Study on superabsorbent composite XVI. Synthesis, characterization and swelling behaviors of poly(sodium acrylate)/vermiculite superabsorbent composites

A series of superabsorbent composites were synthesized by copolymerization reaction of partially neutralized acrylic acid on unexpanded vermiculite (UVMT) micropowder using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator in aqueous solution. And the samples were further characterized by means of fourier-transform spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The effects of vermiculite content on water absorbency were studied. Swelling behaviors of the superabsorbent composites in various cationic salt solutions (NaCl, CaCl₂ and FeCl₃), anionic salt solutions (NaCl, Na₂SO₄ and Na₃PO₄) and pH solutions were also systematically investigated. Results obtained showed that the equilibrium water absorbency increased with increasing UVMT content and the concentration of 20 wt.% clay gave the best absorption (1232 g/g in distilled water and 89 g/g in 0.9 wt.% NaCl). Data achieved also suggested that the water absorbency in various saline solutions decreased with an increase in the ionic strengths of these solutions. And it was found that at a higher ionic strength (>1 × 10⁻³ M), the water absorbency in monovalent cationic solutions was higher than those in multivalent cationic solutions. However, at the same ionic strength (>1 × 10⁻³ M), the effect of three anionic salt solutions on the swelling has the following order: NaCl < Na₂SO₄ < Na₃PO₄.     

Modified carrageenan 3. Synthesis of a novel polysaccharide-based superabsorbent hydrogel via graft copolymerization of acrylic acid onto kappa-carrageenan in air

A novel biopolymer-based superabsorbent hydrogel was synthesized through chemically crosslinking graft copolymerization of acrylic acid (AA) onto kappa-carrageenan (κC), in the presence of a crosslinking agent and a free radical initiator. A proposed mechanism for κC-g-polyacrylic acid was suggested and the affecting variables onto graft polymerization (i.e. the crosslinker, the monomer and the initiator concentration, the neutralization percent and reaction temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Maximum water absorbency of the optimized final product was found to be 789 g/g. The swelling capacity of the synthesized hydrogels was also measured in various salt solutions. The time-temperature profile of the polymerization reaction, in order to investigate the effect of molecular oxygen was conducted in terms of the absence and presence of the atmospheric oxygen. The overall activation energy (E_a) of the graft polymerization reaction was found to be 2.93 KJ/mol.     

Synthesis of fast-swelling superabsorbent hydrogels: effect of crosslinker type and concentration on porosity and absorption rate

Fast-swelling highly porous superabsorbent hydrogels were synthesized through a rapid solution polymerization of concentrated partially neutralized acrylic acid under normal atmospheric conditions. Acetone and sodium bicarbonate were used as porosity generators (porogens) during polymerization process for porosity generation. N,N^′-methylenebisacrylamide (MBA) and 1,4-butanedioldiacrylate were used as the water- and the oil-soluble crosslinkers, respectively. The temperature changing of the reaction mixture during polymerization and foam formation process was monitored and investigated in details. Time and sequence of addition of the porogens and gelation time were recognized to be important to increase efficiency of the porogens. The concentration of the crosslinkers on gelation time was optimized to achieve highly porous products. It was found that higher crosslinker concentration, especially in the case of MBA, causes decreased gelation times. Shorter gelation time resulted in more porogen bubbles trapped in the viscose reaction mixture led to products with higher porosity. The effect of type and concentration of the crosslinking agents on the process and swelling behavior of the hydrogels (in water and saline solutions) were investigated. Power law relationships were found for the variation of swelling in terms of either crosslinker or saline concentration. Less sensitivity to the change of salinity was achieved by employing higher amount of crosslinker.     

Synthesis and water sorption studies of pH sensitive poly(acrylamide-co-itaconic acid) hydrogels

Superabsorbent copolymers of acrylamide (Am) and itaconic acid (ItA) were prepared by free radical solution polymerization using sodium persulfate and N,N,N′,N′-tetramethylenediamine (TMEDA) as initiating system at 35 °C. Two series were prepared. The first series (SA series) used varied amount of itaconic acid and fixed amount of N,N′-methylenebisacrylamide (MBAm), while in the second series (SB series) the amount of (MBAM) changed and the amount of itaconic acid was fixed. The swelling behavior was studied at room temperature and the swelling percentage, swelling kinetics parameters such as initial swelling rate, swelling rate constant, and diffusion parameters were determined. The effect of pH and saline sensitivity on swelling behavior was also studied.     

Application of thermodynamics in a specific force field to the adsorption of Al ions on the chelating resins Ostsorb Oxin, Ostsorb Salicyl, Spheron Oxin, and Spheron Salicyl: Mathematical analysis of sorption isotherms using nonlinear mean square software

The sorption mechanism of Al³⁺ on chelating resins by means of mathematical analysis of sorption isotherms using nonlinear mean square software was studied. This method should yield more detailed information than classical thermodynamics and should be more flexible than the statistical-mechanical method, so that it would make it possible to obtain fairly easily relations directly applicable in practice. This model defined the specific potential Φ_Al^R for the ion in a resin (which depends on properties of resin and ion). On the basis of this model, N and PO isotherms were derived. To study the sorption mechanism, the Freundlich, Langmuir, N and PO equations (models) of isotherms were used. It was estimated that the functional groups (8-hydroxyquinoline and salicylate) in the studied chelating resins influence Φ_Al^R and thus their mechanism and sorption capacity.     

