Surface energies of linear and cross-linked polymers based on isobornyl methacrylate and methacryl-heptaisobutyl POSS

The use of monofunctional polyhedral oligomeric silsesquioxanes (POSS) as polymer modifiers requires controlling the phase separation process producing POSS-rich and polymer-rich domains that occurs in most systems due to the thermodynamic incompatibility between both components. One significant result of this study is the finding that isobornyl methacrylate (IBoMA) is an excellent reactive solvent of a commercial methacryl-heptaisobutyl POSS (MA-POSS). Formulations containing up to 30 wt% MA-POSS in IBoMA or in IBoMA (95 parts by weight)-diethylene glycol dimethacrylate (DEGDMA, 5 parts by weight), were polymerized using benzoyl peroxide as initiator up to complete conversion of CC bonds (determined by FTIR). Transparent POSS-modified materials were obtained without any evidence of a macroscopic phase separation. POSS addition produced a decrease of the glass transition temperature and the glassy and rubbery elastic modulus. A significant decrease in surface energy for both linear and cross-linked polymers was observed. This effect was particularly important for cross-linked polymers where the addition of 30 wt% POSS decreased the surface energy from about 29 mN m⁻¹ to 16 mN m⁻¹, a very low value for hydrocarbon materials. This study opens a way to obtain hydrophobic methacrylic coatings without the use of fluorinated monomers.