Abstract

The development of innovative, easy to implement strategies for polymer synthesis and modification contributes to pushing back the limits of macromolecular engineering. In this context, thiolactones were highlighted as a new powerful “click” strategy involving an amine–thiol–ene conjugation. In order to further explore the potential of thiolactone chemistry for the field of reversible-deactivation radical polymerization (RDRP), we have developed a toolbox of γ-thiolactone-based RDRP agents including xanthates, bromides, and an alkoxyamine. These RDRP agents were used for the polymerization of more activated and less activated monomers using appropriate RDRP techniques such as RAFT/MADIX, ATRP, and NMP. Well-defined thiolactone-terminated polymers were obtained and characterized for different degrees of polymerizations. An example of thiolactone–telechelic PNIPAM using a thiolactone-based xanthate and an ω-end-chain cyclization strategy was reported. The great reactivity of the thiolactone end-group for po...

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