Thermally Regenerable Ion-Exchange Resins by Photografting

Crosslinked polymer beads containing regions of acidic and basic groups are the preferred structures for the efficient operation of a thermally regenerable ion-exchange process. Such systems can be prepared by various methods. Here the approach of using polymers and copolymers containing photo-labile groups as grafting sites is described. The polymers studied were polytriallylamine hydrochloride (polyTAA) and copolymers of propyldiallylamine hydrochloride (PDAA) and allyl benzoin methyl ether (ABME), of ABME and acrylic acid (AA), and of ABME and methyl acrylate (MA). The maximum amount of photografting of MA onto polyTAA was 12%. Very little photografting of MA onto PDAA:ABME copolymers was obtained. Photografting of TAA to AA:ABME and to MA:ABME copolymers occurred readily by using radiation of 360 nm wavelength, with the best yields of photografted polymer being about 60% when a MA:ABME copolymer was irradiated in a suspension. The effect of suspending medium, stirring rate, irradiation time, irradiation intensity, solvent, solids concentration, percentage of ABME in the MA:ABME copolymer, additional crosslinkers, surfactants, and the acid:base ratio in the hy-drolyzed resin prepared by photografting TAA onto MA:ABME copolymers on the yield, physical strength, shape, and ion-exchange properties of the resins is reported.     

Synthesis of Hindered Phenolic Esters over Ion-Exchange Resins

The esterification of 3,5-di-tert-butyl-4-hydroxybenzoic acid with 1-hexadecanol over a series of ion-exchange resins was investigated, in which resin D072 exhibited excellent catalytic performance. The influence of water on the reaction was also investigated, and it was found that water could improve the selectivity and increase the yield of the target product. Treatment of resins with aqueous sodium hydroxide could improve the selectivity of the target product but remarkably decreased the conversion of 3,5-di-tert-butyl-4-hydroxybenzoic acid. This result indicated that strong Brønsted acid sites played an important role in the reaction. Furthermore, D072 was efficiently recycled four runs by simple treatment with mineral acid. Finally, a series of hindered phenolic esters were successfully synthesized under the optimal reaction conditions. Therefore, a simple and versatile method for the synthesis of hindered phenolic esters has been established over ion-exchange resins and the target products were obtained in good yields.     

Preparation of High-Purity Lithium Carbonate Using Complexing Ion-Exchange Resins

Russian Journal of Applied Chemistry - Sorption of a series of alkaline earth and nonferrous metals (Ca, Mg, Cu, Ni, and Zn) from lithium hydrocarbonate and chloride solutions onto ion-exchange...     

Hydroarylation of Styrenes with Electron-Rich Arenes Over Acidic Ion-Exchange Resins

A series of acidic cation-exchange resins were used for the hydroarylation of resorcinol with styrene, in which resin D072 exhibited the excellent catalytic performance in this reaction with 99% conversion of styrene and 90% selectivity of 4-(1-phenylethyl)resorcinol. It was applied to the hydroarylation of various electron-rich arenes with styrenes, and the hydroarylated products were quantitatively obtained. This catalyst could be used for four consecutive runs with slight decrease in activity. The hydroarylation of resorcinol with styrene over resin D072 in a fixed bed was completed effectively with 94% selectivity and 99% conversion, and this green continuous process is potentially applicable to large-scale productions.     

Kinetics Characterization of Ion Release under Dynamic and Batch Conditions. I. Weak Acid and Weak Base Ion Exchange Resins

The aim of the present work is concerned with a study of the kinetics of release of both Ca²⁺ and F⁻ from the corresponding loaded ion-exchange resins (weak acid and weak base character for Ca²⁺ for F⁻, respectively), using both dynamic and batch experimental conditions with an artificial saliva solution as the ion-exchange media at 293 and 310 K. The influence of resin particle size and the temperature were evaluated by the kinetics parameters for the effective rate of release (B) and diffusion coefficient (D). The rate of ion release increases with temperature and decreases with particle size. The experimental data were well fitted by models based on intraparticle diffusion-controlled processes. In dynamic studies, the linear dependence of −log ₁₀(B) with the diameter of the resin particles can be applied for the estimation of B values when resins of low particle size are considered. In batch processes, although resins of low particle size can be studied, a linear relationship was only attained for the case of slow ion-exchange kinetic systems.     

