Biomass- and Carbon Dioxide-Derived Polyurethane Networks for Thermal Interface Material Applications

Recent environmental concerns have increased demand for renewable polymers and sustainable green resource usage, such as biomass-derived components and carbon dioxide (CO₂). Herein, we present crosslinked polyurethanes (CPUs) fabricated from CO₂- and biomass-derived monomers via a facile solvent-free ball milling process. Furan-containing bis(cyclic carbonate)s were synthesized through CO₂ fixation and further transformed to tetraols, denoted FCTs, by aminolysis and utilized in CPU synthesis. Highly dispersed polyurethane-based hybrid composites (CPU-Ag) were also manufactured using a similar ball milling process. Due to the malleability of the CPU matrix, enabled by transcarbamoylation (dynamic covalent chemistry), CPU-based composites are expected to present very low interfacial thermal resistance between the heat sink and heat source. The characteristics of the dynamic covalent bond (i.e., urethane exchange reaction) were confirmed by the results of dynamic mechanical thermal analysis and stress relaxation analysis. Importantly, the high thermal conductivity of the CPU-based hybrid material was confirmed using laser flash analysis (up to 51.1 W/m·K). Our mechanochemical approach enables the facile preparation of sustainable polymers and hybrid composites for functional application.