Thermal Post-Cross-Linking of Siloxane/Silsesquioxane Hybrids with Polycyclic Aromatic Units for Tailored Softening Behavior in High-Temperature Applications

Hybrid siloxane/silsesquioxane materials containing sterically demanding aromatic groups synthesized by hydrolysis and condensation suffer from incomplete cross-linking after thermal consolidation, limiting their thermal and mechanical performance. In this study, we systematically investigated a post-cross-linking strategy using various additives to enhance structural integrity and thermal stability. These include dimethyldimethoxysilane (DMDMS), diphenyldimethoxysilane (DPDMS) and phenyltrimethoxysilane (PTMS), as well as the organotin condensation catalyst di-<i>n</i>-butyltin diacetate (DBTA). Notably, we achieved thermal stability up to 453 °C and long-term transparency (up to 99%) at 200 °C with only little yellowing. Dynamic mechanical analysis demonstrated that post-cross-linking of precondensed siloxanes with PTMS, DPDMS, and DBTA enabled the formation of elastic materials exhibiting a rubbery plateau up to 200 °C. This behavior reflects enhanced structural rigidity and elasticity, which are essential for high-temperature applications. Our results show that high-temperature stability in siloxane/silsesquioxane materials is strongly influenced by factors such as the number of phenyl groups, cross-linking density, structural regularity, and degree of condensation. Most notably, the complete incorporation of a sterically demanding naphthyl-functionalized monomer during consolidation proved to be critical. Post-cross-linking significantly enhances all these parameters, which is essential for achieving robust thermal performance.