Catalytic polymerization in dense CO2 to controlled Microstructure polyethylens

Damien Guironnet, Inigo Göttker-Schnetmann, Stefan Mecking

Research output: Contribution to journalArticlepeer-review

Abstract

A series of partially novel, (K2-N,O) Ni(II) methyl complexes coordinated by pyridine or N, N, N′, N′-tetramethylethylenediamine (tmeda), based on different K2-N,O-chelating salicylaldimines, 2,6-diisopropylanilinotropone, and a ketoenamine, were studied as precatalysts for olefin polymerization in dense carbon dioxide. Bis(trifluoromethyl)phenyl substituents promote solubility in the CO2 reaction medium, as quantified by solubility studies of the free N,OH ligands over a range of CO2 densities (p = 0.2-0.9 g mL-1) at 25 and 50°C and thus enhance catalyst activities. By appropriate choice of the catalyst precursor and polymerization reaction conditions (CO2 density, ethylene concentration, and temperature), strictly linear polyethylene with high molecular weight is obtained (< 1 branch/1000 carbon atoms, Mw = 106 g mol-1; MW /MN= 2) which displays typical thermal characteristics and density of ultrahigh molecular weight polyethylene. Copolymerization with 1-hexene, and particularly with norbornene, allows for controlling polymer crystallinity and melting temperature down to % < 20% and Tm < 70° C.

Original languageEnglish (US)
Pages (from-to)8157-8164
Number of pages8
JournalMacromolecules
Volume42
Issue number21
DOIs
StatePublished - Nov 10 2009
Externally publishedYes

ASJC Scopus subject areas

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

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