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Facile synthesis of poly(isobutylene-co-isoprene) (IIR) carboxylated derivatives by thiol–ene click chemistry

Abstract

The thiol–ene click reaction was applied to modify poly(isobutylene-co-isoprene) (IIR) by two different strategies using carboxylated thiols (mercaptanoic acids) with different alkyl spacer chain lengths. In the first approach, the direct radical-promoted addition of thiols across the 1,4-isoprene units proceeded with 80–90% conversion of the internal double bonds. An alternate method involving the conversion of sterically hindered 1,4-isoprene units to pendant double bonds through epoxidation and hydrolysis prior to the click reaction proceeded with 90–98% conversion of the alkene moieties. The carboxylated IIR derivatives were characterized by 1H NMR, FT-IR spectroscopy, and gel permeation chromatography analysis. Irrespective of the synthetic strategy used, the yields of the reactions decreased as the length of the alkyl spacer in the mercaptanoic acid increased. The outcomes of the reactions also depended on the amounts of solvent and free radical initiator used.

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Acknowledgements

We thank ARLANXEO Canada Inc. and the Natural Sciences and Engineering Research Council (NSERC) of Canada for their generous support of this work. We are also grateful to the late Dr. Lorenzo Ferrari and to Dr. Dana Adkinson for useful discussions related to this research.

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Correspondence to Mario Gauthier.

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Deepak, V.D., Gungör, E. & Gauthier, M. Facile synthesis of poly(isobutylene-co-isoprene) (IIR) carboxylated derivatives by thiol–ene click chemistry. Polym J 53, 323–330 (2021). https://doi.org/10.1038/s41428-020-00425-3

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