Effect of the particle size of the TiCl4-Ali-Bu3 catalyst on the contribution from mono- and bimetallic active sites to the polymerization of isoprene

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• 作者：V. Z. Mingaleev
• 关键词：Ziegler—Natta catalysts ; active sites ; 1 ; 3 ; diene polymerization ; stereospecific polymerization mechanism
• 刊名：Kinetics and Catalysis
• 出版年：2016
• 出版时间：January 2016
• 年：2016
• 卷：57
• 期：1
• 页码：52-60
• 全文大小：385 KB
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• 作者单位：V. Z. Mingaleev (1)
  
  1. Ufa Institute of Chemistry, Russian Academy of Sciences, Ufa, 450054, Bashkortostan, Russia
  
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Catalysis
  Physical Chemistry
  Russian Library of Science
  
• 出版者：MAIK Nauka/Interperiodica distributed exclusively by Springer Science+Business Media LLC.
• ISSN：1608-3210

文摘

The interaction between the coordinatively unsaturated surface of ß-TiCl₃ particles and a liquid phase in the TiCl₄-Ali-Bu₃ catalyst is responsible for the final particle size and the regularities of isoprene polymerization. The correlations of the catalyst activity and the molecular characteristics of polyisoprene with catalyst particle size in the course of catalyst formation and reactivation are indicative of the occurrence of two groups of active sites. “Surface” active sites correspond to the monometallic Cossee model, and they are characterized by low activity and low 1,4-cis specificity in the polymerization of isoprene. “Colloid” active sites have a bimetallic structure and produce polyisoprene at a high rate; the concentration of 1,4-cis units in the resulting polyisoprene is as high as 97%. The contribution from the colloid active sites to the polymerization of isoprene increases with the particle size of ß-TiCl₃.