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A new approach for reprocessing of existing thermoset waste is presented. This work demonstrates that unrecyclable thermoset materials can be reprocessed using the concept of associative dynamic bonding, vitrimers. The developed recycling methodology relies on swelling the thermoset network into a solution of a catalyst, which enables transesterification reactions allowing dynamic bond exchange between ester and hydroxyl groups within the thermoset network. Thermal and mechanical properties for recycled polyurethane and epoxy networks are studied and a strategy to maintain the properties of recycled materials is discussed. The developed methodology promises recycling and even upcycling and reprocessing of previously thought intractable materials. Moreover, processability of vitrimerized thermosets with common thermoplastic manufacturing methods opens up the possibility of tuning recycled networks by adding nanoparticles. This flexibility keeps the application window of recycled thermosets very broad.

Vitrimers are a class of covalent adaptive networks which, unlike other covalent networks, can be thermally reprocessed, recycled, and are self‐healing. In this research, a polyurethane vitrimer network is prepared using 1,4‐phenylene diisocyanate and excess amount of polycaprolactone polyol. The dynamic nature of this network is provided by a dual effect of dynamic transesterification reactions as well as dynamic transcarbamoylation reactions. This vitrimer can be reshaped, be recycled, and heal potential defects at high enough temperatures. A fast healing strategy is developed by the addition of small amounts (0.05 wt%) of carbon nanotubes (CNTs) which enables the use of microwave radiation for an efficient fast healing process. Using this strategy the healing time decreases more than 30 times compared to using a conventional oven. CNTs also enhance the vitrimer mechanical properties and compensate for the mechanical property loss of the dynamic PU network in comparison to the permanent PU network.

Carbon nanotubes (CNTs) were dispersed without any solvent in poly(tetramethylene ether glycol), (PTMEG) well above its melting point by ultrasonication in the pulse mode and different times. The polyol/CNT suspensions were used to prepare in situ polymerized thermoplastic polyurethane TPU/CNT nanocomposites with the CNT concentration of $ 0.05 vol%, much below the CNT geometrical percolation threshold calculated at 0.43 vol%. Results of rotational rheological measurements and ultraviolet-visible (UV-Vis) spectroscopy analysis revealed improvement in the nanoscale CNT dispersion with sonication time. Moreover, the optical microscopic images and sedimentation behavior for these samples pointed out to the formation of segregated CNT networks with different microstructures at different sonication times. Through-plane thermal conductivity measurements showed an increase in thermal conductivity of the in situ polymerized TPU/CNT nanocomposites from polyol/CNT suspensions with increasing sonication time followed by a decrease at long sonication times. Different models were used to evaluate the role of CNT dispersion state and created microstructure on thermal conductivity of nanocomposites. The formation of a segregated network at medium sonication times consisting of large CNT aggregates and small bundles increased the nanocomposite thermal conductivity up to 99.7%, while at longer sonication times, an increase in interfacial area with a corresponding increase in kapitza boundary resistance, effectively decreased the system thermal conductivity. POLYM. ENG. SCI.,

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Thermoplastic polyurethanes (TPUs) are among the most versatile engineering polymers. The presence of hard and soft segments on their backbone and specific hydrogen bond interactions between the hard segments, provide TPUs with outstanding engineering properties while rendering them as very complex systems to study. Knowledge of morphology–property relationship is essential for TPUs since their thermal and mechanical behavior are directly dictated by their complicated morphology. In this research, TPU morphological features related to the hard segment content (HSC) were explored in tandem with system macroscopic properties. It was observed that TPUs display multiscale phase separated morphology with specific morphological features dependent on the HSC. At a certain critical HSC, an interconnected network of hard segments was formed which resulted in significant changes in TPU properties. This was explained in analogy with percolation phenomena in filler reinforced systems and considering the hard segments as reinforcing agent. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1553–1564

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