Synthesis and photopolymerizations of new phosphonated methacrylates from alkyl α‐hydroxymethacrylates and glycidyl methacrylate

Abstract

Novel aromatic mono-and di(phosphonate) or phosphonic acid monomers for use in dental composites were synthesized. Synthesis of monomer 1a involved three steps: (i) reaction of t-butyl a-bromomethacrylate (tBuBMA) and Bisphenol A, (ii) conversion to diacid chloride derivative using thionyl chloride, (iii) reaction of diacid chloride with diethyl (2-hydroxyphenyl) phosphonate. Monomer 2a was synthesized from the reaction of 2-chloromethacryloyl chloride and diethyl (2-hydroxyphenyl) phosphonate. Synthesis of monomer 3a involved reaction of glycidyl methacrylate (GMA) with diethyl (2-hydroxyphenyl) phosphonate. Hydrolysis of the phosphonate groups of monomers 1a and 2a with trimethylsilyl bromide (TMSBr) gave monomers 1b and 2b with phosphonic acid functionality, which is intended to improve binding ability of dental composites. The homopolymerization and copolymerization behaviors of the synthesized monomers with (Bis-GMA) were investigated using photodifferential scanning calorimetry at 40 C with 2,2 0 -dimethoxy-2-phenyl acetophenone as photoinitiator. The interaction of the monomer 1b with hydroxyapatite (HAP) was investigated using Fourier transform infrared technique.

Preparation of photocrosslinked sol-gel composites based on urethane-acrylic matrix, silsesquioxane sequences, TiO2, and Ag/Au Nanoparticles for use in photocatalytic applications

“…A computer‐controlled isothermal method was used to determine the kinetic parameters (the time to reach the maximum polymerization heat, double bond conversion, and rate of polymerization, R p ), knowing that the DSC heat flux is directly related to the rate and extent of photo‐polymerization . The polymerization rates were calculated according to the following formula: where Q / s is the heat flow per second, M is the molar mass of the monomer, n , the number of double bonds per monomer molecule; Δ H p is the theoretical enthalpy of polymerization (for the methacrylate double bond it equals 55 kJ/mol), and m is the mass of monomer in the sample …”

Synthesis and properties of liquid crystalline urethane methacrylates for dental composite applications

“…Under the given photopolymerization conditions, the methacrylic structures are subjected to UV irradiation, and the polymerization enthalpy was measured. Although the photopolymerization behavior of BisGMA and TEGDMA is demonstrated in the literature, 43, 44 for a better correlation of data, we have performed their photopolymerization in identical conditions as those used for the LC urethane methacrylates, taking into account the fact that the conversion degree for methacrylic function depend on different factors (light intensity, initiator type and concentration, temperature). If the rate of polymerization for urethane methacrylate monomers varied between 0.085–0.107 s −1 , for BisGMA or TEGDMA this was around 0.056 s −1 , while for BisGMA‐1 the rate increased slightly (0.085 s −1 ).…”

“…The heat flux as a function of reaction time was monitored using DSC under isothermal conditions, both the rate of polymerization and conversion being calculated as a function of time. 43 PhotoDSC data were analyzed using the one‐way ANOVA test. For the determination of the conversion degree by FTIR, a mixture of 15% UMA‐Q1, 49.25% BisGMA‐1, 34.25% TEGDMA, and camphorquinone (CQ, 0.5%)/4‐(dimethylamino)‐phenylacetic acid (DMPheAA, 1%) as the photoinitiator was homogenized and manually coated on the KBr plate.…”

Patient‐reported outcome measures suitable to assessment of patient navigation

“…Unfortunately, the incorporation of the sulfur methacrylate PA‐10 (Scheme ) in a BisGMA/TEGDMA (1:1) mixture decreased its polymerization reactivity. Moreover, a number of promising cross‐linking phosphonates, such as the bisphenol‐A dimethacrylate derivative MAP‐1, were synthesized (Scheme ) 44,45. Novel N ‐alkylacrylmidophosphonic or bisphosphonic acids, for example, 2‐ N ‐methylacrylamidoethyl, ‐hexyl‐ or ‐decylphosphonic acid (PA‐11a‐c, Scheme ), and 3‐( N ‐alkylacrylamido)propylidenebisphosphonic acids BPA‐1a‐d (Scheme ) were prepared 46,47.…”