Novel Multifunctional Epoxy (Meth)acrylate Resins and Coatings Preparation via Cationic and Free-Radical Photopolymerization

Abstract

In this work, a series of novel multifunctional epoxy (meth)acrylate resins based on a low-viscosity aliphatic triepoxide triglycidyl ether of trimethylolethane (TMETGE) and acrylic acid (AA) or methacrylic acid (MMA) have been synthesized. Thanks to the performed modification, the obtained prepolymers have both epoxides as well as carbon–carbon double bonds and differ in their amount. The obtained results indicate that the carboxyl-epoxide addition esterification occurs in the presence of a catalyst (triphenylphosphine) at a temperature of 90 °C, whilst the required degree of conversion can be achieved simply by varying both the reagents ratio and reaction time. The structure of synthesized copolymers was confirmed by spectroscopic analyses (FT-IR, 1H NMR, 13C NMR) and studied regarding its nonvolatile matter content (NV), acid value (PAVs), as well as its epoxy equivalent value (EE). Due to the presence of both epoxy and double carbon–carbon pendant groups, one can apply two distinct mechanisms: (i) cationic ring-opening polymerization or (ii) free-radical polymerization to crosslink polymer chains. Synthesized epoxy (meth)acrylate prepolymers were further employed to formulate photocurable coating compositions. Hence, when cationic photoinitiators were applied, polyether-type polymer chains with pending acrylate or methacrylate groups were formed. In the case of free-radical polymerization, epoxy (meth)acrylates certainly formed a poly(meth)acrylate backbone with pending epoxy groups. Further, photopolymerization behavior and properties of cured coatings were investigated regarding some structural factors and parameters. Moreover, reaction rate coefficients of photo-cross-linking by both cationic ring-opening and free-radical photopolymerization of the received epoxy (meth)acrylate resins were determined via real-time infrared spectroscopy (RT-IR). Lastly, basic physicomechanical properties, such as tack-free time, hardness, adhesion, gloss, and yellowness index of cured coatings, were evaluated.