Document zb9w016wzLrVJaa7Qa9RBRjLm

r'/V ' B. F. GOODRICH CHEMICAL COMPANY Standard Test Procedure No. 999-T TITLE: Residual Vinyl Chloride Monomer Content of Polyvinyl Chloride Resins TYPE OF ANALYSIS: Vapor Space Equilibrium, Gas Chromatographic PRODUCT: Polyvinyl Chloride Resin, Finished Product I. SCOPE This procedure is suitable for determining the residual vinyl chloride monomer content of polyvinyl chloride (PVC) resins. The method cannot be used for polymer in other forms such as compounds or final fused products. II. PRINCIPLE The basis for this method relates to the vapor equilibrium which is established between residual vinyl chloride monomer (RVCM), PVC resin and air in a closed system. It has been demonstrated that the RVCM in a PVC resin will equilibrate in a closed vessel quite rapidly, provided the temperature of the PVC resin is maintained above the glass transition temperature of that specific resin. III. INTERFERENCES 1) Normally this vapor will contain only air, vinyl chloride monomer and traces of water. Any other volatile material present in the closed vessel could change this equilibrium relationship. Impurities in the low ppm range will generally have only a very small influence on this equilibrium rela tionship . 2) Any material which elutes from the chromatographic column at approximately the same time as vinyl chloride will cause high RVCM results. IV. PRECISION AND REPR0DUCI3ILITY Initial data obtained with this method, covering a range of O.GQ25 to 0.2000 wt. percent, indicates that one standard deviation (determined from duplicate results) is approximately 2.1>. Absolute accuracy has been checked by comparing results to another, totally independent method. In this case agreement between the two methods is + 5$ in the range 0.0025 to 0.2000 wt. %. These results were obtained by two operators in one laboratory. BOR 005819 BFG Standard Test Procedure No. 999-T Page 2 of 7 V. SAFETY 1) Do not release vinyl chloride to the laboratory atmosphere during preparation of standards. Venting and purging with vinyl chloride - air mixtures must be held to an absolute minimum. When venting and/or purging is required the vapor must be routed to outside air. Vinyl chloride, even at low ppm levels, must never be vented inside the laboratory. It can be vented into a properly functioning fume hood. 2) 3e careful not to cone into contact with heated parts of the chromatograph, such as the injection port, detector, heated column, etc. Handle all electrical connections with care. VI. APPARATUS l) Gas Chromatograph, Hewlett Packard Model 5711A, dual flame ionization detector, equipped with following options: (a) 005 Dual flow controller (b) 006 Substitute linear oven programmer (5702a) for isothermal oven controller (c) 011 Substitute auxiliary heated zone controller (57C0A) (d) 017 Substitute universal heated injection port with disposable glass liners (18747) (e) 024 Rotometer kit for carrier gas 2) Integrator -- Hewlett Packard Model 33&OA with built-in recorder Alternate Integrator -- AutoLab System 4 ` 3) Chromatographic Column -- An 8 ft. x l/8 in. stainless steel column packed with 80/100 Poropak QS and conditioned at 200 C. 4) Oven, forced draft capable of maintaining a constant temperature of 90 +1.0* C. (Fisher Cat. No. 13-244-176 Isotemp Oven) 5) Gas Sampling Bottles, 25O ml capacity equipped with glass stopcocks on both ends plus a septum fitting (Fisher Cat. No. 11-134-190) 6) Serum Bottles, 10 cc volume with rubber septums (Fisher Cat. No. 210B serum bottles and Cat, No. 3-215 rubber s toppers. 