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composite: Preparation,swelling investigation and its application as a slow-release fertilizer

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composites (SACs) were prepared by graft copolymerization of acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA) onto sodium alginate (Na-Alg) in the presence of montmorillonite (MMT) using N,N′-methylenebisacrylamide (MBA) as a crosslinker and potassium persulfate (KPS) as an initiator in aqueous solution. The composite structures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Thermal Gravimetric Analysis (TGA) and Scanning Electron Microscope (SEM). The effect of % initiator, crosslinker amount and clay ratio on the swelling capacity was investigated. The results indicated that the highest swelling capacity of the composites in distilled water was 752 g/g by using 1.25% KPS and 0.06% MBA, 75% AA, 6.25% HEMA and 12.5% Na-Alg. Different samples were loaded with urea to evaluate their release potentials, and the release was studied by measuring the conductivity. The amount of urea release increased with increasing MMT amount.     

Synthesis of novel unsymmetrical phthalocyanines substituted with crown ether and nitro groups

This work reports on the synthesis of new unsymmetrically substituted phthalocyanines (M = Zn, Cu, Co, Ni) bearing three benzo-15-crown-5 units through oxy bridges and a nitro group. Phthalocyanines were prepared by a statistical condensation of 4-nitro phthalonitrile and 1-{[(benzo-15-crown-5)-4′-yl]oxy}phthalonitrile in the presence of anhydrous metal salts. All the target unsymmetrical phthalocyanines were separated by column chromatography and characterized elemental analyses, ¹H NMR, IR, mass and UV–Vis spectral data. Electrochemical behaviors of Cu (II) phthalocyanine by cyclic voltammetry and differential pulse voltammetry techniques gave two common phthalocyanine ring reductions and one ring oxidation processes. Peak-to-peak separation of the processes II and III (388 mV) and the measure of gap (1.672 V) between the HOMO and LUMO for the complex, fits a phthalocyanine with electrochemically inactive metal center.     

Synthesis and interfacial properties of amphiphilic β-cyclodextrins and their substitution at the O-6 position with a mono bio-recognisable galactosyl antenna

The synthesis of a mono-galactosylated amphiphilic β-cyclodextrin, in five steps from mono-6-azido-6-deoxy-β-cyclodextrin, via coupling to a N-β-d-galactopyranosylamino-antenna is described. Both characterization by electrospray mass spectrometry and NMR show the presence of only the mono-substituted product. The Langmuir isotherms of the final product and intermediates are described.     

Synthesis of polyfluoroalkylated glycerol and crown ether

Perfluoroalkylated glycerol (5, 9) and crown ethers (22, 23, 24) were synthesized starting from glycerol. 5 was synthesized by allylation of glycerol 1,2-acetonide followed by perflu-oroalkylation initiated with sodium dithionite, reduction of iodide and hydrolysis in good overall yield and was shown to poccess good surface activities. Glycerol bis-ether (9) was synthesized in a similar way. Allyloxymethyl crown ethers (15, 16, 18) were prepared as key intermediates through multi-step reactions, which were then perfluoroalkylated to give the title crown ethers 22, 23 ,24.     

Synthesis, structure, and cation complexation of a novel crown ether porphyrin

A new porphyrin appended with four crown ether units at meso-positions via an acetylene bridge was synthesized and structurally characterized, and its complexation with a variety of metal and diammonium cations was investigated.     

Synthesis and spectroscopic properties of a novel zinc phthalocyanine with four 17-membered crown ether voids

A novel zinc phthalocyanine containing four 17-crown-5 ether voids(17C5ZnPc) has been synthesized and characterized. UV-visible absorption and fluorescence emission spectra and as-sociated photophysical parameters have been determined. In contrast to most of the crown ether substituted phthalocyanines, no cofacial dimer formation is observed in the presence of alkali metal salts. In addition to the fluorescence at 710 nm from S1, a strong upper excited state (Soret 52) emission around 424 nm has been detected for the first time in the phthalocyanine series. Fluorescence decay of S1 and S2 emission can be analyzed by mono- and biexponential fits respectively. X-ray structure analysis showed that the crown ether unit is conformationally deformed and oblate that may account for the unusual spectroscopic properties.     

Synthesis of a novel crown ether derived from chiro-inositol and its catalytic activity on the asymmetric Michael addition

A novel 18-membered chiral crown ether was prepared in four steps starting from L-quebrachitol, a chiro-inositol, and its catalytic activity in the Michael addition reaction of glycine imine with several Michael acceptors was studied.     

