The branching generation during the free radical copolymerization of chain transfer monomer

p

-vinyl benzene sulfonyl chloride (VBSC) with styrene was investigated by a simple mathematic model. Chain transfer constant of VBSC was determined to be around 0.3 by fitting the

1

H-NMR monitored experimental results with a mathematic model. According to the theoretical analysis

the obtained poly(VBSC) and its copolymers were substantiated to have a grafting-like main chain with residual pendent sulfonyl chloride groups after consuming most of the vinyl groups. The copolymerization results of VBSC with styrene at varied feed ratios demonstrated that conversion of sulfonyl chloride groups was lower than that of the monomer

which was in agreement with the theoretical results. The glass transition temperature

number average molecular weight and distribution of those obtained polymers were primarily investigated. Comparing with other chain transfer monomers

VBSC has a chain transfer constant much closer to unity therefore a more branched polymer is expected. Additionally

the branched polystyrene with residual sulfonyl chloride groups is hopefully to be further used as ATRP macroinitiators or reactive intermediates to synthesize functional polymers with complex structure.