离子液体催化合成聚碳酸酯反应过程及产品结构调控机制

项目名称： 离子液体催化合成聚碳酸酯反应过程及产品结构调控机制

项目编号： No.21476245

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 有机化学

项目作者： 孙剑

作者单位： 中国科学院过程工程研究所

项目金额： 90万元

中文摘要： 替代传统光气与二醇缩聚法，建立环氧烷烃与CO2共聚合成聚碳酸酯清洁工艺是聚碳酸酯领域技术发展的重要方向。针对现有研究催化体系结构复杂、成本高、适用性有限，离子液体研究不足等问题，结合离子液体结构可控、酸碱可调及多位点活化等独特性质，本项目拟开展离子液体催化CO2共聚合成聚碳酸酯反应过程及调控研究：以脂环族环氧环己烷，脂链族端位供电子环氧丙烷、端位吸电子环氧氯丙烷为模拟底物，设计合成2-3类铝、锌、锡等金属复配型（季铵、咪唑、三氮唑、四氮唑）离子液体，采用电喷雾质谱、核磁共振、原位红外及量化计算等手段，获取反应底物、离子液体路易斯酸碱性、阴阳离子空间结构、配位离去能力、取代基及氢键结构等对产物、结构、区域及立体选择性影响规律，基于反应动力学、热力学数据，构建离子液体催化新体系，获得聚碳酸酯结构调控新方法，揭示离子液体正负协同催化调控机理，为离子液体催化合成聚碳酸酯酯工艺技术发展提供科学基础。

中文关键词： 离子液体；二氧化碳；聚碳酸酯；反应规律；调控机制

英文摘要： Developing a cleaning process for the copolymerization of epoxide and CO2 to produce poly(carbonate) is an important direction in the technological development, substituting for the synthesis of poly(carbonate) via traditional phosgene method. The disadvantages of current catalysts such as complicated structure, high cost and low temperature applicability, lead to develop new kinds of catalysts. Based on the unique physical and chemical properties of ionic liquids, such as structure controllable, acid/base adjustable and component compatible, the investigation on the polycarbonate synthesis process catalyzed by Lewis acid-base ionic liquid is carried out. First, Lewis acidity/basicity and structure optimization of ionic liquids are realized via molecular simulation and computer calculation based on the ionic liquid hydrogen-bond network structure. Second, 2-3 kinds of Lewis acid-base complex ionic liquids are synthesized, in which, the cations are selected from a hydroxyl group or an amino-substituted imidazole, triazole and tetrazole heterocyclic compound, and the anions are aluminum, zinc, and tin multi-nuclear halides. Third, to obtain the effect laws of spatial structure of the cation and anion, substituent electronic effects, hydrogen bond network structure of product regioselectivity, molecular weight distribution and synthesis kinetics; Finally, by means of electrospray ionization mass spectrometrymass, NMR, in situ FT-IR and computer simulation reveals the copolymerization reaction mechanism,developing a new ionic liquids catalytic system, obtaining a new method on tailoring poly(carbonate) structure, and revealing the ionic liquids synergistic catalytic mechanism.The above research aims to provide the scientific basis for the technology development of ionic liquids catalytic synthesis of poly(carbonate).

英文关键词： ionic liquids;carbon dioxide;poly(carbonate);reaction rules;control mechanism