高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (3): 565.

• 研究论文 • 上一篇    下一篇

可交联的PMMA型和PS型高热稳定性二阶非线性光学材料的合成与表征

王耀1, 傅娜1, 揣晓红2, 吕长利1, 崔占臣1, 张大明2, 衣茂斌2, 刘式墉2, 杨柏1   

  1. 1. 吉林大学超分子结构与材料教育部重点实验室, 化学学院, 长春 130023;
    2. 吉林大学国家光电子集成重点实验室, 长春 130023
  • 收稿日期:2003-01-06 出版日期:2004-03-24 发布日期:2004-03-24
  • 通讯作者: 崔占臣(1962年出生),男,教授,主要从事功能性聚合物光学材料的研究.E-mail;cuizc@jlu.edu.cn E-mail:cuizc@jlu.edu.cn
  • 基金资助:

    国家重大基础研究项目(批准号;G2000036604);国家高技术发展项目(批准号;2001.AA.312160)资助

Synthesis and Characterization of the Crosslinkable PMMA and PS Types of Polymers with High Thermal Stability for Nonlinear Optics

WANG Yao1, FU Na1, CHUAI Xiao-Hong2, L� Chang-Li1, CUI Zhan-Chen1, ZHANG Da-Ming2, YI Mao-Bin2, LIU Shi-Yong2, YANG Bai1   

  1. 1. Key Lab of Supramolecular Structure and Materials of the Ministry of Education, College of Chemistry, Jilin University, Changchun 130023, China;
    2. State Key Lab on Integrated Opto electronics, Jilin University, Changchun 130023, China
  • Received:2003-01-06 Online:2004-03-24 Published:2004-03-24

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被引次数

14

摘要： 采用封管反应的方法,以较高产率(80%以上)合成了一系列含环氧基团的可交联PMMA型和PS型极化聚合物材料,该材料具有很好的成膜性.用DSC和TgA等方法研究了聚合物固化前后的热性能,结果表明,由于聚合物在极化后期经热固化使引入的环氧基团开环交联,聚合物的玻璃化转变温度(Tg)较固化前明显提高30～50K.同时,固化后的聚合物具有较高的热分解温度(Td>543K).对聚合物的二阶非线性光学性质的测试结果表明,在室温下放置100h后,聚合物的电光系数r33值均保持在初始值的75%以上.这是由于环氧基团的开环使固化后的聚合物本身产生一定程度的交联,导致取向后的发色团被聚合物的交联网禁锢而不易弛豫,从而使这类PMMA型和PS型二阶非线性聚合物材料的热稳定性能得以提高.

关键词: 二阶非线性光学材料, 可交联型材料, 热稳定性, 封管反应

Abstract: In this paper, the thermal stability of poly[(DR1M)-co-(MMA)] and poly[(DR1M)-co-(St)] have been evidently improved by copolymerizing with epoxy GMA through sealed-tube reactive method. The two regular crosslinkable PMMA and PS types of nonlinear optical(NLO) polymers with a high yield were acquired. The two types of polymers, to which side chains containing NLO chromophores(DR1) were covalently attached, were of high thermal stability for nonlinear optics. Studied with DSC and TGA, it can be concluded that the glass transition temperatures of the two polymers, 398 and 397 K, respectively, approximately increased 30—50 K compared with that before crosslinked. Besides, the decomposition temperatures(at 5% mass loss) of the polymers were 552 and 546 K, respectively. The second-order nonlinearity of the polymers was measured with the simple reflection technique at 1.3 μm wavelengths. The values of electro-optic coefficient( r33) of the two types of polymers after crosslinking were 12.50, 8.60 pm/V respectively and they were both stabilized around 75% of their initial values after 100 h at room temperature. The above results confirmed that the thermal stability of copolymers was improved significantly, which is due to the opening and crosslinking of the epoxy group in the copolymers.

Key words: Second-order nonlinear optical materials, Crosslinkable materials, Thermal stability, Sealed-tube reactivity

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