Monomers for adhesive polymers, 18. Synthesis, photopolymerization and adhesive properties of polymerizable α-phosphonooxy phosphonic acids

Four polymerizable α-phosphonooxy phosphonic acids 7a, 7b, 9 and 16 were synthesized in seven steps. They were characterized by (1)H, (13)C and (31)P NMR spectroscopy and by high-resolution mass spectroscopy. The copolymerization of acidic monomers 7a, 7b, 9 and 16 with 2-hydroxyethyl methacrylate was studied using a differential scanning calorimeter. Due to the presence of two acidic groups, those monomers are significantly more reactive than 10-methacryloyloxydecylphosphonic acid (MDPA) and 10-methacryloyloxydecyl dihydrogen phosphate (MDP). Self-etch adhesives based on monomers 7a, 7b, 9 and 16 were formulated and used to mediate a bond between a dental composite and the dental hard tissues (dentin and enamel). These adhesives exhibit excellent performances and provide significantly higher dentin and enamel shear bond strength than adhesives based on MDP or MDPA.