Early Transition Metal Catalysis for Olefin–Polar Monomer Copolymerization

Jiazhen Chen, Yanshan Gao*, Tobin J. Marks

*Corresponding author for this work

Research output: Contribution to journalReview articlepeer-review

9 Scopus citations


Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value-added applications. The metal catalyst-mediated copolymerization of non-polar olefins with polar comonomers represents the seemingly most straightforward, atom- and energy-efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)-catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co-monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.

Original languageEnglish (US)
Pages (from-to)14726-14735
Number of pages10
JournalAngewandte Chemie - International Edition
Issue number35
StatePublished - Aug 24 2020


  • catalyst design
  • early transition metal
  • olefin
  • polar monomer
  • polymerization

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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