Document N7XrevErq55V0eGp6VXGzb2V

ALLIED CHEMICAL CORPORATION MEMORANDUM June 20, 1977 TO: R. R. Lamonte FROM: E. R. McCarthy SUBJECT: Identification of Products Resulting From Pyrolysis of VF^-HFIB Copolymers Three samples were received for pyrolysis analysis. Each sample was heated to 650F and 700F and the products evolved were examined at each temperature. One of the samples was also burned in air. The only products, detected in significant amounts were carbon dioxide, hexafluoroisobutylei (HFIB), vinylidene fluoride (VF2) and hydrogen fluoride (HF), the latter component evolved only from the unstabilized sample. Introduction Three samples were received for analysis. These were labeled as follows 504897-24A, 504897-24B and 504897-24C. We were asked to heat each of these samples at temperatures of 650F and 700F in air and to identify the pyrolysis gases evolved at one hour intervals for a period of six hours. Also we were asked to burn 504897-24A in air and to examine the gases. S/N 504897-24A was described as a low molecular weight CM-1 Polymer containing 2% CaO stabilizer. S/N 504897-24B corresponds to -24A which had been heated overnight to 300C. S/N 504897-24C was described as a high molecular weight CM-1 Polymer containing no stabilizer. Experimental For the lower temperature pyrolysis experiments at 650*F and 700F, about one half gram of sample was used. The sample was loaded into a glass tube which was then partially inserted into a furnace maintained at the appropriate temperature. The tube was equipped with a rubber septum for gas sampling purposes. At the one hour intervals the gases were sampled with a lOcc syringe. lOcc were injected into the cold inlet system of the MS 902 Mass Spectrometer and a mass spectrum immediately recorded. For the burning of 504897-24A, about one half gram of sample was loaded into a glass tube and then the contents were heated with a Meeker Burner flame. After burning, the combustion tube was connected to the inlet port of the mass spectrometer introduction system and the gas sampled. ASI 00007805 R. R. Lamonte Page 2 June 20, 1977 Results and Discussion --' The results are presented in the following tables. The only gases detected in significant amounts were CO^ , VF^ , HFIB and HF . The molecular ion (m/e 44) was used to monitor CO. in the mass spectrum. For VF2 , the molecular ion (m/e 64) was usea. For HFIB, m/e 145 corresponding to loss of F from the molecular ion was used. HF was not observed directly but was inferred from the presence of SiF + (m/e 85). The ion corresponding to loss of F from the SiF molecular ion (m/e 85) was used to monitor its concentration. The relative amounts values in the tables were taken directly from the mass spectrometer computer printout. These values are not quantitative because mass spectrometer response factors have not been incorporated into the data. As can be seen from the data in the Tables CO. appears to be the main component formed in each sample. Also the stabilizer seems to be very effective; no HF is detected in -24A and -24B. (Samples -24A and -24B contain 2% CaO .) Also, we observed no detectable pressure increase on the gauge affixed to the combustion tube of the polymer conditioned overnight at 300C. For -24A and -24C, about an atmosphere of pressure developed in the tube very quickly, when it was placed in the furnace. This pressure remained during the course of the six hours. The amount of HFIB relative to CO^ was lower for sample -24B. After the six hours run, each tube contained a yellowish residue that had condensed onto the cooler region of the tube. This represents compound formation