新型聚硅氮氧烷的合成及其热解特性研究

doi:10.3969/j.issn.1001-1935.2024.05.011

耐火材料 ›› 2024, Vol. 58 ›› Issue (5): 424-430.DOI: 10.3969/j.issn.1001-1935.2024.05.011

新型聚硅氮氧烷的合成及其热解特性研究

徐汇, 杜贻昂, 王福稳, 李威, 徐娜娜, 欧钰城, 王兵

国防科技大学新型陶瓷纤维及其复合材料重点实验室湖南长沙 410073

收稿日期:2024-03-12 出版日期:2024-10-15 发布日期:2024-10-16
作者简介:徐汇:男,1999年生,硕士研究生。E-mail:xhxuhuia@nudt.edu.cn
基金资助:
湖南省优秀青年自然科学基金(2021JJ20048)。

Preparation of polysiloxazanes and their pyrolytic properties

Xu Hui, Du Yiang, Wang Fuwen, Li Wei, Xu Nana, Ou Yucheng, Wang Bing

Science and Technology and Composites Laboratory,National University of Defense Technology,Changsha 410073,Hunan,China

Received:2024-03-12 Online:2024-10-15 Published:2024-10-16

摘要/Abstract

摘要： 为了制备具有[SiN₃O]结构单元、陶瓷化温度低的聚硅氮氧烷(PSOZ)先驱体,以三异氰基甲基硅[MeSi(NCO)₃)]为原料,采用部分水解和氨解反应,制备了PSOZ先驱体。通过控制MeSi(NCO)₃水解反应的pH(4.7、5.4、5.9)、物料比[n(H₂O)∶n(MeSi(NCO)₃)=1∶3、1∶2、2∶3]和水解温度(-10、-20、-30、-40、-50 ℃),提高二硅氧烷中间体的产率,进而提高PSOZ先驱体的陶瓷产率,并研究了PSOZ的热解特性。结果表明:1)PSOZ在800 ℃时完成无机化,此时试样中的硅甲基(Si—CH₃)和异氰基(—NCO)完全分解;经 1 400 ℃热处理后,产物开始陶瓷化转变,局部出现Si₂N₂O微晶;经1 600 ℃热处理后,得到高结晶的Si₂N₂O陶瓷;2)在pH=4.7、n(H₂O)∶n(MeSi(NCO)₃)=1∶2,水解温度为-40 ℃的条件下制备的PSOZ先驱体的陶瓷产率最高,为57.1%(w)。

关键词: 聚硅氮氧烷, 无机化, 异氰基, 陶瓷化

Abstract: To possess the [SiN₃O] structure and low ceramization temperatures,polysiloxazane (PSOZ) precursors were prepared using triisocyanomethylsilicon [MeSi(NCO)₃] as the raw material by partial hydrolysis and ammonolysis reactions.The yield of disiloxane intermediate was increased by controlling the pH (4.7,5.4 and 5.9),material mole ratio (n(H₂O)∶n(MeSi(NCO)₃)=1∶3,1∶2 and 2∶3) and hydrolysis temperature (-10,-20,-30,-40 and -50 ℃) of MeSi(NCO)₃ hydrolysis reaction,thus increasing the ceramic yield of PSOZ precursors.The pyrolysis characteristics of PSOZ precursors were further studied.The results show that:(1)PSOZ precursors complete the inorganicization at 800 ℃; the silicomethyl [Si—CH₃] and isocyano [—NCO] in the sample are completely decomposed;after heat treatment at 1 400 ℃,ceramization begins,and Si₂N₂O microcrystals appear locally in the sample;after heat treatment at 1 600 ℃,highly crystalline Si₂N₂O ceramics are obtained;(2)under the conditions of pH of 4.7,n(H₂O)∶n(MeSi(NCO)₃) of 1∶2 and hydrolysis temperature of -40 ℃,the ceramic yield of the PSOZ precursor is the highest,57.1 mass%.

Key words: polysiloxazanes, inorganicization, isocyano, ceramization

中图分类号:

TQ174

徐汇, 杜贻昂, 王福稳, 李威, 徐娜娜, 欧钰城, 王兵. 新型聚硅氮氧烷的合成及其热解特性研究[J]. 耐火材料, 2024, 58(5): 424-430.

Xu Hui, Du Yiang, Wang Fuwen, Li Wei, Xu Nana, Ou Yucheng, Wang Bing. Preparation of polysiloxazanes and their pyrolytic properties[J]. Refractories, 2024, 58(5): 424-430.

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新型聚硅氮氧烷的合成及其热解特性研究

Preparation of polysiloxazanes and their pyrolytic properties

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