Probing the mechanistic aspects of the chromium salen catalyzed carbon dioxide/epoxide copolymerization process using in situ ATR/FTIR
Probing the mechanistic aspects of the chromium salen catalyzed carbon dioxide/epoxide copolymerization process using in situ ATR/FTIR
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DOI：
10.1016/j.cattod.2004.09.017
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发表时间：
2004-12
期刊：
影响因子：
5.3
通讯作者：
D. Darensbourg;Jody L. Rodgers;Ryan M. Mackiewicz;Andrea L. Phelps
中科院分区：
文献类型：
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作者：
D. Darensbourg;Jody L. Rodgers;Ryan M. Mackiewicz;Andrea L. Phelps
二氧化碳与环氧化物的共聚合研究，是本研究组近十年来的主要研究项目。在此期间，衰减全反射傅里叶变换红外（ATR/FTIR）光谱法的结合大大提高了动力学和机理的调查进行。尽管有帮助，但也存在一些困难，例如，我们在同一时期发现并克服了相分离。最大的进步是通过引入2-（3，4-环氧环己基）-乙基三甲氧基硅烷（TMSO）作为环氧化物进行准确的动力学研究。在这里，我们讨论了该技术的发展成为我们实验室的支柱之一，我们最近的催化剂系统使用（salen）CrIIIX/助催化剂，其中salen：N，N′-双（亚水杨基）-1，2-乙二胺，X：Cl−或N3−和助催化剂：N-甲基咪唑，膦和PPN+盐。通过改变助催化剂、配体结构和引发剂，该催化剂体系已被证明是目前正在研究的最具工业可行性的催化剂之一。
Studies of the copolymerization of CO2and epoxides have been the staple of our group's research program for the better part of a decade now. During that time, the incorporation of attenuated total reflectance Fourier transform infrared (ATR/FTIR) spectroscopy has greatly enhanced the kinetic and mechanistic investigations performed. However helpful, there are some difficulties, e.g., phase partitioning, that we have discovered and overcome in that same time period. The greatest step forward was achieved by the incorporation of 2-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane (TMSO) as an epoxide for performing accurate kinetic studies. Herein, we discuss the development of this technique into one of the mainstays within our laboratories, highlighted by our most recent catalyst system that utilizes (salen)CrIIIX/cocatalyst where salen: N,N′-bis(salicylidene)-1,2-ethylenediimine, X: Cl−or N3−and cocatalyst: N-methylimidazole, phosphines and PPN+salts. Through altering the cocatalyst, ligand architecture and initiator, this catalyst system has proven to be one of the most industrially viable catalysts currently being studied.