功能性环状聚合物的精密合成及性能

Nowadays, cyclic polymers have attracted more and more attentions due to its unique performance; however, the synthesis of cyclic polymers has always been a challenge. This proposal focuses on the synthetic methodology of cyclic polymers as well as the synthesis and performance of functional cyclic polymers. The first synthetic methodology is based on ATRP-CuAAC Click and different solubility and volatility for different solvents by the utilization of evaporation-condensation-dissolution to maintain an extremely dilute solution for cyclization reaction, to develop an easy, economical, effective and a high-yield technique for cyclization. The second for cyclic synthesis technique is the utilization of an alkyl halide ATRP initiator bearing alkynyl group with ATRP copolymerization of two different monomers in the presence of sodium nitrine, monomer 1 can form a tertiary carbon radical, and monomer 2 can form secondary carbon radical. Thus, the polymerization can happen concurrently with the SN2 substitution reaction to produce a cyclic polymer in one step. The other keynote of this proposal is the synthesis of functional cyclic polymers with well-defined structures and topologic structures. The azobenzene, crown ether and β-CD functional groups are proposed to be introduced into the cyclic polymers. And, cyclic polymers with star, "8" structure, block structure and cycle-block-cycle structure will be designed and synthesized delicately. The properties and performance of theses cyclic polymers will be investigated and optimized. The implementation of this proposal would eventually set up and develop two easy-handle and highly effective techniques for the production of cyclic polymers, as well as explore and develop novel polymer materials with desirable performance based on cyclic polymers.

环状聚合物由于其独特的结构和性能受到了越来越多的关注，本项目将针对目前环状聚合物合成困难和性能研究较少的现状，对成环方法和工艺、新型成环反应、多种不同拓扑结构的功能性环状聚合物合成以及环状聚合物性能研究等方面进行较为全面的研究。通过项目研究，将a）发展可以实现大批量环状聚合物合成的方法；b）建立新型环状聚合物的合成方法，简化环状聚合物制备步骤；c）创新性的合成功能性环套环、环嵌段和珍珠链状聚合物，丰富环状聚合物的拓扑结构；d）获得环状聚合物的力学性能、结晶行为和玻璃化转变温度等常规物理性能的第一手数据，并将其与线性聚合物的相关性能进行对比，建立可供参考的数据体系；e）对功能性环状聚合物性能进行详细研究，建立拓扑结构对环状聚合物性能的影响规律。通过项目实施将大大推动国内在环状聚合物领域，特别是环状聚合物合成领域的研究，扩大国内环状聚合物合成领域研究在国际上的影响。

项目针对目前环状聚合物合成困难和性能研究较少的现状，项目小组根据项目申请书和计划书的要求，严格按年度计划实施研究内容，围绕环状聚合物的高效合成方法学、复杂拓扑环状聚合物合成以及功能性环状聚合物研究展开。通过项目研究，发展了可以实现大批量环状聚合物合成的方法；建立了新型环状聚合物的合成方法，简化环状聚合物制备步骤；创新性的合成了多种复杂拓扑结构环状聚合物、丰富环状聚合物的拓扑结构；对功能性环状聚合物性能进行详细研究，建立了拓扑结构对环状聚合物性能的影响规律。通过主办环状聚合物国际会议以及参加国际和国内会议，扩大了国内环状聚合物合成领域研究在国际上的影响。在项目基金资助下，共发表SCI 收录论文35 篇，获授权中国发明专利10项，参加国际会议12 次，主办国际环状聚合物合成及性能研讨会1 次，项目资助下，已培养博士毕业研究生4 名，硕士研究生12 名通过项目研究。项目实施大大推动了环状聚合物研究，进一步扩大了项目组在国内和国际环状聚合物领域以及高分子合成的影响力，圆满完成了项目预定目标。