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A series of therm al degrada Lion stud ies on polyisoiJul vlene has beell carried out at rel ative~y low degradation temperatures u sing samples of h igh purit.v, bolh fraclionatrd find unfracbl;lll a ted , and of both hig!' find lowJ1101ecu la r wcight . R at e curves of th e high molecu lar wCJ~ht pol:-'111er show m aXI111l1111S whIle t hose of t he 10\1' m olecul a r \I'e ight polymer sho\l' large Initial rates whIch steachl y decrease with in creased vola tili za t ion . RaJes of degradation of all sa~llples b ecome s\ll1\l a r wllh lIlcreasecl vo la tili zalion. Rale studi es indicate stron g random 1I11llatlOn ,,'Ith th e lIl lll a l ra te of vola lIl lzation sho\\'in g vcr v lillI e dependence on molec ular weight. Th e d rop ill m olecula r weight with in creased degradali on and t he hICk of broad m:txilllums a t mode ml e v:t1u es of con version shows th e influence of an appreci able a moun t of tmnsfer and a lo w kin etic eha illlcngth. The ra le of degmdat ion i ~ found Lo be much fasler lh a n lhat of p olvprop.vlene or pol:-'ethy lene probabl.\· because po l ~· i sob ut .v l e n e disproporllOnales and forms m d icals m ore easily . Equal ions arc s uggl's leci for lhese deg radat ion react Ions.

Thermal degradation of fractionated high and low molecular weight polystyrenes