侧链液晶高分子多层次有序自组装的侧链间距依赖性

作为典型的软物质和功能材料，侧链液晶高分子（SCLCP）的主链和侧链具有显著的化学结构及动力学非均匀性。因此SCLCP研究的核心是如何理解并调控主、侧链间的相互作用。相邻侧链间的柔性主链长度，即侧链间距，是SCLCP的一个关键结构因素。但迄今这一因素对SCLCP液晶行为及粘弹性的影响尚未得到系统研究。本项目针对这一问题开展。拟合成一系列侧链接枝密度不同的SCLCP。运用高分子合成新方法，将以非环二烯易位（ADMET）聚合制备侧链位置明确、侧链间距可调的化学结构精确的SCLCP。所合成的SCLCP可以具有不同的侧链形状和主、侧链联结方式。我们力求定量揭示侧链间距对SCLCP的柔性间隔基“去偶合”效应及侧链“甲壳”效应的影响；揭示侧链间距在SCLCP多层次有序自组装过程中对微相分离、液晶转变、结晶等不同有序化机制的影响。通过调控凝聚态有序结构，我们将制备具有特殊粘弹性质的SCLCP功能体系。

As a typical soft matter and important functional materials, side-chain liquid crystalline polymers (SCLCPs) exhibit pronounced heterogeneities of chemistry and dynamics between their main- and side-chain. Therefore, the essential of SCLCP research is to understand and manipulate the interplay of main- and side-chain. The length of flexible backbone between side-chains, i.e., the side-chain spacing, is one of the key structure factors of SCLCP. Its influence on the liquid crystalline behavior and viscoelastic properties of SCLCP has not been systematically investigated so far, which will be the focus of this project. We will synthesize a series of SCLCP with different side-chain grafting density. Particularly, using the advanced polymerization method, acyclic diene metathesis (ADMET) polymerization, we will prepare the precision SCLCPs with precise location of side-chain and adjustable side-chain spacing. The side-chain shape and the manner of side-chain attached to main-chain will be varied. On the basis of newly designed SCLCPs, we aim to elucidate quantitatively how the variation of side-chain spacing will influence the well-known flexible “decoupling” effect and side-chain “jacketing” effect of SCLCP. The side-chain spacing effect on hierarchical self-assembly, which involves different mechanisms of microphase separation, liquid crystal transition, and crystallization, will be investigated. Upon control of the ordered structure, we will further prepare the SCLCP functional materials with unique viscoelastic properties.