CIESC Journal

• 化工学报 • 上一篇    下一篇

乳液聚合数学模型

曹同玉,A.J.Merry,M.P.Wilson   

  1. 天津大学化工系 ,Patterson Candv,International Ltd.,Whitchcurch,Hants,U.K. ,Dep.of Chem.Eng.,University of Aston Birmingham,U.k.
  • 出版日期:1982-03-25 发布日期:1982-03-25

A Mathematical Model of Emulsion Polymerisation

Cao Tongyu A. J. Merry M. P. Wilson (Dept. of Chem. Eng., (Patterson Candy, (Dept. of Chem. Eng., Tianjin University) Internaional Ltd,, University of Aston Whitchurch, Hants, Birmingham U. K. ) U. K. )   

  • Online:1982-03-25 Published:1982-03-25

摘要: 本文报导了在50℃下苯乙烯乳液聚合和悬浮聚合的试验研究。对在无挡板搅拌釜中的间歇乳液聚合提出了一个数学模型。这个模型不仅考虑了吸附在单体珠滴表面上的乳化剂的影响,而且考虑到凝胶效应。模型所需要的终止速度常数与转化率之间的依赖关系是从悬浮聚合的试验数据整理而成的。结果表明,本模型可以在相当宽的转化率范围内成功地预计转化速率和胶乳中的颗粒尺寸及数目。

Abstract: Experimental studies of emulsion and suspension polymerisation of styrene at 50℃ are reported. It is apparent that the classical model for Stages I and I of an emulsion polymerisation is not valid for the case of low emulsifier concentrations or for the case of high impeller speeds at low or intermediate emulsifier concentrations. A mathematical model for a batch emulsion polymerisation in an unbaffled reactor is proposed which overcomes this problem by taking into account the effect of the adsorption of the emulsifier onto themonomer droplet surfaces. The model is extended into Stage I by incorporation of the effect of the autoacceleration of the conversion rate through reduced radical translational mobility, i. e. the gel-effect. The model presented in this paper for Stage I of an emulsion polymerisation demands knowledge of the total surface area of the dispersed monomer droplets. An existing relationship between dispersed phase droplet diameter and impeller speed and impeller diameter has been incorporated into the model. The predictions of the particle size, particle number and reaction rate obtained via the current model are in good agreement with the experimental data for Stage I and subsequently for Stage I of the reaction. During Stage I of the emulsion polymerisation the increase in polymer particle viscosity reduces the translational mobility of the radicals with the result that the termination rate constant of radicals increases dramatically. The analogous behaviour in a suspension polymerisation of styrene has been investigated and the following relationship between termination rate constant and the level of monomer conversion has been developed. Kt=exp(A1 + A2Xp+A3Xp2+A4Xp3+A5Xp4) where A1=29.5873, A2=-7.4332, A3=45.8577, A4=-95.9184, A5=47.4095. When this relationship is incorporated into the model for emulsion polymerisation, it allows the determination of the average number of radicals per particle. It is apparent that during Stages I and I this value is close to 0.5 as suggested by the Smith and Ewart case II (instantaneous termination)model but for Stage III the average number of radicals per particle increases with increasing conversion. The predictions of the current model are in good agreement with experimental data of emulsion polymerisation of styrene at 50℃ over most of the conversion range.