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    马 辉, 李 明. 基于蒽基团的光交联型非线性光学聚合物的合成与表征[J]. 功能高分子学报,2023,36(2):146-152. doi: 10.14133/j.cnki.1008-9357.20220922003
    引用本文: 马 辉, 李 明. 基于蒽基团的光交联型非线性光学聚合物的合成与表征[J]. 功能高分子学报,2023,36(2):146-152. doi: 10.14133/j.cnki.1008-9357.20220922003
    MA Hui, LI Ming. Synthesis and Characterization of Photocrosslinked Nonlinear Optical Polymers Based on Anthracene Groups[J]. Journal of Functional Polymers, 2023, 36(2): 146-152. doi: 10.14133/j.cnki.1008-9357.20220922003
    Citation: MA Hui, LI Ming. Synthesis and Characterization of Photocrosslinked Nonlinear Optical Polymers Based on Anthracene Groups[J]. Journal of Functional Polymers, 2023, 36(2): 146-152. doi: 10.14133/j.cnki.1008-9357.20220922003

    基于蒽基团的光交联型非线性光学聚合物的合成与表征

    Synthesis and Characterization of Photocrosslinked Nonlinear Optical Polymers Based on Anthracene Groups

    • 摘要: 在有机二阶非线性光学聚合物聚甲基丙烯酸甲酯侧链中引入可交联的蒽基团,合成含蒽基团的甲基丙烯酸甲酯类聚合物。采用紫外-可见光谱法明确蒽基团在薄膜中的光交联时间,利用蒽基团在光照条件下的可控4+4环加成交联反应提高聚合物的取向稳定性。差示扫描量热法(DSC)研究结果表明交联反应后聚合物薄膜的玻璃化转变温度提高了约10 ℃。聚合物在60 ℃条件下加热220 h后电光系数仍可保持原来的90%左右,交联后的二阶非线性聚合物的取向稳定性明显提升。

       

      Abstract: Organic second-order nonlinear optical (NLO) materials have broad application prospects in a new generation of high-performance, high-bandwidth electro-optic modulation devices due to their high responsiveness, high integration, low cost, and good designability. However, the organic second-order NLO materials present relatively lower alignment stability compared with inorganic materials, which limits its wide application. In this paper, cross-linkable anthracene groups are introduced into the side chains of polymer for enhancing alignment stability by 4+4 cycloaddition reaction of anthracene groups under UV light irradiation. Methylmethacrylate based copolymers p1 —p3 containing different concentration of anthracene groups were synthesized by solution polymerization. Then chromophores were doped in p1—p3 to prepare second-order nonlinear optical films. The time required for the complete reaction of anthracene groups in the polymer film was studied by UV-Vis spectroscopy. After 30 min irradiation, the crosslinking reaction could complete and the chromophores during irradiation didn’t exhibit decomposition. The results of differential scanning calorimetry (DSC) showed that the glass transition temperature(Tg) of the polymer film increased by 10 ℃ after the cross-linking reaction. As the TGA analysis, 5% mass fraction decomposition temperature increased with anthracene group from 210 ℃ to 240 ℃. The electro-optic properties and orientation stability of the cross-linked materials were investigated. After heating at 60 ℃ for 220 h, electro-optic properties retained around 90% after photo-crosslinking. Peak temperature of the thermal stimulated current (TSD) of the crosslinked film increased around 15 ℃ compared with uncrosslinked one. The results show that the orientation stability of the second-order nonlinear polymer has been improved to a certain extent.

       

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