From Flexible to Hard Polyurethane Aerogels: The Effect of Molecular Functionality vs. Molecular Rigidity

High performance all-polymer aerogels are not only interesting for their low thermal conductivity, but also for their mechanical strength and their conversion to porous carbons. the prevalent design rule dictates that crosslinking at the monomer level decreases solubility of the developing polymer and induces phase separation of nanoparticles with high surface to volume ratios. Hence, hyperbranched structures based on trifunctional single aromatic core monomers should have enhanced interparticle connectivity and rigidity compared to those based on either difunctional or multiple aromatic core monomers. That design rule is applied here to hyperbranched polyurethane (PU) aerogels synthesized from tris(4-isocyanatophenyl)methane (TIPM) and 1, 1, 1-tris(4-hydroxyphenyl)ethane (HPE) in anhydrous acetone using dibutyltin dilaurate (DBTDL) as catalyst. the resulting materials vary from highly flexible to rigid as the monomer concentration increases. FTIR and ¹³ C solid NMR confirm formation of urethane. SEM shows that the flexible variety is macroporous with a beaded worm-like structure, while the rigid variety is mesoporous and nanoparticulate. Lower-density flexible aerogels are highly porous (92%) with surface area of 132 m ² g ^-1 , while the rigid ones have higher surface areas, up to 256 m ² g ^-1 . Polyurethane aerogels from other triols and diols, e.g., phloroglucinol (POL) and resorcinol (RES), respectively, have also been studied and for similar monomer concentrations shrinkage and bulk density increases.