六亚甲基二异氰酸酯与丙烯酸羟乙酯反应动力学及热动力学研究  

Kinetics and Thermodynamics Study of Hexamethylene Diisocyanate and Hydroxyethyl Acrylate Reaction

作　　者：周瑞翔 李韦龙 董永路 桂雪峰 胡继文[1,2,4,5,6] 林树东 ZHOU Ruixiang;LI Weiong;DONG Yongu;GUI Xuefeng;HU Jiwen;LIN Shudong(Guangzhou Institute of Chemistry,Chinese Academy of Sciences,Guangzhou 510650,China;University of Chinese Academy of Sciences,Beijing 100049,China;Management Committee of Shaoguan NanXiong Hi-Teac Industry Development Zone,Nanxiong 512400,China;CAS Engineering Laboratory for Special Fine Chemicals,Guangzhou 510650,China;CASH GCC Shaoguan Research Institute of Advanced Materials,Shaoguan 512400,China;CASH GCC Fine Chemicals Incubator(Nanxiong)Co.,Ltd,Nanxiong 512400,China)

机构地区：[1]中国科学院广州化学研究所,广东广州510650 [2]中国科学院大学,北京101408 [3]韶关南雄高新技术产业开发区管理委员会,广东韶关512400 [4]中国科学院新型特种精细化学品工程实验室,广东广州510650 [5]国科广化韶关新材料研究院,广东韶关512400 [6]国科广化精细化工孵化器(南雄)有限公司,广东南雄512400

出　　处：《广州化学》2024年第4期22-27,I0002,F0003,共8页Guangzhou Chemistry

基　　金：广东省自然科学基金面上项目(2021A1515012334)。

摘　　要：研究了六亚甲基二异氰酸酯(HDI)与丙烯酸羟乙酯(HEA)在聚氨酯合成反应中的动力学和热动力学特征。在反应动力学方面,采用甲苯-二正丁胺滴定法获取了反应转化率数据,分别构建了二级动力学模型和Sato动力学模型来拟合实验数据。结果表明:该反应符合Van't Hoff近似规则;低转化率时,二级动力学模型拟合效果较好;而在高转化率时,由于存在自催化作用,Sato动力学模型具有更好的拟合优势;在热动力学方面,使用绝热加速量热仪(ARC)对反应放热进行了表征分析,结果显示该反应的热动力学反应级数为0.8,表观活化能为57.51 kJ/mol。该研究为聚氨酯的安全、高效和绿色合成提供了科学理论依据。This study investigates the kinetics and thermodynamic characteristics of the reaction between hexamethylene diisocyanate(HDI)and hydroxyethyl acrylate(HEA)in polyurethane synthesis.In terms of reaction kinetics,the reaction conversion rate data were obtained using the toluene-di-n-butylamine titration method,and both a second-order kinetic model and a Sato kinetic model were constructed to fit the experimental data.The results indicate that the reaction complies with the Van't Hoff approximation rule;the second-order kinetic model performs well at low conversion rates,while the Sato kinetic model exhibits better fitting advantages at high conversion rates due to the presence of autocatalysis.Regarding thermodynamics,adiabatic reaction calorimetry(ARC)was employed to characterize the reaction heat release,revealing a thermodynamic reaction order of 0.8 and an apparent activation energy of 57.51 kJ/mol for the reaction.This study provides a scientific basis for the safe,efficient,and environmentally friendly synthesis of polyurethanes.

关 键 词：六亚甲基二异氰酸酯 丙烯酸羟乙酯 反应动力学 热动力学 绝热加速量热仪 

分 类 号：TQ311[化学工程—高聚物工业]