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

The untapped potential of radical thiol-yne mono-addition chemistry 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. (c) 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015, 53, 319-326