7) Analytical Balance, capable of weighing to + .0001 gram 8) Hydrogen Cylinder with regulator 9) Flowmeter, 0 to 2 liters per minute BOR 005820 BFG Standard Test Procedure No. 999-T Page 3 of 7 VI. APPARATUS (continued) 10) Helium Cylinder with regulator 11) Clean air supply at 25 psig 12) Bubble Flow Indicator VII. REAGENTS Calibration gases, vinyl chloride in air mixtures 1) Low level between 15 and 25 parts per million 2) A high level between 800 and 1200 parts per million These can be obtained from: Precision Gas Products, Inc. P. 0. Box 538 Linden, New Jersey 07036 VIII. PREPARATION OF GAS CHROMATOGRAPH 1) Install the 8 ft. x l/8 in. Poropak QS column and condition at 200 C. 2) Adjust flow rates for the H. P. 5711A according to the operating manual (30 cc's per minute helium carrier gas, 30 cc's per minute hydrogen and 130 cc's per minute air.) 3) Set conditions for analysis as follows: Injection port - 150 C. Detector - 250 C. Oven - 1600 C. U) After these conditions have been reached and the chromatograph has stabilized it is ready for calibration, IX. CALIBRATION ` 1) Fill the clean glass 250 ml gas sample bottle with the low level (15 to 25 ppm) vinyl chloride air standard. The procedure for doing this is detailed in Attachment 1. Always use the same bottle for this low level standard. 2) With the 1 cc gas syringe draw out of the calibration bottle, through the septum, in excess of 1 cc of the gas sample. After the plunger on the syringe is pulled all the way, wait five seconds before removing the syringe needle from bqr 005821 the bottle septum. 3) After the five second delay remove the needle from the septum and move plunger to read exactly 1 cc on the syringe. BFG Standard Test Procedure No. 999-T Page 4 of 7 IX. CALIBRATION (continued) 4) Immediately inject the 1 cc sample into the chromatograph injection port (as rapidly as possible). 5) Remove the needle from the injection port and start the chromatograph recorder and integrator. 6) In approximately three minutes the vinyl chloride will elute. 7) Wait one minute after the VC1 elutes and starting at Step 2 above repeat Steps 2 through 6. Do this four times. 8) Fill in the data obtained in the four runs above on the calibration sheet (Attachment 2). 9) If the peak areas from these four runs do not deviate more than % from the average of the four runs, this step is complete. If there is a deviation greater than 5$ from the average, repeat Steps 1 through 8. See Note 1. 10) After the above calibration is completed, recharge the second glass calibration cylinder with the high level (800 to 1200 ppm) vinyl chloride air standard. Starting at Step 2 above repeat this procedure through Step 9 using the high level standard. 11) This calibration is complete if the requirements of Step 9 are met. If Step 9 is not met, refer to Note 1. 12) For the third calibration point use the high level standard, but in this case use only a 0.5 cc sample. 13) Draw out an excess of 0.5 cc with the gas syringe. 14) Wait five seconds after the plunger is pulled back before removing the syringe needle. 15) After the five second delay remove the syringe and adjust the plunger to read exactly 0.5 cc. 16) Inject this sample into the chromatograph and record the peak area on the calibration sheet. 