Development of reactive phosphonated methacrylates

Abstract

Five novel phosphonated mono‐ and dimethacrylate monomers have been synthesized by two different routes. Monomers 1 and 2 were synthesized by reactions of methacryloyl chloride with diethyl (2‐hydroxyphenyl) phosphonate or tetraethyl (2,5‐dihydroxy‐1,4‐phenylene) bisphosphonate; monomers 3 and 4 by reactions of α‐(chloromethyl)acryloyl chloride (CMAC) first with dimethyl (2‐hydroxyethyl) phosphonate and then with benzoic or formic acids. The reaction of CMAC with two moles of dimethyl (2‐hydroxyethyl) phosphonate gave monomer 5. Thermal homopolymerization of monomers 1, 3, 4, and 5 and copolymerization of monomer 1 with methyl methacrylate (MMA) were investigated using azobisisobutyronitrile (AIBN) at 60 °C. Glass transition temperatures were observed for poly‐1, poly(MMA‐co‐1) (50:50), poly(MMA‐co‐1) (90:10), PMMA, poly‐3, and poly‐5 at 52, 90, 99, 129, 50, and 70 °C, respectively. TGA analysis of these polymers indicated formation of char on combustion. Homo‐ and/or copolymerization behavior of the synthesized monomers with 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloyloxy propyloxy) phenyl] propane (Bis‐GMA) were investigated with photodifferential scanning calorimetry. The maximum rate of polymerizations decreased in the following order: Bis‐GMA∼3 > 1 > 4 > 5. The conversions of monomers 1, 3, 4, and 5 (73.9, 85.9, 98.2, and 62.2%) were very high compared with Bis‐GMA (40.5%). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5737–5746, 2009

Determination of Homopolymerization Kinetics of 10‐(N‐Methylacrylamido)‐decylphosphonic acid, Its Diethyl ester, and 10‐(Methacryloyloxy)‐decylphosphonic acid, and Their Copolymerization with Methyl methacrylate

“…10‐( N ‐Methylamino)‐decylphosphonic acid, diethyl 10‐( N ‐methylamino)‐decylphosphonate, and 10‐(methacrylolyoxy)‐decylphosphonic acid were prepared according to the literature. MMA was purified by distillation under reduced pressure, and azobisisobutyronitrile (AIBN) was recrystallized from methanol.…”

“…(Meth)acrylates are the most commonly used monomers in SEAs. Due to their enhanced hydrolytic stability, ( N ‐alkyl)acrylamides are also incorporated in some adhesive formulations . Knowledge of the polymerization activity of acidic monomers in multicomponent restorative dental materials is important for understanding the curing of the dental adhesive.…”

“…Due to their enhanced hydrolytic stability, ( N -alkyl)acrylamides are also incorporated in some adhesive formulations. [4][5][6][7] Knowledge of the polymerization activity of acidic monomers in multicomponent restorative dental materials is important for understanding the curing of the dental adhesive. The acidic monomer is mixed with different comonomers (both monofunctional and cross-linking), hence the study of copolymerization kinetics of random copolymerization can provide essential information on the system reactivity.…”

New polymer‐chemical developments in clinical dental polymer materials: Enamel–dentin adhesives and restorative composites

“…A number of new polymerizable PA (meth)acrylates for dental application were synthesized by the group of Avci. [36][37][38][39] Examples are aryl diphosphonic acid group-containing dimethacrylates such as 2,5-bis(methacryloyloxy)-1,4-phenylenediphosphonic acid (PA-1) or 2,2-bis[3-(dihydroxyphosphoryl)-4-(2carboxyprop-2-en-oxy)phenyl]propane (PA-3, Scheme 11). Both monomers are high melting solids and their decomposition starts near 200 C. This is a drawback for dental application, because such solids generally show a relatively low solubility, and solutions of these monomers tend to crystallize during storage.…”

Patient‐reported outcome measures suitable to assessment of patient navigation

“…A number of new polymerizable PA (meth)acrylates for dental application were synthesized by the group of Avci 36–39. Examples are aryl diphosphonic acid group‐containing dimethacrylates such as 2,5‐bis(methacryloyloxy)‐1,4‐phenylenediphosphonic acid (PA‐1) or 2,2‐bis[3‐(dihydroxyphosphoryl)‐4‐(2‐carboxyprop‐2‐en‐oxy)phenyl]propane (PA‐3, Scheme ).…”