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Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s

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Abstract

We report a dynamic polymerization system based on the reversible nucleophilic Michael polyaddition of activated alkynes and dithiols. Four poly(dithioacetal)s (P1–P4) were prepared via the base-catalyzed thiol-yne “click” polyaddition of two dithiols (1,4-butanedithiol (4S) and 1,5-pentanedithiol (5S)) and two alkynones (3-butyn-2-one (Y1) and 1-phenyl-2-propyn-1-one (Y2)) at high concentrations. We systematically investigated the base-catalyzed polymerization of 4S and Y1 (for polymer P1) under different conditions, and found that this polymerization was a highly concentration-dependent dynamic system: polymer P1 was formed at high concentration, while seven-membered dithioacetal, 1-(1,3-dithiepan-2-yl) propan-2-one (C1), was obtained at low concentration. The polymerization of 4S and Y2 (for polymer P4) displayed similar polymerization behavior, generating 2-(1,3-dithiepan-2-yl)-1-phenylethanone (C4) at low concentration. On the contrary, polymer P2 (from Y1 and 5S) was exclusively obtained with no formation of eight-membered dithioacetal. The polymerizations of Y1 with 1,2-ethanedithiol (2S) and 1,3-dimercaptopropane (3S) only afforded corresponding five- and six-membered dithioacetals, 1-(1,3-dithiolan-2-yl) propan-2-one (C2) and 1-(1,3-dithian-2-yl) propan-2-one (C3). This dynamic behavior of P1 and P4 was attributed to the concentration-dependent retro-Michael addition reaction between a thiol and a β-sulfido-α,β-unsaturated carbonyl compound catalyzed by bases. Furthermore, polymers P1 and P4 could be depolymerized into C1 and C4 in yields of 58% and 95%, respectively. The ring-opening polymerization of C1 at high concentration could successfully regenerate polymer P1. Thus, a new type of closed-loop recyclable poly(dithioacetal)s was developed.

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Acknowledgments

This work was financially supported by the National Key Research and Development Program of China (No. 2016YFA0201400) and the National Natural Science Foundation of China (Nos. 21971005 and 21534001).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Polym. Chem. & Physics of Ministry of Education, Department of Polymer Science & Engineering, College of Chemistry and Molecular Engineering, Center for Soft Matter Science and Engineering, Peking University, Beijing, 100871, China

    Jin-Xia Lei, Qi-Yuan Wang, Fu-Sheng Du & Zi-Chen Li

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Lei, JX., Wang, QY., Du, FS. et al. Dynamic Ring-chain Equilibrium of Nucleophilic Thiol-yne “Click” Polyaddition for Recyclable Poly(dithioacetal)s. Chin J Polym Sci 39, 1146–1154 (2021). https://doi.org/10.1007/s10118-021-2587-y

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