Highly active bimetallic nickel catalysts for alternating copolymerization of carbon dioxide with epoxides

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Title:	Highly active bimetallic nickel catalysts for alternating copolymerization of carbon dioxide with epoxides
Authors:	Su, YC (Su, Yu-Chia) Tsui, CH (Tsui, Chih-Hsiang) Tsai, CY (Tsai, Chen-Yen) Ko, BT (Ko, Bao-Tsan)
Contributors:	化學系
Keywords:	RING-OPENING POLYMERIZATION CYCLOHEXENE OXIDE MECHANISTIC INSIGHTS TRIBLOCK COPOLYMERS ZINC-COMPLEXES MESO-EPOXIDES ONE-POT CO2 COBALT CYCLOADDITION
Date:	2020-05-14
Issue Date:	2020-11-09 10:58:52 (UTC+8)
Abstract:	We reported a series of well-characterized di-nuclear nickel catalysts containing 1,3-diamine-bis(benzotriazole phenolate) derivatives for high-performance copolymerization of CO2 and epoxides. The di-nickel di-acetate complex 1 was found to be a highly active catalyst to alternatingly copolymerize CO2 with cyclohexene oxide (CHO), producing poly(cyclohexene carbonate)s (PCHCs) with a high turnover frequency (TOF) up to 7800 h(-1) under optimized conditions. Interestingly, complex 1 also appears to be the first example of nickel-catalyzed CO2-copolymerization with CHO that could proceed at 1 atm CO2 pressure. Not only has the excellent catalysis of CO2/CHO copolymerization by di-Ni 1 been enabled, but also 1 has been further applied to effectively catalyze the copolymerization of CO2 with 4-vinyl-1,2-cyclohexene oxide or cyclopentene oxide (CPO) to obtain the corresponding polycarbonates. Particularly, 1 was also reported for the first time to be highly efficient for nickel-catalyzed CO2/CPO copolymerization and enabled the formation of poly(cyclopentene carbonate)s with a TOF > 700 h(-1) and excellent carbonate linkage contents (>99%). Kinetic studies of the Ni-catalyzed CO2-copolymerization of CHO were performed and the activation energy for PCHC formation by 1 is 60.6 kJ mol(-1).
Relation:	POLYMER CHEMISTRY 卷冊: 11 期: 18 頁數: 3225-3236
Appears in Collections:	[Department of Chemistry & Graduate Institute of Applied Chemistry ] journal articles

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