Polymerization of novel trifluorovinyl ethers: Insight into the mechanismsof termination and chain transfer

New trifluorovinyl ether polymers were synthesized with the view toward ove rcoming the high chemical and thermal stabilities commonly associated with fluoropolymers. Trifluorovinyl ether copolymers, with fluorinated pendant g roups, have previously been prepared to overcome limitations in processibil ity. To further enhance solubility in common organic solvents and to improv e processibility, we prepared three new trifluorovinyl ether monomers, havi ng hydrocarbon ether pendant groups, for polymerization: 1-[2-(2-ethoxy eth oxy)ethoxy]-1,2,2-trifluoroethene (Et-TFVE), 1-[2-(2-t-butoxy ethoxy)ethoxy ]-1,2,2-trifluoroethene (t-Bu-TFVE), and 1-(2-phenoxy ethoxy)-1,2,2-trifluo roethene (Ph-TFVE). Homopolymers of these three monomers were prepared by a queous emulsion polymerization with the use of a redox initiator. Poly(Et-T FVE) and poly(Ph-TFVE) were prepared with a range of molar masses, the high est of which had weight average molar masses of 33,800 g mol(-1) and 59,000 g mol(-1), respectively. As a result of monomer reactivity and structure, the polymerization mechanism was complicated, resulting in beta-scission te rmination/chain transfer for all three polymers and hydrogen abstraction ch ain transfer for poly(Et-TFVE) and poly(t-Bu-TFVE). To the best of our know ledge, this is the first example of hydrogen abstraction from the pendant g roup of the trifluorovinyl ether itself. (C) 1999 John Wiley & Sons, Inc.