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    乙烯/双环戊二烯连续溶液聚合及反应动力学

    Continuous solution polymerization of ethylene/dicyclopentadiene and its reaction kinetics

    • 摘要: 为了获得环烯烃单体来源丰富、价格低廉的环烯烃共聚物(COC),以rac-Et(Ind)2ZrCl2为催化剂,有机硼盐Ph3CB(C6F5)4和三异丁基铝(iBu3Al)复配物为活化剂,改变聚合温度、乙烯压力和双环戊二烯(DCPD)质量分数等参数,研究了乙烯/DCPD的连续溶液共聚合。首先在稳态条件下,测定了两种单体的竞聚率,确定共聚物的组成模型,建立了表观聚合速率方程。研究结果表明,rac-Et(Ind)2ZrCl2/Ph3CB(C6F5)4/iBu3Al催化乙烯与DCPD共聚,DCPD竞聚率(rD)小于1,随温度升高而增大;乙烯竞聚率(rE)大于1,也随温度升高而增大;rE rD < 1表明所得共聚物为无规共聚物。随着反应温度的升高,聚合活性先升高后降低,聚合物分子量单调降低;随着DCPD质量分数的增大,环烯烃插入率单调升高。均聚与共聚反应活化能的计算证明,DCPD的加入有利于共聚。乙烯/DCPD共聚物的平均组成符合一阶马尔可夫模型;设定催化剂物质的量浓度为1 μmol·mL−1时,共聚反应的表观动力学方程为Rp = 0.0156MDME0.26。研究结果可为DCPD基COC的工业化生产提供参考。

       

      Abstract: To synthesize cycloolefin copolymers (COC) from readily available and economical monomers, the continuous solution copolymerization of ethylene and dicyclopentadiene (DCPD) was investigated using the rac-Et(Ind)2ZrCl2 / Ph3CB(C6F54 / iBu3Al catalyst system. The effects of key parameters including reaction temperature, ethylene pressure, and DCPD mass fraction were systematically examined. Under steady-state conditions, the monomer reactivity ratios were determined, enabling the establishment of a copolymer composition model and an apparent copolymerization rate equation. The results demonstrated that in this catalytic system, the reactivity ratio of ethylene (rE) exceeds 1 and increases with temperature, whereas that of DCPD (rD) remains below 1 but exhibits a similar temperature-dependent rise. The product rE rD < 1 confirmed the formation of a random copolymer. Polymerization activity displayed a non-monotonic dependence on temperature, initially increasing before declining, while copolymer molecular weight decreases steadily. DCPD incorporation increased with its feed mass fraction. Kinetic analysis indicated that DCPD enhanced copolymerization, as supported by the calculated activation energies for homo- and copolymerization. The copolymer composition follows the first-order Markov model, and the apparent kinetic equation is derived as Rp = 0.0156MDME0.26 when the catalyst molarity sets at 1 μmol·mL−1. The research conclusion provides a reference for the industrial production of DCPD based COC.

       

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