	       5-41
5.4.4          Lower Animal Forms	       5-43
5.4.5          Microorganisms	       5-43

               APPENDIX A.  Table of Flame Retardant Chemicals

               BIBLIOGRAPHY
                                     iii

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                                  LIST OF TABLES
    TAIII
                         TlTUE
PA., i
3-1


3-2

3-3

3-4

4-1


5-1


5-2

5-3

5-4

5-5

5-6

5-7

5-8
 AMOUNT OF  RETARDANT REQUIRED TO PREVENT FUMING AND
 GLOWING (NONDURABLE FINISHES)	     3-3

 VERTICAL FLAME TEST RESULTS OF NONDURABLE TREATMENTS..     3-6

 SUPPLIERS  OF FLAME RETARDANT SALTS	     3-8

 FLAME RETARDANT MARKETS..'.			     3-12

 SUPPLIERS  OF SEMIDURABLE AND DURABLE FLAME RETARDANT
 TREATMENTS	     4-10

 HALOGENATED MONOMERS  FOR FLAME RETARDING TEXTILE
 POLYESTERS, POLYAMIDES AND MODACRYLICS	     5-5

 ORGANOPHOSPHORUS  FLAME RETARDANT..	     5-6

 HIGH TEMPERATURE  SYNTHETIC ORGANIC FIBERS	     5-8

 TRIS - (2,3 DIBROMOPROPYL) PHOSPHATE PROPERTIES	...     5-10

 CHEMICAL MANUFACTURERS	     5-14

 MAN-MADE FIBER PRODUCERS	     5-15

 DYERS AND  FINISHERS	     5-17

 FLAME RETARDANT FIBERS	     5-23






	LIST OF ILLUSTRATIONS	

                      TITLE                                 PAGE



 Textile F,iber Consumption	     4-14
FIGURE
4-1
                                        Iv

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                           SECTION I.  INTRODUCTION

          The advancement of U.S. technology, often accompanied by undesireable
and sometimes hazardous by-products, has led to concern on the part of the
federal government and the public in general over both real and potential en-
vironmental hazards.  This study  focusses upon one segment of this issue:
the potential toxic, carcinogenic, and environmental risks posed by the increas-
ing requirements, under federal legislation, to flame retard textiles for use
in apparel, upholstery, drapes, and other consumer and industrial products.   The
purpose of the study was to perform a comprehensive analysis.  Through published
literature, unpublished reports of manufacturers, review by expert consultants,
and contacts with manufacturer representatives of the state-of-the-art, the
study assessed predictable future trends in textile flame retardant technology,
particularly as these may have an impact upon the environment or human health.
 Support for this study was provided by the Contracts Management Division
 of the Environmental Protection Agency under contract number 68-01-2209.
                                     1-1

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          The study was comprised of two phases, or tasks.  Task I provided a
broad picture of the kinds of flame retardants available, the extent of their
use and the relative threat posed by the alternative technologies to the en-
vironment, the workers, and the community.  Task II was an intensive study of
the major flame retardants for man-made fibers.  It was meant to develop a
full profile of those particular treatments:  the chemistry, production, uses,
engineering problems, contamination and toxicity.

          This volume, A Study of Flame Retardants for Textiles. Final Report
combines the findings of both Tasks.  These observations and conclusions are
based on the open literature published in technical journals, text books, hand-
books, review articles, unpublished research results and manufacturer trade
literature, and expert opinion canvassed from Industry, academia, research labora-
tories, and federal resources.  The literature of chemistry, biology, chemical
economics, environmental studies, public and industrial hygiene, and medicine
is represented throughout.

          Man-made textiles have emerged from this study as the most Important
textiles in the domestic market.  For this reason, the flame retardant tech-
nology of man-made textiles is the class that was selected for the intensive
investigation in Task II of this study.  Halogenated polymers, trialkylated
phosphates,  and aromatic compounds  used in manufacturing  man-made fibers
impart flame retardant properties to them.  In a general sense, organic chemicals
in these classes are known to be of environmental concern and thus further
supported interest in investigating them in detail.

1.1       METHODOLOGY

          Task I 'was purposely designed as a heuristic study.  The earliest
subtask was intended to discover the full range of textile flame retardant
chemical treatments that have been proposed experimentally as well as those
that have achieved commercial success.   Appendix A is a classified list of all
                                                                               \
such processes identified.  It is an aggregate list in that most of the treat-
ments represented have never achieved a degree of commercial use either alone
or in combination with other materials.  However, future  developments,  par-
ticularly in the area of chemical modification of man-made fibers, could well
                                     1-2

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result in the commercial application of several treatments that in today's
market are merely chemical curiosities.  The reality of rapid technological
advancement is emphasized by two factors:  over 20 million dollars a year was
spent by government and industry in 1973 and- 1974 alone on research to develop
new flame retardants; and, the current technology, while theoretically sound,
is inadequate to cope with the combined practical problems of feedstock short-
ages, a highly competitive market place, economical compliance with federal
standards in full production operations, and a relatively limited consumer
demand for flame retardant products should the treatments adversely affect the
cost, or appearance, feel, drape and ease of care that we have come to expect
of textile products.  Not surprisingly, most experts are of the opinion that
manufacturers will continue to use those flame retardant textiles that most
consistently and economically meet the required flammability standards for the
various products, while continuing to look for new, less expensive and more
effective techniques to replace the present methods.

          While recognizing the potential for drastic changes from the recent
practices in flame retardant technology, our methodology was designed to fol-
low the literature and current practice.  It is assumed that the basis for
improved treatments will be found in the current, well developed technologies.
Economic forces outside of the technology of flame retardancy, such as short-
ages of petrochemical feedstocks, fluctuation of cotton prices, patterns of
worldwide demand for textiles, and modifications in the Federal government
product testing methodology have been noted as they were discovered in the
course of the study.  They have not been considered to diminish the importance
of the principal treatments that have been widely used to date.  Pragmatically,
the importance of economic trends was greater in considering an appropriate
direction for the Task II intensive study than in describing the available
technologies that under varying conditions might all find some measure of prac-
tical application.

          Task II zeroed in on the halogenated polymeric flame retardants,
fibers containing organic phosphorus compounds, aramids and related polymers
                   (§)
(specifically Nomex^ ), and other high temperature synthetic organic fibers.
The technical discussion related to Task II is Section V of this report.
Sections III and IV were the result of Task I.
                                     1-3

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1.1.1     Search Scope

          The scope of the study was quite inclusive.  Descriptions•of chemical:
treatments of textile materials with either historical, actual or potential use
as flame retardants were retrieved.  This included coatings and aftertreatments
of fibers and fabrics as well as chemical modifications of cellulose polymers
and thermoplastic polymers that as extruded fibers might be used in textile
materials.

          Subsequently, the study was concentrated on the treatments and
materials that are now most relevant to the textile industry.   Treatments of cellu-
lose have traditionally received the most attention.  Until very recently,
cotton and rayon have been the major substrates.  Man-made fibers, particularly
non-celluloslc thermoplastic polymers have come to greater importance in the
past five years and the technology for imparting flame retardancy to the man-
made fibers is far more complex and diversified than for cotton and rayon.
For the more defined treatments used for cellulosics, the compounds used in
the principal formulations were considered directly within scope.  Thus propri-
etary treatments' including Pyrovatex (Ciba-Geigy), and finishes based on tetra-
kis(hydroxymethy'l)phosphonium chloride were specifically researched under their,
component compounds and in relationship to their actual use in the textile
industry.  Man-made fiber modifications and treatments are not so clear.  Here.
it was necessary for the search to be somewhat more generic.  It was necessary
to concentrate on the monomers most frequently mentioned as having flame re-
tardant characteristics.  In fact, it appears that many man-made polymers in
combination with ammonium phosphates, antimony oxide, mordant9 and various
monomers acting as plasticizers, stabilizers and melt inhibitors are claimed
to be fire retardants by the various definitions of local and state fire codes.
Many such combinations are the basis of proprietary formulations that can be
used to produce textile materials that have flame retardant properties but may
or may not be covered by federal controls.  Greater consideration was given to
Identifying the "important" monomers from the point of view of their widespread
use in textiles or their potential for environmental contamination.  As a re-
sult, the widespread use of vinyl chloride and vinylidene chloride as the prin-
cipal flame retardant monomers in modacrylic fibers, and the limited use of
brominated bis-phenol A and polychlorinated biphenyl compounds are noted as
"important" monomers.

                                     1-4

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          Vinyl Bromide is advertised in the trade Journals for its flame retard-
ant properties but its importance in textile uses is not clear from available
documentation.

          Brominated phthalic esters, and polychlorinated biphenyls are poten-
tially effective flame retardants which would be of environmental concern if
they were widely used.  But here again data to indicate the extent of use are
not available.
          For both  tHe ceTTulosic "and non-cellulosic treatments that have
achieved  an  identifiable role as effective  flame retardan'cs for textiles, the
study was extended  into the  literature of the chemical and textile industry^
textile waste disposal, environmental studies, pharmacology and toxicology.  In
Task II the  effort  was extended further  into the literature of these fields to
look at potential problems that have not surfaced nor have been speculatively
related to flame retardants  by anyone to date.

1.1.2     Time Frame

          The study stresses relevance to the current and foreseeable  technology.
Although  the history  of flame retardant  textiles ia easily traced in the liter-
ature back over 300 years to treatments  for canvas in Paris and London theaters,
books and review articles were sufficient to characterize the early developments
as  they relate to today's technology.  Some inorganic acids and salts  that have
been used from the  earliest  times are used  still.  Borax-boric acid mixtures
are probably the best examples.  However, no attempt has been made to  retrieve
the primary  articles  for such applications.  The indexes and abstracting ser-
vices were searched over a ten year span and selectively for 20 years.  Books
and review articles published in the past 10 years were reviewed.  Significant
primary publications  of the  past 20 years were retrieved.

          In the late 1960s, the U.S. Congress amended the Flammable Fabrics
Act and the  Federal agencies began  to tighten control of the textile industry.
This began the contemporary  period of flame retardancy.  Our study emphasizes
the literature and  technical achievements in the field in this contemporary
period.   So, while  the  time  frame researched for this report is the period
1953  to February 1975,  the  inferences, stress, and interpretations are made
with deference to the contemporary period beginning  in 1967.
                                     1-5

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1,1.3     Study Resources


          The resources used to conduct the literature survey includes,:


          •    Abstracts on Health Effects of Environmental Pollutants.

          •    Air Pollution Abstracts (APTIC)                    ;
          •    Annual Bibliographies, of the Information Council on Fabric
               Flammability

          •    Applied Science and Technology Index

          •    Biological .Abstracts

          •    Bloresearch Index

          •    Chemical Abstracts (Chemical Condensates)

          •    Chemical Economics Handbook

          •    Engineering Index

          •    Excerpta Medica

          •    FDA Clinical Experience Abstracts

          •    Index Medicus

          •    Science Citation Index

          •    Textile Technology Digest
          Journals

          •    Current issues of over  100  journals  covering:

                    Environmental science
                    Pharmacology
                    Chemistry
                    Toxicology
                    Industrial Hygiene
               >-    Medicine
                    Textile Technology


          Primary Articles

          •    Over 500 primary articles,  unpublished and proprietary documents,
               and patents were examined and indexed when relevant.   Each ar-
               ticle was cited, abstracted and duplicated.  One copy of each
               significant article is  submitted under separate cover to the
               EPA Project Officer.

          •    Citations in this report refer to the unique accession number
               assigned to the retrieved articles,  books, monographs, supple-
               mentary documents, and  government reports.

                                   1-6

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 1.2       FLAME RETARDANTS FOR TEXTILES;  AN OVERVIEW

          Historically,  the  technology of imparting flume retardant proper I I.CB
 to textiles has progressed in five stages.  The first attempts consisted of
 solutions of water  soluble salts applied to curtains and drapes in public
 buildings.  The effectiveness of the various treatments was mixed.  The more
 successful formulations  are  still in use for applications in which there is
 little chance  that  the product will be subjected to rain, perspiration or
 washing.  The  class of nondurable fire retardants is representative of this
 first stage.   The second stage of development involved rendering soluble de-
 posits insoluble within  the  fabric.  This was an extension of the work with
 soluble salts.  Studies  involving both water soluble retardants and insoluble
 deposits have  been  carried on concurrently since about 1850.  The third stage
 of development evolved in the 1930s and was spurred on by the outbreak of
World War II.  Flameproof canvas tentage for outdoor use by the military was
 produced with  a treatment of chlorinated paraffin and an insoluble metal oxide,
mostly antimony oxide as a glow inhibitor, together with a binder resin.   The
 treatment required application from an organic solvent.   About the same time  the
 fourth stage in the development of fire retardants was beginning under the spon-
sorship of the U.S. Army Quartermaster and the National Research Council,
National Academy of Science.   The fourth stage investigators conducted basic
scientific studies of the mechanism of flame retardancy.   Resulting treatments
were based on the chemical reaction of the fire retardant with cellulosic
molecules.  The hydroxyl groups of the cellulose molecule can react directly  or
with an acid catalyst with many fire retardants.  If the  fire retardant has no
cellulose reactant groups it  can polymerize to form an insoluble coating on the
cellulose.  Fire retardants can also contain both cellulose reactive  groups and
monomers capable of polymerization thus facilitating the  simultaneous cellulosic
reaction and polymerization.   The modern,  durable treatments of cellulosic
materials discussed In Section III of this volume are  products of this fourth
                     2
stage of development.
2
 Drake, George L., Jr.  Fire resistant textiles
 In  Kirk Othmer Encyclopedia of Chemical Technology
 New York, John Wiley, 1966,  9, 300-315 (OTS-AA-0029).
                                     1-7

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          The fifth stage of development is the contemporary era.  Non'-cellu-

losic thermoplastic polymers are becoming increasingly more important as. the.

basic fibers used for flame retardant applications,.  A dramatic example of the.

superior position, of the non-cellulosics is provided by the diminished position

of cotton fiber for use in children's sleepwear since the inception of new

standards, DOC/FF 3-71.  In 1971 cotton supplied 78 percent, or 27 million

pounds, of the fiber used to produce size 0 to 6X sleepwear.  In 1973 cotton

provided less than 10 percent or only 3% million pounds.  It is assumed that
                                                                 3
the expected standard for sizes 7 to 14 will have an equal effect .  Although
                                                             4
research is continuing in order to improve the role of cotton , the emphasis

seems to be on developing additives, coreactants and finishes incorporating

functional groups containing one or more of these elements for thermoplastic
man-made fibers and fabrics:


               Phosphorus
               Nitrogen
               Antimony
               Chlorine
               Bromine
               Boron


          Generically, the common polymeric backbones are:

               Polyolefins
               Polyvinyl chloride homopolymers
               Polyester
               Acrylics and modacrylics
               Pblyatnides
               Phenolics
               Aromatic polyamides/aramids

          The modification of these polymers by the boreaction of organic monomers
bearing the effective functional groups retards the degradation of the polymers
into their volatile monomers and normally gives, a reduction in flammability.
•5
 Anonymous.  Man-made fiber output hits new high.  Chemical and  Engineering
 News, 52  (9):   11,  (1974)  (OTS-AA-0341).

 Daigle, D.J.; et al.  Modifying THP  (tris  (hydroxymethyl) phosphine.)-amid
 flame retardant.  American Dyestuff Reporter, 62  (6):   57-9,  80 (1973)
 (OTS-AA-0020).
                                     1-8

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Consequently,  In a very general sense, any such monomer can be said to be a
flame  retardant  .

          The most recent developments have produced an entirely new class  of
polymers.  Notably, the new structures include an aramid and a novoloid --  very
high temperature aromatic polymers.  Nomex and Kynol respectively are now
commercially available as textiles.  Other names associated with this class
are polybenzimidazole (FBI), polyimides,  polyimidazoles.  The aramids and the
novoloids have the advantage that when they eventually decompose they form an
ash or char and fall away rather than melt.  They avoid the afterburn affects
associated with the other thermoplastic fibers that melt rather than char even
though they will self extinguish if the source of ignition is removed.
1.2.1     Terminology

          There is no clearly defined meaning for many of the terms used to
describe  flatnmability and flame retardance.  As a result, some confusion is
created by  the interchangeable use of terms such as fire retardant, flame re-
tardant,  flame resistant, and fireproof.  The meaning of these and other terms
is often  clear only in context.  For this report the following meanings apply:

          Flame retardant textile:  a generic term including any fabric that
will not  support combustion after the source of ignition is removed.  It is
used synonymously for fire retardant, flame resistant, and fire resistant tex-
tiles.  The textile is expected to char or melt.  It includes all treatments
short of  fireproofing.

  1        Fireproof textile;  This term applies only to those fabrics which
undergo virtually no change when exposed to flame.  It is not used lightly and
it is not synonymous with flame retardant.

          Afterglow;  A condition of flameless combustion existing after the
source of ignition is removed.  Not all flame retardants are afterglow inhibitors
 Creitz,  Elmer C.  Chemical extinction of diffusion flames as related to flame-
 proofing of plastics. In Society of Plastics Engineers, Annual Technical Con-
 ference, Technical Papers 28th, 1970, 368  (OTS-AA-0296).
                                     1-9

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                         I
nor are afterglow inhibitors particularly efficient flame retardants.  After-
glow inhibitors and flame retardants are often used in combination.  Antimony
oxide is  the most widely used afterglow inhibitor and yet it is an inefficient
flame retardant.
                         I
          Nondurable treatment;  A chemical mixture, usually applied in a
water solution'which imparts flame retardance to a fabric or product.  These
treatments are readily removed by water or perspiration and require replacement
after each exposure of the textile to water.

          Semidurable treatment:  Chemical application of a flame retardant
compound  or combination of several compounds to a textile that will resist
water but will not withstand dry cleaning or more than 10 launderings.

          Durable treatments;  Any chemical process used to impart flame
retardant properties to textiles and textile products that will last without
leaching  through laundering and dry cleaning virtually for the life of the
fabric.

          These definitions are merely functional ones.  Flame retardance and
treatment durability are concepts involving the chemical systems, the product
uses, and the testing procedures.  A treatment may be considered flame retard-
ant when  tested by one method, but not another.  Product design, particularly
in the case of carpets and matresses, affects the pass or fail conditions as
much if not more so than the chemical treatments ' .  The definition of dura-
bility actually must be related to the conditions of use for the textile and
product.  Thus, an ammonium phosphate is a completely durable treatment on
cotton or rayon batting used for insulation purposes and never exposed to water
or washing leaching.  These definitions are intended to differentiate the levels
of durability of the initial level of flame retardancy.  The property of
 Mandel, John; M.N. Steel; L.J. Sharman.  NBS analysis of the ASTM Interlabora-
 tory Study of DOC/FF 3-71 flammability of children's sleepwear.  ASTM Standard-
 ization News, 1 (5);   8-12 (1973)  (OTS-AA-0400).
 Roe,  Richard C.  The impact of the new federal flammability standards on the
 bedding industry.  ASTM Standardization News,  1 (5):  23-25, (1973)
 (OTS-AA-0402).
                                    1-10

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durability to leaching generally determines the practicality of the various
treatments for use in different end products.

1.2.2     Flame Retardance and Product End Use

          As a scientific concept, flame retardance is any treatment that
renders a material less flammable than a similar sample of nontreated material.
In practice, this question requires that we distinguish textile products going
into:

          •    industrial applications (automotive, airplanes, etc.)
          •    institutional applications (hospitals, military, hotels,
               nursing homes, etc.)
          •    consumer products (apparel, home furnishings, etc.)

          Up until 1970 the military, industrial applications and public in-
stitutions provided nearly all the market for flame retardant materials.  In
that time the textile industry had supplied flame retardant tentage for the
military and flame retardant cotton, Npmex, and the modacrylics for a great
variety of institutional home furnishings and hazardous occupation protective
clothing.

          Since 1971 new and stringent demands upon the textile and related
industries have resulted from the implementation of the Flammable Fabrics Act.
of 1967 which covers specific products that the general public as consumers
          '          '                                R
will purchase for personal use at the retail counter .  To date, Federal'Testing
Standards regulated by the Consumer Product Safety Commission determine the
flammability performance of carpets (FF/1-70, FF/2-70), children's sleepwear,
sizes 0-6X (FF 3-71) and mattresses (FF/4-72).  Several standards are pending
covering childrens sleepwear 7-14 (FF/5-75) and blankets.  Jurisdiction for
testing has been transferred to the Consumer Product Safety Commission, from
the Department of Commerce.
8    >
 Baum, Burton M.  Flame retardant fabrics.  I.  Problem and solution via flame-
 resistant fibers.  Chem. Techriol., 3 (3):  167-70, (1973)  (OTS-AA-0005).
                                     1-11
                                                                                 AUER8ACH
                                                                                     «

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          Children's nightgowns, pajamas and bed robes, until the implementation

of the standards, had been 90% cotton.  Because t>he flammability standards

includes the requirement that the flame retardance be tested after 50 machine
                             ...  . _	,  .,_.../*.-.- -•— -          .....      .
washes and following 30 minutes drying at very high temperatures,  the flame

retardant cottons have generally been found inadequate to meet consumer  product

requirements.  Chlorine bleaching,  the use of soap and the deposit of calcium
                                                 9,10
salts, all reduce the flame retardant properties.


          As. a result, fibers such as the modacrylics, flame retardant acetate

and triacetate, flame retardant polyesters and blends of these fibers all of

which have inherent properties favorable to meeting the standards have become

a major factor in these end uses where they have never been used before.  Even

as a blended component, cotton is not a factor since blends of cotton and man-

made fibers tend to be more difficult to flame retard than either fiber  alone
 .   11,12,13
alone  '  '  .

          Even prior to the current, severe petrochemical feedstock shortages,

the demand for man-made fibers had  exceeded world-wide production capacity.

Polyester fibers are in the greatest demand.  The result is a worldwide  short-
                                                14
age of these fibers for flame retardant textiles  .
                                                                               i
          Currently, the fiber producers are spending moire money on the         '

development of new and improved flame retardant man-made fibers than on any

other phase -'f technology and development.  Treatments for polyester fibers

are receiving particular attention as a broad variety of tetrabromophthalimldes
9
   Perkins, R.M.; G.L. Drake, Jr., W.A. Reeves.  Effect of laundering variables
   on the flame retardancy of cotton fabrics.  Colourage, 18 (24):  33-6 (1971)
   (OfS-AA-0222).

   Perkins, R.M.; G.L. Drake, Jr., W.A. Reeves.  Effect of laundering variables
   on the flame retardancy of cotton fabrics.  Journal of American Oil Chemists
   Society, 48 (7):  330-3 (1971)  (OTS-AA-0223).
   Tesoro, Giuliana C.; C.H. Meiser. Effects of chemical composition oh the
   flammability behavior of textiles. Textile Research Journal, 40 (5):  430-6
   (1970)  (OTS-AA-0197).
12
   Tesoro, Giuliana C.; J. Rivlin. Flammability behavior of experimental blends.
   Textile Chemist & Colorist, 3 (7) 7  156-60 (1971)  (OTS-M-0198).
13
   Tesoro, Giuliana C.; S.B. Sello, J.J. Willard. Nitrogen-phosphorus synergism
   in flame-retardant cellulose. Textile Res. Jour., 39(2): 180-90 (1969)(OTS-AA-0199)
14
   Anon. Worldwide boom in textile goods spins prosperity for fiber firms.
   Chemical Week, 113, (2):  18-19 (1973)  (OTS-AA-0391).                           !

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have been reported to impart flame retardance to polyesters  '   .   When other
end uses such as upholstery, blankets, drapery and general apparel are covered
by standards, there will be an even greater demand for flame retardant, man-
made fibers if those standards follow the patterns set ecrlier.

          At the same time, at least one major chemical company, American
Cyanamid, as recently as late 1973 was planning a major capital investment
in a phosphine based flame retardant process for cotton products.   They claim
it is durable, produces a soft hand and a pliant product.  Volume production
of phosphine is claimed to be the key to an inexpensive process  .  In a sepa-
rate investigation, a cotton treatment based on tetrakis (hydroxymethyl) phos-
phine (THP), methoylolurea, and trimethylolmelamine (TMM) was found to be
durable through 50 launderings and passed the FF/3-71 test: for children's
sleepwear.  However, these finishes are still susceptable to chlorine bleaching.
Developments such as these could have a significant effect on the future di-
rection of the textile industry.

          The factors controlling the industry response both in product design
and in the research laboratory, are those that affect fashion,  aesthetics,
comfort and general performance requirements expected by consumers while
achieving the flame resistance demanded by government regulations.

1.2.3     Mechanism of Flame Retardance

          This section presents a brief review of the mechanisms by which flame
retardance is generally achieved.  It is intended to explain the general prin-
ciples or reactivity governing the relative effectiveness of compounds shown
to enhance flame retardance.  Theories on pyrolysis of textile materials and
oxidative degradation studies have not been a significant factor in this study.
However, the mechanism of action can differ depending on the type of compound
used as a flame retardant.  The mechanism affects the generation of products
of combustion, some of which are potentially corrosive and toxic.
  Spatz, Sydney M.; H. Stone.  Some N-substituted tetrabromophthalimide fire-
  retardant additives.  Industrial & Engineering Chem. Prod. Res.  & Dev.,
  8 (4):  397-8, (1969)  (OTS-AA-0193).
  Anon.  Flammability reduced in polyester fibers.  Chemical & Engineering News,
  51 (22):  27, (1973)  (OTS-AA-0396).
  Anon.  Pursuing a hot market.  Chemical Week, 112 (20): 24-25 (1973) (OTS-AA-0393)
18
  Refer to note 4, page 1-8.
                                     1-13

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          The mechanism for  imparting  durable  flame  retardance  to  cellulose  is
that  of  increasing  the  quantity  of  carbon,  or  char,  formed  instead of volatile
products of  combustion,  and  flammable  tars.  Salts that  dissociate to-form acids
or  bases upon heating are usually effective fire  retardants.  Salta of  strong
acids and weak  bases are the most effective compounds, ammonium and amine  salts
are generally effective.  Lewis  acids  -and bases,  either  by  themselves or formed in
                               19
combustion are  also effective.

          One mechanism of imparting decreased flammability to  the thermoplastic
materials is to lower the melting point below  the decomposition point of the flame
retardant chemical.  This results in the formation of free  radical inhibitors in
                                                                                 20
the flame front and causes the material to  recede from the  flame without burning.

          Free  radical  inhibition involves  the reduction of gaseous fuels  generated
by  burning materials.  Heating of combustible  materials  results in the  generation
of  hydrogen, oxygen, hydroxide and  peroxide  radicals that are subsequently 'oxidized
with  flame.  Certain flame retardants  act to trap these  radicals and snuff out
the flame.   Halogens, and bromine is more effective  than Chlorine, 'are  particularly
effective.   One reaction is, for example:

                           RBr + H- -—> HBr + R-

If  the resulting compound R  is less readily  oxidized than the radical that is
                                             21
removed,  the result is reduced flammability.

          The role  of phosphorus compounds has been extensively studied.   In both
cellulose and the thermoplastics, phosphorus salts of volatile  metals,  and most
organophosphorus compounds are known to be effective flame  retardants.  The  forma-
tion  of  char appears to be the key.  For example, where  triphenyiphoephate,  tri-
phenyl phosphite, and triphenylphosphine are all  equivalent on  a phosphorus  basis,
the more effective  flame retardant compounds act  by forming phosphoric  acid  which
19
  Baitinger, William F.  Cellulose reactive fire retardants.  Textile Chemist
  and Colorist, 4 (7):  172-6, (1972)  (OTS-AA-0336).
20
  Fenimore, C. P.; F. J. Martin.  Flammability of polymers. Combustion and Flame,
  10 (2):  13509  (1966)  (OTS-AA-0037).

2llbid.
                                       1-14

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results in changing the course of the decomposition of cellulose to form carbon
          22,23
and water.

          The hazardous nature of many of these acidic ingredients at the for-
mulation stage, in waste by-products and as products of combustion is well known
as they have long been used.  Therefore, they are usually applied in moderate con-
centrations and in protected equipment.  However, the application of these poten-
tially corrosive ingredients in the wet phase of finishing mill processes in a
concentrated environment represents a very distinct hazard of progressive corrosion.
Ventilation and scrubbing operations used to remove these acids from the materials
and processing plants can add to air and water pollution in the neighborhood of
the plant.  The inorganic flame retardants, particularly ammonium phosphates,
represent a very undesirable component of stream pollution, if indeed they are
                                                                               24
present in significant amounts in the effluent of the textile producing plants.
The residue of organophosphorus chars resulting from the reclamation of junk
automobiles, municipal incinerators, or as a result of a major fire in a public
building where flame retardant furnishings have been used extensively might also
be considered as potential pollutants.  Another consideration of the increased
use of flame retardant materials compared to when none are used is the increased
production of smoke, carbon dioxide and toxic carbon mon6xide in the immediate
environment where such materials are burned.  Incineration of flame retardant
materials for trash disposal or in a hplocause may produce a greater concentration
                                                                   2S 26
of these by-products than comparable non-flame retardant materials.  '     .  .
  22Refer to note 2, page 1-7.
  23Refer to note 5, page 1-9.
  2Slark, H.j S.M. Atlas. Environmental hazards of modern textile finishing.  In:
    H. Mark.  Chemical  after-treatment of textiles.  Interscience, N.Y., 1971,
    631-4   (OTS-AA-0348).
  25Carroll-Porczynski, C.Z.  Application of simultaneous DTA/TG and DTA/MS
    analysis for predicting in advance of processing the flammability and toxicity
    of gases of composite textile  fabrics and polymers.  In Thermal Analysis,
    Proceedings of the  International Conference on Thermal Analysis 3rd, 1971,
    (pub. 1972), 3, 273-84  (OTS-AA-0281).
  26Carroll-Porczynski, C.Z.  Fabric flammability.  New texting methods and equip-
    ment.   Textile Institute  and Industry, 9  (7):  188-94,  (1971)  (OTS-AA-0300).
                                       1-15

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            The environmental considerations discussed in this section pertain
  to all flame retardants by virtue of their chemical mechanism of action.
  Specific reactions relating to individual treatments are discussed in the
  appropriate sections to follow.

  1.3       ORGANIZATION OF THE REPORT

            The remainder of this report is organized into the following sections:

            II   SUMMARY AND CONCLUSIONS
            III  NONDURABLE TREATMENTS
            IV   DURABLE AND SEMIDURABLE TREATMENTS
            V    MAN-MADE TEXTILES

            Sections III and IV deal mostly with natural fibers,  and celluldsics,
  particularly cotton, are the most important.

          Flame retardance involving man-made fibers is significantly different
from natural fibers to be treated as a separate section.  Section V deals with
flame retardance of man-made fibers.

          The emphasis in each chapter is on the important treatments, for that
class of flame retardants.  Either technical superiority of a treatment or its
Apparent potential for environmental side effects defines an important treatment.
                                      1-16

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                    SECTION II.  SUMMARY AND CONCLUSIONS


          This section is a condensation of the full report.   It consists of
a brief overview of the project and the findings, conclusions and recommenda-
tions regarding non-durable and durable flame retardant treatments,  mostly
applicable to cotton; and, it reviews the state of flame retardance  technology
for man-made textiles.

2.1       STUDY OVERVIEW

2.1.1     Study Duration

          November 16, 1973 to February 15, 1975.

2.1.2     Study Objective

          The study consisted of two tasks.  Task I provided  a broad picture
of the kinds of flame retardants available, the extent of their use  and the
relative threat posed by the various technologies to the environment, the
worker and the community.
                                     2-1

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          Task II was an intensive study of the flame retardants for "man-made

fibers.                 ,


          1.   Halogenated polymers of textile polyesters, polyamides, and
     (          mbdacrylics.

          2.   Fibers containing coreactive and additive organophosphorus
        '       components, and similar aftertreatments for man-made fibers.

          3.   Aramids - fibers in which the fiber-forming substance is a
               long chain, synthetic polyamide with the amide linkages on
               two aromatic rings.

          4.   Other high temperature synthetic organic fibers.


          Task II concentrated on the collection and analysis of information

in the following areas:


          1.   Environmental fate, including

               a.   biodegradation

               b.   hydrolysis, oxidation,  and other chemical processes
                    occurring in the environment

               c.   thermal decomposition

               d.   radiation-induced changes

               e.   bioaccumulation

               •f.   movement through the environment


          2.   Unreacted monomers and oligomers: levels in the finished fibers
              'and their potential toxicity

          3.  "Possible  toxic (including environmental) effects from

               a.   the  polymers

               b.   degradation products from the polymers

              •c.   waste  products from production,  fabrication,  finishing,
                    cleaning (including laundering), or use of the polymers
                    or products containing  the polymers

          4.   Uses and  production levels,  including trends and projections.
                                     2-2

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2.1.3     Study Methodology

          In a two step process the study first established the state of the
art with regard to chemical flame retardance, textile technology, government
standards and economic pressures bearing on the industry.  Step one highlighted
the trends.  Step two concentrated on the flame retardants most relevant to
today's technology and looked beyond the obvious data directly related to tex-
tiles.  It delved into the basic chemistry and biology of the modern flame
retardants, their chemical families and related moieties in an attempt to
identify potential problems that might be associated with their use.

          Task I was basically an extensive literature search that resulted
in retrieval of over 400 relevant articles.  These were read, abstracted and
analyzed and the results were submitted to EPA in April, 1974.  Task II built
on the literature based analysis of Task I.  Additional subtasks consisted of:

          •    Consultation with-acknowledged flame retardant specialists
               in research, industry and academia
          •    Additional primary references
          •    Unpublished reports of work in progress and proprietary
               reports and data sheets on specific products
          •    Government reports
          •    Current journal scan of scientific journals through February, 1975

          Telephone conversations with executives of the man-made fiber industry
and chemical industry proved helpful , particularly with regard to discussions
of the market trends.  Proprietary data on products in development or those that
were semi commercial was not generally made available, however.

2.2       FINDINGS. CONCLUSIONS AND RECOMMENDATIONS

2.2.1     Nondurable Treatments

          The role of the nondurable flame retardant formulations for use on
                                                                 If
textile materials is characterized by two factors:  their total leachability
and their low cost.  The leachability severely limits their use in the growing
                                     2-3

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market resulting from the Fabric Flatnmability Act of  1967; and, their  low coat
to achieve effective flame  retardance assures their use in applications not
subject to reachability.  In the textile market  this means they will become
increasingly less important in any area covered  by rigid standards.  Draperies,
bedding, plush toys and furnishings not covered  by legislation will-be the
principal, but limited markets.

2.2.1.1   Recommendat ion
          In the course of this study, no reason for environmental concern
was indicated with respect to the nondurable flame retardants.  Ammonium phos-
phates , which are probably the most important ones still in use are of 'far
greater concern, if indeed any is warranted, for their use,in nontextile mar-
kets than as textile flame retardants.  No  follow up investigation is recommended.

2.2.2     Durable Treatments

          For treatment of cotton, rayon and to some extent the other natural
fibers THPC and Pyrovatex^ (Ciba Geigy) are adequate to flame retard textiles.
Pyrovatex*-' has also shown promise as a finish for cotton/polyeste'r blends.
However, some growth markets are closed to  them until they will consistently
pass the leach requirements of 50 home launderings.  Cotton's general loss of
market position is the most significant factor likely to keep the use of dur-
able cellulosic flame retardant treatments a limited specialty market.  The
treatments that, will effectively treat the popular cotton/polyester blends
may be entirely different chemically than those now in use for 100% cotton or
100% polyester.

          As a known hazard, these flame retardant systems present only a minor
occurrence of 'dermatitis.  By-products of the manufacture and products of
degeneration a're more serious problems.  In relation to the overall problems
associated with disposal of textile mill wastes, the by-products of manufacture
are unlikely to be significant.
                                     2-4

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  2.2.2.1   Recommendat ions

            Original Investigation of the products  of decomposition and  interac-
  tions of the flame retardants with other chemicals  commonly encountered  in the
  textile industry should be undertaken.   The special conditions  under which
  THPC/OH systems might result in the generation of bis(chlbromethyl)  ether or
  other obnoxious products is the most important question requiring further
  investigation with regard to the durable flame retardants.   An  original  inves-
  tigation of the problem should be undertaken under  the sponsorship of  an
  appropriate Federal agency.  Additional work to test the validity of Afanas'eva's
  work as reported in Section IV is also  indicated  as this search indicated there
  has  been no follow-up study to date.

  2.2*3     Man-Made Textiles                                    >

            Despite petrochemical feedstock shortages, man-made textile  fibers
  will continue to dominate the market.   Of these,  the cotton/polyester  blends
  will be the most significant.  For special flame  retardant  textile products
  such as apparel and both home and industrial furnishings, the market is  pre-  ,
  dieted to expand from the current 5% level to 20% in 1980.   Flame retarding
  techniques for textiles which will grow will be the use of  coreactives,  additives,
  and  finishes; however,  at this point, it is not predicted that  any one of these
  will be of more significance than another.  The next major  technological growth
  area in textile flame retardant industry will be  the flame  retarding of  blends.
  The  techniques used for blends will be  chemically different from  those used
  either for 100% natural fibers or for 100% man-mades.

