硫化钠法合成聚苯硫醚过程反应动力学研究  

Reaction kinetics of the synthesis process of polyphenylene sulfide using sodium sulfide method

作　　者：曾旭旭 王璐 甄卫军 赵玲 Zeng Xuxu;Wang Lu;Zhen Weijun;Zhao Ling(Key Laboratory of oil&Gas Fine Chemicals of Ministry of Education,College of Chemistry and Chemical Engineering,Xinjiang University,Urumqi Xinjiang 830046,China)

机构地区：[1]新疆大学化学与化工学院石油天然气精细化工教育部重点实验室,新疆乌鲁木齐830046

出　　处：《石油化工》2020年第8期767-772,共6页Petrochemical Technology

基　　金：新疆维吾尔自治区重点研发任务项目(2018B02016-1)。

摘　　要：以氯化锂为催化剂,N-甲基吡咯烷酮为溶剂,进行了硫化钠法合成聚苯硫醚过程的反应动力学研究,在180~260℃温度范围内考察了硫化钠单体转化率和氯化钠生成率随反应时间的变化规律,建立了二级小分子缩合反应和自缩聚反应的动力学模型,采用基团贡献法确定了单体小分子缩合的标准摩尔反应焓,并分析了不同温度下反应的放热强度。实验结果表明,聚苯硫醚合成反应可以简化为A2B2型二级小分子缩合反应和AB型自缩聚反应的串联,反应活化能分别为39.2 kJ/mol和115.0 kJ/mol,低温下聚苯硫醚合成反应以小分子缩合反应为主,单体小分子缩合的平均标准摩尔反应焓为-549.6 kJ/mol,采取前期低温、后期高温的操作方式有利于体系反应热的平稳移出。The reaction kinetics of polyphenylene sulfide(PPS)synthesis process by sodium sulfide method using lithium chloride as catalyst and N-methylpyrrolidone as solvent was studied.The changes of both sodium sulfide conversion and sodium chloride productivity with reaction time in the temperature range from 180℃to 260℃were investigated,the kinetic model of the second-order small molecule condensation reaction and the self-condensation reaction are established,the standard molar reaction enthalpy of small molecule condensation between two reactants was estimated by group contribution method and the exothermic strength of the reaction at different temperatures was analyzed.The result shows that the formation of PPS can be expressed by the cascade reactions of A2B2 type small molecule condensation followed by AB type self-polycondensation,and their activation energies are 39.2 kJ/mol and 115.0 kJ/mol respectively,and second-order small molecule condensation reaction is dominant at a lower temperature.The standard molar reaction enthalpy of small molecule condensation between two reactants is-549.6 kJ/mol.The operation mode of low temperature in the early stage and high temperature in the later stage is conducive to the smooth removal of the reaction heat of the system.

关 键 词：聚苯硫醚 反应动力学 小分子缩合反应 自缩聚反应 放热强度 

分 类 号：TQ328.8[化学工程—合成树脂塑料工业]