Telechelic dithiol copolymers as tunable building blocks for synthesizing multiblock materials

A new strategy is reported to access α,ω‐dithiol polymer building blocks
with tunable molecular weights and compositions for the preparation of
random multiblock copolymers based on styrenic, acrylic, and siloxanes.
This facile synthetic approach provides access to dithiols through a
two‐step process: (1) an initial copolymerization of vinyl monomers with
ethyl lipoate followed by (2) disulfide bond reduction, producing dithiol
terminated polymer products. Thiol‐terminated polymers are easily prepared
over a wide range of molecular weights (2–32 kDa) by simply controlling
the feed ratio of vinyl monomer to ethyl lipoate. Mixtures of these linear
dithiol‐terminated building blocks were repolymerized via oxidative
coupling to create random multiblock copolymers with high molecular
weights (68–95 kDa) and controlled degradability. In summary, this
approach for preparing and recombining telechelic dithiol polymers creates
opportunities to manipulate the mechanical and physical properties of
multiblock copolymers using a synthetically simple and versatile platform.