resulting from thermal cracking of the polymer chain. We did not analyze the yellow residue. It should be mentioned that no trace of the very toxic PFIB was observed in any of the samples. Trace amounts of higher molecular weight species were found, particularly in -24C; a peak at m/| 208 could represent a molecular ion corresponding to l(HFIB + VF2)-HF] Also a peak+at m/e 182 could represent a four carbon heptafluoro species C4HF7 * Recommendations To obtain quantitative information concerning the gases evolved in this experiment, we recommend pyrolysis gas chromatography. ERM/nag Enclosures cc A. R. Paterson J. S. Smith S. Chandrasekaran 6>/?. CCe-jjUj, E. R. McCarthy Q o0007806 6Si t Temperature (F) 650 650 650 650 650 650 TABLE I S/N 504897-24A Interval (Hours Expired) 1 2 3 4 5 6 C0,, 100 100 100 100 100 100 Relative Amount HF1B ---V--F^,, 0.5 0.5 2 2 0.1 700 1 43 1 .6 700 2 61 7 3 700 3 100 30 20 700 4 100 42 34 700 5 96 58 39 700 6 98 55 46 ASI 00007807 Temperature cn 650 650 650 650 650 650 TABLE II S/N 504897-24B Interval (Hours Expired) I 2 3 4 5 6 Relative Amount CO, HF1B 100 ---V--FL,," 100 2 1 100 1 1 100 3 1 100 9 4 100 5 1 700 1 100 . 700 2 100 1 700 3 100 2 700 4 100 3 1 700 5 100 7 2 .700 6 100 8 2 ASI 00007808 TABLE III S/N 504897-24C Temperature (F) 650 650 650 650 650 650 Interval (Hours Expired) 1 2 3 4 5 6 C0,, 70 100 100 100 100 100 700 1 100 700 2 100 700 3 100 700 4 100 700 5 100 700 6 100 HF1B 4 24 27 32 41 41 16 22 23 34 22 27 VF,, HF 3 8 66 10 76 11 93 14 98 13 98 5 53 6 91 6 98 9 120 6 90 8 98 ASI 00007809 1 TABLE IV S/N 504897-24A Relative Amount Temperature COp HF1B (Flamed with Meeker Burner) TOO 63 VF^ 28 ASI 00007810 I A- L QUMgnrmiVB MBASPREMBET of OFT-G^SES FPQM CM-1 POLYMER AT 345C (650F) 20 mgm samples of powder coating grade CM-l powder were sealed into 1 1/2" long capillary tubes, sealed in air and heated in a G.C. probe at 650F for up to 15 hrs. Then the capillary was . broken inside the G.C. inlet port and the gases analyzed. Results are as shown: Heating Tims 15 Mins. 30 Mins. 15 hrs 002 45mqms lb. polymer 45 90 vf2 45 mgms lb. polymer 45 90 HFI3 270 mqms lb. polymer 315 405 There were also detected much smaller amounts of a low boiling and a high boiling component in the off-gases. C?^ ASI 00007811 1 ' !Upd m Chemical CORPORATl. HEMICAL RESEARCH LABQKAIUki REQUEST FOR SERVICES v:T*= BT -S _ ,., iCCOVNT CCCSS v-rc-iY- v DIVISION - N. / LOCATION y>7- /-- IEL. EXT. 3X63 CONTROL CENTER DEPARTMENT or ROOM NO. z^y CCRL ANALYSIS NO. ______________________e^^iLj7!--------------- TMl/2tUo '77 xW PPOUESTER ^ project no. \ ' vPiE DESCRIPTION AND REQUEST (jjs)fs jpsy^7- A//r;s *? fC uZ,(!) -AZARDOUS PROPERTIES I \7 AND DESCRIBE) TOXIC /, 2*. 3. II -S'. t- _Pl_AMMABLE ' ' ., REACTIVE -t .. OTHER Cp} . _ . ., ^ X&,-v-cY, e^6 cs~o af=Y-S.VS'c; U-LUf ANALYST & DATE OPERATION AND RESULL)Ol/sS C^ > <YC C- $0 -w^-1 S-A5\>^M1,. <aw- CHARGE /SA<*j'77 #\ C-O^ -- Q* f S'-Psi-* T > ' V' t v+c - o, / Or tl-f-tfb - O.to ? C.7 Q / (/^ TOTAL CHARGE ASI 00007812 ALLIED CHEMICAL CORPORATION MEMORANDUM DATE: August 29, 1977 SUBJECT: CM-1 Off Gases TO: Dr. R. R. Lamonte Cn January 20, 1977 I wrote a memo to Mr. Jeff Buck stating that two ooaters have ocnplained about chest pains after coating with 05-1. Dr. Minhas has reported another instance where chest pains were encountered. Other coatings, also being applied at the same time could have been the cause of the problem. We need to obtain information on the 05-1 off gases before we have a serious problem. Oould you lose this recent incident to get this work moving. WAMrgp cc: P. Minhas M. B. Berenbaum W- A. Millar ASI 00007813