有机化学 ›› 2021, Vol. 41 ›› Issue (7): 2891-2897.DOI: 10.6023/cjoc202102047 上一篇    下一篇

研究简报

含偶氮苯侧链分子刷聚合物的合成及其光响应自组装

钱鸿宇, 何品, 张璐, 陈珂, 徐彬彬, 林绍梁*()   

  1. 华东理工大学材料科学与工程学院 上海 200237
  • 收稿日期:2021-02-25 修回日期:2021-03-25 发布日期:2021-04-29
  • 通讯作者: 林绍梁
  • 基金资助:
    国家自然科学基金(52073092); 国家自然科学基金(51873061); 国家自然科学基金(22001072)

Synthesis and Photo-responsive Self-Assembly of Azobenzene-Containing Molecular Brushes

Hongyu Qian, Pin He, Lu Zhang, Ke Chen, Binbin Xu, Shaoliang Lin()   

  1. School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237
  • Received:2021-02-25 Revised:2021-03-25 Published:2021-04-29
  • Contact: Shaoliang Lin
  • Supported by:
    National Natural Science Foundation of China(52073092); National Natural Science Foundation of China(51873061); National Natural Science Foundation of China(22001072)

分子刷聚合物伸展的高分子主链、高密度的侧链和较低的侧链空间缠结, 使其展现出独特的流变学、力学性能和特殊的分子聚集状态, 在纳米技术、表面科学等领域有着广泛的应用前景. 基于同时含有2-羰基溴与炔基基团的大分子试剂聚2-((2-溴代丙酰氧基)甲基)丙烯酸丙炔酯, 引发偶氮苯丙烯酸酯单体的原子转移自由基聚合(ATRP)与叠氮功能化的巴比妥酸衍生物的点击反应, 合成了新型含偶氮苯侧链的分子刷聚合物聚丙烯酸酯-g-聚(6-(4-丁基-4′-氧偶氮苯)正己基丙烯酸酯)/巴比妥酸(PA-g-PAzo/Bar), 研究了其在溶液中的自组装和光响应性行为. 随着分子刷聚合物浓度的增加, 聚集体由柱状胶束向复合胶束转变. 由于光响应性偶氮苯侧链的存在, 在紫外光的照射下偶氮苯生色团发生trans-cis异构化转变, 促使柱状胶束融合形成多孔网状聚集体, 同时球形复合胶束融合形成珍珠项链状聚集体.

关键词: 偶氮苯, 分子刷聚合物, 光响应性, 超分子自组装

Molecular brushes (MBs) are a unique type of branched macromolecules which graft polymeric chains onto a linear polymeric backbone densely. Crowded tethered side chains generate strong steric repulsion and force the backbone to stretch out, resulting in a persistent cylindrical shape and low density of entanglements of brushes. Owing to the unique rheological and mechanical properties and self-assembly behaviors, MBs show a great potential in nanotechnology and surface science. Herein, the synthesis of novel MBs of polyacrylate-g-poly(6-(4-butyl-4'-oxyazobenzene)hexylacrylate)/barbituric acid (PA-g-PAzo/Bar) was reported, in which PAzo brushes and hydrogen-bonding barbituric acid were grafted using the combination of concurrent atom transfer radical polymerization (ATRP) and click reaction. MBs-based aggregates change from cylinder to compound micelle by increasing the concentration. It is interesting that morphology transitions of cylinder-to-porous nanosheet and compound micelle-to-pearl-necklace were observed upon UV irradiation, that was ascribed to thetrans-to-cis isomerization of PAzo brushes.

Key words: azobenzene, molecular brushes, photo-responsiveness, supramolecular self-assembly