          The flame retardants we studied, namely haloorganics,  organic  phosphates,
aramids, and other high temperature polymeric structures, are all relatively stable
in the environment.  Very little information is available concerning their decom-
position in sunlight, their  thermal decomposition and combustion products, their
blodegradation, or their  solubility and solubility  products in such matrices as
human saliva, urine, sweat, or  infantile bowel movements.  Further, no long-term
toxicity studies are available on these compounds.
                                       2-5

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          Vinyl bromide is apparently increasing its share at the market.  There
is still insufficient published information to fully characterize Its use and
potential.  Efforts to collect such information may require significant cooperation
from the manufacturers.

2.2.3.1   Recommendations

          We have found no evidence which would lead to exceptional environmental
or toxic concern for the flame retardants for man-made textiles.  Flame retardants
used for non-textile purposes, or related chemicals used in fertilizers and pesti-
cides .would appear, to be of more concern by virtue of their greater volume of use.
However, continued monitoring of technological developments in this field are
warranted.  Specifically, we recommend that tests of these flame retardants and
the chemicals with which they come into frequent contact be conducted.  These
would include chldrine bleach as well as the atmospheric components:  ozone, sul-
fur dioxide, nitrous oxide, and cyanide;  Of particular concern are circumstances
under which the generation of analogs of bis chloromethyl ether might occur from
interactions of chloride and bromide components of flame retardants with other
fabric finishes.  We further recommend legislation to require acute, subacute,
and chronic toxicity testing as well as environmental monitoring of plant sites
involved In manufacture or finishing, coupled with a mechanism for reporting of
the results of these tests on a regular basis.
                                       2-6

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                     SECTION III.  NONDURABLE TREATMENTS


          Nondurable flame retardant treatments are mixtures of chemical salts
applied in a water solution to fabrics and end products that are not likely to
be laundered or subjected to other water, such as perspiration or rain.  His-
torically, nondurables are the oldest class of flame retardants.  These water
soluble treatments are easily applied, but just as easily leached out.  Gen-
erally, they have to be reapplied after any substantial contact with water.
Each of the general articles reviewed are similar in their discussions of the
use of these treatments.  Buck and Bhatnagar among others describe the formula-
tions, uses and chemistry of these treatments in succinct but comprehensive
        12
fashion. '   The definition of durability is a relative one.  A nondurable treat-
ment of a cotton or rayon batting with ammonium sulfamate used for insulation
purposes and never exposed to water or leaching is, in a sense, durable.  How-
ever, the common property of water solubility determines and limits the practi-
cal use of this class of flame retardants.
 Buck, George S.  Fire resistant textiles.  In Encyclopedia of Chemical Tech-
  nology, 1st, Interscience Encyclopedia, N.Y., 1951, 6, 543-558 (OTS-AA-0339).
2
 Bhatnagar, Vijay M.  Fire retardant formulations handbook. Weatport, Conn.
 Technomic, (1972) (OTS-AA-0010).
                                     3-1

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 3.1        NONDURABLE FORMULATIONS


           The list of inorganic  compounds  that have been used at  one time  or

 another as nondurable flame retardants is  quite extensive.   A select list  of

 the  more effective compounds still in use  is  shown in Table 3-1.   Their rela-

 tive effectiveness is indicated  by the percent add-on necessary to prevent
         3
 flaming.


           The more common treatments  are usually synergistic mixtures of two or

 more salts which are more effective than either component alone.   Formulations

 that have been reported  in two or more sources to be useful for textiles are:


           •    seven parts borax,  three parts boric acid;

           •    seven parts borax,  three parts boric acid, five parts
                diammonium phosphate;

           •    one part  sodium phosphate,  one part borax, one part
                b'oric acid, one part diammonium phosphate;

           •    ten parts borax,  seven parts boric acid,  three parts
                sodium phosphate;

           •    ammonium  sulfamate  alone;

           •    three parts ammonium sulfamate,  one part  diammonium phosphate.;

           •    ammonium  bromide  alone;

           •    15  parts  borax, 47  parts boric acid,  18 parts sodium
                phosphate,  20 parts sodium  tungstate.


 3.2        PHYSICAL PROPERTIES

           Water solubility is the  outstanding physical characteristic  common to
 the  nondurable flame retardants.   In  addition to the  relative inflammability of
 the  compounds  shown in Table 2-1,  the effective treatments  exhibit synergistic
 properties in  mixtures.   For example,  an add-on of 60% of borax is required  to
 prevent  fabric  flaming,  and  boric  acid  by  itself is  inefficient as a flame
 retardant  even with an add-on level of  300% by weight.   A mixture  of seven parts
3
 Buok, George S.  op. cit.
                                     3-2
                                                                                 AUCRBACH
                                                                                     «

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             TABLE  3-1.  AMOUNT OF RETARPANT REQUIRED TO  PREVENT
                  FLAMING AND GLOWING  (NONDURABLE FINISHES)
                     Retardant                       Minimum
                                                    add-on. %*
                     Ammonium bromide, NH.Br	7

                     Ammonium molybdate,  (NH,)_MoO,	7

                     Sodium tungstate, Na^O^.Zl^O	9

                     Diatnmonium phosphate,  (NH,)_ HP0^....12

                     Phosphoric acid, H3PO,	 12

                     Zinc chloride, ZnCU	.. 12

                     Ammonium iodide, NH, 1	14

                     Calcium chloride, CaCl,,.6H20	.14

                    Magnesium chloride, MgCl.	16
                    Ammonium
sulfate, (NH4)2S04	18
                    Sodium stannate, Na SnO,	 18

                    Sodium aluminate, NaAlO-	19

                    Sodium silicate, Na2Si03.9H20	20

                    Ammonium chloride, NH.C1.	22

                    Ammonium borate, NH, BO.	24

                    Sodium bisulfate, NaHSO, .H20	30

                    Sodium arsenate, Na AsO,.12H-0	.33

                    Borax, Na B 0 .lOHO	60
* Parts by weight added per 100 parts fabric.
                                     3-3

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borax and  three parts boric acid on  the other hand, gives adequate  flame
retardance with only 6 1/2% add-on.

          Nondurable treatments possess the properties that would make  them
very desirable as flame retardants for many textile uses, if it were not for
their water solubility.  They add little to the fabric weight.  They usually
do not affect the color or tensile strength of the fabric.  When carefully
applied, the small add-on required for the more effective treatments has little
effect on  the hand, drape, flexibility, and tear strength of the treated
fabrics.   Regardless of the various  demands for different finishing properties,
combinations and modified formulations can be made to meet specified require-
ments.  Some formulations may cause  cloth stiffening, as the stiffening effect
of the various salts and mixtures varies considerably.

          The nondurable flame retardants act by a combination of mechanisms.
Some form a foam coating of fused particles that protects the fabric from
further combustion.  They also release mineral acids that alter the cellulose
degradation mechanism.  They can also snuff out a flame by generating a
noncombustible^atmosphere of gases and vapors.  The natural action.-of inorganic
salts to lower the decomposition point of the cellulose polymer is isufficient,
in some cases, to cause gradual yellowing and loss of tear strength in  treated
fabrics if they are subjected to drying or prolonged heating in application
processes.  Although at ordinary temperatures no appreciable deterioration of
finished fabrics is likely to occur with any of the treatments, exposure to
sunlight or elevated temperatures will, in most cases, cause a considerable loss
in strength.  The significance of this phenomenon is that the use of such treat-
ments on materials such as curtains, home and office furnishings and automobile
carpets and upholstery exposed behind windows in direct sunlight would be de-
structive to cellulosic fabrics.
  Kasem, M. Abul; M. Richards.  Flame-retardants for fabrics.  Function of boron-
  containing additives.  Industrial & Engineering Chemistry, Product Research &
  Development, 11 (2):  114-33, (1972).  (OTS-AA-0048).
  Smith, James Kenneth, et al.  Thermochemical investigation of cotton flame
  retardance.  Textile Research Journal, 40 (3):  211-16, (1970). (OTS-AA-0092).
                                     3-4
                                                                                 AUCRBACH
                                                                                    «

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          In the mixtures of salts chosen for flame retardant  formulations,  early
workers with nondurable treatments looked for deposits which would  not crystallize
on the fabric as an important physical characteristic.  Not only would crystalli-
zation have caused aesthetic problems, but it tends to inhibit the  flame retardant
properties of the mixtures.  Thus, the nondurable treatments currently in use do
not crystallize on treated fabrics.
            Lyons provides some comparative flame retardance data on seven non-
  durable formulations studied for their effect on cotton fibers.   Table 3-2
  shows the data collected on the test formulations at a 10% add-on after the
  vertical flame test method.  The inferior position of ammonium sulfamate
  (NH,SO,NH~) compared to the ammonium phosphates is clear. Afterglow with
  boron-treated compounds is also seen as a problem, but they  seem to display a
  superior performance with lower char lengths than the other  retardants.  In
  several similar tests involving more durable phosphate containing retardants,
  the glowproofing superiority of phosphorus-containing flame  retardants is
                    6
  further supported.

  3.3       ECONOMIC CONSIDERATIONS

            The principal advantage of the nondurable treatments has always been
  their relative low cost.  Before the current inflationary period, the nondur-
  able finishes that were easily applied in a commercial laundry with a 10-15%
  dry add-on in a simple pad-dry operation could be produced at approximately 20
  cents per pound of chemical, or approximately 2-3 cents per  pound of cotton
  treated.  This cost was roughly the same for any of the more common formulations
  described in section 2.1, preceding.  For example, an 8 ounce per square yard
  fabric would cost an additional 1 to 1.5 cents per square yard.  If the pad-^dry
  operation costs 2 cents per yard, the final cost at the mill was  3 to 3.5  cents
  per yard of fabric for fire retardance, compared to a cost of  13 to 15 cents per
 i
  square yard for cotton treated by one of the more durable processes.  However,
    Lyons, John W.  The chemistry and uses of fire retardants.   NewjYork,  Wiley-
    Interscience, 1970.  (OTS-AA-0075).
                                       3-5

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                                        TABLE 3-2.  VERTICAL FLAME TEST RESULTS


                                                OF NONDURABLE TREATMENTS1
10
i
Treatment



Borax:  Boric Acid (7:3)



Borax:  Boric Acid (1:1)



(NH4)2HP04



NH4H2P04



Borax:  Boric Acid:  (NH4>2HP04 (7:3:5)



Borax:  Boric Acid:  (NH4)2HP04 (5:5:1)
Afterglow, Sec,



     190



      32



       0



       0



       8



      43



     550
Char length, in.



      2.6



      2.7



      3.9



      3.4



      3.2



      3.1



      5.0
                    Source:  Lyons, John W.  (see note 6, p. -3-5)

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for a hospital or institutions where continual reprocessing was needed,  the
                   789
costs are additive. '  '

          The additive costs for reprocessing institutional materials has in-
creasingly reduced the economic advantage of the nondurables, and, with the
development of inherently flame retardant fabrics of man-made fibers, institu-
tional use of nondurable flame retardants has virtually been eliminated.

          No data were found to identify the economic forces affecting the
individual submarkets of the specific nondurable treatments.  In most instances,
it was not possible to identify the textile flame retardant markets for the
chemicals involved in nondurable treatments, since these are overshadowed by
the wide and varied uses of the chemical compounds involved.  Monoammonium
phosphate and diammonium phosphate, for example, are probably the most heavily
used nondurable textile flame retardants currently employed; however, these
compounds are even more commonly used in agricultural feeds and fertilizers,
and their market as flame retardants is relatively insignificant.

3.3.1     Producers and Production

          Table 3-3 lists the major suppliers of inorganic salts for flame
retardants.  The extent to which these suppliers are responsible for textile
flame retardant formulations is not differentiated from their supplying the
same chemicals for other uses.  Nor is the use for nondurable treatments
differentiated from use in durable formulations.

          Production figures related to fire retardant textiles are not clear.
Ammonium phosphate, ammonium sulfamate, borax, boric acid, ammonium chloride
and ammonium bromide are probably the salts used more than any others.  Figures
on their actual use as textile flame retardant treatments is clouded by their
  Title, M. M.; M. S. Brent.  Purchasing flameproof fabrics that meet the fire
  code.  Part 2.  Hospital Management, 94, 73-6 (1962). (OTS-AA-0366).
8
  Gardner, H.K.; et al.  Applying a durable flame retardant with inplant equip-
  ment.  Hospitals, 37, 123-6, (1963), 16 Nov. 63.  (OTS-AA-0369).
9                                                              t
  Title, Monroe M.; M. S. Brent.  Purchasing flameproof fabrics that meet the
  fire code.  Hospital Management, 94, 74-6, (1962).  (OTS-AA-0398).
  Jacobs,  E. A.;  et  al.  Testing flame retardant  linen  for hospital  use.
  Hospitals, 42,  65-7,  144,  (1968),  16 May  68.   (OTS-AA-0372).
                                     3-7

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             TABLE 3-3.  SUPPLIERS OF FLAME RETARDANT SALTS
          Company and Treatment
      Chemical
      American Cyanamid
        Aerotex Fire Retardants

      Dexter Chemical
        Protonoc

      DuPont
        CM and X-12 Flame Retardants

      Freeport Kaolin
        PA 1

      GAF
        Gaftex Fire Retardant

      Great Lakes

      Humphrey Chemical
        ZB
        HFX-500

      Laurel Products
        Pyrosan

      March Chemical
        Flame-Safe

      Monsanto
        Phos-Chek

      Scholler Brothers
        BR Salts FP-SP

      Selig Chemical
        Flammex

      Sun Chemical
        Warconyl 351-A

      Swift & Co.
        Bromiriex

      Charles S. Tanner
        CST Fire Retardant
        Tanotard

      U.S. Oil
        Usco Fire Retardants

      U.S^ Borax
        FR-28
        Firebrake 2B
Inorganic Salts

Inorganic Salts

Ammonium Sulfamate


Aluminum Phosphate


Inorganic Salts

Ammonium Bromide
Zinc Borates
Proprietary

Inorganic Salts


Fusable Salts

Ammonium Phosphates

Inorganic Salts


Inorganic Salts

Inorganic Salts

Proprietary

Inorganic Salts
Organic and Inorganic Salts

Inorganic Salts
Borax, Boric Acid
Sodium Borate
Zinc Borate
Source:  American Dyestuff Reporter, January and February 1972.

                                   3-8

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use as feedstocks for the production of other flame retarded materials, par-
ticularly halogenated polymers and phosphate polymers for nontextile products.

          Estimates on the use of ammonium phosphates consumed as cellulosic
fire retardants, including paper and wood products, put consumption at about
18 thousand short tons per year.  Monsanto is the principal supplier with over
two thirds of the market.  The primary competitive material in cellulosic fire
retardation is DuPont's ammonium sulfamate.  The products apparently compete
equally on a price basis.  As noted previously, ammonium phosphates are more
effective, but ammonium sulfamate is reported to be less of a skin irritant.
          The relatively minor role of inorganic salts used as flame retardants
is demonstrated by Monsanto's production figures for 1973.  Monsanto's produc-
tion capacity for monammonium phosphates and diammonium phosphate together
                                                                 o
is approximately 45 thousand short tons.  Its principal market consumption is
estimated as:

          Fertilizers                     5,071 short tons
          Livestock feed                     37 short tons
          Fire Control                       45 short tons
            extinguishers                    17 short tons
            flame retardants                 18 short tons
            forest fire control              10 short tons
          Other                              11 short tons
                           Total          5,164 short tons

3.3.2     Principal Markets and Uses

          The use of nondurable flame retardants has steadily declined since
the late 1950's when practical, durable treatments for cellulosic materials
began to become available on a commercial bases.  Institutional uses at hos-
pitals, particularly those of the Veteran's Administration, provided the bulk
of the market for nondurable flame retardants until that time.  A smaller, yet
significant market was also maintained in such industries as steel where ex-
posure to flame was an occupational hazard.  In such applications, which ex-
 i
isted in highly controlled environments, it was possible to reapply a flame
                                                                o
                                     3-9

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retardant  finish  to the  fabric after each use.  Curtains and drapes  in  theaters
and other  public  buildings provided another popular market  for the nondurable
formulations.

           Current nondurable  flame retardant markets are largely  for uses not
covered by federal legislation.  Many of the products are applied in the last
rinse water at  industrial and commercial laundries, where their uses are still
found economical  either  because of limited use, or-to avoid,'a major  capital
reinvestment.   Building  materials, drapes, tapestries and the like are  flame
retarded with a spray application.  In these and other uses, the market is not
readily definable.  Additional, contemporary market consumption patterns that
have been  suggested are  for cotton flote products, or the plush toy market
where there is  not yet any strong legislation, but the manufacturers involved
are concerned about product liability as well as attempting to prevent  the
kinds of fire incidents  that would lead to legislative controls.

           The market position of .the nondurable flame retardant treatments is
directly linked to the overall textile market.  Nondurable  treatments are
effective  on cellulosic  fabric.  The cellulosic textiles are not only losing
market position in general to the man-made fibers, but they are losing put
specifically in the area of flame retardant products since  the standards set
to determine flammability include a leaching procedure that for most of the
products eliminate the water soluble treatments before testing.  In  addition,
it seems that even if the current standards were modified to permit  the use of
less than  permanently durable flame retardants in products  such as carpets or
upholstery, when  those products are covered by legislation, the treatments that
are likely to benefit are semidurable combinations rather than the truly non-
                         12 13
durable treatments here.  '

           For all practical purposes, it appears from the current market trends
that the inorganic salts applied to cellulosic textiles, primarily cotton, are,
  Refer to note 9,  page 3-7.
12
  Friedman, M.;  R.E: Whitfield, S. Tillin.  Enhancement of the natural flame-
  resistance of wool.  Textile Research Journal, 43 (4): 212-17, (1973)
  (OTS-AA-0039).
13
  Gilbert, S.; R. Liepins. Treatment for improving flame retardancy of wool and
  minimizing toxic gas evolution in burning. Journal of Applied Polymer Science,
  16  (4):  1009-16,  (1972) (OTS-AA-0040).    .

                                    3-10

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less desirable than a range of other phosphorus and nonphosphorus chemical
compounds for fire retardant treatments.  Market growth expected as a result
of recent legislation is shown in Table 3-4.  Of the seven major markets that
are likely to be the controlling factors in the growth of flame retardants,
nondurable treatments are apt to benefit mostly from nontextile applications.
Carpet and rug standards (DOC FF-1-70, FF-2-70) require ten scrubbings,
apparel standards, 50 washings.  In these products nondurable treatments will
find no market.  Bedding standards (FF-4-72) have reduced or eliminated the
leaching procedure and may provide some market for the nondurables in the
padding.  However, the full impact on the bedding industry and its response .is
not yet complete.  Industry spokesmen refer to a need to totally redesign
bedding in response to federal standards.  Factors such as the tightness of
weave, the use of nonflammable thread, the design of gatherings at the edges
and corners and the choice of component materials may be more significant than
                                                    14
flame retardant treatments of the textile component.    It seems unlikely that
the forthcoming standards on upholstery and other home furnishings are likely
to be less stringent than the carpeting standards.

          Anticipated growth is seen more directly linked to uses in paper
and wood products, and in some internal insulation materials used in construc-
tion.  Paper products including facial tissue, boxboard, decorative paper,
insulating board, book matches and cigarette papers are more promising markets
for the nondurables than textile products.  Ammonium phosphates are consumed
as flame retardants on cellulose construction products such as beams, insula-
tion, ceilings, chipboard and siding used for internal construction.

          Forest fire control and fire extinguisants are further areas of
growth that are more probably going to receive the impetus of marketing efforts
by the major producers than are nondurable textile treatments.  Solid ammonium
phosphate is the leading chemical used as an active ingredient in these solu-
tions with 45-55% of the total market volume.  Ammonium sulfate represents about
307, with the rest going to ammonium polyphosphate solutions.
14                          '
  Roe, Richard C.  The impact of the new federal flammability standards on the
  bedding industry.  ASTM Standardization News, 1 (5): 23-25, (1973)
  (OTS-AA-0402).
                                    3-11

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                                       TABLE 3-4.  FLAME RETARDANT MARKETS
OJ
i
ro
Market

Carpets and rugs
Construction
Miscellaneous
nondurables*
Estimated Consumption
(Millions of pounds per
1971
100-125
14-22
10-15
Electrical and electronics 11-12
Apparel
Transportation
Home Furnishings

*wood, paper and other
Source: Chemical and
8-10
4-5
3-4
Total 150-193
nondurables
Eng. News Oct. 18, 1971
year)
1975
425-550
75-100
15-20
35-40
34-36
70-80
20-25
674-851
                        (OTS-AA-1346)

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3.3.3     Transportation

          The transportation patterns for  flame retardant materials either as
preprocessing chemicals or  finished goods was not discernable from the data
reviewed.  It does appear that the inorganic materials listed in Table 3-3
are provided to  the textile mills in powder form.  Ammonium phosphates,
ammonium sulfamate, ammonium halides and borax are transported interstate by
rail and truck.  Domestic producers probably account for all the bulk chemicals
used in the nondurable flame retardant textile formulations and products.  Im-
ports do not appear to have a significant  role other than the supply of raw
textile materials.

3.4       ENVIRONMENTAL IMPLICATIONS

          The textile finishes described in this section involve chemical com-
pounds that in large supply could bring with them several environmental haz-
ards.  Air and water pollution by the raw chemicals involved could conceivably
result in corrosion and toxicity problems.  However, the use of phosphates,
ammonium sulfamate, borax, boric acid, and ammonium halides as textile flame
retardants is virtually insignificant compared to their use in agriculture,
other chemical processes and even as flame retardants for nontextile, cellulosic
materials.  The  environmental implications resulting from their use as textile
flame retardants are thus of minor import compared to their contribution to
environmental hazards from  their use in other capacities.

3.4.1     Contamination

          The data reviewed do not indicate that the use of inorganic salts per
Sj2 as textile flame retardants is a source of environmental contamination.
Handbooks, industrial hygiene texts, and journal data covering air, soil and
especially water pollutants emanating from textile mills, at best make reference
15
  Burr, Francis K.  Textile Waste Treatment.  In   Kirk Othmer Encyclopedia of
  Chemical Technology,   (supplement)  Wiley-Interscience, N.Y., 1971, 979-983
  (OTS-AA-0370).
                                    3-13

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to the general problems of  inorganic  salts as a water pollutant.   '   '    The
potential contaminants are  limited principally to  the phosphates as water
pollutants, escaping ammonia  from the drying processes  that  is ventiliated into
the environs of the finishing mills,  and hydrogen  chloride and hydrogen bro-
mide generated in a fire by the ammonium halides.

          In the drying processes, the ammonium compounds tend to  give off
ammonia gas through decomposition.  Diammonium phosphate, in particular, loses
ammonia and is converted to monoammonium phosphate at a rate directly propor-
tional to temperature increases.  This reaction reportedly can proceed with
only sunlight as an energy  source.  At 125 , monoammonium phosphate is stable,
                        i                                     19
but diammonium phosphate is not.  This is described by Lyons according to the
following equation:

            i, H_ PO,
            424
NH, H,, PO, —NH3
              Pmm = 0.05 at 125°C
              log Pmm = 3063 + 1.75 log T -f 3.3
                         T                                       '.    '     .
              where:  P = millimeters of Hg.
                      T = absolute temperature in degrees Kelvin.

          Documentation of phosphate pollution of water is quite extensive and
beyond the scope of this present volume.  An indication of several of the sig-
nificant problems that would be exacerbated by the extensive use of ammonium
              *
phosphates as nondurable flame retardants is provided in a symposium entitled
"Phosphorus in Fresh Water and the Marine Environment", published in Water
Research 71/2 1973.  However, serious consideration of this problem as a result
of the increasing use of these compounds as flame retardants for nontext lie
cellulosic products might be a proper study beyond the present one.
      , H. ;  S.M. Atlas. Environmental hazards of modern textile finishing.  In:
  H. Mark chemical  After-treatment of textiles.  Interscience, N.Y. , 1971,
  631-4  (OTS-AA-0348).
  Anonymous.  Textile waste cleanup.  Environmental Science and Technology,
  7(8): 682-683, (1973) (OTS-AA-0383) .
1 8
  Trobisch,'K.  Measures against water pollution in industries producing petro-
  chemicals  including polymers.  Pure and Applied Chemistry, 29 (1):  57-65,
  (1972)  (OTS-AA-0395)
        to note 6 on page 3-5.
                                    3-14

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          Monitoring and analysis of nondurable flame retardants is a poorly
documented field.  The common chemicals used have been analyzed by both spec-
troscopic and chromatographic methods.  General analytical data is readily
available in the standard handbooks of the appropriate fields.  One newer
                                                           20
technique specific to the present discussion was retrieved. w  Elliott, Heathcqte
and Mostyn report on a procedure for the determination of phosphorus in fire re-
sistant textiles by cool flame emission spectroscopy.  Basically, they show tha.t
this technique is suitable only for nondurable treatments.  Residual acids as
nitrates and sulfates present in extracts with the durable finishes interfere
with the interpretation of data on the durable finishes.  A complete determine?
tion by this method requires about four hours, with an ion exchange stage
accounting for over one half of the overall time.

3.4.2     Biology and Toxicity
                                                                 j
          Borax-boric acid mixtures are the least hazardous components of the
nondurable flame retardant formulations.  In a German study, the boric acid
concentration was measured in the blood of 21 hospitalized patients treated with
wet compresses over several days.  Only one patient showed a significant rise.
There were indications that pre-existing kidney damage was responsible.  Follow
up studies on rabbits with kidney damage indicated that the half time value of
boric acid in the blood was significantly prolonged.  In the diseased state,
                                                                        21
the toxic limit in the blood was easily reached through bioaccumulation.
By analogy, it may be valid to speculate that flame retardant salts would ex-
hibit the same results.  Again, the reduced use of these materials in hospitals,
in particular, limits the significance of these findings for the nondurable
treatments, but raises it where bedding is still so treated.

          The biological implications of the nondurablea are again characterized
•by their solubility.  Any skin contact creates a potential for immediate
absorption.  Toxicity is generally low.  Ammonium sulfamate is sold under the
  Elliot, W.N.; C. Heathcote, R.A. Mostyn.  Determination.of phosphorus in
  fire-resistant textiles by cool-flame emission spectroscopy.  Textile Re-
  search Journal, 42  (2):  86-8,  (1972)   (OTS-AA-0035).         '
  Schuppli,  R.; et al.  On the  toxicity of boric acid.  Dermatologlca, 143 (4):
  227-234,  (1971)  (OTS-AA-0354).
                                    3-15

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name  "Animate" as a»weed killer and reportedly has an oral LD-n in rats of 3.9 g/kg.
Although similar data were not obtained for the other major compounds, ammonium
phosphates can cause skin irritations more readily than ammonium sulfamate.  The.
ammonium halides are both more active.  Ammonium chloride is used as an expectorant
and is a diuretic for human and veterinary purposes.  It has an intramuscular LD
in rats of 30mg/kg.  Ammonium chloride is known to cause pulmonary edema in humans
                     22 23                                                        '
cats and guinea pigs.  '    Ammonium bromide is a sedative at an oral dose of
0.6 to 2g.   Gastrointestinal dlstrubances have been reported as side effects.
  3.5       SUMMARY AND CONCLUSIONS

            The role of the nondurables in  the overall flame retardant picture
  is characterized by two factors:  their total leachability and their low cost.
  The leachability severely limits their use in the growing market resulting from
  the Fabric Flammability Act of 1967; and, their low cost to achieve effective
  flame retardance assures their use in applications not subject to leachability.
  In the textile market this means they will become increasingly less important
  in any area covered by rigid standards.   Draperies, bedding, plush toys and
  furnishings not covered by legislation will be the principal, but limited
  markets.

            The effective combinations and  formulas have been fully developed.
  With no need for further development, the compounds discussed in section. 3.1
  will constitute the basic ingredients of  formulations that could find use in
  future markets.  These compounds are relatively innocuous, particularly since
  they will not be used to the extent that  strong concentrations are likely to
  result except in the immediate processing areas of a textile finishing mill.

            Additional data that might be developed from an intensive study of
  nondurable textile flame retardant formulations would be germane, but dated.
  22
    Nltta, Sumio; N.C. Staub.  Lung fluids in acute ammonium chloride toxicity
    and edema in cats and guinea pigs.  American Journal of. Physiology, 224 (3):
    613-617, (1973)  (OTS-AA-0360).
  23szam, Istvan; E. Vincze, J. Szentner. The pathogenesia of ammonium chloride
    pulmonary edema. Zeitschrift flier die Gaesamte Innere Medizin and Ihre
    Grenzgebiete, 26 (12): 378-383, illus., (1971)  (OTS-AA-0350).
                                      3-16

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The most significant, contemporary data that might be developed in addition to
this volume, is a detailed characterization of the nonlegislated uses of the
nondurable treatments, but such data is not readily available,  and of minor
importance both from the point of view of volume of use and potential hazard.
                                    3-17

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                    SECTION IV.  DURABLE AND SEMIDURABLE
                                 TREATMENTS

          Durability is a relative concept relating to the ability of a flame
retardant chemical, system for textile materials to withstand water and washing
to some degree.  Although most authors on flame retardants for textiles
differentiate between the two classes, both the semidurable and durable treat-
ments are intended for use on products that will retain their flame retardance
for the useful life of the product under normal circumstances.  The semidurable
treatments have little or no resistance to dry cleaning solutions and will not
withstand more than a few launderings.  The loss of flame retardance for both
durable and semidurable treatments depends on the progressive leaching of the
flame retardant, and ion exchange aggravated by the ionic contents of hard
water and/or deposition of insoluble carbonate precipatates on the fabric.
Chlorine bleaching, weathering and sun exposure are also antagonists to durable
treatments.  The relative resistance of the various flame retardant systems
determines their ultimate "durability".
                                     4-1

-------
             In  the context  of  the  literature  of  textile  finishing,  the  terms
   durable  and semidurab\e generally  have  been applied  to cotton and rayon  finish-
   ing.  Wool, oilk and other natural fibers have also  been treated  by modified
   systems  based on those developed for  cellulosics.  As  such,  this  section is
   concerned  with treatments of cellulosics, especially cotton,  and  includes
   references to the  other natural  fibers.  Discussion  of durable treatments of
   man-made fibers and end products is reserved for Section V.

   4.1        SEMIDURABLE AND DURABLE  FORMULATIONS

   A.1.1      Semidurable Flame  Retardant Treatments

             In  an,effort to improve  the resistance of  flame retardant treatments
   to  leaching and laundering,  various inorganic  materials  have  been us.ed in a
   variety  of systems.  Metal oxides  precipitated in cotton fabric were  an  early
   example  of these attempts.   Titanyl chloride and zinc  compounds proved to be
   somewhat effective, but only in  combination with other flame  retardants.  None
   of these flame  retardants has  found any commercial success to date and are
   chemical curiosities more than anything else.   However,  the natural flame re-
   tardant  properties of several  metal salts have been  found to  add  to the  in-
                                                            vi 0 3
   herent flame  retardance of wool  when  employed  as mordants,' '  '
          Cellulose phosphate esters formed by direct esterification of the
cellulose molecule with phosphoric acid have provided systems with some commercial
success.  The most successful approaches have employed a urea-phosphate treatment
and a melamine-formaldehyde-phosphate system.  Other nitrogen bases have been
substituted for. the urea on an experimental basis including guanidine, ammonium
   Iflenisek, L.  New aspects of flame protection using wool:  versatile, simple,
    inexpensive.  Internet. Dyer Textile Printer Bleacher & Finisher, 147 (7):
    414-16, 418-19, (1972)  (OTS-AA-0008).
   2Refer to note 12,  Section III,  page 3-10.
   ^Benisek, L.  Use of titanium complexes to improve the natural flame retardancy
    of wool.  Journal of the Society of Dyers & Colourists, 87 (8):  277-8,
    (1971)  (OTS-AA-<)146).
                                       4-2

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sulfamate and cyanamide.  The cyanamide-phosphoric acid process has been refined
by O'Brien and is the basis of Pyroset, an'American^Cyanamid proprietary pro-
     4,5,6,7
cess.
             The  cyanamide-phosphoric  acid  formulation is  applied  by  the  pad-dry-
   cure  technique using a formulation  of three  parts  cyanamide  to  one part  phos-
   phoric  acid.   Durability to  laundering is  limited  to five  to ten home  launder-
   ings.   Loss  of the  resin and the precipitation of  sodium phosphates as a result
   of  ion  exchange antagonize the flame retardance.

             Chlorinated paraffin wax  (40 to  70% chlorine) with antimony  oxide
   and stabilizers have been used widely in outdoor military  applications since
   World  War II.  Chlorinated  paraffin wax is  the actual  flame retardant in  the
   formulations.   The  antimony  oxide is added for its effectiveness as an after-
   glow  inhibitor.  A  ratio of  approximately  1-1 is most effective.  Several
   mixtures  are described by Bhatnagar.8  The formulations are  prepared by  tech-
   niques  used  for paints.   The solids are  ground in  the presence  of  the  resins
   or  chlorinated paraffin wax  and then diluted to an appropriate  consistency with
   organic solvents.  The fabrics are  saturated and squeezed  through  padded rollers
   to  remove the  excess material, and  dried.  Curing  is not required.  Other
                                                        •&**':
   chlorocarbons  have  been used in place of the chlorinated paraffin  waxes.   Latex
   resins  of vinyl chloride containing polymers, polyvinyl chloride•,  and chlori-
   nated rubber have been reported to  be successful replacements.
   ^Kovacs,  J.; C.S. Marvel.   Synthesis  of  1,4,5,6,7,7-hexachloro-  and  hexabromo-
    bicyclo-(2,2,l)-5-heptene-2carboxylic acid  vinyl  esters  and  copolymerization
    with  acrylonitrile.   Journal  of  Polymer Science,  Part A-l, 5 (6): 1279-87,
     (1967)   (OTS-AA-0055).
   5 Krackeler, Joseph  J.; D.  Hoogensen.  Halogenated  hydrocarbons  flame retard
    polyurethanes.   Rubber World,  163  (2):  53-7,  (1970)   (OTS-AA-0056).
   6  Lam,  L.K.M.;  et  al.   Identification  of  cis-4,5-epoxy-2-pentenal from pyrolysis
    of  phosphoric acid treated cellulose.   Journal  of Applied  Polymer Science,
     17  (2):   391-9,  (1973)   (OTS-AA-0057).
   7 O'Brien,  S. James; R.G. Weyker.  Application  of Pyroset  CP flame retardant  to
    wool.  Textile Chemist &  Colorist, 3 (8):   185-8, (1971)   (OTS-AA-0155).
   8 Refer to  note 2, Section  III,  page 3-1.
                                       4-3

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 4.1.2      Durable Flame Retardant Treatments

           Esters  of phosphonoalkanolcamides and several variations  of treatments
 based  on tetrakis (hydroxymethyl) phosphonium compounds now dominate the flame
 retardant finishing of  cotton fabrics.

           Ciba-Geigy's  Pyrovatex FR is  a treatment based on N-methylol dimethyl
 phosphonopropionamide.   The  compound is padded on the  fabric by the conventional
 pad-dry-cure  procedures.   The treated fabric  is dried  and cured for one to  two
 minutes  at 175  .  '      Commercially,  it is used with a triazine resin,  a sur-:
 factant,  urea,  polyethylene  softener, and ammonium chloride.

           Th'e treatments  based on tetrakis (hydroxmyethyl)  phosphonium compounds •
 are derived from  tetrakis (hydroxymethyl) phosphonium  chloride  (THPC).   THPC  can
 be reacted with sodium  hydroxide on a 1:1 basis to produce  tetrakis (hydroxy-
 methyl)  phosphoniura hydroxide (THPOH) which provides a series of variant treat-
 ments.   The importantTHPC/OH systems that are in use  are as  follows:

           THPC, methylol  melamine,  urea,  heat
           THPC, methylol  melamine,  urea,  partial heat  cure,  partial NH.  cure
           THPC  &  tris(l-aziridinyl)phosphine oxide with heat
           THPC  + NaOH,  methylol  melamine, urea,  heat
           THPC  + NaOH,  amide,  partial heat cure,  partial NH. cure
           THPC  + NaOH,  methylol  melamine, urea,  copper
           THPC  + NaOh,  NH- cure
                          •J
           The significance of  textile flame retardance as a chemical system ,is
 Incisively shown by  the numbers  and nature of  the  performance variations possible
with just  a few basic compounds  and technical  processing modifications.  Beninate
 ^Aenishanslin, R. ; et al.  A new chemical approach to durable flame retardant
  cotton fabrics.  Textile Research Journal, 39 (9):  375-381, (1969)
  (OTS-AA-0001) .
       ,  George L. , Jr.  Flame resistant and rot resistant finishes:  applica-
  tion to cellulose.  American Dyestuff Reporter, 56 (15):  560-!-4> (1967)
 . (OTS-AA-0125) .
                                     4-4

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 compares several curing techniques  and demonstrates  that  the THPOH-«mmcmi« cure
 process, which is the nevest development,  not  only has  greater durability and
 results  in a relatively good fabric condition,  but simplifies the  processing
 while making it less  hazardous  through eliminating the  need for gaseous ammonia
             fc 11,12
 as  a  reactant.

