High-Performance, UV-Curable Cross-Linked Films via Grafting of Hydroxyethyl Methacrylate Methylene Malonate

Thermoset coatings have been used extensively to protect and enhance the appearance of substrates for industrial maintenance and architectural applications. Here, we demonstrate that anionic polymerization can be used to first graft hydroxyethyl methacrylate methylene malonate (HEMA-MM) onto latex particles at ambient conditions, while subsequent ultraviolet (UV) exposure enabled their cross-linking into robust coatings. At room temperature, in the presence of air and water, the polymerization of HEMA-MM was initiated by anionic carboxyl groups present on the MAA latex particles and subsequently grafted onto the surface of particles. The pendent hydroxyethyl methacrylate (HEMA) group enabled UV curing via free radical polymerization and the formation of a cross-linked network. Systematic investigations were conducted to study the formation and performance of the cross-linked coatings as a function of HEMA-MM incorporation. The incorporation of 10 wt % HEMA-MM into MAA latex yielded cross-linked coatings with decreased swelling, a heightened glass transition temperature (by ∼20 °C), and a 2.9-fold improvement in the Young’s moduli compared to controls (without HEMA-MM). Here, we demonstrate a facile method that provides a one-step grafting-functionalization approach using functional methylene malonates to produce UV-curable and high-performance coatings at room temperature and under atmospheric environments.