RESIDUAL MONOMERS IN ACRYLIC AND
       MODACRYLIC FIBERS  AND  FABRICS
                 FINAL REPORT
          Contract No. 68-01-4746

              Task Order  No. 3
         OFFICE OF TOXIC SUBSTANCES
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
          Washington, D. C.  20460

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                             EPA Report No,
                             July 1979
      RESIDUAL MONOMERS IN ACRYLIC AND
        MODACRYLIC FIBERS AND FABRICS
                     by

               Joe M. Finkel
               Ruby H. James
              Herbert C. Miller

         Southern Research Institute
           2000 Ninth Avenue South
          Birmingham, Alabama 35205
           Contract No. 68-01-4746
              Task Order No. 3
        Project Officer:  James Darr
                Prepared for

         OFFICE OF TOXIC SUBSTANCES
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY
        401 M Street, S.W. (TS-792)
          Washington, D. C.  20460

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                         DISCLAIMER





     This report has been reviewed by the Office of Toxic



Substances, U.S. Environmental Protection Agency, and



approved for publication.  Approval does not 'signify that



the contents necessarily reflect the views and policies



of the U.S. Environmental Protection Agency, nor does



mention of trade names or commercial products constitute



endorsement or recommendation for use.
                          11

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                          PREFACE





     This report describes a study conducted under Task



Order No. 3 of the U.S. Environmental Protection Agency



Contract No. 68-01-4746.  This effort was part of an



overall service performed under task requests to generate



analytical data on a specified chemical, a group of



chemicals, or commercial products by conducting spe-



cific tests, analyses, or experiments within several



broad areas of interest.
                          111

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                        TABLE OF CONTENTS






                                                            Page




SECTION 1    INTRODUCTION  	      1




SECTION 2    CONCLUSIONS 	      2




SECTION 3    RECOMMENDATIONS 	      3




SECTION 4    EXPERIMENTAL PROCEDURES  	      4




             EVOLUTION APPARATUS 	      4




             EVOLUTION, ADSORPTION, AND DESORPTION




             OF MONOMERS	      4




             GAS CHROMATOGRAPHIC ANALYSIS  	      6




             DIRECT INSERTION MASS SPECTRAL ANALYSIS  .  .      7




SECTION 5    EXPERIMENTAL RESULTS  	      8




EPA Form 2220-1	     10
                              IV

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                            SECTION 1



                           INTRODUCTION





      This report deals with the detection and quantitation



of acrylonitrile, vinylidene chloride, and vinyl bromide, which



are used as monomers in the production of acrylic and modacrylic



fibers.  These three monomers were selected for study because



of concern over their adverse health effects  (e.g., their poten-



tial carcinogenicity).





      The task order for the analytical work described in this



report called for the detection and quantitation of specific



residual monomers in six samples of materials furnished by the



Environmental Protection Agency.  The samples were labeled Blue



Carpet, Yellow Carpet, Brown Carpet, Fiber A, Fiber M, and Blue



Fabric.  The samples representing three types of products—car-



pets, fibers and fabrics—were analyzed for acrylonitrile,



vinylidene chloride, and vinyl bromide by gas chromatography



with a flame ionization detector and by direct insertion probe



mass spectrometry.

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                            SECTION 2



                           CONCLUSIONS






      The results of the gas chromatographic studies indicate



that detectable amounts of residual acrylonitrile, vinylidene



chloride, and vinyl bromide are not released from the carpet,



fiber, and fabric samples under the conditions selected for



analysis.  On the other hand, analysis of the six samples by



direct insertion mass spectrometry indicate that methyl bro-



mide is evolved from the Yellow Carpet, Brown Carpet, Fiber A,



and Fiber M.  Three halogenated compounds—dibromodichloro-



ethanol, tetrabromoethanol, and tribromochloroethanol—were



identified from one sample, Blue Fabric.  Traces of fatty acids



were found in all of the samples, and sulfur dioxide was found



in all of the samples except the Blue Fabric.

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                            SECTION 3

                         RECOMMENDATIONS


      Because of the potential toxicity of methyl bromide, addi-

tional studies are recommended to quantify the amounts that

were identified in some of the samples.  Methyl bromide is a

potent fumigant gas, and it is one of the most toxic of the

common alkyl halides.1  Death following acute poisoning is

usually caused by the irritating effect of methyl bromide on

the lungs.  In chronic poisoning, death is due to the toxic

effect of methyl bromide on the central nervous system.  Fatal

poisoning in man has always resulted from exposures to relatively

high concentrations of methyl bromide vapors  (8,600 to 60,000

ppm), whereas nonfatal poisoning has resulted from exposure

to concentrations as low as 100 to 500 ppm.  Locally, methyl

bromide is an extreme irritant to the skin.


