硼硅氧烷树脂热解行为及动力学研究
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摘要
采用热重分析法和裂解质谱红外联用技术考察了硼硅氧烷树脂的热解反应行为,将Malek法与Coats-Redfern积分法结合,对实验数据进行动力学解析,得到了硼硅氧烷树脂热解反应的动力学参数。结果表明硼硅氧烷树脂的热解反应分为三段:在250℃以下的低温区,小分子气体放出的同时伴有熔融等发生;在250℃~650℃的高温区,以脱硅甲基反应为主;在650℃~800℃为稳定阶段。通过分析热解过程中产生的气体和固体成分及含量,得出硼硅氧烷树脂热解可能发生的反应。硼硅氧烷树脂的热解反应可以用2/3级动力学方程来描述;随着升温速率的增加,活化能和指前因子均先增加后减小。
The pyrolysis characteristic of polyborosiloxane resin has been investigated by means of thermogravimetric analysis and pyrolysis-GCMS analysis. Models of the pyrolysis kinetics were derived using the coats-redfern integral method. The results show that the pyrolysis reactions of phenolic resin have two types: reaction of chain breaking( <250 ℃ in the low temperature region),reaction of desilicon methylation(250 ℃ to 650 ℃ in the high temperature region) and stable phase(650 ℃ to 800 ℃),Through analysis of component and content of gas and solid during pyrolysis of polyborosiloxane resin,the possible reaction occurring in the is derived. The pyrolysis of borosiloxane resin pyrolysis of polyborosiloxane resin can be described by two thirds-order kinetics equations in main pyrolysis temperature regions. Active energy and pre-exponential factor increased and then decreased with increasing of heating rates.
The pyrolysis characteristic of polyborosiloxane resin has been investigated by means of thermogravimetric analysis and pyrolysis-GCMS analysis. Models of the pyrolysis kinetics were derived using the coats-redfern integral method. The results show that the pyrolysis reactions of phenolic resin have two types: reaction of chain breaking( <250 ℃ in the low temperature region),reaction of desilicon methylation(250 ℃ to 650 ℃ in the high temperature region) and stable phase(650 ℃ to 800 ℃),Through analysis of component and content of gas and solid during pyrolysis of polyborosiloxane resin,the possible reaction occurring in the is derived. The pyrolysis of borosiloxane resin pyrolysis of polyborosiloxane resin can be described by two thirds-order kinetics equations in main pyrolysis temperature regions. Active energy and pre-exponential factor increased and then decreased with increasing of heating rates.
引文
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[2]Pillot Cestas J P,Birot M,Dunogues J,et al.Method of preparing silicon and boron oxynitrides:US 6180809[P].2001-1-30.
[3]张天才,程玉鹏,吉法祥.有机硅硼杂链聚合物的合成与热性能[C]//江苏省复合材料科学技术与工程学术研讨会论文集.江苏:2003:166-170.
[4]Deepa Devapal S,Packirisamy K J,Sreejith P V,et al.Synthesis,characterization and ceramic conversion studies of borosiloxane oligomers from phenyltrialkoxysilanes[J].Journal of Inorganic&Organometallic Polymers&Materials,2010,20(4):666-674.
[5]Schiavona M A,Armelinb N A,Yoshida I V P.Novel poly(borosiloxane)precursors to amorphous Si BCO ceramics[J].Materials Chemistry and Physics,2008,112(3):1047-1054.
[6]晏义伍,范震,曹海琳,等.高抗冲击聚硼硅氧烷微凝胶的合成和性能表征[J].中国个体防护装备,2016(6):5-8.
[7]王丹,郝志峰,吴雅红,等.含硼有机硅树脂的合成及其耐高温性能的研究[J].化工新型材料,2015,43(10):70-72.
[8]Siqueira R L,Yoshida I V P,Pardini L C,et al.Poly(borosil oxanes)as precursors of ceramic matrix in carbon fiber composites[C]//10th Int.Inorganic Bonded Fiber Composites Conference Sao Paulo,Brazil,2006.186-187.
[9]Zhao H Y,Zhao J B,Li H,et al.Preparation and characterization of polyborosiloxanes and their blends with phenolic resin as shapeable ceramic precursors[J].Chinese Journal of Polymer Science,2014,32(2):187-196.
[10]张斌,孙明明,张绪刚,等.聚硼硅氧烷改性酚醛树脂耐高温胶粘剂的制备及性能[J].高分子材料科学与工程,2008,24(6):152-155.
[11]张爱华,何明中,秦芳芳,等.高岭土热分解动力学[J].硅酸盐学报,2009,37(10):1678-1684.
[12]鲍士龙,陈网桦,陈利平,等.2,4-二硝基甲苯热解自催化特性鉴别及其热解动力学[J].物理化学学报,2013,29(3):479-485.
[13]肖卓炳,赵艺楠,刘建兰,等.非等温热分析法研究白藜芦醇及其苷的熔点、热稳定性及分解动力学[J].分析测试学报,2015,34(10):1119-1125.
[14]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].北京:科学出版社,2008:54-160.
[15]琼斯,安藤亘,乔努斯基,等.含硅聚合物——合成与应用[M].北京:化学工业出版社,2008:23-25.
[16]张志杰.材料物理化学[M].北京:化学工业出版社,2016:2-5.
[17]刘振海.热分析导论[M].北京:化学工业出版社,1991:115-116.
[18]王文钊.纤维素热重分析及热解动力学研究[D].重庆:重庆大学,2008:1-58.