           A number of flame  retardant  compounds have been synthesized  from
 specific amine-phosphorus  reactions in addition to those  already discussed.  A
 great interest  has been shown in  reaction  products of POC1, and NH,  in
 particular.   Only one compound  has  gone beyond  the research stage.   Tris(l-
 aziridinyl)  phosphine oxide,  the  reaction  product of ethyleneimine and phos-
 phoryl trichloride, has been used commercially, but  it  has not been  as success-
 ful as originally anticipated.  Toxicity with  the unreacted monomer  has severely
 limited  its  use.   Dow Chemical, the major  producer,  has reportedly discontinued
         fac
         14
                *o
its manufacture.   Efficacy and durability tests have been encouraging,
however.

4.2        PHYSICAL PROPERTIES

4.2.1      Physical Characteristics  of  Semidurable Treatments

           The  cellulose  phosphate esters  produce finishes  that have  little
effect on  the  hand of the fabric.   The treated  finishes are physically  stable
and  they also  provide rot and  crease resistance.  The  urea-phosphate treatment
degrades the cellulose.   Tensile strength is  lost depending on the amount of
urea present in treatment.  Normal  tensile strength  loss is 35 to 457,.  However,
excess urea is needed to resist  ion exchange.   Commercially, cyanamide  has been
used in place  of some of the urea.  Even  in formulations where cyanamide is
used in place  of 75% of  the urea, tensile strength loss is still significant.
The  susceptability of the cellulose phosphate esters to ion exchange, which
11 Beninate,  John V.,  et  al.   Application of  a  new phosphonium flame  retardant.
   American Dyestuff Reporter,  57 (25):   981-985,  (1968)   (OTS-AA-0144).
1* Beninate,  John V.,  et  al.   Economical  durable flame-retardant  finish  for
   cotton.  Textile Research  Journal,  39  (4):   368-74,  (1969)   (OTS-AA-0145
13 Refer to note 6, flection III,  page  3-5.
14
   Drake op.  cit.
                                     4-5

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reduces the flame retardance of this combination, is the characteristic that
most limits its utility.  The ammonium ions in the compound are gradually re-
placed with sodium.  When this happens, the fabrics burn, although the basic
ester 'group is still present.  The reaction is reversible, and flame retardance
can be restored with a treatment of an acid, followed by a water solution of
ammonium hydroxide.  The treatment is unsuited for products that might be sub-
jected to home laundering.
                                                                /
          Chlorinated paraffin wax-antimony oxide formulations produce finishes
that are durable to water leaching, but are readily removed by hot water,
alkaline laundering.  The fabrics tend to have a heavy, greasy hand, poor drape,
and are difficult to dye.  The flame retardance effectiveness is attributed to
the thermal stability of the paraffin wax or other chlorocarbcns that might be
used.  The mechanism of action is related to the creation of hydrogen chloride
in combustion.  The antimony oxide acts as a glow inhibitor.  Modern prepara-
tions involving oil in water and water in oil emulsion systems have been de-
veloped to replace the use of the highly flammable and toxic solvents originally
used in the manufacture of these flame retardant treatments.1- 5

4.2.2     Physical Characteristics of Durable Treatments

          Pyrovatex is an ester generated as a reaction product of a dialkyl
phosphite and acrylamide*    The compound is a methylolated derivative with
one mole of formaldehyde to one mole of the dialkyl phosphonopropionamide:
                 0              0                 0        0
          (CH30)2P-H + CH2 = CH-C-NH2
,1
                                                   HCHO
                                                0*       0
                                         (CH30)2P-CH2CH -C-NHCH2OH

          Excess formaldehyde in the process is released during fabric process-
ing and the subsequent use of an acid catalyst causes a reaction with cotton.
Efficacy and durability are added to the finish through use of an appropriate
        ,  Ma.urice W.  Flame retardant textiles. Noyes Data Corp., Park Ridge,
  N.J., 19?6, 373pp.  (OTS-AA-0207).
        to note  9   page 4-4.
                                     4-6..

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crosslinking agent, trlmethylolmelamlne, for example.  Ciba-Gelgy publications
claim the finished product iB nonirritating to the skin and produces a soft to
slightly full hand.  About 25% tensile strength loss is reported, which is more
than that experienced with the THPC-ammonia finish.    Add-ons for cotton tex-
tiles are about 20-35% to produce effective flame retardance.

          THPC was first reported by Hoffman in 1921.*   It is a crystalline
compound that is readily soluble in water.  It is produced in high yield through
the reversible reaction of formaldehyde with phosphine and hydrogen chloride:

          PH  + HC1 + 4 CH2 0 - * ((HOCH2)4P) Cl

Curing is accomplished by reacting the tetrakia (hydroxymethyl> phosphine (THP)
group with an ami ne, involving aminized cotton or a suitable curing agent.
The methylol groups react with the amino groups:

          (HOCH2)4PC1 + RNH2 - ^ RNHCH2PC1(CH2OH)3 + H20

and RNHCH? replaces some methylol groups, the chlorine is hydrolyzed and the
reaction proceeds:
          (RNHCH2)3 (CH2OH)PC1 + H20 — *-HCl + CH^H + (RNHCH^PO

The finish contains no chlorine and the phosphorus is a true phosphine
the most stable phosphorus state with regard to> hydrolysis.  The generation of
HC1 and formaldehyde in curing THPC is the most significant technical problem
with THPC based systems.  Formulations to replace the chloride use sodium
hydroxide which does not yield the phosphonium hydroxide, per se. but rather
a mixture of phosphines and phosphine oxides. 19,20,21  ^e THPC/OH systems have
17Refer to note 10, page 4-4.
18Hindersinn, Raymond R. ; G.M. Wagner. 'Fire retardancy.  In Encyclopedia of
  Polymer Science and Technology, John Wiley. & Sons, N.Y. , 1967  (OTS-AA-0338)
        , D.J.; et al.  Modifying THP (tris KJhydroxymethyl) phosphine)-amid=flame
  retardant.  American Dyestuff Reporter, 62 (6):  57-9, 80, (1973) (OTS-AA-0020)
20Linden, P.; S.B. Sello, H.S. Skovronek. Flame resistance of polyester/cellulosic
  blends.  Texilveredlung, 6  (10):  651-6, (1971)  (OTS-AA-0067)
21Daigle, Donald J.; D.J. Donaldson.  Less expensive durable flame retardant.
  Textile Chemist & Colorist, 1 (24):  534-6, (1969)  (OTS-AA-0271)
                                     4-7

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removed the HC1 by-products from the process and they make less probable the
release of formaldehyde on curing.  In the most recently developed formulations,
THPOH-trimethylolmelamine-ammonia and tHPOH-amide, 1 mole of THPC is reacted with
one mole of NaOH and the NaCl is removed by filtration from a methanol-water
solvent.  The other ingredients are added to the solution, the fabric is padded,
dried and cured, by gaseous ammonia or by heating at 150 .  The fabric has ex-
cellent durability to laundering, and has passed the test for children's sleep-
wear aft;er 50 launderings.  It gives char lengths in the range of 2.5*4.5 inches.
The product is a wash and wear fabric with permanent press properties and is
resistant to chlorine bleaching.  Tear strength is moderately reduced.'   '''

          Mazzeno has studied the .major phosphorus-based system for the effect
of u.v. radiation.  All the present systems were found to decompose to water-
soluble products including formaldehyde and hydrogen chloride.  The .products of
degeneration were subject to leaching.  Tris(l-aziridinyl) phosphine oxide was
found most resistant.  Heat, moiftture and u.v. radiation resulted in decompo-
sition of the finishes.27

          Effects of laundry variables have been investigated by Perkins,
Drake and Reeves. °»2?  Although modifications in the application procedures
have significant effect on the resistance of the durable flame retardant fin-
ishes to ion exchange and leachability, the effectiveness of all cotton        •   -
  Beninate, John V.; et al.  Conventional pad-dry-cure process for durable-flame
  and wrinkle resistance with tetrakis (hydroxymethyl) phosphonium hydroxide
  (THPOH).  Textile Research Journal, 38 (3):  267-72, (1968) (OTS-
-------
 treatments is reduced by laundry detergents.  As with the semidurable cellulose
1 phosphate esters, the loss of efficacy is most likely a result of ion exchange
 rather than leaching of the phosphate-containing components.  Nonphosphate
 detergents are significantly more deleterious than phosphate detergents, although
 phosphate retention in the treated fabric remains fairly constant through
 successive washings with either type detergent.  Soap and softwater washings
 have little or no effect on the efficacy of the flame retardants, thus bolster-
 ing the theory that ion exchange is responsible for loss of flame retardance in
 the wash.  In a later study, Le Blanc reported similar results for the THPC-
 based systems, but Pyrovatex^ the phosphonoalkanoicamide-based treatment, showed
                                                             30
 superior resistance to ion exchange from calcium antagonism.

           The physical properties of THPC-finished cotton vary considerably
 depending on the applications.  It is possible to produce finished {products
 with an acceptable hand and drape.  This is usually accomplished with some
 loss of effectiveness.  The newer methods have wash and wear characteristics.
 Fabric stiffness and reduction in tearing strength are still a problem.

4.3        ECONOMIC CONSIDERATIONS

           Economic considerations are a factor of:
         •    Producers
         •    Markets and uses
         •    Transportation
4.3.1       Producers

            Table  4-1  lists  the  commercial durable  and  semidurable  flame  retar-
dants  and  their manufacturers.

            Specific production  figures  for  the different  treatments were not
identified.  There are clear  implications that Ciba-Geigy's Pyrovatex, the
ammonia-THPC finish,  and  the  THPC-trimethylolmelamine  (TMM) finishes now dominate
 "*  LeBlanc,  R. Bruce; D.A.  LeBlanc.   Effects of calcium deposits on  fire retar-
   dant  cotton.  Araer. Dyest.  Rep.,  62  (3):  50,  (1973)   (OTS-AA-0063).
                                       4-9

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                                                      AND DURABLE  FLAME  RETARDANT TREATMENTS1
i
i-1
o
•LfUSUM — -
Company and Trade Names Active Chemicals Form Durability
Amalgamated Chemical
Fireseal Organic Phosphorus
.
American Cyanamid
Pyroset-
Apex Chemical
Flameproof
Ciba-Geigy
Pyrovatex
Dooley Chemical
D-C Tex 2 IIP
D-C Tex 220
Dover Chemical
Chlorez •
Rez-0-Sperse
TJ«i w»y«k4 1
Faroil
Dow Chemical
(Tris- (1-Aziridinyl)
phosphine oxide
(may be discontinued)
Faricourt
Fire Retardant
Hooker Chemical
THPC
Ihmont
•- 01 CO
Phosphorus, Nitrogen
Not available
N-methylol dimethyl
phosphonopropion-
amide
inorganic chemical
complex
Not available

Chlorinated Paraffins
Chlorinated Paraffins
Chlorinated Paraffins


APO
Boro-Phosphate
Tetrakis
(hyd roxymethy 1 )
phbsphohium chloride
Liquid
Water solution
Liquid , Powder
Water solution
Liquid
Liquid

Powder
Water solution
Emulsion
Liquid

Liquid

Powder

Water solutio

Semidurable
Semidurable &
Semidurable &
durable
Durable
Semidurable
Semidurable

Semidurable
and
Durable
Treated Fibers


Cellulosica
Silk, Cellulosics,
Wool
Varied
Cellulbsica
Varied
Varied

Latexes
Latexes
Latexes

Durable

* I >»•! _i
Durable

n Durable
Ant-tmonv oxide Liquid Semidurable
Cellulostcs

Cellules i«*

Cotton, Wtwcli
Varied
                Betardant 9153

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                                             TABLE  4-1.   (Contd.j
o
p>
Company and Trade Names
Monsanto
MCC/100
Moretex Chemical
Moretex TOP Emulsion
National Lead
Oncor
Neville Chemical
Unichlpr
Dr. Quehl
Aflamman
Aflammit
Proban
Sanitized Chemical
Saniflamed
Swift & Co.
Brominex
Synt.heron
Fyre-Fix
White Chemical
Series C
Active i*nenu.i;a j. a * 	
Proprietary
phosphorus
Phosphate ester
Antimony Oxide
Chlorinated Paraffins
Phosphorus -Nitrogen
Organic Phosphorus-
Nitrogen
THPC
Organic Phosphorus,
Nitrogen
Bromine, Nitrogen &
Phosphorus
Not available
Bromine, Phosphorus
& Bromine Phos*-
phorus organics
Water solution
Emulsion
Powder
Liquid &
Powder
Dispersions,
Water & Oil
Solutions
Water Solution
Water Solution
Liquid
Liquid
Water Solution
Not Available
Durable
Not available
Not available
Semidu rabies
Semidurable
Durable
Durable
Durable
Semidurable
Durable
Durable
Source: American Dyestuff Reporter, January 1972.
                                                                                             Treated  Fibers
                                                                                             Varied
                                                                                              Cellulostc*  &
                                                                                                non-cellulosics
                                                                                              Cellulosics  &
                                                                                                Blends
                                                                                              Cellulosics, Wool
                                                                                               Cellulosics

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the flame retardant  finishing of cotton  fabrics.  Several chemical companies
may market THPC-based systems under proprietary manufacturing patents, but
Hooker Chemical Co.  is the  leading manufacturer of the compound.  Textile fin-
ishing companies are responsible for production of the actual flame retardant
fabrics and employ the systems described previously to produce the final product,

          When THPOH is used alone, the  chemical cost to.consumers, prior to
the current inflationary period  (1972), was about 12•'   American Cyanamid is reportedly
planning a major capital investment in a Canadian plant to produce phosphine
less expensively than it is currently produced.  Since phosphine is the most
costly starting compound, this development could eventually lead to a lower
cost of THPC/OH-based systems.

4.3.2     Principal  Markets and Uses

          Until recently, textile uses for chloroparaffin-antimony oxide systems
have been almost exclusively for outdoor canvas and cotton duck treatment for
military products such as tents and tarpaulin.  The growth market currently
31
  Chance, Leon H.; J.P. Moreau, G.L. Drake, Jr.  Flame retardant for cotton
  based on THPOH  (tetrakis(hydroxymethyl) phosphonium hydroxide) and guanazole.
  Journal of Coated Fibrous Materials, 2 (3): 161-72, (1973) (OTS-AA-0017).
32
  Chance, Leon H.; W.E. Reeves, G.L. Drake, Jr.  Phosphorus-containing carbox-
  amides and their evaluation on cotton fabrics.  Textile Research Journal,
  35 (4): 291-8,  (1965) (OTS-AA-0137).
33
  Chance, Leon H.; E.K. Leonard, G.L. Drake, Jr.  Methylol derivatives of
  halocyanoacetamides and their evaluation on cotton fabrics.  Textile Research
  Journal, 37 (5):  339-43, (1967)   (OTS-AA-0153).
                                     4-11

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   being experienced is related to the use of these systems  in conjunction with
   thermoplastic  polymers  such as  polyvinyl chloride,  rather than for textile use..
   The construction industry and the automotive industry are now using these, as
   additives  to produce a  variety  of flame retardant polymer products,  especially.
   electrical coatings.

             Thi^re  is  a civilian consumer  market for flame retardant  finishes
   durable  through  five to ten launderings and dry  cleaning.   Cost  is an  important
   factor and should add no more than 10-15 cents per  yard of finished  goods .
   Any higher co:it  puts  fabrics  so treated into competition  with durable  treatments
   where the  advantages  of superior performance, particularly with  regard to
   flammability testing standards,  outweigh modest  cost  differentials.  The semi-
   durable  treatments  have no  clearly defined  consumer market of their  own.   They
   compete  with both nondurable  treatments and durable treatments for fabrics  used
                                                                   O/
   as  curtains, drapery, mattress  ticking,  blankets, and plush toys.    The origi-
   nal  standards  for testing of  mattresses included  a  leaching procedure  that
  might have adversely  affected the  semidurables in that market, but revised
   standards  (DOC FF-4-72)  have  been  more  lenient.   However,  no  data  were retrieved
   to  show  specifically  that the semidurable treatments  have  benefited  from the
                                            35
   growth market  for flame  retardant  bedding.

           In  general, the market for durable  flame retardant  fabrics produced by
chemical after treatment and finishing has benefited very little from the growing
interest in flame vetardant products.  The THPC/OH systems and Pyrovatex have
accounted  for virtually all the permanent fire retardant systems for cotton since
they have  been introduced commercially.  Outside of the markets created by flammable
fabric legislation, there has been limited  consumer demand for fl.ame retardant
cotton.  Until 1968,  the military and some  institutional uses were the principal
markets.   In  1971,  when the civilian uses began to be significant,  it was possible
to produce flame retardant cottons for an additional  13-15 cents per square yard
in full production.   In practice, the still limited market made flame retardant
fabrics a  specialty business  that actually  cost about 25 cents per square yard or
             R.  Bruce.  Flammability and fire resistance of textiles.  American
    Dyestuff Reporter, 57 (27):  P1093-P1096, (1968)  (OTS-AA-0348) .
  35Refer to note 14,  Section III, page 3-11.
                                       4-12

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higher.  By 1973, non-flame retardant cotton flannel cost 45 cents a square yard
and flame retardant cotton flannel cost 72 cents a square yard.   By the end of
1974 flame retardant cotton flannel ranged from $0 cents to $1.05 «
            In addition to these direct cost considerations,  testing of end  pro-
  ducts using cotton adds to the processing time and complicates  inventory con-
  trol systems.  While the tests are in progress,  the product continues to roll
  off the finishing line at a rate of 50 to 100 yards per minute.   Test failures
  or inconclusive results require a decision to reprocess the goods or  to hold
  them in inventory and delay shipping to customers  pending the outcome of the
  testing.  These problems put cotton at a significant disadvantage in  compe-
  tition with man-made fibers that are inherently more flame  retardant  than  cotton
  and have a better chance of consistently passing the product flammability  tests.

            The drastic effect that the flammable fabrics testing program has had
  upon the flame retardant textile market is demonstrated both in the American
  and the British markets.  In Britain, the pretesting period gave  Proban cotton,
  a THPC-treated fabric, the dominant position for children's sleepwear.  With
  the advent of testing, there is practically no cotton being consumed  by this
  market.  In the United States, cotton in 1971supplied 78  per cent,  or 27 million
  pounds of the material used to produce size 0-6X sleepwear.  In 1973,  treated
  cotton provided less than 10 percent, or only 3 1/2 million pounds.

            The initial effectiveness of the THPC/OH systems  and  Pyrovatex have
  never been in question for use on cellulose.   In markets  where  cotton is able
  to compete,  THPC/OH systems and phosphonoalkanoicamides will hold their re-
  spective positions as the treatments of choice.  Government contracts for  mili-
  tary textile products and Veteran's Administration Hospitals will- continue to
  provide the largest market.  Non-military hospitals have  also been  a  fair
  sized market for durably treated cubicle curtains.   Steel mills were  previously
  a significant market for flame retardant work clothes,  but  automated  processing
  has reduced the number of people who work around open flames and  blast furnaces.
                                       4-13

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          Three factors have combined to prevent the increased use of the dur-

able flame retardant treatments for cellulosic fabrics:


          1.   Cotton has lost much of its market position to man-made fibers.
               Polyesters, acetate and triacetate fibers have gained market
               position at the expense of cotton.
    '                    t

          2.   Flame retardant cotton has been unable to consistently pass the
               stringent test for durability used to measure flame retardance
               of apparel, carpets and sheeting.

          3.   The durable cellulosic treatments have only limited effective-
               ness for use with cotton/man-made blends.

          The diminished role of cotton, rayon and wool in the worldwide textile

market is a result of short supply, rising costs and stiff competition from

the man-made fibers.  The U.S. Department of Agriculture predicts this trend
to continue through 1979, at least.  Cotton markets that will suffer include

apparel, home furnishings, automotive and industrial markets.  Polyester fibers

will be the leading gainer.  The changing market picture from 1960 projected

through 1978 is shown in Figure 4-1.
L                         Textile Fiber Consumption

          5 (Mill consumption, in million pounds)
                      JSynthetic organic fibers
               LliLIUljJjRayon, acetate and glass fibers
                      j Natural fibers
         0
                    '60          '66        '72        '78(proj.) .
               Sources:  Chemical Week (OTS-AA-0391)            ^S
                                 Figure 4-1
                                     4-14

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          The cost and processing difficulties brought about by durable flame
retardant treatments notwithstanding, cotton's use in textile* is declining.
The reasons for this decline have not b««n investigated within thi» study and
there may not be a direct correlation between the declining cotton market and
the decline of cotton in the flame retardant textile market.  However, an
apparent correlation does seem to exist, at least for the civilian consumer
market.

          Factors that could favor cotton are increased cotton crops, which
are not expected for this year, and a shortage of feedstock chemicals for the
man-made fibers.  Ethylene glycol shortages have already caused production
cutbacks of polyester supplies.  Restricted production of polyvinyl chloride
due to toxicity will reduce the supply of modacrylics.  Shortages of dimethyl-
terephthalate, terephthalic acid, caprolactam and cyclohexane are-.also predicted
and will further reduce the supply of the man-made fibers. °  The real influ-
ences specifically affecting the flame retardant textile markets cannot be
predicted with any accuracy.  These influences are mentioned because of their
potential to drastically change the current and predicted textile market pic-
ture and indirectly affect the textile flame retardant market.

          The THPC/OH systems and Pyrovatex have both been unable to consistently
pass the 50 laundering requirements for durability.  While it has been shown
experimentally that careful formulation, application and product design can
produce the durability required of the tests, until it can be done commercially
in a full plant operation, treated cotton will be at a serious disadvantage
compared to modified man-made fibers.^7

          The loss of flame retardant effectiveness in laundering short of
50 washes has also prevented the use of cotton in blended fabrics with the
man-made fibers.  Untreated cotton, when present in blends, tends to act as a
wick in combustion.  Blended fabrics that would otherwise snuff out a flame
continue to burn with the cotton acting as a wick to hold the flame and the
^Anonymous.  Worldwide boom in textile goods spins prosperity for fiber firms.
  Chemical Week, 113, (2):  18-19, (1973) (OTS-AA-0391).
        to note 19, page 4-7.
                                    4-15
                                                                                 AUERBACH

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 thermoplastic  fibers  feeding the  flame.  The blends  are .more hazardous  than a
 fabric  of  either  fiber:  alone.  Tesoro  arid  associates have  described  this
 phenomenon and demonstrated  the need to  apply  topical  finishes  to  fabric* made
 from blends of a  non-flammable fiber with  a flammable  one, whether it is cellu-
                    38 39 40
 lose or some other.   '   '     Le Blanc  further  tested a variety  of  cotton/poly-
 ester treated blends  and came to  the conclusion that THPC  systems  are superior
 to Pyrovatex tor  use  on cotton/polyester blends.  But, THPC gives  a  finish
 having adequate fire  retardance and adequate hand only when the polyester con-
 tent is 25 percent  or less.   Pyrovatex gives a superior hand but is  said to be
 ineffective with  blends of more than 12.5  percent'polyester.

 4.3.3      Transportation

           No clear  inferences on  transportation patterns or practices relating
 to textile flame  retardants were  taken from the data retrieved  in  this  study.

 4.4        ENVIR01IMENTAL IMPLICATIONS

           Environmental implications of  semidurable  and durable flame retardant
 textile treatments  relate to their manufacture and  use.  The meaning is inter-
 preted broadly to include air, water,  and  soil pollution, as well  as toxicity
 to humans  and other living organisms.  Enviornmental contamination, monitoring
 and analysis techniques, reactivity, biology, environmental effects, and toxicity
 are specific items incorporated into this  section.  The flame retardants them-
 selves, and the by-products of their manufacture and use are the compounds of
 interest.
38
  Tesoro, Giuliana; S.B. Sello, J.J. Willard. Flame-retardant properties of
  phosphonate derivatives of cotton cellulose.  Textile Research Journal,
  38 (3):  245-55, (1968) (OTS-AA-0196)
39
  Tesoro, Giuliana C.; C.H. Meiser. Effects of chemical composition on the
  Elammability behavior of textiles. Textile Research Journal, 40 (5): 430-6,
  (1970)  (OTS-AA-Oj.97)
40
  Tesoro, Giuliana C.; J. Rivlin. Flatnmability behavior of experimental blends.
  Textile Chemist & Colorist, 3 (7):  156-60, (1971) (OTS-AA-0198)
41
 ,Le ,Blanc,  R. Brucii; E.R. Gray.  Fire retardant finishing of polyester/cotton
  blends.  Textile Jhemist & Colorist, 3 (12): 263-5, (1971)  (OTS-AA-0062)
                                     4-16

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4.4.1     Contamination

     ,     The textile industry is a significant source of localized environmental
contamination.  Pressure is being exerted to reduce or control the industry's
waste production.  The literature indicates a willingness on the part of the
industry to comply with regulations and public demands, but the mills are
scattered and the diversity of materials used in textile processing make total
compliance a complex and costly procedure.  Resins, including flame retardant
treatments, are only a minor part of the overall problems created by the textile
mills.  A general review of the contamination contribution from textile wastes
is provided by Burr.*2  Major types of textile mills and their wastes are listed.
Biochemical oxygen demands (BOD) of principal chemical wastes are listed, but
textile resins are not seen as a serious problem.

          Contamination control in the textile industry requires a balanced
state considering water pollution, air pollution, solid waste disposal, and
occupational safety and health problems.  Water pollution is the most serious
problem because water treatments have been used extensively in the industry
for applying textile finishes.  Moves to employ organic solvent systems are
resisted because of the capital investment required, and the technology seems
to exist that would enable manufacturers to easily reduce their water usage and
meet with the federal guidelines set at 5000 to 35,000 gallons of water per
1000 Ibs. of cloth or fiber.43  improvement of the water usage problem can
create problems in other ways.44  More concentrated effluent will raise the
BOD and the solid contents will be higher.  Use of organic solvents creates
problems of worker exposure to toxic fumes.  Concentrated ammonia fumes, hy-
drogen chloride and formaldehyde are the most serious volatiles associated with
flame retardant materials.  Where gaseous vapors are not recovered in solution,
concentrated vapor fumes are often ventilated into the atmosphere.45
42Refer to note 15, Section III, page 3-13.
 ,              / '              .
43Refer to note 17, Section III, page 3-14.
44Alspaugit, T.A.  Textile wastes.  J. Water Pollution Control Fed., 43 (6):
  lOpl-1008, (1971)   (OTS-AA-0381).
43Refer to note 18, Section III, page 3-14.
                                     4-17
                                                                                  AUERBACH

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           In  textile mill water effluent discharges,  the  finishing chemicals
are usually biodegradable, but they are also highly reactive and  form, deriva-
tives  in reaction ,with other chemicals present in the water systems.  The col-
loidal resins themselves are not biodegradable.  Whether  these initial products
                                  44
are toxic  or harmful is not known.    The components of the resin systems are
known  to continue-to resinify in sewage lines and occlude other undesirable
ingredients, such as dyes and unreacted molecules of the finishing processes.

           Heat and moisture have been shown to degrade the permanent finishes
of treated fabrics.  Some of the THPC/OH finishes have been shown experimentally
to give off detectable formaldehyde, hydrogen chloride and phosphine for up to
                           48 49
two months after finishing.'  '

           Several methods for qualitative or quantitative analysis of durable
flame  retardant-treated textiles were retrieved.  One method potentially useful
for monitoring water pollution related to textile finishes was also retrieved.
Analytical methods for determining flame retardant finishes were described
for cool flame emission spectroscopy,   gasometric determination of THPC
                          s?
and infrared spectroscopy.    The cool flame spectroscopic technique, of Elliot
is inappropriate-for durable finishes, since residual acids as nitrates and.
sulfates gave high background emission readings that interfere with the results.
Ellzey and Connick have developed a gasometric analysis technique for assaying
THPC in commercial solutions.  It involves the collection and measurement of
  Porter, John J. ; D.W. Lyons, W.F. Nolan.  Water uses and wastes in the textile
  industry.  Environmental Science and Technology, 6 (1): 36-41, (1972)
  (OTS-AA-0361) ,.
^7Refer to note 16, Section III, page 3-14.
^Afanas'eva, L.V.; N.S. Evseenko . Hygienic evaluation of fireproof textiles pro-
  cessed with an organophosphorus imp regnant based on tetrahydroxymethyl phosr
  phonium chloride. Hygiene and Sanitation, 36 (3): 450-453 (1971) (OTS-AA-0363) .
49Refer to note 27, page 4-8.
  Refer to note 20, Section III, page 3-15.
  Ellzey, S.W., Jr., W.J. Connick, Jr.  Gasometric determination of THPC (tetra?-
  kis (hydroxymethyl) phos phonium chloride) . Amer. Dyestuff Reporter, 62 (6):,
  47, 50, (1973) (OTS-AA-0036).
        ,  K.H.; W.D. Brown, S.J. Staruch. Rapid determination of bromine -contain-
  ing flame retardants on fabrics.  Textile Research Journal,  43(6):  357-61,
  (1973)  (OTS-AA-0083).
                                     4-18

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the volume of hydrogen evolved from the reaction of THPC and NaOH.  It is in-
expensive, rapid and precise for the intended use.  Results were compared with
NMR techniques, titrations, infrared spectroscopy and precipitation.  The re-
port ec} method was shown to be as accurate as any other.  Morris and associates
have described a method for extracting THPC from fabric finishes in such a way
as to facilitate infrared identification of the compound.^*  They were concerned
that there is no special catalog of infrared spectra for the components of
fabric finishes.  In an effort to start such a catalog, they publish their
spectrographs for the most popular THPC/OH finishes.

          A very recent procedure has been published by Lysyj for a qualitative
analysis of mixed organic industrial composition wastes by pyrographic tech-
niques.  Textile mill wastes are discussed by way of example.  An automated
monitoring procedure is claimed to have resulted from Lysyj's work that is
sensitive to single organic compounds that manifest themselves on a pyrogram
as peaks with identical retention times by varying intensities.  The varia-
tions produce common patterns specific to parent materials.54  Production-
type instruments have been produced and fabricated.  Practical implementation
of pyrography for stream surveillance has been achieved in two sites.  The
author claims that overall patterns of river water can be interpreted in terms
of specific contributing waste patterns.

          Although inferences of potential contamination resulting from the
use of durable flame retardants for textiles have been made in this section,
the only clearly dangerous textile flame retardant per se_ is tris(l-aziridinyl)
phosphine oxide (APO).  The chemical reactivity of APO would facilitate its
hydrolysis in waste effluence and it is unlikely that the unreacted monomer
would reach even the treatment plant.  As noted previously, APO may not be
available at this time.  But the nature of textile mill effluent Is not known
and there is little indication in the literature that the industry has considered
53Morrls, Nancy M.; E.R. McCall, V.W. Tripp.  Identifying finishes by infrared
  spectroscopy,  Fluorochemicals and flame retardants.  Textile Chemist &
  Colorlst, 4 (12); 283-6, (1972).
       , Thor.  Pyrographic analysis of waste waters.  Environmental Science
      Technology, 8 (1):  31-34, (1974)  (OTS-AA-0384).
                                    4-19

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 the  contamination problem posed by &  known toxicant  that had been widdly used
 in combination with  THPC  until very recently.   The need to  characterize indus-
 trial waste  in general, and  the textile  finishing wastes in particular, is
 quite clear.

 4.4.2     Biology anc.  Toxicity

          The toxicology  profile  of the  durable flame  retardants for  textiles
 is likely to be unique for each of the systems. The crosslinking agents, the
 amount of add-on,  the  different cures, the substrate material, and  even the
 processing conditions  affect the  durability, the presence of residue  in the
 fabric and the products of decomposition.  What is true for one treatment is
 not  necessarily true for  all.  Thus,  each  variation  would have to be  studied
 independently in  order to fully characterize the toxicology of the  class.  No
 studies were identified which approach such a broad-baaed comparison.'  Specific
 studies did document the  particular treatments  investigated.

          The THPC-ammonia systems might be expected to have a somewhat different
 toxicology than the  THPC-TMM systems  by  virtue  of the  relative difference in
 the  amount of formaldehyde groups  present  in the two product polymers.  The
 THPOH ammonia cute process reduces  the presence of HCl in the manufacturing
 processes and may result  in  a lower level  of chloride  residue on finished
                        i
 fabrics.

          For THPC/OH  systems, the most  serious  problems seem to be related to
 formaldehyde1and hydrogen chloride.   The spontaneous formation of these com-
 pounds or their presence  as  a residue is a source of toxicity.  Notably, in
 general use there has been an extremely  low incidence of reactions  to THPC/OH
 based flame retardant materials.   In  one study,  less than one percent in a
 study group of over  200 men  and women exhibited  any  reaction and formaldehyde
was assumed to be the toxicant.55  Wilson, in a  comparative study of APO solu-
 tion, THPC solution and respectively  treated cloths,  found no evidence of
55Martin-Scott, Ian.  Contact textile dermatitis (with special reference to
  fireproof fabrics).  British Journal of Dermatology, 78 (12):  632-635,
  (1966)  (OTS-AA-0365).
                                    4-20
                                                                                 MJERBACM
                                                                                     «

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significant THPC toxicity when topically applied to guinea pigs and rabbits, al-
though slight leukopenia was observed.  However, other investigators have note.d
that the popular THPC/OH systems decompose in a warm, moist environment and yield
formaldehyde and hydrogen chloride.  Mazzeno has shown this is true in vitro for
the finishes now used in the American market.    Afanas'eva, in a Russian study,
showed that six THPC formulations, including Proban, would liberate formaldehyde
into the air, and formaldehyde, hydrogen chloride, and organophosphorus compounds
into an aqueous medium continuously for one to two months.  Both local irritantt
and systemic effects were noted.  Blood counts showed leukopenia and the organo-
phosphorus compounds inhibited cholinesterase activity 20 to 40%.  Topical applica-
tions of aqueous extracts resulted in death of 50-70%.of the experimental mice.
However, the dosage was not reported.  Afanas'eva concluded that THPC-treated
materials were inappropriate for work clothes worn in a warm, and humid environ-
ment.    If these facts are borne out, THPC-treated fabrics may also be hazardous
when used for sleepwear and blankets for children at an age when they tend to suck
the products, or might wet their bedclothes.

          The decomposition of THPC/OH into formaldehyde and hydrogen chloride
raises another serious question.  Investigators have shown that bis-chloromethyl
ether (bis-CME), a carcinogen, can form spontaneously in ordinary humid air.
Although there is some disagreement about its carcinogenicity in humans, bis-CME
has caused lung cancer in rats and the evidence strongly suggests it has produced
cancer in chemical workers.  The current controversy centers on whether sufficient
concentrations of formaldehyde and hydrogen chloride are present in work environ-
ments to form bis-CME that can threaten workers.  Investigations specific to THPC
textile flame retardants apparently have not been made.

          Abnormally high concentrations of formaldehyde and hydrogen chloride in a
humid atmosphere could exist in textile waste effluents, THPC in treated clothing
that is wet and warm, or in the superheated environment of a building fire.  It is
conceivable that THPC could generate sufficient formaldehyde and hydrogen chloride
                                                                         CO
to spontaneously produce traces of bis-CME under such special conditions.
  56Refer to note 27, page 4-8.
    Refer to note 48, page 4-18.
  58
    Kallos, GJJ.; R.A. Solomon. Investigations of the formation of bis-chlortnethyl
    ether lln simulated hydrogen chloride-formaldehyde atmospheric environments. Amer-
    ican Industrial Hygiene Assoc. Journal, 34 (11): 469-473, (1973) (OTS-AA-0376).

                                        4-21

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          A limited  Incidence of contact  dermatitis  attributed  to formaldehyde
has  also been associated with flame retardant  clothing.   '
          Pyroyatex. by comparison, Is  claimed to  be less toxic than the  THPC
systems  and APO.   Only the  original papers  describing the Ciba-Geigy phosphono,-
proprlonamlde compounds make  mention of its toxicIty and they provide no  data
                     61 fi9
to support  the claim.   '    Pyrovatex has been shown to decompose to water
                                               63
soluble  products  In a manner similar to  THPC.    Trie (1-azirdlnyl) phosphine,
although It Is no  longer used as extensively as once was thought,  Is the  most
toxic chemical used  In durable flame retardant treatments for celluloslc  tex-
tiles. The  unreacted monomer  was shown  by Wilson to be lethal when topically
applied In solution to mice and rabbits. AfO treated fabrics, on the other handover e
          64
not toxic.     Mazzeno, in his study of the resistance of treated fabrics to u.v. radi-
ation, concluded the APO performed better than other treatments and did not degrade
to the toxic monomer. The performance.'bf APO in combustion was not  investigated, so
that the question  of whether  or not APO monomer could be generated  in a fire is
     /• C                                              CC
open.    Sram investigated  APO as a genetic mutagen.   He demonstrated a  direct
correlation between  dose  of APO and the frequency of dominant lethal alleles
manifested  in male mice.  Doses of 1 mg. of APO per kg. of body weight were
sufficient  to induce mutagenicity.
59
  Jordan, William P. Clothing and  shoe dermatitis.   Recognition and management.
  Postgraduate Medicine, 52  (5):   143-148,  (1972)  (OTS-AA-0364).
  Refer to note 58, page 4-22.
  Refer to note 9, page 4-4.
62      '
  Refer to note 10, page 4^4.
63
  Refer to note 27, page 4-8.
  vJilson, Robert H.  A note on skin tests of flame retardant materials.  Textile
  Research Journal, 32 (5): 424-425,  (1962)  (OTS-AA-0371).
  Mazzeno, L.W.; et al.  Degradation of selected flame retardants on exposure to uv and
  elevated temperatures. Text. Chem.  Color, 5 (3): 55-9, (1973) .(OTS-AA-0077).
  Sram, R.J.; Z. Zudova. Effect of the dose-fractionation on  the frequency of
  Chromosome abberations Induced in mice by TEPA. Folia Blologica, 19 (1):
  58-67, (1973) (OTS-AA-0357).
                                     4-22

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4.5       SUMMARY AND CONCLUSIONS

          For treatment of cotton, rayon and to some extent the other natural
fibers, THPC and Pyrovatex are adequate to flame retard textile products.  How-
ever, some growth markets are closed to them until treatments are perfected for
commercial use that will consistently pass the leach requirements of 50 home
launderings.  Cotton's general loss of market position is the most significant
factor likely to keep the use of durable cellulosic flame retardant treatments
a limited specialty market catering mostly to the military contracts and insti-
tutional drapery and bedding.  In the current market, any additional finishing
costs are detrimental to the sale of cotton products.  The inefficient flame
retardance of cellulosic treatments on blended fabrics is particularly limiting,
as it ties their use to products made of 75 percent or more cotton.

