Synthesis and Self-assembly of Asymmetric Molecular Brushes with Azobenzene-containing Side Chains

Yuan Yao; Pin He; Xin-feng Tao; Bin-bin Xu; Shao-liang Lin

doi:10.11777/j.issn1000-3304.2023.23269

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Synthesis and Self-assembly of Asymmetric Molecular Brushes with Azobenzene-containing Side Chains

Research Article | 更新时间：2024-04-16

- Synthesis and Self-assembly of Asymmetric Molecular Brushes with Azobenzene-containing Side Chains
  增强出版
- Acta Polymerica Sinica Vol. 55, Issue 4, Pages: 407-418(2024)
- 作者机构：
  
  上海市先进聚合物材料重点实验室华东理工大学材料科学与工程学院上海 200237
- 作者简介：
  
  Bin-bin Xu, E-mail: binbinxu@ecust.edu.cn
  Shao-liang Lin, E-mail: slin@ecust.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23269
  CLC：
- Published：20 April 2024，
  
  Published Online：26 January 2024，
  
  Received：21 November 2023，
  
  Accepted：15 December 2023
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姚远, 何品, 陶鑫峰, 徐彬彬, 林绍梁. 含偶氮苯侧链不对称分子刷聚合物的合成及其自组装研究. 高分子学报, 2024, 55(4), 407-418

Yao, Y.; He, P.; Tao, X. F.; Xu, B. B.; Lin, S. L. Synthesis and self-assembly of asymmetric molecular brushes with azobenzene-containing side chains. Acta Polymerica Sinica, 2024, 55(4), 407-418
姚远, 何品, 陶鑫峰, 徐彬彬, 林绍梁. 含偶氮苯侧链不对称分子刷聚合物的合成及其自组装研究. 高分子学报, 2024, 55(4), 407-418 DOI： 10.11777/j.issn1000-3304.2023.23269.

Yao, Y.; He, P.; Tao, X. F.; Xu, B. B.; Lin, S. L. Synthesis and self-assembly of asymmetric molecular brushes with azobenzene-containing side chains. Acta Polymerica Sinica, 2024, 55(4), 407-418 DOI： 10.11777/j.issn1000-3304.2023.23269.

摘要

设计合成了含有2-羰基溴和烷基氯基团的功能性丙烯酸酯单体(Br-acrylate-Cl)，利用可逆加成断裂链转移(RAFT)聚合得到大分子试剂poly(Br-acrylate-Cl). 首先通过poly(Br-acrylate-Cl)引发偶氮苯丙烯酸酯单体(Azo)的原子转移自由基聚合(ATRP)，然后用取代反应接入六甘醇修饰的四苯乙烯(OH-TPE-HEG)，合成了同时含有偶氮苯侧链、四苯乙烯侧基和六甘醇侧链的不对称分子刷聚合物PA-

-PAzo/(TPE-HEG). 偶氮苯侧链和四苯乙烯侧基的

相互作用和有序堆积，赋予了PA-

-PAzo/(TPE-HEG)组装体规整的分子排布. 系统研究了PA-

-PAzo/(TPE-HEG)在甲醇/四氢呋喃混合溶剂中的自组装行为，得到了束状、捆状和片状等形貌组装体，并探究了捆状组装体的形成过程以及组装体的光响应形貌调控. 本文的研究不仅提供了构建不对称分子刷聚合物的新合成方法，还丰富了分子刷组装体的种类.

Abstract

Self-assembly of amphiphilic copolymers presents a promising platform for the design and synthesis of nanomaterials

depending heavily on the topological polymer chemistry and properties of their compositions. In particular

asymmetric molecular brushes are composed of two different side chains grafted on a linear backbone

possessing distinct assembly behaviors in comparison with conventional linear copolymers

owing to the asymmetric double-brushes and combined effects of backbone and brushes. Additionally

the introduction of unique functionalities and responsiveness into the self-assembly system of asymmetric molecular brushes endows extra opportunities to pursue morphologic diversity and intriguing functionalities. In this study

a novel functional acrylate monomer Br-acrylate-Cl with Br-containing initiating group and alkylchlorine group was designed and synthesized. The functional macro-agent

poly(Br-acrylate-Cl)

was first prepared by reversible addition-fragmentation chain transfer (RAFT) homopolymerization of Br-acrylate-Cl monomer. Azobenzene-containing side chains were then directly grown from the backbone

via

atom transfer radical polymerization (ATRP) of azobenzene-containing monomer initiated by the pendant Br-containing initiating groups on the backbone

affording PA-

-PAzo molecular brushes. The obtained PA-

-PAzo molecular brushes were subsequently used in postpolymerization substitution to generate PA-

-PAzo/(TPE-HEG) asymmetric molecular brushes with azobenzene and hexaethylene glycol-containing side chains and tetraphenylethylene groups. Due to the special architecture and inter/intramolecular association of pendant azobenzene and tetraphenylethylene groups

PA-

-PAzo/(TPE-HEG) asymmetric molecular brushes exhibited unique self-assembly behavior. Therefore

π‍

-‍

and solvophobic interaction-driven self-assembly of PA-

-PAzo/(TPE-HEG) in CH

OH-THF mixed solvents was studied

and the morphologies of the assemblies were characterized by transmission electron microscopy (TEM). Well-defined bundle-like aggregates

sheaf-like aggregates

and 2D platelets were constructed

via

self-assembly of PA-

-PAzo/(TPE-HEG) through a heating-cooling-aging process. The formation of sheaf-like aggregates was systematically investgated. Intriguingly

the azobenzene moieties undergo

trans

cis

isomerization upon UV irradiation and further promote a morphology evolution of the assemblies

leading to the formation of rectangular platelets. Our study presents an efficient method for preparing asymmetric molecular brushes based on the functional monomer stragtegy

and opens a new avenue to design molecular-brush-based nanomaterials with tunable morphologies.

关键词

分子刷偶氮苯捆状组装体光响应性自组装

Keywords

Molecular brushesAzobenzeneSheaf-like aggregatePhoto-responsivenessSelf-assembly

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