17) Repeat Steps 13 through 16 four times. * 18) If the peak areas from these four runs do not deviate more than 5$ from the average of these four runs, this- calibration is complete. If there is a deviation greater than 5$ from the average, repeat Steps 13 through 16. See Note 1. BOR 005822 BKG Standard Test Procedure No. 999-T 5 of 7 IX. CALIBRATION (continued) 19) The data generated in the above calibration is used to calculate the response factor for the calculation of residual vinyl chloride in the samples analyzed. The response factor calculations are detailed on the cali bration sheet. Note 1: If the deviation is still greater than 5shut down and locate the source of the problem. X. SAMPLE ANALYSIS (Samples must be run at same range and attenuation used for calibration standards. If range or attenuation is changed for the sample, then new standards must be run at this range and attenuation. 1) All samples should be kept in tightly sealed glass jars. Samples must be run promptly (within 30 minutes) from the time they are received in the laboratory. Y/ithin 30 minutes the sample should be weighed into the serum bottle and placed in the oven. The exact total volume of the serum bottles must be measured. See Attachment 5- 2) Prepare duplicates for each sample. Take one serum bottle plus rubber septum, mark with identification and obtain a tare weight to four decimal places. Record tare weight on analysis work sheet. See Attachment 3* 3) Remove serum bottle from balance, remove septum and pour in the proper amount of resin to be analyzed. Replace rubber septum. Be certain that rubber septum is fully seated and sealed. Approximate Bottle Volume Add 12 cc 2 grams + .5 A, simple technique can be devised based on a volumetric resin addition. Small cups, having the proper volume, can be used to rapidly obtain the resin sample. This can then be added to the serum bottle with a tiny funnel. 4) Replace serum bottle on balance and record the weight to four decimal places. 5) Remove bottle from balance. 6) Place bottle in oven (at 90" + 1.0 C.) and allow it to remain 15 -0 +1 minutes. 7) At the end of the heating cycle remove the bottle from the oven and immediately insert the needle from the 1 cc gas syringe into the bottle through the septum. (Do not allow the needle to contact the resin sample.) BOR 005823 o o o o o o o o o O O O O O o G BFG Standard Test Procedure No. 999-T Page 6 of 7 x. SAMPLE ANALYSIS (continued) 8) Sample Size - Use a 1 cc sample volume when the RVCM content is expected to be less than 100 ppm. Use a 0.5 c..3 err r' ''cr oxccocci v"`7her concentrations. 9) Draw out the proper volume sample (plus slight excess) from the bottle. Wait 5 seconds after pulling the plunger back before removing the needle from the sample bottle. 10) After the 5 second delay remove the syringe needle from the serum bottle and adjust plunger to read the proper volume. 11) Inject the sample into the chromatograph, start integrator and recorder. 12) The vinyl chloride peak will elute in approximately 3 minutes. 