Synthesis and curing behavior of a novel ferrocene-based epoxy compound (original) (raw)
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Synthesis and physicochemical studies of ferrocene-containing materials
Applied Organometallic Chemistry, 2007
Low-temperature solution-phase polycondensation of 1,1 -ferrocenedicarboxylic acid chloride with newly synthesized aromatic diamines was carried out in tetrahydrofuran in the presence of triethylamine to form several new organometallic aromatic polyamides containing ferrocene units. The organometallic aromatic polyamides derived were in good yields ranging from 75 to 80%, amorphous with melting temperatures of >350 • C. The monomers and the resulting polymers were characterized by their physical properties, elemental analysis, 1 H NMR and FTIR spectroscopy. The differential scanning calorimetry and thermogravimetric studies of the resulting aramids were also carried out. All the polymers were insoluble in common organic solvents. However, all dissolved in concentrated H 2 SO 4 forming reddish brown solutions. Their glass transition temperatures were quite high, which is characteristic of aramids. They were also stable up to 450 • C with 10% mass losses (14-23%) recorded in the range 400-470 • C. The activation energies for decomposition of each aramid were also calculated using the Horowitz and Metzger method. All polymers showed reduced solution viscosities in concentrated sulphuric acid, which may be attributed to non-Newtonian behavior.
Materials Science and Engineering B-advanced Functional Solid-state Materials, 2008
Functionalized ferrocenecarboxymethylated polymers, i.e. poly(vinylbenzyl ferrocenecarboxymethylate) (PVBFCC), poly(vinylbenzyl ferrocenecarboxymethylate-co-ethoxyethylmethacrylate) with the mole ratio between vinylbenzyl ferrocenecarboxymethylate and ethoxyethylmethacrylate of 75:25 (Co-PVBFCC 75/25) and 50:50 (Co-PVBFCC 50/50), and ferrocenecarboxymethylated polysulfone (BPSFCC) were investigated for their electrical behavior under the vapors of methanol and acetone and nitrogen gas. Electrical conductivity responses of the four ferrocenecarboxymethylated polymers in the presence of lithium perchlorate were measured when they were exposed to nitrogen gas, and methanol and acetone vapors. Main factors that affect the electrical conductivity and sensitivity of these electroactive ferrocene polymers originate from the polymer structure and the type of the passing gas or vapor. Ferrocenecarboxymethylated polymers with higher degrees of substitution of ferrocene units possess good electrical conductivity under the atmosphere of mixed N2/methanol vapor, while ferrocenecarboxymethylated polymers with more flexible chain and/or larger free volumes give higher electrical conductivity under the atmosphere of mixed N2/acetone vapor. The gas or vapor molecule with higher polarity and smaller size enhances the electrical conductivity of the ferrocene polymers. Our results clearly indicate that the synthesized ferrocenecarboxymethylated polymers have potential to be used as methanol or acetone sensor materials.
Macromolecules, 2013
The first ferrocene-containing epoxide monomer, ferrocenyl glycidyl ether (fcGE), is introduced. The monomer has been copolymerized with ethylene oxide (EO). This leads to electroactive, water-soluble, and thermoresponsive poly(ethylene glycol) (PEG) derived copolyethers. Anionic homo-and copolymerization of fcGE with EO was possible. Molecular weights could be varied from 2000 to 10 000 g mol −1 , resulting in polymers with narrow molecular weight distribution (M w /M n = 1.07−1.20). The ferrocene (fc) content was varied from 3 to 30 mol %, obtaining watersoluble materials up to 10 mol % incorporation of the apolar ferrocenyl comonomer. Despite the steric bulk of fcGE, random copolymers were obtained, as confirmed via detailed 1 H NMR kinetic measurements as well as 13 C NMR studies of the polymer microstructure, including detailed triad characterization. In addition, the poly(fcGE) homopolymer has been prepared. All water-soluble copolyethers with fc side chains exhibited a lower critical solution temperature (LCST) in the range 7.2−82.2°C in aqueous solution, depending on the amount of fcGE incorporated. The LCST is further tunable by oxidation/reduction of ferrocene, as demonstrated by cyclic voltammetry. Investigation of the electrochemical properties by cyclovoltammetry revealed that the iron centers can be oxidized reversibly. Further, to evaluate the potential for biomedical application, cell viability tests of the fc-containing PEG copolymers were performed on a human cervical cancer cell line (HeLa), revealing good biocompatibility only in the case of low amounts of fcGE incorporated (below 5%). Significant cytotoxic behavior was observed with fcGE content exceeding 5%. The ferrocenesubstituted copolyethers are promising for novel redox sensors and create new options for the field of organometallic (co)polymers in general.
Journal of Thermal Analysis and Calorimetry, 2014
Novel copper containing epoxy polymers have been synthesized using copper(II) formamidine complex [Cu(ampf)Cl 2 ], ampf = N,N'-bis(4-acetyl-5-methylpyrazole-3-yl)formamidine, as curing agent for diglycidyl ether of bisphenol A based epoxy resins (Araldite and its oligomer consisting of 3-4 monomer units). The curing reaction was performed at room temperature without catalyst. In order to prove the polymerization reaction, differential scanning calorimetry (DSC) was applied. Highly exothermic peaks around 150 o C refer to the polymerization and according to DSC results the epoxy resins above 200 °C were almost completely converted to the corresponding metal-containing polymer. The proposed structure of the hybrid polymers was confirmed by FT-IR analysis. Gel permeation chromatography analysis shows that the average molar masses of the polymers are in the range from 3000 to 50000 g mol-1. The low conductivities of the hybrid materials in tetrahydrofuran confirm the non-ionic structure of the new polymers in solution. The thermal stability and the decomposition mechanism of the components of the reaction mixture and the new polymers were studied by coupled TG/DTA-MS measurements. The thermal data were analyzed also with the aim to obtain additional information about the composition of the synthesized materials.
