Study on reaction mechanism of vinyl polysilazane/benzoxazine

doi:10.19936/j.cnki.2096-8000.20210828.005

Abstract

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

CLC Number:

TB332

XU Ya-feng, SONG Jin-mei. Study on reaction mechanism of vinyl polysilazane/benzoxazine[J]. COMPOSITES SCIENCE AND ENGINEERING, 2021, 0(8): 31-38.

References

[1] 胡继东, 刘峰, 郑知敏, 等. 一种新型烯丙基酚醛/含乙烯基聚硅氮烷杂化树脂体系的制备及性能研究[C]//复合材料-基础、创新、高效: 第十四届全国复合材料学术会议论文集. 2006: 207-211.
[2] RIBEIRO L F B, FLORES O, FURTAT P, et al. A novel PAN/silazane hybrid polymer for processing of carbon-based fibers with extraordinary oxidation resistance[J]. Journal of Materials Chemistry A, 2017, 5(2): 720-729.
[3] 杨建辉, 周燕, 汪强, 等. 硅氮烷改性含硅芳炔树脂及其复合材料的性能[J]. 宇航材料工艺, 2014(6): 37-41.
[4] 林先凯, 王锐, 曾凡, 等. 含炔基有机硅杂化聚合物的合成及热稳定性[J]. 宇航材料工艺, 2014, 44(1): 69-71.
[5] WANG R, FANG L, XU C. Synthesis, characterization, and thermal properties of new silarylene-siloxane-acetylene polymers[J]. Eur Polym J, 2010, 46(3): 465-471.
[6] 胡继东. 郑知敏, 刘锋, 等. 一种有机硅/烯丙基酚醛杂化树脂: CN200310001434.4[P]. 2005-09.
[7] 陈少杰等. 乙烯基聚硅氮烷PSN-1热裂解研究[J]. 有机硅材料, 2009, 23(4): 246-249.
[8] 李彦武, 胡海峰, 陈朝辉. 含乙烯基聚硅氮烷的裂解过程分析[J]. 有机硅材料, 2002, 16(2): 14- 17.
[9] 李光珠, 罗振华, 韩伟健, 等. 苯并噁嗪杂化树脂及其复合材料的制备与性能[J]. 宇航材料工艺, 2014(1): 75-78.
[10] GHOSH N N, KISKAN B, YAGCI Y. Polybenzoxazines-new high performance thermosetting resins: Synthesis and properties[J]. Progress in polymer Science, 2007(32): 1344-1391.
[11] TAKEICHI T, KAWAUCHI T, AGAG T. High performance polybenzoxazines as a novel type of phenolic resin[J]. Polymer Journal, 2008(40): 1121-1131.
[12] 向海, 顾宜. 新型酚醛树脂——苯并噁嗪树脂的研究进展[J]. 高分子材料科学与工程, 2004, 20(3): 1-4.
[13] 李玲, 陈剑楠. 改性BMI/苯并噁嗪树脂的固化反应及其动力学的研究[J]. 中国胶粘剂, 2008, 17(10): 23-26.
[14] 邱海鹏, 孙明, 韩立军. 聚硅氮烷裂解过程中结构变化的研究[C]//复合材料-基础、创新、高效: 第十四届全国复合材料学术会议论文集. 2006: 531-533.
[15] 胡海峰, 陈朝辉, 冯春祥, 等. 聚硅氮烷在氨气中的裂解研究[J]. 高分子学报, 1998(1): 104-108.
[16] 陈文瑾. 苯并噁嗪树脂的合成、改性与性能研究[D]. 成都: 电子科技大学, 2016.
[17] 郑知敏, 胡继东, 赵彤, 等. 聚硅氧硅氮烷/烯丙基酚醛杂化树脂研究[C]//第十四届全国复合材料学术会议论文集. 2007: 324-329.
[18] 郑知敏, 胡继东, 赵彤, 等. 聚硅氧硅氮烷改性烯丙基酚醛杂化树脂的研究[J]. 有机硅材料, 2007, 21(5): 253-257.
[19] 王焱, 王先胜, 陈海生. 树枝形大分子/环氧树脂体系固化反应动力学研究[J]. 高分子通报, 2006(11): 40-43.