苯并菲盘状侧链液晶聚合物的大分子工程

发布时间：2018-03-19 11:13

本文选题：侧链盘状液晶聚合物　切入点：分子量效应　出处：《高分子学报》2017年10期 　论文类型：期刊论文

【摘要】：盘状液晶聚合物兼具盘状液晶的光电性能和聚合物的柔韧性以及优异的成膜加工性能,有望发展成为新一代先进有机聚合物柔性光电功能材料.本文介绍苯并菲盘状侧链液晶聚合物的研究进展,主要结合我们研究组的工作,重点评述采用受控/活性自由基聚合方法可控合成这类侧链液晶聚合物以及对分子量效应和间隔基长度影响等基本问题的阐明.我们采用可逆加成-断裂链转移(RAFT)聚合第一次成功实现了分子量窄分布的苯并菲聚丙烯酸酯侧链盘状液晶聚合物的可控制备.首先提出盘单元局部簇集的分立短柱堆积(DCS)模型,合理解释了聚合度20左右出现的显著分子量效应,尤其揭示并提出了盘状侧链液晶聚合物的正耦合效应(PCE)理论,即短间隔基的较强耦合作用更有利于其有序柱状相的形成,与棒状侧链液晶聚合物经典的柔性长间隔基去耦合理论形成鲜明对照,补充了缺失的理论短板.基于这些原则,我们设计合成的丁氧基苯并菲聚丙烯酸酯侧链盘状液晶聚合物,经飞行时间谱(TOF)测试,表现出比文献报道值高1~2个数量级的载流子迁移率.进一步在手性客体分子掺杂诱导组装形成单手性螺旋结构聚合物复合物,以及拓扑受限环状聚合物和嵌段共聚物的受控制备等方面开展了比较系统的大分子工程实践.盘状侧链液晶聚合物的可控制备及其显著不同于棒状液晶聚合物体系的一些基本特征的阐明,为这类重要有机聚合物半导体材料的理性设计与可控合成提供理论指导,也为加速推进其光电器件化应用奠定基础.
[Abstract]:Disk liquid crystal polymer has both the photoelectric properties of disk liquid crystal, the flexibility of polymer and the excellent film-forming performance. It is expected to develop into a new generation of advanced organic polymer flexible optoelectronic functional materials. This paper introduces the research progress of benzophenol disk-chain liquid crystal polymer, mainly combined with the work of our research group. The controlled / active radical polymerization method for the controllable synthesis of this kind of side chain liquid crystalline polymers and their effects on molecular weight effect and spacer length are reviewed in detail. Reversible addition-break chain transfer is used. The controlled preparation of poly (phenanthrene polyacrylate) side-chain disk liquid crystal polymer with narrow molecular weight distribution was successfully achieved for the first time. A discrete short column stacking model for local clustering of disk units was proposed. The remarkable molecular weight effect about 20 degree of polymerization is reasonably explained, and the PCEtheory of the positive coupling effect of the liquid crystal polymer with disk-like side chain is revealed and put forward, that is, the strong coupling effect of the short spacer group is more favorable to the formation of the ordered columnar phase. In contrast to the classical decoupling theory of flexible long spaced group of liquid crystalline polymer with rod chain, the missing theoretical short plate is supplemented. Based on these principles, we designed and synthesized the side chain disk-like liquid crystal polymer of butoxy benzophenanthrene polyacrylate. Time of flight spectroscopy (TOF) measurements showed that the carrier mobility was 1 ~ 2 orders of magnitude higher than the reported values in the literature. Furthermore, the chiral guest molecules were doped and assembled to form a single chiral helical polymer complex. The controlled preparation of topologically confined ring polymers and block copolymers has been carried out systematically in the field of macromolecular engineering. Controllable preparation of Disc side chain liquid Crystal Polymers and their differences from Rod liquid Crystal Polymers. The elucidation of some of the basic features of the system, It provides theoretical guidance for the rational design and controllable synthesis of this kind of important organic polymer semiconductor materials, and also lays a foundation for accelerating the application of optoelectronic devices.
【作者单位】：南京大学化学化工学院生命化学协同创新中心高性能高分子材料与技术教育部重点实验室;
【基金】：国家自然科学基金(基金号21574062)资助项目
【分类号】：O631.1;O753.2

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