Acta Chimica Sinica ›› 2010, Vol. 68 ›› Issue (04): 351-357. Previous Articles     Next Articles

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氢键缔合主链超分子液晶聚合物: 间隔基及扩展介晶元长度的影响研究

岳力挽1,2,张淑静1,吴斌1,陆正宇1,方江邻*,2,谌东中*,1   

  1. (1南京大学化学化工学院高分子科学与工程系 介观化学教育部重点实验室 南京 210093)
    (2南京大学现代分析中心 南京 210093)
  • 投稿日期:2009-03-26 修回日期:2009-07-22 发布日期:2010-02-28
  • 通讯作者: 谌东中 E-mail:cdz@nju.edu.cn
  • 基金资助:

    国家自然科学基金

Hydrogen-bonding Associated Main-chain Supramolecular Liquid-crystalline Polymers: Influence of Variant Spacers and Rigid Cores

Yue Liwan1,2 Zhang Shujing1 Wu Bin1 Lu Zhengyu1 Fang Jianglin*,2 Chen Dongzhong*,1   

  1. (1 Key Laboratory of Mesoscopic Chemistry of Ministry of Education, Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, China)
    (2 Center for Materials Analysis, Nanjing University, Nanjing 210093, China)
  • Received:2009-03-26 Revised:2009-07-22 Published:2010-02-28
  • Contact: CHEN Dongzhong E-mail:cdz@nju.edu.cn

A series of hydrogen-bonding associated main-chain complexes based on dipyridyl and dicarboxylic acid derivatives have been prepared by slow solvent evaporation, and a comparative investigation has been conducted on their thermotropic phase transitions and liquid crystalline (LC) behavior by FTIR, DSC and polarized optical microscopy. All the complex series based on 4',4''-dicarboxy-1,6-diphenoxyhex- ane (C6-2COOH) and 4',4''-dicarboxy-1,10-diphenoxydecane (C10-2COOH) possessed higher melting and clearing points, usually showed soft crystal or crystalline smectic phases and crystal polymorphs except C10-2COOH/p-PhBPy complex displaying also an enantiotropic nematic phase, while the complexes based on 4,4'-dicarboxy-α,ω-diphenoxy tetraethyleneglycol ether (C8O4-2COOH) with a longer flexible spacer exhibited monotropic fluidic smectic SmA and/or nematic phases. On the other hand, for those complexes based on such variant dipyridyls as 4,4'-bipyridine (4,4'-BPy), trans-1,2-bis-(4-pyridyl)ethene (4,4'-BPyE) and bis-isonicotinic ester of hydroquinone (p-PhBPy) with the same dicarboxylic acid, the LC order decreased and the fluidity increased accordingly. This kind of phase transition behavior could be mainly ascribed to the decrease in rigidity and increase in deformability and polarity from 4,4'-BPy to 4,4'-BPyE then to p-PhBPy. Furthermore, some discrepancies in earlier literature have been pointed out and our results may provide guidance for hydrogen-bonding association, in particular for the design and assembly of supramolecular polymers based on carboxylic acid/pyridyl pairs.

Key words: liquid crystal, supramolecular polymer, carboxy-pyridyl hydrogen bonding association, fluidic smectic phase, nematic phase