钛酸四丁酯催化甲基丙烯酸甲酯与正丁醇酯交换反应动力学研究

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摘要由于设备腐蚀和环境污染等问题,甲基丙烯酸丁酯生产工艺逐渐倾向于更为经济环保的酯交换生产工艺。以钛酸四丁酯为催化剂,甲基丙烯酸甲酯与正丁醇通过酯交换法合成甲基丙烯酸丁酯的反应及机理进行了初步研究。首先,根据路易斯酸催化理论,在合理假设和简化的基础上对该反应的机理进行了分析,在此基础上分别建立了基于理想溶液和非理想溶液的动力学模型。通过酯交换反应实验,主要研究了反应温度、反应物初始物质的量之比和催化剂量等因素对反应速率的影响,并根据实验数据回归得到了动力学模型参数和反应的基本热力学数据。结果显示,该酯交换反应为吸热反应,标准摩尔反应焓为14.406 kJ·mol^-1,正、逆反应活化能分别为70.2和51.1 kJ·mol^-1。通过模型计算值与实验数据的比较,证明了推导得到的动力学模型具有较高的可靠性,将为钛酸四丁酯催化甲基丙烯酸甲酯与正丁醇酯交换合成甲基丙烯酸丁酯反应提供一定的理论指导。

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关键词：酯交换反应甲基丙烯酸甲酯反应动力学甲基丙烯酸丁酯正丁醇钛酸四丁酯

Abstract： Due to the problems such as the equipment corrosion and environmental pollution, the production process of butyl methacrylate is gradually replaced with the more environment-friendly transesterification process. In this paper, the reaction and mechanism of the synthesis of butyl methacrylate by transesterification of methyl methacrylate and n-butanol with tetrabutyl titanate as catalyst were initially investigated. Based on the Lewis acid catalysis theory, the mechanism of the reaction was proposed through the reasonable assumptions and simplifications, and the kinetic models based on idea solutions(IS) and non-ideal solutions(NIS) were established, respectively. Through the transesterification experiments, the effects of factors such as reaction temperature, initial molar ratio of reactants and the catalyst amount on the reaction rate were studied, and the model parameters of the kinetic model and the thermodynamic data were obtained from the regression of the experimental data. The results show that the transesterification reaction is an endothermic reversible reaction, the standard molar reaction enthalpy is 14.406 kJ·mol^-1, and the activation energies of the forward and reverse reactions are 70.2 and 51.1 kJ·mol^-1, respectively. The comparison between the calculated values and the experimental data demonstrates that the derived kinetic model is highly reliable and will provide some theoretical guidance for the synthesis of butyl methacrylate by transesterification of methyl methacrylate and n-butanol with tetrabutyl titanate catalyst.

Keywords： transesterification reaction methyl methacrylate reaction kinetics butyl methacrylate 1-butanol tetrabutyl titanate

Received 2022-01-24;

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Corresponding Authors: 蔡旺锋,副教授,E-mail:wfcai@tju.edu.cn。 Email: wfcai@tju.edu.cn

About author: 彭世仁(1996-),男,硕士研究生,现从事反应工程方面的研究。

引用本文:

彭世仁, 王燕, 蔡旺锋.钛酸四丁酯催化甲基丙烯酸甲酯与正丁醇酯交换反应动力学研究[J]. 化学工业与工程, 2024,41(1): 1-11

PENG Shiren, WANG Yan, CAI Wangfeng.Kinetics of the transesterification of methyl methacrylate and n-butanol with tetrabutyl titanate as catalyst[J]. Chemcial Industry and Engineering, 2024,41(1): 1-11

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