Structure‐Property Relationships of Hydrogenated Polyisoprene as a Robust Polyolefin Alternative

To enhance the thermal stability and solubility of the polymer, we investigated the hydrogenation of polyisoprene in both its free form and on silica‐grafted surfaces via reversible addition‐fragmentation chain transfer polymerization. We assessed the thermal degradation behavior of polyisoprene with thermogravimetric analysis, before and after hydrogenation. The hydrogenated samples demonstrated increased stability. To evaluate compatibility and potential processing applications, we also examined the dispersion of hydrogenated polyisoprene grafted onto silica nanoparticles (0.1 chains/nm 2 ) in various solvents, including 1,2‐dichlorobenzene, o‐xylene, benzene, and tetrahydrofuran. Hydrogenation of polyisoprene, both free and grafted onto silica nanoparticles (0.1 chains/nm 2 ), achieved 90% saturation, eliminating olefinic bonds ( 1 H NMR) while preserving backbone integrity ( Ð < 1.35). Hydrogenated PIP exhibited a 40°C–60°C increase in thermal stability (thermogravimetric analysis onset: 320°C) and superior dispersion in nonpolar solvents (Flory‐Huggins χ < 0.5). These results demonstrate polyisoprene's potential as a polyolefin alternative for energy storage and aerospace applications, where oxidative stability is critical. This research advances our understanding of hydrogenation in polymer functionalization, offering guidance for developing sophisticated polymeric materials with tailored solubility and thermal properties.