Homo(co)polymerization of bio-derived long alkyl chain methacrylate and methyl methacrylate using a readily accessible aminophosphine-based Lewis pair

Lewis pair polymerization (LPP), emerging as an effective polymerization method, has been broadly investigated and applied in the synthesis of diverse polymers, e.g. poly(meth)acrylates, polyester, polyethers et al. Introduction of P-N bonds showed great promise in mediating controlled/living (co)polymerization of short alkyl acylates and short alkyl methylacrylates. However, there have been far fewer experimental studies on long alkyl chain of acylates or methyl acrylates using LPP. Introduction of long alkyl side chain would offer the opportunity to explore its influence on basic materials parameters and tune the physical properties of copolymers to cater the society demands. In this contribution, we synthesized the new aminophosphine LB bis(N, N-diethylamino)methylphosphine [(Et2N)2PMe] via variating the numbers of P-N bonds, and combined it with iBu3Al to form the Lewis pair (LP) for the (co)polymerization of MMA and bio-derived lauryl methacrylate (LMA). (Et2N)2PMe / iBu3Al showed both controlled polymerization of MMA and LMA in a monomer/ (Et2N)2PMe molar ratio of 1600/1 or 700/1, respectively. Taking advantage of the linear chain end of PLMA, block copolymer of PLMA-b-PMMA was synthesized via sequential addition method and its physical property was investigated.