Phosphine-functionalised polymer resins as Pd scavengers

Three phosphine-functionalised polymer resins were used as scavengers of palladium catalysts from Buchwald-Hartwig aryl amination reactions. The purity of the products was assessed, and residual palladium analysed by ICP-AES. Scavenging efficiencies of up to >98.5% were demonstrated.     

Thermoanalytical investigation of ion exchange resins. The swelling water of anion exchange resins

The water uptakes of completely swollen and air dried anion exchange resins were investigated by traditional and also by thermoanalytical measurements. In investigations on the air dried resin samples of HSO₄, H₂PO₄, SO₄, HPO₄ and PO₄ forms, two types of water (strongly and loosely bound) were found. The sequence of water uptake on the resins investigated was compared to the opposite order of the adsorption strengths of the anions and to the entropies of the hydrated anions. A conclusion was made regarding the role of the hydration of the anions in the selectivity sequence of anion exchange.

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Zusammenfassung Die Wasseraufnahme vollständig angequollener und lufttrockener Anionenaustauscherharze wurde mittels herkömmlicher sowie auch thermoanalytischer Messungen untersucht. Bei den Prüfungen der lufttrockenen Harzproben in den HSO₄-, H₂PO₄-, SO₄-, HPO₄-, und PO₄-Formen wurden zwei Arten von Wasser gefunden: stark und schwach gebundenes. Die Reihenfolge der Wasseraufnahme wurde mit der umgekehrten Reihenfolge der Adsorptionsstärke der Anionen und mit der Entropie der hydratisierten Anionen verglichen. Schlüsse bezüglich der Rolle der Hydratisierung der Anionen bei der Selektvititätsreihenfolge des Anionenaustausch wurden gezogen.

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Résumé On a étudié par des mesures traditionnelles et par analyse thermique l'absorption d'eau par des résines échangeuses anioniques totalement gonflées et séchées à l'air. Lors de l'étude des échantillons de résines séchées à l'air, de formes HSO₄, H₂PO₄, SO₄, HPO₄ et PO₄, on a trouvé deux types d'eau: de l'eau fortement liée et de l'eau faiblement liée. On a comparé l'ordre de l'absorption d'eau des résines étudiées à l'ordre inverse des forces d'adsorption des anions et à l'entropie des anions hydratés. On en tire des conclusions sur le rôle de l'hydratation des anions sur la sélectivité de l'échange anionique.

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- , . - HSO₄-, H₂PO₄-, SO₄-, HPO₄-, PO₄- : . . .

     

The sorption of polymetaphosphate on anion exchange resins

From a solution of sodium polymetaphosphate, strongly basic anion exchange resins can retain a greater amount of polymetaphosphate than that corresponding to the exchange capacity. Sodium ions are held by the polymetaphosphate form of the resin and these sodium ions can be exchanged for other ions.     

离子交换树脂催化合成碳酸亚丙酯

碘型离子交换树脂在某些偶极非质子性溶剂的作用下，能有效地催化二氧化碳与环氧丙烷合成碳酸亚丙酯，并能重复使用至少10次而仍能保持较高的催化活性。     

Synthesis and characterization of periodic mesoporous organosilicas as anion exchange resins for perrhenate adsorption

A new methodology to immobilize ionic liquids through the use of a bridged silsesquioxane N-(3-triethoxysilylpropyl), N(3)-(3-trimethoxysilylpropyl-4,5-dihydroimidazolium iodide that incorporates an ionic functionality for the assembly of novel periodic mesoporous organosilica (PMO) materials has been developed. The resulting PMO materials were investigated for use as novel anion exchange resins for the separation of perrhenate anions in aqueous solution. As compared with cetyltrimethylammonium chloride, 1-hexadecane-3-methylimidazolium bromide has been demonstrated to be a more efficient surfactant template for the generation of mesopores and surface areas for such PMO materials.     

The immobilisation of anion exchange resins in polymer modified cements

Organic anion exchange resins, loaded with⁹⁹Tc pertechnate were incorporated into polymer modified cements and BFS/OPC(9∶1) cements. The composites formed were tested for initial compressive strenghts, underwater and radiation stabilities and leach rates. IAEA standard leach testing was with simulated sea and ground waters. Ground water leaching was also carried out on composites subjected to 1.1 MGy (γ). Polymer modified composites performed better than the BFS/OPC mix under all the conditions studied and, in most cases, were able to encapsulate high resin loading.     

Evaluation of anion exchange resins for plutonium-uranium separations in nitric acid

Pellicular, macroreticular and microreticular (gel-type) anion exchange resins were compared for the separation of plutonium from nitric acid solutions of mixed plutonium-uranium. AS Pellionex SAX (pellicular resin) and Amberlite IRA-93 (weak base macroreticular anion exchange resin) were found to have better uranium washing and plutonium eluting characteristics than any of the resins tested. However, the capacity of the pellicular resin was much lower than the other resins.     

Radiation resistance of pyridine type anion exchange resins for spent fuel treatment

The resistance against radiation of the tertiary pyridine resins synthesized for the treatment of spent nuclear fuels and high level radioactive waste was evaluated. After irradiation at 10 MGy, only approximately 10% or less of the exchange groups were lost in HCl solutions regardless of their concentrations, while 3040% were lost in HNO₃. The pyridine resin has shown remarkable resistance against radiation particularly in HCl solution. It has been revealed that the decomposition of pyridine type resins results from the scission of the principal chains. An irradiation study was conducted also on the quaternary ammonium resins. Quatemization ratio was found to be reduced in HNO₃ solutions at 10 MGy irradiation.     

Ion-isotopic exchange reaction kinetics using organic base anion exchange resins Indion-102 and Indion GS-400

The present study deals with the kinetic study of iodide and bromide ion-isotopic exchange reactions in organic based anion exchange resins Indion-102 (nuclear grade) and Indion GS-400 (non-nuclear grade) using radiotracer isotopes. The resins in iodide and bromide form were equilibrated respectively with iodide and bromide ion solutions which were previously spiked with ¹³¹I and ⁸²Br radiotracer isotopes. For both bromide and iodide ion-isotopic exchange reactions, it was observed that the values of specific reaction rate increase with increase in ion concentration from 0.001 to 0.004 M at a constant temperature of 40.0°C. However, at constant ion concentration of 0.003 M, the specific reaction rate was observed to decrease with rise in temperature from 30.0 to 45.0°C. Also it was observed that for iodide ion-isotopic exchange reaction by using Indion-102 resin, the values of specific reaction rate, amount of iodide ion exchanged, initial rate of iodide ion exchange and logK _d were 0.258 min^?1, 0.492 mmol, 0.127 mmol/min and 19.2, respectively, which were higher than 0.208 min^?1, 0.416 mmol, 0.087 mmol/min and 17.6, respectively, obtained by using Indion GS-400 resin under identical experimental conditions of 40.0°C, 1.000 g of ion exchange resin and 0.003M labeled iodide ion solution. The same trend was observed for the two resins during bromide ion-isotopic exchange reaction. The overall results indicate that, under identical experimental conditions, Indion-102 resin shows higher performance than Indion GS-400 resin.     

Radiotracers in kinetics of ion-isotopic exchange reactions using anion exchange resins indion-103 and indion-870

The kinetics of iodide and bromide ion-isotopic exchange reactions was studied by radio analytical technique using ¹³¹I and ⁸²Br as tracer isotopes. The parameters like specific reaction rate (min^?1), amount of ions exchanged (mmol), initial rate of ion exchange (mmol/min) and logK _d were studied to evaluate the performance of nuclear and non-nuclear grade anion exchange resins Indion-103 and Indion-870. For iodide ion-isotopic exchange reactions under experimental conditions of 35.0°C, 1.000 g of ion exchange resins and 0.002 M labeled iodide ion solution, the parameters were 0.223 min^?1, 0.300 mmol, 0.067 mmol/min and 18.7, respectively, for Indion-103, and those of 0.165 min^?1, 0.251 mmol, 0.041 /min and 16.2, respectively, for Indion-870. The similar tendency was observed during bromide ion-isotopic exchange reactions. The results suggest that Indion-103 shows greater performance than Indion-870 resin under similar experimental conditions.     

Aqueous-phase ion solvation and the selectivity of anion exchange resins for monovalent ions

This research examines and quantifies the influence of ion solvation parameters on the affinity of monovalent anions for strong-base anion resins. A data set comprising resin selectivity coefficients and solvation parameters from the literature is statistically analyzed using correlation and multiple regression techniques. The affinity of monovalent anions for the resin phase correlated well to ionic radii. Solvation parameters such as the hydration number, and entropy, enthalpy and free energy of hydration are also strongly correlated to selectivity. Using the stepwise regression procedure on subsets of independent variables, the entropy of hydration, which characterizes the structure-influencing nature of ions in solution, is incorporated as the sole parameter in the predictive model for resin selectivity. The data are best correlated by the exponential form of the regression equation, and the physical meaning of the correlation is shown to be reasonable. A simple rule for categorizing ions as structure-makers and structure-breakers is proposed, and the results are consistent with conventional classifications.     

