AA/HPHP与AA/NPG聚酯化反应的动力学研究

Reaction Kinetics in Polyesterification of AA/HPHP and AA/NPG

考虑缩合水的排除对反应体系的影响 ,用体积浓度单位推导出一个新的聚酯反应总包动力学方程 ,并应用到 AA/HPHP和 AA/NPG两个聚酯化反应的动力学研究中 .研究发现 ,自催化聚酯反应的反应级数并不是固定值 ,对于 AA/HPHP和 AA/NPG两个聚酯化反应而言 ,低温时反应级数为 2 .5 ,高温时反应级数为 3 .0 .此外 ,忽略缩合水的排除对聚酯化反应的动力学参数会产生较大误差 .对于 AA/HPHP和 AA/NPG聚酯化反应 ,活化能相对误差分别达 2 1 .5 1 %和 1 1 .3 3 % ;指前因子误差达到 97.40 %和 87.96% .

A new general kinetic equation was derived in which the effect of the removal of condensation water was taken into account completely,and was applied to the polyesterification kinetic study of AA/HPHP and AA/NPG. It was found that the reaction order of self-catalyzed polyesterification was not constant. For these polyesterifications,the reaction order was 2.5 at a low temperature ,while 3.0 at a high temperature. Moreover,if the effect of the removal of condensation water was neglected,the kinetic parameter would have more deviation. For polyesterifications of AA/HPHP and AA/NPG,the relative deviation of activation energy was 21.51%,11.33%,respectively. The relative deviation of frequency factor was 97.4%,87.96%,respectively.