Flexible Aerogels From Hyperbranched Polyurethanes: Probing the Role of Molecular Rigidity with Poly(Urethane Acrylates) vs. Poly(Urethane Norbornenes)

Flexible and foldable aerogels have commercial value for applications in thermal insulation. This study investigates the molecular connection of macroscopic flexibility using polymeric aerogels based on star-shaped polyurethane-acrylate versus urethane-norbornene monomers. the core of those monomers is based either on a rigid/aromatic, or a flexible/aliphatic triisocyanate. Terminal acrylates or norbornenes at the tips of the star branches were polymerized with free radical chemistry, or with ROMP, respectively. at the molecular level, aerogels were characterized with FTIR and solid-state 13C NMR. the porous network was probed with N2-sorption and Hg-intrusion porosimetry, SEM and SAXS. the interparticle connectivity was assessed in a top-down fashion with thermal conductivity measurements and compression testing. All aerogels of this study consist of aggregates of nanoparticles, whose size depends on the aliphatic/aromatic content of the monomer, the rigidity/flexibility of the polymeric backbone, and generally varies with density. at higher densities (0.3-0.7 g cm-3), all materials were stiff, strong, and tough. Aerogels based on urethane-acrylates built around a rigid/aromatic core exhibited a rapid decrease of their elastic modulus with density (slopes of the log-log plots \u3e5.0), and at about 0.14 g cm-3, they were foldable. Data support that molecular properties of the monomer affect macroscopic flexibility indirectly, not so through the particle size, but rather through the growth mechanism and consequently through the interparticle contact area. Thus, flexible aerogels of this study showed no indication for polymer accumulation onto the primary nanostructure (particle sizes via N2-sorption and SAXS were comparable), and their interparticle contact area was comparatively lower. Because for flexibility purposes, interparticle contact area is related to interparticle bonding, it is speculated that if the latter is controlled properly (e.g., through adjustment of the monomer functional group density) it might lead to superelasticity and shape-memory effects