Synthesis of a symmetric cylindrical bis(crown ether) host and its complexation with paraquat

The first cylindrical host for paraquat derivatives was prepared and characterized by X-ray analysis. Its complex with paraquat has 1:2 stoichiometry. The complexation is statistical and strong as shown by proton NMR characterization, electrospray mass spectrometry, and X-ray analysis.     

Synthesis and Micromechanistic Studies of Sensitized Bentonite for Methyl Orange and Rhodamine-B Adsorption from Wastewater: Experimental and DFT-Based Analysis

This work reports the formation of a novel adsorbent, prepared by activating bentonite with cinnamic acid, which is highly efficient to remove dyes from wastewater. The adsorption efficiency of the cinnamic acid activated bentonite was compared with unmodified bentonite by removing methyl orange and rhodamine-B from polluted water. The characterization was performed through X-ray diffraction (XRD) Fourier transform infrared (FTIR) and scanning electron microscopy (SEM). The results indicated that acidic pH and low temperature were more suitable for the selected dyes adsorption. The analysis of the data was done by the Langmuir and Freundlich isotherms; the Freundlich isotherm showed more suitability for the equilibrium data. The data were further analyzed by pseudo-first and pseudo-second-order models to study adsorption kinetics. The results showed that methyl orange and rhodamine-B adsorption obeyed pseudo-order kinetics. The results obtained from this research suggested that acid activation of bentonite with cinnamic acid increased the surface area of the clay and hence enhanced its adsorption efficiency. The maximum adsorption efficiency for the removal of methyl orange and rhodamine-B was up to 99.3 mg g⁻¹ and 44.7 mg g⁻¹, respectively, at 25 °C. This research provides an economical modification technique of bentonite, which makes it cost-effective and a good adsorbent for wastewater treatment.     

Synthesis,characterization, and electroluminescent performance of a novel copolyfluorene containing pendant crown ether groups

Copolyfluorene PFC containing pendant crown ether moieties was prepared by the palladium‐catalyzed Suzuki coupling reaction. The photo‐physical and electrochemical properties were investigated by absorption, photoluminescence (PL) spectroscopy, and cyclic voltammetry to elucidate the influence of the crown ether groups. In film state, its PL spectra (peaked at 430 and 452 nm) show noticeable red‐shift relative to 423 and 448 nm of poly(9,9‐dihexylfluorene) ( PF ). Thermal annealing leads to appearance of new emission at about 520 nm which has been attributed to formation of excimer. The highest occupied molecular orbital and lowest unoccupied molecular orbital levels of PFC were estimated to be ?5.68 and ?2.65 eV which contributed to balanced charges injection. Double‐layer electroluminescent device using PFC as emitting layer (ITO/PEDOT:PSS/ PFC /Ca/Al) revealed maximum luminance (7910 cd/m²) and maximum luminance efficiency (2.3 cd/A) superior to those of PF device (860 cd/m², 0.29 cd/A). Moreover, inserting a PFC layer between the PF emitting layer and calcium cathode led to reduced turn‐on voltage (4.1 V), much lower than 7.1 and 6.6 V of the double‐layer PFC and PF devices, respectively, and enhanced device performance (2800 cd/m² and 0.53 cd/A). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2985–2995, 2009     

Synthesis of a new enantiopure chiral aza crown ether and its application in enantiomeric separation

A new enantiopure chiral aza crown ether (S,S)‐1,7‐bis(4‐phenyl‐5‐hydroxy‐2‐oxo‐3‐ zapentyl)‐1,7‐diaza‐12‐crown‐4 ligand (1) has been synthesized and used as a chiral selector in the enantiomeric separation of D/L‐carnitine by capillary electrophoresis.     

提篮型杯[4]芳烃冠醚的合成及其对铯离子络合性能的研究

本文从去叔丁基化的杯[4]芳烃出发,先后分别在1,3-和2,4-酚羟基位点上引入正辛烯基和支链冠醚,最后通过烯烃复分解反应,合成了一种新型的提篮型杯芳烃冠醚化合物,产物结构经过1H NMR和HRMSESI表征确定.分别采用1H NMR和UV-vis方法,研究了1,3-桥联成环后张力对另一端冠醚环络合选择性的影响.结果表...     

Tetraphenylporphyrins monosubstituted with a crown ether in one phenyl ring. Synthesis and characterization

Summary The synthesis and spectroscopic characterization of seven new tetraphenyl-porphyrins (1–7) derivatized with 12-crown-4, 14-crown-4, 15-crown-5, or 18-crown-6 ether units inortho orpara position of one of the phenyl rings is described.

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In einem Phenylring mit Kronenethern monosubstituierte Tetraphenylporphyrine. Synthese und Charakterisierung

Zusammenfassung Die Synthese und die spektroskopische Charakterisierung sieben neuer Tetraphenylporphyrine (1–7), die mit 12-Krone-4, 14-Krone-4, 15-Krone-5 oder 18-Krone-6 in derortho-oderpara-Position eines Phenylrings substituiert sind, werden beschrieben.