Polymerization of α-(halomethyl)acrylates through sequential nucleophilic attack of dithiols using a combination of addition-elimination and click reactionsElectronic supplementary information (ESI) available: Additional data on the effects of temperature and heating process on the polymerization. See DOI: 10.1039/c6py02145j

Polymerization of α-(halomethyl)acrylates and dithiols was achieved by the combination of S N 2′ (addition-elimination) and subsequent thiol-ene click reactions. A Bu 3 P catalyst and an excess amount of a base that does not yield an acidic salt, e.g. , 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) or K 2 CO 3 , were key for achieving M n > 10 4 . Polycondensation involving sequential nucleophilic attacks of a dithiol on an α-(bromomethyl)acrylate efficiently yielded a polysulfide.