Hybrid free-radical/cationic systems can generate phase-separated polymers or interpenetrating networks driven by photopolymerization. In this study, phase separation of a ternary mixture composed of a polybutadiene urethane diacrylate (PBUDA), a cycloaliphatic diepoxyde (CE), and hexanediol dimethacrylate (HDDMA) was investigated. Using systematic variations of the initial composition of the mixture, a miscibility phase diagram of the ternary mixture was established. Based on this diagram, a reactive copolymer (poly(butyl acrylate-co-glycidyl methacrylate) (PBGMA)) was introduced in a reference hybrid system to manipulate the crosslinking network, polymer morphology, and properties (e.g., roughness, gloss, strain at break, and glass transition temperature Tg). When cured as a coating, the ternary hybrid system showed a depthwise gradient of epoxy conversion, and thereby developed a mostly cured skin above a viscous sublayer of uncured monomer. This skin can develop compressive stress due to the swelling from the diffusion of unreacted monomers beneath, and if the compressive stress is significantly high, wrinkles appear on the coating's surface. This work highlights how both skin thickness and elastic modulus impact wrinkle frequency and amplitude. It was demonstrated that these wrinkle parameters can be manipulated in the ternary system by the addition of PBGMA. We also demonstrated that by employing UV irradiation and varying the PBGMA content, it is possible to engineer coatings that range from smooth surfaces with high gloss to wrinkled topographies with a very low associated gloss.
Keywords: UV-curable coating; phase separation; radical/cationic hybrid system; self-matting; surface wrinkle.