          The nature of flame retardant cotton finishings is unlikely to take
any drastic changes from the treatments described here.  A clearer picture of
the civilian market for treated cotton might be developed by more intensive
study; and the relative uses of the many variant systems might be investigated
further.  The chemistry of the technology as it affects the products and by-
products of the variant treatments is also worth further study.

          As a known hazard, these flame retardant systems present only a minor
occurence of dermatitis.  By-products of the manufacture and products of
degeneration are more serious problems.  In relation to the overall problems
associated with disposal of textile mill wastes, the by-products of manufacture
are unlikely to be significant.  The special conditions under which THPC/OH
systems might result in the generation of bis(chloromethyl) ether or other ob-
noxious products are of particular interest with regard to the durable flame
retardant.  It is not likely that such investigations have been reported pre-
viously, or they would have been revealed in the literature.  An original in-
vestigation of the problem should be undertaken under the sponsorship of an
appropriate Federal agency.  Additional work to test the validity of Afanas'eva
is also indicated, as a search of Science Citation Index indicated there has
been no follow-up study to date.
                                    4-23

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                        SECTION V.  MAN-MADE TEXTILES

          The current era of textile flame retardance is characterized by
flammability standards that define the effectiveness and pertnissable uses of
flame retardant chemicals according to their durability and performance in
standardized test procedures.  Products rather than textiles are the subject of
testing.  The standards not only affect the natural and man-made fibers used in
the tested products, but also the design and construction of the products.  The
fibers used in carpets, rugs and bedding, are generically the same as those used
indiildren's sleepwear and other apparel.  But chemical modifications and treat-
ments that impart flame retardance to acrylic fibers used for carpeting may be
unacceptable or inadequate as flame retardants for children's sleepwear.  Either
test failure or failure to meet aesthetic, comfort, and ease of care requirements
demanded by consumers is sufficient to limit the usefulness of a technically
effective flame retardant.  Manufacturers have a choice whether to make flammable
fibers flame retardant, or to use materials in product construction that are
inherently less flammable than traditional fibers.  In the choice of textile
fibers, should a manufacturer choose to use cotton fabrics, an aftertreatment such
                                      5-1

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as those described  in Sections  III  and  IV are  adequate to  the task given appro-
priate1 emwS aises aw& conupdiance with SF  iv«ie
man made fibers, the fibers themselves  can be  tailored  to  meet the specific
                                                                     i
requirements of appropriate standards through  chemical modification with appropri-
ate comonomers or addition of additives and  coreactants  in their manufacture; or
they can be aftertreated like the cotton materials.  Initially, manufacturers chose
to use inherently less flammable textile fibers as a starting material,  particular-
ly where compliance with flame retardant standards was required.  When shortages
of inherently flame retardant fibers (e.g.,  modacryllcs) occurred,  new techniques
for aftertreatment of polyesters and po.lyolefin were developed which proved  to be
superior to treatments of cotton.

            With the demand for flame retardant textile  products increasing  as a
  direct result of legislation, man-made fiber producers and  the chemical industry
  turned to the technology of flame retardance for plastics and used it  to create
  thermoplastics and resins for textile uses in products designed  to meet the
  standards through a combination of less  flammable materials  and product design.
  This is borne out by the character of the  flame retardant textile literature
  since 1972.   At that time,  there was a paucity of journal articles on  effective
  flame retardant man-made fibers.   Modacrylics, vinyl fibers and specialty high
  temperature  nylon were available and were considered to be  inherently  flame
  retardant textiles.  No truly effective treatments were claimed for  the popular
  polyesters,  polyolefins,  polyamides or blends of these fibers alone  and with
  cotton.   In  the literature  retrieved since 1972, over 600 patents (-.657, of  the
  literature base)  were  noted that claimed flame retardant modifications to pro-
  duce inherently less  flammable polymeric materials.  Modified and treated
  polyesters are particularly well represented.  However, a comparison of the
  patent  claims  with general  articles on plastic techndiogy showed that  the trend
  is  to add flame retardant properties to man-made fibers with the use of resins.,
  plasticizers,  and stabilizers developed for plastic products that incidentally
  have been shown to impart some"degree of flame retardance or melt inhibition
  to  the  resulting polymer.
                                       5-2

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          The great variations possible in synthetic polymer chemistry, and the
control of the physical properties that can be exercised by additives and precise
tailoring of the comonomers make the ultimate situation with regard to flame
retardant, man-made textile fibers less clear than with cotton and other natural
fibers.  Lyons has provided a general review of flame retardance of polymers.
In the process, he has related the technology to the production of man-made
fibers from polyolefins, vinyls, acrylics, polyesters, and polyamides.  However,
what remains particularly unclear with regard to the man-made fibers is whether
the breakthroughs in the technology of flame retardance will come by incorporat-
ing comonomers containing flame retardant elements (phosphorus,  nitrogen, volatile
metals, chlorine and bromine) into today's textile polymers, or from improved
aftertreatment; or, entirely new, textile polymer structures will be synthesized
which are inherently flame retardant or even fire proof.

          The chemical industry alone is reportedly spending between 10 and 20
million dollars annually on flame retardancy research.  With the intensity of
current research, it is likely that a number of important, new chemical prin-
ciples will be commercially developed in the next few years that are not signifi-
cant as of this writing.  However, the flame retardants investigated in the
course of the intensive phase of this study represent virtually all of what is
being used to achieve durable flame retardancy in textile materials at this time.

5.1       STRUCTURES AND PROPERTIES
          The chemicals with which the project was concerned in the intensive
phase of the investigation consisted of four chemical types used in the manufac-
turer of man-made fibers and textiles derived therefrom.
          The broad scope the subject area required that the materials be con-
sidered in an order of priority:
          1.   Halogenated polymers of textile polyesters, polyamides,  and
               modacrylics.  Homopolymers, copolymers, and oligomers solely of
               haloolefins (e.g., vinyl chloride, vinylidene chloride and
               vinyl alcohol) and all elastomers were specifically de -
               emphasized.
   Lyons, John W.  The chemistry and uses of fire retardants, New York,
   Wiley-Interscience, 1970 (OTS-AA-0075)
                                     5-3

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          2.   Fibers containing coreactive and additive organophosphorus
               components and similar aftertreatments for man-made  fibers.
          3.   Aramids'- fibers in which the fiber-forming substance is a
               long chain, synthetic polyamide with the amide  linkages on
               aromatic rings.
          4.   Other high temperature, synthetic, organic fibers.

          Clearly relevant data that was retrieved for any of  the four types has
been incorporated into- this report.  Intensive investigation of the chemistry
and toxicology of the halogenated polymers and phosphorus containing polymers
was more extensive than the lower two priority types.  Thus, the coverage of
the higher priority types is most comprehensive.

5.1-. 1     Halogenated Polymers

          Halogenated monomers that are used or have been reported,as commercially
viable flame retardants for man-made textiles are listed in Table 5-1.  The list
is comprehensive and overly representative of organohalogens that are used as
coreactants in the manufacture of flame retardant fibers.  It  is important to note
that the variety of chemical groups listed does not imply that organohalogen
coreactants are currently the most important flame retardants.  In  fact, they are
not very effective in aftertreatment processes, which account  for a large share
of the market.

          Unless the flame retarded fiber is designed for a very specific 'market
or product, it is more economical and marketable if the finisher treats only those
fabrics which will go into the manufacture of regulated products.  Less than 10%
of all fibers used today require flame retardant properties.

5.1.2     Organophosphorus Coreactives, Additives and Finishes

          Organophosphorus-based fiber modification in finishing account for the
most successful techniques used for polyesters, acetates and blends, but not
modacrylic fibers.  Organic phosphorus compounds that are reported as commercial,
semi-commercial and developmental products are shown In Table 5-2.
                                       5-4

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             TABLE 5-1.  HALOGENATED MONOMERS FOR FLAME RETARDING
              TEXTILE POLYESTERS. POLYAMIDES AND MODACRYLICS
Diol Moiety Modification
Phthalic Anhydride Moiety
Modification
Vinyl Monomers
Pentaerythritol Dichloride

Chloropropanediols

Mono-, Di - and Trlchlorobutanediol

Epoxylated Tetrachlorohydroquinone

Halogenated Bisphenol A

Glycidyl Ether of Pentahalophenol



Tetrachlorophthalic Anhydride

Tetrabromophthalic Anhydride

Chlorendic Anhydride


Vinyl Chloride

Vinylidene Chloride

Vinyl Bromide
                                                                        5   \
                                      5-5

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Tris (2,3-di-bromdpropyl) phosphate, by virtue of the fact that it is a successful
additive for use with aceLate and triacetate fibers, as well as the basis for. a
successful finish to polyester, nylon and acrylic fabrics is, by far, the moat
important flame retardant compound in use for man-made fibers, on a .volumerused
basis.
                  TABLE 5-2.  ORGANOPHOSPHORUS FLAME RETARDANT


                      Tris  (2,3-Dibromopropyl) Phosphate
                      Bis (2,3-Dibromopropyl) Allyl Phosphate
                      Bis (2-Chloroethyl) Vinyl Phosphonate
                      Diethyl Vinyl Phosphate
                      Dialkylchloromethly Phosphonates
                      Diallyl-2-3-Dibromopropyl Phosphate
                      Diallylphenyl Phosphonate
                      Triaryl Phosphates
                      Polychlorophosphonates
                      Triallylphosphene Oxide
                      N-Methylol Dimethyl Phosphonopropionamide
                                      5-6

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5.1.3
Agamlds
          Aramids are a generic class of fibers having at least 85% aromatic-
 amide linkages.  The first commercial aramid was marketed by E.I. duPont
                                                 (to
de Nemours & Company.  The JduPont product (Nomexr ia spun as a multifilament
by a proprietary duPont process.  The fiber is thermally stable above 3000.
The approximate structure is:
          Monsanto has reported that they also have a semi-commercial aramid
but the structure was not available.

          The textile importance of the aramids is limited due to cost.  Uses
include hot air filtration fabrics, protective clothing for hazardous occupa-
tions, and special use materials for aircraft and boats.
5.1,. 4
Other High Temperature Synthetic Organic Fibers
          Aromatic components tend to impart thermal stability to polymers.
Some heterocyclic rings have also been claimed to enhance flame retardance.
Developments in the field of polymer chemistry, spurred mostly by the space
exploration program,have resulted in fibers and polymers that conceivably
could be used extensively in textile products by 1984.  High production costs
and limited supplies are the controlling factors for the moment that restrict
their use to applications for which no substitute material is acceptable. As
with the aramlds, some have been used in race car driver gloves and overalls,
firemen's clothing and space programs as well as high temperature industrial
filters.
                                     5-7

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          Kynol  is a formaldehyde cross-linked aromatic fiber that is nearly
 fireproof.  It is a product of the Carborundum Co.  The structure was not avail-
 .able, but it is known to contain only carbon, hydrogen and oxygen.  Kynol has
 had limited application for general consumer use because it has a brown color
 and it is brittle,  A new version which is white is now in development.  It
 can be dyed to any shade.

          Other developmental high temperature  fibers  that appear  to  have sig-
nificant potential for commercial development include  polybenztsaidazoles,
polyoxadiazoles and a new duFont polyflaide Kapton, which is a  polypyromellitide
more stable than Nomex.  The generic structures for  these, synthetic polymers
are shown in Table 5-3.
             TABLE 5-3.  HIGH TEMPERATURE SYNTHETIC ORGANIC FIBERS
polybenzimidazole  (FBI)
polyoxadiazole (PODZ)
poiypyrotnellitide  (Kapton)
                                     5-8

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 5.1.5     Physical Properties

           The choice of organohalogen and  organophosphorus  coreactants  and addi-
 tives is so varied that few generalizations  can be made about  the physical
 properties of man-made  textiles made  from  these compounds.   It has been claimed
 that  except for  the phenolic polymers,  the flame retardant  man-made  textiles
 tend  to yield more smoke,  carbon monoxide  and  toxic  fumes in laboratory-controlled
                                   234
 combustion than  natural materials.  '  '   The halogenated polymers yield
 hydrogen chloride  or hydrogen bromide on heating.

           Tris - 2,3 dibromopropyl phosphate as a commercial product is avail-
 able  in several  grades. The major manufacturers - Michigan Chemical, Stauffer
 Chemical and Tenneco -  report that the product used  for flame  retardant textile
 processes is a high grade  compound that is 98% to 99% tris.    A  list of tris
 properties is provided  in  Table 5-4.

           Aromatic components of polymers  add  inherent thermal stability  to
 thermoplastic polymers. Some heterocyclic compounds do the same.  Phenolic
 resins, aromatic and heterocyclic  polymers,  aromatic epoxides  and aromatic
 bromides are extremely  unreactive  and resist hydrolysis.  As a result,  this
 approach to flame  retardance results  in a  relatively noncombustible  char  that
 forms at temperatures below the melting point  of the fiber,  but  sufficiently
 high  to resist combustion  from ordinary sources of ignition.'
2  Gaskill, James R., Smoke development in polymers during pyrolysis or combus-
   tion.  Journal of Fire & Flammability, 1 (July):  183-216, 1970 (OTS-AA-0261)

3  Carroll-Porczynski, C.Z., Application of simultaneous DTA TG and DTA/MS
   analysis for predicting in advance of processing the flammability and toxi-
   city of gases of composite textile fabrics and polymers, In Thermal Analysis,
   Proceedings of the International Conference on Thermal Analysis 3rd, 1971,
   published 1972, 3, 273-84 (OTS-AA-0281)

4  Carroll-Porczynski, C.Z., Fabric flammability.  New testing methods and
   equipment.  Textile Institute and Industry, 9 (7):  188-194, 1970 (OTS-AA-0300)

 ^  Personal Communications

-------
         TABLE 5-4.   TRIS  -  (2.3  DIBRQMOPROFYL)  PHOSPHATE PROPERTIES
 CHEMICAL NAME:
 V
 Tris-(2,3 d'ibromopropyl) phosphate
 STRUCTURE:
 Br    Br
ci,
                                           -  CH-C
H2-
GENERAL DESCRIPTION:
 Tris is offered In two grades:   standard
 and purified.   The purified grade is offer-
 ed for application in areas where improved
 heat stability, UV light stability,  low
 volatiles and  low color are of importance,
 e.g., polyurethane foams, expandable poly-
 styrene beads  and transparent or trans-
 lucent polymers such as polyacrylates or
 polyesters.
MOLECULAR WEIGHT:
 697.7
BROMINE CONTEHT, %:
  68,7
PHOSPHORUS CONTENT,
   4.4
DENSITY @ 25 C:
 g/ml 2,2 -  2.3
 Ibs/gal 18.4 - 18.6
VISCOSITY, CS @ 25 C:
 4000 -  4200 (purified)
ACID NUMBER (mg KOH/g) :
 nil -  0.05
COLOR (APHA):
 25-125 (purified)
VOLATILES:
  1.5  (purified)
SOLUBILITY:
 Insoluble  in water; miscible with
 CC14, CHC13, CH2C12
   OTS-AA-0434  ?.'enneco Chemicals.  Product Data Sheet, NUOGARD™ 23p
   OTS-AA-0492  Stauffer Chemicals.  Product Data Sheet, FYROLR  HB-32
                                     5-10

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                            TABLE 5-4. (CONTINUED)
HEAT STABILITY:
Although working temperatures as high as
390C  have been encountered in extrusion,
calendering and milling, prolonged tempera-
tures above 325 C ate not recommended.
LIGHT STABILITY:
Good in most resin systems.
HYDROLYTIC STABILITY:
Exposure of  trte2,3P to water at 25 C for
24 hours does net result In a detectable
change in acid number.  Exposure to strong
caustic at elevated  temperatures results
in dehydrohalogenation.
HANDLING:
Use protective means to avoid contact with
eyes, skin and clothing.  Wash immediately
with soap and water if contact is made.
Do not take internally.
AVAILABILITY:
Container

\\ gal. pail
5 gal. can
30 gal. drum
 Net Weight-Ibs,

 26
 87
550
                                     5-11

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 5.1.5.1  . Commercial Products

           The prtfcess of manufacturing a flame retarded textile product for re-
 tail sales is at the tail end of a multi-faceted production process leading
 from the chemical producers,  to fiber producers, textile mills, and dyers and
 finishers.   Properties of the starting materials,  intermediary products and
 the final product are all important to understand in order to completely assess
 the potential impact of flame retardants environmentally.
                                                              .  . • I
           To  date there is very little known about  the possible decomposition
 products and  what is likely to occur in actual use  from synergistic interactions
 of  the  flame  retardant with other components of the various products.

           In  the course of the interview phase of the study,  much effort was
 devoted to investigating possible decomposition products and spontaneous reaction
 products which may occur in manufacture or by interaction with  other components
 in  the  fiber  and/or  the finish formulations.   No evidence  was uncovered to  indic-
 ate a threat,  environmentally or  toxicologically from the  use of flame  retardants
 for textiles,  or textile product  fills such  as flexible polyurethane foams.

           Rigid  urethane which is not  a textile component  is  suspect.   Certain
 products  of combustion are said to be  toxic  but investigation of the issue was
 beyond  the scope of  this study.

           Speculative  concern has surfaced with regard  to  a potential for inter-
 action  of  hydrogen chloride and hydrogen bromide  introduced by  flame retardance
 technology with  formaldehyde  based finishes  to  form carcinogenic bis chloromethyl
 ether and  the bromo analog.

           Areas  for future chemical and physical  investigation  that have not
been reported on may require  laboratory testing or  legislative  authority to  solicit
proprietary data directly  from manufacturers.  Some areas were  addressed in  this
 study without successful retrieval of data.  Where compounds  such as brominated
bis phenol A,  tetra bromophthalic  anhydrides and  even tris  (2,3 dibrombpropyl)
phosphate are used in melt spinning of polyester or nylon fibers, very high
temperatures (300-350 C) are involved and decomposition products may
    Man-Made Fiber Producers Association, Inc.  Man-Made Fiber Fact  Book
    Washington, D.C., 1974, 64pp.   (OTS-AA-0418).

                                     5-12

-------
result.  These may  be precipitated  in an  afterwash or  they may  leave oligomara
and monomers unreacted on  the product to be  leached out during the  dyaing process
or end up on  the  final product.

          Questions that  remain unanswered  are:  will  there be  chemical  changes
of environmental  concern  occuring in normal use?  For  example, will they hydrolze
on repeated washings?  Will they oxidize on  bleaching or chlorinate with  chlorine
bleach?  How will they or their products  react with exposure to sunlight, ozone,
NO- and SO. in the  atmosphere?

          Until more is known about the specific products of decomposition these
questions cannot  be accurately answered.

5.2       PRODUCTION

          Production includes these subsections:
          •    Producers
          •    Uses
          •    Current practice

5.2.1     Producers

          Producers involved in the tnanfacture of flame retardant products
include:
          •    Chemical Manufacturers
          •    Fiber Producers
          •    Dyers and  Finishers

          Producers with  major investments  in flame retardant compounds  are
provided in the following tables along with plant site locations:

          Table 5-5  Chemical Manufacturers
          Table 5-6  Man  Made Fiber Producers
          Table 5-7  Dyers and Finishers
                                      5-13

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                    TABLE 5-5.  CHEMICAL MANUFACTURERS:
               PRODUCER



1)  American Cyanamid

2)  Clba-Gelgy Corporation

3)  Dow Chemical Company
    i
.4)  Great Lakes Chemical Company

5)  Hooker Chemical Company

6)  Michigan Chemical Company

7)  Monsanto Chemical Company

8)  Stouffer Chemical Company

9)  Tenneco dnUmtcals, Inc.
             SITE'



Bound Brook, New Jersey.-.

Ardsley, New York

Midland-, Michigan

Lafayette, Indiana

Niagra Falls, New York

Chicago, Illinois

St. Louis, Missouri

Westport, Connecticut

Piscataway, New Jersey
                                     5-14

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                    TABLE  5-6.  MAN-MADE  FIBER PRODUCERS
            Producers
                 Plant Locations and Fibers Produced
Allied Chemical  Corporation
Fibers Division
One Times Square
New York, New York   10036
               Columbia, S.C. (nylon & polyester)
               Hopewell, Va.  (nylon and  polyester)
               Moncure, N.C.  (polyester)
American Cyanamid Company
Fibers Division
Berdan Avenue
Wayne, New Jersey  07470
               Pensacola, Florida (acrylic)
American Enka Company
A Part of Akzona,  Inc.
Enka, North Carolina  28728
               Central, S.C. (nylon & polyester)
               Enka, N.C. (nylon & rayon)
               Lowland, Tetln. (nylon, polyester & rayon
Beaunit Corporation
Fibers Division
261 Madison Avenue
New York, New York  10016
               Elizabethton, Tenn. (nylon, polyester &
                rayon)
               Etowah, Tenn. (nylon)
Carborundum Company
P.O. Box 337
Niagara Falls, New York
               Sanborn, N.Y. (novoloid)
14302
Celanese Corporation
Celanese Fibers Company
P.O. Box 1414
Charlotte, North Carolina  28201
               Cumberland,  Md. (acetate & triacetate)
               Narrows,  Va. (acetate)
               Rock Hill,  S.C. (acetate & triacetate)
               Rome, Ga. (acetate)
Courtlauds North America Inc.
104 West 40th Street
New York, New York  10018
               Le Moyne,  Ala.  (nylon & rayon)
Dow Badische Company
Williamsburgj Virginia  23185
               Anderson,  S.C.  (nylon & polyester)
               Williamsburg,  "a.  (acrylic & metallic)
E.I. du Pont de Nemours and
 Company, Inc.
Textile Fibers Department
Wilmington, Delaware  19898
               Camden; S.C.  (acrylic,  nylon & polyester
               Chattanooga,  Tenn.  (nylon & polyester)
               Kinston, N.C. (polyester)
               Martinsvilie, Va.  (nylon)
               Old Hickory,  Tenn.  (olefin & polyester)
               Richmond, Va. (aramid,  fluorocarbon,
                nylon & olefin)
               Seaford, Delaware  (nylon)
               Waynesboro, Va.  (acrylic, acetate &
                spandex)
               Wilmington, N.C.  (polyester)
                                     5-15

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                              TABLE 5-6.  (Contd.)
             Producers
              Plant Locations and Fibera Produced
  Eastman Kodak Company
  Carolina Eastman Company Division
  Kingsport, Tennessee  37662
            Columbia, S.C. (polyester
  FMC Corporation
  Fiber Division
  1617 John F. Kennedy Boulevard
  Philadelphia, Pennsylvania  19103
            Front Royal, Va. (polyester & rayon)
            Lewistown, Penna. (polyester)
            Meadville, Penna. (acetate & vinyon)
            Radford, Va. (polyester)
            Nitro, W. Va. (rayon)
            Parkersburg, W. Va. (rayon)
  Hercules Incorporated
  Fibers Division
  910 Market Street
  Wilmington, Delaware  19899
            Covington, Va. (olefin)
            Oxford, Ga. (Olefin)
  Hoechst Fibers Incorporated
  1515 Broadway
  New York,  New York  10036
            Spartanburg, S.C. (polyester)
  Monsanto Textiles Company
  800 N. Lindbergh Boulevard
  St. Louis,  Missouri  63166
            Decatur, Ala. (acrylic, modacrylic &
             polyester)
            Greenwood, S.C. (nylon)
            Guntersville, Ala. (nylon & polyester)
            Pensacola, Florida (nylon)
  Phillips Fibers Corporation
  Subsidiary of Phillips Petroleum
   Company
  P.O.  Box 66,  Interstate 85
  Greenville,  South Carolina  29602
            Rocky Mount, N.C. (polyester)
            Seneca, S.C. (carpet backing)
            Spartanburg, S.C. (olefin)
            Guayama, Puerto Rico (nylon)
  Rohm and Haas Company
  Fibers Division
  Independence Mall West
  Philadelphia, Pennsylvania
            Fayetteville, N.C. (nylon & polyester)
19105
  Union Carbide Corporation
  Films-Packaging Division
  Fibers Department
  270 Park Avenue
'  New York, New York  10017
            South Charleston, W. Va. (modacrylic)
                                       5-16

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                      TABLE 5-7.  DYERS AND FINISHERS
            MANUFACTURER

1)  Burlington Mills

2)  Collins and Aikman

3)  Cone Mills

4)  Dan River

5)  Deerlng Milliken Corporation

6)  Fieldcrest

7)  Granitevllle Company

8)  Guilford Mills

9)  M. Lowenstein and Sons

10) Reeves Brothers

11) Riegel Textile Corporation

12) Russell Corporation

13) Springs Mills

14) J.P. Stevens and Company

15) United Merchants and Manufacturers

16) United Piece Dye Works

17) West Point Pepperell
             SITE

Greensboro, North Carolina

New York, New York

Greensboro, North Carolina

Danville, Virginia

Spartanburg, South  Carolina

Eden, North Carolina

Granlteville, South Carolina

Greensboro, North Carolina

New York, New York

New York, New York

New York, New York

Alexander City, Alabama

Fort Mill, South Carolina

Garfield, New Jersey

New York, New York

Hightstown, New Jersey.
/
West Point, Georgia
                                     5-17

-------
          Tris (2,3 dibromopropyl) phosphate is available from Stauffer Chemical,
Michigan Chemical, Dow Chemical, Great Lakes Chemical and Tenneco.  While other
organo-halogens and organo-phosphates are listed in the product lines a* dis-
cussed in Section 5.1, tris Is regarded as the only  commercially sighifleant
flame retardant for man-made textile products in the civilian marketplace.

          Other somewhat less significant flame retardant chemicals at present
may become commercially more significant as the demand for flame retarded pro-
ducts grows.  Brominated bis phenol A and the less important chlorinated analog
is produced by Dow Chemical, Great Lakes Chemical, Michigan Chemical and Stauffer
Chemical.

          Diamines of polyhalogenated biphenyls are made by dn Pont, "Monsanto and
Celanese.  Tetrbbromophthalic anhydride and tetra chlorophtalic anhydride are
produced by Dow, Great Lakes, Michigan, Stauffer, du Pont, Rohm and Haas and
Celanese.

          Vinyl chloride and vlnylldene chloride, in addition to being used as  .
copolymer reactants for modacrylic or saran fibers, may be applied as fabric
finishes to produce coated fabrics.  The production of vinyl chloride has come
under strict regulation in the United States.    Companies most associated with
it are Dow Chemical, Goodrich and Union Carbide.

               Pyrovatex is a product of Ciba-Gelgy that is currently in develop-
ment for use on-cotton-polyester blend fabrics.  Its effectiveness for use oh
100% cotton and blends have given it a strong market position.  It fs reported
to be the market leader, at present, for cotton use, surpassing THPC.  However,
it has not proved to be as effective for man-made fibers as tris 2,3 (dibrbmb-
propyl) phosphate.
           To many,  the dyeing and finishing operations is synonomous with
 textile manufacturing.  There are more than fifty companies either using flame
 retardant  fibers for the manufacture of flame retardant fabrics or treating
 fabrics with flame  retardant finishes.  The list in Table 5-7 represents the
 largest corporations.
                                     5-18

-------
           The textile industry was one of five worst affected by the economic
 recession of 1974.  For thefftvftt time In 15 years, the growth of man-made
 fiber output was reversed.  Global output of cellulesics and synthetics fell
 37. from 1973.  The 1974 output equaled 11.27 million metric tons.  World wide
 output of thermoplastic staple and filament yarns fell 2.77. to 7.53 million
 metric tons.  Domestically, the decline of synthetic production was down 17o
 to 2.69 million metric tons.
          At  the  same  time,  countries outside  the United States, Western Europe
and Japan increased  fiber production by 4.27, to nearly  3.1 million metric  tons,
including rayon.  Their  thermoplastics production was up 670 and rayon 2.47«.
Their overall production constitutes 277. of the total world wide market.

          Globally, polyester staple and fiber  gained an Improved position by mov-
ing up 2.27. over  1973  to 3.24 million metric tons solely in countries outside the
United States, Europe  and Japan.  The acrylics and poly amides   slipped 87. to
1.43 million  metric  tons.  Polypropylene and polyvinyl  alcohol fibers held  steady
at 0.3 metric tons.  The polyester fibers now  account for 437. of the total.  Poly-
amides  have 347<>, acrylics 197. and other classes of thermoplastics 47..

          The United States is the largest producer of  man-made fibers.  U.S.
output exceeded 2.7 million metric tons in 1974;  This was 367. of the world wide
production.  Polyesters made up 1.4 million metric tons.  This is 527. of the
                  7
total U.S. output.
                                                                         !
               On a global or even total domestic output scale, the production
of flame retarded textiles is less than 57. of  the total.  This is less than
0.3 million metric tons of flame retardant fabric.  On  a weight basis, flame
retardant additives, coreactants and finishes make up less than 107. of the pro-
duct.  Therefore, the  total textile flame retardant material produced Is estim-
ated at less than 0.03 million metric tons per year from all sources.  Companies
   Chemical and Engineering News.  "Prospects for Fibers Continue to be Good."
   V. 53 (6) February 10, 1975, p. 12
                                      5-19

-------
that have not had significant earnings in the specialty chemical marketplace
or fiber manufacturing may divest themselves of flame retardant products if
the'trend-continues.  Union Carbide was the first such casualty. In November
1974 it was announced that the fiber manufacturing operation in West Virginia.
would be discontinued.  The company gave the official reasons as feedstock short-
ages, high labor cost, EPA waste treatment regulations and OS HA. regulations of.
                                                                     8"'
vinyl chloride production used in its only product, modacrylic Dynel.

          The turmoil in the industry made it virtually impossible to .develop
accurate estimates of current and future production levels and prices.

5.2.1.1   Production Trends/Volume

          Since the trend in textile manufacturing continues to favor'the man
made fibers, particularly the thermoplastic polyesters, polyamides and polyole—
 fins(6-7 billion Ibs. per year) the question to be answered is whether these will
be manufactured as flame retardant fibers or whether chemical finishes will be
applied in a finishing process.  The impact of shortages of petroleum based
feedstock vis a vis crop fluctuations for cotton is very uncertain for both
the short and long term outlook.  Still, there is no clear indication as to
whether the future development of flame retardant textiles and end products will
favor intrinsically modified fiber raw materials or whether the flame: retardant
                                                        9,10
chemicals will be applied in a fabric finishing process.

          There is conflict between government and Industry as to: which pro-
ducer group should be responsible for meeting the flame retardance* performance
standard.   The textile, manufacturers favor looking to the fiber producer.  The
Consumer Product Safety Commission places the responsibility on the fabric
producer and the end product manufacturer.

          Because of these uncertain economic factors and since all present efforts
to meet flame retardance standards' have required trade offs in economy, aesthe-
tics, wear properties and the like, it can be anticipated that intensive research
to find the "ideal" product (particularly for popular cotton/polyester blends)
 a .
    Personal Communications
    LeBlanc, R.B.  What's Available  for  Flame  Retardant Textiles
    Textile  Industries,  138  (2):   115-120  (1974)   (OTS-AA-0480).
    Eisenberg, B.J.; E.D. Weil  A  Review of  Durable  Flame  Retardants
    Textile  Chemistr& Colorist, 6  (12):  23-27,  (1974)   (OTS-AA-0474).
                                      5-20

-------
will continue.  Three approaches are being made:  modification of the polymer
base, the use of improved additives in fiber production and the application of
finishes.  All will continue to be important.  It is almost certain that the
ultimate answer, which many textile professionals and executives anticipate in
the next five years, will require totally different chemicals thai are now com-
monly used for thermoplastic fibers.

          Because of this likelihood, it will be necessary for the EPA to con-
tinue to monitor developments in the field of textile flame retardance for new
chemicals and chemical classes until a truely effective flame retardant process
is developed.

5.2.2     Uses

          Use is of two kinds.  First, there is the use of chemicals to produce
flame retardant fibers and fabrics through coreactants and additive monomers
and oligpmers.  Second, there is the use of finishes to impart flame retardance to
                                         i
fabrics used in end products.  In addition, product design is an important aspect
of the textile flame retardancy issue,/especially as federal regulations are
                                      ]
mostly directed at the end product.

          This study has pragmatically concentrated on the production of fibers
and fabrics and has only marginally been concerned with developments in product
design.  Certain products can be designed ,to meet published standards without
special flame retardant fibers and fabrics.. To that extent, those products are
not likely to be sources of environmental concern as a result of their need to be
flame retardant.  For example, carpet standards FF 1-70 and 2-70 can be met by
proper construction employing most pile yarns, without the need to incur
additional costs for flame retardance.  Matresses can meet the matress standard
FF 4-72 without special finishing.  Thus, mattresses are rot of general concern.
Automobile furnishings have tended to use more flat laid plastics and saran   .
based upholstery.

          Practically, acrylics and nylons are not effectively flame retarded
by finishes.  Therefore, it is more common to modify the polymer backbone and
                                     5-21

-------
produce modacrylics and high  temperature polyamides with  inherent  stability.
This eliminates these special fibers  from use  in many product end  uses, unless
the fiber/fabric was especially produced for a specially  designed  retail product
                               i                    "              .      .
for a specific market, for example  flame retardant, light weight nylon tents
or modacrylic children's sleepwear.

5.2.2.1   Plane Retardant Fibers

          Table 5-8 gives the list  of flame retardant fibers currently available.
Each of the  fiber types has a somewhat different profile.

          Cellulose acetate and triacetate is  effectively flame retarded by
adding tris-(2,3 dibromopropyl) phosphate to the material melt prior to spin-
ning.   The  process involves  the thermal diffusion of tris by driving the tris.
into the fiber, under pressure dyeing.  Some work is being done on a process
using organic solvents to apply solution of tris onto a dyed fabric and then
setting it into the fiber with dry  heat.  The  tris is theoretically padded on
at 8-10% add on by weight for polyester fabric.  It is durable through 50 warm
water washings.  Tris will be leached out by solvent dry  cleaning.  It is not
soluble in water.

          Acrylics can also be flame  retarded with tris but the usual approach
is to coreact 35^85% acrylonitrile monomers with vinyl chloride, vinylidene
chloride or vinyl bromide.  Modacrylics are often used in blends with cotton and
polyesters to achieve flame retardance in a finished fabric.  The  addition of
small amounts of a vinyl phosphpnate monomer has been used by Asalln in Japan
to achieve flame retardance and Improved aesthetics.

          Polyester Is the least costly thermoplastic fiber and it is also the
volume leader.  Because of this, much research is aimed at various polyester
fibers and polyester blend fabrics.  The problem of the polyester  blend is not
yet solved,. and It is,likely to require a finish compatible with the after-
treatment of cotton since the cotton component will always require aftertraatment.
1007. polyester treatments, have been successful.  The flame retardant moiety used
   Refer to note 6,  page 5-12.
                                     5-22

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                      TABLE 5-8.  FLAME RET&RMNT FIBERS
Fiber
Company
Chemical
Mature
Composition of
Fabrics
Cotnntants  and
      Markets
Acele FLR      Du Pont
(TK)
PR Acetate     Celanese
Sayfr (TK)     FMC
Arnel FR
(TM)

Dacron 489
(TK)
Extar FR
(TM)

Orion FLR
(TK)

SEF 
-------
                              gABLE  5-8.   (CONTINUED)
Fiber
Company
Chemical
Nature
Composition of
Fabrics
Comments and
Major Market's
Lenvll (TM>    Montedison
C levy I T.
(TM)
Cordelan
(TM)
Rhone Poulenoi
Textile
Valren (TM)    Teljln
Kohjln Co.
Avrll PFR      FMC
(TM)
Bell Flame PR  Kanebo Co.
(TM)

Wool
Flberglas      Owens-Corning
(TM)
Nomex (TM)     Du Pont
Kynol (TM)     Carborundum
                 Vlnyon
Vinyon
                 Vlnyon
Vlnal-Vlnyon
Matrix
                 Rayon with «  .
                 Phosphazene
                 derivative added
                 Rayon with FR
                 additive

                 Protein
                 Glass
100% Vinyon
and blends with
polyester or cotton

100% Vinyon and
blends with poly-
ester or cotton
100% Vinyon and
blends with poly-
ester or cotton

100% Cordelan and
blends with up to
20% of cotton or
polyester

100% rayon and
blends with fibers
such as Nomex
                  100% wool and blends
                  with Fiberglas, Vln-
                  yon, Nomex, etc.
                  100% Fiberglas and
                  blends
                 Aramid            100% Nomex and blends
                 (Aromatic Nylon)  with Kynol, Wook, etc.
                 Phenolic-based    100% Kynol and blends
Apparel,
drapery and
others

Apparel,
drapery,
carpet, and
others

Apparel,
drape ry
Apparel
Safety ap-
parel, air-
craft, upholst-
ery and others;
Developmental
product

Developmental
product

Apparel,  In-
dustrial  work
clothes,  air'
craft upholst"
ery and others

Drapery,  in-
dustrial  work
clothes and
others

Appavelf  in-
dustrial  fab-
rics  & airline
upholstery

Industrial
fabrics;  semi-
commercial
product
                                          5-24

-------
must be thermally stable at temperatures exceeding the 300 C baths needed in
melt spinning processes.  Trie Is not recommended above 350 C.  The most useful
compounds have been 2,5 dlbromotere^hthalic acid from Amoco Chemicals and
                      12 -
Tetrabromobisphenol A.

