研究了反应温度、稀释剂种类和稀释剂与环戊二烯的质量比(稀释比)对环戊二烯聚合速率的影响,并对其进行了本征动力学建模。结果表明,低温、高稀释比有利于降低环戊二烯的聚合速率,10℃时环戊二烯的聚合速率约为-20℃时的30倍。以非极性物质二甲苯和极性物质乙腈作稀释剂,分别在0~90℃和0~105℃之间进行动力学数据采集。根据二聚反应特性建立了环戊二烯二聚反应动力学模型,通过实验数据拟合获得模型参数。结果表明,当环戊二烯的稀释剂从二甲苯更换为乙腈时,聚合反应速率常数降低,聚合反应活化能变化不明显(从7.00×10⁴ J/mol增加至7.19×10⁴ J/mol)。通过实验数据对模型进行检验,结果表明模型计算值与实验值吻合较好,进一步证实了模型的可靠性。

The effects of reaction temperature,type of diluent and dilution ratio (mass ratio of diluent to cyclopentadiene) on the dimerization of cyclopentadiene are studied,and the intrinsic kinetic models are developed for the dimerization.Results show that both low temperature and high dilution ratio are beneficial to decrease the polymerization rate of cyclopentadiene.The polymerization rate of cyclopentadiene at 10℃ is about 30 times that at -20℃.The kinetic data are collected at 0-90℃ and 0-105℃ with non-polar xylene and polar acetonitrile as diluent,respectively.According to the dimerization characteristics,the kinetic model is developed for cyclopentadiene dimerization reaction,and the model parameters are obtained by fitting the experimental data.Results show that the rate constant of the polymerization reaction drops but the activation energy for the reaction does not show significant change (from 7.00×10⁴ J·mol^-1 to 7.19×10⁴ J·mol^-1) when the diluent of cyclopentadiene is changed from xylene to acetonitrile.The model is validated with further experimental data,and it is shown that prediction values are in agreement with the experimental ones,which further confirms the reliability of the model.

冯瑾(1999-),女,硕士生,研究方向为化工过程模拟与技术经济,2973618015@qq.com;周利平(1986-),男,博士,高级工程师,研究方向为催化反应工程,通讯联系人,zhouliping@synfuelschina.com.cn。