高校化学工程学报2025，Vol.39Issue(6)：1002-1013,12.DOI:10.3969/j.issn.1003-9015.2025.00.012
4-羟基-2-苯甲酸和6-羟基-2-萘甲酸的乙酰化动力学
Kinetics of acetylation of 4-hydroxy-2-benzoic acid and 6-hydroxy-2-naphthoic acid
摘要
Abstract
The acetylation of 4-hydroxybenzoic acid(HBA)and 6-hydroxy-2-naphthoic acid(HNA)with acetic anhydride is a key step in synthesizing high-performance liquid crystalline polyarylate monomers.A real-time moni-toring method using in situ Raman spectroscopy was developed to investigate the kinetics of acetylation reactions at various temperatures and feeding ratios.The reaction kinetics were modeled with experimental data,yielding root mean square errors of 5.57×10-3 and 2.71×10-3 for the predicted conversions.Results indicate that both reactions are reversible reactions,with apparent activation energies of 53.5 kJ·mol-1(HBA)and 45.1 kJ·mol-1(HNA),and pre-exponential factors of 2.9×103 and 9.2×102 L·mol-1·min-1,respectively.The equilibrium constants as a func-tion of temperature were given by 14.5exp(396.29/T)for HBA and 18.4exp(565.31/T)for HNA.The phenolic hydroxyl conversion in the acetylation of both HBA and HNA increased with higher temperatures or feeding ratios.In the HBA system,decreasing the temperature or increasing the feeding ratios favored a product acetoxy-to-carboxyl ratio closer to 1.In contrast,the acetoxy-to-carboxyl ratio in the HNA system remained stable around 0.9 under various experimental conditions.关键词
液晶聚芳酯/乙酰化/原位拉曼光谱/动力学模型/转化率Key words
liquid crystalline polyarylate/acetylation/in situ Raman spectroscopy/kinetic modeling/con-version分类
化学化工引用本文复制引用
姚家锐,吴雨轩,常诚,张才亮,顾雪萍,冯连芳..4-羟基-2-苯甲酸和6-羟基-2-萘甲酸的乙酰化动力学[J].高校化学工程学报,2025,39(6):1002-1013,12.基金项目
浙江省自然科学基金(LZY22E030004). （LZY22E030004）
