Synthesis and polymerizations of phosphonated‐bis(methacrylamide)s for dental applications

Abstract

Novel phosphonate and phosphonic acid‐containing bis(methacrylamide)s were synthesized. The phosphonate‐containing monomers (1a and 1b) were synthesized by amidation of 2‐(2‐chlorocarbonyl‐allyloxymethyl)‐acryloylchloride with diethyl 2‐aminoethylphosphonate and diethyl 1‐aminomethylphosphonate. The phosphonic acid‐containing monomers (2a and 2b) were synthesized by hydrolysis of 1a and 1b with trimethylsilyl bromide (TMSBr). All monomers were liquids and dissolved in water and ethanol. Thermal homopolymerization of 1a and 1b in bulk and solution using 2,2′‐azobis(isobutyronitrile) (AIBN) at 80 °C gave crosslinked polymers indicating low cyclization tendencies of these monomers. They were also homopolymerized using photo‐DSC with 2,2′‐dimethoxy‐2‐phenyl acetophenone (DMPA) as photoinitator, and their maximum rates of polymerization were found to be higher than commercial monomers 2,2‐bis[4‐(2‐hydroxy‐3‐methacryloyloxy propyloxy) phenyl] propane (Bis‐GMA) and 2‐hydroxyethyl methacrylate (HEMA), indicating their potential as reactive diluents or crosslinkers in dental materials. In fact, copolymerization with monomer 1a resulted in improvements in photopolymerization kinetics of both Bis‐GMA and HEMA. The acidic nature of the aqueous solutions (pH of 2a: 1.42, 2b: 1.53), stability under aqueous conditions after 1 month of study at 37 °C, interaction of 2a with hydroxyapatite (HAP) as representative of both monomers, and copolymerizability of the same with HEMA make these monomers suitable as adhesive monomers in dental adhesives, although their low observed reactivities may present a drawback. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Polyglycidol-based metal adhesion promoters

“…When performing this calculation while considering the signal intensity of the acrylic moieties (19,20) to the phenyl group, we can determine that 13 acrylates are attached to the polyether chain. The degree of functionalization with acrylate groups (G AC ) is calculated by comparing the intensity of the phenyl group signal with signal 17.…”

“…The concomitance of acylation and silylation is conrmed by 1 H Table 5 Acylation of P(G 10 DEPE -co-G 16 ) and P(G 7 DEPE -co-G 19 ) with acryloyl chloride: ratios of AC-Cl to hydroxyl groups adjusted in the feed, reaction times, degree of functionalization with acrylate groups (G AC ) and number average molecular weights of P(G 10 DEPE -co-G y AC ) determined by 1 NMR spectra of P(G 7 DEPE -co-G 14 AC ) measured prior to the addition of TMS-Br and P(G 7 PE -co-G 16 AC ) aer 4 h of silylation (Fig. Aer having discussed the acylation and silylation steps individually, we perform the acylation-and silylation-reactions consecutively in one-pot to streamline the reaction process.…”

“…[4][5][6][7] Most commonly however, low molecular weight molecules carrying phosphonic acids are studied, as these form well-dened selfassembled monolayers. [14][15][16][17][18][19][20] Poly(phosphonate)s and phosphonated (meth-)acrylates are biocompatible, which permits their in vivo application for medical purposes. These phosphonates are hydrolytically more stable compared to the corresponding phosphates, since they possess a phosphorus-carbon bond.…”

Bis[3‐(diethoxyphosphoryl)propyl]diallylammonium chloride: Synthesis and use of its cyclopolymer as an antiscalant

“…Phosphonates are utilized as adhesion promoters to dental tissue and bone . Two recent reports describe the polymerizations of phosphonated‐ bis (methacrylamide)s for dental applications . While some linear polyaminophosphonates, prepared by Butler's cyclopolymerization technique, have been used as antiscalants and as polymer components in the construction of aqueous two‐phase systems, the aminophosphonate resins are found to be very effective in the removal of toxic metal ions …”

Monomers for adhesive polymers, 13.1 Synthesis, radical photopolymerization and adhesive properties of polymerizable 2-substituted 1,3-propylidenediphosphonic acids

“…[5][6][7] This last parameter being obviously related to the structure of the acidic monomer, a wide range of polymerizable dihydrogen phosphates, phosphonic and bisphosphonic acids were synthesized in order to improve the SEAs performance. [1,2,[8][9][10][11][12][13] Recently, the synthesis of the 3-(methacryloyloxy)-2,2-[di((dihydroxyphosphoryl)methyl)]propyl methacrylate (MDMP) was reported ( Figure 1). [8] This monomer exhibits great adhesive properties and is a potential candidate to enter new adhesive formulations.…”