多种立构嵌段共轭双烯烃共聚物的合成与性能研究

In recent years, achievements were made to synthesis stereoblock copolymer consisting of different stereospecific sequences in one polymer chain, they show special physical properties from the original stereoregular polymer which could be applied as thermoplastic polymer. Stereoblock polydienes also attracted much attention for their diverse microstructures which could dramatically influence the properties of resulting materials. However, several problems emerged that the feasible catalytic systems are still limited, some polymerization process demanding strict conditions is not easy to control and the obtained stereoblock polymer is often with low stereoregularity. Besides, the study on the properties of stereoblock copolymers also requires more attentions. In the current project, we plan to design and synthesize several trans 1,4-b-cis-1,4 stereoblock PB, cis-1,4-b-1,2 regioblock PB, cis-1,4 and trans-1,4 multiblock PB with adjustable chain stereoregularity, stereotacticity and chain length ratios, to study the co-relationship of these stereoblock polybutadienes macrostructure with their mechanical properties, which is of significant importance in preparing excellent integral rubber to satisfy the demand of high performance tires in nowadays.

近些年来，立构嵌段聚合物的合成获得了人们的极大关注，它是由具有相同的结构单元但不同构型的嵌段链组成，独特的链结构可赋予此类嵌段共聚物一些新的性质。将结构多样的共轭二烯烃聚合物通过共价键链接在一起, 使其兼具不同结构聚合物的性能, 对于制备高性能橡胶材料同样具有重要的实用价值。但有限的催化体系、聚合操作不易控制、立构选择性不高等问题的出现，使得对于立构嵌段聚合物的结构与性能关系的研究仍然较少。本项目拟制备各嵌段链的区域和立构选择性可调、立构规整度可控、链段长度比例可调的顺反立构嵌段、顺1,4与间同1,2立构嵌段、以及超分子结构的顺反立构多嵌段等多种共轭双烯烃的立构嵌段共聚物，建立嵌段共聚物结构与性能的关系，本项目研究对于制备综合性能优异的集成橡胶，满足当下对高性能轮胎的要求具有重大的实际意义。

立构嵌段聚合物是由具有相同的结构单元但不同构型的嵌段链组成，独特的链结构可赋予此类嵌段共聚物一些新的性质。将结构多样的共轭二烯烃聚合物通过共价键链接在一起,使其兼具不同结构聚合物的性能,对于制备高性能橡胶材料同样具有重要的实用价值。本项目从催化剂的筛选出发，实现了对聚合物分子结构的精确控制，成功制备了反-顺两嵌段、顺-反多嵌段等几种立构嵌段共轭双烯烃共聚物，并初步建立起立构嵌段聚合物结构与性能的关系。此外，在本项目的研究中成功开发了具有可逆配位链转移聚合特征的稀土催化体系，方便高效地制备了几种极性官能化的共轭双烯烃聚合物，对制备高性能绿色轮胎奠定了基础。同时，研究了此稀土催化体系对丁二烯/异戊二烯及丁二烯/异戊二烯/月桂烯的共聚合行为，并与中国石油独山子石化公司展开技术合作，开展丁戊橡胶成套技术及中试催化剂配方优化的技术研究。综上，本项目研究对于制备综合性能优异的集成橡胶，满足当下对高性能轮胎的要求具有重大的实际意义。项目执行期间，在Materials Today Communications、高分子学报等期刊以第一作者发表基金标注文章3篇，授权中国发明专利1项，参加国内学术会议2次，获得辽宁省教育厅面上青年人才项目 (LJKZ0249)的资助。