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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
Author(s) -
Pan Jinlong,
Zhang Bingjie,
Jiang Xiaowu,
Zhang Lifen,
Cheng Zhenping,
Zhu Xiulin
Publication year - 2014
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.201400277
Subject(s) - atom transfer radical polymerization , methyl methacrylate , catalysis , polymerization , miscibility , polymer chemistry , materials science , polymer , molar mass distribution , chemical engineering , chemistry , organic chemistry , engineering
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, CuBr 2 as a catalyst, and AIBN as a reducing agent. By heating to 70 °C, unlimited miscibility of both solvents is achieved and the polymerization can be carried out under homogeneous conditions; then on cooling to 25 °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.