          Nylon, aside from the aramids, has not been satisfactorily flane
retarded with simple additives or coreactants.  In fact, in nylon, 6 some bromine
additives can increase flammability by causing a more rapid deterioration to the
caprolactam monomer.  Nylon 66 has been treated with limited results with poly-
bromobiphenyl and polybtoomodiphenyl oxide.

          Polyolefins have a need for an effective treatment for use in carpets,
curtains, and tenting.  Moieties that have reached the semi-commercial stage of
development are a Cities Service product that is bicycllc with bromine and chlor*
                                         11          •
Ine attachments to the rings, and a Phillips Petroleum hexabromide of dicyclo-
hexenylethylene.

5.2.2.2   Flame Retardant Finishes

          Although we can expect improved fiber modification and increased con-
sumption of flame retardant fibers in the future, there will always be an Import-
ant proportion of all flame retardant fabrics, especially blends that will be
treated by the dyer and finisher.  Chemical companies seem to be more interested
In developing new chemicals for use by the textile producers than the fiber pro-
ducing Industry.
           Tris (2,3 dibromopropyl)  phosphate is being used with "limited success
 as a fabric finish for polyesters,  nylons and acrylics.   Two techniques are
 available.  The conventional pad-dry application with heat fixation is  most
 commonly used on woven fabric.   The tris is generally applied in  an aqueous
 emulsion and deposits 5-10% add on.  The treated fabric  is dried  at high heat,
 quickly and the residue is removed  by afterwash scouring.

           Cotton/polyester fabrics  have  been treated  with Ciba-Geigy's  Pyroatex.
 However, there are conflicting  reports about its effectiveness  for  blends contain-
 ing more than 25% polyester fiber.   Adverse effects to the fabric hand  and weight
 have also resulted.
 12Refer to note 10,  page 5-20.
                                     5-25

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           The tore of the dyers and finishers In flame retarding man made

 textiles will defend on several factors:


           1.   TVve rate at which compulsory regulations from the Consumer
                Product Safety Commission will Increase the demand for
                flame retardant fibers beyond the capacity of the flbe'r
                producers to produce.  (This is the current situation for
                the modacrylics, polyester and triacetate.)  As a result,
                most polyester fabrics and a considerable amount of
                nylon is being treated by the dyer-finisher.

           2.   The degree to which the fiber producers can impart
                flame resistance to generic fiber type without.de-
                tracting from the other desired properties expected
                oT these fibers in the end-use performance.  Chemical
                modification of fibers to impart flame retardancy oftSn
                influences dyeing properties, whiteness, thermal stabil-
                ity 'and mechanical properties.

           3.   The degree to which chemicals become available for
                more effective and more economical application In dye-
                ing and finishing.  Thus, if chemicals become available
                Which are selectively substantive onto the specific
                fibers during the dyeing operation thts will signifi-
                cantly reduce cost and improve effectiveness.

           4i   The degree  to which the present  blend  levels  of  polyester/cotton
                (65/35,  50/50) -and  poly ester/wool  (55/45)  remain the  major, blend's.
                For example, there  are  already a group of  blended fabrics,  75 -
                $0% modacrylic with 25-30% Of  cotton,  which pass 'sle'epwear
                standard FF-5-74.   65%  cotton-35%  polye'ster can  be finished -as
                flame  retarded fabrics.   Cotton, Inc.. recently announced -"a
                finish which when applied to a 60/40 cotton/polyester ^fabric
                Resulted "in durable flame retardancy.   This is not t-rue of the
                657JE-357. cotton blend.
 5'. 2." 3    "G^r-ren-t":HandliriK^Erac'ttces
         t

           Points of contact where handling 'practices are of concern' include

 tn'e "manufacture, shipping'and'hand ling of the flame retardant chemicals,  the

 •fibers and "the'retail products in the home.  In-use,'melt spun fibers .(nylon

Vnd polyester)'may contain a small atnount
-------
 Ing.   The  chemical  additives  to  the man-made  fibers will  leach off  in washing
 very  slowly,  e.g.,  less  than  407. of total  in  50 wash cycles which
 amounts  to less  than  a  . 1%  chemical per wash.  It  is not  known what the chemical
 reaction is of oxygen and chlorine bleaches with the particular fibers ami
 chemical additives  and whether the resultant  oxidized or  halogenated additive
 represent  hazards of  dermatitis  or toxicity through contact or ingestion.

           Since  the advent  of permanent press  fabrics, consisting of chemical
 cross-linking cotton  in blends with polyester, all washing machine cycles have
 trended  toward lower  and lower washing temperatures.  Very little hot water to-
 day enters the washing machine at higher than  65 C and most washing is carried
 out at the warm  setting which is between   40-50  C  .  We no longer boil clothes
.and relatively little of the  family wash goes  to the commercial laundry.

           In  any event,  the product data safety sheets of the chemical manufac-
 turers and expert opinion solicited in the course  of the  project indicated that
 no extraordinary measures were necessary in the handling  of common textile flame
 retardant  materials.  Typical precautions were advised:   avoid contact with
 skin,  eyes and clothing.  In  case of contact,  wash immediately with soap and
 water.  Do not take internally.   In case of ingestion, induce vomiting.

 5.3        ENVIRONMENTAL EFFECTS
                                             \
           The predicted  increase in requirements for flatne retardant textiles
                                               F
 will  increase the production  volume of these materials, and thus the potential
 environmental hazards.  Pollution could emanate from several sources:
           •    textile production and finishing mills
           •    laundering of  flame retarded products
           •    disposal of the finished materials
           The textile industry is concentrated primarily  in the southeastern
 U.S.  and produces a large diversity of waste  products.  These waste effluents
 appear both in the  atmosphere and in waterways.  Each of  the waste products
                                      5-27

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                                                   13
require  treatments 'tailored  to  the specific waste.    In addition to water and ..
air pollution,  solid waste disposal must  be considered.

5.3.1     Chemistry Involved

          In  general,  the flame retardant substances  are relatively stable and.
thus pose no  overt .environmental hazards  in themselves.  However, under!con-
ditions  of  exposure to ultraviolet light  and extreme- heat,  decomposition >occurs's
Further, unreacted'monomers, oligimers,   platicizers , and the.'like may '>be  pres- >•
ent in the  flame  retardant material which, unlike the base  material are? reaci- •
tive and have a different chemical'profile. They can  pose a potential1 environ*-
mental threat.  For example, the melamine/formaldehyde-resins,  which^are used;
in flame retardant" finishing operations are innocuous in themselves-.  However;>
they do  allow finite amounts of formaldehyde to  be*liberated during the  drying-
and curing  operations.  Some may be liberated  from finished-products as  well.
In the presence of  chloride  ions, commonly associated with  flame retardants,
the concern is  far  greater than with either the'formaldehyde or chloride, alone.-.
Formaldehyde  is known  to react  with chloride to  yield bis (chlor"bmethyJ]l 'ethtet'-'
                                                             j
(BGME),  a known carcinogen:
                   2 Cl   + 22CHO  + 2H ^±-ClGH2OCH2Cl+H20

This material causes  lung cancer in rats  on exposure to levels of 100'.ppb-in'
the air  for  several months \  and-could thus pose  a serious-atmospheri'c con-
tamination problem;
          Another class of potential additives, the polychlorinated biphenyls,
are environmental1 contaminants which have been reported *in:air, water, sediment,1
arid'food chain samples.    These compounds have been' shown to-produceilesions<  4
in various animal's and-to induce pathologic changes in -rhesus monkeys:
            Billy  H.   Textile'Wastes.   J.  Water Pollution"'Coritrol.  Fed.
  46(6):   1286-1290V (1974)   (OTS-AA-0450).
  Hurwitz j  Melvin   Rohm &• Haas.   Assessing the 
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          Structurally, there are molecular similarities between organophos-
phorus flame retardants and  agricultural  products,  and  between organochloride
flame retardants and pesticides.  However, these superficial similarities can
be misleading.  Molecular modifications of a very minor typ&ccan produce gross
changes in biological activity or inactivity.  Hence,  it is  not surprising  that
the toxicity of the flame retardants under review was seen to be low.

5.3.2     Biology Involved

          The absorption, distribution, metabolism, and excretion of the flame
retardant materials, their decomposition products or their starting materials
have not received extensive study.  Indeed, our intensive literature search
revealed no studies in either laboratory or uncontrolled situations.  Toxicity
data, however, has been collected.  This is described in the next section.

5.3.3     Blodegradatlon

          Biodeterioration is the breakdown of a material by living organisms.
It can occur in three ways:  a colony of microorganisms may feed on detritus
which is on the surface of the material; rats or other organisms may mechanically
gnaw or tear at the material; or biochemical attack by microorganisms may occur.
Polymers and plastics are unique among waste materials in that they resist all
three forms of biodegradation.  They especially resist attack by microbial
enzymes, and it is doubtful that a mutant organism will emerge which has an
enzyme system capable of degrading  synthetic,  thermoplastic  polymers.

          Activated sludge is recommended as the best practical control tech-
nology for treatment of textile mill waste treatment, including mills whose
operations include flame retardance.  However, such a process is of little value
                                               18
when the waste products are non-biodegradeable.    For such materials, recovery
of energy or useful products may be more practical through pyrolysls or In-
cineration with steam recovery.
1''Mills, John  The Biodeterioration of Synthetic Polymers and Plasticizers.
  CRC Critical Reviews in Environmental Control, 4 (3)j  341-351 (1974),(OTS-AA-0449).
  Ameen, Jospeh S.  How the Effluent Guidelines Affect You.  Textile Industries,
  138 (10):  36,37,38,39, & 41 (1974) (OTS-AA-0481).
                                    5-29

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         „ The biodegradability of tris  (2,3 dibromopropyl) phosphate was
                         19
determined in one study.    A microbial innoculum was  taken  from raw sewage,
and the  test sample was matched against a blank  containing no  innoculum and a
control  containing the innoculum and  linear allkylated sulfonate  (LAS), but no
tris.  Bromine content of the liquor  of each of  the  test  solutions was measured
at 0, 5, 10, and 15 days.  Allowing for the normal solubility  of tris in,water
(1.6 ppm), an amount of  tris equal to 2.4 times  the  dissolved  txtis was degraded
in 5 days.  Thus, the tris was broken down by the microorganisms in the .raw
sewage.

5.3.4     Radiation, and Thermal Decomposition
                      R                  -
          Dupont Nomex  is degraded by ultraviolet waves of natural and arti-
ficial light.  Results of exposure include discoloration and loss of teajr
         20
strength.    This yellowing effect causes some loss in the reflective qualities
of the material, which may be related to a decrease in tear strength and an
                                                                           21
increase of burning rate (in inches/min.) as a result of exposure to light.
Long-term exposure to sunlight may result in similar degradation of other flame
retardant chemicals,,  but studies have not been performed to indicate this.
          Thermogravimetric analysis  (TGA) combined with mass spectroscopy
(MS) has proved a useful tool for identification of polybenzimidazoles.'. The
TGA curve shows weight loss when a given temperature  is attained and the
MS provides the .composition of gasses given off.  When thermal decomposition
of the FBI's takestplace in the presence of air, water and C0~ are the  primary
degradation products.  Further decomposition results  in the production  of car-
bon monoxide.22
        , Fred A.  'Toxicology of Tris(2,3 dibromppropyl)  Phosphate.  Unpublished
  manuscript, Sept^. 20,  1974   (OTS.-AA-0435).              _
20s.I. du.Pont detNemours & Co.,  Inc.  Properties of Nomex*^ High Temperature.
  Resistant Nylon.Fiber.  N-236, Wilmington, Del., Dupont Technical Information
  Bulletin, 12 pp'(1969)  (OTS-AA-0421.
2lDay, M.; D.M. Wiles  Effect  of Light on the Flammability  of Nomex Fabric.
  Textile Research Journal, 44 (11): 888-891 (1974)  (OTS-AA-0487).
2?Tsur, Ypel; Y.L. Freilich, M. Levy  TGA-MS Degradation Studies of Some New
  Aliphatic-Aromatic Polybenzimidazoles.  Journal of Polymer Science  (Poly
  Chem), 12 (7):  1531-1539 (1974)  (OTS-AA-0452).
                                     5-30

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                       23
          Another study   applied the same TGA-MS technique to a FBI sample
in an argon atmosphere and to a Nomex sample.   Again,  the first step of weight
loss of the PBI was attributed to water, with the same result for Nomex.  No
appreciable amounts of other evolved gasses from the Nomex sample up to 405 C
were found.  The authors concluded that these data did not give rise to any
particular concern with respect to the usage of these two materials, particularly
in applications as materials for interiors of passenger and cargo aircraft.

          The combustion of flame retardant materials, in general, gives rise to
a variety of thermal degradation products, including formaldehyde and (particu-
larly for the chlorinated polymer products) hydrogen chloride and other break-
down productst  Heat may also result in the production of bis-chloromethyl ether
(BCME), which is carcinogenic.  The concern for this event should be
minimal in the case where an accidental fire occurs0  However, in chronic situa-
tions, such as incinceration, the presence of these products and their environ-
mental effects should be investigated.

          The Environmental Protection Agency has recently approved the incin-
eration of chlorinated hydrocarbon wastes, resulting from Shell Oil Company's
production of glycerine, allyl chloride, epichloride, and vinyl chloride,
aboard the special incinerator ship Vulcanus in the Gulf of Mexico.  Surface
monitoring at 1000 feet behind the vessel showed a concentration of 1 ppm
hydrogen chloride.  No detectable changes in environmental stress were noted,
although both phyto and zooplankton were monitored.

          The primary hazard in all acute fire situations is the presence of
carbon monoxide in lethal doses.  The amount of carbon monoxide formed is
proportional to the carbon content of the burned material.  When organic mater-
ials are burned, sufficient carbon monoxide can Ue  prjfeiuoad  to be Lethal.

          Nitrogenous organic substances, such as nitrile plastics, produce
cyanide upon combustion.  As little as one percent cyanide in breathing air
can result In death in 20 minutes.
23Rleinberg, Gerd A.; D.L. Geiger  Tandem Thermogravimetric Analyzer -- Time-of-
  flight Mass Spectrometer System Designed for Toxicological Evaluation of Non-
  metallic Materials.  AMRL-TR-71-71, Wright-Patterson A.F.B. (OTS-AA-0514).
                                     5-31

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5.3.5     BioaccumulatiQn

          The stable chlorinated .molecules,  when introduced to the food chcin,
accumulate in various organs of animals and  produce reproductive hazards.  'These
stable compounds also have tumorigenic potential.  It is quite likely'that
stable bromo and iodo analogs have qualitatively similar behavior, although
most of the research has been performed on the chlorinated compounds.
          A recent incident involving poly-brominated biphenyls demonstrated
 the proclivity of these materials, when ingested, to be passed on .in dairy
 cattle through milk used for human consumption.  Farm Bureau Services, Battle
 Creek Michigan, unknowingly blended this  (non-textile) fire retardant chemical
 with animal feed in place of magnesium oxide, a nutrient additive.  Extensive
 laboratory testing and research by state, U.S. Department of Agriculture, 'Food
 and Drug Administration, and private laboratories resulted in seizure of lots
 of butter and cheese containing the polybrominated biphenyls„  Tons of .milk
 from quarantined dairy herds were destroyed.  Possible effects of the b4phenyls
 on human health are under investigation by the Michigan Department of Public
 Health.

          Polychlorinated biphenyls (PCB) are used in flame retardant mixtures,
 such as polyolefin yarns.  Various studies have been undertaken to show that
 measurable amounts of PCB's may be found in human and cow's milk as well as in
 human adipose tissue.  PCB's have been blamed for premature births and early
 deaths in California sea lion pups, and breeding mink and their offspring have
                                              2fy
 been shown to be sensitive to these compounds.

          Stable opmpounds such as tris (2,3 dibromopropyl) phosphate will tend
 to accumulate in tprash dumps and other disposal sites, resulting in environ-
 mental, rather than biological accumulation.  It is not likely that tris will
 be readily degraded by the effects of weather or other environmental agents,
 due to its relative stability.

          Tissue residue analysis of rats  fed. tris (2,3 dibromopropyl) phosphate
 for a period of 28 days at levels of 100 ppm and 1000 ppm have shown dose rela-
 ted high residue levels in the muscle, liver, and fat of the test animals,
24 Refer to note 16, page 5-28.

                                    5-32

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although no hIstopathological effects were noted.  Bromine levels in these
tissues were determined using the neutron activation technique.  After six
weeks withdrawal, residue levels essentially disappeared, with bromine levels
from the dosed animals returning to the normal background levels of the control
        23
animals.    These data demonstrate the stability of the brotninated organophos-
phorous flame retardant in a biological system.

          Chlorinated polymers are likewise stable in themselves, but carry
the potential for presence of unreacted monomers and oligimers.  When these
highly: reaoCive compounds leach out of the polymers, they pose toxic and car-
cinogenic hazards, if they are not effectively degraded in the environment.
However, it is purely speculative as to whether these oligimers and monomers will
enter  the food chain.

5.3.6     Environmental Transport

          Studies of environmental transport of substances related to those
included in this report have been somewhat limited, but provide a model for
                                        26
future research.  For example, one paper    discussed results of sampling the
waters of the Northwestern Atlantic Ocean with a plankton net.  Samples of vari-
ous types of plastics were recovered, none of which were toxic.  At the same
time,  they are not biodegradeable.  Samples of plastic particles have been found
in the digestive tracts of various marine species.  While these particles are
non-toxic, they may lead to intestinal tract blockage and possible mortality
                 27
in larval fishes.
          Other investigators measured PCB concentrations in the atmosphere over
the western North Atlantic and concluded that the PCB concentrations in the
atmosphere decrease exponentially with the distance from land.  Thus, wind
                                                                        28
transport is the major source of chlorinated hydrocarbons in the oceans.
25^efer to note 19, page 5-30.
26Colton, Jr., John B.; F.D. Knapp, B.R. Burns  Plastic Particles in Surface
  Waters of the Northwestern Atlantic.  Science, 185 (4i50):  491-497 (1974)
  (OTS-AA-0445).
27Ibid.
no                                                '                    .
  Harvey, G.R.; W.G. Steinhauer  Atmospheric Transport of Polychlorinated
  Biphenyls to the North Atlantic.  Atmospheric Environment,  8 (8):  777-782
  (1974)  (OTS-AA-0456).
                                     5-33

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However,  the  incineration of chlorinated hydrocarbon wastes at sea by  the
Vulcarius, which exceeds  In 99.9% combustion, results In no evidence of organic
chlorides in  the sea water at the detection level of 25 ppb.
                                                                      j
5.3t6.1   Monitoring and Analysis
                                     29
          Eichelberge'r and co-workers   suggest a method for monitoring of con-
taminants such as PCB's  in the environment.  This'subset data acquisition'"
technique employs a computer-controlled quadripole mass spectrometer to sample
specific ions, sequences of ions, and varying dwell times of each*  This
technique was applied to an environmental sample from Ground Lake,  St. Mary's.,
Ohio, and found suited to the analysis of the many iwcawse of PCB's.  The
authors conclude that this technique is clearly adaptable to analysis of other
environmental pollutants, where increased sensitivity permits clear observation
of molecular  ions from saturated aliphatic hydrocarbons.
5.3.7     Unre'acted 'Monomers

          As previously mentioned, the halogenated polymers, when introduced
to the environment,  have the  potential of giving off  reactive  monomers  and
unreacted oligomers into the soil and effluent streams.  This problem is a
relatively small one, considering the amounts of these compounds in finished
materials.  The hazards exist only when the unreacted materials, such as vinyl
chloride are either tumorigenic or tetatogenic.  Toxic potential for natural
flora and fauna due to leaching of unreacted monomers from PVG-like material
is negligible.  Further, since these compounds are reactive, there is little
possibility for bioaccumulation.  However, it is not known whether they will
react With organic materials, which then become part of the food chain or
whether they will introduce altered viruses or chemically altered information
into plants and then into animalsaaddultimately into man.
  Refer to note 15,  page 5-28.
                                    5-34

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5.3.8     Waste Treatment Problems

          The 1972 Amendment to the Federal Water Pollution Control Act
(PC 92-500) requires textile plants which are paints of discharge to navigable
streams to:
          A.   Meet the national goal of zero discharge by 1985
          B.   Provide Level I Treatment (Best Practical Control Technology
               Currently Available) by 1977
          C.   Provide Level II Treatment (Best Available Technology Economically
               Achievable) by 1983
          D.   Operate under National Pollutant Dischnrge Elimination System
               Permits with designated monitoring and zeporting procedures

          For textile plants which discharge into municipal sewers, the Act re-
quires pretreatment of non-compatable waste discharges, flow equalization, and
neutralization; and repayment of Federal funds on the basis of waste load, in-
cluding volume discharge.

          On July 5, 1974, EPA published Effluent Limitation Guidelines for the
textile industry pursuant to the provisions of Section 301 of the Act (Federal
Register. Vol. 39 No. 130, July 5, 1974).  These provide limitations on efflu-
ent loads based upon in-plant process production, including flame
           30,31,32
retardance.
          Many of the flame retardants are applied to textiles as finishes, ut-
ilizing the padding method.  This method results in a small volume of effluent
which, as in the case of the formaldehyde melamine resins, can be of an unde-
sireable nature.  As a remedy, these finishes can be applied from solvent using
closed systems.  In fact, synthetic fibers are better suited to solvent pro-
    .   33
cessing.
30Refer to note 18, page 5-29.
31Masselli, Joseph W.J N.W. Masselli, M.G. Burford  Let's Try 90% First.
  Textile Industries, 138 (10): 32,33,356,145 (1974)  (OTS-AA-0482).
32Anon.  Effluent Guidelines Issued.  American Dyestuff Reporter, 63 (8):
  26658 (1974)  (OTS-AA-0468).
•^Davis, W.S.; J. Park  Practical Steps to Reduce Pollution From the Textile
  Industry.  Textile Institute & Industry, 12 (8): 241-243 (1974) (OTS-AA-0483).
                                    5-35

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           Michigan Chemical Company, the largest producer of tris (2,3 dl-
 bromopropyl) phosphate*recommends disposal of this compound from finishing
 afterbaths In the following manner:  Since trls Is of low solubility, It
 precipitates from the afterwash solution.  This precipitate  is  then removed'-
 from the afterwash vessel, and either Incinerated or recycled.

           The National Bureau of Standards vertical flame-test for  fabric
 flammability was developed at a time when most U.S. laundry detergents contained
 50% sodium trlpolyphosphate.  NBS selected 50 lauriderings and tumble-dryings-
 as the durability requirement for flame retardant garments.  Since that titrte,
 phosphorus-containing detergents have been replaced by those containing carbon-1
 ates.  When flame retardant garments are laundered with carbonate detergents';'
 they will often fail the vertical flame test in less than 50 launderings due to'
 alkaline hydrolysis, ion exchange, and/or deposition of calcium carbonate*
               34
 Leblanc argues   that, while the phosphate detergents were banned because?of•:••
 their eutrophication effects on lakes and other waters, these account for less.
 than'20% of the total phosphate runoff into lakes and streams.  Over half- comes*
 from agricultural and natural sources.  The other half comes from sewage,; which
 is about equally divided between detergent and human waste;  Even if all-this
 sewage' were treated for phosphate removal, no one knows whether eutrophication
 would be significantly alleviated, because fertilizer and'natural phosphate run**
 off into lakes may be sufficient to achieve theppeoper nutrient-balance to cori--
 tinue algae growth at the current level.  By the same 'token, the phosphate
 contribution of flame'retardants such as tris (2,3 dlbrdmbpropyl) phosphate
 should be insignificant-.

 5.4    '   TOXfrCITY .;•
                                         ^
           The primary concerns 'for toxicity of f lame-retar-dant agents used in ,
 garments such as-children's sleepwear or work clothes are those of contact'
 irritation and solubility In such-matrices 'as aal'lva, urinej and infantile •
 bowel movements, then systemic absorption of the dissolved material.  As will
 be "discussed below, the -'compounds' under review In this section have demorir-r
 strated-'almost no skin Irritancy.  Further, oral-.doses-'Of tris (2,3 dibromb^ •
3^'teBlan'c'v R.B.  Detergents, Water and-Flammability Standards:  The Need to
  Bring Order Out of Chaos.  American Dyestuff Reporter, 62(10): 72,74,75,76','
  77 & 93 (1973)  (OTS-AA-0462).
                                     5-36

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> propyl) phosphate have been administered to rats and shown to be of very low
 toxicity, with the lowest published lethal dose of 300 tng/kg (Toxic Substances
 List, 1974 Edition).  In general, commercial  flame  retardants were  found  to be
 of very low acute toxicity.   However,  no data have  been retrieved regarding long
 term or tumorigenic effects  of the flame retardant  compounds.

 5.4.1     Toxicology Studies of Tris  (2.3 Dibromopropyl) Phosphate
                             oc n&
           Laboratory studies  '   of  tris (2,3 dibromopropyl) phosphate indicate
 that this material is of very low oral and dermal toxicityt is not a skin or eye
 irritant, and has a low order of subacute toxicity, as determined by 28-day
 rat feeding studies.

 5.4.1.1   Oral Toxicitv in Rats

           Rats were dosed at 5 dosage levels and observed for mortality and
                               37
 weight loss in the Kerst study '.  Table 5-9 summarizes the results:

           TABLE 5-9.  RESULTS OF ACUTE ORAL TOXICITY STUDY IN RATS

 Dosage Level (g/kg)                   Mortality (No. Dead/No. Dosed)
 1.98                                  0/5
 3.15                                  0/5
 5.00                                  3/5
 7.94                                  4/5
12.50                                  5/5

           Surviving rats at 5.00 and  7.94 g/kg levels were observed to exhibit
 less than normal body weight gain, as did one rat dosed at the 1.98 g/kg level.
 LDcn was calculated to be 5.24 g/kg.
                                                         3,8
           These data tend to agree with the second study   where the acute oral
 ID., value in rats was calculated to be greater than 5.0 g/kg.
   Refer to Note 19, page 5-30
   Tenneco Chemicals, Inc., Tris (2,3-dibromopropyl)  phosphate-Proprietary
   Reports, 11 pp. (OTS-AA-0432)
   Refer to Note 19, page 5-30
 38
   Refer to Note 36, page 5-37
                                     5-37

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 5.4.1.2    Dermal Toxictoy

           Results of  p$tch  tests  in both  normal  and  abraided  skin of rabbits
 showed no  signs  of dermal irritation and  no mortality  at  a  dose  of up to 8g/kg.
 According  to  the Food and Drug Administration, compounds-producing combined,av
 arages of  2 or less on  the  primary  irritation index  scale are classified as.
 "mildly  irritating".  Tris  was found to have  a primary irritation index of :0.3.

 5.4.1.3    Eve Irritation

           The two independent studies each tested  for  eye irritation by applica-
 tion of  the tris (2,3 dibromopropyl) phosphate to  the  eyes  of six albino rabbits.
 labbits were observed jEor changes in the  cornea, iris, palpebral conjunctiva.
 Jo effects were  noted -in  any of the animals.

 -.4.2      Human  Toxictty

           Human  studies of  tris (2,3 dibromopropyl)  phosphate have taken the form.
 of insult  patch  tests and both simulated  and  actual  human saliva dissolution
 xtraction tests.   Manufacturer safety data provide  special protective informs?
 tion on  this and other  flame retardants.

 5.4.2.1    Insult Patch Tests

           Fifty-two human subjects  completed  a patch test for skin irritation*
 Fifty showed no  adverse reactions.   Ten patches were applied  to  the upper,,arm
 over a 24  day period, and a single  challenge  patch was applied 14 to 21 days.
 later.  Of the two  instances where  reactions were exhibited,  neither could be
 directly attributed to applications  of the test material,

           It was  concluded,  that tris (2,3 dibromo.propyl)  phosphate did no£ .pro^
 duce primary skin  irritation, skin  fatigue or skin sensitizatipn in the subjects.
     ,39           "                             	' '  '  •
 tested.

 5.4.2.2    Saliva Dissolution Studies

           Since  infants and small children tend to suck pillows-  and sleepwear
which may have been treated with flame retardant material.,,  such  as tris (2,3
 39.^ .
  Refer to Note  19, page  5-30
     I
                                  5-38

-------
dibromopropyl) phosphate, several independent studies have been undertaken to
determine the extent to which tris or its dissolution products will leach out
of treated material and thus pose both acute and longer term oral ingestion
hazards.
                      40
          In one study  , extraction tests were carried out by incubation of
test samples for 72 hours with water at various pH levels and a simulated
saliva solution, prepared for laboratory use.  Extracts were found to contain
low amounts of.sodium bromide or hydrobromic acid, but the phosphate was not
found in any extract.

          One limitation of this study is the fact that although the simulated
saliva solution was prepared to match the pH of natural human saliva, it did
not contain such enzymes as amylase, which occur in human saliva.  Therefore,
brominated phosphates were subjected to natural human saliva in a study
                    41
reported by Rieders.    The bromide content in the saliva at the completion of
the experiment was found to be small.  Increasing temperature increased the
solubility somewhat.

          No data on the solubility of flame retardants in other matrices, such
as urine, perspiration infantile bowel movements, were retrieved.  It is not
known whether the presence of urine will either affect irritancy or solubility
of the components of the flame retardants and whether they will then be ab-
sorbed through the skin.

5.4.2.3   Manufacturer Safety Data
                              42,43
          Specification sheets      prepared by tris (2,3 dibromopropyl) phos-
phate iupplies provide the following safety precautions fpr handling of this
compound during finishing operations:
40
  Refer to Note>i'iB6V.page':6-37
41
  PersonaliCommunication
42                                                                     R
  Michigan Chemical Corporations, Material Safety Data Sheet Firetnaster
  LV-T23P, Chicago, Illionois, 2pp.  (OTS-AA-0430) ,
43
  Tenneco-Chemicals, Inc., Intermediates Division; Material Safety Data Sheet
  Nuogard  , Piscataway, New Jersey, 2pp.  (OTS-AA-0431)
                                    5-39

-------
          •    Health Hazard Data

               1.   Eye Contact

                    Flush eyes Immediately with water for at least 15;minutes,,
                    and, if irritation persists, get medical attention immedi-
                    ately*

               2.   Skin Contact

                    Wash skin with soap and water.  Remove contaminated clothing.
                    and wash before reuse.

               3.   Oral Ingestion

                    If swallowed, induce vomiting               .,

               4'.   Inhalation

                    If inhaled, move to fresh air.

          •    Special Protective Information

               1.   Respiratory Protection

                    None generally required.  For hot vapors, use respirator.

               2.   Ventilation

                    Local exhaust required for hot vapors.  Mechanical ventila-
                    tion acceptable at room temperature*

               3.   Protective Gloves

                    Rubber or leather gtoves required

               4.   Bye Protection

                    Use chemical safety goggles for splash; face shield if hot.
                                                                              i
          These? are general safety precautions advised by major chemical
companies for the most innocuous products.  Both Tenneco and Michigan Chemical
report that their highgrade tris product for flame retardant use is.not.a
known hazardous material.  Regular grade products for other uses, can be a prob-
lem as a result of volatile contaminants.^
44
   Personnel Communication
                                    5-40

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5.4.3     Toxicity to Birds and Mammals

          The organophosphorus compounds, under certain conditions, such as
thermal combustion, exposure  to sunlight, weathering, etc. have the potential
for degrading into toxic phosphines or phosphides, which are hemolytic agents
with toxic properties similar to  those of yellow phosphorus.  However, the
organophosphorus  flame retardants are extremely stable and we have found no
evidence  to  indicate that  these decomposition products occur under natural
conditions.

          Due to the potential increase in the use of these compounds,  however,
some consideration should be given to investigation of the potential  for  phos-
phine/phosphate production.  Phosphorus,  phosphines,  and phosphide^ are general,
indiscriminate protoplasmic toxins and they will attack any cells  with which
they come in contact.   Thus, once they enter the circulatory system,  they
cannot only cause hemolysis, but they can also damage any tissues  and organs
through which the contaminated blood flows,  including bone.

          These types of compounds are unstable, so  that they would be toxic
only to  the  primary contact species, such as rats  in a municipal  dump, but  they
would  not be carried further  in a food chain.  Further, they are  subject to
rapid  degradation, so that they do not pose either cumulative hazards or run-
off hazards  from  soil.

          Subacute toxicity studies of tris  (2,3 dibromopropyl) phosphate were
performed in rats   .  The  compound was fed  for  four  weeks  to male weanlings at
dietary  levels of 100 ppm  and 1000 ppm.  Body weights, feed consumption, and
clinical  studies were performed,  and compared with negative controls.  Rats at
both dose levels  exhibited decreases in body weight, attributed in part to
decreased feed consumption.   However, the slightly poorer  feed efficiency
of the high  dose  (1000 ppm) test  group indicate a possible  toxic  effect.  Body
weight differences between the test and control groups lessened or disappeared
during withdrawal.  Hematology, blood chemistry, and urine  analysis showed no
untoward  changes.  Reduced organ weights of the test animals were attributed
45
  Refer  to Note 19, page 5-30
                                    5-41

-------
to decreased  feed consumption, as noted above.  These results do not appear to
indicate:any  cause1for alarm regarding phosphorous toxicity.

          The toxic effects of halogenated organic compounds upon lower animals
are different from the phosphine/phosphide effects.  Halogenated alkanes are
likely to present a long term presence in a form which can be biologically dam-
aging to the environment.  The chorinated molecules accumulate in the lipid
tissues, and  they-have been related to carcinogenicity (e.g., vinyl chloride
and vinylidine chloride) arid to adrenal cortical changes with resultant hormone
and metabolic anomalies.  Changes in calcium metabolism attributable to
chlorinated molecules have resulted in bird egg fragility.  Reproductive changes
have been observed in lower animals.
                   46
          One study   showed that infant rhesus monkeys, when subjecte'd to doses
of polychlbririated biphenyls (PCS) which produce extreme morbidity in ••adult
monkeys, were able to survive without exhibiting any overt symptoms of PCB
intoxication.  The investigators hypothesized that the tissues of the;infant
monkeys are unable to store the PCB's as readily as are the-.tissues of the
adult monkeys.  Since- the major storage depot for absorbed PCB's is adipose
tissue and the infant-monkey has little fat, there are fewer cells in-which
the compounds may be stored.  A second depot are the membranes of the hepatic
endbplasmic retifculum.  Here agAin, the storage capacity of the v.inf ari"t monkeys
would not be as great as that of the adult, since the infant monkey liver shows
only minimal proliferation of hepatic eridoplasmic reticulum.

          In spite of these facts, we have riot been able to determine that the
halogenated organic flame retardarits give rise to any carcinogenic or otherwise
toxic substance, dither in their finished state or through degradation,, includ-
ing combustion.  The primary concern, then, is that in an acute situation, such
as a'fire will produce toxicants, so that survival from the carbon monoxide
and any burns which may occur may be followed by sequelae.
  Anonymous; Emerging Technology o'f Chloririolysis, Environmental Science arid
  Technology, Vol. 8 (1): 18-19 (1974)  (OTS-AA-0444)
                                     5-42

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5.4.4     Lower Animal Forms

          The PCB's have been found to be very stable.  Much of the data that
refer to DDT in the environment have been shown, through the use of newer,  more
sensitive analytic techniques, to actually refer to PCB's.  Some DDT recently
found in polar bears was shown to be PCB's rather than DDT.

          One study   was undertaken to determine acuf.e toxicity of the PCB
Archlor 1016 in flowing sea water to the American oyster (Crassostrea virginica),
brown shrimp (Penaeus aztecus), grass shrimp (Palaemonetes pugio) and pinfish.
(Lagodon rhomboides).  The study also investigated the chronic toxicity, to
uptake and retention of the PCB by pinfish.  Arochlor 1016 was found to be
acutely toxic to all species tested.  Shell growth in oysters was greatly in-
                                                               t
hibited by exposure to lOOmg per liter for 96 hours.  All animals accumulated
Arochlor 1016.  Toxicity of Arochlor 1016 to .juvenile pinfish was greater in
tests lasting 6 weeks than in 96-hour exposures.

          The possibility of stable chlorinated organic flame retardants leach-
ing out of treated fabrics through laundering, or exposure to weather when dis-
posed of, may exist, thus posing a potential hazard to lower life forms. How*
ever, there has not been any evidence of such occurrences to date, so such
assumptions are purely speculative.

