对二氯苯和N-甲基-4-氨基丁酸钠的反应动力学  

Reaction kinetics of p-dichlorobenzene with sodium N-methyl-4-aminobutyrate

作　　者：尹红[1,2] 申尧 陈志荣 袁慎峰[1] 贾艳宇[3] 蒋杰 李沃源 贾锦波 邓杭军 李鹏 竹弘 周银娟 YIN Hong;SHEN Yao;CHEN Zhirong;YUAN Shenfeng;JIA Yanyu;JIANG Jie;LI Woyuan;JIA Jinbo;DENG Hangjun;LI Peng;ZHU Hong;ZHOU Yinjuan(College of Chemical and Biological Engineering,Zhejiang University,Hangzhou 310058,China;Zhejiang Key Laboratory of Smart Biomaterials,Zhejiang University,Hangzhou 310058,China;Zhejiang NHU Special Materials Co.Ltd.,Shangyu 312369,China;Zhejiang NHU Research Center,Xinchang 312599,China)

机构地区：[1]浙江大学化学工程与生物工程学院,浙江杭州310058 [2]浙江省智能生物材料重点实验室,浙江杭州310058 [3]浙江新和成特种材料有限公司,浙江上虞312369 [4]浙江新和成研究院,浙江新昌312599

出　　处：《高校化学工程学报》2023年第6期925-935,共11页Journal of Chemical Engineering of Chinese Universities

摘　　要：为了探究对二氯苯(DCB)与N-甲基-4-氨基丁酸钠(SMAB)的反应对聚苯硫醚(PPS)聚合反应的影响,采用动力学方法研究PPS聚合条件下DCB与SMAB的反应。通过分析反应网络、简化反应过程,建立产物N,N′-二甲基-N,N′-(1,4-亚苯基)-4,4′-二氨基二丁酸钠、N,N′-二甲基-N,N′-(1,3-亚苯基)-4,4′-二氨基二丁酸钠(均记为d-SPMAB)、N-甲基-N-(3-氯苯基)-4-氨基丁酸钠(m-SCMAB)、N-甲基-N-(4-氯苯基)-4-氨基丁酸钠(p-SCMAB)和对氯苯酚钠(p-SCP)的生成反应动力学模型;根据质量作用定律、采用稳态假设,推导出各产物的生成反应动力学方程,并运用实验数据进行线性拟合。结果表明:产物d-SPMAB、m-SCMAB、p-SCMAB和p-SCP的生成反应表观活化能分别为168.8、154.5、120.3和131.6 kJ·mol^(-1);增大SMAB与DCB物质的量比可以加快反应,但不改变反应机理;水有利于DCB的水解反应,但溶剂化作用会阻碍DCB与SMAB的取代反应。In order to investigate the effect of p-dichlorobenzene(DCB)and sodium N-methyl-4-aminobutyrate(SMAB)reaction on the polymerization of polyphenylene sulfide(PPS),reaction kinetics of DCB and SMAB under conditions similar to the preparation of PPS was studied.After the analysis of reaction network and simplifications of reaction processes,kinetic models of the formation of sodium N,N′-(1,4-phenylene)-N,N′-dimethyl-4,4′-diaminobutyrate and sodium N,N′-(1,3-phenylene)-N,N′-dimethyl-4,4′-diaminobutyrate(both denoted as d-SPMAB),sodium N-(3-chlorophenyl)-N-methyl-4-aminobutyrate(m-SCMAB),sodium N-(4-chlorophenyl)-N-methyl-4-aminobutyrate(p-SCMAB),and sodium p-chlorophenolate(p-SCP)were established.Following mass action law and steady state theory,the kinetic equations were derived and fitted with experiment data through linear regression.The fitting results show that the apparent activation energies for the formation of d-SPMAB,m-SCMAB,p-SCMAB,p-SCP are 168.8,154.5,120.3 and 131.6 kJ·mol-1,respectively.A higher ratio of SMAB to DCB can accelerate the reaction but don't change the reaction mechanism.Moreover,water is favorable to the hydrolysis of DCB,while the solvation of water hinders the substitution reaction between DCB and SMAB.

关 键 词：反应动力学 对二氯苯 N-甲基-4-氨基丁酸钠 活化能 聚苯硫醚 

分 类 号：TQ324.8[化学工程—合成树脂塑料工业]