Thermal degradation of tetrafluoroethylene and hydrofluoroethylene polymers in a vacuum

T e fl on and tetrafluoroethyle ne photopolymers, on py rolysis in a vacuum at 423.5 0 to 513.0 0 C, yield almost J 00 per ce nt of monom er. The r ate of formation of monome r at a n., given tem p e rat ure fo llows a first-order react ion and is independe nt of t he method of pre pa ration of poly mer or its initial ave rage molecu lar weight. The activation energy was determined by a press ure method and a wei gh t met hod , and a value of 80.5 k cal was found b.' both methods . A prelimina ry heating of Teflo n in air a t 400 0 to 470 0 C did not change a ppreciably its rate of degradation into mono me r when it was s ubseque ntl y heated in a yacuum . Polyvinyl fluorid e, 1,I -polyv in y li dene fluorid e, and polytrifluo roethylene were pyr olyzed in t he range 372 0 to 500 0 C. The volatiles consisted in all cases of HF and a wax-lik e mate rial co nsisting of chain fragments of low volatili ty. P olyvinyl fluoride and polyt rifl uoroet hyle ne deg rade to co mplete volatilization, whereas 1,1-poly viny li dene fluoride becomes stabilized at about 70-pe rcent loss of we ig ht. The rate-of-volat ilization curves indicate a fi l'st-o rder reaction for poly vinyl fluo ri de, a zero-order reaction fo r t riflu oroethy le ne, alld an undeterm in ed ord er for 1,1-polyvinyli dene fluoride. The orde r of t hermal s tabili ty for t hese poly me rs, as com pared with polymet hy lene, is as follows: Poly vin yl f1uoride < poly me th,vle ne < polyt riflu oroethylene < ] . J -polyvi nylidene f1uor idc < polytetrafluoroeth ylene.