Journal of Inorganic and Organometallic Polymers and Materials, 2013
Three kinds of polyfunctional polyols with hydroxyl values of 180-320 mg/g were prepared by the reaction of hydrogenated terpinene-maleic ester type epoxy resin with secondary amines (diethylamine, N-methylethanolamine, and diethanolamine), and the chemical structures were characterized by Fourier transform infrared spectroscopy and NMR spectroscopy. These polyols were used in place of commonly used polyols to prepare twocomponent polyurethanes when reacted with polyisocyanates. The crosslinking reactions of the polyols with polyisocyanate could be catalyzed by the tertiary amine groups included in the polyols, and the reaction rate was affected by hydrochloric acid and the polarity of the solvents. The mechanical, water-resistance, and chemical-resistance properties of the crosslinked products of the polyols were evaluated by standard tests, and the thermal properties were examined by differential scanning calorimetry and thermogravimetric analysis. The results show that these epoxyurethane polymers, with glass-transition temperatures (T g 's) in the range À5 to 37 C, had good thermally resistant properties, and the temperatures at 5% weight loss were in the range 235-280 C. All of the polymers formed transparent, strong, flexible films, with good chemical-resistance properties and excellent impact strengths of greater than 50 cm, a flexibility of 0.5 mm, adhesions of 1-2, and pencil hardnesses of HB-2H. The larger OH functionality and OH value of the polyol resulted in higher T g and pencil hardness values and better alcohol resistance and thermal stability in the crosslinked product of the polyol. V
Designed Monomers and Polymers, 2013
Poly(diethyleneglycol 1,1′-ferrocene dicarboxylate) (PDEFD) was synthesized by solution polycondensation reaction of diethylene glycol with 1,1′-ferrocenyl chloride. The synthesized polymer was characterized via the measurement of its 1 H NMR spectrum, UV-vis spectrum, and FTIR spectrum. X-ray diffraction pattern was measured to investigate the crystallinity of the synthesized polymer and it was found that the polymer was mostly amorphous. The molecular weight of the polymer was determined by gel permeation chromatography. In addition, the electrochemical properties of the synthesized polymer were examined and the influence of many parameters, including the solvent, the scan rate, and the electrolyte concentration was studied. The electrode processes were found to be controlled by both electrode reaction and the mass diffusion. In addition, the electrochemical processes of PDEFD in dimethyl sulfoxide (DMSO) were confirmed neither to be totally reversible nor completely irreversible. Moreover, the thermogravimetric analysis and differential thermal analysis were employed to examine the thermal properties of the polymer. Finally, the liquid crystalline properties of the synthesized polymer were investigated via the polarizing optical microscope technique.
Journal of Polymer Science Part A: Polymer Chemistry, 2006
Ytterbium and lanthanum triflates were used as initiators to cure a mixture of diglycidylether of bisphenol A (DGEBA) and 5,5-dimethyl-1,3-dioxane-2-one (DMTMC). The evolution of the curing was studied by differential scanning calorimetry (DSC) and Fourier transform infrared in the attenuated-total-reflection mode (FTIR/ATR). FTIR/ATR was used to monitor the competitive reactive processes and to quantify the evolution of the groups involved in the curing process. We observed the formation of a five-membered cyclic carbonate, which remains unreacted at the chain ends because of an equilibrium process between the spiroortho carbonates that had formed as intermediate species and also the loss of CO 2 , which was quantified by thermogravimetry. The kinetics were studied by DSC and analyzed by isoconversional procedures. Thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) experiments were used to evaluate the properties of the thermosets obtained. The phenomenological changes that take place during curing were studied and represented in a time-temperature-transformation (TTT) diagram. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: [4546][4547][4548][4549][4550][4551][4552][4553][4554][4555][4556][4557][4558] 2006
Effect of Ferrocene on the Structures and Properties of Epoxy–Polyurethane Composites
Polymer Science, Ser. A, 2014
Effects of various ferrocene concentrations on the tensile strengths, elongations at break, and glass-transition temperatures of ferrocene-containing epoxy–polyurethane composite materials are studied. As shown by IR spectroscopy and X-ray diffraction analysis, ferrocene affects the structuring of epoxy–polyurethane composites via redistribution of intermolecular hydrogen bonds between amide, hydroxyl, and urethane groups of the polymer basis and formation of metal–polymer complexes between ferrocene and polar groups of the polymer carrier.
Electrochemical studies of ferrocene and maleimide containing alternating copolymers
Journal of Electroanalytical Chemistry, 2017
Copolymers from vinylferrocene and 3-phenyl[5]ferrocenophane with N-ethyl and N-phenylmaleimide were electrochemically characterized. The deposition method of the polymer onto the electrode by oxidative deposition or cast film was studied and showed that films produced by cast film exhibited a greater electrochemical response. The oxidation potentials of these materials were dependent on supporting electrolyte when using NaClO 4 , NaNO 3 or phosphate buffered saline, varying from 0.46 to 0.53 for oxidative deposited films and 0.35 to 0.43 V for cast films. Also, multiple redox waves were observed in the cyclic voltammograms of these materials at a pH of 1. Molecular modeling showed a low energy conformation with the ferrocenyl moiety in close proximity to the maleimide.