5.4.5     Microorganisms

          There have been no studies of the effects of flame retardants upon
microorganisms.  However, the current trend toward cold water laundering brought
about by the increasing amounts of permanent press fabrics and cold water deter-
gents, have resulted in potential for bacterial retention.  The use of chlorine
bleaches in amounts as little as 25 ppm of chlorine in the wash cycle will  kill
bacteria at any temperature.  Further, increased drying temperature will elim-
inate 'any residual bacteria.
4T
  Hansen, D.J.; P.R. Parrish, J. Forester; Aroclor 1016:  Toxicity to and Uptake
  by Estuarine Animals, Vol. 7 (3):  363-373 (1974) (OTS-AA-0442)
                                    5-43

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 TABLE OF FIRE RETARDANT CHEMICALS

 A.       Ammonium Salts
 A.I     Ammonium Sulfamate
 A.2     Ammonium Phosphates
 A.3     Ammonium Phosphates with Boric Acid              >
         and Ammonium Sulfate
 A.4     Diammonium Phosphate; Dicyandiamide;
         Hexamethylene Tetramine
 A.5     Ammonium Phosphates; Urea
 A.6     Ammonium Bromide
 A.7     Ammonium Chloride
 B.       Borates
 B.I     Boric Acid-Polyhydroxy Alcohol Condensation
         Products
 B.2     Boric Acid; Alkali metal fluorides
 B.3     Fluoborate treatment of asbestos - cotton fabric
 B.4     Boric Acid; Sodium Borate
 C.       Antimony & Titanium Metal Oxides
 C.I     Antimony Oxide
 0.2     Antimony Oxide;  Polyvinyl Chloride
 C.3     Antimony; Titanyl Chlorides and Phos.  Oxychlorlde -
         •Ammonia Products
 C.4     Antimony Trifluoride
 C.5     Antimony Phosphate; Vinyl Chloride resin
 C.6     Potassium Dihydroantimoniate
 C.-7     Copper Antimdritate; Chlorinated ^Paraffin
 D.       Titanium compounds
 D.l     Titanium Tetrachloride - Antimony Oxide
         prdducts
 D.2     titanium Chloride Acylate
'
-------
 TABLE OF FIRE RETARDANT CHEMICALS

E.      Zinc
E.I     Amraoniacal Zinc; Chlorinated Hydrocarbons
F.      Misc. Metal-containing Combinations
F.I     Metal Oxide; Urea; Amine Phosphate Combinations
F.2     Ethylsilicate; Vinyl Copolymers
F.3     Aluminum Sulfate; Lead Acetate; Amine Treatments
F.4     Calcium Alginate
F.5     Alkali Metal Formates
F.6     Organo-Tin Polyesters
G.      Amine - Phosphorus Products
G.I     Ammonia; Polyamine Reaction Products       t
G.I.I   Phosphorus Oxychloride - Ammonia Reaction
        Products
G.I.2   Phosporus Oxychloride; Ammonia; Ethylenediamine
        Reaction Products
G.I.3   Phosphorus Pentoxide; Ammonia products
G.I.4   Phosphoric Acids; Alkylene Polyamine; 2, 3 -
        Dibromosuccinic Acid Reaction Products
G.I.5   PhosphoriclAcid - Amine Condensation Products -
G.2     Aminoplast Phosphates
G.2.1   Phosphoric Acid - Melamine - Dicyandiamide
                       "«
G.2.2   Dicyandiamide; Formaldehyde Phosphates
G.2.3   Urea; Formaldehyde;; Phosphoric Acid; Pyridines
                           \v
G.2.4   Urea; Pyrophosphorie Acid Products
G.2.5   Urea; Glycerine; Phosphoric Acid Products
G.2.6   Guanylmelamine Pyrophosphate
G.2.7   Methylol Melamine; Aliphatics
G.2.8   Methylol Melamine; Phosphonamides
G.3     Phosphoric Acid, Polyvinylpyridine
                A-2

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                                                                    I
 TABLE OF FIRE RETARDANT CHEMICALS                                  i

H.      Aziridines APO, APS
H.1     Tris - (1-aziridinyl) Phpsphiire Sulfide
          Synonyms:  N, N* N" - Trietbylene Thiophosphpramide
                     APS
H.2     Tris - (1-aziridinyl) phosphine oxide
          Synonyms:  N, N', N" - Triethylene Phosphoramide
                     APO           •-...'
H.3     Aziridines with Amines
H.4     Aziridines with Glycols
H.5     APO - Methylol Phosphorus Polymers
H.6     APO - Sulfur-Phosphorus Containing Polymers
H.7     Aziridines with Carboxyalkyl Cellulose
H.8     APO with Anhydrous Ammonia - Phosphorus Pentoxide
        Reaction Products
H.9     APO with Diammonium Phosphate Solutipns
H.10    APO with Sulfamides
H.ll    APO; Thiourea
H.12    Phosphine derivatives
H.12.1  Monocarbamol - Substituted Tertiary Phosphines
H.12.2  Methylol Derivatives of Tris' (2-Carhamoylethyl),
        Phosphine
H.12.3  Aziridinyl N-Alky Phosphinic Amides
I,      Methylol - Phosphorus Polymers, THPC
I.I     Tetrakis (hydroxymethyl) Phpsphonium Chloride
1.2     Tetrakis (Hydroxymethyl) ^hpsphonium Hydroxide
1.3     THPC with methylQl Melamine
1.4     THPC with Urea
1.5     THPC with Ammonia
1.6     THPC with Tris (2-Carhampylethyl) Amines
1.7     THPC with Tris. (Carbampylethyl) Pho.sphine,
        and Phosphoroxytriatnides
I.B     THPC with Triallyl Phosphate and Phosphonitr^itic
        Chloride
1.9     THPC with Urea and formaldehyde
                 A.-3

-------
 TABLE OF FIRE RETARDANT CHEMICALS

I. 10    TMPC with -Pol.yvi.ny1 Chloride and Antimony Oxide
I.IJ    THPC with Po'lyvinyl. Chloride and
        Chlorinated Paraffin
1.1.2    THPC with Polyvinyl Chloride, Polysiloxane ,
        and Zirconium Acetate
I»13    IHPC with Bromine containing Resins e.g.,
        Polybromo Esters of Phosphonitrilic Halides
1.14    THPC with Melamine and Formaldehyde
1.15    IHPC and Diisocyanate Reaction Products
J.      Phosphonitrilic Chlorides
J.I     2.3 - Dibromopropyl Esters of Phosphonitrilic
        Chlorides
J.2     Phosphonitrilic Chlorides and Alkenyl Esters  -
        Polyhalohydrocarbon Adducts
J.3     Phosphonitrilic Chlorides - Hydroxy and
        Hyc'razino Substituted Products
J.4     Phcsphonitrilic Chlorides - reaction with
        Methy Alcohol and Ammonia
J.5     Pheiyl Phosphonitrilic Polymers
K.      Triallyl Phosphates and Phosphonates
K.I     Trirllyl Phosphate - Monomeric
K.2     Brominated Triallyl Phosphates
K.3     Brominated Phosphates
K.4     Haloalkyl Phosphate - Amino Resins
K.5     Triallyl Phosphates - Halogenated Polymers
K.6   '  Polybromb Phosphate Polymers
K.6.1   Bromallyl Phosphate
           Synonyms:  BAP
      '          '      Brominated Polymeric allyl Phosphate Ester
K.6.2   Triallyl Phosphate - Polyhalomethane Polymers
K.6.3   Brominatud Phosphonate Polymers
K.6.3.1  Tris (2-3 dibromopropyl) phosphate
K.7     Triallyl Phosphates - Nonhalogenated Polymers
                   A-4

-------
 TABLE OF FIRE RETARDANT CHEMICALS

K.7.1   Diallyl Cyanoethane Phosphonate Polymers
K.7.2   Diallyl Garboxyroethy1 Propanephosphonatc Polymers
K.8     Phosphonates and-Phosphates
K.8.1   Bis - (2^Bromoethyl) -2-Bromoethane -Phiosphonate
K.8*2   Bis - (2,3 - Dihalopropyl)'Chlorophosphonate
K.8.3   Bis (2-rHaloalkyl) Alkenyl Phosphonates
K.8.4   Bis (Bromochloropropyl) Bromo -
        Chloropropylphosphonate ••- Cellulose "Acretate
K.8.5   Phosphonoroethyl Ethers
K.8.6   Diethyl Chlorophosphate Phosphorylation
K.8.7   Phosphorus Esters and Polyesters
K.8.8   Tris (2,2,2 - Tris  (Chloromethyl) Ethyl)
        Phosphate
K.8.9   2- Phosphotoethyl Ethers
K.8.10  Mesyl -6- Halo - Cellulose Derivatives
L.      Silicones
L.I     Aminoplasts Containing Silicon
L.2     Quaternary Ammonium Salt Derivatives of
        Silicon Compounds
L.3     Polymeric Silicone Resins
M.      Isocyanates
M.I     Phosphous, PhosphorylTriisocyanates
M.2     Polyispcyanates
M.3     Polyvinyl Alcohol
M.4     Diethyl Phosphoric Acid           ,
M.5     Tolylene Diisocyanate Dimer
N.      Phosphono Carboxamides
           Synonym:  Phosphonoalkanoic Amides
0.      Halocycloalkenyl.Acyl Halides
P.      Synthetic Polymers
                 A-5

-------
  TABLE OF FIRE RETARDANT CHEMICALS

P.I       Nylon Flame Retardants
P.I.I     Dimethylol Ethylene Urea - Thiourea
P.1.2     Urea - Thiourea - Formaldehyde Resins
P.1.3     Aminoplast - Melatnine - Carbohydrate
          Formulations
P.1.4     Ammonium Bromide and Aminoplast Resins
P. 1.5     Nomex
P.2       Acrylics
P.2.1     Urea - Formaldehyde and Ammonium Bromide
          Formulations
P.2.2     Phytic Acid - Urea
P.2.3     Hydroxylamine Sulfate and Urea-Formaldehyde,
          Melamine Resins
P.2.4     Modified Acrylic Fibers
P.2.5     Carbonized Polyacrylonitrile Impregnated
          Cellulose
P.2.6     Chlorinated Atactic Polypropylene on
          Non-woven fabrics
P.2.7     Phosphorylated Polyvinyl Alcohol Fibers
P.3       Vinyl Halides
P.3.1     Vinyl Chloride
P.3.2     Vinyl Bromide
Q.        High Temperature Aromatic Polymers
Q.I       Nomex
Q.2       Kapton
Q.3       Polybenzimidazole
Q.4       Phenolics
Q.4.1     Novolaks
Q.5       Brominated Bisphenol A
Q.6       Polybrominated Biphenyl
Q.7       Biphenyl ethers
                 A-6

-------
'BIBLIOGRAPHY

-------
OTS-AA-0001
Aenishanslin, R.; et al
   A new chemical approach to durable flame
retardant cotton fabrics
Textile Research Journal, 39 (9):  375-381, (1969)

OTS-AA-0002
Avny, Yair; I. Peri, A. Zilkha
   Bromine-containing oligomers of dimethyl itaconate
European Polymer Journal, 8 (5):  681-6, (1972)

OTS-AA-0003
Barker, R. H.
   Flame Retardant Finishing
Textilveredlung, 8 (3):  180-6, (1972)

OTS-AA-0005
Baum, Burton M.
   Flame retardant fabrics.  I.  Problem and solution
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Chem. Technol., 3 (3):  167-70, (1973)

OTS-AA-0006
Bell, K. M.; B. W. MeAdam, H. T. Wellington
   Chlorinated paraffins as fire-retardant additives
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OTS-AA-0007
Beninate, John V.; et al
   Conventional pad-dry-cure process for durable-flame
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OTS-AA-0008
Benisek, L.
   New aspects of flame protection using wool:
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OTS-AA-0009
Bennett, F. E.; L. Chesner, R. Preston
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OTS-AA-0011
Boros, Eugene J.; W. M. Lanham, C. Wu
   Base-catalyzed reactions of white phosphorus with
alcohol-epoxide mixtures
Ind. Eng. Chem., Prod. Res. Develop., 12 (3):  221-6, (1973)

-------
OTS-AA-0012
Bostic, J. E., Jr.; K. Yeh, R. Barker
   Pyrolysis .and combustion of polyester.  I...
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OTS-AA-0013
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OTS-M-0014
Bremmer, Bart J.                                                    .
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OTS-AA-0015
Brysson, Ralph J.; et al
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OTSrAA-0016
Bullock, Joel B.; Clark M. Welch
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APO-THPC flame retardant
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pTS-AA-0017                                                                                  ;
Chance, keen H.; J. P. Moreau, G. L. Drake, Jr.                                           ,   j
   Flame retardant for cotton based .on  THPQH (tetrakis                                       I
(hydroxymethyl) •.phosphonium hydroxide)  and guanazole                                         '•
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               v                                        '                                  \
                                                                                             I
OTS-AA-0018
Church, James, M.
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OTS-AA-0019
Cope, J. F.
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OTS-AA-0020
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                                B-2

-------
OTS-AA-0021
Daigle, D. J.; et al
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OTS-AA-0022
Daigle, D. J.; et al
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OTS-AA-0023
Daigle, D. J.; et al
   THP (tris  (hydroxymethyl) phosphine)-amide flame retardant finish
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OTS-AA-0024
Daigle, Donald J.; W. A. Reeves, J. V. Beninate
   Oxidation state of phosphorus in flame retardant polymers based
upon THPC (tetrakis (hydroxymethyl) phosphonium chloride)
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OTS-AA-0025
Dannels, B. F.; A. F. Shepard
   Inorganic esters of novolaks
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OTS-AA-0026
Defosse, T. C.; I. H. Welch
   Practical performance of fire retardant rayon
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OTS-AA-0027
Deverell, D.
   Synthetic resin developments and behavior
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OTS-AA-0028
Donaldson, Darrel J.; et al
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OTS-AA-0029
Drake, George L., Jr.
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   In   Kirk Othmer Encyclopedia of Chemical Technology
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                                    -  3

-------
 OTS-AA-0030
 Drake,  George L., Jr.; E. K. Leonard, W.  A.;Reeves
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    Special finishes for textile-flame retardant finishestand soil
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    Finishing synthetic-polymer materials
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    Determination of phosphorus in fire-res isjtant textiles ;by co.ol-flame
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                                     •4

-------
OTS-AA-0039
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   Flameproofing of cellulosic materials.  I.
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OTS-AA-0040
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   Treatment for improving flame retardancy of wool and minimizing
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Journal of Applied Polymer Science, 16 (4):  1009-16, (1972)

OTS-AA-0041
Gilliiand, B. F.; B. F. Smith
   Flame-retardant properties and thermal behavior of selected
flame-retardant cotton fabrics
Journal of Applied Polymer Science, 16 (7):  1801-16, (1972)

OTS-AA-0042
Godfrey, Leonard E. A.
   Differential thermal analysis (DTA) and thermo-gravimetric
analysis (TGA) studies of flame-retardant rayon fibers
Textile Research Journal, 40 (2):  116-26, (1970)

OTS-AA-0043
Coins, 0. K., Jr.; Y. C. Chae
   Tetrachlorophthalic anhydride polyesters.  Flame recardancy, uv
stability, and reduced smoke.
27, (19A):   1-10, (1972)

OTS-AA-0044
Hendrix, James E.; et al
   Pyrolysis and combustion of cellulose.  I.  Effects of triphenyl
phosphate in the presence of nitrogenous bases
Journal of Applied Polymer Science, 14 (7):  1701-23, (1970)

OTS-AA-0045
Hendrix, James E.; G. L. Drake, R. H. Barker
   Pyrolysis and combustion of cellulose.  III.  Mechanistic basis
for the synergism involving organic phosphates and nitrogenous bases
Journal of Applied Polymer Science, 16 (2):  257-74, (1972)

OTS-AA-0046
Hendrix, James E.; G. L. Drake, R. H. Barker
   Pyrolysis and combustion of cellulose.  II.  Thermal analysis of
mixtures of methyl alpha-D-glucopyranoside and levoglucosan with model
phosphate flame retardants
Journal of Applied Polymer Science, 16 (1):  41-59, (1972)

-------
OTS-AA-0047
Hoke, Charles E.
   Practical management of product  flammab11ity
Soc. Plast. Erig., Technical Paper,  19;,  548-52,  (1973)

OTS-AA-0048
Kasem, M. Abul; M. Richards
   Flame-retardants for fabrics.  Function  of boron-containing  additives!
Industrial & Engineering Chemistry,  Product Research & Development,
11 (2):  'll4-33,  (i972)

OTS-AA-0049
Kausen,  R. C.; F. E. Corse
Syntactic foam prepreg
Modern Plastics, 46 (12):  146-8, (1969)

OTS-AA-0050
Kenaga,  Duane L.
   Heat  cure of high boiling  styrene-type monomers, in.wood*.
Wood Fiber, 2 (1):  40-51, (1970)

OTS-AA-0051
King, Henry Lee; &. L. Ringwald
   Testing the flammability of thermoplastic fibers
Textile  Chemist & Colorist", 1 (17):  356-8, (1969)

OTS-AA-0052
Knoepfler, Nestor B.
   Status of research to develop flame  retardant  cotton*, fIbte-
products for cushioning applications
Journal  of Fire fit-Flammability, 2 (July,) :   219^30;. (1971) •

OTS-AA-0053
Koroskys, Michael J.
   Mordanting of wool
American Dyestuff*Reporter, 60 (5):  48-50, (1971)

OTS-AA-0054
Kbsik, Martin; V. Luzakova, V. Reiser
   Thermal destruction of cellulose  and its- derivatives'
Cellul'bse Chemistry & Technology, 6  (5):  589^97v (1972)

CTS-AA-0055
Kdvacs; J.; C. S. Marvel
   Synthesis of I,4,5,6v7,7-hexachioro- and hexabromo-bicyclb-(2',2^1)-'
5Lheptene-2carbbxylic adld-vinyl esters and copolymerization withi
acrylpnitrile
Journal of Pblyine'r Science, Part A-1, 5 (6):  1279^-87,  (1967)
                                    -61

-------
OTS-AA-0056
Krackeler, Joseph J.; D. Hoogensen
   Halogenated hydrocarbons flame retard polyurethanes
Rubber World, 163 (2):  53-7, (1970)

OTS-AA-0057
Lam, L. K. M.; et al
   Identification of cis-4,5-epoxy-2-pentenal from pyrolysis of
phosphoric acid treated cellulose        - -
Journal of Applied Polymer Science, 17 (2):  391-9, (1973)

OTS-AA-0058
Laur, T. L.; L. B. Guy
   Flame retardant silicone elastomers
Rubber Age, 102 (12):  63-8, (1970)

OTS-AA-0059
Learmonth, G. S.; A. Nesbit
   Flaimnability of polymers.  V. Thermal volatilization
analysis of polyester resin compositions
British Bolymer Journal, 4 (4):  317-25,  (1972)

OTS-AA-0060
Learmonth, George S.; D. G. Thwaite
   Flammability of plastics.  IV.  An apparatus for investigating the
quenching action of metal halides and other materials on premixed flames
British Polymer Journal, 2 (5):  249-53,  (1970)

OTS-AA-0061
LeBlanc, R. Bruce
   Fire-retardant finishing of carpet
Textile Industries, 136 (9):  68, 72, 104, (1972)

OTS-AA-0062
LeBlanc, R. Bruce; E. R. Gray
   Fire retardant finishing of polyester/cotton blends
Textile Chemist & Colorist, 3 (12):  263-5, (1971)

OTS-AA-0063
LeBlanc, R. Bruce; D. A. LeBlanc
   Effects of calcium deposits on fire retardant cotton
Amer. Dyest. Rep., 62 (3):  50, (1973)

OTS-AA-0064
Lewin, M; et al
   Flame Retardant Modification of Cellulose
Textilverdlung, 8 (3):  158-61, (1973)

-------
OTS-AA-0065
Leipins, R.; et a?.
   Organoboron compounds  as  durable flame retardants for cotton fabric
Journal of Applied Polymer Science,  17  (8):   2523-32,  (1973)

OTS-AA-0066                                                          i
Liepins, R.; E. Yasuda
   Barrier coatings  on  cellulose  fiber  mat.
Journal pl: Applied Polymer Science,  15  (12):   2957-64,  (1971)

OTS-AA-0067
Linden, P.; S. B. Sello,  H.  S.  Skovronek
   Flame resistance  of  polyester/cellulosic blends
Texilveredlung, 6 (10):   651-6,  (1971)

OTS-AA-0068
Lipska, A. E.
   Isothermal degration of untreated and fire retardant treated
cellulose at 350
U.S. Clearinghouse Fed. Sci.  Tech.  Inform, 1970,  2.7 pp.

OTS-AA-0069
Lipska, Anne E.
   Isothermal degration of untreated and fire retardant treated
cellulose at 350 JC.
West. States Sect;.,  Combustion  Inst., 1967, 13 pp;.

OTS-AA-0070
Litchfield, E. L.,; T. A.  Kubala                              •
   Flatnmability of fabrics and  other materials in oxygen enriched,
atmospheres. II. 'Minimum  ignition energies                    '
Fire Technology, 5 (4):   341-5,  (1969)

OTS.-AA-0071
Lokhande, H. T.
   Phosphorus-nitrogen  synergism  in flame proofing* of cotton fabrics
Colourage, 17 (16):  25-6, (1970)

OTS.-AA-0072
Lyon, Cameron K..; T. H-. Applewhite
   Castor .-oil-based, flame-resistant, rigid urethan foams
Journal of Cellular  Plastics, 3  (2): 91-5, (1967)

OTS-AA-0074
Lyon, Cameron K.; G. Fuller
   Flame-resistant urethane  foams from  adducts- of. hexachlorocyclopentadl'enet
and castor oil
Industrial & Engineering  Chemistry,  Product. Research 6e  Development,
8 (1):  63-4, (L969)

-------
OTS-AA-0075
Lyons, John W.
   The chemistry and uses of fire retardants
New York, Wiley-Interscience, 1970

OTS-AA-0077
Mazzeno, L. W.; et al
   Degradation of selected flame retardants on exposure to uv and
elevated temperatures
Text. Chem. Color, 5 (3):  55-9, (1973)

OTS-AA-0078
Meazey, A.E.; D. W. A. Farmer
   Latexes of vinyl chloride polymers
British Plastics, 38 (2):  98-105, (1965)

OTS-AA-&079
Miller, Bernard; R. Turner
   Transfer of flame-retardant effects
Textile Research Journal, 42 (11):  629-33 (1972)

OTS-AA-0080
Morris, Cletus E.; et al
   Flame retardant finishing of cotton fabric with a methylol derivative
of tris (2-carbamoylethyl) phosphine oxide
Textile Chemist & Colorist, 3 (6):  136-9, (1971)

OTS-AA-0081
Morris, Cletus E.; Leon H. Chance
   Comparison of some phosphorus amides as flame retardants for cotton
Textile Research Journal, 43 (6):  336-41, (1973)

OTS-AA-0082
Morris, Nancy M.; E. R. McCall, V. W. Tripp
   Identifying finishes by infrared spectroscopy.  Fluorochemicals
and flame retardants
Textile Chemist & Colorist, 4 (12):  283-6, (1972)

OTS-AA-0083
Nelson, K. H.; W. D. Brown, S. J. Staruch
   Rapid determination of bromine-containing flame retardants on fabrics
Textile Research Journal, 43 (6):  357-61, (1973)
                                                                        i
OTS-AA-0084
Nelson, K. H.; H. J. Kelly, Jr.
   Nondestructive determination of phosphorus flame r<-
Text. Chem. Color,  5 (6):  29-31, (1973)

-------
 OTS-AA-0085
 Normand, F. L.; D. J. Donaldson, G. L. Drake, Jr.
    Durable flame tetardant finish for cotton using cyanamide-THPC
 (tetrakis (hydroxymethyl) phosphbnium chloride) resins
 American Dyestuff*Reporter, 59 (9):  46-8, (1970)

 OTS-AA-0087
 Pape, Peter G.
    Flammability characteristics of polyester resins based on
 tetrachlorophthaldc and tetrabromophthalic anhydrides
 Poliplasti e Plastic! Rinforzati, 19 (163):  24-31, (1971)

 OTS-AA-0088
 Perkins, R. M.; G. L. Drake, Jr., W. A. Reeves
    DTA and TGA studies of flame-resistant fabrics
 Journal of Applied Polymer Science, 10 (7):  1041-66, (1966)

 OTS-AA-0089
 Raff, R. A. V.; U. A. K. Sorathia
    In situ formation and incorporation *of additives:into,polymers
 during interfacial polycondensation reactions
 Journal of Applied Polymer Science, 17 (5):  1327-38, (1973)

 OtS-AA-0090
 Rajagopalan, S.
    Development of textile auxiliaries in India
 Colourage, 19 (1*3):  18-19, (1972)

 OTS-AA-0091
 Reeves, Wilson A.
    Fire resistant textiles --a handbook
 West•Port, Conn., Technomic, 1973

 OTS-AA-0092
 Reeves, Wilson A.; G. L. Drake, Jr.
   -Flame-Resistant Cotton
 Merrow'Monographs;  Textile Technol. -Series,Aflo. 11,^Watford,
'Merrow, 1971

 OTS-AA-0093
 Reeves, Wilson A.; R.M. Perkins
    Chemistry off THPC (tetrakis (hydroxymethyl)-i*phbaphonium chloride) ;in
 flame retardants for'cotton
 Colourage, 1-7,: (1971)

 OTS-AA-0094
 Reeves, • W. A.;  H. M.  Rob ins on,»R.  M. s'.-Re inhard t
    Finishing cellulosic  materials
 Review of Textile Progress, 15,  396-411,  (1963)
                                     -. lo

-------
 OTS-AA-0095
 Schneider, John A.; R. G. Pews, J. D. Herring
    Fire-retardant unsaturated polyesters.  Comparisons of analogous brominated
 and chlorinated reactive intermediates
 Industrial and Engineering Chemistry, Product Research & Development,
 9 (4):  559-63, (1970)

 OTS-AA-0096
 Sello, Stephen B.; J. B. Gaj, C. V. Stevens                                •
    Hydrolytically stable organophosphorus cellulose reactants
 Textile Research Journal, 42 (4):  241-8, (1972)

 OTS-AA-0097
 Spatz, Sydney M., et al
    Use of tetrabromophthalic anhydride (TBPA) in the construction of
 fire-retardant polyester- and epoxy resins
 Industrial & Engineering Chemistry, Product Research and Development,
 8, (4):  381-91, (1969)

 OTS-AA-0098
 Stepniczka, H.; J. DiPietro
    Flammability characteristics of cotton and polyester fibers
 Journal of Applied Polymer Science, 15, (9):  2149-71, (1971)

 OTS-AA-0099
 Strzelbicki-Sas, Guido
    Fire hazards of plastics in chemical plants and equipment
 Chemistry & Industry, (8):  349-52, (1973)

 OTS-AA-0100
 Syzmanski, Walter A.; D. W. Kloda
    New fire retardant chemical resistant polyester
 27, (3A):  1-4, (1972)

 OTS-AA-0101
 Tesoro, Giuliana C., J. Rivlin, D. R. Moore
    Flame retardant finishing of polyester-cellulose blends
 Industrial & Engineering Chemistry, Product Research & Development,
 11, (2):  164-9, (1972)

 OTS-AA-0102
 Thiery, Pierre
>    Fireproofing chemistry, technology and applications
 New York, Elsevier, 1970

 OTS-AA-0103
 Tillin, Sandra; C. E. Pardo, W. Fong
    Flame and shrink-resistant wool
 Textile Research Journal, 42 (2):  135-6, (1972)

-------
OTS-AA-0104
Turner, John D.
   Reaction of a brominated N-methylolallyl carbamate derivative
with cellulose
Textile Research Journal, 41 (8):  709,  (1971)
                                                                    i
OTS-AA-0105
Uehara, Y.; E. Yanai
   Smoke, carbon monoxide, and carbon dioxide from cellulosic material's
treated with DAP (diammonium phosphate in a fire environment)
J. Fire Fl.ammability, 4  (Jan.):  23-41,  (1973)

OTS-AA-0106
Vigo, T. L.-, C. M. Welch
   Reaction of cotton
Textilverecllung, 8 (3):  93-7, (1973)

OTS-AA-0107
Weaver, J. W.
   Burning behavior of marginal flame retardant fabrics
Textile Chemist & Colorist, 4 (5):  116-18, (1972)

OTS-AA-0108
Weil, E. D.
   Phosphorus containing flame retardants - a survey.  Flame Retardancy
in polymers
Hoboken, N.J., Stevens Institute, 1971

OTS-AA.-0109
Whitfield, Robert E.; M. Friedman
   Chemical modification of wool with chlorendic and related •
halo-organic acid anhydrides
Text. Chem. Color, 5 (4):  76-8, (1973)

OTS-AA-0110
Whitfield, Robert E.; M. Friedman
   Flame-resistant wool.  IV. Chemical modification of wool with
haloorganic acid halides
Textile Research Journal, 42 (9):  533-5, (1972)

OTS-AA-0111
Yeh, Kwan-Nan; R. H. Barker
   Pyrolysis and combustion of cellulose. IV. Thermo-chemistry of
cotton cellulose treated with selected phosphorus-containing flame retardants
Textile Research Journal, 41 (11):  932-8, (1971)

OTS-AA-0112
Yeh, Kwan-Nan; M. M. Birky, C. Huggett
   Calorimetric study of flammable fabrics. II. Analysis of flame
retardant-treeted cotton
Journal of Applied Polymer Science, 17 (1):  255-68, (1973)

-------
OTS-AA-0113
Slezak, Frank B.
   Reaction of xylene dihalldes with dlols.
Industrial Engineering Chemistry, Product Research and Development,
4, 259-61, (1965)

OTS-AA-0114
Decossas, K. M., et al.
   Flame-resistant cottons
Textile Industries, 130 (7):  128, (1966)

OTS-AA-0115
Nametz, R. C.
   Self-extinguishing polyester resins
Industrial & Engineering Chemistry, 59 (5):  99-112, (1967)

OTS-AA-0116
Agarwal, S. K.
   Flame-proofing in polymers
Indian Chem. J., 5 (9):  40-2, (1971)

OTS-AA-0117
Alaminov, Kh.; M. Mikhailov, I. Damynova
   Maleate oligoesters containing .isbcyanuric rings
Journal of polymer Science, Part C., No. 22 (Pt 1), 419-30, (1967)

OTS-AA-0118
Abbot, C.
   Effect of GRP (glass reinforced plastic) variables on burning properties
British Plastics, 43 (7):  95-8, (1970)

OTS-AA-0119
Adler, A.; W. Brenner
   New durable flame-retardant finish for polypropylene textiles
Nature, 225 (5227):  60, (1970)

OTS-AA-0121
Woods, William G.; J.G. Bower
   New heat-stable zinc borate fire retardant
Modern Plastics, 47 (6):  140-1, 144, 149-50, (1970)

OTS-AA-0122
Aenishaenslin, Rudolf
   Flame-retardant finishes for cellulosic fibers
Ciba Review, (4):  35-43, (1969)

OTS-AA-0123                                  .
Matthews, C. J.
   The reduction of polymer inflammability
Proceedings of Royal Australian Chem Institute, 34  (7): 186-7, (1967)

-------
OTS-AA-0124
Tesoro, Glullana C.
   Flame retardants  for  cotton  fabrics.
Textllveredlung,%2 (7):   435:40,  (1967)

OTS-AA-0125
Drake, George L., Jr.
   Flame resistant and rot  resistant  finishes:  application to cellulose.
American Dyestuff Reporter,  56  (15):    560-4,  (1967)

OTS-AA-0126
Barber, Richard P.,  et.  al
   Effects of THPC (tetraki8(hydroxymethyl)phosphonium chloride)  on £he
light-fastness o.f dyes and  pigments.
Textile Chemist & Color.lst,  1  (5):    124-9,  (196,9)

OTS-AA-Q127
Ball, G. W., et. al.
  New heat resistant rigid  foam.
Journal of Cellular  Plastics, 4 (7):    248r6l,  (19,68)

OTS-AA-0128
Beninate, John V.
   Better flame resistant finish for  cottons.
Textile Industries,  131  (11):    110,  112,  114,,  116,  118,  (1967).

