A “Bottom-Up” Strategy for High-Performance Benzocyclobutene (BCB)-Subnanometer Inorganic Nanocomposites

Developing benzocyclobutene (BCB) nanocomposites with ultra-small inorganic sizes represents a formidable challenge, although it offers great potential to produce materials with customizable structural and rich functional properties. In this study, we present a "bottom-up" design strategy for creating cross-linked benzocyclobutene (BCB) nanocomposites with highly dispersed nanodomains, such as organoalkoxysilane. This approach leverages ring-opening metathesis polymerization (ROMP) and thermally induced cycloaddition reactions to embed oligomeric silsesquioxanes, achieving a unique molecular structure with promising low-dielectric applications. The synthesis involves organoalkoxysilane and BCB as pendant groups of polynorbornenes that are covalently integrated. Additionally, the methoxyl groups of linear polymers could be further hydrolyzed under acidic conditions, and BCB groups could undergo thermal-induced ring-opening at high temperatures and Diels-Alder addition between themselves and vinyl groups, respectively. Fourier transform infrared (FTIR) spectroscopy analyses suggested the presence of ladder or network structures and high-resolution transmission electron microscopy (HRTEM) images presented the well-dispersed inorganic clusters, facilitating excellent dielectric properties with a dielectric constant (<i>D</i>_k) of 2.25 and a dissipation factor (<i>D</i>_f) of 2.27 × 10^-4. Compared with previously reported low-<i>D</i>_k materials, the cured nanocomposites also exhibited a significantly balanced enhancement of their comprehensive properties. This molecular bottom-up strategy provided a simple and universal method for constructing BCB-inorganic nanocomposites featuring a subnanometer inorganic structure, paving the way for future investigation into new classes of polymer-inorganic nanocomposites with a low <i>D</i>_k.