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Thioglycolic acid added exothermally to butadiene polymers and copolymers in benzene solution under mild conditions to give apparent double-bond saturation values of 38 to 47 per cent. When the same polymers reacted with aliphatic thiols of C2 to C16 chain length, in mass or latex reactions, saturation values were obtained which were in accord with those found by thioglycolic acid addition. It is suggested that the double bonds in butadiene polymers and copolymers which were readily saturated by the above thiols are predominately those present in the polymer chains as vinyl side groups.

I tie iporitaneous f o r m a t i o n of a n i n s o~i~e , infii-il>lv 1,utacliene popcorn pol?;mer ha$ been encountered i n c o~i i t . o f Lhe commercial clibtillation u n i t s w h i c h are ic-etl t o purify butadiene for the s?;nthetir r u b b e r proprani. On( t' initiated, the p o l > m e r Shows a logarithmic pro\+ t h i t i b u t a d i e n e monomer and has caused fouling and etet] hurstiiig of large scale distillation e q u i p m e n t i n relatit el? short times. h l t h o u g h it can be initiated in n %ariety of w a y s , iron and a c t i t e oxygen play a11 i m p o r t a n t p a r t i r i its formation. Its growth is retarded b u t n o t t e r m i n a t e d by ~ulcanization accelerators, n hereas c.on\eritional ' i n t ioxidants have little effect.

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