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本文研究了羧甲基纤维素和水溶性酚醛树脂的交联缩合动力学的测试方法并得到了该反应的动力学方程。因为水溶性酚醛树脂是多种活性中间体的混合物,羧甲基纤维素是受羧甲基取代度和聚合度影响的大分子,两者的交联缩合反应可以同时发生在多点、多分子之间,动力学研究较为复杂,所以本文分别采用Borchardt-Daniels模型和Kissinger模型方法,根据差示扫描量热仪(DSC)测定不同升温速率下的羧甲基纤维素和水溶性酚醛树脂交联缩合反应的热流曲线数据,计算得到反应动力学方程。利用非等温单一扫瞄速率法的Borchardt-Daniels模型得到的动力学参数为:反应级数n 1.05,反应活化能E 93.86kJ/mol,指前因子InA16.23。采用非等温多加热扫描速率法的Kissinger模型计算得到的动力学参数为:反应级数n 1.04,反应活化能E 94.37 kJ/mol,指前因子InA15.96。3个热力学参数值分别相差0.55%、1.71%和1.14%,证明2种模型计算结果较一致。水溶性酚醛树脂与羧甲基纤维素缩合交联缩合反应的动力学方程为(dα)/(dt)=e~(-16.24E/(RT))(1-α)~(1.05)。
In this paper, the test method of crosslinking and condensation kinetics of carboxymethyl cellulose and water-soluble phenolic resin was studied and the kinetic equation of the reaction was obtained. Because water-soluble phenolic resin is a mixture of a variety of active intermediates, carboxymethyl cellulose is affected by the degree of substitution of the degree of carboxymethyl and the degree of polymerization of macromolecules, the two cross-linked condensation reaction can occur at the same time, multi-molecule In this paper, the Borchardt-Daniels model and the Kissinger model method are respectively used to study the kinetics of carboxymethyl cellulose and water-soluble phenolic resin crosslinking under different heating rates according to differential scanning calorimetry (DSC) Condensation reaction heat flow curve data, calculate the reaction kinetics equation. The kinetic parameters obtained by the Borchardt-Daniels model using a non-isothermal single scan rate method are as follows: reaction order n 1.05, reaction activation energy E 93.86 kJ / mol, and finger pre-factor InA16.23. The kinetic parameters calculated by Kissinger model with non-isothermal and multi-heating scanning rate method are as follows: the reaction order n 1.04, the activation energy E 94.37 kJ / mol and the pre-factor InA 15.96.3 thermodynamic parameters are 0.55% , 1.71% and 1.14% respectively. It is proved that the calculated results of the two models are more consistent. The kinetic equation of condensation reaction of water-soluble phenolic resin with carboxymethyl cellulose was (dα) / (dt) = e ~ (-16.24E / (RT)) (1-α) ~ (1.05).