A method for the production of poly(vinyl trifluoroacetate) and copolymers thereof with vinyl esters is described. Poly(vinyl trifluoroacetate) (PVTFA) is obtained in relatively high yield under mild conditions by using carbon dioxide under supercritical conditions as a solvent. Synthesis of syndiotactic PVTFA on a commercial scale without the use of environmentally-harmful solvents is made possible by the invention, which provides a convenient route to syndiotactic polyvinyl alcohol.
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