系统测定了近临界水中210℃～290℃下聚甲基丙烯酸甲酯的无催化和醋酸催化下水解反应动力学数据,并采用傅立叶变换红外光谱仪、凝胶色谱仪、热重分析仪对水解产物进行了表征。结果表明,近临界水中聚甲基丙烯酸甲酯水解改性是可行的,通过改变水解工艺条件可获得一系列不同酯基及羧基含量的水解产物;以自催化反应动力学模型对实验数据进行拟合,得到了无催化和1 mol/L醋酸催化条件下聚甲基丙烯酸甲酯水解反应活化能分别为47.3 kJ/mol和34.2 kJ/mol。
The hydrolysis kinetics of polymethyl methacrylate（PMMA） was systematically studied under the conditions of non-catalyzed and catalyzed for acetic acid in near-critical water in the temperature range from 210 ℃ to 290 ℃ and hydrolysis products were characterized by infrared spectrum（IR）,gel permeation in chromatography（GPC） and thermogravimetry（TG）.The results reveal that hydrolysis of PMMA in near critical water is feasible.Binary copolymers with different contents of functional groups can be obtained by altering the reaction conditions.Both temperature and the material ratio play an important role in hydrolysis rate of PMMA.The same time,the introduction of acetic acid in near critical water（NCW） can greatly increase the reaction rate.Using the assumption of autocatalytic kinetics equation,the activation energies evaluated are 47.3 kJ/mol for non-catalyzed hydrolysis and 34.2 kJ/mol for acetic acid catalyzed hydrolysis at the acetic acid concentration of 1 mol/L,respectively.
参考文献
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