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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (20): 2111-2118. 上一篇    下一篇

研究论文

离子自组装合成侧链型偶氮复合物及其聚集形态研究

沙静1，林坤华1，赵永超1，刘明2，江波1，肖德泉*,3，殷勤俭*,1   

  1. (1四川大学化学学院 成都 610064)
    (2四川大学分析测试中心 成都 610064)
    (3耶鲁大学化学系 康奈迪克州纽黑文市 06522)
  • 投稿日期:2009-11-19 修回日期:2010-03-16 发布日期:2010-05-06
  • 通讯作者: 殷勤俭 E-mail:changer05@126.com

Study on the Aggregation Morphology of Side-Chain Azocomplex Synthesized by Ionic Self-Assembly

Sha Jing1 Lin Kunhua1 Zhao Yongchao1 Liu Ming2 Jiang Bo1 Xiao Dequan*,3 Yin Qinjian*,1   

  1. (1 College of Chemistry, Sichuan University, Chengdu 610064)
    (2 Analysis and Testing Center, Sichuan University, Chengdu 610064)
    (3 Department of Chemistry, Yale University, New Have, CT 06522)
  • Received:2009-11-19 Revised:2010-03-16 Published:2010-05-06
  • Contact: YIN Qin-Jian E-mail:changer05@126.com

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用溶液聚合法制备了4-乙烯基吡啶与丙烯腈的无规共聚物(P4VP-r-AN), 采用1H NMR, 13C NMR, DSC和FTIR等手段确定了其结构和组成. 粘度法测得其粘均分子量为1.06×104 g/mol, 由其1H NMR 谱峰面积估算得到4-乙烯基吡啶链段的质量百分含量约为87.1%. 以质子化的4-乙烯基吡啶-丙烯腈无规共聚物(P4VP＋-r-AN)为模板, 与酸性间胺黄(MY)在水溶液中通过离子自组装, 制备了一种侧链型偶氮复合物(P4VP-r-AN/MY). 用1H NMR, FT-IR, DSC, UV-Vis, SEM, TEM和HRTEM&EDS(高分辨率透射电镜与X射线能谱联用)等手段研究了该复合物的聚集形态及自组装过程. 研究发现MY通过静电相互作用复合到P4VP＋-r-AN链上并发生聚集, 使复合物分子链聚集形成尺寸为10～200 nm的球形聚集体. P4VP-r-AN/MY中, MY与P4VP-r-AN的物质的量之比为0.575. HRTEM&EDS测试结果显示P4VP-AN/MY球形聚集体中硫元素的分布接近球形, 与聚集体的形状几乎一致, 表明MY分子在该组装物中主要以球形纳米聚集体的形式存在.

关键词: 离子自组装, 聚电解质, 酸性间胺黄, 偶氮复合物, 球形聚集体

A random copolymer poly(4-vinylpyridine-co-acrylonitrle) (designated as P4VP-r-AN) was synthesized by solution polymerization, and characterized by the average viscosity molecular weight measurement, along with 1H NMR, 13C NMR, DSC, and FTIR spectroscopy. The viscosity-average molecular weight of the P4VP-r-AN is 1.06×104 g/mol, and the mass content of P4VP is about 87.1%. A new method based on ionic self-assembly technology was provided for design of side chain azocomplex (P4VP-r-AN/MY) from the protonated P4VP-r-AN (P4VP＋-r-AN) and azobenzene dye metanil yellow (MY) in aqueous solution. The self-assembly behaviors and morphologies of P4VP-r-AN/MY were investigated by means of 1H NMR, FTIR, DSC, UV-vis, SEM, TEM and High-resolution transmission electron microscopes and X-ray energy dispersion spectrometer (HRTEM&EDS). It was found that azobenzene complex P4VP-r-AN/MY could be self-assembled and aggregated in aqueous solution, and the aggregations shown to be solid polymeric nanospheres on the sizes of 10～200 nm in diameters. The molar ratio of MY and P4VP-r-AN in P4VP-r-AN/MY was measured at about 0.575. HRTEM&EDS were used to study the morphology and composition of the organic nanospheres. The EDS elemental analysis indicated that the spherical organic nanoparticles are indeed composed of MY dye molecules.

Key words: ionic self-assembly, polyelectrolyte, metanil yellow, azocomplex, spherical nano-aggregation