We have carried out initial studies into the methanol-controlled visible light photoinitiated polymerization of 4-methoxystyrene using pyrylium salts. First order kinetic behavior, linear Mn growth with respect to monomer consumption, narrow dispersity, and continued polymerization upon monomer addition all indicate the controlled/living nature of the polymerization. The accumulated data suggest methanol plays a role as a reversible chain transfer agent, analogous to that of dithiocarbamates in RAFT polymerization. The polymerization does not require the use of strong Lewis or Brønsted acids or the prior synthesis or formation of small molecule co-initiators. Poly(4-methoxystyrene) of low dispersity can be prepared, with Mn controlled by the concentration of methanol.

Living cationic polymerization of 4-methoxystyrene via a novel RAFT mechanism

254th National Meeting (2017)

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