毕业论文-新型侧链含炔基偶氮苯聚合物的性能的研究.doc

摘 要：侧链含偶氮苯聚合物由于其具有良好的液晶性能，热力学性能和光致异构化活性，所以成为最有趣的高分子材料之一，受到了越来越多的研究者们的重视。本课题首先以4-硝基苯酚和溴丙炔为初始原料，制备出含活性炔基的偶氮苯单体(HPAMA)。然后，通过常规自由基聚合法以AIBN为引发剂，苯甲醚为溶剂，合成新型侧链含炔基偶氮苯聚合物。通过凝胶渗透色谱(GPC)测得聚合物的分子量为14000 g/mol及分子量分布为1.44；通过核磁共振氢谱(1H-NMR)对聚合物进行表征，证明成功制备出了侧链含炔基偶氮苯聚合物。最后，以溴化亚铜和N,N,N',N'',N''-五甲基二乙烯基三胺为催化剂体系，N,N-二甲基甲酰胺为溶剂，聚合物和叠氮化合物发生“Click”反应，制备出具有优异光学性能的新型高分子材料。通过核磁共振氢谱(1H-NMR)和红外光谱(FT-IR)的表征，证明了“Click”反应的成功；通过差示扫描量热仪(DSC)和热台偏光显微镜(POM)研究了其热力学性能和液晶性能；最后通过紫外可见分光光度计(UV-VIS)对聚合物的光致顺反异构化行为和动力学性质进行研究，表明聚合物具有较快的顺反异构化速率。

关键词：自由基聚合；偶氮苯聚合物；液晶聚合物；顺反异构化；“Click”反应

       

Properties of Novel Side-Chain Alkynyl-Containing Azobenzene Polymers

Abstract: Side-chain azobenzene-containing polymers have become one of the most interesting polymer materials due to the good properties of liquid crystalline, thermotropic phase and optical trans-cis-trans isomerization behaviors, which are paid more and more attentions by the researchers. In this topic, azobenzene monomer containing active alkynyl group was first prepared by 4-nitrophenol and 3-bromo-1-propyne as the initial materials (HPAMA). Novel side-chain alkynyl-containing azobenzene polymers were then synthesized by conventional radical polymerization using AIBN as the initiator, anisole as the solvent. By gel permeation chromatography (GPC), we have measured that the molecular weight of the polymer is 14000 g/mol and the polydipersity is 1.44. The structure of the polymer was characterized by 1H-NMR, we proved that side-chain alkynyl-containing azobenzene polymers were successfully synthesized. Finally, novel polymer materials with excellent photoresponsive behaviors were synthesized by using CuBr/PMEDTA as a catalyst system, DMF as the solvent, “Click” reaction between the terminal alkynyl and the azide was performed. It was characterized by 1H-NMR and FT-IR, which was proved the success of the “Click” reaction. The liquid crystalline properties and the thermodynamic properties were studied by differential scanning calorimetry (DSC) and thermal polarized optical microscopy (POM), and, we studied the optical trans-cis-trans isomerization behaviors and kinetics of the side-chain azobenzene polymers through the ultraviolet and visible spectrophotometer (UV-

VIS). The polymer has a higher rate of cis-trans isomerization.

Key words: radical polymerization; azobenzene polymers; liquid crystal polymers; trans-cis

- trans isomerization; “Click” reaction

目  录

摘  要．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅰ

目  录．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅲ

术语表．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅳ

1 前言．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

  1.1 课题研究的意义．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

  1.2 偶氮苯聚合物．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

    1.2.1 偶氮苯聚合物概述．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

    1.2.2 偶氮苯化合物的光致色变及其机理．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

  1.3 侧链型偶氮苯液晶聚合物．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

  1.4 “Click chemistry”点击化学．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

    1.4.1 点击化学概述．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

    1.4.2 端炔基和叠氮化合物的环加成反应．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

  1.5 研究目的和研究内容．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

    1.5.1 研究目的．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

    1.5.2 研究内容．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

2 实验部分．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

  2.1 原料、试剂及实验仪器．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

    2.1.1 主要原料、试剂及规格．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

    2.1.2 主要仪器及规格．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．5

  2.2 单体甲基丙烯酸-(4-己氧基-4'-丙炔氧基)偶氮苯酯(HPAMA)的制备．．．．．．．．．．．．6    

  2.3 聚甲基丙烯酸-(4-己氧基-4'-丙炔氧基)偶氮苯酯(PHPAMA)的制备．．．．．．．．．．．．．7

  2.4 烷基叠氮化合物的制备．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．8

  2.5 叠氮化合物与PHPAMA的“Click”反应．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．8

  2.6 表征和测试方法．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．9

3 结果与讨论．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

  3.1 单体的结构表征．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

    3.1.1 中间体的核磁共振氢谱．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

    3.1.2 单体HPAMA的核磁共振氢谱．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．13

　3.2 PHPAMA分子量及其分子量分布．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．13

  3.3 端炔基和叠氮化合物的“Click”反应的结构表征．．．．．．．．．．．．．．．．．．．．．．．．．14

  3.4 偶氮苯聚合物的液晶性能．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．16　　 

3.4.1 “Click”反应对偶氮苯聚合物的液晶性能影响．．．．．．．．．．．．．．．．．．．．．．．．16

3.4.2 偶氮苯聚合物的液晶结构．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．17

  3.5 偶氮苯聚合物的光致异构化行为．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．18                                                                                                           

    3.5.1 偶氮苯聚合物的紫外吸收光谱．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．18

    3.5.2 偶氮苯聚合物的异构化动力学．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．20

4 结论．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．21

参考文献．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．22

致谢．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．23