Preparation and characterization of carboxylic cation exchange resins from the reaction of poly(vinyl alcohol) with melamine-formaldehyde and some hydroxy acids

The synthesis of cation exchange resins via the reaction of poly(vinyl alcohol) as a carrier, citric acid as a catalyst and reactive additive to produce resin structures with grafted carboxy groups, along with a melamine-formaldehyde precondensate, responsible for crosslinking-reinforcing and insolubilizing the resin structure as well as for fixing and binding the acidic functional groups onto the resin structure, has been investigated using varied molar ratios of reactants and varied time as well as temperature. Reaction conditions were selected to prepare a cation exchange resin based on citric acid. Two other cation exchange resins based on tartaric acid and glycolic acid, were also prepared under the same selected reaction conditions. These three resins were characterized by potentiometric titration, water solubility and swellability, as well as durability to use.     

Comparative adsorption isotherms and modeling of nickel and cobalt citrate complexes onto chelating resins

The sorption characteristics of nickel and cobalt-organic acid complexes on two commercial chelating resins (Purolite S930 and S950) were compared. Purolite S390 is based on an iminodiacetic funtional group and S950 is an aminophosphonic acid resin. Batch equilibrium adsorption tests of these resins were examined and compared using various metal citrate concentrations (15–2000 mg/L) and solution pH. The solution pH of complex solutions was varied by preparing metal solutions in 0.01, 0.1, 0.5 and 1.0 M of citric acid. Equilibrium adsorption data were fitted to empirical isotherm models; linear, Langmuir, Freundlich and Redlich–Peterson (R–P) equations to establish the mechanism for the uptake of the metal complexes onto the resins. Our study showed that nickel-citrate complex adsorption exhibited both monolayer and multilayer adsorption; the mechanism on both resins varying with acid concentration, whereas cobalt complex adsorption was independent of acid concentration but the mechanism of metal loading was found to be influenced by the nature of the resins.     

Preparation of waterborne phosphated acrylate–epoxy hybrid dispersions and their application as coil coating primer

In this paper, a series of waterborne acrylic-modified epoxy hybrid dispersions were synthesized and successfully used as primers for coil coatings. Epoxy was phosphated to improve its adhesion to the metal substrate. The grafting reaction of acrylate monomers onto the high molecular weight epoxy resins was studied with infrared spectroscopy, differential scanning calorimetry, and nuclear magnetic resonance. The structure and resin molecules were found to be as expected and the film had the best performance when the acrylate monomer made up less than 40 wt% of the epoxy resin. Modification of the epoxy with phosphoric acid could increase the adhesion to the metal substrate. Better adhesion was achieved with greater amounts of phosphoric acid. R578 urea resin was found to be the most suitable for crosslinking of the resin in this system, and a paint film based on the resulting resin had excellent overall performance.     

Bifunctional Phosphinic Acid Resins for the Complexation of Lanthanides and Actinides

Abstract

Phosphinic acid ion exchange/redox resins are synthesized by the reaction between polystyrene beads and phosphorus trichloride followed by base hydrolysis. The reaction requires a temperature of 73°C for full functionalization to occur. The effect of lower functionalization temperatures on resin acid capacity was determined and the concomitant effect on ion exchange investigated. The acid capacity was found to vary from 1.68 mequiv/g to 4.79 mequiv/g in the functionalization temperature range studied (15°C to 73°C). The percent resin sites loaded with zinc ions is independent of the actual capacity. The extracting ability of the phosphinic acid resin for europium, thorium, uranium, americium, and plutontutn was examined as a function of acid concentration from acid nitrate solutions both at varying and constant ionic strength. The phosphinic resins show better extraction for these ions than the sulfonic resins, especially from high acid solution (4M HNO₃) due to the superior coordination ability of the phosphoryl oxygen. They also show a higher selectivity for the ions tested over sodium. For example, under conditions where sulfonic resins absorb 85% of the plutonium in solution, the phosphinic acid resins absorb 99.7%.     

