复合材料科学与工程 ›› 2021, Vol. 0 ›› Issue (8): 31-38.DOI: 10.19936/j.cnki.2096-8000.20210828.005

• 基础研究 • 上一篇    下一篇

乙烯基聚硅氮烷/苯并噁嗪反应机理研究

许亚丰1,2, 宋金梅1   

  1. 1.北京玻钢院复合材料有限公司,北京102101;
    2.武汉理工大学 特种功能材料教育部重点实验室,武汉430070
  • 收稿日期:2020-11-27 出版日期:2021-08-28 发布日期:2021-09-09
  • 作者简介:许亚丰(1993-),男,硕士研究生,工程师,研究方向为聚合物基功能和结构复合材料,yafengxu_hh@163.com。
  • 基金资助:
    特种纤维复合材料国家重点实验室应用基础性研究项目(YJ2019SYS08)

Study on reaction mechanism of vinyl polysilazane/benzoxazine

XU Ya-feng1,2, SONG Jin-mei1   

  1. 1. Beijing Composite Materials Co., Ltd., Beijing 102101, China;
    2. School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
  • Received:2020-11-27 Online:2021-08-28 Published:2021-09-09

摘要: 采用乙烯基聚硅氮烷(PSN)与纯化后的苯并噁嗪单体(BZ)熔融共混杂化制备了一种兼具可陶瓷化和较高力学性能的PSN/BZ热熔树脂。通过分步骤多因素控制变量的DSC实验对比分析PSN、BZ、DCP三种成分对PSN/BZ反应性的影响,通过非等温DSC研究了PSN/BZ的固化反应动力学,通过IR和DSC综合分析PSN/BZ官能团演变从而表征PSN/BZ固化反应机理。结果表明,PSN/BZ的固化反应机理主要为PSN在DCP引发下发生C=C打开加成聚合,N-H键间脱氨缩合反应,BZ在高温引发下发生开环聚合。同时BZ聚合物中的酚羟基与PSN中的Si-N键也可以部分反应生成Si-O-Si。PSN/BZ固化反应近似一级反应,固化反应级数非整数,证明固化过程较为复杂,其活化能较低,反应易进行,但固化温度相对较高。

关键词: 乙烯基聚硅氮烷, 苯并噁嗪, 杂化树脂, 反应机理, 复合材料

Abstract: Vinyl polysilazane (PSN) and purified benzoxazine monomer (BZ) melt blending were used to prepare a PSN/BZ hot melt resin with both ceramicization and higher mechanical properties. The effect of PSN, BZ, and DCP on the reactivity of PSN/BZ were compared and analyzed by a step-by-step multi-factor controlled variable DSC experiment. The curing reaction kinetics of PSN/BZ were studied by non-isothermal DSC, and comprehensive analysis by IR and DSC PSN/BZ functional group evolved to characterize the curing reaction mechanism of PSN/BZ. The results show that the curing reaction mechanism of PSN/BZ is mainly the C=C opening addition polymerization of PSN initiated by DCP, the deamination condensation reaction between N-H bonds, and the ring-opening polymerization of BZ initiated at high temperature. At the same time, the phenolic hydroxyl group in the BZ polymer and the Si-N bond in the PSN can also partially react to form Si-O-Si. The curing reaction of PSN/BZ is approximately a first-order reaction, and the curing reaction order is not an integer, which proves that the curing process is more complicated, its activation energy is low, and the reaction is easy to proceed, but the curing temperature is relatively high.

Key words: vinyl polysilazane, benzoxazine, hybrid resin, reaction mechanism, composites

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