Document 11r1o6V9ppNvY0XB0DrxjYBa

OuPonl WishinstKi Works P. 0. Bin 121? Pjrkiisbn, WV26102 1217 Septem ber9,1997 TO: R. BRANDENBERG - DORDRECHT WORKS H. TOTSUKA - MDF, JAPAN S. PECK - W SHINGTON WORKS D. KROTTINGER - PONCA CITY FROM: R. J. ZIPFEL - WASHINGTON LABORATORY C-8 DECOMPOSITION Attached is some recent work done at the Experimental Station on the thermal decomposition of C-8. R J Z :s s b P - J , fc h ts * c> :. W AB002832 E ID 7 1 5 5 4 8 009068  . i ' w vh *7 xc.wo iu*u*jru^> eia. oihi oua o V Hflet 2 Recent Applications of High-temperature Gas-phase NM R to Reactions of Interest to Fluoroproducts Paul Krusic Chris Roe Acknowledgments: Steve Hill Roger Zipfel Ming Hung W eim ing Qiu Bruce Smart WAB002833 E ID 7 1 5 5 4 9 C000G9 JL-L Vw. **cw c i x. * w 4 u * y v r u iii u n v i m v u u mc*u \a. vhxc. '"Hrtoc ~o" Ampoule for gas-phase NM R reaction kinetics studies SXI 5 mm W' V (int.) = ~ 5.8 ml P (Int.) = ~ 3 atm @ 4 00 QC n (max) = 0.31 mmol 12 mm NMR ampoule is not spun No deuterium lock WAB002834 E ID 7 1 5 5 5 0 C00070 M L t NO. v a s w "Hf iz:u y UI-'UUKJNI kX. S lfll BL6 328 302 695 8412 PAGE 4 C 8 surfactant (ammonium perfluorooctanoate) )> CF3(CF2)6COONH4 F i F \cr\ -VcN- F c -c t \ F F FFF 1 F c o Major surfactant ( - $ 7 M M ) for emulsion polymerization leading to fluoropolymers of the Teflon and Viton families. Toxic and highly bioretentive. Significant fraction is recovered for refining and recycling, balance is released to environment. 21 M lb atmospheric losses in 1996. Search for less toxic and more biodegradable alternatives. Best candidate: H 4C 8 surfactant - Ming Hung: ammonium salt of C F3(C F2)3CH2CH2C F2COOH Improved waste m anagem ent needed. Filtering particulates in exit flues - Roger Zipfel. WAB002835 E ID 7 1 5 5 5 1 000071 n Kinetics of formation of C F3(CF2)6H in the thermal decomposition . of perfluorooctanoic acid studied by gas-phase 1^F NM R *- CF3(CF2)0H + co2 1W 100-^ T a 360*0 | 60- | 40- 20- 0--I' 0 y = 55.056*( 1-exp(-0.239*t 1-r-r-i' ' 1* 1 ' 1 . '> II-' '" SO 100 150 time (min) 200 >-5> Therm al decomposition is catalyzed by C8 ammonium salt which releases NH3. W AB002836 E ID 7 1 5 5 5 2 000072 FU- No. 493 09/04 '97 12:10 ID:KJPGNT EX. STAT ELG 328 302 695 8412 > PflGE 6 Kinetics of formation of CF3(CF2)6H in the thermal decomposition of C 8 surfactant studied by gas-phase 19F NM R CF3(CF2)6COONH4 -- CF3(CF2)6H + c o 2 + n h 3 m(M) 29333 - 17.a79(1000rn AE* a 35.1 kcai/moi logA a 12.7 ic o iy r 8.16 6 s I4 a X 2- 09 1i 8 t1(180C)~15hrs 6Un (300C) - iLfi I See. 3 0 0 *4 -./ Sec. **i 1p > r *r T |- 1 f - p f 180 2C0 220 240 260 T (*C) 280 Above 300C C8 can be rapidly decomposed to "environmentally benign* CF3(CF2)6H. Install heaters at points of emission. WABO02837 E ID 7 1 5 5 5 3 000073 Wl ' Wv *W WV irti CU vvc. s*OV & **! , rhbC S> Thermal decomposition of C8 acid and C8NH4 T 250 C C F 3(C F 2)eC O O H 400'--------- -------- 300 100 i 100 0 9 t a i s sa Im(min) as a0 c f4 1 i _______ .------ -------60 -70 -60 -90 -100 6C F2 * ** j# 9 J JL * _ - L -T------ -1----- " n -110 -120 -130 -140 ppm C F 3(C F 2)e C O O H C F a (C F 2) 8H + co2 T =200 C t(1/2) * 1 . 5 hrs (1 7 5 C ) t(1/2) = 41 mfn (200 C) aoo- 0 1 0 0ttnafnin)30 400 CFj L C F 3 (C F 2) 6H f b ra n c h e d is o m e rs 1 *c f 2 h 6CF2 _ J L _ jj!-ri- -60 -70 -80 -90 -100 -110 -120 -130 -140 ppm W AB002838 E ID 7 1 5 5 5 4 C00074 6X Half Life for APFO Thermal Decomposition O o o 0001110w0oo C/1 too 150 E. I. DuPONT Confidential 200 250 300 Temperature oC 9/5/97 350 Page 1 C00076 n H o MODERN COATING TOWERS Countercurrent Flow Each Zone or Direct Impingement Slot Dryers or i Radiant Heat:-- Separate Exhausts Each Zone CAUTION: KEEP AIR VELOCITIES LOW TO AVOID FABRIC FLUTTER AND EXCESS P~" -Q S)ntor 370"C lo 420*C Alternate: Air Cushion Rolls P' I Bake 200*C la31b"C Dry 30'C to 100"C 0 O Pk 1I I < it it t t r I I t I > I bf W b Accumulator Optional: Multiple Rolls in Dip Tank FIGURE 2 FIGURE 3