Role of Bio-Based and Petroleum-Origin Monomers on the Tailoring of Thermoplastic Elastomer (TPE) Properties and Structure as a Matrix for Composites with Plant-Based and Inorganic Fillers

Abstract

This study investigates how natural fillers of different origins and morphologies influence the structural, thermal, rheological, and mechanical properties of thermoplastic elastomers (TPEs). Two series of materials were prepared: one based on a biobased matrix, poly(butylene 2,5-furandicarboxylate)-block-poly(tetramethylene oxide) (PBFPTMO), and one based on a petroleum-derived matrix, poly(butylene terephthalate)-blockpoly( tetramethylene oxide) (PBT-PTMO). Both series incorporated a range of natural modifiers, i.e., lignocellulosic fibers and ground fractions of Arundo donax L., cyanobacterial biomass (Spirulina platensis), and silica-rich mineral dust originating from volcanic stone quarries. The materials were obtained via melt blending, while the reference matrices (neat block copolymers) were synthesized through melt polycondensation. The chemical structure and limiting viscosity number (LVN) of the neat matrices were confirmed, while differential scanning calorimetry (DSC) provided insight into their morphology and phase composition. Scanning electron microscopy (SEM) was employed to evaluate the morphology and distribution of the modifiers within the polymer matrices. To assess how the fillers influenced processing windows and performance, thermogravimetric analysis (TGA), oscillatory rheological measurements, and tensile testing were performed. The results provide insight into structure–property relationships governing natural filler–TPE interactions and support the development of more sustainable elastomeric composites with tailored performance.