Synthesis and Photopolymerizations of New Phosphonated Monomers for Dental Applications BAHAR YENIAD, AYLIN ZIYLAN ALBAYRAK, NIHAN CELEBI OLCUM, DUYGU AVCI Department of Chemistry, Bogazici University, 34342 Bebek, Istanbul, Turkey Received 31 October 2007; accepted 30 November 2007 DOI: 10.1002/pola.22564 Published online in Wiley InterScience (www.interscience.wiley.com). ABSTRACT: Three novel phosphonated methacrylate monomers have been synthesized and studied for use in dental applications. Two of the monomers were synthesized from the reactions of glycidyl methacrylate (GMA) with (diethoxy-phosphoryl)-acetic acid (monomer 1) and (2-hydroxy-ethyl)-phosphonic acid dimethyl ester (monomer 2). These monomers showed high crosslinking tendencies during thermal bulk and solu- tion polymerizations. The third monomer (monomer 3) was prepared by the reaction of bisphenol A diglycidylether (DER) with (diethoxy-phosphoryl)-acetic acid and sub- sequent conversion of the resulting diol to the methacrylate with methacryloyl chlo- ride. The homopolymerization and copolymerization behaviors of the synthesized monomers were also investigated with glycerol dimethacrylate (GDMA), triethylene glycol dimethacrylate (TEGDMA), and 2,2-bis[4-(2-hydroxy-3-methacryloyloxy propy- loxy) phenyl] propane (bis-GMA) using photodifferential scanning calorimetry at 40 8C using 2,2 0 -dimethoxy-2-phenyl acetophenone (DMPA) as photoinitiator. Mono- mer 1 showed polymerization rate similar or greater than dimethacrylates studied here but with higher conversion. The maximum rate of polymerizations decreased in the following order: 1TEGDMA>GDMAbis-GMA3>2. A synergistic effect in the rate of polymerization was observed during copolymerizations. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2290–2299, 2008 Keywords: adhesives; crosslinking; dental polymers; glycidyl methacrylate; photo- polymerization INTRODUCTION In recent years, organophosphorus monomers and polymers have attracted attention because of their variety of applications. Generally, they are known as flame retardants and are used in the electrical, transportation, and construction industries. Besides their flame-retardant proper- ties they are used as adhesive promoters for paints and adhesives. 1,2 For example, monomers with phosphoric acid, phosphonic acid, and phos- phinic acid esters have been synthesized and used in dental composites and as dentin adhe- sives. 3–8 These groups increase biocompatibility and adhesion to tooth by chelating with calcium in the tooth. High rate of homo- and co-polymer- ization with other monomers in the adhesive or composite is also a desired characteristic for dental materials. Therefore it is important to understand the effect of molecular structure on polymerization reactivity. In recent years, we synthesized phosphorus- containing monomers based on alkyl a-hydroxy- methacrylates via different routes. 9–11 This arti- cle is focused on one step synthesis of two new phosphonated methacrylate monomers based on glycidyl methacrylate (GMA). We also describe synthesis of a new monomer by a similar reac- Correspondence to: D. Avci (E-mail: avcid@boun.edu.tr) Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 46, 2290–2299 (2008) V V C 2008 Wiley Periodicals, Inc. 2290