羧甲基纤维素交联缩合反应的动力学研究  

Study on the kinetics of crosslinking reaction of carboxymethyl cellulose

作　　者：张晋[1] 黎钢[1] 杨芳[1] 邢鹏云[2] 

机构地区：[1]河北工业大学化工学院,天津300130 [2]新疆油田公司勘探公司,新疆克拉玛依834000

出　　处：《计算机与应用化学》2010年第3期364-368,共5页Computers and Applied Chemistry

摘　　要：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)。It is estimated the research methods of crosslink reaction kinetics between carboxymethyl cellulose and phenol-formaldehyde resol resin in order to get the kinetic equation. Because phenol-formaldehyde resol resin have lots of active intermediates with different functional groups, furthermore, carboxymethyl cellulose are more impacted by substitute degree and polymeric degree, crosslink reaction would take place at many positions in several molecules with differential chemical environment. So there are complex crosslink reactions which are not available to be studied by mechanistic methods. It is studied on the reaction kinetic by Borchardt-Daniels method and Kissinger method based on the heating/low data determined by the different scanning calorimetry （DSC） in order to get the kinetic equation. The values of reaction energy, reaction order and pre exponential factor calculated by Borchardt-Daniels method are respectively 93.86 kJ/mol, 16. 23 and 1.05. Kissinger method is based on the variation of the exothermal peak temperature with heating rate, at least three heating rates. The values of reaction energy, reaction order and pre exponential factor calculated by Kissinger method are respectively 94. 37 kJ/mol, 15.96 and 1.04. As the tolerance between the Borchardt-Daniels method and Kissinger method are 0. 55%, 1.71% and 1.14% as the value of energy, reaction order and pre exponential factor separately. It is certain that the kinetic parameters are much better consistent with two methods. The kinetic equation of the crosslink reaction between carboxymethl cellulose and phenol-formaldehyde resol resin isdα/dt=e-16.24E/RT（1-α）^1.05.

关 键 词：羧甲基纤维素 水溶性酚醛树脂 交联缩合反应 动力学参数 Borchart—Daineils模型 

分 类 号：TQ03-3[化学工程] TQ015.9