Preparation of epoxy/zirconia hybrid materials via in situ polymerization using zirconium alkoxide coordinated with acid anhydride

Novel epoxy/zirconia hybrid materials were synthesized using a bisphenol A epoxy resin (diglycidyl ether of bisphenol A; DGEBA), zirconium(IV)-n-propoxide (ZTNP), and hexahydrophthalic anhydride (HHPA) via in situ polymerization. HHPA played two roles in this system: it acted as a modifier to control the hydrolysis and condensation reactions of zirconium alkoxide and also as a curing agent – the half-ester compound of HHPA desorbed from zirconium reacted with the epoxy resin to form the epoxy network. As a result, both the sol–gel reaction and epoxy curing occurred simultaneously in a homogeneous solution, and organic–inorganic hybrid materials were readily obtained. Further, the zirconia produced by the in situ polymerization was uniformly dispersed in the epoxy matrix on the nanometer or sub-nanometer scale; thus, hybrid materials that exhibited excellent optical transparency were obtained. Furthermore, the heat resistance of the hybrid materials could be improved by hybridization with zirconia. And, the refractive indices of the hybrid materials significantly improved with an increase in the zirconia content.

► Novel epoxy/zirconia hybrid materials were synthesized via in situ polymerization using zirconium alkoxide coordinated with acid anhydride.
► The half-ester compound of acid anhydride desorbed from zirconium played as curing agent of epoxy resin.
► The zirconia was uniformly dispersed in the epoxy matrix on the nanometer or sub-nanometer scale by synchronizing the epoxy curing and sol–gel reactions.
► The refractive indices of the hybrid materials significantly improved with an increase in the zirconia content.