13) Wait one minute after the vinyl chloride peak elutes and repeat Steps 7 through 11 using a duplicate sample. Ik) Record sample peak area, gas sample size, attenuation, sample identification, etc, on work sheet (Attachment 3)* 15) One minute after the vinyl chloride elutes you are ready to run another sample. BOR 005824 BFG Standard Test Procedure No. 999"T Page 7 of 7 XI. CALCULATION OF RVCM IN SAMPLE BOR 0 0 5 8 2 5 The following information is needed to calculate the residual vinyl chloride content of the resin. l) Response factor for vinyl chloride = R (counts/nanograra VCl) (as determined in the calibration step) 2) Weight of polyvinyl chloride resin in vial = W (grams) 3) Volume of sample injected into chromatograph = V (cc) 4) Area of the chromatograph peak for the vinyl chloride = A (integrator counts) 5) Volume of sample bottle (serum vial) = B (cc) 6) Atmospheric Pressure = P (mm Hg) ppm RVCM *1 A x 10 -9 -3) _A x 10 + (1.16 RV x 10 100 - -7 A x 10 A x 10'+ (1,16 rv x 10~3 (6.5 -6. JL 10 )+ 62,3 X " 1,l4) r&400)(363)(w) This calculation can very easily be set up on a Monroe i860 Programmable Calculator. It should not be routinely performed on a hand calculator because of a high probability for errors. The Monroe i860 program for this method is attached. See Attachment 4. ooo 'v-' w w C- w-J BFG Standard Test Procedure Ho. 999_T* 1 2 3 * 5 6 7 8 ATTAC; 7* ` i i 'a r_.. i Method for Procuration of Standard VCM/Air Mixtures 1) Clean the 250 ml gas sampling bottler, with acetone and blow tho roughly dry with clean air or nitrogen. 2) Apply low vapor pressure stopcock grease to both stopcocks after washing and drying. 3) Attach a septum to the septum stem. U) Using the proper standard VCM/air cylinder equipped with regulator attach the sample bottle using a short piece of tubing. Attach the other end of the bottle to the rotometer. 5) Open both stopcocks on the gas sampling bottle. Open valve on gas cylinder. Very slowly and carefully open fnc regulator on the cylinder to provide a flow rate of approximately 1.5 liter per minute. 6) Purge for two minutes. 3e certain that the VC.M/air mixture is properly vented as stated in Section V. 7) At the end of the purge time turn off the valve at the cylinder and then both stopcocks to off, closing the stopcock closest to the cylinder first. 8) Cas sampling bottle is now ready to use. BOR 005826 BFG Standard Test Procedure No. 999~T Injected Run Sample Sample No. Identification Size, cc ATTACHMENT 2 Calibration Data Sheet and Calculations Peak Area Avg. Peak Area Deviation from Avg. Counts per Nanograra VC1 1 19 ppm Std 2 11 3 4 tt ta 5 6 805 ppm Std Tl 7 8 rr 11 9 10 805 ppm Std Tl ll tl 12 tr 1.0 4600 4565 4690 4585 4610 .2 1.0 .4 5 0.5 95370 96485 95732 96901 96122 .8 .4 .4 .8 1.0 193946 1.4 190241 189789 .5 1.4 190916 191,223 .2 95.7 94.2 93.7 Using a 1.0 cc sample, each ppm VC1 in the standard contains 2.5352 nanograms VCM. Runs 1 through 4 each contain (19}(2.5352) = 48.17 nanograins VCM Runs 5 " 8" " (805)(2.5352)(.5) = 1020.4 nanograms VCM Runs 9 " 12 " '' (805)(2.5352) = 2040.8 nanograras VCM ThenAverage Peak Area 7 Nanograms VCM = Counts per Nanograra VCM The Response Factor = Avg. Counts per Nanogram VCM = 94*53 A28S00 HOS Avg. Counts per Nanogram VC1 94.53 BFG Standard Test Procedure No. 99 82 0 H03 GC Run No. 1 2 3 4 5 6 Sample Identification "A" "B" "C" "D" "E" "F" Sample Weight (grams) W 2.0012 1.9873 2.1249 2.0141 1.9981 2.0476 ATTACHMENT 3 Analysis Work Sheet and Results Vapor Sample Volume (cc) V 1 .3 .5 5 5 .5 GC Peak Area A 43,210 769,343 143,356 19,423 117,324 4,422 Atm. Pressure mm P TSS3 \ Response Factor Date Volume of Serum Bottle PPM RVCM in Resin R 94. 