| Abstract: | Free-radical polymerization of vinyl esters including vinyl propionate (VPr), vinyl isobutylate (ViBu), vinyl 2,2-dimethylbutylate (VDMB), vinyl 2,2-dimethylvalerate (VDMV), vinyl 2,2-bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) was carried out using fluoroalcohols as solvents, and the tacticity of the obtained polymers was determined by NMR analysis of the produced poly(vinyl alcohol) (PVA). The polymerization of VPr, ViBu, VDMB, and VDMV, which are bulkier than VAc, in fluoroalcohols afforded polymers rich in heterotacticity (up to mr = 61%) similar to that of vinyl pivalate (VPi) whereas VAc is known to give a syndiotactic polymer under the reaction conditions used here. The polymerization of VF6Pi, which is the bulkiest among the monomers used in this study, gave a polymer rich in syndiotacticity in bulk and in fluoroalcohols regardless of the structure of the solvents. On the other hand, the polymerization of VBz in fluoroalcohols gave polymers with a higher isotacticity (up to mm = 33%) than bulk polymerization. Thus the monomer structure strongly affected the stereochemistry of the free-radical polymerization of vinyl esters in fluoroalcohols. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2677–2683, 1999 |
