The present study explores the exploitation of ladder-like polysilsesquioxanes (PSQs) bearing reactive functional groups in conjunction with SiO₂ nanoparticles (NPs) to produce UV-curable nanocomposite coatings with increased hydrophobicity and good thermal resistance. In detail, a medium degree regular ladder-like structured poly (methacryloxypropyl) silsesquioxane (LPMASQ) and silica NPs, either naked or functionalized with a methacrylsilane (SiO₂@TMMS), were blended and then irradiated in the form of a film. Material characterization evidenced significant modifications of the structural organization of the LPMASQ backbone and, in particular, a rearrangement of the silsesquioxane chains at the interface upon introduction of the functionalized silica NPs. This leads to remarkable thermal resistance and enhanced hydrophobic features in the final nanocomposite. The results suggest that the adopted strategy, in comparison with mostly difficult and expensive surface modification and structuring protocols, may provide tailored functional properties without modifying the surface roughness or the functionalities of silsesquioxanes, but simply tuning their interactions at the hybrid interface with silica fillers.

α,β-unsaturated esters are usually synthesized for polymer applications. However, the addition of maleate (cis-configuration) to a fluorinated moiety is challenging due to its potential isomerization during esterification. Various synthetic routes were attempted and led to very low conversion or side-products. The immiscibility of both reagents combined with an easy isomerization or attack on the double bond were potential explanations. In this paper, the synthesis of maleates oligo(hexafluoropropylene oxide) is reported by Steglich esterification and the reaction conditions are discussed depending on the molecular weight of the fluorinated moieties. After UV-curing, hydrophobic polymers were obtained by copolymerization with vinyl ethers by electron acceptor–donor systems.