Polymers from S-vinyl monomers: reactivities and properties

Abstract

The large variety of available functional groups, their versatility, and the various polymerization techniques have made vinyl monomers the prevalent source for preparation of polymers. Interestingly, among this wide variety of applied structures S-vinyl monomers have remained a niche for the last decades despite their unique set of properties and early reports on their reactivities. An obstacle has been the limited access on a technical scale, but recent developments in sulfur chemistry and the request for more diverse reactivities might lead to a renaissance of these often neglected compounds. In particular, the different variations of sulfur moieties and the correlating diversity of properties render these compounds increasingly attractive for fundamental research as well as applications. A challenge, however, remains the detailed understanding and control of their polymerization behavior, as these S-vinyl compounds might be prone to side reactions depending on the applied reactions. In this regard, this review intends to provide a comprehensive overview of reported polymerization techniques, their challenges and limitations with regard to the sulfur compounds, and the resulting reactivities of the corresponding monomers in homopolymerizations but as well copolymerizations with various other vinyl monomers. We further include reports on characteristic properties and tried to highlight some potential applications of the resulting polymers. Considering the various modifications of sulfur, we distinguished according to electron rich S-vinyl monomers, such as vinyl sulfides and electron deficient compounds including the various oxidized variants. In accordance, the reactivities differ significantly and suitable polymerization techniques are summarized for each class of monomers.