COPOLYMERIZATION OF POLAR/NON-POLAR MONOMERS: FREE RADICAL POLYMERIZATION AND PALLADIUM CATALYZED POLYMERIZATION

Open Access
Author:
Chen, Ying
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
February 17, 2010
Committee Members:
  • Ayusman Sen, Dissertation Advisor
  • Ayusman Sen, Committee Chair
  • Harry R Allcock, Committee Member
  • John V Badding, Committee Member
  • T C Mike Chung, Committee Member
Keywords:
  • Palladium catalyst
  • Lewis acid
  • insertion polymerization
  • Radical polymerization
Abstract:
The primary theme of this thesis is the copolymerization of polar and non-polar monomers. On the one hand, chapter 2 and chapter 3 focus on the copolymerization via a free radical polymerization route. In chapter 2, I compare the effects of various Lewis and Brønsted acids on the 2,2’-azobis(isobutyronitrile) (AIBN) initiated (meth)acrylates/olefin copolymerization, and find a simple way to assess an acid’s efficacy in promoting (meth)acrylate (co)polymerizations. In chapter 3, I continue to explore the potential of Lewis acid catalysts for the (meth)acrylates/olefin copolymerization by calculating the monomer reactivity ratios. Chapter 4, on the other hand, deals with late transition metal catalyzed (co)polymerizations. The synthesis of two asymmetric palladium complexes and their activities for polymerization are presented. On a different note, chapter 5 investigates a simple nickel system that oligomerizes ethylene and has high butene productivity. The final chapter, chapter 6, describes the chain transfer effects of adding olefin into the nickel(II) acetylacetonate/methylaluminoxane (Ni(acac)2/MAO) catalyzed methyl methacrylate (MMA) polymerizations.