Abstract
Abstract1,2‐Epoxycyclohexane (1) was found to behave differently from propylene oxide (PO) in polymerization reactions with organozinc compounds as initiators. A chair‐type complex, [Zn‐MP]2,2, is the only compound that shows high catalytic activity for both polymerization of 1 and PO, following an anionic coordination mechanism. On the other hand, the polymerization of 1 with ZnEt2 or (EtZnOMe)4 as initiator proceeds according to a cationic mechanism. Cationic polymerization of 1 with ZnEt2 has two modes of termination reaction resulting in the formation of terminal units containing vinyl ether and allyl ether moieties. The initiation and propagation mechanism of 1 by [Zn‐MP]2;2 is similar to that of PO, but chain transfer reaction takes place in the polymerization of 1 owing to the low stability of the growing chain end. By using [Zn‐MP]2,2 as initiator, it was possible to prepare a block copolymer consisting of an isotactic sequence of monomeric units of PO and a syndiotactic sequence of monomeric units of 1.
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