基于蒽基团的光交联型非线性光学聚合物的合成与表征

马辉; 李明

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

doi: 10.14133/j.cnki.1008-9357.20220922003

马辉,
李明^,

长春工业大学化学与生命科学学院，长春 130012

基金项目: 国家自然科学基金（21704006）

详细信息

作者简介:
马辉：马　辉（1981—），男，硕士，主要研究方向为高分子材料。E-mail：530238247@qq.com

通讯作者:
李　明，E-mail：liming15@ccut.edu.cn

中图分类号: O631; TQ322.4; TQ324.8
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- 被引次数: 0
出版历程
- 收稿日期: 2022-09-22
- 录用日期: 2022-12-02
- 网络出版日期: 2022-12-06
- 刊出日期: 2023-04-01

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

MA Hui,
LI Ming^,

College of Chemistry and Life Science, Changchun University of Technology, Changchun 130012, China

摘要

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。
- 二阶非线性光学材料 /
- 光交联 /
- 聚甲基丙烯酸甲酯 /
- 取向稳定性 /
- 环加成
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（T_g） 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.
- second-order nonlinear optical material /
- photo-crosslinking /
- polymethyl methacrylate /
- alignment stability /
- cyclo-addition

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图 1 化合物1及聚合物p1～p3的合成路线

Figure 1. Synthetic scheme of compound 1 and p1−p3

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图 2 聚合物的¹H-NMR谱

Figure 2. ¹H-NMR spectra of polymers

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图 3 聚合物薄膜的FT-IR光谱

Figure 3. FT-IR spectra of polymer films

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图 4 聚合物薄膜的UV-Vis光谱

Figure 4. UV-Vis spectra of polymer films

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图 5 薄膜(a)p2/chr1.25%和(b)p2/chr5%的UV-Vis光谱

Figure 5. UV-Vis spectra of (a) p2/chr1.25% and (b) p2/chr5% film

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图 6 聚合物的TGA曲线

Figure 6. TGA curves of polymers

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图 7 (a) 聚合物p1，p2，p3的DSC曲线; (b) p2光照前后的DSC曲线

Figure 7. DSC curves of (a) p1, p2, p3; (b) DSC curves of p2 before and after irradiated

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图 8 p2/chr10%薄膜的 (a) 取向稳定性和(b) 交联前后的TSD曲线

Figure 8. (a) Alignment stability and (b) TSD curves before and after irradiated of p2/chr10% film

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