Synthesis of New bis-Iminocoumarins by Schmidt Reaction Catalyzed by Ion-Exchange Resins

Abstract

A new synthetic route to bis-iminocoumarins is proposed which involves the synthesis of iminocoumarins from reaction of 2-hydroxybenzaldehydes with arylacetonitriles and their coupling with aromatic diamines. Ion-exchange resins were used as catalysts in both steps of this synthesis. The reaction parameters were varied and obtained using Amberlyst 15 resin in cyclohexane at 80°C.     

pH Neutralization while Succinic Acid Adsorption onto Anion-Exchange Resins

Succinic acid is a useful chemical and its purification from fermentation broth by ion-exchange resins has widely drawn attention. In this study, pH neutralization in the process of adsorption of succinic acid from model solutions and fermentation broth by anion-exchange resin NERCB 04 has been tested. Adsorption capacity of NERCB 04 was about 0.41 g succinic acid/g resin at concentrations of succinic acid in the range of 10–50 g/L in packed column. In the process of succinic acid removal, pH of the system could also be neutralized. The neutralizing ability of the resin as a neutralizing agent has also been studied in the model cycle system and in the real fermentation cycle process. It was found that NERCB 04 showed stable adsorption capacity and pH neutralization ability after each regeneration. A certain amount of anion-exchange resin could neutralize the low pH values (pH 2–5) and maintain the system around pH 7.0. This means the anion-exchange resins have the function of neutralizing reagent in the process of adsorbing succinic acid.     

Kinetics of Potassium Ion-Exchange in a Cation-Exchange Resin

The kinetics of the exchange of potassium ions in a cationexchange resin has been studied. The rate measurements have been made by a potentiometric technique, and both the kinetic and the activation parameters of the reaction were determined. The rate-controlling step, at the beginning of the reaction, has proved to be the diffusion of the K⁺ ions through the film surrounding the resin beads.     

Preparation of Thermally Regenerable Ion-Exchange Resins by Polymerizing a Heterogeneous Mixture of Monomers

Crossinked resin beads containing regions of acidic and basic groups are the preferred structures for the efficient operation of a thermally regenerable ion-exchange process. In the present study they were prepared by polymerizing a heterogeneous mixture of acrylic esters and allylamines. Polymerization of unstable emulsions of acrylic esters and allylamines by heating the stirred emulsions gave very hard, strong resins which after hydrolysis had good acid, amine and thermally regenerable capacities. The thermally regenerable capacity depended very much on the nature of the acrylic ester and the allylamine. The order of increasing thermally regenerable capacity for the resins prepared is methyl acrylate (MA)/triallylamine (TAA), MA/diallylamine (DAA), MA/methyldiallylamine (MDAA) < ethyl acrylate (EA)/TAA, EA/DAA < EA/MDAA, butyl acrylate/MDAA. The dispersion of the unstable emulsions in a third phase resulted in immediate breakdown of the emulsion. The dispersion of partly prepolymerized emulsions in a third phase of paraffin oil containing talc, followed by completion of the polymerization and hydrolysis, gave hard resin beads with acid, amine and thermally regenerable capacities comparable to those prepared as a two-phase emulsion. Their shape, size, strength, and degree of agglomeration depended on the stirring rate, the shape and material of construction of the stirrer, the potential acid/base ratio of the monomers, the nature of the solid dispersant, and the acrylic ester and the allylamine. Satisfactory resin beads could be obtained from only the MA/TAA and MA/DAA combinations which are those that give resins with the poorest thermally regenerable capacities. Partial prepolymerization of the two-phase emulsion is easy on the laboratory scale, but would be impracticable on the commercial scale. Although polymeric dispersants gave stable two-phase emulsions, the amine monomer migrated into an aqueous third phase more rapidly than it polymerized.     

Nuclear Magnetic Resonance Studies of Ion-Exchange Resins. I. Effect of Counter Ion

The nuclear magnetic resonance spectra of packed beds containing the cation exchanger Dowex 50W-X8 in water vary with counter ion. Chemical shifts for water protons internal to the resin bead are in the order H⁺ (lowest frequency) » Zn²⁺ ? Cd²⁺ ≤ Pb²⁺ ? Mg²⁺ ≤ Ag⁺ ≤ Ca²⁺ ? Tl⁺ ? NEt⁺ ₄ ? Ba²⁺ ? Li⁺ ? NMe₄ ⁺ ? Sr²⁺ ≤ NH₄ ⁺ ≤ Rb⁺ ? K⁺ ? Na⁺ ? NBu₄ ⁺. The concentrated electrolyte model of ion-exchange resins is substantiated by generally good agreement between 1) chemical shifts/g equiv./kg for cations in aqueous solutions referred to NH₄ ⁺ and 2) chemical shifts/g equiv./kg for resin forms referred to NH₄ ⁺ form resin.     

Nuclear Magnetic Resonance Studies of Ion-Exchange Resins.II. Additivity of Counter Ion Effects

Abstract

The nuclear magnetic resonance chemical shins for the internal water protons of the cation exchanger Dowex 50W-X8 equilibrated with solutions containing the counter ions, H⁺ and Na⁺, are linearly proportional to the equivalent fraction composition of the mixed form resin. Better agreement between observed and calculated chemical shifts is obtained if the water contents of the various mixed form resins are taken into account.     

