Polyethylene Aerogels with Combined Physical and Chemical Crosslinking: Improved Mechanical Resilience and Shape‐Memory Properties

While the introduction of polymers into aerogels strongly enhances their toughness, truly elastic monolithic aerogels which restore their dimensions upon extensive compression are still challenging to synthesize. In this context hydrophobic semi‐crystalline polymers with low glass transition temperatures, and combined stiffness and flexibility, have only recently attracted attention. Shown here is that polyethylene aerogels with a low density, and combined chemical crosslinking and high crystallinity, display high moduli and excellent mechanical resilience. To maximize the crystallinity of these aerogels while maintaining a high crosslinking density, polyethylene networks with well‐defined segments were synthesized by hydrosilylation crosslinking of telechelic, vinyl‐functionalized oligomers obtained from catalyzed chain‐growth polymerization. Recoverable deformations both above and below the melting temperature of polyethylene affords remarkable shape‐memory properties.