Novel Bifunctional Resins in Metal Ion Separations: Ion Exchange/Coordination Resins and Ion Exchange/Precipitation Resins

Abstract

Dual mechanism bifunctional polymers (DMBP's) as metal ion extractants are described within the context of two new examples. The carboxylic acid/pseudocrown resin is a new example of the DMBP class of resins described as ion exchange/ coordination resins. The polyethylene glycol ligand within the resin functions as a coordinating site for metal ions which are brought into the resin via ion exchange with the acid ligand. Initial studies with alkali metal ions are presented. The third general class of DMBP's is also presented. In this case, precipitation is the reaction occurring along with ion exchange thus yielding the ion exchange/precipitation resins. Barium recovery from aqueous solution via barium sulfate precipitation is described.     

Effect of gamma irradiation on the metal sorption and separation of some divalent metals by some new polymeric bifunctional resins

The metal sorption and separation of some divalent metals from solutions of varying acidity by a new series of gamma-irradiated ionic polymer resins have been investigated. Three polymeric resins, viz., phosphonic acid, phosphonate monoethyl ester, and phosphonate diethyl/monoethyl ester, were used in this study. The results of metal sorption and separation were compared with those of the well-known cation exchange resin Dowex X8. The results were correlated in the usual manner of distribution coefficients (D) of three divalent metals Sr(II), Co(II), and Ni(II). The results of metal sorption by the ionic resins under investigation compared with that of sulfonic acid resin, showed that Ni showed the highest affinity for the unirradiated monoethyl ester/phosphonic acid resin, while Sr showed the highest affinity for phosphonic acid resin and Co showed the highest affinity for mono/diethyl ester phosphonic acid resin. Moreover, the three metals (Sr, Co, Ni) showed the lowest affinity toward sulfonic acid resin. The calculated separation factors for the different resins indicate that the unirradiated phosphonic acid resin has the highest capacity to separate Sr from Ni, whereas mono/diethyl ester/phosphonic acid resins have the highest capacity to separate Co from Sr and Ni. Furthermore, the affinity of the ionic polymers for the metal ions was not greatly changed after gamma irradiation. © 1997 John Wiley & Sons, Inc. J Appl Polm Sci 65:1091–1101, 1997     

An ion-exchange process with thermal regeneration XI. The Ca/Na selectivity behavior of weakly acidic resins

Calcium-sodium selectivity data for a number of carboxylic acid resins were obtained under constant solution conditions with the object of determining the effects of variations in resin structure. As weakly acidic resin ionization is pH dependant, plots of selectivity versus fraction ionized were obtained from measurements over a range of pH values.Calcium retention was found to be favoured by higher levels of resin ionization, greater degrees of crosslinking, by deliberate building in of chelating residues, and in commercial resins by acrylic over methacrylic acid types. In experimental composite resins comprising micro particles of active material embedded in an inert matrix, no difference in behavior of the two acid types was discernible, but the methacrylic variety is preferred for low calcium retention because of its more weakly acidic nature. The enhanced performance of a snake-cage acidic resin containing polyether and of a copolymer system containing ether groups in this regard was attributed to their greater swelling tendencies, arising from the incorporation of hydrophilic groups. In another copolymer system, however, the presence of amide groups was found to approximately halve the high affinity of acrylic acid resins for calcium, in particles which had normal swelling properties, and a reasonable high exchange capacity of 8.4 meq/g.     

