树枝-甲壳型液晶嵌段聚合物的合成及其本体性质研究.docVIP

  树枝-甲壳型液晶嵌段聚合物的合成及其本 体性质研究# 吴极文，汤慧，武培怡** 5 10 15 20 25 30 35 40 （复旦大学高分子科学系 聚合物分子工程国家重点实验室, 上海 200433） 摘要：利用树枝状引发剂引发甲壳型液晶单体的聚合，制备了树枝-线性液晶嵌段共聚物。 研究表明树枝段与液晶链段热力学上不相容，样品形成层状相分离结构且相分离尺寸随液晶 聚合物分子量而变化，液晶链段在其富集微区中采用叉指排列方式，其液晶相结构由有序度 较高的六方柱状向列相退化为有序度较低的柱状向列相，推测液晶有序度的降低可能与微相 分离导致分子被限制在受限空间内有关。相较于其他树枝-线性嵌段聚合物，该包含液晶链 段的树枝-线性嵌段聚合物的本体行为与相分离结构间存在相互影响，聚合物最终的微结构 取决于液晶有序堆积需求与微相分离而造成空间位阻二者间的平衡。 关键词：高分子; 树枝状分子；液晶聚合物；嵌段聚合物 中图分类号：请查阅《中国图书馆分类法》 Synthesis and thermotropic mesomorphic behavior of dendron–liquid crystalline block copolymers Wu Jiwen, Tang Hui, Wu Peiyi (State Key Laboratory of Molecular Engineering of Polymers, Department of Macromolecular Science and Laboratory of Advanced Materials, Fudan University, Shanghai, 200433) Abstract: Novel dendron–liquid crystalline block copolymers integrating dendron molecules and liquid crystalline polymer blocks were prepared by atom transfer radical polymerization. Thermal property investigation of the copolymers revealed that the dendron molecule and the liquid crystalline polymer block were immiscible and the phase transition of the dendron molecule was restrained. The subtle interplay between the thermotropic mesomorphic behaviors and the microphase structure in these copolymers was discussed. With increasing molecular weight of the liquid crystalline block, a morphological evolution from bilayer to interdigitated lamellar structure was proposed. More importantly, a less-ordered columnar nematic phase instead of a hexatic columnar nematic phase was identified. The degradation of the hierarchical packing was attributed to the confinement effect originating from the interdigitated microphase structure. Key words: polymer; dendron molecule; liquid crystalline polymer; block copolymer 0 引言 近年来将超支化结构、星状结构或树枝分子等非线性结构引入嵌段共聚物而研究分子的 拓扑结构对共聚物相行为的影响颇受关注。其中，树枝分子由于具有完美三维结构、分子量 精确可控及分子量单分散等优点而被广泛应用于构造新型的树枝-线性非对称性嵌段共聚物 [1-11] 的影响也具有重要意义。传统的液晶聚合物一般可分为侧链型液晶聚合物与主链型液晶聚合 物。主链型液晶聚合物其液晶单元位于主链之中，合成过程一般较为复杂。而对于侧链型液 晶聚合物，其液晶单元作为侧基与主链相连接，其一般可以通过较为简便的聚合过程制备