新型基于大体积甲基丙烯酸酯类手性聚合物的不对称合成与性能研究

项目名称： 新型基于大体积甲基丙烯酸酯类手性聚合物的不对称合成与性能研究

项目编号： No.21474024

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 无机化学

项目作者： 沈军

作者单位： 哈尔滨工程大学

项目金额： 83万元

中文摘要： 大体积甲基丙烯酸酯及其同系物能够形成高度全同立构的手性聚合物，其大体积侧基是形成稳定螺旋构象的关键。但直至目前，其手性单元的引入主要通过手性配体或引发剂来实现。同时，噁唑啉类聚合物由于在生物医学等领域展现出的应用潜能近年来已成为研究热点。针对该研究现状，通过不对称阴离子和自由基共聚方法，将具有不同结构的手性噁唑啉单体引入具有螺旋结构的甲基丙烯酸三芳甲酯（和丙烯酰胺）主链中，通过手性噁唑啉单元诱导主链形成单手螺旋构象，并赋予聚合物新的结构特征，设计合成具有高度立构规整性、高光学活性和新功能特性的甲基丙烯酸酯（和丙烯酰胺）类手性聚合物，并对新型共聚物的聚合机理及其分子结构与性能之间关系进行系统研究。进一步揭示不同聚合条件及共聚单体的分子结构与组成对该类聚合物的二级结构、立构规整性、光学活性以及手性识别性能的影响规律，为探索开发新型甲基丙烯酸酯（和丙烯酰胺）类手性聚合物和功能高分子提供新思路。

中文关键词： 不对称合成；大体积甲基丙烯酸酯；手性噁唑啉；手性聚合物；螺旋构象

英文摘要： Bulky methacrylate monomers and their analogues can form chiral polymers with high isotacticity, where the stable one-handed helical conformation is mainly governed by the bulkiness of the side groups. By far, the introduction of a chiral unit is mainly realized by a chiral ligand or initiator. On the other hand, poly(2-oxazoline) exhibits attractive potential in multidisciplinary applications including biomedical fields and has become a hot topic in recent years. Based on these facts, asymmetric anionic and radical copolymerization of oxazoline and triarylmethyl methacrylate (and methacrylamide) were designed and performed to develop novel optically active methacrylate (and methacrylamide) polymers with high isotacticity, high optical activity and new functions by introducing chiral oxazoline monomers with different structures into the helical structure of the main chain composed of triarylmethyl methacrylate (and methacrylamide). The chiral oxazoline unit was expected to induce the one-handed helical conformation of the main chain and also enable the obtained polymers to possess new structural characteristics. The polymerization mechanism in different systems was systematically investigated, and the relationship between the molecular structure and property of the polymers was then evaluated to elucidate the effects of molecular structure and incorporation of the comonomers on the higher order structure, tacticity, optical activity and chiral recogntion ability of the obtained polymers. This will open up a new idea for the development in asymmetric polymerization, and also design and development of new chiral helical methacrylate (and methacrylamide) polymers and the related new polymer-based functional materials.

英文关键词： asymmetric synthesis;bulky methacrylate;chiral oxazoline;chiral polymer;helical conformation