反相悬浮聚合法制备腐殖酸高吸水性树脂进展

反相悬浮聚合法制备腐殖酸-聚丙烯酸高吸水性树脂(HA-PAA),论述了高吸水性树脂的结构及复合机理,阐明了高吸水性树脂的应用领域。腐植酸树脂具有良好的吸附、吸水、降滤失和抗温、抗盐性能,得到了广泛的应用。随着腐植酸树脂研究的进展,其应用前景将更加广阔。     

The conditions of cationic exchange with the use of recycling polystyrene derivative,the product of sulfonation by silica sulfuric acid

Growing amount of waste plastics has become an environmental problem on a global scale. This study presents an investigation of the conditions of cleaning water from heavy metal ions using chemically recycled polystyrene. To get effective ion exchangers, the sulfonation of virgin polystyrene and expanded polystyrene wastes were obtained using silica sulfuric acid. As it turned out, the use of this solid sulfonating agent simplifies the separation of the polymeric product from the acid and the solvent in comparison to conventional sulfonation methods. The ion exchange behavior of copper and zinc cations in the yielded sulfonated derivatives of polystyrene was studied. Batch shaking adsorption experiments depending on contact time, pH, temperature, and dosage of adsorbate were carried out. The stability of resin to cyclical adsorption and regeneration (column experiment) was also investigated. We report that resins have a high adsorption efficiency with total ion exchange capacity (IEC) about 2.6 meq g^?1, which drops with decreasing pH owing to competition between protons H⁺ and metal cations, whereas with the increasing resin doses the removal of cations rises for a constant initial metal concentration. The speed of cation exchange for yielded adsorbents was even better than for commercial resins. After 360 cyclical adsorption and regeneration in column, resin had working IEC of about 2.3 meq g^?1. The study shows that cation exchange resin from polystyrene wastes can be used as an efficient adsorbent for the removal of heavy metal ions from water. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

碱性离子交换树脂分离L-苹果酸的研究

考察了 7种阴离子交换树脂对L 苹果酸及杂质氯离子的吸附行为。通过静态交换实验 ,初步选择了实验所用树脂 ,同时考察了温度对吸附过程的影响并确定实验在室温下进行 ,在此基础上 ,考察了所选树脂对L 苹果酸、氯离子的动态吸附性能及选择性能 ,选择D30 1为提纯L 苹果酸的树脂 ,对模拟生产中混合料液的质量浓度的L 苹果酸溶液进行分离 ,在 pH =3 4,流速为 2mL/min左右时 ,经处理后的料液中检测不到氯离子     

Synthesis of functionalized phenolformaldehyde polymer resins by the reaction of 2,4‐dihydroxyacetophenone formaldehyde resin with various amines and their metal ion uptake properties

A series of functionalized phenolformaldehyde polymer resins have been synthesized by the reaction of 2,4‐dihydroxyacetophenone‐formaldehyde resin with the amines, such as ethanolamine, aminophenol, ethylenediamine, and propylenediamine in dichloromethane. The Schiffbase polymers were characterized by IR and ¹H‐NMR spectroscopic techniques. Thermal stabilities of the polymers were determined by TG and DTA studies. Heavy and toxic metal ions viz., Pb(II), Hg(II), Cd(II), and Cr(VI) have been removed using these polymer resins. Metal uptake efficiency, reusability, effect of pH, effect of time, and effect of initial concentration on the metal uptake were also studied. Amount of metal removed by the resin was determined using atomic absorption spectrophotometry. The retention properties were also tested under competitive conditions and were found to be depend strongly on the pH. Elution of metal ions were investigated in acid media. The uptake behaviour of the resins was approximately described by Freundlich's equation. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1501–1509, 2004     

阳离子交换树脂改性研究进展

强酸性阳离子交换树脂含有大量的强酸性基团,具有选择、交换、吸收和催化等功能,但其存在耐高温性能差、酸强度低等问题,故需要对其进行改性。改性的阳离子交换树脂广泛应用于水处理、有机合成、分离处理、环境保护及生物制药等领域。本文简要介绍了近年来强酸性阳离子交换树脂的改性方法,主要包含:金属离子改性(Al³⁺、Sn⁴⁺、Zn²⁺、Ti⁴⁺、Fe³⁺和Fe²⁺、Ce⁴⁺和Ga³⁺、Ni²⁺、Zr⁴⁺、Pd²⁺等)、磺化改性、巯基改性、胺化改性及其他类改性等方法;指出了其存在的问题,分析了改性阳离子交换树脂的未来发展方向,开发和研制具有耐高热和化学稳定性的树脂载体材料成为其研究的关键。除此之外,对树脂进行各种改性处理也是改善树脂综合性能、扩大其应用范围的重要方法。     

