Preparation of New Amphiphilic Liquid-Crystal Diblock Copolymers Bearing Side-on Cholesteryl Mesogen and Their Self-aggregation

doi:10.6023/A12121107

Acta Chimica Sinica ›› 2013, Vol. 71 ›› Issue (03): 351-359.DOI: 10.6023/A12121107 Previous Articles Next Articles

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具有侧挂胆固醇液晶元的两亲嵌段功能大分子的合成及自组装研究

胡方振^a,b, 陈圣典^b, 李慧^b, 孙景景^b, 盛瑞隆^b, 罗挺^b, 曹阿民^b

a 华东理工大学材料科学与工程学院上海 200237;
b 中国科学院上海有机化学研究所高分子材料研究室上海 200032

投稿日期:2012-12-27 发布日期:2013-01-23
通讯作者: 曹阿民 E-mail:acao@mail.sioc.ac.cn
基金资助:
项目受国家自然科学基金(Nos.20874114,21174160,21002116)资助.

Preparation of New Amphiphilic Liquid-Crystal Diblock Copolymers Bearing Side-on Cholesteryl Mesogen and Their Self-aggregation

Hu Fangzhen^a,b, Chen Shengdian^b, Li Hui^b, Sun Jingjing^b, Sheng Ruilong^b, Luo Ting^b, Cao Amin^b

a School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237;
b Laboratory for Polymer Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2012-12-27 Published:2013-01-23
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 20874114, 21174160, 21002116).

Amphiphilic block copolymers bearing rigid hydrophobic liquid crystal mesogen have recently attracted broad interests since they could spontaneously self-assemble into functional objects at the micron and/or nanometer scales, and these soft matters bearing high-order hierarchical structures have potential applications in micro-reactors, advanced catalysts, biosensors, drug delivery, biotechnology and so forth. In this work, we designed and successfully prepared a new series of amphiphilic liquid crystal poly(glyceryl methacrylate)-b-poly(6-cholesteryloxyhexyl methacrylate) (PGMA-b-PMA6Chol) with hydrophobic PMA6Chol block bearing end-on cholesteryl mesogen through sequential controlled reversible addition- fragmentation chain transfer polymerization (RAFT) and successive removal of ketal protection groups. Then, their structures and comonomer composition were examined by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). Liquid crystal phase structures and their transition as well as thermal stability of the prepared LC copolymers were characterized by differential scanning calorimeter (DSC), polarized optical microscope (POM), 2D small angle X-ray scattering (2D-SAXS) and thermogravimetric analytic instrument (TGA). Moreover, self-aggregation of these amphiphilic LC block copolymers in mixed solution was investigated by means of UV spectrometer, and the aggregate sizes and morphologies were examined by scanning electron microscopy (SEM) and dynamic light scattering (DLS), respectively. As a result, it was revealed that the LC to isotropic phase transition temperature (T_LC-I) of as-synthesized LC block copolymers increased with an increase in rigid LC block content, and the presence of bishydroxyl groups of hydrophilic PGMA strongly influenced the self-assembly and LC phase of rigid hydrophobic block in bulk state. In mixed solvent, the synthesized amphiphilic LC copolymers were found to preferably self-aggregate into core-shell spherical objects with average sizes spanning a range from 0.7 to 2.0 μm when the hydrophobic LC block content was less than 93%, in contrast, the LC copolymer with 93 wt% LC block tended to form open hollow spherical aggregates, showing interesting thermal responsive particle sizes in aqueous solution.

Key words: controlled polymerization, LC block copolymer, amphiphilic polymer, cholesteryl mesogen, self-assembly

Cite this article

Hu Fangzhen, Chen Shengdian, Li Hui, Sun Jingjing, Sheng Ruilong, Luo Ting, Cao Amin. Preparation of New Amphiphilic Liquid-Crystal Diblock Copolymers Bearing Side-on Cholesteryl Mesogen and Their Self-aggregation[J]. Acta Chimica Sinica, 2013, 71(03): 351-359.

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具有侧挂胆固醇液晶元的两亲嵌段功能大分子的合成及自组装研究

Preparation of New Amphiphilic Liquid-Crystal Diblock Copolymers Bearing Side-on Cholesteryl Mesogen and Their Self-aggregation

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