Synthesis and physicochemical characterization of a well-defined poly(butadiene 1,3)-block-poly(dimethylsiloxane) copolymer

For the first time, order-order and order-disorder transitions were detected and characterized in a model diblock copolymer of poly(butadiene-1,3) and poly(dimethylsiloxane) (PB-b-PDMS). This model PB-b-PDMS copolymer was synthesized by the sequential anionic polymerization (high vacuum techniques) of butadiene 1,3 (B) and hexamethylciclotrisiloxane (D₃), and subsequently characterized by nuclear magnetic resonance (¹H and ¹³C NMR), size exclusion chromatography (SEC), Fourier Transform infrared spectroscopy (FTIR), Small-Angle X-ray scattering (SAXS) and rheology. SAXS combined with rheological experiments shows that the order-order and order-disorder transitions are thermoreversible. This fact indicates that the copolymer has sufficient mobility at the timescale and at the temperatures of interest to reach their equilibrium morphologies.