阴离子交换树脂对茶氨酸的吸附动力学和热力学

以酶法制备茶氨酸,研究了碱性条件下阴离子交换树脂对茶氨酸的吸附与分离. 结果表明,强碱性树脂对茶氨酸的吸附性能优于弱碱性树脂,且其吸附容量受pH值的影响较小,pH=9.0时凝胶型强碱性树脂HZ202对茶氨酸的平衡吸附量可达96.3 mg/g. 对HZ202吸附茶氨酸的吸附等温模型及动力学、热力学参数进行了分析,结果表明,茶氨酸在HZ202树脂表面为非均一分布,Spis模型可较好模拟其吸附等温线数据;热力学参数计算结果显示,不同温度下吸附过程的吉布斯自由能变DG均为负值,表明吸附为自发的放热过程;吸附过程的焓变DH=20.9~418.4 kJ/mol,可判断其为化学吸附. 茶氨酸吸附过程符合准二级动力学方程,吸附过程受化学反应控制,提高茶氨酸初始浓度可提高吸附速率.     

Metal recovery from jarosite waste – A resin screening study

Work has been carried out screening hydrometallurgical resins for application in the valorization of industrially produced jarosite. Of the seven resins tested, anion exchange resins performed poorly for valuable metal recovery. Purolite S950+ and S957, along with a strong acid resin, show good extraction properties, but are selective for Fe³⁺ over the other (divalent) metals. Purolite S930+ (iminodiacetic acid-functionalized resin) demonstrates selectivity for Cu²⁺ over Fe³⁺, but poor selectivity for Ni²⁺, Zn²⁺, and Co²⁺. Dowex M4195 (bispicolylamine-functionalized resin) demonstrates promise for extracting metals of value away from a mixed metal pregnant liquor solution (PLS). A three-stage column-based recovery process is proposed for jarosite leachate treatment.     

Ion‐exchange kinetics based on film theory

The ion‐exchange kinetics in polymer complexes was theoretically formulated. The regeneration of metal species from an ion‐exchange or chelate resin was described as a competitive reaction between metal ions and protons. We considered the ion‐exchange terms and the Langmuir terms to describe the rate of reaction, and film diffusion was also taken into account to describe the profile of the kinetics. In contrast to early methods, the surface concentrations were determined so that the rates of the chemical reactions and diffusion were self‐consistent. Although in the initial stage ion exchange was controlled by diffusion, in the last stage ion exchange was controlled by chemical reactions, particularly under excess acid. The kinetics were supported by experimental data for an iminodiacetic acid chelate resin and amidinourea resins. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39358.     

离子交换法分离DMF溶液中低浓度甲酸性能的研究

采用离子交换树脂分离DMF中低浓度甲酸溶液,筛选出D301树脂,分别考察了其在静态交换和动态交换中的分离性能。结果表明,在静态交换温度35℃,振荡速度160 r/min,树脂浓度30 g/L时,树脂平衡交换量为11.55 mg/g。高径比为2∶1的离子交换柱,在35℃、溶液流速5 mL/min条件下,对甲酸含量586 mg/L的甲酸-DMF溶液的动态交换和连续循环交换均具有很好的交换性能。     

Synthesis and characterization of some new chelating amphoteric ion-exchange resins

Some new chelating amphoteric ion exchange resins have been synthesized by condensing catechol, 8-hydroxyquinoline, hydroquinone, salicyclic acid, sulfosalicyclic acid, 3-hydroxy-2-naphthoic acid, p-hydroxybenzoic acid, β-resorcylic acid, and anthranilic acid with epichlorohydrin employing diethylenetriamine as a cross linking agent in a nonaqueous medium, toluene. These resins are characterized by their physicochemical properties such as moisture retention ability, true density, apparent density, void fraction, concentration of ionogenic groups, volume capacity, total ion exchange capacity, copper exchange capacity, rate of ion exchange, pH titration curves, apparent pK_a and pK_b values, isoionic point values, oxidative degradation, thermal stability, the effect of temperature of equilibration on the capacity of the resin, swelling behavior in various solvents, and absorption specificity towards certain bivalent metal cations in ammonium acetate–dimethylformamide media.     

