Living anionic polymerization of 1,4-divinylbenzene and its derivatives

Abstract The living anionic polymerization of 1,4-divinylbenzene and its derivatives was reviewed. With the use of a specially-designed initiator system prepared from oligo(α-methylstyryl) lithium and potassium tert -butoxide, the living anionic polymerization of 1,4-divinylbenzene was successfully realized for the first time. During this polymerization, one of the two vinyl groups was selectively polymerized in a living manner, while the other vinyl group remained completely intact in the main chain. Soluble linear polymers with well-controlled molecular weights up to 60.5 kg mol −1 and narrow molecular weight distributions ( M w / M n tert -butylethenyl)styrene, underwent the living anionic polymerization with the same designed initiator system under similar conditions. New well-defined block polymers and star -branched polymers with reactive poly(1,4-divinylbenzene) segment(s) could be successfully synthesized by using the living anionic poly(1,4-divinylbenzene). Throughout the block copolymerization study, it was found that the reactivities of 1,4-divinylbenzene and the generated chain-end anion were comparable to those of 2-vinylpyridine. Although 1,4-divinylbenzene is a styrene derivative, it was higher in monomer reactivity than styrene, but its chain-end anion was less reactive than that generated from styrene.