Herein we report a metal-free, acid initiated living cationic polymerization of 4-methoxystyrene. The molecular weight and dispersity of the synthesized poly(4-methoxystyrene) are controlled by the concentration of methanol. We propose that methanol acts as a reversible chain-transfer agent, analogous to reversible addition fragmentation chain-transfer (RAFT) polymerization, regulating the equilibrium between the propagating active cation chain and the resulting oxonium intermediate (Scheme 1). The molecular weights of the synthesized polymers were in good agreement with theoretical molecular weight assuming that each molecule of methanol generates one polymer chain. A study using alcohols of different nucleophilicity indicated that the molecular weight and dispersity of the synthesized polymers varies inversely with the nucleophilicity of the alcohol additive.

Methanol-mediated living cationic polymerization of 4-methoxystyrene via oxonium intermediate

253rd National Meeting (2017)

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