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

Abstract

A family of polymerizable 2-substituted-1,3-propylidenediphosphonic acids was successfully synthesized for an application in dental adhesives. Methacrylates as well as N-alkyl-acrylamides were prepared. Those monomers were synthesized in 4 to 6 steps and were fully characterized by 1 H NMR, 13 C NMR, 31 P NMR spectroscopy and by HRMS. In order to evaluate their reactivity, the copolymerization of each monomer with N,N'-diethyl-1,3-bis-(acrylamido)-propane (DEBAAP) in DMF was investigated by photo-DSC. Bis-(4-methoxybenzoyl)diethylgermanium (BMDG) was added as the photoinitiator to each mixture of acidic monomer/DEBAAP/DMF (2/3/5: mol/mol/mol). It was demonstrated that each monomer efficiently copolymerized with DEBAAP. Self-etching enamel-dentin adhesives containing these new diphosphonic acids were formulated and used to mediate a bond between the dental hard tissues (dentin and enamel) and a restorative material. According to both dentin and enamel shear bond strength measurements, 2-methacryloyloxymethyl-1,3-propylidenediphosphonic acid 8, 2-[N-(2-methacryloyloxyethyl)-carbamoyloxymethyl]-1,3-propylidenediphosphonic acid 10a and 2-[N-(10-methacryloyloxydecyl)-carbamoyloxymethyl]-1,3-propylidenediphosphonic acid 10b were the best candidates to enter new formulations. Those diphosphonic acids were significantly more efficient regarding the etching of enamel than the 1,3-bis(methacrylamido)propane-2-yl dihydrogen phosphate 17, a monomer already used in some commercially available dental formulations.

Polyglycidol-based metal adhesion promoters

“…1 13 31.0 (ArCH 2 CH 2 ), 31.6 (ArCH 2 ), 60.9, (d, 2 1 13 31.0 (ArCH 2 CH 2 ), 31.6 (ArCH 2 ), 60.9, (d, 2 …”

“…Since then, many industrial formulations make use of the outstanding complexation properties of the phosphonic acid moiety and a multitude of applications has been presented, ranging from metal-organic frameworks to thin lm adhesion promoters. [8][9][10][11][12][13] In particular in dentistry, polymerizable phosphonic acid compounds are applied widely as reactive monomers in tooth-lling composites. 4 Lately, the synthesis of different (meth-)acrylates and (meth-) acryl amides with phosphonic acid groups has been reported.…”

New fluorescent hyperbranched polymeric sensors as probes for monitoring photopolymerization reactions

“…It is still highly interesting and attracts a large attention in materials science. Elucidation of its mechanism and kinetics is of crucial importance for the development of new monomers [7], photoinitiators [8] and materials, such as optoelectronic materials [9], biomaterials [10], nanocomposites [11], IPNs [12], holographic recording [13], multilayer hydrogels [14], and many more. With the emergence of LEDS as new irradiation sources new environmental and economic possibilities have put increasing interest in the field [15,16].…”

Monomers for Adhesive Polymers, 14 Synthesis and Radical Polymerization of 4-[11-(Acryloyl-methyl-amino)-undecyloxy]-phthalic Acid and {10-[1,3-Bis(methacrylamido)-propoxy]-decyloxy}-phthalic Acid

“…In restorative dentistry, self‐etching enamel‐dentin adhesives (SEAs) are applied in order to create a strong bond between the dental hard tissue (enamel and dentin) and the restorative composite by etching of the tooth structure and formation of insoluble calcium salts. Therefore, the major components of currently used SEAs are strongly acidic monomers, e.g., polymerizable phosphoric, phosphonic, or carboxylic acids, along with crosslinking monomers, solvents and, in the case of light‐curing adhesives, a photoinitiating system . 4‐Methacryloxyethyl trimellitic acid (4‐MET, Scheme ) and its anhydride (4‐META), which is readily hydrolyzed in the presence of water, are polymerizable phthalic acid derivatives, which induce excellent adhesion properties on dental hard tissues as well as on metallic substrates and have been a component of numerous dentin bonding agents .…”