氧硫化碳-环氧化物可控催化共聚及机理研究

项目名称： 氧硫化碳-环氧化物可控催化共聚及机理研究

项目编号： No.21274123

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 张兴宏

作者单位： 浙江大学

项目金额： 86万元

中文摘要： 聚硫代碳酸酯兼具聚碳酸酯和含硫聚合物的优势性能，在光导纤维、重金属离子吸附剂和锂离子电池材料等方面有广泛用途。但迄今尚无催化氧硫化碳（COS）和环氧化物交替共聚合成聚硫代碳酸酯的报道，催化二硫化碳（CS2）和环氧化物共聚也只能得到含多种硫代碳酸酯链节的聚合产物，聚合可控性差，关键制约因素是催化过程中单体间的氧－硫交换反应导致聚合产物链结构复杂。针对这一问题，本项目将系统地研究氧－硫交换反应机理，以此为指导，拟制备烷氧基和酚氧基化的双金属氰化络合物（DMCC）催化剂、并通过引入亲金属性和疏水性的"两性"助催化剂等措施来抑制氧－硫交换反应，实现催化COS－环氧化物可控共聚、合成结构明确的聚硫代碳酸酯，研究催化共聚动力学和机理，在理论上将发展新的共聚机理和聚硫代碳酸酯的可控合成方法，丰富高分子合成化学和C1化学的内容，在应用上获得新的含硫高分子材料。

中文关键词： 羰基硫；环氧化物；共聚；聚单硫代碳酸酯；催化

英文摘要： Poly (thiocarbonate) has attractive features of polycarbonate and sulfur-containing polymer. It is potential to the application of photoconductive fiber, heavy metal scavengers and lithium ion battery materials due to its high optical and thermal properties, excellent chemical resistance, and heavy-metal recognition ability. However, to our knowledge, there is still no report on synthesizing well-defined poly (thiocarbonate)s by direct catalysis of alternating copolymerization of carbonyl sulfide (COS) and epoxides, and it is also unsuccessful to synthesize poly (dithiocarbonate)s by catalyzing alternating copolymerization of CS2 and epoxides. This is attributed to the oxygen/sulfur exchange reaction between monomers during copolymerization, which caused multiple thiocarbonate units (i.e.: -S(O)CO-, -S(O)CS-, -S(S)CO- and -S(S)CS-) in the copolymer. Aimed to solve this problem, this project will firstly focus on disclosing the mechanism of the oxygen/sulfur exchange reaction in detail. Under the guidance of the proposed mechanism, we then intend to prepare double metal cyanide complex (DMCC) catalysts with zinc-alkoxy or zinc-phenoxy groups, and use metal-nucleophilic and hydrophobic "gender" cocatalyst to suppress the oxygen- sulfur exchange reaction, to realize an easy-to-control alternating copolymerization

英文关键词： Carbonyl Sulfide；Epoxide；Copolymerization；Poly(monothiocarbonate)s；Catalysis