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设计、合成了一系列含有手性烷氧基末端的乙烯基二联苯单体,进行了普通自由基、原子转移自由基以及负离子聚合反应.所有单体中,只有手性烷氧基苯基位于乙烯基邻位的聚合物的比旋光度与其单体相比有比较大的区别,且在对应于其侧基的紫外吸收处呈现明显不同于单体的Cotton效应,说明可能形成了某一方向占优的螺旋构象.在所研究范围内,聚合条件和聚合物分子量对聚合物的旋光度没有明显的影响.比较负离子聚合和自由基聚合所获得聚合物的比旋光度发现,负离子聚合有利于增加聚合物螺旋链构象的完整性.切除能形成螺旋链的聚合物侧基上的手性烷氧基,所得到的聚合物虽然不含手性原子但依然表现出光学活性,说明其具有一定的手性记忆效应.
A series of vinylbiphenyl monomers containing a chiral alkoxy terminal were designed and synthesized, and the common free radical, atom transfer radical and anionic polymerization were carried out.Only monomers, only chiral alkoxyphenyl The specific rotation of the vinyl ortho-position polymer is significantly different from that of its monomer, and at the UV absorption corresponding to its pendant group, the Cotton effect obviously differs from that of the monomer, indicating that it is possible to form a certain Direction dominated the helical conformation.In the studied range, polymerization conditions and the molecular weight of the polymer had no significant effect on the optical rotation of the polymer.Comparing the specific rotation of the polymers obtained by anionic polymerization and free-radical polymerization found that anionic polymerization Conducive to increasing the integrity of the conformation of the polymer helical chain.Collecting the chiral alkoxy group on the side chain of the polymer capable of forming a helical chain, the obtained polymer, though not containing chiral atoms, still shows optical activity, indicating that it has Certain chiral memory effect.