Stereo- and Temporally Controlled Coordination Polymerization Triggered by Alternating Addition of a Lewis Acid and Base

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• 作者：Dr. Bo Liu ; Prof. Dongmei Cui and Prof. Tao Tang
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：September 19, 2016
• 年：2016
• 卷：128
• 期：39
• 页码：12154-12157
• 全文大小：853K
• ISSN：1521-3757

文摘

Significant progress has been made with regard to temporally controlled radical and ring-opening polymerizations, for example, by means of chemical reagents, light, and voltage, whereas quantitative switch coordination polymerization is still challenging. Herein, we report the temporally and stereocontrolled 3,4-polymerization of isoprene through allosterically regulating the active metal center by alternating addition of Lewis basic pyridine to “poison” the Lewis acidic active metal species through acid–base interactions and Lewis acidic AlⁱBu₃ to release the original active species through pyridine abstraction. This process is quick, quantitative, and can be repeated multiple times while maintaining high 3,4-selectivity. Moreover, this strategy is also effective for the switch copolymerization of isoprene and styrene with dual 3,4- and syndiotactic selectivity. Tuning the switch cycles and intervals enables the isolation of various copolymers with different distributions of 3,4-polyisoprene and syndiotactic polystyrene sequences.