Preparation and Properties of Alkyl Trifluorovinyl Ethers and Related Compounds

Abstract

Trifluorovinyl methyl, ethyl, isopropyl and tert-butyl ethers have been prepared. These trifluorovinyl ethers show C=C absorption at such a short wavelength as 5.46∼5.50μ. The methyl and ethyl ethers can be polymerized by free-radical initiators. Halogen addition products of trifluorovinyl- and 1, 2-difluoro-2-chlorovinyl ethers have also been prepared. With α-halo or vinyl ethers, the reactions that are catalyzed by acids, including decomposition, are best interpreted as proceeding through the carbonium ion stabilized by carbonium-oxonium resonance.

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

“…Et-TFVE and Ph-TFVE were synthesized as previously described 4 and according to published methods 11 and purified by vacuum fractional distillation to greater than 97% purity as determined by GC, 1 H and 19 F NMR. EVE and VAc were purchased from Aldrich (Ontario, Canada) and purified by short path distillation prior to use.…”

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

“…The three TFVE monomers, Et-TFVE, t-Bu-TFVE, and Ph-TFVE, were prepared as previously described 5 and according to published methods. 10 The monomers were purified by fractional distillation to greater than 99% purity, as determined by gas chromatography, F-NMR spectra were obtained on a Varian Gemini 300 MHz spectrometer in CDCl 3 , using TMS and CFCl 3 as external references, respectively. FTIR spectra were obtained using a Galaxy Series 5000 spectrometer.…”

Synthesis of perfluoro-t-butyl trifluorovinyl ether and its copolymerization with TFE

“…Among all perfluoroalkyl trifluorovinyl ethers, perfluoro-t-butyl trifluorovinyl ether has not been explored. The synthesis of perfluoro-t-butyl trifluorovinyl ether monomer has not been reported, though its hydrocarbon counterpart, t-butyl trifluorovinyl ether, was reported a long time ago [9]. Herein, we describe the synthesis of perfluoro-t-butyl trifluorovinyl ether and its copolymerization with TFE.…”

“…R could be a variety of alkyl groups, such as methyl, ethyl (including trifluoroethyl), isopropyl, tert-butyl, etc. The apparent reactivity of the alcoholates toward tetrafluoroethylene increased in the following order: methyl, ethyl < isopropyl, tert-butyl [9]. However, tert-butyl trifluorovinyl ether was very unstable and decomposed, upon standing, to the acyl fluoride and isobutene.…”

“…Later on, fluorinated vinyl ethers were directly synthesized by the reaction of alcohol-free sodium alcoholates with fluoroolefins [7]. When tetrafluoroethylene (TFE) was used as the fluoroolefin, the resulting products were trifluorovinyl ethers ROCF5 5CF 2 [8,9]. R could be a variety of alkyl groups, such as methyl, ethyl (including trifluoroethyl), isopropyl, tert-butyl, etc.…”