Darensbourg Donald J, Rodgers Jody L, Fang Cindy C
Department of Chemistry, Texas A&M University, College Station, Texas 77843, USA.
Inorg Chem. 2003 Jul 28;42(15):4498-500. doi: 10.1021/ic034363m.
The copolymerization of 2-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane and carbon dioxide catalyzed by (salen)Cr(III)Cl (H(2)salen = N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-ethylenediimine) with 2.5 equiv of N-MeIm as cocatalyst affords a polycarbonate devoid of polyether linkages, along with only a trace quantity of cyclic carbonate. The presence of the trimethoxysilane functionality in the epoxide not only provided the reactant monomer and product copolymer high solubility in liquid carbon dioxide but also provided the ability to cross-link the copolymer and thereby greatly alter the physical properties of the thus formed polycarbonate. In addition, the enhanced solubility of the copolymer in liquid CO(2) furnishes a ready means of removing the highly colored metal catalyst from the polycarbonate product.
由（salen）Cr（III）Cl（H₂salen = N，N'-双（3,5-二叔丁基水杨基亚甲基）-1,2-乙二胺）催化、2.5当量的N-甲基咪唑作为助催化剂，使2-（3,4-环氧环己基）乙基三甲氧基硅烷与二氧化碳发生共聚反应，得到一种不含聚醚键的聚碳酸酯，同时仅生成痕量的环状碳酸酯。环氧化物中三甲氧基硅烷官能团的存在不仅使反应物单体和产物共聚物在液态二氧化碳中有高溶解性，还赋予了共聚物交联的能力，从而极大地改变了由此形成的聚碳酸酯的物理性质。此外，共聚物在液态CO₂中溶解性的增强为从聚碳酸酯产物中除去高显色金属催化剂提供了一种简便方法。
