水介质中铁氰化钾作用下2,6-二甲基苯酚氧化聚合初始动力学  

A Kinetic Study of Oxidative Polymerization of 2,6-Dimethylphenol with Potassium Ferricyanide in Water

作　　者：刘群[1] 朱金华[1] 顾成[1] 申屠宝卿[1] 翁志学[1] 

机构地区：[1]浙江大学化学工程与生物工程系化学工程联合国家重点实验室,浙江杭州310027

出　　处：《高校化学工程学报》2009年第5期791-795,共5页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金资助项目(20674075);浙江省自然科学基金资助项目(Y404299)

摘　　要：采用电化学方法研究了水介质中铁氰化钾作用下2,6-二甲基苯酚(DMP)氧化聚合初始动力学,确定了各反应参数对DMP氧化聚合的影响。发现DMP聚合初始速率随DMP和铁氰化钾浓度的增加而增加,DMP聚合初始速率与DMP浓度的一次方呈正比,与铁氰化钾浓度的二次方呈正比。DMP聚合初始速率随NaOH浓度的增加而增加,这是因为DMP的氧化电位随NaOH浓度的增加而降低,DMP聚合初始速率与NaOH浓度的二次方呈正比。DMP聚合初始速率随温度的升高而增加,根据初始速率求出了不同温度下DMP聚合初始速率常数,并由Arrhenius方程求得DMP氧化聚合的表观活化能为47.7kJ·mol-1。最后根据Arrhenius方程和聚合初始速率与反应物浓度的关系建立了DMP聚合初始动力学模型,并验证了模型的正确性。The initial oxidative polymerization kinetics of 2,6-dimethylphenol （DMP） in water with potassium ferricyanide （K3Fe（CN）6） was investigated by the electrochemical method. The effect of reaction parameters on the oxidative polymerization of DMP was studied. It was found that the initial polymerization rate of DMP increases with the increase of DMP and K3Fe（CN）6 concentrations,and the reaction orders with respect to the concentration of DMP and K3Fe（CN）6 are 1 and 2,respectively. The initial polymerization rate of DMP increases with the increase of NaOH concentration due to the decrease of the oxidative potentional of DMP with the increase of NaOH concentration,and the reaction order with respect to the concentration of NaOH is 2. The initial polymerization rate of DMP increases with the increase of temperature. The initial polymerization rate constant of DMP was calculated based on the initial polymerization rate. The apparent activation energy of the oxidative polymerization of DMP was calculated to be 47.7 kJ·mol^-1 according to Arrhenius equation. The initial polymerization kinetics model of DMP polymerization under the action of K3Fe（CN）6 was proposed according to the reaction order and Arrhenius equation,and the proposed model was verified.

关 键 词：2 6-二甲基苯酚(DMP) 氧化聚合 动力学 铁氰化钾 电化学方法 

分 类 号：Q813.11[生物学—生物工程]