Controlled and Efficient Polymerization of Conjugated Polar Alkenes by Lewis Pairs Based on Sterically Hindered Aryloxide-Substituted Alkylaluminum

Reported herein is the development of an effective strategy for controlled and efficient Lewis pair polymerization of conjugated polar alkenes, including methyl methacrylate (MMA), n-butyl methacrylate ((n)BuMA), and γ-methyl-α-methylene-γ-butyrolactone (γMMBL), by the utilization of sterically encumbered Al(BHT)(2)Me (BHT: 2,6-di-tert-butyl-4-methylphenol) as a Lewis acid that shuts down intramolecular backbiting termination. In combination with a selected N-heterocyclic carbene (NHC) as a Lewis base, the polymerization of MMA exhibited activity up to 3000 h(−1) TOF and an acceptable initiation efficiency of 60.6%, producing polymers with high molecular weight (M(n) up to 130 kg/mol) and extremely narrow dispersity (Đ = 1.06~1.13). This controlled polymerization with a living characteristic has been evidenced by chain-extension experiments and chain-end analysis, and enabled the synthesis of well-defined diblock copolymers.