Introduction of bifunctionality into the phosphinic acid ion-exchange resin for enhancing metal ion complexation

In nuclear industry the role of conventional strong cation exchange resins is limited as they function less in high acid media. The phosphorous group that has got more affinity towards actinide elements is chosen as a chelating group and the phosphinic acid ion exchange resin was synthesized. The extraction ability of the phosphinic acid resin for plutonium (Pu) from HNO₃ medium as well as from H₂SO₄ medium was studied. Though the resin shows better extraction for Pu than the strong cation exchanger resins at higher acidities, its kinetics is slow. In order to enhance the kinetics as well as to improve upon selectivity, a sulphonic group is introduced into the phosphinic acid resin. To verify the effect of bifunctionality extraction studies have been carried out with Pu from different acid media of varying concentrations. Sulphonated phosphinic acid resin shows a 2-fold increase in distribution coefficient (k_d) as well as it reached equilibrium very fast compared to the phosphinic acid resin. It is postulated that the sulphonic acid ligand provides an access mechanism for the metal ions into the polymer matrix while it is the phosphinic acid group that is responsible for selective coordination of metal ions. Thus bifunctionality is coupling of an access mechanism to a recognition mechanism. The experiments carried out demonstrated the applicability of sulphonated phosphinic acid resin in the nuclear industry.     

Polymerization of epoxide with aluminum complex/silanol catalyst. VII. Thermal and electrical properties of epoxy resin cured with the new catalyst

Curing catalyst for epoxy resins was newly found. The catalyst consists of aluminum complex and silanol. Lack of one component of the pair does not cure epoxy resins. The epoxy resins cured with the catalyst are characterized by excellent electrical properties, especially at high temperature, due to the absence of strong acid species in the cured epoxy resin matrix. Heat-resistant property of the resin was also excellent. These properties were compared with those of epoxy resin cured with commonly used BF₃ complex.     

Kinetics and Equilibrium Studies for the Removal of Cobalt,Manganese, and Silver in Ethanol using Dowex 50W-x8 Cation Exchange Resin

Organic solvents such as ethanol, find a wide range of applications in fuel, pharmaceutical industries, food industries, and paint formulations, among others. The removal of Ag(I), Co(II), and Mn(II) ions in ethanol by cation exchange resin, Dowex 50W-x8, was investigated. The adsorption characteristics of metal ions onto Dowex 50W-x8 resin were described by Langmuir isotherms. The maximum sorption exchange capacities at 298 K were obtained as 47.4 mg g^?1, 52.6 mg g^?1, and 58.5 mg g^?1 for Ag(I), Co(II), and Mn(II), respectively. The data was also fitted to Temkin and Dubinin-Radushkevich adsorption isotherm models to evaluate other adsorption properties. The ion exchange of silver, cobalt, and manganese on cation exchange resin followed pseudo-second-order kinetics, and the intraparticle diffusion was rate-determining step. The thermodynamic parameters indicated that the sorption of metal ions onto Dowex 50W-x8 resin was spontaneous (negative ΔG°) and endothermic in nature (positive ΔH°) implying that the adsorption capacity increased with increasing temperature. The resin can be regenerated by eluting metal ions with 3.0 mol L^?1 HNO₃ followed by washing it with 10 mL of Millipore water and 10 mL of 2.0 M NaOH, respectively. The proposed method was applied for metal ion removal in real ethanol samples.