Radical copolymerization of novel trifluorovinyl ethers with ethyl vinyl ether and vinyl acetate: Estimating reactivity ratios and understanding reactivity behavior of the propagating radical

Two novel trifluorovinyl ether (TFVE) monomers were copolymerized with eith er ethyl vinyl ether (EVE) or vinyl acetate (VAc) in a redox-initiated aque ous emulsion: 1-(2-phenoxyethoxy)-1,2,2-trifluoroethene (Ph-TFVE) and 1-[2- (2-ethoxyethoxy)ethoxy]-1,2,2-trifluoroethene (Et-TFVE). Previous studies d emonstrated a propensity for radical hydrogen abstraction from the oligoeth er pendant group during the homopolymerization of Et-TFVE with continued pr opagation of the resulting radical, thereby providing the rationale to inve stigate the copolymerization of our new TFVEs with EVE or VAc. Reactivity r atios were estimated using the error-in-variables model from a series of bu lk free radical copolymerizations of Ph-TFVE with EVE or VAc. The reactivit y ratios were r(Ph-TFVE) = 0.25 +/- 0.07, r(EVE) = 0.016 +/- 0.04; r(Ph-TFV E) = 0.034 +/- 0.04, r(VAc) = 0.89 +/- 0.08. Partial hydrolysis of polymers containing VAc to vinyl alcohol (VA) resulted in two terpolymers: poly(Ph- TFVE-co-VAc-co-VA) and poly(Et-TFVE-co-VAc-co-VA), respectively. We investi gated the possibility of hydrogen abstraction from VAc during polymerizatio n by comparing the molar mass before and after hydrolysis. Abstraction from VAc was not apparent during polymerization; however, abstraction from the oligoether pendant group of Et-TFVE was again evident and was more signific ant for those copolymers having a greater fraction of Et-TFVE in the monome r feed. (C) 2000 John Wiley & Sons, Inc.