Synthesis, photopolymerization, and adhesive properties of hydrolytically stable phosphonic acid-containing (meth)acrylamides

Abstract

Three novel dental monomers containing phosphonic acid groups (1a and 2a, based on diethyl amino(phenyl)methylphosphonate and 3a based on diethyl 1-aminoheptylphosphonate) were synthesized in two steps: the reaction of a-aminophosphonates with acryloyl chloride (for monomers 1a and 3a) or methacryloyl chloride (for 2a) to give monomers with phosphonate groups, and the hydrolysis of phosphonate groups by using trimethyl silylbromide. Their (and the intermediates') structures were confirmed by FTIR, 1 H, 13 C, and 31 P NMR spectroscopy. All the monomers dissolve well in water (1<pH<2) and are hydrolytically stable. Their homo-and copolymerizations with 2-hydroxyethyl methacrylate (HEMA) and HEMA/glycerol dimethacrylate were investigated with photo-DSC. Thermal polymerization of the new monomers in water or in ethanol/water solution was investigated, giving polymers in good yields. X-ray diffraction results showed only dicalcium phosphate dehydrate formation upon interaction of 1a-3a with hydroxyapatite indicating its strong decalcification and that monomer-Ca salts are highly soluble. Some results were also compared to those with a bisphosphonic acidcontaining methacrylamide (4a) previously reported; and the influence of monomer structure on polymerization/adhesive properties is discussed. These properties, especially hydrolytic stability and good rates of polymerization, make these new monomers suitable candidates as components of dental adhesive mixtures.

Antibacterial Modification of Microcrystalline Cellulose by Grafting Copolymerization

“…In particular, the signals from 60 to 67, 80 to 92, and 100 to 110 ppm were assigned to C6, C4, and C1, and the signals from 70 to 80 ppm were ascribed to C2, C3, and C5 (Martins et al 2006). The signals at 17, 46, 56, and 183 ppm were assigned to the carbons of the -C-CH3 (C9), -CH2-C-(C7), -CH2-C-(C8), and C=O(C10) groups, respectively (Shang et al 2013;Altin et al 2014). These signals further confirmed that MAM was successfully chemically bonded to MCC.…”

Monomers for adhesive polymers, 17.aSynthesis, photopolymerization and adhesive properties of polymerizable phosphonic acids bearing urea groups

“…Among these monomers, (meth)acrylamides were the most efficient. [11,21,[28][29][30][31] The second part of our synthetic work consisted therefore in the preparation of methacrylamides 9a and 9b. Those monomers were synthesized in three steps starting from amines 2a and 2b (Scheme 2).…”

“…H NMR, 13 C NMR, and 31 P NMR spectra were recorded on a DPX-400 spectrometer using TMS as internal reference for 1 H NMR and 13 C NMR spectroscopic chemical shifts and using H 3 PO 4 (85%) as external reference for 31 P NMR spectroscopic chemical shifts. Data are given in the following order: chemical shift in ppm, multiplicity (s, singlet; ls, large singlet; d, doublet; t, triplet; q, quadruplet; m, multiplet), coupling constant in Hertz, assignment.…”

Hybrid polyion complex micelles from poly(vinylphosphonic acid)-based double hydrophilic block copolymers and divalent transition metal ions

“…Phosphonic acid-containing polymers are typically produced by free-radical polymerization of styrene [44], (meth)acrylate [45], (meth)acrylamide [46] or vinyl [47] derivatives bearing either a free phosphonic acid group or a phosphonic ester that is subsequently converted to the phosphonic acid via hydrolysis. Reversible deactivation radical polymerization (RDRP) technologies such as nitroxide mediated polymerization [48] and atom transfer radical polymerization [49] allow precisely controlled phosphonic esterfunctional polymers to be synthesized.…”