摘要
以硅乙烯基1,7-碳硼烷为B源与含乙烯基硅氮烷反应生成了一种新型的SiBCN杂化树脂。采用FT-IR、DSC、TGA和Py GC-MS对树脂的结构、固化行为、热稳定性、热裂解反应和过程进行了研究,并用Kissinger方程和FWO法计算出了固化反应和热裂解的表观活化能,分析了树脂的裂解过程及机理。结果表明:这种杂化树脂在固化过程中存在一个放热峰,固化表观活化能为113.55 k J/mol,具有较好的热稳定性,N_2气氛下,T_d^5为459℃,900℃下的残碳率为73.1%。随着裂解反应程度的增加,树脂裂解的表观活化能增加,动力学热稳定性增强。当裂解温度为300℃时,树脂主要发生转氨基反应,裂解产生NH_3;500℃时,有机基团脱除,树脂裂解产生NH_3、CH_4和CH_2=CH_2等烯烃;650℃时,裂解气体种类进一步增加,生成一系列烷烃和烯烃。
A novel SiBCN hybrid resin was prepared from 1,7-bis（dimethylsilyl）-m-carborane and viny-con- taining polysilazane. Composition, curing behavior, thermal stability,thermal pyrolysis reaction and process were studied by FT-IR, DSC, TGA and PyGC-MS. The curing and pyrolysis reaction activation energy were calculated by Kis- singer equation and Flynn-Wall-Ozawa（FWO） methods. The pyrolysis mechanism of cured SiBCN was also analyzed. The results showed that there is one exothermic peak during the curing reaction, and its curing reaction activation energy is 113.55 kJ/mol. SiBCN possessed an excellent thermal stability with the Td^5 and the residue weight of 73.1% at 900℃ in N2.The decomposition reaction activation energy of the resin and the thermal stability increased following by the reaction conversion. When the pyrolysis temperature reached 300℃, NH3 apperad resulting from the transamination reaction, whereas CH4,CH2=CH2 and alkene produced at 500℃ and further species of the pyrolysis gas such as al- kanes and alkenes oeeured at 650℃.
作者
姚祺
肖鲁
韩大为
左小彪
冯志海
YAO Qi XIAO Lu HAN Dawei ZUO Xiaobiao FENG Zhihai(Aerospace Reserch Institute of Materials ＆ Processing Technology, Beijing 100076 Beijing Institute of Aerospace Systems Engineering, Beijing 100076)
出处
《宇航材料工艺》
CSCD
北大核心
2017年第3期42-45,52,共5页
Aerospace Materials & Technology
