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Polycondensation, which was based on sequential conjugate substitution (SN2′) reactions of β-bromo-α-(bromomethyl)acrylates and dithiol, afforded diverse structures of polysulfides with exo- and endo-olefin units. The polymer structure was controlled by choosing bases with different nucleophilicities to tune glass transition temperatures.

Graphical abstract: Divergence of polycondensation by a tandem reaction based on sequential conjugate substitutions

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