Monomers for adhesive polymers. XV. Synthesis, photopolymerization, and adhesive properties of polymerizable β-ketophosphonic acids

Catel, Yohann; Bock, Thorsten; Moszner, Norbert

doi:10.1002/pola.27423

Cited by 7 publications

(13 citation statements)

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“…Figure 4 shows the cyclic voltammograms of the polymer films on Platinum electrode in 0.1 mol L À1 TBAP in DMF medium. 32 The onset oxidation potential (E of the polymers, HOMO energy levels as well as LUMO energy levels of the polymers were calculated according to the equations:…”

Section: Electrochemical Propertiesmentioning

confidence: 99%

Synthesis of Polyacrylate‐Based Chalcone Containing Different Donor Moieties and Studies on their Optical, Electrochemical, and Thermal Properties

Selvam

Subramanian

2016

Adv Polym Technol

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Four novel metal-free acrylate polymers were synthesized via free radical polymerization using AIBN, in which a phenyl-chalcone-phenyl unit was connected with donor moieties such as fluorene, indole, anthracene, and benzophenone along with an acrylic acid group. The molecular weights of the polymers (P1-P4) were determined by gel permeation chromatography and their molecular structures were confirmed by FT-IR, 1 H-NMR and 13 C-NMR spectroscopy. The polymers were studied for their thermal properties by using DSC and thermo gravimetric analysis, which showed glass transition temperature (T g ,°C) in the range of 140-165°C. The relationship between molecular structure and optoelectronic properties of the synthesized polymers were investigated by UV-Visible, cyclic voltammetry, and electrochemical impedance spectroscopy.

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Section: Electrochemical Propertiesmentioning

confidence: 99%

Synthesis of Polyacrylate‐Based Chalcone Containing Different Donor Moieties and Studies on their Optical, Electrochemical, and Thermal Properties

Selvam

Subramanian

2016

Adv Polym Technol

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“…1 ; i = BEA, ΔH 0i = 74.7 kJ mol −1 , [13] M i its molar mass and P i is the amount used in the formulation (wt%). The rate of polymerization (R p ) was calculated according to the following formula (Equation (3)): where Q is the heat flow per s during the reaction and m is the mass of the mixture in the sample.…”

Section: Synthesis Of Acidic Monomers 9a and 9bmentioning

confidence: 99%

“…This monomer, which spacer is a decyl group, was prepared according to the literature procedure. [22] All new monomers were characterized by 1 H NMR, 31 P NMR, and 13 C NMR spectroscopy. For example, the 1 H NMR spectrum of monomer 4b is shown in Figure 2.…”

Section: Photopolymerization Proceduresmentioning

confidence: 99%

“…[6][7][8][9] According to the 'adhesion-decalcification' concept described by Yoshida et al, the ability of a monomer to achieve a strong chemical bond with HAP is correlated to the solubility of its corresponding calcium salt in water (the lower the solubility, the better the adhesion). [7] In order to improve the interaction with HAP, monomers exhibiting strong chelating properties like diphosphonic acids [10][11][12] or β-ketophosphonic acids [13] were therefore prepared. Recently, Avci et al described the synthesis of two monofunctional phosphonated urea methacrylates for dental materials.…”

Section: Introductionmentioning

confidence: 99%

“…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.…”

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

Tauscher

Catel

Moszner

2015

Designed Monomers and Polymers

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Four polymerizable phosphonic acids bearing urea groups 4a, 4b, 9a, and 9b as well as the 10-(methacryloyloxy)decylphosphonic acid 10 were synthesized in four to six steps. They were characterized by 1 H, 13 C, and 31 P NMR spectroscopy and by high-resolution mass spectroscopy. Contrary to methacrylates 4a and 4b, methacrylamides 9a and 9b were hydrolytically stable in deuterated water/deuterated ethanol solutions. The photopolymerization behavior of acidic monomers 4a, 4b, 9a, 9b, and 10 and their corresponding phosphonates were studied using a differential scanning calorimeter. Homopolymerizations and copolymerizations with N-butyl-N-ethylacrylamide were carried out. The presence of a urea group was found to significantly increase the rate of polymerization. Monomers bearing a phosphonic acid group were more reactive than their corresponding phosphonates. Self-etch adhesives based on monomers 4a, 4b, 9a, and 9b were able to provide a strong bond between a composite and the dental hard tissues (dentin and enamel). The presence of a urea group led to a significant increase in the shear bond strength to both dentin and enamel.

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Monomers for Adhesive Polymers, 16 Synthesis of Acidic Dimethacrylates Starting from Thioglycerol

