Synthesis of iodine-containing cyclophosphazenes for using as radiopacifiers in dental composite resin

In this study, a strategy of using iodine-containing cyclophosphazenes as radiopacifiers for dental composite resin was evaluated. It was hypothesized that cyclophosphazenes bearing both iodine and acrylate group swere able to endow composite resins radiopacity without compromising mechanical properties. The cyclophosphazene compounds were synthesized by subsequently nucleophilic substitution of hexachlorocyclotriphosphazene with hydroxyethyl methacrylate (HEMA) and 4-iodoaniline. Cyclotriphosphazenes containing two different molar ratios of HEMA to 4-iodoaniline (1:5 and 2:4) were obtained, and were identified with 1H NMR, FT-IR, UV and mass spectroscopy. The iodine-containing cyclophosphazenes were able to dissolve well in bisphenol A glycidyl methacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) resin, and were added at two contents (10 or 15%wt. of the resin). The resins were photo-cured and post-thermal treated before characterizations. The resulting composite resins demonstrated the ability of blocking X-ray. And the addition of HEMA-co-iodoaniline substituted cyclotriphosphazenes caused minor adverse effect on the mechanical properties of the resins because the cyclotriphosphazenes could mix well and react with the resins. The presence of rigid phosphazene rings between resin backbones displayed an effective function of decreasing polymerization shrinkage. In summary, soluble and reactive iodine-containing cyclotriphosphazenes demonstrated advantages over traditional heavy metals or metal oxides in being used as additives for producing radiopaque dental resins.