Syntheses and radical ring - opening polymerization of 2 - vinyl cyclic 1,3 - disulfone derivatives

Abstract

In the present study certain new features of ring-opening polymerization were investigated with 2-vinyl cyclicl,3-disulfones which are of particular interest because they provide method to introduce the specific groups, sulfonyl and olefinic groups, into the polymer backbone. 2-Vinyl cyclic 1,3-disulfones, 2-methyl-2-vinyl-1,3-dithiane-1,1,3,3-tetraoxide, 2-methyl-2-vinyl-1,3-dithiolane-1,1,3,3-tetraoxide, 2-methyl-2(2-propenyl)-1,3-dithiolane-1,1,3,3-tetraoxide were synthesized, and their radical polymerization behavior were inverstigated. Polymerization of the above monomers were carried out with common radical initiators such as 2,2``-azobisisobutyronitrile, dibenzoyl peroxide, ditert-butylperoxide. 2-Methyl-2-vinyl-1,3-dithiane-1,1,3,3-tetraoxide polymerized well and cleanly via quantitative ring-opening, which was confirmed by $^1H$-NMR, IR and $^{13}C$-NMR spectra of monomers and polymers. The polymerization results showed that benzoyl peroxide was the most effective initiatos for radical polymerization. All the polymers obtained by various initiators were white powders and possessed almost the same structure exhibiting the similar IR, $^1H$-NMR and $^{13}C$-NMR spectra. All the polymers obtained were not soluble in common organic solvent but soluble in dimethyl sulfoxide and trifluoroacetic acid. TGA and DTGA data indicated that the polymers decomposed around 210$^\circ$C 2-Methyl-2-vinyl-1,3-dithiolane-1,1,3,3-tetraoxide was synthesized and subjected to polymerization, but only small yield of polymer was obtained. In the case of 2-methyl-2-(2-propenyl)-1,3-dithiolane, the structure confirmed by NMR and IR spectra of polymer indicated that some of the monomer molecules incorporated into the polymer backbone without ring opening. The tendency of partial ring-opening polymerization suggests that the presence of methyl group unterfere significantly with its radical polymerziation. 2-Methyl-2-vinyl-1,3-dithiane-1,1,3,3-tetraoxide copolymerzed well with acryl...