Synthesis, photopolymerization and adhesive properties of new hydrolytically stable phosphonic acids for dental applications

Abstract

Novel monomers 2-(N-methylacrylamido)ethylphosphonic acid, 6-(Nmethylacrylamido)hexylphosphonic acid, 10-(N-methylacrylamido)decylphosphonic acid, and 4-(N-methylacrylamidomethyl)benzylphosphonic acid have been prepared in good yields for use in dental adhesives. They have been fully characterized by 1 H-NMR, 13 C-NMR, 31 P-NMR, and by HRMS. All monomers are hydrolytically stable in aqueous solution. Free radical homopolymerizations of these monomers have been carried out in solution of ethanol/water (2.5/1:v/v), using 2,2 0-azo(2-methylpropionamidine) dihydrochloride (AMPAHC) as initiator. They lead to homopolymers in moderate to excellent yields. Structure of the polymers has been confirmed by SEC/ MALLS and 1 H-NMR spectra. The photopolymerization behavior of the synthesized monomers with N,N 0-diethyl-1,3-bis(acrylamido)propane has been investigated by DSC. New self-etch primers, based on these acrylamide monomers, have been formulated. Dentin shear bond strength measurements have shown that primers based on (N-methylacrylamido)alkylphosphonic acids assure a strong bond between the tooth substance and a dental composite. Moreover, the monomer with the longest spacer group provides the highest shear bond strength. V

Effect of the electron donor structure on the shelf‐lifetime of visible‐light activated three‐component initiator systems

“…[1][2][3][4][5][6][7][8] For example, owing to the safety advantages for biological applications as well as in thick section photo-curing, visible-light activated three-component initiator systems have been expanding into application areas such as dental restorative materials, bio-detections, color printing, holographically photopolymerized composites and microencapsulation. [9][10][11][12][13] Three-component initiator systems are very efficient for the production of free radical active centers and tremendously promising for a number of industrial and biomedical applications; however, a potential problem in many of these systems is thermal stability and long-term dark storage stability. 14,15 For practical consideration in all applications, initiator systems must provide adequate shelf-life stability while also producing efficient, rapid polymerization on demand.…”

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

“…Dry THF was purchased from Sigma-Aldrich. Diethyl 2-aminoethylphosphonate 2a, [20] diethyl 6-bromohexylphosphonate, [21] 10-(methacryloyloxy)decylphosphonic acid 10, [22], and N-(2-aminoethyl)methacrylamide 7 [23] were prepared according to the literature. TMSBr (Sigma-Aldrich, Switzerland) was distilled prior to use.…”

“…First of all, amine 2a and bromophosphate 5 were prepared according to literature procedures. [20,21] Aminophosphonate 2b was then obtained from phosphonate 5 by a Gabriel synthesis. Bromophosphonate 5 was treated with potassium phthalimide in DMF at 100 °C to provide phthalimide 1b in 72% yield.…”

“…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).…”

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

“…[23,24] It was also demonstrated that N-alkylacrylamides exhibit a great stability in such acidic conditions. [2,9,10,25] Monomers 4, 8, 10a and 10b bearing a methacrylate group, their storage in aqueous solutions would require low temperatures (storage in the refrigerator). In this context, we took an interest in the synthesis of the monomers 12, 16a and 16b, which exhibit a higher stability in aqueous media (Figure 2).…”