松香改性酚醛环氧树脂的固化反应动力学研究

以自制的松香改性酚醛环氧树脂（RPAE）为对象,采用差示扫描量热法研究了其与4,4．二氨基二苯砜组成的体系（RPAE／DDS）的固化动力学,利用Kissinger方程计算得到体系的固化热约为109．29J／g,表观活化能为51．56kJ／mol,该体系反应级数为0．85,近似为1级反应,反应速率常数为2．69×10^4／s。采用Ozawa-Flynn-Wall方程分析,得到体系的表观活化能为70。1kJ／mol。     

弱电解质的电离创新教学设计与反思

弱电解质的电离教学设计主要由5个环节组成,重点是教学流程的创新设计,由5个师生课堂活动构成,这样创新教学设计对实施课堂有效教学起着重要的作用.     

Kinetics and Thermodynamics of Synthesis of Tertiary-Amyl Methyl Ether Catalyzed by Ion-Exchange Resin

Synthesis of tertiary-amyl methyl ether (TAME) was carried out in the temperature range 40–70 ° Cusing a sulfonic acid resin as the catalyst. Thermodynamic data were calculated from the equilibrium concentration of the components in a stirred batch reactor by the Unifac method. The enthalpy change of TAME formation was calculated to be (?20.4 ± 0.8) kJ/mol and the equilibrium constant is expressed as Ka = 3.94 × 10^?4 exp (20400/RT). For the kinetic tests, a homogeneous solution system was selected to interpret experimental results. The activation energy of the forward reaction was calculated to be (94.0 ± 1.5) kJ/mol and the rate constant is expressed as k₂ = 5.31 × 10¹¹ exp (?94000/RT). The validity of this kinetic model was verified by fitting experimental data.     

Application of Ion-Exchange Membranes for Stabilizing Acidity of a Chromium-Plating Electrolyte Based on Chromium(III) Sulfate

The acidity of a chromium-plating electrolyte based on chromic sulfate may be stabilized in a two-chamber electrolyzer with an anion-exchange membrane (AEM). The optimum concentration of sulfuric acid in the anolyte (c _sa) may be selected on the basis of the material balance equation for the catholyte, which allows for the dependence of the transport number of hydronium ions in AEM on c _sa. No considerable accumulation of Cr²⁺ occurs in the catholyte during a prolonged electrolysis. The transport of formate ions through AEM at working values of electrolyte pH is inconsiderable.     

Removal of Cs-137 Radionuclide by Resorcinol–Formaldehyde Ion-Exchange Resins from Solutions Simulating Real Liquid Radioactive Waste

The efficiency of the removal of Cs-137 radionuclides with porous and non-porous resorcinol–formaldehyde resins from alkaline solutions simulating the composition of real liquid radioactive waste (LRW) streams has been evaluated. Resins were synthesized through the polycondensation of resorcinol and formaldehyde in an alkaline medium at a molar ratio of 1.8/2.2 and a temperature of 210 °C. The Cs-137 distribution coefficients on RFRs in alkaline solutions simulating LRW were above 10³ mL/g under static sorption conditions. In a model solution with pH 11, the full dynamic sorption capacity of non-porous RFR was 0.178 mmol/g. The values of the full dynamic sorption capacities of porous RFRs were 0.274 and 1.035 mmol/g for resins obtained with calcium carbonate and toluene as templates, respectively. When the sizes of RFR beads increased two-fold, the volume until 5% cesium breakthrough decreased by 20–40%. The most pronounced beneficial effect of the RFR’s porosity was observed at flow rates from 25 to 50 BV/h. It was shown that the negative effect of metal cations on Cs-137 uptake increases in the following order: Na⁺ < Mg²⁺ < Ca²⁺ < K⁺. The number of bed volumes of LRW-simulating solution decontaminated with RFRs until 5% cesium breakthrough was above 450; that is higher than the value of known commercially available analogs. The latter shows that the developed RFRs are promising for application in technological schemes of alkaline LRW processing.     

混合溶剂中弱电解质解离热力学(I)

溴酚蓝(BPB)是分析化学中常用的指示剂,它有一个等吸收点的特征吸收谱图,利用这种吸收谱图可以确定溴酚蓝热力学解离常数K°.用通常的化学法和电化学法测定弱电解质的解离度,不能区分没解离的部分是分子还是离子对.用分光光度法测定解离度,可以找出这个区别,因为分子和离子有不同的吸收光谱.在溶液中离子对的形成主要靠离子间的库伦力,而光学性质通常受库伦力影响不大.因此,用具有等吸收点的吸收谱图来确定弱电解质的解离度的方法被称作真解离度测定法.在pH=2—5范围内,溴酚蓝的解离是从第二个羟基上脱下质子的过程     

Kinetics and Mechanism of Ion-Exchange Sorption of Organic Cations on the Surface of Liquid Ion-Selective Membranes

Kinetics of ion-exchange sorption of organic cations on the surface of ion-exchange membranes with low permittivity, which are the base of the majority of ion-selective electrodes, is studied and quantitatively described. It is disclosed that the rate of ion exchange is primarily governed by the lypophilicity of displacing ions, but the time of the establishment of equilibrium state is the diffusion-limited parameter. A mechanism of ion exchange of hydrophobic organic cations on the surface of selective membranes is proposed.