Structure–Property Relationship and Multiple Processing Studies of Novel Bio-Based Thermoplastic Polyurethane Elastomers

Currently, the growing demand for polymeric materials has led to an increased need to develop effective recycling methods. This study focuses on the multiple processing of bio-based thermoplastic polyurethane elastomers (bio-TPUs) as a sustainable approach for polymeric waste management through mechanical recycling. The main objective is to investigate the influence of two reprocessing cycles on selected properties of bio-TPUs. Two series of bio-based TPUs were synthesized via a solvent-free two-step method with the use of hexamethylene diisocyanate or hexamethylene diisocyanate/partially bio-based diisocyanate mixtures, bio-based poly(triamethylene ether) glycol, and bio-based 1,3 propanediol. Both the raw bio-TPUs and those subjected to two reprocessing cycles were examined with respect to their chemical, physical, thermal, thermomechanical, and mechanical properties. The conducted research revealed that reprocessing led to changes in the phase separation between the hard and soft segments, thereby affecting the bio-TPUs’ properties. Both series of materials showed similar chemical structures regardless of reprocessing (slight changes were observed in the range of carbonyl peak). The thermal properties of TPUs exhibited slight differences after each reprocessing cycle, but generally, the non-processed and reprocessed bio-TPUs were thermally stable up to about 300 °C. However, significant differences were observed in their mechanical properties. The tensile strength increased to 34% for the twice-reprocessed bio-TPUs, while the elongation at break increased by ca. 200%. On the other hand, the processing cycles resulted in a decrease in the hardness of both bio-TPU series (ca. 3–4 °ShA). As a result, the prepared bio-TPUs exhibited characteristics that were closer to those of the sustainable materials model, promoting the circular economy of plastics, with environmental benefits arising from their recyclability and their high content of bio-based monomers (78.4–78.8 wt.%).