Catel

Schörpf

Moszner

2015

Macro Materials & Eng

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Six novel acidic monomers were synthesized in three to six steps, starting from thioglycerol. Four phosphonic acids, a dihydrogen phosphate, and a bisphosphonic acid were prepared. They were characterized by 1 H-NMR, 13 C-NMR, 31 P-NMR spectroscopy, and by HRMS. Their free radical polymerization was carried out in a water/ethanol solution, using 2,2 0 -azobis(2methylpropionamidine) dihydrochloride as an initiator. Photopolymerization of these acidic monomers as well as of their corresponding diethyl phosphonates and phosphates was investigated using photo-DSC. Self-etch adhesives were formulated and used to mediate a bond between the dental hard tissues and a composite. Dentin and enamel shear bond strength tests showed that each acidic monomer was able to provide a good adhesion. The adhesive based on the bisphosphonic acid monomer led to the best adherence.Excepted for the preparation of compounds 2c, 7, 9, 13, 14, and 16, all reactions were carried out under an argon atmosphere. DCM and MeOH were dried over molecular sieves. Diethyl 6,7-dihydroxy-4thia-heptylphosphonate 2a, [18] diethyl 4-bromobutylphosphonate 1b, [19] diethyl 6-bromohexylphosphonate 1c, [20] and di-tert-butyl phosphate [21] were prepared according to the literature. Methacrylic anhydride was purchased from Evonik (Germany). All other reagents used in the syntheses were purchased from Sigma-Aldrich (Switzerland) and were used without further purification. TMSBr and methacrylic anhydride were distilled prior to use. Column chromatographies were performed on Macherey-Nagel silica gel 60 (40-63 mm). Thin layer chromatography (TLC) was performed on silica gel 60 F-254 plates. Bis-GMA (Esschem, USA), Figure 1. Structure of the monomers 4a-c, 6, 11, and 16.H NMR (400 MHz, CDCl 3 ): d ¼ 1.31 (t, 3 J HH ¼ 7.1 Hz, 6H, OCH 2 CH 3 ); 1.63-1.79 (m, 6H, CH 2 P, CH 2 CH 2 P, and CH 2 CH 2 CH 2 P); 1.90-1.95 (m, 6H, CH 3 C¼CH 2 ); 2.54-2.63 (m, 2H, CH 2 CH 2 S); 2.76 (d, 3 J HH ¼ 6.6 Hz, 2H, SCH 2 CH); 4.01-4.16 (m, 4H, OCH 2 CH 3 ); 4.33 (dd, 3 J HH ¼ 6.0 Hz, 2 J HH ¼ 12.0 Hz, 1H, OCH 2 CH); 4.46 (dd, 3 J HH ¼ 3.5 Hz, 2 J HH ¼ 12.0 Hz, 1H, OCH 2 CH); 5.19-5.27 (m, 1H, CHO); 5.56-5.60 (m, 2H, C¼CH 2 ); 6.09 (ls, 1H, C¼CH 2 ); 6.10 (ls, 1H, C¼CH 2 ). 31 P NMR (162 MHz, CDCl 3 ): d ¼ 31.7. 13 C NMR (101 MHz, CDCl 3 ): d ¼ 16.5 (d, 3 J CP ¼ 5.8 Hz, OCH 2 CH 3 ); 18.2 (CH 3 C¼CH 2 ); 21.6 (d, 2 J CP ¼ 4.7 Hz, CH 2 CH 2 P); 25.2 H NMR (400 MHz, CDCl 3 ): d ¼ 1.33 (t, 3 J HH ¼ 7.1 Hz, 12H, OCH 2 CH 3 ); 1.34-1.44 (m, 2H, CH 2 ); 1.52-1.65 (m, 4H, CH 2 ); 1.81-1.99 (m, 8H, CH 2 , and CH 3 C¼CH 2 ); 2.25 (tt, 3 J HH ¼ 6.0 Hz , 2 J HP ¼ 24.1 Hz, 1H, CHP 2 ); 2.57 (t, 3 J HH ¼ 6.8 Hz, 2H, CH 2 CH 2 S); 2.76 (d, 3 J HH ¼ 6.6 Hz, 2H, CHCH 2 S); 4.11-4.22 (m, 8H, OCH 2 CH 3 ); 4.34 (dd, 3 J HH ¼ 6.0 Hz, 2 J HH ¼ 11.9 Hz, 1H, CHCH 2 O); 4.47 (dd, 3 J HH ¼ 3.4 Hz, 2 J HH ¼ 11.9 Hz, 1H, CHCH 2 O); 5.19-5.27 (m, 1H, CHO); 5.56-5.61 (m, 2H, C¼CH 2 ); 6.07-6.12 (m, 2H, C¼CH 2 ). 31 P NMR (162 MHz, CDCl 3 ): d ¼ 24.0. Scheme 3. Synthesis of the acidic monomer 11. Scheme 4. Syn...

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Monomers for adhesive polymers. XV. Synthesis, photopolymerization, and adhesive properties of polymerizable β-ketophosphonic acids

Cited by 7 publications

References 33 publications

Synthesis of Polyacrylate‐Based Chalcone Containing Different Donor Moieties and Studies on their Optical, Electrochemical, and Thermal Properties

Synthesis of Polyacrylate‐Based Chalcone Containing Different Donor Moieties and Studies on their Optical, Electrochemical, and Thermal Properties

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

Monomers for Adhesive Polymers, 16 Synthesis of Acidic Dimethacrylates Starting from Thioglycerol

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Monomers for adhesive polymers. XV. Synthesis, photopolymerization, and adhesive properties of polymerizable β-ketophosphonic acids

Cited by 7 publications

References 33 publications

Synthesis of Polyacrylate‐Based Chalcone Containing Different Donor Moieties and Studies on their Optical, Electrochemical, and Thermal Properties

Synthesis of Polyacrylate‐Based Chalcone Containing Different Donor Moieties and Studies on their Optical, Electrochemical, and Thermal Properties

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

Monomers for Adhesive Polymers, 16 Synthesis of Acidic Dimethacrylates Starting from Thioglycerol

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