RAFT homopolymerization of vinylbenzyl chloride with benzyl ethyl trithiocarbonate and synthesis of block copolymers from poly(VBC) macro-RAFT agent and N-isopropylacrylamide

Poly(vinylbenzyl chloride) (PVBC) is an important polymer that has a reactive benzyl chloride group and is thus easily converted to various functional polymers.¹ Radical polymerization is one of the most widely used processes for commercial production of vinyl polymers. Conventional radical polymerization, however, severely limits the control of molecular-weight distribution, copolymer composition and molecular architecture. To remedy these problems, many living radical polymerization methods, such as nitroxide-mediated polymerization, atom transfer radical polymerization and reversible addition-fragmentation chain transfer (RAFT), have been developed.^{2, 3}

Living radical polymerizations were applied to the polymerization of vinylbenzyl chloride (VBC) to obtain the well-defined PVBC polymer. However, the atom transfer radical polymerization of VBC yielded hyperbranched polymers because benzylic chloride acts as an inimer.⁴ In addition, PVBCs with high polydispersity indices were produced by nitroxide-mediated polymerization with 2,2,6,6-tetramethyl-1-piperidinyloxyl because of radical transfer to chloromethyl groups, accompanied by the formation of the hydroxylamine of 2,2,6,6-tetramethyl-1-piperidinyloxyl and/or the corresponding oxoaminium chloride that can initiate new controlled PVBC chains.⁵ However, most RAFT polymerizations of VBC have been performed for the synthesis of copolymers with styrene, whereas few studies have dealt with the homopolymerization of VBC. Among them, ABA and BAB triblock copolymers of VBC and styrene with low dispersity were prepared by RAFT polymerization using a symmetrical trithiocarbonate, butan-1,4-diyl-bis(1-phenylethyl)trithiocarbonate, as the RAFT agent.⁶

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