Bis(trithiocarbonate) Disulfides: From Chain Transfer Agent Precursors to Iniferter Control Agents in RAFT Polymerization

While disulfide compounds have long been known to act as iniferters in radical polymerizations, the usage of bis(trithioacarbonates) directly in the RAFT process has been studied relatively little. Typically, these compounds are considered as precursors to other RAFT agents, either through organic synthesis or in situ generation during polymerization. Herein, we study the behavior of dodecyltrithiocarbonate disulfide in detail, using either thermal azo initiator or photoiniferter reaction conditions with a range of mononmers. We find that the iniferter product is mainly obtained, although side reactions lead to a mixture of end-group species. Control is highly dependent on the monomer family, with methacrylates yielding the narrowest dispersity polymers.