Polysulfide Networks. In Situ Formation and Characterization of the Elastomeric Behavior

Polysulfides with narrow polydispersity and variable chain length and density of polymerizable units have been synthesized through the use of a methacrylate-bearing and thiol-reactive compound as an end-capper for episulfide anionic polymerization. These macromonomers have been photopolymerized to yield materials with controlled cross-linking density, which translates into a controlled number of cross-links, branching points, and dead-ends. The resulting networks show elastomeric behavior that can be easily described through a simple affine chain model; in the analysis of the network behavior we here also present the calculation of a solvent-independent parameter for rationalizing the behavior of the Flory−Huggins parameters. These materials combine simple preparation (→ in situ processes), easy description of the mechanical properties, and responsiveness (to oxidation not studied here), features that could make them attractive for biomedical applications.