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    PCTG终缩聚动力学及模型化研究

    Kinetics and Modeling of PCTG Final Polycondensation

    • 摘要: 采用静态薄膜实验装置,在温度250~290℃、绝对压力40~1000 Pa条件下,研究了聚对苯二甲酸环己烷二甲酯-乙二醇酯(PCTG)终缩聚阶段的反应动力学。针对PCTG终缩聚阶段高粘度熔体中挥发分的传质过程,以及反应过程中物质浓度与聚合度随时间的动态演化特征,通过核磁共振氢谱(1H NMR)测定不同反应条件下样品的平均分子量,建立了包含四种反应路径的PCTG缩聚动力学模型,并将小分子(乙二醇和环己烷二甲醇)的传质过程与化学反应相耦合,实现了对端基浓度、分子量随时间变化的定量描述。采用最小二乘法拟合实验数据,求解了22个模型参数,模型决定系数R2达0.968。结果表明:升高温度和降低压力均可促进缩聚反应正向进行,提高产物平均分子量;薄膜厚度减小有利于挥发分脱除,从而加速反应;四种反应路径的速率常数大小顺序为k1>k2>k3>k4,且表观活化能相近。将动力学参数应用于圆盘反应器的计算示例表明,该模型可用于指导PCTG工业化生产操作条件的优化。

       

      Abstract: The reaction kinetics of the final polycondensation stage of poly(cyclohexylene dimethylene terephthalate-co-ethylene terephthalate) (PCTG) was studied using a static thin-film experimental apparatus under conditions of 250–290℃ and 40–1000 Pa. A polycondensation kinetic model featuring four reaction pathways was developed to elucidate the mass transfer behavior of volatiles and the dynamic evolution of composition in high-viscosity PCTG melts. By integrating 1H NMR measurements of average molecular weights with a coupled mass-transfer and reaction scheme for ethylene glycol and cyclohexanedimethanol, the model quantitatively predicts the time-dependent profiles of end-group concentrations and molecular weights.Twenty-two model parameters were obtained by least-squares fitting of experimental data, with a coefficient of determination R2; of 0.968. The results showed that increasing temperature and decreasing pressure promoted the forward polycondensation reaction, leading to higher average molecular weights. Reducing film thickness facilitated volatile removal and accelerated the reaction. The rate constants followed the order k1>k2>k3>k4 with similar apparent activation energies. An application example for a disc reactor demonstrated that the model can guide the optimization of operating conditions for industrial PCTG production.

       

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