含偶氮苯侧链分子刷聚合物的合成及其光响应自组装

doi:10.6023/cjoc202102047

摘要/Abstract

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

引用此文

钱鸿宇, 何品, 张璐, 陈珂, 徐彬彬, 林绍梁. 含偶氮苯侧链分子刷聚合物的合成及其光响应自组装[J]. 有机化学, 2021, 41(7): 2891-2897.

Hongyu Qian, Pin He, Lu Zhang, Ke Chen, Binbin Xu, Shaoliang Lin. Synthesis and Photo-responsive Self-Assembly of Azobenzene-Containing Molecular Brushes[J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2891-2897.

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图/表 6

图式1. (A) poly(Br-acrylate-alkyne) (1)和(B) PA-g-PAzo/Bar (4)的合成

Scheme 1. (A) Syntheses of poly(Br-acrylate-alkyne) (1), and (B) PA-g-PAzo/Bar (4)

图1. 分子刷聚合物PA-g-PAzo/Bar (4)的(A)核磁共振氢谱和(B) GPC谱图

Figure 1. (A)1H NMR spectrum and (B) GPC trace of PA-g-PAzo/Bar (4) of PA-g-PAzo/Bar (4)

图2. 分子刷聚合物PA-g-PAzo/Bar胶束溶液(0.2 mg•mL–1, CHCl3/MCH, V∶V=1∶0.2)的紫外吸收光谱图

Figure 2. UV-Vis absorption spectra of PA-g-PAzo/Bar micelle solution (0.2 mg•mL–1, CHCl3/MCH, V∶V=1∶0.2) (A) Upon irradiation of 365 nm light; (B) upon irradiation of 450 nm light

图3. 分子刷聚合物PA-g-PAzo/Bar胶束溶液(A, B) 0.2 mg• mL–1样品、(C) 0.2 mg•mL–1样品存储7 d后和(D) 1 mg•mL–1样品的TEM图像; (E)制备所得的柱状胶束和复合胶束的示意图

Figure 3. TEM images of PA-g-PAzo/Bar micelle solution: (A, B) 0.2 mg•mL–1 micelle solution, (C) 0.2 mg•mL–1 micelle solution after storing 7 d, and (D) 1 mg•mL–1 micelle solution; (E) Schematic illustration of the obtained cylinder and compound micelles

图4. (A), (B)分子刷聚合物柱状胶束经过紫外光照后的TEM形貌图像. (C)柱状胶束经过紫外光照后形成多孔网状胶束的示意图

Figure 4. (A), (B) TEM images of PA-g-PAzo/Bar cylinder micelles after UV irradiation. (C) Simplified schematic illustration of the obtained porous nanosheet after UV irradiation

图5. 分子刷聚合物PA-g-PAzo/Bar复合胶束经过紫外光(A, B)照射1 h和(C, D)3 h后的TEM形貌图

Figure 5. TEM images of PA-g-PAzo/Bar compound micelles after UV irradiation (A, B) 1 h, and (C, D) 3 h

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