Revisiting Thiol-yne Chemistry: Selective and Efficient Monoaddition for Block and Graft Copolymer Formation

Sprafke, J. K.; Spruell, J. M.; Mattson, K.M.; Montarnal, D.; McGrath, A. J.; Pötzsch, R.; Miyajima, D.; Hu, J.; Latimer, A. A.; Voit, B. I.; Aida, T.; Hawker, C. J.
J. Polym. Sci. A Polym. Chem.
18 August 2014

The untapped potential of radical thiol-yne mono-addition che​mistry is exploited to overcome the known limitations of thiol-ene chemistry in polymer coupling and block copolymer formation. By careful choice of alkyne, the reaction can selectively lead to the mono-addition product with efficiencies surpassing those achieved by traditional thiol-ene chemistry. This improvement is illustrated by the nearly quantitative synthesis of a variety of diblock and graft copolymers.