      In future work, an analytical procedure for the detection

and quantitation of methyl bromide could be based on Sampling

and Analysis Method No. S-372 developed by the National Insti-

tute for Occupational Safety and Health.2  In this procedure,

the evolved gas is sorbed on charcoal, desorbed with carbon

disulfide, and analyzed by gas chromatography.
*Sax, N. I.  Dangerous Properties of Industrial Materials.
 5th ed. Van Nostrand Reinhold Co., New York, 1979  p. 810.

2NIOSH Manual of Analytical Methods, Vol. 3, Part II, 2nd ed.
 National Institute for Occupational Safety and Health, Cincin-
 nati, Ohio, 1977.  Method Number S-372.

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                            SECTION 4



                     EXPERIMENTAL PROCEDURES






EVOLUTION APPARATUS





      The apparatus that was constructed to simulate environ-



mental conditions for the collection of residual monomers



evolved from the carpet, fiber, and fabric samples is illus-



trated in the figure on page 5.  The insulated air chamber was



a Styrofoam ice chest containing a light bulb as a heat source



and a paddle-blade fan to circulate the warmed air through the



chamber.  Temperature was controlled by a Matheson Labstat.



The specimen chamber was connected to a charcoal prefilter and



a humidifier at the inlet side, and a charcoal sorbent tube



was located at the outlet side for collection of monomer vapor.



The chamber temperature was maintained at 50 °C, and the rela-



tive humidity of the air within the chamber was 50%.  Air was



drawn through the chamber and through the sorbent tube at



1.2 L/min.  The conditions within the chamber were selected



because they probably represent the most adverse conditions



that carpets, fibers, and fabrics may be exposed to in their



natural environment.





EVOLUTION, ADSORPTION, AND DESORPTION OF MONOMERS





      Weighed portions of the samples furnished by EPA were



equilibrated for 30 min at 50 °C in the all-glass specimen cham-



ber.  Subsequently, moistened air was swept through the speci-

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CHARCOAL
PREFILTER
                                                        INSULATED AIR CHAMBER
                T	
                  WATER
               HUMIDIFIERS
                                      STOP
                                      COCK
                                WATER
                                                 HEAT
                                                 SOURCE
                                                                           FAN
                                                                         THERMOMETER
                                                                          o o
                                                                           o
                                                                        LAB-STAT
CHARCOAL
SORBENT
TUBE
                                                                                               wt itIMII in.
                                                                                        SENSING
                                                                                        ELECTRODE
                                                                                        linitTTTITIIIH THI 1
                          TO VACUUM
                          PUMP
                                        Schematic Diagram of the Monomer Evolution Apparatus

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men chamber and then the sorbent tube.  The evolved  gases were



adsorbed on chromotographic grade, activated charcoal  (Applied



Science Laboratories, Inc., State College, Pa.) packed  in the



sorbent tube.  After collection of the sample, the adsorbed



volatiles were extracted from the charcoal with 1 mL of methanol,



and aliquots of the extract were analyzed for acrylonitrile,



vinylidene chloride, and vinyl bromide by gas chromotography.





GAS CHROMATOGRAPHIC ANALYSIS





      The gas chromatographic analyses were performed with a



Per kin-Elmer Model 910 gas chromatograph equipped with a flame



ionization detector.  Separation of the monomers was performed



on a 1.8 m x 2 mm  (i.d.) glass column packed with Chromosorb 101.



A temperature program was used in which the initial temperature



was maintained for 4 min at 75 °C, then increased at 5 °C per



min to a final temperature of 120 °C, and held at 120 °C for



2 min.  Injector and detector temperatures were both 120 °C.



Nitrogen was used as the carrier gas at a flow rate of 20 mL/min.



Under these conditions, the limits of detection for acryloni-



trile, vinylidene chloride, and vinyl bromide were typically



1, 2, and 2 ng, respectively, at a signal-to-noise ratio  of



2 to 1.   As explained on page 8 of this report,  the limits of



detection are equivalent to 0.02 and 0.04 ppm of monomer in a



10-g sample of polymer.





      The gas chromatograph was calibrated by injecting stan-



dard solutions of  acrylonitrile, vinylidene chloride, and vinyl



bromide.  The following retention times were typical:  acryloni-

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trile, 12.4 min; vinylidene chloride, 11.4 min; and vinyl



bromide, 8.8 min.





DIRECT INSERTION MASS SPECTRAL ANALYSIS





      Mass spectral measurements were made by the direct inser-



tion technique with a Varian MAT 311A mass spectrometer.  Use of



the direct insertion technique involves the introduction of a



small portion of the sample, as is, into the ion source of the



mass spectrometer.  The technique may be used with or without



temperature programming.  Since many factors affect the intensi-



ties of the peaks, the technique is not strictly quantitative;



however, the limit of sensitivity of the method is in the subnano-



gram to nanogram range.  In this manner, the fibers of each sample



were introduced into the mass spectrometer under a reduced pressure



of about 1 x 10~6 torr.  The spectra were recorded at probe tem-



peratures ranging from 20 to 300 °C.  All compounds that were



identified were evolved at temperatures as low as 20 °C and the



amounts evolved increased with increasing temperatures until the



quantities present were depleted.

