Abstract
AbstractVinyl trifluoroacetate was polymerized by free radicals in various aldehydes at temperatures between −40 and 60°C. The syndiotactic and isotactic diad contents of the polymer were determined through the triads obtained by NMR spectra. The differences of activation enthalpies and entropies of isotactic and syndiotactic arrangement were calculated from the temperature dependence of the ratio of isotactic and syndiotactic diads. In the case of the applied aldehydes, a compensation effect exists between the two quantities, the values of which differ from the values of alkanes, vinyl trifluoroacetate, esters and ketones. The syndiotactic diads of a polymer prepared in aldehydes at 60°C vary from 54 to 56% and are higher than those for the other solvents (50–53%), but the temperature dependence is scarcely low. We consider that the interaction between the fluor atoms in the trifluoroacetyl group of vinyl trifluoroacetate and the π‐bond in the aldehyde affect the stereoregularity.
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