Morphological Control and Mechanical Properties of Porous Phenolic Resins Derived from Poly(4‐Vinylphenol): Effects of Molecular Weight and Polydispersity of Prepolymer

Improvement of mechanical stability for porous polymer monoliths is one of the prime concerns as represented by the long‐standing research efforts on resorcinol‐formaldehyde (RF) aerogels. To this end, it is imperative not only to tailor mechanically robust porous morphology but also to design macromolecular structure of polymer scaffolds. Previously, we have developed porous RF gels showing a unique mechanical feature combining high mechanical strength and outstanding flexibility against uniaxial compression. Comparison of mechanical properties between the porous gels with varied morphologies has elucidated the influence of porous structure, whereas effects of macromolecular structure still remain elusive. Herein, we have fabricated a series of macroporous phenolic resins from three types of linear prepolymers with phenol pendant groups, poly(4‐vinylphenol) or poly(4‐hydroxystyrene), which differ in molecular‐weight properties, by the sol–gel process in conjunction with spinodal decomposition. The difference in gelation and phase separation behaviors observed for the discrete systems indicates the dissimilar cross‐linked networks developed in the respective gels, which consequently influence the mechanical strength and flexibility against uniaxial compression. This study also demonstrates the improvement of mechanical features by thermal treatment for the porous monoliths derived from the high‐molecular‐weight prepolymer with a view to the application in mechanical energy absorption.