摘 要：側(cè)鏈含偶氮苯聚合物由于其具有良好的液晶性能，熱力學(xué)性能和光致異構(gòu)化活性，所以成為最有趣的高分子材料之一，受到了越來(lái)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(guò)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(cè)鏈含炔基偶氮苯聚合物。通過(guò)凝膠滲透色譜(GPC)測(cè)得聚合物的分子量為14000 g/mol及分子量分布為1.44；通過(guò)核磁共振氫譜(1H-NMR)對(duì)聚合物進(jìn)行表征，證明成功制備出了側(cè)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(yīng)，制備出具有優(yōu)異光學(xué)性能的新型高分子材料。通過(guò)核磁共振氫譜(1H-NMR)和紅外光譜(FT-IR)的表征，證明了“Click”反應(yīng)的成功；通過(guò)差示掃描量熱儀(DSC)和熱臺(tái)偏光顯微鏡(POM)研究了其熱力學(xué)性能和液晶性能；最后通過(guò)紫外可見分光光度計(jì)(UV-VIS)對(duì)聚合物的光致順?lè)串悩?gòu)化行為和動(dòng)力學(xué)性質(zhì)進(jìn)行研究，表明聚合物具有較快的順?lè)串悩?gòu)化速率。

關(guān)鍵詞：自由基聚合；偶氮苯聚合物；液晶聚合物；順?lè)串悩?gòu)化；“Click”反應(yīng)

       

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(shù)語(yǔ)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(jī)理．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．1

  1.3 側(cè)鏈型偶氮苯液晶聚合物．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

  1.4 “Click chemistry”點(diǎn)擊化學(xué)．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

    1.4.1 點(diǎn)擊化學(xué)概述．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．2

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

  1.5 研究目的和研究?jī)?nèi)容．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

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

    1.5.2 研究?jī)?nèi)容．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．3

2 實(shí)驗(yàn)部分．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．4

  2.1 原料、試劑及實(shí)驗(yàn)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(yīng)．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．8

  2.6 表征和測(cè)試方法．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．9

3 結(jié)果與討論．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．11

  3.1 單體的結(jié)構(gòu)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(yīng)的結(jié)構(gòu)表征．．．．．．．．．．．．．．．．．．．．．．．．．14

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

3.4.1 “Click”反應(yīng)對(duì)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(jié)構(gòu)．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．17

  3.5 偶氮苯聚合物的光致異構(gòu)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(gòu)化動(dòng)力學(xué)．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．20

4 結(jié)論．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．21

參考文獻(xiàn)．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．．22

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