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    手性聚炔基偶氮苯液晶聚合物的合成及其性能

    Synthesis and Properties of Azobenzene-Containing Chiral Liquid Crystal Polymer with Polyacetylene Mainchain

    • 摘要: 以二氯二铑双降冰片二烯为催化剂,制备了手性聚炔基偶氮苯聚合物,其手性中心一端与主链直接相连,另一端通过醚键与偶氮苯连接。通过引入不同长度的间隔基和偶氮苯端基,调节手性碳与偶氮苯基团之间的距离,对两种手性聚炔基偶氮苯聚合物的液晶性进行了调控。使用紫外-可见吸收光谱测试了两种手性聚炔基偶氮苯聚合物溶液的光异构化性能,用圆二色光谱表征了聚合物溶液在紫外光和蓝光照射下手性信号的变化,并对手性聚炔基偶氮苯衍生物薄膜的液晶性质、光异构化和手性光学性质进行了研究。结果表明:两种手性聚炔基偶氮苯聚合物的手性光学性质不受紫外光和蓝光的影响。在薄膜中,偶氮苯与手性部分的相互作用导致光异构化会影响聚乙炔主链和侧链的螺旋排列,利用紫外光和蓝光的照射,实现了对手性聚炔基偶氮苯衍生物薄膜手性信号的控制。

       

      Abstract: Azobenzene-containing chiral liquid crystal polymers (P(S)A-(CH2)6-Azo and P(S)A-(CH2)10-Azo-C4H9) with a polyacetylene main chain were designed and synthesized by Rh(nbd)Cl2-catalyzed homopolymerization. The chiral carbon was directly connected to the main chain, while the azobenzene group was linked through ether spacer. The polyacetylene backbone provided the rigidity, while the azobenzene mesogen on the side chain provided the photosensitivity and the ability for ordered arrangement. The liquid crystal properties of the two chiral liquid crystal polymers were regulated by introducing spacer groups and azobenzene end groups of different lengths and adjusting the distance between chiral carbon and azobenzene group. The photoisomerization properties of chiral liquid crystal polymers in tetrahydrofuran(THF) were measured using ultraviolet-visible(UV-Vis) absorption spectra, and the changes in chiral signals were characterized by circular dichroism spectra. The chiral signals did not change under UV and blue light irradiation, suggesting that the helical arrangement of the main chain and expression of chirality were not affected by the photoisomerization. The liquid crystal properties, photoisomerization, and chirality of films based on chiral liquid crystal polymer were also studied. Only a P(S)A-(CH2)10-Azo-C4H9 film exhibited a cholesteric phase. The chiral signals of films based on chiral liquid crystal polymer could be controlled by the irradiation of UV light and blue light.

       

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