Polythioethers by thiol-ene click polyaddition of α,ω-alkylene thiols

The straightforward synthesis of a series of poly(thioether)s by photoinduced thiol-ene click polyaddition of α,ω-alkylene thiols is reported. It is found that linear and telechelic poly(thioether)s can be directly obtained from α,ω-alkylene thiols with, for example, alkyl chain length of m = 1,2,3, and 9. The reaction proceeds without additives such as (radical) initiators or metal compounds and can simply be carried out by UV-irradiation of the bulk monomer or monomer solution. Ex situ kinetic studies reveal that the reaction proceeds by a typical a step-growth polyaddition mechanism. As the homologue series of poly(thioether)s are now synthetically accessible, new direct pathways to tailored poly(alkyl sulphoxide)s and poly(alkyl sulfone)s are now possible. Thiol-ene click polyaddition. α,ω-Alkylene thiols are polymerized to telechelic poly(thioether)s by photoinduced thiol-ene click polyaddition. The poly(thioether)s are found to be linear and semicrystalline. The melting points increase systematically with the count of the main chain methylene groups.