应用化学 ›› 2009, Vol. 26 ›› Issue (10): 1211-1215.

• 研究论文 • 上一篇    下一篇

聚硼硅氮烷的合成及其流变性能研究

王小宙,王军,唐云,李文华,王浩   

  1. (国防科技大学新型陶瓷纤维及其复合材料国防科技重点实验室 长沙 410073)
  • 收稿日期:2008-09-25 修回日期:2009-02-12 出版日期:2009-10-10 发布日期:2009-10-10
  • 通讯作者: 王军,男,教授,博士生导师; E-mail:csgl4519783@hotmail.com; 研究方向:特种陶瓷纤维
  • 基金资助:
    国防基础科研(A2820060068)国家自然科学基金(50702075)和国防科技重点实验室基金(9140C8203050603,9140C8202050804)资助项目

Synthesis and Rheological Property of Polyborosilazane

WANG Xiao-Zhou, WANG Jun, TANG Yun, LI Wen-Hua, WANG Hao   

  1. (State Key Laboratory of Advanced Ceramic Fibers & Composites,National University of Defense Technology,Changsha 410073)
  • Received:2008-09-25 Revised:2009-02-12 Published:2009-10-10 Online:2009-10-10

摘要:

以二氯甲基硅烷、三氯化硼、六甲基二硅氮烷为起始原料,采用缩聚法合成了一种新型SiBNC陶瓷先驱体—聚硼硅氮烷(PBSZ)。通过调节原料二氯甲基硅烷的用量可获得不同软化点的先驱体。通过改进的毛细管流变仪,首次对熔融纺丝状态时聚硼硅氮烷(PBSZ)的流变特性展开了研究。结果表明:PBSZ熔融纺丝时,剪切速率在10~110s-1时,为切力变稀流体。非牛顿指数为0.83~0.90,粘流活化能约为142KJ/mol,表观粘度440~2460Pa·s,PBSZ对温度变化的敏感性较聚碳硅烷小,可纺温区较宽。PBSZ纺丝性能良好,纤维连续无断头长度﹥1600m,纤维直径﹤20μm。

关键词: 聚硼硅氮烷, 合成, 流变性, 熔融纺丝

Abstract:

Polyborosilazane (PBSZ), a novel precursor to SiBNC ceramic, was synthesized via cocondensadition approach by using dichloromethylsilane (MeHSiCl2), boron trichloride (BCl3) and hexamethydisilazane ((CH3)3SiNHSi(CH3)3) as the starting materials. Precursors with different softening point can be obtained by altering the dosage of MeHSiCl2. Rheological property study show that PBSZ melt is a typical shear stress diluting fluid and the shear rate, the flow index, the viscous flow activation energy, the apparent viscosity is 10~110 s-1, 0.83~0.90, 142 kJ/mol, 400~2400 Pa·S, respectively. The as-synthesized polyborosilazane shows good processability in wide temperature range and endless polymer fibers can be obtained in 87℃ in N2 atmosphere.

Key words: Polyborosilazane, Synthesis, Rheological Property, Melt-spinning

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