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). !
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
«
-------
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
-------
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
«
-------
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
-------
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)
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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)
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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..
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
«
-------
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
-------
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
-------
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
-------
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
-------
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
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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
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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
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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
-------
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
-------
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
-------
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
-------
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
-------
„ 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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
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
-------
> 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
-------
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
-------
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
-------
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
-------
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
-------
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
via flame-resistant fibers
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
Plastics, 31 (349): 1439-40, 1442, 1444, (1969)
OTS-AA-0007
Beninate, John V.; et al
Conventional pad-dry-cure process for durable-flame
and wrinkle resistance with tetrakis (hydroxymethyl)
phosphonium hydroxide (THBOH).
Textile Research Journal, 38 (3): 267-72, (1968)
OTS-AA-0008
Benisek, 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-0009
Bennett, F. E.; L. Chesner, R. Preston
Improved flame-retardant polyester resins
Applied Plastics, 10 (1): 45-51, (1967)
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...
Journal of Applied Polymer Science, 17 (2): 471-82, (1973)
OTS-AA-0013
Bower, J. G.; S. M. Draganov, R. W. Sprague
Comparative evaluation of zinc borate 2:3:3.5 with antimony
oxide using various fire testing .methods
Journal of Fire & FlammabiHty, 3 (July): 226-3.7, (1972)
OTS-M-0014
Bremmer, Bart J. .
Halogenated polyepoxide-amine compositions
Industrial and Engineering Chemistry, Product Research and Development:,
5 (4): 340-6, (1966)
OTS-AA-0015
Brysson, Ralph J.; et al
Reducing sunlight degradation of flame retardants
Textile Industries, 136 (10): 139-41, 154, (1972)
OTSrAA-0016
Bullock, Joel B.; Clark M. Welch
Weathering durability of cotton fabrics treated.with :
APO-THPC flame retardant
Textile Research Journal, 36 (5): 441-51, (1966) ;
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 '•
Journal of Coated Fibrous Materials, 2 (3): 161-72, ^1973) i
v ' \
I
OTS-AA-0018
Church, James, M.
Fundamental §tudies of chemical retardants .for the fire
resistant treatment of textiles
Office of Technical Services, 1952
OTS-AA-0019
Cope, J. F.
Identificatipn of flame retardant ^textile finishes by
pyrolysis-gas chromatography
Analytical Chemistry, 45 (3): 562-4, (1973)
OTS-AA-0020
Daigle, D. J.; et al
Modifying THP (tris (hydroxymethyl) phosphine)-araid=flame retardant
American Dyestuff Reporter, 62 (6): 57-9, 80, (1973)
B-2
-------
OTS-AA-0021
Daigle, D. J.; et al
Flame-retardant finish based upon tris (hydroxymetbyl) phosphine
Textile Research Journal, 42 (6): 347-53, (1972)
OTS-AA-0022
Daigle, D. J.; et al
Effect of hypochlorite bleach on flame-retardant finishes
based upon tetrakis (hydroxymethyl) phosphonium chloride
Textile Research Journal, 41 (6): 550-2, (1971)
OTS-AA-0023
Daigle, D. J.; et al
THP (tris (hydroxymethyl) phosphine)-amide flame retardant finish
Textile Research Journal, 42 (10): 601-2, (1972)
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)
Journal of Fire & Flammability, 1 (July): 178-82, (1970)
OTS-AA-0025
Dannels, B. F.; A. F. Shepard
Inorganic esters of novolaks
American Chemical Society. Division of Organic coatings and Plastic
Chemistry. Preprints, 27 (1): 125-31, (1967)
OTS-AA-0026
Defosse, T. C.; I. H. Welch
Practical performance of fire retardant rayon
Modern Textile Magazine, 52 (9): 65-6, 68-9, (1971)
OTS-AA-0027
Deverell, D.
Synthetic resin developments and behavior
British Plastics, 39 (11): 650-6, (1966)
OTS-AA-0028
Donaldson, Darrel J.; et al
THPC (tetrakis (hydroxymethyl) phosphonium chloride) cyanamide
flame retardant finish for sleepwear cotton
Textile Research Journal, 42 (6): 331-4, (1972)
OTS-AA-0029
Drake, George L., Jr.
Fire resistant textiles
In Kirk Othmer Encyclopedia of Chemical Technology
New York, John Wiley, 1966, 9, 300-315
- 3
-------
OTS-AA-0030
Drake, George L., Jr.; E. K. Leonard, W. A.;Reeves
Flame-resistant duck defies.weather
Textile Industries, 130 (12): 145, ,147, 192, .(19.66)
OTS-AA-OQ31
Drake, George L., Jr.; W. A. Reeves
Technology of cellulose and its derivatives. F.lame-resistant ,j:extties
High Polymers, 5 (Pt.5): 1293-331, (1971)
OTS-AA-0032
Drake, G. L., Jr..; et al
.How moisture^affects flame retardancy
Textile Chemist .& Colorist, 4 (12): 287^-94, (.197,2)
OTS-AA-0033
Drake, George, L., Jr.; R. M. Perkins, W. A. .Reeves
Special finishes for textile-flame retardant finishestand soil
resistant finishes
Colourage, 18 (1,7): 35^44, 56, (1971)
OTS-AA-0034
Edwards, H. D.
Finishing synthetic-polymer materials
Review of Textile Progress, 15, .422-7, »(196;3)
OTS-AA-0035
Elliot, W. N.; C. Heathcote, R. A. Mostyn
Determination of phosphorus in fire-res isjtant textiles ;by co.ol-flame
emission spectroscopy
Textile Research Journal, ,42 .(?-): <86-8, (1972)
OTS-AA-0036
Ellzey, S. W., jlr.; ,W. J. Connick, Jr.
Gasometric determination of THP.C (tetrakis (hydroxymethyl;)
phosphonium chloride)
.American Dyestxijff :Reporter, 62 ,(.6,):,, (47,5,50,, X(i973)
OTS-AA-0037
JF^enimor.e, C. t.; F. ,J,. ;Mar,t.in
Flammab^iiity ,of po^ymej^
Combustion and jPlame, ,10 (2): )}.35r9, (19.66,)
OTS-AA-0038
Friedman, M., R. E. iWhit.fielvd, {S. T-Ll;lin
Enhancement of .the .natural flame-resistance -of -wool
Textile Research .Jpurnai, 43 .(4): ,2;12-17, (.Ii97;3)
•4
-------
OTS-AA-0039
Ganhdl, R. S.
Flameproofing of cellulosic materials. I.
Colourage, 16 (4): 61-4, (1969)
OTS-AA-0040
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-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)
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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
-------
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)
-------
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
-------
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
-------
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
-------
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
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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
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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
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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
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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
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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)
-------
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
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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
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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
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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
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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
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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)
-------
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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