Cationic Copolymerization of Isobutylene with 4-Vinylbenzenecyclobutylene: Characteristics and Mechanisms.

A random copolymer of isobutylene (IB) and 4-vinylbenzenecyclobutylene (4-VBCB) was synthesized by cationic polymerization at -80 °C using 2-chloro-2,4,4-trimethylpentane (TMPCl) as initiator. The laws of copolymerization were investigated by changing the feed quantities of 4-VBCB. The molecular weight of the copolymer decreased, and its molecular weight distribution (MWD) increased with increasing 4-VBCB content. We proposed a possible copolymerization mechanism behind the increase in the chain transfer reaction to 4-VBCB with increasing of feed quantities of 4-VBCB. The thermal properties of the copolymers were studied by solid-phase heating and crosslinking. After crosslinking, the decomposition and glass transition temperatures (Tg) of the copolymer increased, the network structure that formed did not break when reheated, and the mechanical properties remarkably improved.