摘要
聚丙烯腈(PAN)是一种典型的高分子聚合物,在电化学、纤维工业等方面有广泛应用。当前对纯PAN高温热解的理论研究还不够充分,机理尚不明确。文中使用基于ReaxFF力场的分子动力学方法对该体系展开了研究。对聚合度为10和20的PAN体系进行了恒温热解模拟,设定1800 K,2400 K,2800 K和3200 K这4种温度。计算发现,较低温度时以“环化与交联”反应为主,而较高温度时“脱氢”和“环化与交联”反应都很显著。另外,主要气体产物为H_(2),大部分碳原子通过交联反应生成少数的多碳分子,且几乎没有发生“脱氮”反应。结果表明,PAN的真空高温热解不利于纯碳结构的生成,但是可能有助于氮掺杂碳材料的研究。
Polyacrylonitrile(PAN)was a typical polymer with extensive applications in the fiber industry and electrochemistry.The current theoretical research on the high-temperature pyrolysis of pure PAN under vacuum conditions was deemed insufficient,and the mechanism remained unclear.Therefore,a study on the vacuum and high-temperature pyrolysis of PAN through ReaxFF force field-based molecular dynamics method was conducted in this work.Isothermal pyrolysis simulations were carried out for PAN systems with polymerization degrees of 10 and 20.The temperature settings were 1800 K,2400 K,2800 K,and 3200 K,and the simulation duration was set to 200 ps.The calculation shows that at lower temperatures,the“cyclization and crosslinking”reactions dominate,while at higher temperatures,both“dehydrogenation”and“cyclization and crosslinking”reactions are significant.In addition,the primary gas product is H_(2),and most of the carbon atoms undergo crosslinking reactions to form a small number of multicarbon molecules.In the meantime,there is almost no occurrence of“denitrification”reaction.The results indicate that the vacuum and high-temperature pyrolysis of PAN is adverse to the formation of pure carbon structures,but may be helpful for the study of nitrogen doped carbon materials.
作者
刘怡婷
王庚乾
和小虎
邱选兵
田亚莉
郭古青
宫廷
孙小聪
周月婷
李传亮
李光跃
Yiting Liu;Gengqian Wang;Xiaohu He;Xuanbing Qiu;Yali Tian;Guqing Guo;Ting Gong;Xiaocong Sun;Yueting Zhou;Chuanliang Li;Guangyue Li(School of Applied Science,Shanxi Engineering Research Center of Precision Measurement and Online Detection Equipment,Shanxi Center of Technology Innovation for Light Manipulations and Applications,Taiyuan University of Science and Technology,Taiyuan 030024,China;College of Chemical Engineering,North China University of Science and Technology,Tangshan 063210,China)
出处
《高分子材料科学与工程》
北大核心
2025年第6期40-48,共9页
Polymer Materials Science & Engineering
基金
国家自然科学基金资助项目(52076145,62475182,12304403)
山西省科技创新人才团队专项资助(202304051001034)
山西省重点研发计划(202302150101006)
中央引导地方科技发展资金项目(YDZJSX2025C026)
山西省留学人员科技活动项目(20230031)
山西省省筹资金资助回国留学人员科研资助项目(2023-151)
山西省基础研究计划(202303021221147,202203021222204,202303021212224)
江淮前沿技术协同创新中心追梦基金课题(2023-ZM01C002)
太原科技大学启动资金(20222121,20232033)。
关键词
聚丙烯腈
高温热解
ReaxFF力场
分子动力学
polyacrylonitrile
high-temperature pyrolysis
ReaxFF force field
molecular dynamics
