摘 要：側鏈含偶氮苯聚合物由于其具有良好的液晶性能，熱力學性能和光致異構化活性，所以成為最有趣的高分子材料之一，受到了越來越多的研究者們的重視。本課題首先以4-硝基苯酚和溴丙炔為初始原料，制備出含活性炔基的偶氮苯單體(HPAMA)。然后，通過常規(guī)自由基聚合法以AIBN為引發(fā)劑，苯甲醚為溶劑，合成新型側鏈含炔基偶氮苯聚合物。通過凝膠滲透色譜(GPC)測得聚合物的分子量為14000 g/mol及分子量分布為1.44；通過核磁共振氫譜(1H-NMR)對聚合物進行表征，證明成功制備出了側鏈含炔基偶氮苯聚合物。最后，以溴化亞銅和N,N,N',N'',N''-五甲基二乙烯基三胺為催化劑體系，N,N-二甲基甲酰胺為溶劑，聚合物和疊氮化合物發(fā)生“Click”反應，制備出具有優(yōu)異光學性能的新型高分子材料。通過核磁共振氫譜(1H-NMR)和紅外光譜(FT-IR)的表征，證明了“Click”反應的成功；通過差示掃描量熱儀(DSC)和熱臺偏光顯微鏡(POM)研究了其熱力學性能和液晶性能；最后通過紫外可見分光光度計(UV-VIS)對聚合物的光致順反異構化行為和動力學性質進行研究，表明聚合物具有較快的順反異構化速率。

關鍵詞：自由基聚合；偶氮苯聚合物；液晶聚合物；順反異構化；“Click”反應

       

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  錄

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

目  錄．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅲ

術語表．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．Ⅳ

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

  1.1 課題研究的意義．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．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變及其機理．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

  1.3 側鏈型偶氮苯液晶聚合物．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

  1.4 “Click chemistry”點擊化學．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

    1.4.1 點擊化學概述．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

    1.4.2 端炔基和疊氮化合物的環(huán)加成反應．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

  1.5 研究目的和研究內(nèi)容．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

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

    1.5.2 研究內(nèi)容．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

2 實驗部分．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

  2.1 原料、試劑及實驗儀器．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

    2.1.1 主要原料、試劑及規(guī)格．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

    2.1.2 主要儀器及規(guī)格．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．5

  2.2 單體甲基丙烯酸-(4-己氧基-4'-丙炔氧基)偶氮苯酯(HPAMA)的制備．．．．．．．．．．．．6    

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

  2.4 烷基疊氮化合物的制備．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．8

  2.5 疊氮化合物與PHPAMA的“Click”反應．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．8

  2.6 表征和測試方法．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．9

3 結果與討論．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

  3.1 單體的結構表征．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

    3.1.1 中間體的核磁共振氫譜．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

    3.1.2 單體HPAMA的核磁共振氫譜．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．13

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

  3.3 端炔基和疊氮化合物的“Click”反應的結構表征．．．．．．．．．．．．．．．．．．．．．．．．．14

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

3.4.1 “Click”反應對偶氮苯聚合物的液晶性能影響．．．．．．．．．．．．．．．．．．．．．．．．16

3.4.2 偶氮苯聚合物的液晶結構．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．17

  3.5 偶氮苯聚合物的光致異構化行為．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．18                                                                                                           

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

    3.5.2 偶氮苯聚合物的異構化動力學．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．20

4 結論．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．21

參考文獻．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．22

致謝．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．23