高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (4): 803-810.doi: 10.7503/cjcu20190595

• 高分子化学 • 上一篇    下一篇

利用静电界面制备高性能蒙脱石/氢化丁腈橡胶

张继华(),王超,皂伟涛,李莉,刘小艳,杨元,王昊   

  1. 航天材料及工艺研究所, 北京 100076
  • 收稿日期:2019-11-18 出版日期:2020-03-17 发布日期:2020-02-26
  • 通讯作者: 张继华 E-mail:zjhicca@iccas.ac.cn

Preparation of High-performance Montmorillonite/hydrogenated Butadiene-acrylonitrile Rubber by Using Electrostatic Interfaces

ZHANG Jihua(),WANG Chao,ZAO Weitao,LI Li,LIU Xiaoyan,YANG Yuan,WANG Hao   

  1. Aerospace Research Institute of Material and Processing Technology, Beijing 100076, China
  • Received:2019-11-18 Online:2020-03-17 Published:2020-02-26
  • Contact: Jihua ZHANG E-mail:zjhicca@iccas.ac.cn

摘要:

将甲基丙烯酸(MA)和烷基胺改性蒙脱石(MMT)混合成浆料后, 加入到氢化丁腈(HNBR)橡胶中, 通过热硫化工艺, 制备了MMT/HNBR橡胶复合材料. 采用扫描电子显微镜、 透射电子显微镜、 小角X射线衍射仪、 傅里叶变换红外光谱仪和转矩流变仪研究了MA改性的MMT与橡胶间的界面及分散性, 并对复合材料的各种性能进行分析. 结果表明, 在热硫化过程中, 不仅形成了橡胶的交联网络, 而且也促使MA在橡胶中发生原位聚合. 生成的聚甲基丙烯酸与MMT表面的烷基胺形成离子对, 从而在橡胶和MMT间构筑了强的静电界面. 同时MA在MMT层间发生聚合反应, 提高了MMT在橡胶中的分散性. 动态机械性能和200%应变的应力松弛实验表明, 良好分散的MMT和静电界面有效约束了橡胶分子链在力学拉伸过程中的运动. 与纯橡胶相比, MMT/HNBR橡胶复合材料具有更大的拉伸强度和韧性. 此外, 橡胶复合材料还具有良好的N2气阻隔性能. 因此, 配制MA/MMT浆料是一种简单方便的MMT改性方法, 制备的MMT/HNBR橡胶复合材料可用于制造具有高强韧性和气体阻隔性要求的橡胶产品.

关键词: 氢化丁腈橡胶, 烷基胺改性蒙脱石, 甲基丙烯酸, 强韧化, 气体阻隔性

Abstract:

After amine-modified montmorillonite(MMT) and methacrylic acid(MA) were mixed to prepare a slurry, they were added to the hydrogenated butadiene-acrylonitrile rubber(HNBR). By thermal vulcanization, MMT/HNBR composites were successfully achieved. The MA-modified MMT/rubber interfaces and their dispersion were carefully investigated by scanning electron microscopy, transmission electron microscopy, small angle X-ray scattering pattern, Fourier transform infrared spectroscopy and vulcameter. Moreover, various properties of rubber composites were analyzed. The experimental results showed that chemical crosslinking networks were developed during vulcanization. In the meantime, MA was in-situ self-polymerized in the rubber matrix and ion pairs were formed between polymethacrylic acid and amine on MMT, which therefore constructed strong electrostatic interfaces between MMT and rubber matrix. The self-polymerization of MA extended interlayer spacing of MMT, leading to a good dispersion of MMT in rubber matrix. MMT with good dispersion and ion interfaces constrained the slippage of rubber chains during stretching, which was proved by the dynamic mechanical properties and stress relaxation at 200%. So the tensile strength and toughness of rubber composites were greatly improved. In addition, the N2 permeability of rubber composites was reduced, showing a good gas barrier property. Therefore, the preparation of MA/MMT slurry is a simple and convenient method to modify the MMT. We believe that as-prepared MMT/HNBR composites can be used in the rubber products with the requirements of high mechanical and good gas barrier properties.

Key words: Hydrogenated butadiene-acrylonitrile rubber, Amine-modified montmorillonite, Methacrylic acid, Strengthening and toughening, Gas barrier property

中图分类号: