Synthesis of resins with crown ethers units as anchor groups

Summary Polymers containing benzo-13-crown-4 (1) and benzo-9-crown-3 (2) units (1) were crosslinked with formaldehyde, phenol/formaldehyde, and resorcin/formaldehyde (2,3). Resins (3–8) were contacted with aqueous solutions of lithium and aqueous solutions of sodium chloride at pH=7 and pH=11. Finally, re-extraction analysis were carried out by two systems, in methanol and in water. The extraction and re-extraction results were analyzed by atomic absorption.     

Ion-Pair Sorption of Alkali Metal Chlorides by Crown Ether Carboxamide Resins

Abstract

Ten crown ether carboxamide resins are prepared by condensation polymerization of N,N-dialkyl sym-(R)dibenzo-16-crown-5-oxyacetamide monomers with formaldehyde in formic acid. Competitive ion-pair sorption of alkali metal chlorides from aqueous methanol solutions by these novel resins reveals that both sorption selectivity and efficiency are influenced by: 1) the conformational positioning of the pendant carboxamide group with respect to the crown ether cavity; 2) the length of the N,N-dialkyl chains on the pendant carboxamide group; 3) the methanol content of the aqueous methanol solution; 4) the concentration of alkali metal chlorides in the sample solution; and 5) the temperature of the sample solution. The highest sorption efficiency and Na⁺ selectivity are obtained for a resin prepared from N.N-dibutyl sym-(propyl)dibenzo-16-crown-5-oxacetamide monomer in which the geminal propyl group orients the carboxamide-containing side arm over the crown ether cavity. Lengthening the alkyl chains in the carboxamide group is detrimental to both sorption efficiency and selectivity. A very sharp response of alkali metal chloride sorption to the methanol content of the sample solution is noted for the crown ether resins which possess preorganized carboxamide side arms.     

Characterization of a Macrocycle-Mediated Dual Module Hollow Fiber Membrane Contactor for Making Cation Separations

Abstract

Separation of metal cations in aqueous solution by a macrocyclemediated Dual Hollow Fiber Membrane Contactor is described. The advantages of this type of supported liquid membrane configuration include easily accessible source, receiving and membrane phases; transport rates competitive with those of other types of membranes; and the potential for continuous operation. The new system was investigated to determine the effect of aqueous solution flow rate and membrane solvent stirring rate on Na⁺ and K⁺ transport using dicyclohexano-18-crown-6 as the carrier. The results demonstrated that transport increases with increasing stirring speed, but remains constant with increased aqueous flow rate through the fibers within the range of four to twelve m1/min. The membrane solvents hexane, toluene, octane, 1-octanol, 4-methyl-2-pentanone, octanal, and 2-octanone were tested for their ability to preserve membrane integrity in the presence of aqueous solutions of low pH, and to maximize transport. Of these solvents, 2-octanone was found to be most effective in minimizing acid diffusion across the membrane, while giving the highest facilitated K⁺ transport rate. Quantitative transport using 18-crown-6 was observed for K⁺ over Na⁺ (all solvents studied) and Ba²⁺ and Sr²⁺ over Ca²⁺ (only octanol was studied).     

Synthesis and properties of a cellulose exchanger with the crown ether diaminodibenzo-17-crown-5 as anchor group

A new cellulose exchanger was synthesized from “o-aminophenolcellulose” by diazotation and coupling with diaminodibenzo-17-crown-5. The distribution coefficients for Ca²⁺, Sr²⁺, Ba²⁺, Na⁺ and K⁺ were determined in water/methanol mixtures as a function of the water content. Separation of Ca²⁺, Na⁺ and K⁺ and fractionation of the calcium isotopes ⁴⁸Ca and ⁴⁰Ca were investigated. The enrichment factor ε = 4.9 · 10^?3 for ⁴⁸Ca²⁺ is appreciably higher than that found for cation exchange resins with ? SO₃H groups, but lower than that reported for certain cryptands.     

Stripping and recycling of metal ions in aqueous nitric acid solutions: Experimental and molecular dynamics insights

Stripping of metal ions (i.e., Cs⁺ and Na⁺) in presence of ionophore such as dibenzo-18-crown-6, (DB18C6) from the ionic liquid phase to the aqueous nitric acid phase by molecular dynamics simulation is reported. The experimentally determined stripping percentages of Na⁺ (i.e., 43.4, 38.5, 34.4, and 31.9%) were found to be higher than the same for Cs⁺ (i.e., 32.6, 32.0, 31.3, and 30.2%). The nonbonded and the hydrogen bond energies between Na⁺ and water (i.e., −356.41 and −363.77 kcal/mol) were higher when compared with Cs⁺ (i.e., −212.43 and −221.04 kcal/mol). The spatial distribution functions further confirmed that the surfaces of Na⁺ were very closely distributed around the active sides of water whereas for Cs⁺, it was distributed very far from the water molecules. In the penultimate section, the effect of methanol to the aqueous phase was studied so as to enhance the extraction efficiency of the complex.     

Design and Evaluation of Chelating Resins through EDTA- and DTPA-Modified Ligands

Ion-exchange resins through EDTA or DTPA moieties are synthesized and evaluated for the co-extraction of Cs⁺ and Sr²⁺ radionuclides for wastewater treatment. EDTA-bis(amide) and DTPA-bis(amide) derivatives bearing phenol or catechol moieties obtained from tyramine or dopamine, respectively, were used as building blocks to prepare ion-exchange resins. Their synthesis involved the condensation of formaldehyde with various phenolic rings, catechol (C), resorcinol (R), or calixresorcinarene (CR) under alkaline conditions. The resulting formo-phenolic-like resins have both ion-exchange and chelating groups in their structure and are indeed efficient in the remediation of Cs⁺ and Sr²⁺, even in salted aqueous solutions.     

Ligating behavior and metal uptake of N‐sulphonylpolyamine chelating resins anchored on polystyrene‐divinylbenzene beads

Amberlite XAD‐2 has been functionalized by coupling through –SO₂‐with ethylenediamine, propylenediamine, and diethylenetriamine to give the corresponding polyamine chelating resins I–III. The solid metallopolymer complexes of the synthesized chelating resins with Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ were synthesized. The polyamine derivatives and their metal complexes were characterized by elemental analysis, spectral (IR, UV/V, and ESR), and magnetic studies. The batch equilibrium method was utilized for using the chelating polyamines for the removal of Cu⁺², Zn⁺², Cd⁺², and Pb⁺² ions from aqueous solutions at different pH values and different shaking times at room temperature. The selective extraction of Cu⁺² from a mixture of the four metal ions and the metal capacities of the chelating resins were evaluated using atomic absorption spectroscopy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1839–1846, 2005     

SPOTLIGHT ON MANUFACTURING TRENDS IN JAPAN

Three reactive and functional polymers were synthesized by reacting formaldehyde with the phenolic Schiff bases derived from 4,4′-diaminodiphenylsulfone and o-, m-, and p-hydroxybenzaldehydes, respectively. The metal ion uptake behavior of these resins towards Cu²⁺, Ni²⁺, Co²⁺, and UO₂ ²⁺ ions in dilute aqueous media was studied. The optimum conditions for the absorption of metal ions were determined by varying the various parameters like contact time, size of the sorbents, concentration of the metal ion solutions, and the pH of the reaction medium. Suitable conditions were ascertained for preferential adsorption of the above metal ions from the salt solutions containing other interfering ions such as Na⁺, K⁺, and Mg²⁺. Presence of these alkali and alkaline earth metal ions in the salt solutions did not affect the adsorption behavior of the resins. It was observed that the structural features of the resins have a profound effect on the uptake characteristics. The position of the OH group present in the meta position with respect to the imine nitrogen atom in the resin, demonstrated a significant influence on the extent of metal ion adsorption by the resin. Out of the three resins reported here, the resin derived from the Schiff base of m-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone showed higher efficiency in uptake of metal ions from the solutions than the corresponding resins derived from the Schiff bases of o- and p-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone.     

Solvent Extraction of Alkali Metal Cations from Aqueous Solutions by Crown Ether Carboxylic Acids

Abstract

Competitive solvent extractions of alkali metal cations from aqueous solutions by the crown ether carboxylic acids sym-dibenzo-13-crown-4-oxyacetic acid, 2; sym-dibenzo-19-crown-6-oxyacetic acid, 3, and sym-dibenzo-14-crown-4-oxyacetic acid, 4, in chloroform have been conducted. Influences of aqueous phase pH and metal ion concentrations upon the concentrations of metals and complexing agent in the organic phase are assessed and compared with those reported for sym-dibenzo-16-crown-5-oxyacetic acid, 1. Extraction selectivity orders of K > Rb > Na ≈ Cs > Li, K > Rb ≥ Na ≈ Cs > Li, and K > Na > Rb > Cs ≈ Li were found for extractions using 2, 3, and 4, respectively. In terms of selectivity and metal extractability, 3 surpasses 1, 2, and 4.     

Effect of Receiving Phase Anion on Macrocycle-Mediated Cation Transport Rates and Selectivities in Water—Toluene—Water Emulsion Membranes

Abstract

Relative transport rates of metal nitrates (Na⁺, K⁺, Rb⁺, Cs⁺, Ag⁺, T1⁺, Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Zn²⁺, and Pb²⁺) were measured alone and in combination with either Pb²⁺, Ag⁺, or T1⁺ in a water-toluene-water emulsion membrane system. The toluene phase contained the surfactant Span 80 and the crown ether dicyclohexano-18-crown-6 (DC18C6). The aqueous receiving phase contained the lithium salt of one of the following anions: pyrophosphate, thiosulfate, hydroxide, chloride, formate, nitrate. In the case of the metal combinations, chloride and formate ions were not studied. Unless significant complexation occurred both between the transported cation and the anion in the receiving phase and between the cation and DC18C6 in the membrane phase, there was little or no transport of the cation from the source phase to the receiving phase. Selective removal of Pb²⁺ and of Ag⁺ from binary mixtures of these cations with each of the cations listed was demonstrated using the emulsion membrane.     

The assessment of removing strontium and cesium cations from aqueous solutions based on the combined methods of ionic liquid extraction and electrodeposition

The extraction of Sr²⁺ and Cs⁺ from aqueous solutions by using the ionophores dicyclohexano-18-crown-6 (DCH18C6) and calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6), respectively, was demonstrated in the hydrophobic, room-temperature ionic liquid (RTIL), tri-1-butylmethylammonium bis((trifluoromethyl)sulfonyl)imide (Bu₃MeN-TFSI). The water contents of several hydrophobic ionic liquids and the absorption/desorption reversibility of oxygen and moisture in the Bu₃MeN-TFSI ionic liquid were determined by electrochemical techniques. The relationship between the distribution coefficient, D_M, and the concentration ratios of C_ionophore,IL/C_{metal ion,aq} were investigated. The values of D_M increase with increasing the concentration ratios and they are also influenced with the counter ions of Sr²⁺ and Cs⁺ in the aqueous solutions. In the previous study, it was demonstrated that the Sr²⁺ and Cs⁺ cations in the Bu₃MeN-TFSI ionic liquid could be coordinated by DCH18C6 and BOBCalixC6, respectively, and formed the DCH18C6·Sr²⁺ and BOBCalixC6·2Cs⁺ ions, which would be cathodically reduced to Sr- and Cs-amalgam at a mercury film electrode (MFE). In this study, the probability was evaluated if the Sr²⁺ and Cs⁺ cations extracted from the aqueous solutions can be really reduced to respective amalgam.     

Study on Industrial Scale Chromatographic Separation Methods of Galactose from Biomass Hydrolysates

Galactose is an aldohexose, which has commercial uses in the pharmaceutical and food industries. Since monomeric galactose is not a freely occurring compound, it must be produced from galactose‐containing hydrolysates. This paper reports the results of experimental studies of the chromatographic separation of galactose in aqueous solutions by ion exchange resins on an industrial scale. Until now, galactose has only been determined from various solutions by liquid chromatography (HPLC) on an analytical scale. Chromatographic separation of galactose from carbohydrate mixtures was studied with strong acid cation exchange resins in Na⁺, Ca²⁺ forms and strong base anion exchange resin in SO₄^2– form. The feed solutions were hydrolysates from three possible galactose sources: lactose, gum arabic and hemicellulose in spent sulfite liquor. The main monosaccharide impurities in these raw materials were glucose, arabinose, and xylose. It was demonstrated that large scale liquid chromatography can be used effectively for galactose separation from complex carbohydrate mixtures such as plant hydrolysates as well as lactose hydrolysate.     

Pervaporation separation of water–ethanol mixtures using metal‐ion‐exchanged poly(vinyl alcohol) (PVA)/sulfosuccinic acid (SSA) membranes

Poly(vinyl alcohol)/sulfosuccinic acid (PVA/SSA) membranes in the hydrogen form were converted to monovalent metal ion forms Li⁺, Na⁺, and K⁺. The effect of exchange with metal ions was investigated by measuring the swelling of water–ethanol (10/90) mixtures at 30 °C and by the pervaporative dehydration performance test for aqueous ethanol solutions with various ethanol concentrations at 30, 40, and 50 °C. In addition, electron spectroscopy for chemical analysis (ESCA) analysis was carried out to study the quantity of metal ions in membranes. From the ESCA analysis, the lithium ion quantity in the resulting membranes is greater than that of any other metal ions in question because of the easy diffusion of a smaller metal ion into the membrane matrix. The swelling ratio was in the following order: PVA/SSA‐Li⁺ > PVA/SSA‐Na⁺ > PVA/SSA‐K⁺ membranes. For pervaporation, the PVA/SSA‐Na⁺ membrane showed the lowest flux and highest separation factor for all aqueous ethanol solutions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1867–1873, 2002     

Effect of Macrocycle Type on the Extraction into Toluene of Ag+, Pb2+, and Cd2+ Using a Combination of a Macrocycle and Di(2-ethylhexyl)phosphoric Acid as Extractants

Abstract

The nitrate salts of Ag⁺ and Pb²⁺ are extracted into toluene solutions of one of the following macrocycles: dicyclohexano-18-crown-6 (DC18C6); 1,10-dithia-18-crown-6 (DT18C6); 1,10-diaza-18-crown-6 (2.2); hexathia-18-crown-6 (HT18C6); or cryptand 2.2.1. In addition, the nitrate salt of Cd²⁺ is extracted into toluene solutions of DC18C6 or DT18C6. Ag⁺, Pb²⁺, and Cd²⁺ are also extracted into toluene containing di(2-ethylhexyl)phosphoric acid (HDEHP) and toluene containing a combination of HDEHP and one of the macrocycles. Metal ion extraction is synergistic for the systems containing HDEHP and DC18C6, 2.2, or 2.2.1, but is antagonistic for the systems containing HDEHP and DT18C6 or HT18C6.     

Highly Efficient and Selective Transport of Cu(II) with a Cooperative Carrier Composed of Tetraaza-14-Crown-4 and Oleic Acid through a Bulk Liquid Membrane

Tetraaza-14-crown-4 and oleic acid was successfully applied for transport of Cu(II) in chloroform bulk liquid membrane. The uphill moving of Cu(II) during the liquid membrane transport process has occurred. The main effective variable such as the type of the metal ion acceptor in the receiving phase and its concentration, tetraaza-14-crown-4 and oleic acid concentration in the organic phase on the efficiency of the ion-transport system were examined. By using L-cysteine as a metal ion acceptor in the receiving phase, the maximum amount of copper (II) transported across the liquid membrane was achieved to 96 ± 1.5% after 140 minutes. The selectivity of copper ion transport from the aqueous solutions containing Pb²⁺, Tl⁺, Ag⁺, Co²⁺, Ni²⁺, Mg²⁺, Zn²⁺, Hg²⁺, Cd²⁺ and Ca²⁺ ions were investigated. In the presence of CH₃COONH₄ and Na₄P₂O₇ as suitable masking agents in the source phase, the interfering effects of Pb⁺² and Cd²⁺ were diminished drastically.     

Influence of guests and protonation on the conformation of N,N′-dipyridyl-bis-aza-18-crown-6

Crystallisation of the sodium perchlorate adduct of N,N^′-dipyridyl-bis-aza-18-crown-6 from acidic aqueous conditions yielded [(H₃O)(N,N^′-dipyridyl-bis-aza-18-crown-6)][ClO₄] and [Na·N,N^′-dipyridyl-bis-aza-18-crown-6]₂ [(H⁺)₂N,N^′-dipyridyl-bis-aza-18-crown-6][ClO₄]₄·2H₂O. The conformations of crown ethers were significantly influenced by incorporation of an H₃O⁺ or sodium ion, or protonation of the amino nitrogen atoms resulting in three different structures for the macrocycle.     

Selective Extraction of Cu2+ and Ag+ Ions from Sulfuric Acid by Synergistic Combinations of Tetradentate Thia Macrocycles with Dioodecylnaphthalene Sulfonic Acid

Abstract

The aqueous-insoluble thia macrocycles tetrathia-14-crown-4 (TT14C4) and tetrathia-16-crown-4 (TT16C4) strongly and selectively synergize the extraction of Cu²⁺ and Ag⁺ ions from aqueous sulfuric acid solutions by the organophilic cation exchanger didodecylnaphthalene sulfonlc acid (HDDNS) in toluene diluent. Over a range of sulfuric acid concentrations, the selectivity is given by the order Ag² > Cu²⁺ > Mn²⁺, Fe²⁺, Fe³⁺, Co²⁺, Ni²⁺, and Zn²⁺, where synergism occurs only for Ag⁺ and Cu²⁺. Selectivity factors greater than 300 have been achieved for Cu²⁺ over ubiquitous Fe³⁺. The synergistic extraction of Cu²⁺ and Ag⁺ was explored as a function of sulfuric acid concentration, relative concentration of macrocycle vs. HDDNS, and loading.     

NEW NITROGEN-CONTAINING MACROCYCLIC LIGANDS COVALENTLY ATTACHED TO SILICA GEL AND THEIR USE IN SEPARATING METAL CATIONS

Several polyaza-crowns and cyclams, each containing an allyl-oxymethyl or other monofunctional group capable of further reaction to attach it to silica gel, have been prepared. As an example of an attachment of a crown to silica gel, allyloxymethyl-substituted diaza-18-crown-6 was reacted with triethoxysilane to form the crown-substituted triethoxysilane This crown-silane material was heated on silica gel to effect a covalent attachment of the crown. The silica gel-bound macrocyclic ligands were found to interact with various metal cations with log K ( H2O) values similar to those of the same cations with unbound macrocycles. A tetraaza-crown bound to silica gel was found to quantitatively remove toxic heavy metal ions, such as Pb²⁺, Hg²⁺ Cd²⁺ Ag⁺and others at the ppb level, from large volumes of aqueous solutions containing those metal ions and much larger amounts of Na⁺Mg²⁺and Ca²⁺ions     

The Synerqistic Solvent Extraction of Manganese by Macrocyclic Crown Ethers in Combination with Didodecylnaphthalene Sulfonic Acid: Effect of Macrocycle Substituents

Abstract

Crown ethers in combination with organophilic cation exchangers synergize the extraction of certain metai ions from aqueous solutions, and their selectivity has been thought largely dependent on the correspondence between the crown other's cavity diameter and the metal ion diameter. This work focuses on two crown ethers, tert. -butylbenzo -15-crown-5 (tBB15C5). and tert, -butylcyclohexano 15-crown-5 (tBC15C5) each of which has a cavity diameter of 1.7 to 2.2 × 10^?10 m. and their extraction of Mn²⁺ (ionic diameter 1.4 to 2.2 × 10^?10 m) from aqueous nitrate solutions. The organophilic cation exchanger used was didodecylnaphthalene sulfonic acid (HDDNS). The data show no observable complexes of the manganese salt of HDDNS     

Electrochemical Recovery of Lithium Ions in the Aqueous Phase

Abstract

The electrochemical insertion of lithium ions into a Pt/λ-MnO₂ electrode was investigated in various metal chloride solutions. The Li⁺ insertion occurred effectively in LiCl solutions with higher concentration than 10 mmol/dm³, but it could hardly occur in a 0.1 mmol/dm³ LiCl solution. Alkaline earth metal ions showed a stronger inhibition effect against the Li⁺ insertion into the Pt/λ-MnO₂ electrode than alkali metal ions. However, since only Li⁺ ions were taken up from a mixed solution of lithium and alkaline earth metal chlorides, a high selectivity of the electrode for lithium ions was shown.

It was possible to recover lithium ions from geothermal water by this electrochemical method using the Pt/λ-MnO₂ electrode; the lithium uptake was 11 mg/g-MnO₂.