Palladium Catalyzed Copolymerizations of Polar and Non-polar Monomers

Open Access
Author:
Newsham, David K.
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
August 03, 2009
Committee Members:
  • Ayusman Sen, Dissertation Advisor
  • Ayusman Sen, Committee Chair
  • John V Badding, Committee Member
  • Alan James Benesi, Committee Member
  • T C Mike Chung, Committee Member
Keywords:
  • polymer
  • copolymer
  • ethene
  • ethylene
  • carbon monoxide
  • styrene
  • norbornene
  • polar monomer
  • nonpolar monomer
  • alternating copolymer
  • nonalternating copolymer
  • phosphine-sulfonate
  • ligand
  • chelate
  • block copolymer
  • polyketone
Abstract:
Herein, a well-defined, neutral, phosphine-sulfonate ligated, palladium catalyst for the production of polyethene, poly(ethene-co-carbon monoxide, and polyethene-block-poly-(ethene-alt-carbon monox- ide) co-oligomers is reported. The system is living under mild conditions and produces poly(ethene-co- carbon monoxide) with carbon monoxide content ranging from 0–50 mol %. Mechanistic studies suggest that an unusually small difference in the ethene and carbon monoxide binding affinities as well as en- hanced decarbonylation play important roles in determining the copolymer composition. Furthermore, this system was found to be exceptionally tolerant of polar functional-groups, protic solvents, and aque- ous emulsion. This allows for the production of copolymers of ethene with polar monomers, including functionalized norbornenes and styrenes. Finally,the effects of anions and N-substituted imines on the palladium-catalyzed copolymerization of imines with carbon monoxide was investigated.