This study was directed to metal-free living cationic polymerization that proceeds via reversible or degenerative chain-transfer mechanism between the growing carbocationic species and the dormant C–S or C–OP(O) bonds derived from chain-transfer agents (CTA). The living cationic polymerization was achieved using thiocarbonylthio compounds, thioethers, and phosophoric acids esters as CTAs in conjunction with a trace amount of triflic acids as a source of cationic species. This living system was applicable to various cationically polymerizable monomers such as vinyl ethers and styrene derivatives. In addition, we also developed a facile and ecofriendly method for this living cationic polymerization simply using combination of weak and superstrong protonic acids with no need for preparation of CTAs.

Metal-free living cationic polymerization based on degenerative chain-transfer mechanism

2019 Fall National Meeting

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