OTS-AA-0129
Walsh, Edward N.; E. N.  Uhing,  T. M.  Beck
   Flame-retardant polyurethan  and polyester resins.
American Chemical Society.   Division  of Organic Coatings, and Plastics         ,
Chemistry.  Preprints, 23 (1):    1-14,,  (1963)

OTS-AA-0130
Slchhorn, J.
   Self-extinguishing polystyrene by  a  new synergistic concept.       ;?-':•..
American Chemical Society.   Division  of Organic Coatings  and; Plastics Chemistry.
Preprints, 23 (1):   37-49,  (1963)

OTS-AA-0131
Ingram, Alvln R.
   N-Chloro and--N-nitroso organic compounds  as  synergists for the s&lfr-      : .1
extinguishing action of  bromine compounds  in polystyrene,.
American Chemical Society.   Division  of organic, CpatingS: and Plastics; Chemistry.
Preprints, 23 (1):  95-114,  (1963)

OTS-AA-0132
Hindersinn, Raymond R.;  N.  E. Boyer
   Fire resistant unsaturated polyester resins  from  trialkyl phospfeites.
American Chemical Society.   Division  of Organic Coatings,and Plastics Chemistry.
Preprints 23 (1):    50-60,  (1963)                                  "
                                     •  14

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OTS-AA-0133
Hill, D. W.
   Chemistry  In  the  textile  Industry.
Chemistry  in  Britain,  1  (11):    525-30,  (1969)

OTS-AA-0134
Mirhej, M.-E.; J.  F. Henderson
   High polymers of  alkoxy and halo  alkoxy phosphonitriles.
Journal of Macromolecular Science  -  Part  A Chemistry,  1  (1):    187-94,  (1966)

OTS-AA-0135
Byrne, G.  A.; D. Gardiner, F. H. Holmes
   Pyrolysis  of  cellulose and the  action  of  flame-retardants.   II.   Further
analysis and  identification  of products.
Journal of Applied Chemistry, 16 (3):   81-8,  (1966)

OTS-AA-0136
Chen, H. H.;  A.  C. Nixon
   Heat-resistant  epoxy-boroxine foams for high  temperature  applications.
Society of Plastics  Engineers Transactions,  5  (2):   90-100  (1965)

OTS-AA-0137
Chance, Leon  H.; W.  E. Reeves, G.  L. Drake,  Jr.
   Phosphorus-containing carboxamides and their  evaluation on  cotton fabrics.
Textile Research Journal, 35 (4):    291-8, (1965)

OTS-AA-0138
Perkins, Rita M.;  G. L.  Drake, Jr.,  W. A. Reeves
   Imparting  durable flame resistance to  the surface of  low-density  cotton
textiles.
American Dyestuff  Reporter,  54  (15):   17-18,  (1965)

OTS-AA-0139
Connolly,  W.  J.; A. M. Thornton
   Alumina hydrate filler in polyester systems.
Modern Plastics, 43  (2):   154,  156, 202, (1965)

OTS-AAi-0140
Bremmer, B. J.
   Factors influencing the heat  stability of fire-retardant  epoxy resins.
American Chemical  Society Division of Organic  Coatings and Plastics
Chemistry.  Preprints, 23 (1):   115-25,  (1963)

'OTS-AA-0141
Elchhorn,  J.
   Synergism  of  free radical initiators with self-extinguishing additives  in
vinyl aromatic polymers.
Journal of Applied Polymer Science,  8 (6):   2497-524, (1964)
                                    •S-15

-------
 OTS-AA-0142
 Ingram,  Alvin R.
    N-Chloro and N-nitroso compounds as synergists.for•selfrextinguishing
 action of bromine compounds in polystyrene.
 Journal of Applied Polymer Science, 8 (6):   2485-95, (1964)

 OTS-AA-0143
 Woods, William George; J. G. Whiten
    Potential use  of inorganic.borates as fire-r.etardant additives in*plastics.
 American Chemical Society, Division of Organic Coatings and Plastic "Chemistry.
 Preprints, 27 (2):   210-17, (1967)

 OTS-AA-0144
 Beninate, John V., et. al
    Application of a new phosphonium flame retardant.
.American Dyestuff Reporter, 57 (25):    981-985, (1968)

 OTS-AA-0145
 Beninate, John V., et. .al
    Economical durable flame-retardant finish for cotton.
.Textile.Research  Journal, 39 (4):    368-74, (1969)


 OTS-AA-0146
 Benisek,  L.
    Use of titanium complexes to improve the natural flame retardancyiof-wool.
 Journal  of the Spciety of Dyers &. Colour 1sts., '87 (8):   i277-'8, '(1971)

 OTS-AA-0149
 Brysson, .Ralph J.; B.  Piccolo,/A.  M.  Walker
    Calcium-phosphorus deposition during home laundering.
 Textile  Research  Journal, 41 (1):    86-7, (1971)

.OTS-AA-0150
Wilson,  Joseph J.
    Insulation.  (Neglected stepchild of -fire,protection  specifications.
 Chemical Technology,  189-90, (1971)

 OTS-AA-015.1
 Jynghans,  P.  R.
    Modified polypropylenes for  automotive applications.
 Chem.  Eng.  Progr., 63 (4):   94-8,  (1967)

.QTS-AA-0152
Jackson, W.  J., Jr.;  J.  R. Caldwell
    Antiplasticization.   II.   Characteristics of antiplasticizers.
Journal  of Applied Polymer Science, 11 (2):    211-:26, (19670
                                        16

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OTS-AA-0153
Chance, Leon H.; E. K. Leonard, G. L. Drake, Jr.
   Methylol derivatives of halocyanoacetamides and their evaluation on cotton
fabrics.
Textile Research Journal, 37 (5):   339-43,  (1967)

OTS-AA-0154
Slagel, R. C.; G. P. Shulman, F. M. Young
   A new flame retardant polyester system based on 2,3-bls  (carboxyethyl)-l,
4,5,6,7,7 - hexachlorobicycle (2.2.1)-5-heptene.
Industrial Engineering Chemistry, Product Research & Development, 6 (2):
100-4, (1967)

OTS-AA-0155
O'Brien, S. James; R. G. Weyker
   Application of Pyroset CP flame retardant to wool.
Textile Chemist & Cblorlst, 3 (8):   185-8, 1971

QTS-AA-0156
O'Brien, S. James
   New trends In fire retardants.
Textile Chemist & Colorist, 2 (12):   201-4, (1970)

OTS-AA-0157
O'Brien, S. James
   Cyanamide-based durable flame-retardant  finish for cotton.
Textile Research Journal, 38 (3):   256-66,  (1968)

OTS-AA-0158
Normand, F. L.; D. J. Donaldson, G. L. Drake, Jr.
   Durable flame retardants (for cotton fabrics).
Textile Industries, 134 (6):   169-70, 176, 186, 188, (1970)

OTS-AA-0159
Nametz, Richard C.
   Flame-retarding synthetic textile fibers.
Industrial and Engineering Chemistry, 62 (3):   41-53,  (1970)

OTS-AA-0160            ..
Nakasato, Satoshi, K. Hlguchi
   Synthesis of dialkyl trichloromethylphosphonates and their properties  for
additives.
Journal of American Oil Chemists Society, 47 (8):   283-5,  (1970)

OTS-AA-0161
Morris, Cletus E.; G. L. Drake, Jr.
   APO (tris(l-aziridtnyl)pho8phine oxide)-silicone emulsions as multi-
purpose finishes for cotton.
American Dyestuff Reporter, 58 (2):   31-3,  (1969)
                                       17

-------
OTS-AA-0162
Morgan,  A. W.;  C.  P.  Farley
   Flame retarding' and plastlcizlng efficiencies of phosphate esters.
Soc. Plastic  Engineers Journal,  Tech;-,  Pap.,  1971, 17, 417-20; (1971)

OTS-AA-0163
Morgan,  A. W.;  C.  P.  Farley
   Flaramabillty of plastics and  flame test methods.
Plast. Furniture,  Nat.  Tech.  Conf.  Soc. Plast.  Eng., 1970, 59-62

OTS-AA-0164
Moreau,  Jerry P.;  et.  al.
   Imparting  flame; retardancy to cotton knit's.
Anterican Dyestuff  Reporter,  61 (1):    29-31-2,  (1972)

OTS-AA-0165
Moreau,  Jerry P.;  Chance L. H.
   Flarae-retardant cottons  using phosphorus-containing' triazines.
American Dyestuff  Reporter,  59 (5):    37-8, 64-5,  (1970)

OtS-AA-0166
Mitchell, George Redmond
   Low-cost new flame-retardant,  high-service-temperature:'glass-reinforcedv
electrical-grade laminate.
Proc. Annlv.  Conf;  SPI Plast./Compos*  Div., 25th,  197'Oj 2-A, 6 pp;

OTS-AA-0167
Miller,  Bernard; C. H.  Metser, Jr.
   Measuring  the burning rates of fabrics.
Textile  Chemist  &  Colorist, 3  (5):    118-22,  (1971)

OTS-AA-0168
Miller,  Bernard; C. H.  Meiser, Jr.
   Steady state  burning of  textiles  In  flowing  02/N2 mixture's.
Textile 'Chemist  fc.COlorlst, 2  (12):    205-8,  (1970)

OTS-AA-0169
Miller,  Bernard;;T. M.  Gorrie
   Chars  produced  from cellulose  under  various^ conditions of thermal.decomposir
tiori.                                                       :   ...
Journal  of Polymer  Science, Part  C,  (36):    3-19.;  (19.fi)'-

OTS-AA-0.170
Miles,  Thomas D.; A. C. Delasanta
   Laboratory study of  flame-retardant  textiles produced;' by 'an- ionizing;radd'ar-
tion cure.                                                                 .
Textile  Research Journal, 39  (4):    357-62,  (1969)
                                     - 18

-------
OTS-AA-0171
Miles, T. D.; A. C. Delasanta
   Durable nonreactive flame-retardant finishes for cotton.
Textile Research Journal, 38 (3):   273-9, (1968)

OTS-AA-0172
Meggos, Haralambos, Y. C. Chae
   Tetrachlorophthalic anhydride-based flame-retardant polyesters.
Annl. Conf., SPI Reinf. Plast./Compos. Div. Proc., 1971, 12B, 1-6, (1971)

OTS-AA-0173
Meggos, Haralambos N.; Y. C. Chae
   Tetrachlorophthalic anhydride-an effective flame-retardant Intermediate
for polyesters.
Proc. Anniv. Conf. SPI, Reinf. Plast./Compos. Div., 9-A, 6 pp.,  (1970)

OTS-AA-0174
McNally, John S.; M. Baum, C. W. Morgan
   Properties of a fire-retardant, thermally stable, electrical-grade thermoset.
Annu. Tech. Conf., SPI Reinf. Plast./Compos. Div., 1969, 16-E-1-4

OTS-AA-0175
Markarian, Haig, et. al.
   The compatibility of arthropod repellents with certain functional finishes
of cotton uniform fabric.
Journal of Econ. Entomol., 61 (2):   464-7, (1968)

OTS-AA-0176
MacNair, Richard N.; J. T. Stapler
   Intumescent fabric coatings for protection against thermal radiation and
flame.
American Dyestuff Reporter, 59 (3):   27-9, 32, 34-36, (1970)

OTS-AA-0177
Lyons, John W.                                                       '
   Mechanisms of fire retardation with phosphorus compounds: some speculation.
Journal of Fire & Flammability, 1 (Oct):   302-11, (1970)

OTS-AA-0178
Gandhi, R. S.
   Properties of Viscose rayon fabrics treated with tetrakis (hydroxymethyl)
phosphonium chloride (THPC) resins.
Textile Research Journal, 40 (5):   437-44, (1970)                        '

OTS-AA-0179                               .
Lhuede, E. P.; T. A. Pressley, R. J. Rowlands
   Gaseous treatments of textiles.  I.  Development of equipment.
Text. Inst. Ind., 9 (1):   15-19, (1971)
                                   "&-19

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  OTS"AA-0180
  LeBlanc,  R. Bruce
     Fire-retardanti cotton-textiles.
  Int.  Dyer.  Text.  Printer,  Bleacher Finish, 141 (4):  -231-2,  (1969)

  OTS-AA-0181
  Rubens,  L.  C.;  D. Urchick
     Fluid resin  systems for reinforced plastics based on dispersions of-poly
  (vinyl chloride)'plastisol resins in reactive vinyl monomers.
  Technical Paper Reg.  Technical Conference, Society of"Plastic Engineers,
  Cleveland Sec., September, 1966, 52-63

  OTS^AA-0182
  Jahn,  A.  K.;  J. W.  Vanderhoff
     Self-extinguishing polystyrene foaming In-place beads.
  American Chemical Society.  Division of Organic Coatings 'and-: Plastics
  Chemistry.   Preprints, 23  (1):   61-81, (1963)

  OTS-AA-0183
  Cass,  R.  A.;  L. 0.  Raether
     New Phosphorus-containing esters for flameproofing acrylic'resins.
  American Chemical Society.  Division of Organic Coatings and'Plastics
  Chemistry.   Preprints, 23  (1):   82-94, (1963)

  OTS-AA-0184
•  Cicione,  R. J., «t. -al.
     Crosslinking «reactions  in fibers and multifunctional'e-ffeets.
 •American Dyestuff Reporter,  57 (3):   66-9,  (1968)

  OTS-.AA-0185
  Sather,  J.  M.;  H. R.  Richards
     Efficiency of  phosphorus-containing compounds, *'for "Inhibiting'1 :a'f t erg low-'In
  cellulose fabrics.
 .American Dyestuff Reporter,  59 (3):   21-6,  (1970)

  OTS-AA^0186
  Schneider,  John: A.; R. G.  Pews,  J. D.^Herring
     Comparisons  bf analogous  brominatedvand 'chlorinated ireactive'.intrfrmedl'ates
  In  fire .retard-ant polyesters.
• American  Chemical Society, Dlv.  of -Organic -Coatings &'El-a'stics'lGhemUstry,
  Papers,  29  (9):    382-92,. (:1969)

•OTS-AA-0187
  Scholick,  F., en.  al.
    Urethane fcams from, animal' fats. V.  Flame-resistant -foams ^from hypohalo-
.  genated glycerides.               -                              i
  Journal' of  Amer.  Oil  Chemists Society, 47 (5):   180.-2, (1970)

-------
OTS-AA-0188
Schumm, R. W.; C. J. Cruz
   Dyeing and finishing Nomex nylon.
Textile Chemist & Colorist, t (18):   388-91, (1969)

OTS-AA-0189
Sello, Stephen B.; G. C. Tesoro, R. Wurster
   Flame retardant cellulose.
Textilveredlung, 5 (5):   391-9, (1970)

OTS-AA-0190
Siconolfi, C. A.
   Fire retardancy in chemical process ductwork.
Fire Technology, 5 (3):   217-24,  (1969)

OTS-AA-0191
Slama, W. R.; R. E. McMahon
   Testing plastics for fire snuff-out.
Chemical Engineering, 77 (24):   120, 122, 124-5 (1970)

OTS-AA-0192
Smith, James Kenneth, et  al.
   Thermochemical investigation of cotton flame retardance.
Textile Research Journal, 40 (3):   211-16,  (1970)

OTS-AA-0193
Spatz, Sydney M.; H. Stone
   Some N-substituted tetrabromophthalimide  fire-retardant additives.
Industrial & Engineering Chem. Prod. Res. &  Dev., 8 (4):   397-8, (1969)

OTS-AA-0194
Spatz, Sydney M., et  al.
   Discoloration of tetrabromophthalic anhydride polyester resins.
Ind. Eng. Chem., Prod. Res. Develop., 8 (4):   391-6, (1969)

OTS-AA-0195
Temin, Samuel C.
   Flame retardant treatments of FBI (polybenzimidazole) fabric.
Journal of Fire & Flammability, 3  (Jan.):    19-28, (1972)

OTS-AA-0196
Tesoro, Giuliamr; S. B. Sello, J. J. Willard
   Flame-retardant properties of phosphonate derivatives of cotton cellulose.
Textile Research Journal, 38 (3):   245-55,  (1968)

QTSTAA-0197   l
Tesoro, Giuliana C.; C. H. Me leer
   Effects of chemical composition on the flammabllity behavior of textiles.
Textile Research Journal, 40 (5):   430-6, (1970)

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                                                                                             I  I
 OTS-AA-0198
 Tesoro,  Giuliana C.l;  J.  Rivlin
    Flammability behavior of experimental blends.
 Textile  Chemist & Colorist,  3 (7):    156-60,  (1971)

 OTS-AA-0199
 Tesoro,  Giuliana C.;  S.  B.  Sello,  J.  J.  Willard
    Nitrogen-phosphorus synergism in flame-retardant cellulose.
 Textile  Research Journal,  39 (2):    180-90,  (1969)

 OTS-AA-0200
 Tsuchiya,  Yoshio;  K.  Sum!
    Thermal decomposition products  of  cellulose.
 Journal  of Applied?Polymer Science,  14 (8):    2003>13,  (1970)

 OTS-AA-0201
 Tesoro,  Giuliana C.
    Flame retardant' fabrics:  are researchers  on the right, track.
 Textile  Chemist & Colorist,  1 (14):    307-10,  (1969)

 OTS-AA-0202
 Sule, Anil D.
    Developments in finishing of textiles.  2.   Flameproofing of textiles.
 Textile  Dyer Printer,  3  (5):    73-8.,  (1970)

 OTS-AA-0203
 Pitts, James J.;  P. H. Scott,  D. G. Powell
    Thermal decomposition of  antimony  oxychloride  and  mode' in flame refeardancy.
 Journal  of Cellular Plastics,  6 (1):   35-7,  (1970)

 OTS-AA-0204
 Pruitt,  R.  M.
    Self-extinguishing  characteristics of flame-resistant- flexible urethane?
 foam.
 Journal  of Cellular Plastics,  6 (6):   262-6,  (197,0)

 OTS-M-0205
 Rangarajan, K.
    Flame-retardant synthetic  textiles.
 Chemical, Age of India* 22  (3):   137-40,  (1971)

 OTS-AA-0206)
 Ranney, M'.
    Flame retardant polymers.
Noyes Data  Corp., Park Ridge,  N; J.,  1970, 263, pp.

OTS-AA-0207,
Ranney, Maurice W.
    Flame retardant textiles..
 Noyes Data Corp., Park. Ridge, N.J., 1970., 373pp.
                                       22,

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OTS-AA-0208
Reeves, Wilson A.
   Durable phosphorus-containing flame retardants for cellulosic textiles.
Textile Chemist & Colorist, 4 (2):   45-7, (1972)

OTS-AA-0209
Reeves, Wilson A.; G. L. Drake, Jr., J. V. Beninate
   Durable and semidurable flame retardants based on methylol phosphorus com-
pounds.
Textilveredlung, 5 (6):   498-505,  (1970)

OTS-AA-0210
Roebuck, A. H.; H. H. Kline
   New developments in thermosetting resins.
Materials Protection & Performance, 9  (2):   19-20, (1970)

OTS-AA-0212
Sander, Manfred
   Phosphorus-containing polymers.  Survey.
Encycl. of Polymer Science & Technology,  (10):   123-39,  (1969)

OTS-AA-0213
Ross, Jack H.; S. Schulman, R. M. Stenton
   Nonflammable fiber for personnel protection systems.
Textile Research Journal, 41 (2):   146-53, (1971)

OTS-AA-0214
Reynolds, Joel R.
   Fire and safety materials utilization  at the John F. Kennedy Space Center.
NASA Spec. Publ., 1971

OTS-AA-0215
Reeves, Wilson A., et  al.
   Methylol phosphorus polymers used for  flame retardants.
Textile Chemist & Colorist, 2 (16):    283-5, (1970)

OTS-AA-0216
Reeves, Wilson A., et  al.
   Comparison of four flame retardants.
Textile Chemist & Colorist, 1 (17):    365-9, (1969)

OTS-AA-0217
Reeves, Wilson A.
   Flame, weather, and soil resistant  cotton fabrics.
Textile Dyer Printer, 1 (2):   59-63,  (1967)

OTS-AA-0218
Reeves, Wilson A.
   New techniques in cotton finishing.
American Dyestuff Reporter, 57 (4):    P107-P111, (1968)
                                   ^•23

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  OTS-AA-0219
  Qulnn,  J.  A.  W.
     Newly available trialkyl .phosphates.
  Paint,  Oil, & Colour Journal, 158 (37.64):   949-53,  (1970)

  OTS-AA-0220
  Quinn,  Edwin J.
     Properties and stability of fire-retardant rigid polyurethane  foams  from
  phosphonopropionate polyols.
  Ind.  Eng.  Chem. ,  Product -.Research & Development, . 9 (1) :   n48r,53»  (1970)

  OTS-AA-0221
  Pitts,  James J.
     Metal ainnine  complexes.  New class of flame retardants.
  Journal of Cellular Plastics, 7 (4):   202-7, (1971)

 •OTS-AA-0222
  Perkins,  R. M. ;  G. L.  Drake, Jr., W. A. -Reeves
     Effect  of laundering variables on -the flame retardancy of cotton  fabrics.
  Colourage,  18 (24):    33-6, (1971)

  OTS-AA-0223
  Perkins,  R. M. ; ,G. L.  Drake, Jr., W. A. Reeves
     Effect, of laundering variables on the flame retardancy, of cotton , fabrics.
  Journal pf American Oil Chemists Society, 48 (7) :    ;330-3, 0971)

  OTS-AA-0224
 • Parr ish, .Donald ^B. ;  R. :M.  Pruitt
     Thermal stability of flame resistant flexible, ur ethane. foam.
  Journal of Cellular Plastics, 5 (6):   348-57, (1969)

  OTS-AA-0226
  Pape, Peter G.;>J. E.  Sanger, R.  C.  Nemetz
     Tetr,abromophthalic  anhydride in f lame-ret ar.dant.urethane foams.
  Journal of Celljilar  Plastics, :, 4 (11) :   ,438-42,  (196,8)

  OTS-AA-0227
  Gupta,  S.  K.; Y.  N. .Sharma,  R.  T. Thampy
     ChemicalTreslst ant, polymers .based pn.bisphenpl>A:,';der:iyuat,ive.8.
  Die Makrpmoleku'lene .Chemie,  120,  137,r47,  (1968)

Fire, & 'Flammability,, 1                  '
 .OTS-AA-0229
 •Hendrix, James E., et  al.                                  .   x
    Effects of moisture on oxygen index -(01)  value 8; Jor text;ile8.
 Textile Research Journal, 41  (1.0):   ' 854r-6,  (1971)
                                        -24

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OTS-AA-0230
Hendrlx, James E., et  al.
   Environmental temperatures and oxygen Index  (01) values for textile fabrics.
Journal of Fire & Flammability, 3 (Jan.):   2-18,  (1972)

OTS-AA-0231
Hendrix, James E.; G. L. Drake, Jr., W. A. Reeves
   Effects of fabric weight and construction on oxygen index  (01) values for
cotton cellulose.
Journal of Fire & Flammability, 3 (Jan.):   38-45,  (1972)

OTS-AA-0232
Hilado, Carlos J.
   Flammability characteristics of cellular plastics.
Industrial Engineering Chemistry, Product Research  & Development, 6  (3):   254-66,
(1967)

OTS-AA-0233
Godfrey, Leonard E. A.; J. W. Schappel
   Alkoxyphosphazenes as flame retardants for rayon.
Industrial Engineering Chemistry, Product Research  & Development, 9  (4):   426-36,
(1970)

OTS-AA-0234
Hilado, Carlos J.
   Effect of chemical and physical factors on smoke evolution from polymers.
Journal of Fire & Flammabilitx 1 (July):   217-38,  (1970)

OTS-AA-0235
Holmes, Robert L.
   Elastomeric coatings aid flame retardance.
Rubber World, 164 (2):   65-9, (1971)

OTS-AA-0236
Ingham, Peter E.
   Pyrolysis of wool and the action of flame retardants.
Journal of Applied Polymer Science, 15 (12):   3025-41, (1971)

OTS-AA-0237
Jackson, W. J. Jr.; J. R. Caldwell, K. P. Perry
   Chlorination of polyesters.
Journal of Applied Polymer Science, 12 (7):   1713-33, (1968)

OTS-AA-0239
Isaacs, Jack L.
   Oxygen index flammabllity test (of plastics).
Modern Plastics, 47 (3):   124-5, 128, 130, (1970)
                                    B-25

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OTS-AA-0240
Hollies, Norman  F. "S.
    Physical properties  of finished cotton fabrics related to clothing, comfort
Textile Dyer  Printer, 2 (10):    63-8,  (1969)

OTS-AA-0241
Hllado, Carlos J.
    Boron, and  antimony compounds  as flame retardants; in rigid polyurethane foao.
Journal of Cellular  Plastics,  6  (5):    215-20,  (1970)

OTS-AA-0242
Hilado, Carlos J.
    Flame-retardant urethane  foams.
Journal of Cellular  Plastics,  4  (9):    339-44,  (1968)

OTS-AA-0243
DiPletro, J.; H. Stepniczka, R.  C.  Nametz
    Flammabillty  of cotton, polyester,  and their blends;
Textile Resaarch Journal  41  (7):    593-9,  (1971)

OTS-AA-0244
Donaldson, Darrell J.;  D.  J. Daigle
    Phosphorus-nitrogen  flame retardant via copper complex.
Textile Research Journal,  39  (4):   363-7,  (1969)

OTS-AA-0245
Donaldson, D. J.; F. L. Normand,  G. L.  Drake, Jr.
    Effect of  pH  on THPC-cyanamide flame retardant.
American Dyestuff Reporter, 61 (2):    48,  50-1,  (1972)

OTS-AA-0246
Dorset, B. C. M.^
    Developments  in flameproofing treatments and techniques;
Textile Manufacturer, 96  (1146):    240-6,  (1970)

OTS-AA-0247
Dorset, B. C. M.
    Flame retardant and  crease-resist finishing  processes.
Textile Manufactures, 97  (1154):    68-75,  (1971)

OTS-AA-0248
Drake, George L. Jr.
    Fire retardaricy:  its status today.
American byestuff Reporter, 60 (5):    43-4, 46-7,  (1971)         l>

OTS-AA-0249
Drake, George L., Jr.;  R. M. Perkins, W.  A. Reeves                          •
    Special finishes  for textiles:  flame  retardant-finishes and V8oil-resistant
finishes.
Textile Dyer Printer, 2 (10):    69-77,  (1969)
                                  ^ - 26

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OTS-AA-0250
Dupraz, Carol A.
   How to apply a flame resistant  finish to wool  fabrics.
American Dyestuff Reporter, 60  (10):   54, 56,  (1971)

OTS-AA-0251
Economy, James; L. Wohrer
   Phenolic fibers.
Ency. of Polymer Science & Technology, 15, 365-75,  (1971)

OTS-AA-0252
Eitel, Michael J.
   Incineration of flame retardant materials.
American Dyestuff Reporter, 60  (5):   52-3, (1971)

OTS-AA-0253
Finley, E. L.; W. H. Carter
   Temperature and heat-flux measurements on life-size garments ignited by
flame contact.
Journal of Fire & Flammability, 2  (Oct.):   298-320,  (1971)

OTS-AA-0254
Fitzgerald, Warren E.
   Acrylic fibers.
Chemical Engineering World, 5 (10):   47-51, (1970)

OTS-AA-0255
Freeston, W. Denney, Jr.
   Flammability and heat transfer characteristics of  cotton, Nomex and PBI
(pplybenzimidazole) fabric.
Journal of Fire & Flammability, 2  (Jan.):   57-76,  (1971)

OTS-AA-0256
Frick, John G., Jr.; G. A. Gautreaux, J. D. Ried
   Absorption of formaldehyde on cotton in finishing  treatments.
Textile Chemist & Colorist, 2 (20):   345-6, (1970)

OTS-AA-0258
Gandhi, R. S.
   Absorption of THPC  (tetrakis(hydroxymethyl)phosphonium chloride) on textile
fabrics.                                                                  •   •
Textile Research Journal, 38 (12):   1180-8, (1968)

OTS-AA-0259  •
Gandhi, R. S.
   Flameproofing of cellulosic materials.  II.  Phosphorus compounds.
Colourage, 16 (8):   53-9, (1969)

OTS-AA-0260
Ghlonls, C. A.; C. L. Browne
   Aspects and trends of finishing polyester-cotton blend fabrics.
American byestuff Reporter, 57  (8):   P254-P260,  (1968)
                                  "B  27

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OTS-AA-0261
Gasklll, James R.
   Smoke development  In polymers during pyrolyeis  or  combustton.
Journal of Fire & Jlammabllity, 1  (July):    183-216,  (1970)

OTS-AA-0262                                                    ,
Gandhi, R. S.
   FlameproofIng of celluloslc materials.   IV.  Mechanism of  fiameprooilug.
Colourage, 16  (12):   47-51,  (1969)

OTS-AA-0263
Gandhi, R. S.
   FlameproofIng of celluloslc materials.   III.  Recent  trends.,
Colourage, 16  (10):   46-50,  53,  (1969)

OTS-AA-0264
Elnhorn, Irving N^, et  al.
   Smoke development  In urethane  foams.
Journal of Cellular Plastics, 4 (5):    188-97,  (1968)

OTS-AA-0265
Brzozowskl,  Zblgniew
   New chlorobisphenyl  macromolecular compounds.
Polimery,  15(8):   393-6,  (1970)                                ;
OTS-AA-0268                   "~                   	    		
Cleaver, R. F.
   Formulation and testing of fIre-retardant GRP  (glass-reinforced polyester)
compounds.
Plastics & Polymers, 38  (135):   198-205,  (1970)

OTS-AA-0269
Crook, James W.; G. A. Haggis
   Behavior of halogen-containing phosphates and  phosphonates  In urethane
foams.
Journal of Cellular Plastics, 5  (2):   119-22,  (1969)

OTS-AA-0270
Darby, Joseph R.; J. K. Sears, N.  W. Touchette
   How to combine flame and weather resistance  In PVC.
Soc. of Plastic Engineers Journal, 27 (2):   32-6;  (4), 74-9,  (1971)

OTS-AA-0271
Dalgle, Donald J.; D. J. Donaldson
   Less expensive durable flame retardant.
Textile Chemist & Colorlst, 1 (24):   534-6, (1969)

OTS-AA-0272                 f
DIPtetro, Joseph H. Barda, H. Stepnlczka
   Burning characteristics of cotton, polyester,  and nylon fabrics.
Textile Chemist & Colorlst, 3 (2):   40-8,  (1971)
                                   "B -28

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OTS-AA-0273
DiPietro, Joseph; H. Stepnlczka
   Flame retarded systems.  ABS (acrylonltrlle-butadlene-styrene), polystyrene,
and polyester.
Plastics In Australia, 22 (5):   7-9, 11-13, (1971)

OTS-AA-0274
DiPietro, Joseph; H. Stepniczka
   Factors affecting the oxygen index flammabllity ratings.
Society of Plastic Engineers Journal, 27 (2):   23-31,  (1971)

OTS-AA-0275
Deanin, Rudolph D., et. al.
   Polymers of hydrogenated and chlorinated naphthalene-2, 6-dicarboxylic acids.
Journal of Polymer Science, Part A-l, 6 (1):   235-40,  (1968)

OTS-AA-0276
Davis, Charles A.
   Relations of flammability measurements.
Textile Chemist & Colorist, 1 (25):   540-8, (1969)

OTS-AA-0277
Stepnlczka, Heinrich E.
   Flame-retarded nylon textiles.
Industrial & Engineering Chemistry, Product Research and Development, 12 (1):
29-41, (1973)

OTS-AA-0278
Eitel, Michael J.
   Combustion processes with polymer products containing flame retardant
additives.
Technical Paperv Reg. Tech. Conf. Soc. Plast. Eng., Chicago, Sect., Oct. 11-
12, 1972, 57-62                                              ,    ;
         /
OTS-AA-0279
Arney, W. C., Jr.; W. C. Ruryla
   Structure-property relations in flame retardant systems.  Relative effects
of alkyl phosphates, phosphonates, and phosphites on cellulose flammability.
Journal of Fire & Flammability, 3 (July):   183-91, 1972

OTS-AA-0280
Lipscomb, Charles, A.; C. W. Muessig
   Zelec as in antistatic, flame retardant additive -- preliminary investigation.
A D 699500 U.S. Clearinghouse Fed. Sci. Tech. Inform., 1969, 16 pp.            '

OTS-AA-0281
Carroll-Porczynski, C. Z.
   Application of simultaneous DTA/TG and DTA/MS analysis for predicting in ad-
vance of processing the flammability and toxicity of gases of composite textile
fabrics and polymers.
In Thermal Analysis, Preceedings of the International Conference on Thermal
Analysis 3rd, 1971, (pub. 1972), 3, 273-84
                                     - 29

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OTS-AA-0283
Vogt, Herwart C., et  al.
   Flame-resistant chlorine-centaIning polyester resins.
Ind. Eng. 'Chem., Product Research & Development, 9  (1):    105-13,  (1970)

OTS-AA-0284
Waldron, Earl T.
   Effect of textile finishes on thermal protection.
Textile Chemist & Colorist,  1 (5):    130-4,  (1969)

OTS-AA-0285
Wadia, M. J.
   Finishing of synthetic blends.
Colourage Annual, 122-6, (1968)

OTS-AA-0286
Walker, A. G.
   Flame-retardant plastics.
British Plastics, 42 (7):    128, 131-2,  (1969)

OTS-AA-0287
Flaherty, R. T., et  al.                                         ,
   Effect of Phosphate esters on PVC  flammability.   '
In Society of Plastics Engineers, Technical  Papers,  17, 412-16,  (1971)

OTS-AA-0288
Grossman, Richard F.; D. I.  Myer
   Flame resistance of wire  and cable insulations.
In Society of Plastics Engineers, Technical  Papers,  17, 23-7,  (1971)

OTS-AA-Q289
Zieman, Carl
   Chlorinated PVC-processing and properties
In Technical Papers, Regional Technical Conference,  Society  of Plastic  Engineers',
Philadelphia Section, 49-56

OTS-AA-0290
Cipriani, L.
   Phosphonium bromides as flame retardants  for thermoplastics.
In Technical Papers,, Regional Technical Conference,  S-P-E  Palisades-Section,
Oct. 27-28, 1970, 3i7-47

OTS-AA-0291
Bartrum, David E.
   CPVC (chlorinated poly(vinyl chloride))-an engineering  thermoplastic with'
inherent flame resistance.
In Technical Papers, Regional Technical Conference,  Society  of Plastic  Engineers,
Akron Section, Sept. 1970, 58-63
                                     -30

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OTS-AA-0292
Dalzell, Darwin A.; R. J. Nulph
   Flame-retardant compositions of styrene-butadiene foams.
In Society of Plastic Engineers, Annual Technical Conference.  Technical
Papers, 28th, 1970, 215-18

OTS-AA-0293
DiPietro, Joseph; H. Stepnlczka
   Study of flame retarded ABS (acrylonltrlle-butadlene-ntyrene), polystyrene,
and polyester systems.
In Society of Plastic Engineers, Annual Technical Conference, Technical Papers,
28th, 1970, 463-8

OTS-AA-0295
Pape, Peter G.; J. E. Sanger, R. C. Nametz
   Tetrabromophthalic anhydride In flame-retardant polyurethane foams.
In Society of Plastics Engineers, Annual Technical Conference, Technical
Papers, 26th, New York, N. Y., May 6-10, 1968, 695-8

OTS-AA-0296
Creitz, Elmer C.
   Chemical extinction of diffusion flames as related to flameprooflng of
plastics.
In Society of Plastics Engineers, Annual Technical Conference, Technical
Papers 28th, 1970, 368

OTS-AN-0297
Behnke, W. P.; R. E. Seaman
   Laboratory tests which predict end-use performance under high temperature
conditions.
Applied Polymer Symposia, 1969, No. 9, 49-62

OTS-AA-0298
Hlrsch, Stephen S.; J. R. Holsten
   Enhancement of aromatic polyamide thermostablllty by heat treatment In air.
Applied Polymer Symposia, 1969, No. 9, 187-94

OTS-AA-0299
Frazer, August H.; W. Memeger, Jr.
   Ordered aromatic copoly(l,3,4-oxadiazole-l,-3,4-thiadiaz.ole)fibers.
Polymer Preprints, Amer. Chemical Society, Div. of Polymer Chemistry, 9 (2):
1150-7, (1968)

OTS-AA-0300                                            ••   i .,.-!,
Carroll-Porczynski, C. Z.
   Fabric flammability.  New textIng methods and equipment.
Textile Institute and Industry, 9 (7):   188-94, (1971)

-------
OTS-AA-0301
Pape, Peter G.; &. C. Nulph
   Flatmnability characteristics of polyesters based on tetrabromophthalic.^and
tetrachlorophthalic anhydrides.
Annual Technical Conference, Society of the Plastics  Industry, .Reinforced
Plastic Composites Division.  Proceedings, 23rd,  1968, 19A-1-19A-6

OTS-AA-0302
Chae, Y. C.
   Chemical resistant and  flame retardant polyesters  based on tetrachlorophthalic
anhydrideJ
In Annual Technical Conference, Society of the Plastics  Industry, Reinforced
Piasties/Composites Division, 1967, 6-E/8 pp.

OTS-AA-0303
Thomas, James  L.; C. L. Wright
   Dapon FR +  for improved flame resistance.
In Annual Technical Conference, Society of the Plastics  Industry,.Reinforced
Plastics/Composites Division, 6-D/8 pp

OTS-AA-0304
Vogt, Herwart  C.; P. Davis, L. Sobel
   Unsaturated polyesters based on octachlorobiphenyl derivatives.
Annual Conf. Society of the Plastics Industry/Compos. Div. Proc.  26th, New
York, N. Y., 1971, 12A, 1-18                                    .

OTS-AA-0305
Barrentine, Eugene M.; et  al.                 -
   Synergistic fire-retardant additives for chemical  resistant polyesters.
Annual Conf. Society of the Plastics Industry/Compos. Div., Proc. 26th, New
York, N. Y., 1971, 2-D, 1-8

OTS-AA-0306
Draganov, Sam  M.; R. W. Sprague, J. .G. Bower
   Comparative .evaluation of Firebrake ZB with antimony  oxide using'.various
fire-testing methods.
Annual Conf.,  Society of the Plastics Industry/Compos. Div., Proc. 26th, New
York, N. Y., 1971, 2-E, 1-6

OTS-AA-0307                                                     ,
Barton, Kenneth R.; W. C. Wooten, Jr., C. C. Dannelly
   Flame-resistant backing adhesives for polyester carpets.
Textile Chemist & Colorist, 4 (1):   22-8, (1972)

OTS-AA-0309
Goynes, W.  R.; L.  L. Muller, .E. K. Boylston
   Effect of fire retardant treatment on the structure of the cotton  fiber.
In Proceedings, Electron Microscopy Society of America,  1972, 30, 210-:11
                                  ^•32

-------
OTS-AA-0310
Strzelblcki-Sas, Guldo; T. A. Hlnson
   Safety margins afforded by Het acid based polyester resins in large scale
fire retardance and antlcorrosion applications.
In Protection 69, Plastics - Fire-Corrosion, International Symposium on
Corrosion Risks in Connection with Fire in Plastics, 1969, R1-R9

OTS-AA-0311
Nametz, R. C.; J. DIPietro, I. N. Einhorn
   Halogenated anhydrides as fire retardants for unsaturated polyester resins.
Amer. Chem. Soc., Division of Organic Coatings and Plactlc Chemistry. Papers,
28 (1):   204-24, (1968)

OTS-AA-Q312
Delman, Alvin D.
   Recent advances in the development of flame-retardant polymers.
Journal of Macromolecular Science, (Part C), Reviews in Macromolecular
Chemistry, 3 (2):   281-311, (1969)

OTS-AA-0313
Parker,i William James; A. E. Lipska
   Decomposition of cellulose and the effect of flame retardants.
WSCI-69-25, Western States Section, Combustion Institute, Pittsburgh, 1969,
47 pp.

