改性HTPE和HTPB的多谱学表征和热裂解机理研究  

Study on Multispectral Characterization and Pyrolysis Mechanism of Modified HTPE and HTPB

作　　者：钱莹莹 王占东[2] 李恒 庄海锋 陈林 贾良元 徐司雨[3] QIAN Ying-ying;WANG Zhan-dong;LI Heng;ZHUANG Hai-feng;CHEN Lin;JIA Liang-yuan;XU Si-yu(College of Chemistry and Chemical Engineering,Hefei University of Technology,Hefei 230009,China;National Synchrotron Radiation Laboratory,University of Science and Technology of China,Hefei 230029,China;Key Laboratory of Combustion and Explosion Technology,Xi’an Institute of Modern Chemistry,Xi’an 710065,China)

机构地区：[1]合肥工业大学化学与化工学院,安徽合肥230009 [2]中国科学技术大学国家同步辐射实验室,安徽合肥230029 [3]西安近代化学研究所燃烧与爆炸技术重点实验室,陕西西安710065

出　　处：《质谱学报》2023年第4期476-485,I0001,共11页Journal of Chinese Mass Spectrometry Society

基　　金：中央高校基本业务经费(JZ2022HGTB0260)。

摘　　要：为研究端羟基聚丁二烯(HTPB)和端羟基聚醚(HTPE)黏合剂端基和主链改性对其热解特性的影响,本工作利用U型固定床热解反应器结合光电离质谱(SPI-MS)在线检测装置开展改性后黏合剂的热解实验。首先,采用红外光谱(FTIR)仪、核磁共振氢谱(1H-NMR)仪和热重分析(TGA)仪表征和分析改性后黏合剂的结构和热解性能,再通过在线质谱实时动态分析改性黏合剂热解产物的组分变化,研究改性黏合剂的热解反应机理。结果表明,HTPB和HTPE的端基和主链改性后的黏合剂表现出不同的热稳定性,其中,主链改性对HTPB热解行为的影响大于端基改性,这2种改性方法都使热解过程中反应类型增多,进而导致产物种类增加。Hydroxyl-terminated polybutadiene/polyether(HT-PB/PE),serving as binders and fuel for rocket propellants,has been widely studied and applied.To meet the developing demand of industrialization,the modification of HT-PB/PE based on their structural and functional characteristics has become one of the hot topics.In this study,the modified HTPB and the modified HTPE were prepared by modification of end groups and main chains.After the preparation,the characteristic functional groups of the binders were characterized by infrared spectroscopy(FTIR)to determine the effective end-group modification.Nuclear magnetic resonance hydrogen spectroscopy(1H-NMR)was used to characterize the main chain on modified binders through the variation of chemical environment of hydrogen.The analysis of the pyrolysis properties of the modified binders was performed by thermo gravimetric analyzer(TGA).The results effectively reflected the initial and maximum decomposition temperatures,as well as the pyrolysis stage of the above binders.The above characterization results confirmed the effective synthesis of modified binders and their good thermal properties.However,the present reports lacked the studies on the pyrolysis mechanism of these modified binders.To further investigate the effect of end group and main chain modification on the pyrolysis properties of binders,the pyrolysis of modified binders was conducted in a U-shaped fixed-bed reactor,which was connected to photoionization mass spectrometry(SPI-MS).SPI-MS was used to monitor the dynamic evolution of the pyrolysis product as a function of temperature in real-time.The mechanism of the pyrolysis process of the modified binders was studied based on the above tests.The results showed that the end-groups and main-chain modified binders of HTPB exhibited different thermal stabilities.The influence of main chain modification on the pyrolysis behavior was greater than that of end group modification.The pyrolysis mechanism of modified binders followed random bond breaking of C—C and C—O

关 键 词：光电离质谱(SPI-MS) HTPB改性 HTPE改性 热解 反应机理 

分 类 号：O657.63[理学—分析化学]