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Abstract <p>We investigated the kinetics of ethylene polymerization using a metallocene/MAO/ Al(Et)<sub>1.5</sub>(OC<sub>2</sub>H<sub>5</sub>)<sub>1.5</sub> ternary catalytic system at 60–90°C and 600 kPa. Three different unbridged metallocene catalysts were used: (Ind)<sub>2</sub>ZrCl<sub>2</sub> (<b>I</b>), (BenzInd)<sub>2</sub>ZrCl<sub>2</sub> (<b>II)</b>, and (Flu)<sub>2</sub>ZrCl<sub>2</sub> (<b>III)</b>. We studied the effects of ligand structure, co-catalysis, and the activation energy of the deactivation reaction. Depending on the catalyst concentration, deactivation proceeds as a first-order reaction. In the ternary catalytic system, the half-life is highly dependent on the ligand structure, with the activation energy of deactivation for catalyst <b>I</b> being lower than for catalysts <b>II</b> and <b>III</b>. At 60°C, the half-lives of unbridged metallocenes <b>I</b> and <b>II</b> are slightly lower than that of <b>III</b>. With increasing temperature, the half-lives of <b>II</b> and <b>III</b> decrease similarly, but <b>I</b> deactivates much faster.</p>

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Deactivation Kinetics of Zirconocene-Catalyzed Ethylene and 1-Butene Copolymerization

  • 期刊论文

  • 发表日期：

    2026年2月1日

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  • Hyon-Ung Ri,
  • Wi-Song Kim,
  • Thae-Won Maeng,
  • Ju-Gyong Kim,
  • Ki-Chol O,
  • Hyok-Chol Jo,
  • Chung-Hyok Sin

摘要

Abstract

We investigated the kinetics of ethylene polymerization using a metallocene/MAO/ Al(Et)1.5(OC2H5)1.5 ternary catalytic system at 60–90°C and 600 kPa. Three different unbridged metallocene catalysts were used: (Ind)2ZrCl2 (I), (BenzInd)2ZrCl2 (II), and (Flu)2ZrCl2 (III). We studied the effects of ligand structure, co-catalysis, and the activation energy of the deactivation reaction. Depending on the catalyst concentration, deactivation proceeds as a first-order reaction. In the ternary catalytic system, the half-life is highly dependent on the ligand structure, with the activation energy of deactivation for catalyst I being lower than for catalysts II and III. At 60°C, the half-lives of unbridged metallocenes I and II are slightly lower than that of III. With increasing temperature, the half-lives of II and III decrease similarly, but I deactivates much faster.