Tertiary amine and tooth mineral hydroxyapatite facilely trigger self-cure of 10-MDP based adhesives

The present work aims to investigate if a novel self-cure system, mediated by tertiary amine ethyl 4-(dimethylamino)-benzoate (4E) and tooth mineral hydroxyapatite (HAp), would trigger polymerization of model adhesives based on a popular self-etch monomer, 10- methacryloyloxydecyl dihydrogen phosphate (10-MDP). The effect of 4E and HAp contents on degree of conversion (DC), polymerization rate (Rp), and induction period (IP) was investigated. The occurrence of such self-cure phenomenon in adhesives that underwent prior inadequate light cure was also evaluated. Model self-etch adhesives were prepared by using a monomer mixture of 10-MDP with 2-hydroxyethyl methacrylate at1:1 wt. ratio. 4E (0.3-1.3 wt%), and HAp (0.5-2 wt%) were added to the mixture. Benzoylperoxide and N,N-dihydroxyethyl-p-toluidine were used as conventional chemical-cure system, and trimethylbenzoyl-diphenylphosphine oxide as light-curing photoinitiator. The polymerization processes and mechanical properties of model adhesives were evaluated by real time ATR/FT-IR and nanoindentation, respectively. The 4E- HAp system successfully triggered self-cure of 10-MDP based model adhesives. DC, Rp and IP were apparently affected by both 4E and HAp contents. DC of self-cure of the model adhesives was much higher than that of the conventional chemical-cure system. 4E-HAp initiated self-cure further boosted DC to ~100% regardless of prior light exposure, and significantly improved elastic modulus and hardness, thus provided a novel polymerization method to effectively salvage curing of the adhesives after inadequate light-cure.