文献类型：期刊文献

中文题名：含偶氮苯侧链分子刷聚合物的合成及其光响应自组装

英文题名：Synthesis and Photo-responsive Self-Assembly of Azobenzene-Containing Molecular Brushes

作者：钱鸿宇[1];何品[1];张璐[1];陈珂[1];徐彬彬[1];林绍梁[1]

机构：[1]华东理工大学材料科学与工程学院,上海200237

年份：2021

卷号：41

期号：7

起止页码：2891

中文期刊名：有机化学

外文期刊名：Chinese Journal of Organic Chemistry

收录：CSTPCD;;Scopus;WOS:【SCI-EXPANDED(收录号:WOS:000691058000033)】；北大核心:【北大核心2020】；CSCD:【CSCD2021_2022】；

基金：Project supported by the National Natural Science Foundation of China (Nos. 52073092, 51873061, 22001072).

语种：中文

中文关键词：偶氮苯;分子刷聚合物;光响应性;超分子自组装

外文关键词：azobenzene;molecular brushes;photo-responsiveness;supramolecular self-assembly

摘要：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.
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 the trans-to-cis isomerization of PAzo brushes.