固体酸催化苯基多元羧酸酯化反应动力学研究  

Study on esterification kinetics of phenyl carboxylic acid catalyzed by solid acid

作　　者：曹枭汉 孙国静 蒋燕迪 彭翠娜 张范 杨成 Cao Xiaohan;Sun Guojing;Jiang Yandi;Peng Cuina;Zhang Fan;Yang Cheng(Department of Chemistry and Chemical Engineering,University of Jinan,Jinan Shandong 250022,China;Weifang Hongrun New Material Co.,Ltd.,Weifang Shandong 261000,China)

机构地区：[1]济南大学化学化工学院,山东济南250022 [2]潍坊弘润新材料有限公司,山东潍坊261000

出　　处：《石油化工》2022年第9期1069-1074,共6页Petrochemical Technology

基　　金：山东省重点研发计划项目(2019GSF111068);济南市科技发展计划项目(201602103)。

摘　　要：对苯基多元酸酐与异辛醇的酯化反应动力学进行比较研究,采用工业成型固体酸催化剂,在间歇釜式反应器中研究了均苯四甲酸二酐、偏苯三甲酸酐和邻苯二甲酸酐与异辛醇的酯化反应宏观反应动力学,考察了反应物分子空间结构、反应过程位阻及反应速率之间的变化规律。实验结果表明,在醇羟基与苯环取代基的摩尔比为1.75、催化剂用量为酸酐质量的5%(w)、搅拌转速350 r/min反应条件下,均苯四甲酸二酐、偏苯三甲酸酐和邻苯二甲酸酐反应活化能分别为111.66,120.13,96.75 kJ/mol。宏观反应速率受自催化过程中的反应过渡态的空间位阻影响较大,在微观反应过程中过渡态的空间位阻大小顺序为:偏苯三甲酸酐>均苯四甲酸二酐>邻苯二甲酸酐。The kinetic characteristics of esterification reaction between phenyl polyanhydrides and isooctanol were compared.The macro kinetic parameters of esterification reaction between pyromellitic dianhydride,trimellitic anhydride,phthalic anhydride and isooctanol were studied in a batch reactor using industrial solid acid as catalyst.The spatial structure of reactants,steric hindrance and reaction rate were investigated.Activation energies of the reaction were 111.66,120.13,96.75 kJ/mol respectively,under the conditions of the molar ratio of alcohol hydroxyl to benzene ring substituent of 1.75,catalyst dosage of 5%(w)anhydride mass and stirring speed of 350 r/min.The macroscopic reaction rate is greatly affected by the steric hindrance of the transition state in the autocatalytic process.In the microscopic process of the reaction,the steric hindrance of the transition state is in the order of trimellitic anhydride>pyromellitic dianhydride>phthalic anhydride.

关 键 词：苯基多元羧酸酯 催化酯化 空间位阻 反应动力学 

分 类 号：TQ342[化学工程—化纤工业]