OTS-AA-0314
Grazley, R. C.
   Fire retardant polymers and textiles.  An overview.
In Specialty Chemicals, A Symposium at the 160th Meeting of the American
Chemical Society, Chicago, Sept. 14-18, 1970, Amerlcah.CNemical Society,
Division of Chemical Marketing and Economics, New York, N. Y., 1970, 23-31

OTS-AA-0315
Lund, G. V.
   Markets for fire retardant systems in apparel and bedding.
In Specialty Chemicals, A symposium at the 160th Meeting of the American
Chemical Society, Chicago, American Chemical Society, N. Y., N.Y., 1970, 45-54

OTS-AA-0316
Reeves, W. A.; V. R. Bourdette
   Flame-resistant cotton fabrics from USDA.
Textile Industries, 128 (1):   105-9, (1964)

OTS-AA-0317
Hunt, R. E.; F. H. Burkitt
   Cellulose materials-finishing.
Review of Textile Progress, 12, 350-60, (1960)
                                   ^•33

-------
OTS-AA-0318
Roberts, Carleton W.; D. H. Haigh,  R. J.  Rathsack
   Fi.re-retardant polyesters based  upon  2,3-dicarboxy-5,8rendomethylene.^5,
6,7,8,9,9-hexachloro-l,2,3,4,4a,5,8,8a-octahydronaphthalene anhydride.
Journal of Applied Polymer Science, 8  (1):   363-83,  (1964)

OTS-AA-0319
Miles, Thomas D.; F. A. Hoffman, A. Merola
   Replacing THPC in the APO-THPC flame-resistant finish for textiles.
American Dyestuff Reporter, 49  (17):   596-9,  (1960)

OTS-AA-0320
LeBlanc, R, B.
   Pilot-plant and mill applications of  tris(l-aziridinyl)  phosphine  oxide
finishes to cotton fabrics.
American Dyestuff Reporter, 53  (8):   42-4,  (1964)

OTS-AA-0321
Simpson, W. S.
   Efficient flameproofing agents for wool.
Applied Polymer  Symposia, 1971, No. 18 (pt.  2)  1177-82

OTS-AA-0322
Crawshaw, G. H.; P. A. Duffield, P. N. Mehta
   Flammability  and flameproofing of wool fabrics.
Applied Polymer  Symposium, 1971, No. 18  (Part 2)  1183-97

OTS-AA-0323
Smith, Arthur Raymond
   Textile finishing.
Reports on the Progress of Applied  Chemistry, 52,  663-79,  (1967)

OTS-AA-0324
Turner, Laurence W,; S,. G. Mullett
   Epoxy resins.
Reports on the Progress of .Applied  Chemistry, 52,  626-33,  (1967)

OTS-AA-0326
Sherr, Allan E.;,H. C. Gillham, H.  C. -Klein
   Fire retardates for thermoplastics.  Phosphonium ha1ides.
Advances in Chemistry Series, Nto. 85, 318-25, (196,8)

OTS-AA-0328
Anonymous
   Flame-retardant market is hinged to plastics.
Chemical Engineering Nevs, 42 (22):   32-3,  (1964)
                                      34

-------
OTS-AA-0329
Hindersinn, Raymond R.; N. E. Boyer
   Phosphorus-containing unsaturated polyester resins from trialkyl phosphites.
Industrial Engineering Chemistry, Product Research and Development, 3  (2):
141-5, (1964)

OTS-AA-0330
Gallagher, Dudley W.
   Phosphorylation of cotton vith inorganic phosphates.
American Dyestuff Reporter, 53  (10):   23-4,  (1964)

OTS-AA-0331
Hobart, Stanley R.; G. L. Drake, Jr., J. D. Guthrie
   Changes in the properties of partially phosphonomethylafced cotton caused
by cross-linking prior to phosphonomethylation.
American Dyestuff Reporter, 50  (3):   30-4, (1961)

OTS-AA-0332
Rockey, K. W.
   Flame-retardant polyester and epoxide resins.
International Reinforced Plastics Conf., 3rd  London, 1962, 11.0-11.12

OTS-AA-0333
Bullock, Joel B.; C. M. Welch, J. D. Guthrie
   The weathering characteristics of lightweight, flame-retardant finishes for
cotton fabrics.
Textile Research Journal, 34 (8):   691-700,  (1964)

OTS-AA-0334
Hay, Peter M.
   Flame-retardant cellulose:  a new method of evaluation.
American Dyestuff Reporter, 53  (19):   23-6 (1964)

OTS-AA-0335
Pacheco, J. F.; P. P. Carfagno
   How laundering practices Influence the flame retardancy of fabrics.
Textile Chemist & Color1st, 4 (11):   255-9,  (1972)

OTS-AA-0336
Baitinger, William F.
;   Cellulose reactive fire retardants.
Textile Chemist & Colorist, 4 (7):   172-6, (1972)

OTS-AA-0337
Collins, J. R.
   Flame-resistant fibers.
Plastics & Polymers, 40 (149):   283-9, (1972)

-------
OTS-AA-0338
Hinders inn, Raymond  R.; G. M.Wagner
   Fire retardancy.
In Encyclopedia of Polymer Science  and Technology,  John Wiley &.Spris,.vN.Y.,
1967

OTS-AA-0339
Buck, George S.
  -Fire resistant textiles.
In Encyclopedia of Chemical Technology,  1st,  Interscience  Encyclopedia,  N.Y.,
1951, 6, 543-558

OTS-AA-0'340
Anonymous
   Bromine outlook tied to clean  air  rules
Chemical and Engineering News  52  (8):    11-12,  (1974)

OTS-AA-0341
Anonymous
   Man-made fiber output hits  new high.
Chemical and Engineering News,  52 (9):    11,  (1974)

OTS-AA-0342
Mark, H.; N. S. Wooding, S. M.  Atlas
   Chemical aftertreatment of  textiles
Wiley-Interscience,  N. Y., 1971,  638  pp.

OTS-AA-0343
Baetjer, Anne M.
   Dehydration and susceptability to toxic chemicals
Archives of Environmental Health, 26  (2):   61-63,  (1973)

OTS-AA-0344
Healy, T. V.
   Ammonia and related atmospheric  pollutants at Harwell.
Atmospheric Environment, 8 (1):   81-83,  (1974)

OTS-AA-0345
Martens, Christopher S.; et  al.
   Lead and Bromine  Particle size distributions in  the San Francisco Bay area
Atmospheric Environment, 7 (ft):   905-914,  (1973)

QTS-AA-0346
Anonymous      '   •
   Flame retardants  growth flares up.
Chemical and Engineering News,  49 (43):   16-19, (197,1)
                                      36

-------
OTS-AA-0347
LeBlanc, R. B.
   A durable flame retardant textile finish with tris(l-aziridlnyl)-pho8phine
oxide.
Textile Research Journal, 35 (4):   341-346, (1965)

OTS-AA-0348
Mark, H.; S. M. Atlas
   Environmental hazards of modern textile finishing. In H. Mark chemical
After-treatment of textiles.
Interscience, N. Y., 1971, 631-4

OTS-AA-0349
LeBlanc, R. Bruce
   Flammabillty and fire resistance of textiles.
American Dyestuff Reporter, 57 (27):   P1093-P1096,  (1968)

OTS-AA-0350
Szam, Istvan; E. Vincze, J. Szentner
   The pathogenesis of ammonium chloride pulmonary edema.
Zeitschrift Fuer Die Gaesamte Innere Medizin uno ihre Grenzgebiete, 26 (12):
378-383, illus., (1971)

OTS-AA-0351
Eloeva, A. A.; M. K. Chedzhenova
   Experimental studies of the toxicity of Mekapol, Premlx Powder EFP-60 and
Thermoplast PLS.
Referatlvnyi Zhurnal Otdel'Nyi Vypusk Farmakologiya Khimioter sredstva
Toksikologiya, 27, 47-48, (1970)

OTS-AA-0352
Batyrova, T. F.; I. K. Astaf'eva
   Comparative study of the toxicity of two ammonium sulfate specimens.
Gigiena Truda i Professional'nye Zabolevaniya, 15 (10):   53-54 illus., (1971)

OTS-AA-0353
Logan, William S.; H. 0. Perry
   Cast dermatitis due to formaldehyde sensitivity.
Archives of Dermatology, 106 (5):   717-721 Illus.,  (1972)

OTS-AA-0354
Schuppli, R.; et  al.
   On the toxicity of boric acid.
Dermatologica, 143 (4):   227-234, (1971)

OTS-AA-0355
Mllkov, L. E.; et  al.
   Health status of workers exposed to phthalate plastici.-.ers in the manu-
facture of artificial leather and films based on polyvinyl chloride resins.
Environmental Health Perspectives, (3):   175-178, (1973)

-------
OTS-AA-0356
Waller, Julian A.
   Non-highway' injury  fatalities:  II.   Interaction  of product  and human
factors.
Journal of Chronic Diseases,  25  (1):    47-52, .(1972)

OTS-AA-0357
Sram, R. J.; Z. Zudova
   Effect of the dose-fractionation on  .the  frequency  of chromosome
aberrations induced  in mice by TEFA.
Folia Biologica, 19  (1):   58-67,  (1973)

OTS-AA-0358
Voge'l, E.
   Differential; sensitivity of immature and mature  oocytes  of  Drospphlla
melanogaster to the  induction of dominant lethals following treatment of
mono and polyfunctional aziridine  analogues.
Mutation Research, 14  (2):    250-253,  (1972)

OTS-AA-0359
Logan, W. S.; H. 0.  Perry
   A contact dermatitis to resin-containing casts.
Clinical Orthopaedics  and Related  Research, 90,  150-152,  (1973)

OTS-AA-0360
Nitta, Sumio; N. C.  Staub                                    (
   Lung fluids in acute ammonium chloride toxicity  and edema in  cats  and
guinea pigs.
American Journa.1 of  Physiology, 224 (3):    613-617,  (1973)

OTS-AA-0361
Porter, John J.; D.  W. Lyons, W. F. Nolan
   Water uses and wastes in the textile industry.
Environmental Science  and Technology, 6 (1):   36-^41,  (1972)

OTS-AA-0362
Onuska, Brands I.                                                             ,
   Gas chromatcjgraphic determination of aliphatic amines and quantitative
analysis of small amounts of  dimethylamine  in wastewater.
Water Research, 7 (6):  835-841, (1973)
               »                                                             i
OTS-AA-0363
Afanas'eva, L. V.; N.  S. Evseenko
   Hygienic evaluation of fireproof textiles processed with an organophosphorus
impregnant based on  tetr;ahydroxymethyl  phosphonium  chloride.
Hygle.ne and Sanitation, 36 (3):    4,50-453 (1971)
                                     , 38

-------
OTS-AA-0364
Jordan, William P.
   Clothing and shoe dermatitis.  Recognition and management.
Postgraduate Medicine, 52 (5):   143-148, (1972)

OTS-AA-0365
Martin-Scott, Ian
   Contact textile dermatitis  (with special reference to fireproof  fabrics)
British Journal of Dermatology, 78 (12):   632-635,  (1966)

OTS-AA-0366
Title, M. M.; M. S. Brent
   Purchasing flameproof fabrics that meet the fire  code.  Part 2.
Hospital Management, 94, 73-6  (1962)

OTS-AA-0367
Reith, B. G.; et  al.
   Patient tests flame retardant linen.
Hospitals, 45, 79-83, (1971)

OTS-AA-0368
Allison, F. M.
   How to make fabrics resistant to flame.
Modern Hospital, 100, 134-6,  (1963), Jan. 63

OTS-AA-0369
Gardner, H. K.; et  al.
   Applying a durable flame retardant with inplant equipment.
Hospitals, 37, 123-6, (1963),  16 Nov. 63

OTS-AA-0370
Burr, Francis K.
   Textile Waste Treatment;   In   Kirk Othraer Encyclopedia of Chemical
Technology,  (supplement)
Wiley-Interscience, N.Y., 1971, 979-983

OTS-AA-0371
Wilson, Robert H.
   A note on skin tests of flame retardant materials.
Textile Research Journal, 32  (5):   424-425, (1962)

OTS-AA-0372
Jacobs, E. A.; et  al.
   Testing flame retardant linen for hospital use.
Hospitals, 42, 65-7, 144, (1968), 16 May 68

OTS-AA-0373
Allison, F. M.
   How to process flame retardant linens.
Modern Hospital, 100, 130-2,  (1962), Feb 63
                                      39

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OTS-AA-0374
Altman, Philip L. ed.
   Environmental Biology.
Fed.' of American Soc.  for  Experimental Biology,  Bethesda,  Md.,  1966,f694 pp.

OTS-AA-0375
Noweir, Madbull H.;  E.  A.  Pifltzer,  T. F.  Hatch
   Decomposition of  Phosgene  In Air.
American  Ind. Hygiene  Ass.  Journal,  34 (3):    110-119,  (1973)

OTS-AA-0376
Kallos, G. J.; R. A. Solomon
   Investigations of the formation of bis-chlormethyl ether in  simuTated
hydrogen  chloride-formaldehyde  atmospheric environments.
American  Industrial  Hygiene Assoc. Journal, -34 (11):    469-473,  (197)3)

OTS-AA-0377
Taylor, Larry R.; D. C. Johnson
   Determination of  Antimony  using forced-flow liquid chromatography with ia
coulotnetrlc detector.
Analytical Chemistry,  46 (2):    262-266, (1974)
                                                          . •     »:

OTS-AA-0378
Deutsch,  Yoetz
   Direct x-ray spectrometic  determination of bromine in -water.
Analytical Chemistry,  46 (3):    437-440, (1974)

OTS-AA-0379
Walton, M.
   'Industrial Ammonia-Gassing.
British Journal of Industrial Medicine, 30 (1):    78-86.,  (1:973)

OTS-AA-0380
Ahmad, I.; Whitson,  T.  C.
   Formaldehyde: how much of 'a  hazard.
Itidustrial Medicine  and Surgery, 42^8)':   26>27,  -(l^)

OTS-AA-0381
Alspaugit, T. A.
   Textile wastes.
J. Water  Pollution Control*Fed.., 43(6):  1001-1008,'(1971*)

OTS-AA-0382
Drake, George L., Jr.
   Fire-resistant text!les.  In Kirk 06hmer"EncycIdpedla-6f Chemtcal
Technology,   (supplement)
Intersclence, N.Y.,  1971,  944-64

:ot-S-AA-0383
Anonymous
   Textile waste cleanup.                                     '
Environmental Science  and  Technology, 7(8):-682-683,  (1973)
                                      --40

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OTS-AA-0384
Lysyj, Ihor
   Pyrographic analysis of waste waters.
Environmental Science and Technology, 8 (1):   31-34, (197'4)

OTS-AA-0385
Anonymous
   Decision nears on vinyl chloride rules.
Chemical and, Engineering News, 52 (11):   4-5, (1974)

OTS-AA-0386
Duncan, Acheson, J.
   Committee E-ll on statistical methods - report pertaining to sampling plan
amendment to the children's sleepwear standard.
ASTM Standardization News, 1  (5):   26-27, (1973)

OTS-AA-0387
Broadhurst, Martin G.                                            •
   Use and replaceability of polychlorinated biphenyls  (PCB)
Environmental Health Perspectives, Experimental Issue #2, pp. 81-102,  (1972)

OTS-AA-0388
Wallace, Peter T.
   Vinal fibers.
Chemical Economics Handbook, 543, 5921A- .5922M, (1972)

OTS-AA-0389
Wallace, Peter T.
   Vinyon fibers.
Chemical Economics Handbook, 543.9101A- .9103A, (1972)

OTS-AA»-0390
Anonymous
   Hot market for antimony oxide.
Chemical Week, 113 (3):   21-22,  (1973)

OTS-AA-0391
Anonymous
   Worldwide boom in textile goods spins prosperity for fiber firms.
Chemical Week, 113, (2):   18-19, (1973)

OTS-AA-0392
Anonymous
   Multinational pact to cover all fibers.
Chemical and Engineering News, 51 (41):   6-7, (1973)

OTS-AA-0393
Anonymous
   Pursuing a hot market.
Chemical Week, 112 (20):   24-25, (1973)

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OTS-AA-0394
Anonymous
   Congress  probes ways  to cut  fire tolls.
Chemical and Engineering News,  51 (29):    9-10,  (1973)

OTS-AA-0395
Trobisch,  K.
   Measures  against water pollution in industries 'producing petrochemicals
Including  polymers.
Pure and Applied  Chemistry,  29  (1):   57-65,  (1972)

OTS-AA-0396
Anonymous         •    •
   Flarranability reduced  in polyester fibers.
Chemical and Engineering News,  51 (22):    27,  ,(1973)

OTS-AA^0398
Title, Monroe M.; M.  S.  Brent
   Purchasing flameproof fabrics  that meet  the fire code.
Hospital Management,  94,  74-6,  (1962)

OTS-AA-0399
Beach, Robert
   Conformance sampling  for  children's sleepwear flammability.
ASTM Standardization  News,  1 (5):    13-15,  (1973)

OTS-AA-0400
Mandel, John; M:  N. Steel, L. J.  Sharman
   NBS analysis-of the ASTM Inter laboratory Study of  DOC/FF 3-71 flamnabll't'ty
of children's sleepwear..
ASTM Standardization  News,  1 (5):    8-12,  (1973)

OTS-AA-0401
Huggett, Clayton
   Carpet  flammability and the  NBS  corridor fire program.
ASTM Standardization  News, 1 (5):    16-20,  (1973)

OTS^AA-0402
Roe, Richard  C..
   The Impact oif  the  new federal  flammability standards  on the  bedd'itig
industry.
ASTM Standardization  News, 1 (5):    23:-25,  (1973)

OTS.TAA-0403
Segall, William M.
   Effect of  flammability standards on the  carpet- industry.
ASTM Standardization  News, 1 (5):    21-22,  (1973)
                                     - 42

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OTS-AA-0404
Borisov, Georgi; K. Sivrlev
   Preparation of polyesters with bis (p-chlorofonnyl)-phenoxy)methyl)
methlphosphine oxide.
Die Makromolekulare Chemle, 158, 215-22 (1972)

OTS-AA-0405
Kuryla, William C.; N. R. Lawson
   Flatnmablllty references from a computer-based system.
Journal of Fire & Flammablllty, 2 (Jan.):    54-6, (1971)

OTS-AA-0406
Juehe, S.; C. E. Lange
   Scleroderma-like skin changes:  Raynaud's syndrome and acrosteolyses
In workers In the polyvlnyl chloride producing Industry.
Clinical Orthopaedics and Related Research, 97 (49):   1922-1923, (1972)
 6TS-AA-0407   '
 Beaunlt Corporation, Personal Communication

 OTS-AA-0408
 Courtaulds, Personal Communication

 OTS-AA-0409
 Dow Badische, Personal Communication

 OTS-AA-0410
 Du Pont Product Information, Personal Communication

 OTS-AA-0411
 Phillips Petroleum, Personal Communication

 OTS-AA-0412
 Hercules Inc., Personal Communication

 OTS-AA-0413
 FMC Fibers Division, Personal Communication

 OTS-AA-0414
 Celanese, Personal Communication

 OTS-AA-0415
 Michigan Chemical Corporation, Personal Communication

 OTS-AA-0416
 American Cyanamld Company,  Personal Communication

 OTS-AA-0417
 American Enka Company, Personal Communication
                                    "&• 43

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OTS-AA-.0418
Man-made Fiber 'Producers Association,  Inc.
   Man-Made Fiber Fact Book
Washington, D.C., 1974, 64pp;

OTS-AA-0419
FMC Corporation                          _ (
   PFR Permanent Flame Retardant:  Avisco^ Rayon1 Staple
Marcus Hook, Pennsylvania  ..... <
Technical Service Bulletin, S-51, 22pp.,  (1972)

OtS-AA-0420
FMC Corporation
   Sayfr  F-4 Acet!ate Flame 'Retardant'
Marcus Hook, Pennsylvania
Technical Service "'Bulletin AF-l,12pp;',  (1973)

OTS-AA-05Z1 " "
E.I. du Pont de Nemoura and Company, Inc.
   Properties of Noine*'' High Temperature Resistant
Wilmington, Delaware
Du Pont Technical Information Bulletin, N-236,  12pp. ,  (1969)"

OTS-AA-0422
Everett, Lewis B.->
   What Executives Need to "Know About 'Protective Clothing.-
Wilmington, Delaware,  (n.d.), lOpp;

OTS-AA-0423    '
E.I. du Pont de Nemours and Comnahy, Inc'.
   Protective Clothing of Nbmej? Pays  for Itself the First Time "You .Need It ;
Wilmington, Delaware, 14pp., (n.d.)

OTS-AA-0424'
E.'I. du Pont de Nemours, Textile ^Fibers Department
   Protective Clo«thing of NdmejJ8'' NYLON'1
Wilmington, Delaware,  (n.d.)

OTS-AA-0425
Behrike, WiP.
   Dev'elopme'nf" of Protective Clothing :of
U^S^ Air Fbrce/IrJdustry -Life i -Support Confer'ence <
LaB'Vegasl Nevadl'i November v28-D6cember  1, 1967^
E .-I . du Pont de 'Nemours and' Company , Textiles* Flb.er s^Depar.tment;;
   Launder ing and Drycleaiiing5' Garments' of 'Notfei^ 'High -Tempera tyre^^
Resistant Nylon
Bullet iri*N-25 7
Du' Pont" Technical Information Fibers Nyloh; March'; 1972V

-------

 OTS-AA-0427
 E.I.  du Pont de  Nemours  and  Company,  Inc.      ^
    Laundering and  Drycleaning Garments of Horned Aramid Fiber
 Wilmington,  Delaware
 Preliminary Information  Memo, 335, 2pp., August  12, 1974

 OTS-AA-0428
 E.I.  du Pont de  Nemours  and  Comnany,  Inc.
    Protective Clothing of Nome*5:., Manufacturer's Source List
Wilmington,  Delaware, (n.d.), 8pp.

OTS-AA-0429
 Industrial Bio-Test Laboratories, Inc.
    Protocol  for  Celanese Corporation
Schwartz-Peck Human Skin Irritation and Sensitizatioh Study
7 PP.,  (n.d.)                                             '

OTS-AA-0430                                     '.
Michigan Chemical  Corporations          -^
    Material  Safety Data  Sheet Firemaster® LV-T23P
Chicago, Illinois, 2pp., (n.d.)

OTS-AA-0431
Tenneco Chemicals, Inc., IntermediatefljJDivision
    Material  Safety Data  Sheet NuogarerS?
 Piscataway,  New  Jersey,  2pp., (n.d.)

OTS-AA-0432
Tenneco  Chemicals, Inc.
    Tris  (2,3-dibronopropyl)  phosphate - Proprietary Reports, llpp.

OTS-AA-0433
Michigan Chemical  Cornoration
   FiremasteP'LV-T23P* Tris (2,3 dibromopropyl)  Phosphate
Chicago, Illinois:
Product  Information Bulletin, F 4041, 2pp.  (1974)

OTS-AA-0434
Tenneco Chemicals, Inc.                                   gp&,
    Product Data:  Tris 2,3 Dibromopropyl Phosphate NuogartfS' 23P—Flame
Retardant
Piscataway, New Jersey, 5pp., (n.d.)

OTS-AA-0435
Kerst, A. Fred
   Toxicology of Tris (2,3 dibromopropyl) Phosphate
Unpublished manuscript, September 20, 1974
                                 "?>' 45

-------
OTS-AA-0436                    ~"~                                  	"	"
Packham, S.C«; J.». Peta.jan; I.N.  Einhorn                                                    i
   The Physiologieal Response to Smoke and Combustion Products. 106,tb                        '•
Meeting of the Rubber Division of  the American Chemical Society
Philadelphia, Pennsylvania, October 14-17, 1974                                              '

OTS-AA-0437    '"                                                                             :
Crown Zellerbach Corporation
   Material Safety Data Sheet:  4,4-Thiqdiphenol, bis (p-hydr,oxyphe,nyl')
Sulfide                                                                                      ,
Camas, Washington-, 2pp.,  (n.d.)                                                              !
                                                                                             i

OTS-AA-0438
Crown Zellerbach                                                                             ;
   Product Information Bulletin, 4?4'-Thiodiphenol                                           i
Camas, Washington, 12pp., May 1973                                                          j

"OTS-AA^0439                                                                                  !
Crown Zellerbach-                                                                            i
   Preliminary Data Sheet:  4,4'-Sulfonyldiphenol  (SDP)
 (n.d.), 2pp.
                                                                                             i
OTS-AA-0440                                                                                  !
Dover Chemical Corporation
   Flame Retardant Chemicals
Dover, Ohio, 31pp., (n.d.)                                                                   j

OTS-AA-0441                                                                                  i
Abrahamson, L.J.; J.R. Allen                                                                 !
   The Biologica]! Response of Infant NonHuman Primate to a                                   '
Polychloririated Biphenyl                                     '             .                   |
Environmental Health Perspectives, Exp.  (4):  81-86,  (1973,)

OTS-AA-0442                                                                                  !
Hansen, D.J.; P.R. Parrish, J. Forester                                                      j
   Aroclor 1016^  Toxicity to and  Uptake by Estuarlne Animals
Environ. Res. 9 (3): 363^373, June,1974
                                                                            '                I
OTS-AA-0443
Rizwanul Haque; Dav-id W. Schmedding and Virgil H. Freed,
   Aqueous. Solubility, Adsorption, and Vapor Behay.ipr of
Biphenyl Arocolor 1254
Environmental Science and Technology, 8  (3).:  13.9,^142 March  1974

OTS-AA-0444
Anonymous
   Emerging Technology of Chlorinolysist
Environmental Science and Technology,, 8  (1): 18-19, January-1974

OTS-AA^0445
Colton, Jr.; John B.; F.D. Knapp, B.R. Burns
   Plastic Particles in Surface Waters of the Northwestern.
Atlantic
Science, 185 (4150):  491-497, August 1974

                               "B*-- 46

-------
 OT8-AA-0446
 London, J.; J. Kelley
    Global Trends in Total Atmospheric Osone
 Science, 184 (4140): 989, 1974

 OTS-AA-0447
'Dube,  D.J.; G.D. Veith,  G.F.  Lee     •• «  i  „»• '• ' \  '
    Polychlorinated  Biphenyls  in Treatment  Plant Effluents
 Journal Water Pollution  Control Federation,  46  (5):  966-972,  1974
 OTS-AA-W5B
 Hedberg, F.L.; C.S. Marvel
    A New Single Step Process for Polybenzimidazole
 Synthesis
 Journal of Polymer Science (Polymer Chemistry Ed.), 12 (8):   1823-1828,  1974

 OTS-AA-0449
 Mills, John
    The Blodeterioration of Synthetic Polymers and
 Plasticizers                                                       (\
 CRC Critical Reviews in Environmental Control, 4 (3):  341-351,  1974 £
                                               ' •          .          ' 
-------
0OTS-AA-p455
  Eicheiberger, James  W.; W.L. Budde, L.E.  Harris
11 lu'V Analysis of  the  Polychlorinated Biphenyl Problem
  Analytical Chemistry,  46' (2):  227-232,  1974
1C:"-  '.   ,-.....   .: . •       ,.   •_>    • ' .  .* •' :
  OTS-AA-.0456
\'Harviey',"*G.R.; W.G.  Steinhauer
^tU|iTAtoinspheric  Transport of Pplychlorinated.....
 ,Biphenyls to the North Atlantic
 ^tiriospheric Environment, 8  (8): 777-782,  1974
Golurwitz, tMelvih; Rohm and Haas
   Tc Assessing- the Hazar.dvfrotiuBCME in Formaldehyde
i,. containing Acrylic Emulsions    .    '     :    '       •'
  American  Oyestuff Reporter, 63  (3):  62-64 & 77, 1974
OK  ,'.,:,;•.
'!'QTS.-rAA-0458 ' •- • i .
  Anonymous. '    ••>.••'•••...        •   •  . ;-      -.•  ..- '. .
Jo •••.,. ASHA Chemical Standards draw industry Law Suit
'•.American  Dyes tuff Reporter, 63  (3): 68 & 69, 1974
L-Anonymous-i .
    • ••Flame ,'Retardants :  Textile -Men,  Government Moving
jL'fG.lqs.er iTo'gether'  .,                    . '  •
  American  Dyestuff Reporter, 63  (4):  72, 74 & 76, 1974
Uj\: -~r •''-•''
> ,OTS-AA-0460
If-ri. ?rpj;ec,tjed: Growth .of Man -rMade Fibers
  American Dy€ stuff Reporter, 63  (9):  74 & 76 & 107,  1974
  Anonymous
Ter;.iGpvernment  Finqncipg spurs Gotton:/PE 'FR Research
  American Dyestuff Reporter, 63  (9):   64 & 66, 1974
oW".*fk  \t-t--.:
U^PTSrAA-04,62 -    ;> ,
  LoBlancV.R.ii;.   f   '  '•        •    •-    \
Tp>ti;iU.o.tergen^s,r Water and Flammability Standards:  The
TdSpcclj  to.rBring^Order, Out of Chaos  ."'•;•  ••••' ,:
  American Dyestuff Reporter, 62  (10):   72, 74, 75, 76,  77  & 93, 1973
  IJapiiir^ --Jackson  •.•..-.- •' -n',-^.'" •', '-.•;.. -.s.i.' '«'•'•.,<•  .' -',--..'
Tt'x*. A.jPrpppsal t:or. Test-Methpd for- Ease .of Extinguishment
  American Dyestuff Reporter, 63  (11):  64 & 66, 1974
OT;* = -A  •". •. ••      i1
SOTSrAA-0464              .
  Anflpr.spn,%i Jolin; M. Grasso'  .' .
T.dxt?P'?,el.iminar-y  report pn the ASTM Round  Robin for the Semi-restrained
  Flainmability Test
  American Dyestuff Reporter, 63  (11):  60-62, 1974


                                   % 48

-------
OTS-AA-0465
Jakes, K.A.; et al.
   Apparel Seam Test:  Comparison of Seam and Fabric
Tested on Children's Sleepwear
American Dyestuff Reporter, 63 (11):  58-59 & 62,  1974
 OTS-AA-046T                             "  "-"
 Miller,  Bernard
    Research Test Methods  for  Flatnmabillty
 American Dyestuff Reporter, 63  (11):   51-55  & 58,  1974

 OTS-AA-0467
 Bauer, Jackson
    ICFF  Testing Committee Report Introduction
 American Dyestuff Reporter, 63  (11):   50,  1974

 OTS-AA-0468
 Anonymous
    Effluent Guidelines Issued
 American Dyestuff Reporter 63 (8):   26 & 58,  1974

 OTS-AA-0469
 McSherry, W.F.; et al.
    Accelerated Laundering Method for Flame-Retardant Fabrics
 American Dyestuff Reporter, 63  (7):  52 &  67, 1974

 OTS-AA-0470
 Anonymous
    New Finishes and Fibers Impart Fire Retardance
 American Dyestuff Reporter, 63  (7):  47-48, 1974

 OTS-AA-0471
 Mehta, R.D.,  J.E. Loughlin, E.Y. Kim
    How to Dye Flame Resistant Polyester
 American Dyestuff Reporter, 63  (6):  48, 50,  51 & 81, 1974

 OTS-AA-0472
 Joseph,  Majory L.; M.  Bogle
    How Laundering Affects Flame  Retardant  Fabrics
 American Dyestuff Reporter 63 (5):  29, 42, 44, 46,  47, 57, 59 , 1974

 OTS-AA-0473
 Holmes,  T.L.
    Dyeing and Finishing F.R.  Arnel  Triacetate/Polyester Blends
 American Dyestuff Reporter, 63  (5):  17, 18,  19, 22 & 59, 1974

 OTS-AA-0474
 Eisenberg, B.J.; E.D.  Weil
    A Review of Durable Flame  Retardants
 Textile  Chemist and Colorist  6  (12): 23-27,  1974

 OTS-AA-0475
 Suchecki, Stanley M.
    'Flammabili'ty:  Progress at a  Price
 Textile  Industries, 138 (9):  45, 47,  49,  51, 53,  55, 59 (1974)

                                  6-49

-------
 OTS-AA-0476
 Anonymous
    Flanimability:   Research Pace Quickens
 Textile  Industries1;  138 (8):  94* 95j  120, 121, 122, 123, 124^(1974)

 OTS-AA-0477
 Anonymous
    How to Make a  Cigarette Proof Mattress Ticking
 Textile  Industries*  138 (4):  48, 49,  84, 85, 86, 157, (1974)

 OTS-AA-0478                  .
 Gbldberg, J.B.
    Textile  Research  Achievements
 Textile  Industries1,  138 (1):  44, 47,  50, 51, 75, (1974)

 OTS-AA-0479
 Woodall, Jr.,  Leigh  C.
    Coordinating Pollution Control in  Multi-Location-
 Companies
 Textile  Industries,  138 (5):  87, 89,  91, (1974)

 OTS-AA-0480
 LeBlanc, R;B.
    What's Available  for Flame Retardant Textiles
 Textile  Industrie!,  138 (2):  115-120, 1974

 OTS-AA-0481
 Ameen, Joseph  S.
    How the  Effluent  Guidelines Affect You
 Textile  Industries,  138 (10): 36•, 37^ 38, 39, & 41, (1974)

 OTS-AA-0482
 Masselli, Joseph W.; tt.W; Masselli, MiG* Burford
    Let's. Try 90% frirst
 textile  Industrie^,  138 (10)":  32,33,35, & 145, (1974)

 OTS-AA^0483
 Davis, W.S'.; J. Park
    Practical Step*s to -Reduce  Pollution From the
 Textile  Indus tir-y
 Textile  institute and Ihaustry., 12 (8'): 241-243, '(1974-)

 6TS-AA-0484
 Towns end', M .W .
    Effluent and Water'cbnaervat ion, -aha Noifse -lEbhtroi
'textile Institute &  industry, 12 '(8) :  237-240., (;i974't)

 OTS-AA-04a5
 Sltfte'r, "K.
    Textiles arid Noi'ae Pbllutibn
 Textile  Institute arid Industry, '12 (8):  236-237;, (1974)

-------
OTS-AA-0486
Blair-McGuffe, M.H.
   Mill Design and the Environment
Textile Institute and Industry, 12 (8): 231-235, (1974)

OTS-AA-0487
Day, M.; D.M. Wiles                           
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 OTS-AA-0496
 Stauffer Chemical 'Company
    Product Data Sheet:  Fyrol^PCF :(,Tris;(B-,chloriQprQpyl) .phosphate)
 Westport, Connecticut,  2 .pp., '(n»dv)

 OTS-AA-0497
 Monsanto Industrial Chemicals, Go.
    Product Catalog, (n.d.)

 OTS-AA-0493
 U.S. Department of Hea'ith,  Education •& Welfare Food rand .Drug v
.Bureau of ProductVSafety
    Flammable fabri.cs:   Fourth annual Deport :to..;the .'President *and ''the ^Congress
 on the studies of (deaths, injuries -and • (economic losses .•r.esulting •from gacci-
 dental burn:tng of ^products,  fabrics, ;or -related materials.
 Washington, D,'.C . , ;U.S .  Government .Printing :0ff ice, -1973
 Harshaw Chemical Co.
    Harshaw aatimony oxide:  -Flame  retardant, pigment catalyst, ceramic
 opacifier, chemical intermediate
 Cleveland, Ohio, '»(ti.d.)

 OTS-AA-0500
 Diamond Alkal a:  Company
    Flame retardants for polyester (r;es ins
'Diamond Chemicals Technical. Bulletin, V£B-#, ,1^7,, (L965)

 OTS-AA-^0501
 Diamond 'ShamrcickvChemical Comnany        .--j.
    Your fact J:ile on Chlorowalc ;and rDelv^^:
 Diamond Shamrockl»Chlorinated- additives
 Cleveland, Ohio, |L-12, (nid.)

 OTS-AA-0502
 Ciba-Geigy Corpofation
    PyrovatexvCP : _  An '.idea •• tha t -won !.t icateh ^f ire
'Forest Park, '. Georgia, ' (n.
 OTS-AA-0503
 Stauffer Chemical Company
    Produc t "Da ta ;phee t : ^F.yrdfT  '99 -E.ire •'Retardant
 Wes t:por t , . Gpnnecfeicut , '3 ;'pp * , > (*n .'d .' )

;OTSrAA-0504
•Anonymous
    Flame Retardants
 Modern Plastics, 51 (9): 68-60,  (1974)

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OTS-AA-0505
Baum, Bernard; C.H. Parker
   Plastics Disposability and Recycling
Society of Plastic Engrs. Annual Technical Conf.  31,  296-299,  (1973)

OTS-AA-0506
Kracklauer, J.J.; C.J. Sparkes
   Less Smoke from PVC
Plastics Engineering, 30 (6): 57 & 58, (1974)

OTS-AA-0507
Belyakov, V.K.; et al.
   Thermo-oxidative Degradation of Polyamides and Polyimides
July, 1974, Polymer Science U.S.S.R. 15 (7): 1660-1674,  (1973)

OTS-AA-0508
Anonymous
   New VCM Regulation is only one influence on a  changing outlook for
PVC
Modern Plastics 51 (10):  20, (1974)

OTS-AA-0509
Soulier, J.; et al.
   Synthesis & Properties of Some Polyamides and
Polysulfonamides
Journal of Applied Polymer Science, 18 (8): 2435-2447,  (1974)

OTS-AA-0510
Wilson, B.N.; I. Gordon, R.R. Hindersinn
   Phosporamidates as Reactive Fire-Retardant Polymer
Modifiers
Ind. and Eng. Prod. Research and Development, 13  (1):  85, (1974)

OTS-AA-0511
Reardon, T.J.; R.H. Barker
   Pyrolysis and Combustion of Nylon 6.  I. Effect of Selected
Brominated Flame-Retardants
Journal of Applied Polymer Science, 18 (7):  1903-1917,  (1974)

OTS-AA-6512
Gilleo, Kenneth B.
   Nylon Flammability-Effects of Thiourea, Ammonium Sulfamate,
and Halogen Compounds
Ind. and Eng. Chem. Prod. Research and Development, 13 (2): 139-143,  (1974)

OTS-AA-0513
Keifer, David M; et al.
   World Chemical Outlook  '75:
1)  U.S. Industry girds for no-growth years.
2)  Inflation masks world trade slowdown.
3)  Demand dip worries West Europe's firos.
4)  Japan's first postwar slump hits chemicals.
Chemical and Engineering Hews, 52 (51): 17-28, (1974)

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OTS-M-0514
Kleinberg, Gerd A. ; D.L. Geiger
   Tandem Thermogrtaviraetric' Analyzer -- T-itne-of-Flight
Mass Spectrometer^System Designed for Toxicological-Evaluation
of Nonmetallic Materials
AMRL-TR-71-71, Wright-Patterson A.F.B., Ohio, Air Force Sys. Command
Aerospace Me,. Res. Lab., Aerospace-'Med. Div.   (Oc'tober 1971)

OTS-rAA-0515
Johnson, M.K,    "
   The influence of some aliphatic eofflpounds oh rat l.'iver
glutathion>2 levels
Biochemical Pharmacology, 14, 1383-1385,  (1965)

OTS-AA-0516
•Eckardt, Robert E.*, R. Hind in
   The health hazards of plastics
Journal of Occupational Medicine, 15 (10):  808-819,  (1973)

OTS-AA-0517
Gaffney, Peter E.
   PGB's:  another source
Science, 183 (4123):  363-368, (1974)
                                     54

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