53 > B 12 .0 \' 6.4 213 22.6 3.2 19.4 0.7 BFG Standard Test Procedure No. 999-T ATTACHMENT k Program for Calculating ji RVCM in Resin - Monroe i860 Operating Procedure: 1) Br ( ) ( ); 0; 0 Program No. 133 prints 2) Enter A) Area Counts B) Response Factor, counts/nanogram VCM C) Syringe Volume, cc D) Atm. Pressure, mm E) Sample Weight, grams F) Volume of Serum Bottle, septum in place, cc 3) Prints answer in ppm RVCM in resin 13 3* 0 0 0 0 1 4 4,7 3 5 0 0 0 0 94 5 300 0 3000 753 . 0000 2 0 0 12 X 2 * 0000 39 as4 i PROGRAM NO. AREA COUNTS RESPONSE FACTOR SYRINGE VOLUME ATM. PRESSURE SAMPLE WEIGHT SERUM BOTTLE VOLUME BOR 005829 1 33 0000 0000 1 2 3 4 5 6 7 8 9 0 0 10 1 2 3 4 5 6 7 8 9 0020 1 2 3 4 5 6 7 8 9 0030 1 2 3 4 5 6 7 8 s - 1 16 00Q 0o 1 003 003 060 1 76 056 1 10 00 1 060 056 1 1o 002 060 056 1 10 003 060 056 1 10 004 060 056 1 10 005 060 056 1 110 010 060 065 '111 00 1 023 026 00 1 000 025 nA 1 , di 0 t J 3 4 r 4 2 1 Jr ; 4 4 s 4 a t / X ( t 0 av % 004 0 01 3 -1 1 027 ) o c\ o 2= '3 1 10 4 4 . 006 e 5 111 t 6 00 1 / 7 023 X 8 026 ( 9 00 1 /* 0050 oon 0 1 0 2 5 03 2 01 1 9 3 013 - 4 027 ) 5 020 -- 6 02 1 + `7 026 ( ; 8 111 t 9 002 P 0060 023 X 1 111 t 2 003 J -3 0 2 3 X 4 012 5 ` 000 o 6 000 7 00 1 0 fc / 8 00 1 / 9 006 6 0070 027 ) 1 020 - J .2 1 10 4 3 007 7 4 111 t 5 006 6 024 r 7 111 t 8 9 0080 1 007 020 1 10 '006 7 = 4 5* 2 111 t 3 oo i 4 . 023 5 026 /o i( x 1* 6 00 1 7 oon / /O PS O n 8 0 2 5 nv r, 0090 1 2 3 4 5 6 7 8 9 0 10 0 1 3 4 5 6 7 a 9 0 110 1 2 3 4 5 6 7 8 9 0 12 0 1 2 3 4 . 56 7 8 9 0 13 0 1 2 3 4 5 6 7 8 013 027 020 024 111 007 020 0 13 02 1 ' 00 1 000 000 020 1 10 007 111 006 024 111 007 020 1 10 00 1 003 006 003 023 111 004 - 023 002 01 1 020 02 4 026 002 01 1 005 023 006 002 012 00 5 027 020 1 10 002 006 00 2 - ) -- t 7 = + / 0 0 - 4 7 t 6 * t 7 -- 4 / J S J X t. 4 X 2 9 -- * ( 2 9 S X 6 2 \ Ss ) -- 4 2 e 2 0 14 0 1 2 3 4 i5 6 7 8 9 , 0 15 0 1 2 3 4 5 6 7 a ' 9` 0 16 0 1 2 3 4 5 6 7 8 9 0 17 0 1 2 3 4 5 6 7 a 9 0 180 1 2 3 4 5 6 .. 7 a 005 02 3 026 111 0 10 022 026 111 00 5 024 00 1 012 004 027 027 020 024 026 111 005 023 006 002 004 000 000 023 003 006 00 3 027 020 02 1 026 006 012 005 023 012 000 000 '000 000 000 00 1 027 020 110 00 3 5 X ( t 9 < I 5 ~ / 4 ) ) = t C t S X 2 o o X j s ) = + ( $ 5 X o o o o o / ) = 4 BOR 0 0 5 8 3 1 0 19 0 1 2 3 4 5 6 7 a 9 0200 1 2 3 4 5 6 7 8 9 00 1 025 111 002 02 3 111 003 020 05 1 1 76 1 76 065 065 065 1 27 000 000 000 000 377 X t X t jr A o 0 0 0 BOR 005832 1o o o o o o G O O O G O o O 4 BFG Standard Test Procedure No. 999"? ATTACHMENT 5 Establishing True Volume of Serum Bottle 1) Clean serum bottle (water and detergent) and rinse with acetone. Air dry thoroughly. 2) Allow to condition for at least 15 minutes at room temperature. 3) Weigh serum bottle plus septum to 0.0001 gram on an analytical balance. 4) Using distilled water which has been conditioned to within +2" F. of room temperature fill the bottle to the very top. 5) Carefully insert and seal the septum. This will tend to force a small amount of water out of the bottle. 6) Dry the outside of the bottle and weigh again on the analytical balance. 7) Knowing the temperature of the water, determine, using a table of density of water at various temperatures, the volume of the bottle. 8) Check three bottles and average the results. Individual results should not differ more than +0,3 cc from the average. (Bottles normally have a volume of approximately 12.0 cc.) BOR 005833