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.%).

Polyurethane Glycerolysate as a Modifier of the Properties of Natural Rubber Mixtures and Vulcanizates.

Chemical recycling of polyurethanes can be realized in several different ways, but the most important methods are glycolysis and glycerolysis. Both methods permit recovery of polyols (when the process is realized with the mass excess of depolymerizing agent) or substitutes of polyols, which contain urethane moieties in the main chains and terminate mainly in hydroxyl groups (when the process is realized with the mass excess of depolymerized polyurethane). Oligomeric products with urethane groups in the chemical structure can also be used as modifiers of rubber mixtures and vulcanizates. The main aim of the presented work is to study the effect of polyurethane glycerolysate on the performance of natural rubber mixtures and vulcanizates. The influence of the modifier on the vulcanization kinetics and swelling of rubber mixtures, and the thermo-mechanical and mechanical properties of rubber vulcanizates, was studied. The prepared materials were also subjected to accelerated thermal aging in air. It was found that polyurethane glycerolysate affects the vulcanization process of rubber mixtures (for example, promotes the activation of vulcanization) and acts as an antidegradant under thermoxidative conditions (higher stability of mechanical properties was observed in comparison to a reference sample without modifier). The obtained results show that chemical recycling products can be valuable modifiers of natural rubber mixtures and vulcanizates, which extends the possible applications of polyurethane chemical recycling products.

Preparation and Properties of Thermoplastic Polyurethane Composites Filled with Powdered Buckwheat Husks.

Bio-based fillers for the polymer composites are still interesting from the scientific and industrial point of view, due to their low cost and renewable nature. In this work partially green composites were obtained by the mixing of thermoplastic poly(ester-urethane) with the unmodified and modified (by acetylation) grinded buckwheat husks. Obtained biocomposites were characterized in the terms of their chemical structure (FTIR), microstructure (SEM), thermal stability (TGA), thermomechanical properties (DMTA), and selected mechanical properties. The results showed that introduction of grinded buckwheat husks (even if the amount is 60 wt%) permit retaining high values of tensile strength (around 8-10 MPa), but the increasing amount of applied filler is connected with the decreasing of elongation at break. It can result from good interaction between the polymer matrix and the bio-based filler (confirmed by high values of polymer matrix-filler interaction parameter determined from Pukánszky's model for the tensile strength of composites). The applied chemical treatment results in changing of mechanical properties of filler and composites. Obtained results confirmed the possibility of using powdered buckwheat husks as filler for thermoplastic polyurethane.