Preparation and properties of anion exchange membranes having pyridinium or pyridinium derivatives as anion exchange groups

Anion exchange membranes with pyridinum groups and various pyridinium derivative groups were prepared from a copolymer membrane composed of chloromethylstyrene and divinylbenzene, and pyridine and pyridine derivatives. The anion exchange membranes obtained showed excellent electrochemical properties in electrodialysis. The transport numbers of sulfate ions, bromide ions, nitrate ions, and fluoride ions relative to chloride ions were evaluated in connection with the species of a substituent and the position of the substituent in the pyridinium groups. In general, when a hydrophilic substituent (methanol groups) existed at the 2-position of the pyridinium groups, nitrate ions and bromide ions, which are less hydrated, permeated through the membranes with difficulty, and sulfate ions permeated selectively through the membranes. On the other hand, when hydrophobic groups, for example, ethyl groups, existed at the 2-position of the pyridinium groups, bromide ions and nitrate ionspermeated selectively through the membranes and fluoride ions had difficulty permeating through the membranes. The carbon number of the alkyl chain of 4-alkyl pyridinium groups also affected permeation of nitrate ions and bromide ions due to the change in hydrophilicity of the membranes. Though the hydration of the anions and the species of the substituent at the 2-position of the pyridinium groups were related to selective permeation of the anion through the membranes, permeation of sulfate ions was not as sensitive to the hydrophilicity of the membranes. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 49–58, 1998     

Remazol Black B removal from aqueous solutions and wastewater using weakly basic anion exchange resins

In this study, the use of the weakly basic anion exchange resins of phenol-formaldehyde (Amberlyst A 23), polyacrylate (Amberlite IRA 67) and polystyrene (Lewatit MonoPlus MP 62) matrices for removal of the reactive dye Remazol Black B (RBB) from aqueous solution and wastewater were investigated. RBB sorption on the anion exchangers was a time dependent process. Color reduction percentiles of 75.2, 33.9 and 25.1% in wastewater treatment were found after 216 h of phase contact time with Lewatit MonoPlus MP 62, Amberlyst A 23 and Amberlite IRA 67, respectively. Inorganic salts and anionic surfactant action influenced RBB uptake by the anion exchangers. The amounts of dye retained by the anion exchangers increased with a rise in temperature. The maximum sorption capacities calculated from the Langmuir model were 66.4, 282.1 and 796.1 mg g⁻¹ for Amberlite IRA 67, Amberlyst A 23 and Lewatit MonoPlus MP 62, respectively. Regeneration of phenol-formaldehyde and polystyrene resins were possible using 1 M NaOH, 2 M KSCN, 1M KSCN in 40–60% methanol as well as 1 M NaOH in 60% methanol.      

D301R树脂吸附-解吸钼的行为研究

对D301R型阴离子交换树脂吸附-解吸钼的条件进行了研究，采用静态法试验了pH值、钼的浓度等因素对该树脂吸附钼的影响；采用动态法讨论了该树脂对钼的饱和吸附量、解吸剂及其浓度对解吸钼的影响。结果表明在pH2．5，钼的浓度为20g/L时吸附效果最好，树脂对钼的饱和吸附量为1020mg／g，而采用150g/L NaOH溶液解吸钼效果最佳。     

Functionalized cross-linked poly(vinyl alcohol) resins as reaction scavengers and as supports for solid-phase organic synthesis

New hydrophilic poly(vinyl alcohol) (PVA-OH) resins were prepared by an inverse suspension polymerization using epichlorohydrin as a cross-linker. These novel resins swell in a variety of solvents commonly used in solid-phase organic synthesis, such as dicholomethane, dioxane, methanol, tetrahydrofuran, and dimethylformamide. In addition, PVA-OH shows excellent swelling in water. The cross-linked PVA-OH beads were functionalized with an aldehyde group and were tested as scavengers for primary amines in three different reactions: amide bond formation, reductive amination reaction, and urea formation. With 1-2 equiv of the PVA aldehyde resin, all the excess primary amines were successfully scavenged. The utility of PVA-OH resins as solid supports in mono- and dipeptide synthesis was also investigated using symmetrical anhydride and MSNT/MeIm (2,4,6-mesitylenesulfonyl-3-nitro-1,2,4-triazolide in the presence of 1-methylimidazol) methods.     

Metal-cation-based anion exchange membranes

Here we present the first metal-cation-based anion exchange membranes (AEMs), which were synthesized by copolymerization and cross-linking of a norbornene monomer functionalized with a water-soluble bis(terpyridine)ruthenium(II) complex and dicyclopentadiene. Each ruthenium complex has two associated counteranions, unlike most ammonium- and phosphonium-based membranes with single cation-anion pairs. The resulting AEMs show anion conductivities and mechanical properties comparable to those of traditional quaternary-ammonium-based AEMs as well as good alkaline stability and methanol tolerance. These results suggest that metal-cation-based polymers hold promise as a new class of materials for anion-conducting applications.