Manipulating Molecular Shapes and Phase Structures of Mesogen-Jacketed Liquid Crystalline Polymers: From Sheet-like to Rod-like Molecule and from Smectic to Columnar Phase

Jun-feng Zheng; Yun-chong Ge; Xiao-fan Cheng; Ya-ting Wu; Peng Xu; Er-qiang Chen

doi:10.11777/j.issn1000-3304.2023.23031

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Manipulating Molecular Shapes and Phase Structures of Mesogen-Jacketed Liquid Crystalline Polymers: From Sheet-like to Rod-like Molecule and from Smectic to Columnar Phase

Research Article | 更新时间：2023-08-21

- Manipulating Molecular Shapes and Phase Structures of Mesogen-Jacketed Liquid Crystalline Polymers: From Sheet-like to Rod-like Molecule and from Smectic to Columnar Phase
- ACTA POLYMERICA SINICA Vol. 54, Issue 9, Pages: 1343-1354(2023)
- 作者机构：
  
  1.南京林业大学化学工程学院应用化学系南京 210037
  2.北京大学化学与分子工程学院高分子科学与工程系北京 100871
- 作者简介：
  
  Jun-feng Zheng, E-mail: jfzheng@njfu.edu.cn
  Peng Xu, E-mail: xupeng@njfu.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23031
  CLC：
- Published：20 September 2023，
  
  Published Online：08 June 2023，
  
  Received：19 February 2023，
  
  Accepted：18 April 2023
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郑军峰,葛云翀,程晓帆等.甲壳型液晶高分子的分子形状和相结构调控：从片状分子到柱状分子和从层状相到柱状相[J].高分子学报,2023,54(09):1343-1354.

Zheng Jun-feng,Ge Yun-chong,Cheng Xiao-fan,et al.Manipulating Molecular Shapes and Phase Structures of Mesogen-Jacketed Liquid Crystalline Polymers: From Sheet-like to Rod-like Molecule and from Smectic to Columnar Phase[J].ACTA POLYMERICA SINICA,2023,54(09):1343-1354.
郑军峰,葛云翀,程晓帆等.甲壳型液晶高分子的分子形状和相结构调控：从片状分子到柱状分子和从层状相到柱状相[J].高分子学报,2023,54(09):1343-1354. DOI： 10.11777/j.issn1000-3304.2023.23031.

Zheng Jun-feng,Ge Yun-chong,Cheng Xiao-fan,et al.Manipulating Molecular Shapes and Phase Structures of Mesogen-Jacketed Liquid Crystalline Polymers: From Sheet-like to Rod-like Molecule and from Smectic to Columnar Phase[J].ACTA POLYMERICA SINICA,2023,54(09):1343-1354. DOI： 10.11777/j.issn1000-3304.2023.23031.

摘要

为调控甲壳型液晶高分子(MJLCPs)的分子形状和相结构，以“苯-苄酯-苯”为柔性连接基团设计了一个新的MJCLP

，为对比研究，又设计了一个化学结构相似但含有“苯-酯-苯”刚性连接基团的MJLCP

. 研究结果表明，参考聚合物

呈现稳定的层状液晶相，其分子形状应为片状构象；目标聚合物

低温时形成层状液晶相，高温则为柱状液晶相，其分子形状应分别为片状和棒状. 本研究提出了

的分子形状和相转变的机理：低温时，“苯-苄酯-苯”采取反式构象，侧链类似于棒状液晶基元，整个分子为片状，进而形成层状液晶相；高温时，“苯-苄酯-苯”采取旁氏构象，侧链对主链的甲壳效应增加，驱动整个分子为棒状，进而形成柱状液晶相. 通过在MJLCPs的侧链中引入“苯-苄酯-苯”柔性连接基团，实现了MJLCPs的分子形状和相结构调控.

Abstract

Aiming at manipulating the molecular shapes and phase structures of mesogen-jacketed liquid-crystalline polymers (MJLCPs) polymers

we designed a new MJLCP

containing the flexible "benzene-benzyl ester-benzene" units in its side-chains and another MJLCP

as reference containing the rigid "benzene-ester-benzene" units.

renders extremely stable lamellar liquid crystalline phase probably with sheet-like conformation. However

forms lamellar liquid crystalline phase at the low-temperature range and columnar liquid crystalline phase at the high-temperature range

probably with sheet-like and rod-like conformations

respectively. We also proposed the mechanisms for transitions of molecular shapes and phase structures of

: at the low temperature range

the "benzene-benzyl ester-benzene" units mainly adopt the tans conformation and hence the side-chains behave like flexible rod-like mesogens

leading to the sheet-like molecules and their further lamellar packing; at the high temperature range

the "benzene-benzyl ester-benzene" units mainly adopt the gauche conformation and thus increases their jacketing effect on the main-chain

generating rod-like molecules and further columnar packing. In this work

through incorporating the flexible connecting units

we successfully manipulated the molecular shapes and phase structures of a MJLCP. This work will pave a way to tune molecular shapes and phase structures of side-chain liquid crystalline polymers.

关键词

甲壳型液晶高分子层状液晶相柱状液晶相片状分子柱状分子

Keywords

Mesogen-jacketed liquid crystalline polymers (MJLCPs)Lamellar liquid crystalline phaseColumnar liquid crystalline phaseSheet-like moleculeRod-like molecule

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