Beyond Traditional RAFT: Alternative Activation of Thiocarbonylthio Compounds for Controlled Polymerization

• Published in: Advanced science 2016-09, Vol.3 (9), p.1500394-n/a
• Main Authors: McKenzie, Thomas G., Fu, Qiang, Uchiyama, Mineto, Satoh, Kotaro, Xu, Jiangtao, Boyer, Cyrille, Kamigaito, Masami, Qiao, Greg G.
• Format: Article
• Language: English
• Subjects: Acids; Catalysis; controlled/living polymerization; Free radicals; Nanoparticles; photochemistry; polymer structures; Polymerization; Polymers; Propagation; reversible addition‐fragmentation chain transfer (RAFT); Sulfur; thiocarbonyl chemistry
• ISSN: 2198-3844; 2198-3844
• DOI: 10.1002/advs.201500394

Recent developments in polymerization reactions utilizing thiocarbonylthio compounds have highlighted the surprising versatility of these unique molecules. The increasing popularity of reversible addition–fragmentation chain transfer (RAFT) radical polymerization as a means of producing well‐defined, ‘controlled’ synthetic polymers is largely due to its simplicity of implementation and the availability of a wide range of compatible reagents. However, novel modes of thiocarbonylthio activation can expand the technique beyond the traditional system (i.e., employing a free radical initiator) pushing the applicability and use of thiocarbonylthio compounds even further than previously assumed. The primary advances seen in recent years are a revival in the direct photoactivation of thiocarbonylthio compounds, their activation via photoredox catalysis, and their use in cationic polymerizations. These synthetic approaches and their implications for the synthesis of controlled polymers represent a significant advance in polymer science, with potentially unforeseen benefits and possibilities for further developments still ahead. This Research News aims to highlight key works in this area while also clarifying the differences and similarities of each system. The versatility of thiocarbonylthio compounds in the control of a range of radical and cationic polymerization reactions has been recently expanded. In addition to the increasingly popular reversible addition–fragmentation chain transfer (RAFT) polymerization employing a radical initiator, other means of activation have been developed. Key examples of alternative activation are discussed and the implications on the synthesis of functional materials are highlighted.