异戊二烯高反-1,4选择性聚合稀土催化剂的合成及其聚合物的功能化

项目名称： 异戊二烯高反-1,4选择性聚合稀土催化剂的合成及其聚合物的功能化

项目编号： No.21304088

项目类型： 青年科学基金项目

立项/批准年度： 2014

项目学科： 数理科学和化学

项目作者： 刘东涛

作者单位： 中国科学院长春应用化学研究所

项目金额： 25万元

中文摘要： 高反-1,4 聚异戊二烯具有滚动阻力小，动态生热低以及耐磨性好等优点，是一种新型高性能轮胎用橡胶材料，同时还可以用做形状记忆材料，医用矫形材料等。迄今能催化异戊二烯反-1,4 聚合的催化体系还十分有限。本课题拟在前期工作基础上设计与合成胺基双膦亚胺和膦亚胺-亚胺稀土配合物，研究这些配合物在助催化剂活化下对异戊二烯的反-1,4聚合的催化作用；考察配体的结构、中心金属和引发基团及助催化剂的种类、聚合反应条件对催化体系的活性和聚合产物微观结构的影响；分离聚合反应的活性种，提出相应的聚合机理，建立配体结构-催化剂活性-聚合物性能的关系，为催化剂的有效设计提供指导。同时利用链末端功能化的方法，在高反-1,4聚异戊二烯链末端引入呋喃环，并与含有活泼双键的聚合物链或化合物通过Diels-Alder反应制备嵌段结构和星形结构的共聚物。研究共聚物的微观相结构和力学性能等，为制备高性能胎面胶提供新材料。

中文关键词： 稀土配合物；异戊二烯；月桂烯；反-1;4选择性聚合；嵌段共聚物

英文摘要： Highly trans-1,4 regulated polyisoprene (TPI) possesses excellent dynamic mechanical properties, including excellent anti-fatigue properties, low rolling resistance, low heat buildup, good strength and low abrasion loss. It is now an important component of long-life "green" tires. TPI is also widely used in heat-stimulated shape memory materials, medicine used orthopaedic materials, and so on. Up to now, however, the catalyst systems that can initiate the trans-1,4 selective polymerization of isoprene have remained less explored. Based on our previous results, the purpose of the project is to design and synthesize new rare-earth metal complexes with amino-bisphosphinimine ligands and phosphinimino-imine ligands; the catalytic behavior of the resultant complexes under the presence of activators towards the trans-1,4 selective polymerization of isoprene will be investigated; the influences of the electronic and steric effects of ligands, the types of the central metals, initiation groups as well as the activators, and the polymerization conditions on the microstructures of the obtained polymer will be examined; the mechanism of the polymerization will be presented by means of isolating the reaction intermediate, and the relationship between the structure of the ligand-catalytic performances-properties of the polym

英文关键词： rare-earth-metal complex；isoprene；myrcene；trans-1;4 selective polymerization；block copolymer