Computational modeling of heterogeneous Ziegler-Natta catalysts for olefins polymerization

Naeimeh Bahri-Laleh*, Ahad Hanifpour, Seyed Amin Mirmohammadi, Albert Poater, Mehdi Nekoomanesh-Haghighi, Giovanni Talarico, Luigi Cavallo

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

128 Scopus citations


Since 1963, when Karl Ziegler and Giulio Natta were jointly awarded the Nobel Prize for their discoveries of the catalytic polymerization of olefins with Ti-chlorides and Al-alkyls, heterogeneous Ziegler-Natta (ZN) catalysts have become the main catalysts for the industrial production of polyolefins. Despite of the relevance of ZN catalysts for the large-scale production of polyolefins, a clear mechanistic understanding of these catalysts is still incomplete due to the elusive nature of the active site structures. Over the last two decades, researchers have used density functional theory (DFT) methods to clarify the polymerization mechanisms and to identify the nature of the active sites, unraveling the influence of supports, cocatalysts, and the effect of internal and external donors on the polymerization processes. Major efforts were dedicated to understanding the origin of stereoselectivity in α-olefin polymerization as well as the termination reactions mechanisms, and the role that impurities can play in heterogeneous ZN catalysis. Here, we review the DFT studies on heterogeneous ZN catalysts and suggest promising areas for future research.

Original languageEnglish (US)
Pages (from-to)89-114
Number of pages26
JournalProgress in Polymer Science
StatePublished - Sep 2018

Bibliographical note

Publisher Copyright:
© 2018 Elsevier B.V.


  • Computational modeling
  • DFT
  • Olefin polymerization
  • Polyolefin
  • Ziegler-Natta catalysts

ASJC Scopus subject areas

  • Ceramics and Composites
  • Materials Chemistry
  • Polymers and Plastics
  • Surfaces and Interfaces
  • Organic Chemistry


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