Perfectly Alternating Copolymerization of CO2 and Epichlorohydrin Using Cobalt(III)-Based Catalyst Systems

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• 作者：Guang-Peng Wu ; Sheng-Hsuan Wei ; Wei-Min Ren ; Xiao-Bing Lu ; Tie-Qi Xu ; Donald J. Darensbourg
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：September 28, 2011
• 年：2011
• 卷：133
• 期：38
• 页码：15191-15199
• 全文大小：1030K
• 年卷期：v.133,no.38(September 28, 2011)
• ISSN：1520-5126

文摘

Selective transformations of carbon dioxide and epoxides into biodegradable polycarbonates by the alternating copolymerization of the two monomers represent some of the most well-studied and innovative technologies for potential large-scale utilization of carbon dioxide in chemical synthesis. For the most part, previous studies of these processes have focused on the use of aliphatic terminal epoxides or cyclohexene oxide derivatives, with only rare reports concerning the synthesis of CO₂ copolymers from epoxides containing electron-withdrawing groups such as styrene oxide. Herein we report the production of the CO₂ copolymer with more than 99% carbonate linkages from the coupling of CO₂ with epichlorohydrin, employing binary and bifunctional (salen)cobalt(III)-based catalyst systems. Comparative kinetic studies were performed via in situ infrared measurements as a function of temperature to assess the activation barriers for the production of cyclic carbonate versus copolymer involving two electronically different epoxides: epichlorohydrin and propylene oxide. The relative small activation energy difference between copolymer versus cyclic carbonate formation for the epichlorohydrin/CO₂ process (45.4 kJ/mol) accounts in part for the selective synthesis of copolymer to be more difficult in comparison with the propylene oxide/CO₂ case (53.5 kJ/mol). Direct observation of the propagating polymer-chain species from the binary (salen)CoX/MTBD (X = 2,4-dinitrophenoxide and MTBD = 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene) catalyst system by means of electrospray ionization mass spectrometry confirmed the perfectly alternating nature of the copolymerization process. This observation in combination with control experiments suggests possible intermediates involving MTBD in the CO₂/epichlorohydrin copolymerization process.