Transition-metal-catalyzed functional polyolefin synthesis: Effecting control through chelating ancillary ligand design and mechanistic insights

Brad P. Carrow, Kyoko Nozaki

Research output: Contribution to journalArticle

138 Scopus citations

Abstract

The incorporation of polar functional groups into polyolefins can significantly alter the adhesion, barrier and surface properties, dyeability, printability, and compatibility of the resulting "functional polyolefin". Thus, the development of methods for the controlled synthesis of functional polyolefins from industrially relevant monomers holds the potential to expand the range of applications available to this already ubiquitous class of materials. In this Perspective, recent advances in transition-metal-catalyzed functional polyolefin synthesis will be reviewed. A common thread among the innovations discussed here is the perturbation of catalyst function by tailored design of the chelating ancillary ligand, aided in many cases by improved mechanistic understanding. Specific topics discussed here include rare examples of catalyst control over the regio- and stereochemistry of polar monomer insertion by phosphine-sulfonato palladium complexes (Drent-type), rate acceleration of insertion polymerization by binuclear cooperativity using salicylaldiminato nickel complexes (Grubbs-type), and formation of linear copolymers of ethylene and polar vinyl monomers using a cationic palladium catalyst ligated by a bisphosphine monoxide (BPMO) that contrasts the typical polymer microstructures formed by other cationic group 10 catalysts ligated by an α-diimine (Brookhart-type).

Original languageEnglish (US)
Pages (from-to)2541-2555
Number of pages15
JournalMacromolecules
Volume47
Issue number8
DOIs
StatePublished - Apr 22 2014

All Science Journal Classification (ASJC) codes

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Fingerprint Dive into the research topics of 'Transition-metal-catalyzed functional polyolefin synthesis: Effecting control through chelating ancillary ligand design and mechanistic insights'. Together they form a unique fingerprint.

  • Cite this