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PyGC-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 kJ/mol,具有较好的热稳定性,N2气氛下,T5d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NH3;500℃时,有机基团脱除,树脂裂解产生NH3 、CH4和CH2=CH2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-containing 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 Kissinger 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 T5d 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 alkanes and alkenes occured at 650℃.
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