Novel hybrid materials of the PB-b-P(o-Bn-L-Tyr) and PI-b-P(o-Bn-L-Tyr) type (where PB: 1,4/1,2-poly(butadiene), PI: 3,4/1,2/1,4-poly(isoprene) and P(o-Bn-L-Tyr): poly(ortho-benzyl-L-tyrosine)) were synthesized through anionic and ring-opening polymerization under high-vacuum techniques. All final materials were molecularly characterized through infrared spectroscopy (IR) and proton and carbon nuclear magnetic resonance (1H-NMR, 13C-NMR) in order to confirm the successful synthesis and the polydiene microstructure content. The stereochemical behavior of secondary structures (α-helices and β-sheets) of the polypeptide segments combined with the different polydiene microstructures was also studied. The influence of the α-helices and β-sheets, as well as the polydiene chain conformations on the thermal properties (glass transition temperatures, thermal stability, α- and β-relaxation) of the present biobased hybrid copolymers, was investigated through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and dielectric spectroscopy (DS). The obtained morphologies in thin films for all the synthesized materials via atomic force microscopy (AFM) indicated the formation of polypeptide fibrils in the polydiene matrix.
Keywords: anionic polymerization; biobased hybrid copolymers; fibril morphology; molecular characterization; polybutadiene; polyisoprene; polypeptide; thermal properties.