Synthesis and polymerizations of six aminophosphonate‐containing methacrylates

Abstract

Two different groups of novel aminophosphonate‐containing methacrylates were synthesized. The route to the first group involves reactions of ethyl α‐bromomethacryate (EBBr) and t‐butyl α‐bromomethacryate (TBBr) with diethyl aminomethylphosphonate and diethyl 2‐aminoethylphosphonate. Bulk and solution polymerizations at 60–80 °C with 2,2′‐azobis(isobutyronitrile) (AIBN) gave crosslinked or soluble polymers depending on monomer structure and polymerization conditions. Increasing bulkiness from ethyl to t‐butyl decreases the polymerization rate, correlated well with the chemical shift differences of double bond carbons and consistent with the lower molecular weights of t‐butyl ester polymers (Mn = 1800–7900 vs. 50,000–72,000). The route to the second group involves the Michael addition reaction between diethyl aminomethylphosphonate and diethyl 2‐aminoethylphosphonate with 3‐(acryloyloxy)‐2‐hydroxypropyl methacrylate (AHM) to give secondary amines. The photopolymerization using differential scanning calorimeter showed that these monomers have similar or higher reactivities than AHM, even though AHM has two double bonds. The high rates of polymerization of these monomers were attributed to both hydrogen bonding interactions due to additional NH groups as well as chain transfer reactions. All the homopolymers obtained produced char (17–35%) on combustion. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.

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

“…Recently, six aminophosphonate-containing methacrylates (e.g., MAP-2a, b, Scheme 13) were described by Avci and coworkers. 49 The high rate of polymerization of the monomers was attributed to both hydrogen bond interactions due to NH groups as well as chain-transfer reactions. Because of the basic properties of the amino phosphonates, the corresponding PAs were not synthesized.…”

Patient‐reported outcome measures suitable to assessment of patient navigation

“…Among the monomers presented in Scheme , the monomer PA‐11c showed the highest adhesion values in a two‐step SEA. Recently, six aminophosphonate‐containing methacrylates (e.g., MAP‐2a, b, Scheme ) were described by Avci and coworkers 49. The high rate of polymerization of the monomers was attributed to both hydrogen bond interactions due to NH groups as well as chain‐transfer reactions.…”

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 …”

“…[16][17][18] Two recent reports describe the polymerizations of phosphonated-bis(methacrylamide)s for dental applications. 19,20 While some linear polyaminophosphonates, prepared by Butler's cyclopolymerization technique, [1][2][3][4] have been used as antiscalants 21,22 and as polymer components in the construction of aqueous two-phase systems, 23 the aminophosphonate resins are found to be very effective in the removal of toxic metal ions. 8,[24][25][26] pH-Responsive bisphosphonates R 1 R 2 C(PO 3 H) 2 , analogues of pyrophosphates O(PO 3 H) 2 , have also significant industrial importance: They are used as corrosion inhibitors 27 in concrete, complexing agents in oil industries, 28 and inhibitors of boneresorption 29 in bone-related diseases.…”