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                            SECTION 5


                       EXPERIMENTAL RESULTS


      Gas chromatography and direct insertion mass spectrome-

try indicated that acrylonitrile, vinylidene chloride, and

vinyl bromide were not evolved in detectable amounts from any

of the six samples of carpets, fibers, and fabric furnished

by EPA.  The minimum detectable amounts of the monomers were

1, 2, and 2 ng for acrylonitrile, vinylidene chloride, and

vinyl bromide, respectively, by gas chromatography.  These

values correspond to detection limits of 0.02 or 0.04 ppm of

monomer in a 10-g sample of polymer.*


      Direct insertion mass spectrometry, however, did reveal

the presence of methyl bromide in four of the samples:  Yellow

Carpet, Brown Carpet, Fiber A, and Fiber M.  Also, three halo-

genated compounds—dibromodichloroethanol, tetrabromoethanol,

and tribromochloroethanol—were identified in one sample,  Blue

Fabric.  Traces of palmitic and stearic acids were found in

all of the samples.  Sulfur dioxide was also found in all of

the samples except the Blue Fabric.
*The maximum volume of methanol in which 1 or 2 ng of monomer
could be detected was 5 uL.  The total volume of methanol
extractant was 1 mL.  Thus, the minimum quantity of monomer
in the methanol that could be accounted for was 0.2 or 0.4 ug,
representing 0.02 or 0.04 ppm of the polymer.
                              8

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      All of the organic halides were observed at a probe tem-
perature of 20 °C and, therefore, do not appear to be thermal
decomposition products.  The halogenated ethanols evolved from
the sample may have been hydrolysis products of flame retardants
At this time, an explanation for the presence of methyl bromide,
a fumigant, is not available.  A possible source of the fatty
acids is the esters that may have been used as spin finish
agents during the manufacture of the fibers.  The sulfur diox-
ide may have resulted from an anti-oxidant formulation.
                              9

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                              TECHNICAL REPORT DATA
                        (Please read Instructions on the reverse before completing)
 1. REPORT NO.
                         2.
                                                  3. RECIPIENT'S ACCESSION-NO.
 4. TITLE AND SUBTITLE

 RESIDUAL MONOMERS IN ACRYLIC AND  MODACRYLIC
 FIBERS AND  FABRICS
              EPORT DATE
              July T.979
           6. PERFORMING ORGANIZATION CODE

              SORI-EAS-79-504
 7. AUTHOR(S)

 Joe M. Finkel,  Ruby H. James, Herbert C,
           8. PERFORMING ORGANIZATION REPORT NO.

     Miller   Project 4045-T3-XV
9. PERFORMING ORGANIZATION NAME AND ADDRESS
 Southern Research Institute
 2000 Ninth  Avenue South
 Birmingham,  Alabama 35205
                                                  10. PROGRAM ELEMENT NO.
           11. CONTRACT/GRANT NO.
              68-01-4746, Task 3
 12. SPONSORING AGENCY NAME AND ADDRESS
 EPA, Office  of  Toxic Substances
 401 M Street,  S.W.  (TS-792)
 Washington,  D.  C.  20460
            13. TYPE OF REPORT AND PERIOD COVERED
           14. SPONSORING AGENCY CODE
 15. SUPPLEMENTARY NOTES
 Project Officer  is James Darr  (TS-792)
 16. ABSTRACT
       The report deals with the  detection and quantitation of acryloni-
 trile, vinylidene chloride, and  vinyl bromide, which  are used as
 monomers in  the  production of  acrylic and modacrylic  fibers.  The
 amounts of monomers evolved from samples of carpets,  fibers, and   fab-
 rics at 50 °C  and 50% relative humidity were determined by gas chroma-
 tography with  a  flame ionization detector and by direct insertion  probe
 mass spectroscopy.  The results  of  the gas chromatographic studies indi-
 cate that detectable amounts of  residual acrylonitrile, vinylidene
 chloride, and  vinyl bromide were  not released from, the carpet, fiber,
 and fiber samples under the conditions selected for  analysis.  Direct
 insertion mass spectrometry indicated that methyl  bromide was evolved
 from all of  the  fiber samples  and from two of the  three carpet samples.
 From the remaining carpet sample, three halogenated  compounds—dibromo-
 dichloroethanol, tetrabromoethanol, and tribromochloroethanol—were
 identified.  Traces of fatty acids  were found in all  of the samples, and
 sulfur dioxide was evolved  from  all of the samples except the fabric
 sample.
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EPA Form 2220-1 (9-73)
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