Cu(II)-Mediated Atom Transfer Radical Polymerization of Methyl Methacrylate via a Strategy of Thermo-Regulated Phase-Separable Catalysis in a Liquid/Liquid Biphasic System: Homogeneous Catalysis, Facile Heterogeneous Separation, and Recycling

A strategy of thermo-regulated phase-separable catalysis (TPSC) is applied to the Cu(II)-mediated atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) in a p-xylene/PEG-200 biphasic system. Initiators for continuous activator regeneration ATRP (ICAR ATRP) are used to establish the TPSC-based ICAR ATRP system using water-soluble TPMA as a ligand, EBPA as an initiator, CuBr2 as a catalyst, and AIBN as a reducing agent. By heating to 70 degrees C, unlimited miscibility of both solvents is achieved and the polymerization can be carried out under homogeneous conditions; then on cooling to 25 degrees C, the mixture separates into two phases again. As a result, the catalyst complex remains in the PEG-200 phase while the obtained polymers stay in the p-xylene phase. The catalyst can therefore be removed from the resultant polymers by easily separating the two different layers and can be reused again. It is important that well-defined PMMA with a controlled molecular weight and narrow molecular weight distribution could be obtained using this TPSC-based ICAR ATRP system.