Synthesis and performance characteristics of methylmethacrylate–divinylbenzene copolymer-based chelating resin for gallium metal recovery

A chelating ion exchange resin based on a methylmethacrylate and divinylbenzene copolymer has been designed through suspension polymerisation and subsequent functionalisation to hydroxamic acid as chelating group. The chelating resin has been characterized by infrared spectroscopy, its particle size, stability in acid/alkaline media, specific gravity and its use in gallium recovery. The use of resin has been demonstrated to effect gallium recovery with an efficiency of about 80%.     

Treatment of wastewater containing Pb and Fe using ion‐exchange techniques

Treatment of wastewater containing lead and iron was examined using two different ion‐exchange resins namely Duolite ES 467 (containing amino‐phosphonic functional groups) and a chelating ion‐exchange resin (containing hydroxamic acid functional groups). Initially different sorption parameters such as contact time, pH, concentrations of sorbent, sorbate and chloride ion were studied. The sorption kinetics was observed to be fast and equilibrium could be reached within 30 min. Lead sorption efficiency increased with increase in pH whereas the opposite trend was observed with iron. The presence of chloride ions greatly reduced the Pb sorption efficiency in the case of Duolite ES 467. Column studies were carried out to recover Pb and Fe individually using Duolite ES 467 resin. The maximum uptake of Pb at pH 2 and 3 was observed to be 11.63 and 33.96 g dm^?3 of resin respectively. Similarly, for Fe at pH 2 and 3 the uptake was observed to be 10.07 and 6.96 g dm^?3 of resin respectively. In the presence of chloride ions, column studies were carried out using Duolite ES 467 for iron and chelating ion‐exchange resin containing hydroxamic acid functional groups for lead sorption. Hydroxamic acid resin's loading capacity remains constant for at least up to 20 cycles. Copyright © 2005 Society of Chemical Industry     

Preferential extraction of gallium from Bayer liquor using ion exchange chelating resin containing hydroxamic acid functional group

Gallium extraction studies were carried out using resin containing an hydroxamic acid functional group. Extraction was dependant on reaction time and alkali concentration. The resin did not extract aluminium. Vanadium extraction kinetics were slower than those of gallium. The gallium and vanadium separation efficiency increased with decreasing contact time with extractions of 64% and 32% respectively after 1 min. Gallium extraction was independent of alkali concentration up to 250 g dm^?3 and thereafter decreased with increasing alkali concentration. Vanadium extraction decreased with increasing alkali concentration. Cyclic batch and column studies were carried out with synthetic as well as actual Bayer liquor to test the stability and preferential extraction of gallium using the resin. It was observed that using resin partially loaded with gallium, the co‐extraction of vanadium could be minimised. Copyright © 2003 Society of Chemical Industry     

Synthesis and characterization of poly(hydroxamic acid) chelating resin from poly(methyl acrylate)‐grafted sago starch

A new chelating ion‐exchange resin containing the hydroxamic acid functional group was synthesized from poly(methyl acrylate) (PMA)‐grafted sago starch. The PMA grafted copolymer was obtained by a free‐radical initiating process in which ceric ammonium nitrate was used as an initiator. Conversion of the ester groups of the PMA‐grafted copolymer into hydroxamic acid was carried out by treatment of an ester with hydroxylamine in an alkaline solution. The characterization of the poly(hydroxamic acid) chelating resin was performed by FTIR spectroscopy, TG, and DSC analyses. The hydroxamic acid functional group was identified by infrared spectroscopy. The chelating behavior of the prepared resin toward some metal ions was investigated using a batch technique. The binding capacities of copper, iron, chromium, and nickel were excellent and the copper capacity was maximum (3.46 mmol g⁻¹) at pH 6. The rate of exchange of the copper ion was very fast that is, t_1/2 < 5 min. It was also observed that the metal ion‐sorption capacities of the resin were pH‐dependent and its selectivity toward the metal ions used is in the following order: Cu²⁺ > Fe³⁺ > Cr³⁺ > Ni²⁺ > Co²⁺ > Zn²⁺ > Cd²⁺ > As³⁺ > Pb²⁺. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1256–1264, 2001     

大孔偕胺肟树脂的合成及其对镓的吸附性能

采用悬浮聚合法先合成出了丙烯腈(AN)-二乙烯基苯(DVB)交联骨架,制备了具有偕胺肟基团的大孔螯合树脂,表征了其结构和形貌,并用于拜耳溶液中镓的吸附. 研究了二乙烯苯含量、油相稀释剂种类及用量、第三单体、胺肟化反应条件对树脂吸附镓的性能的影响. 结果表明,螯合树脂的吸附性能随DVB含量增加先增加后降低,DVB含量为8%(w)时吸附性能最好,选用60%(w)甲苯和30%(w)航油作油相稀释剂,树脂的吸附率最大,分别为46%和52%. 添加少量(2%)第三单体甲基丙烯酸甲酯使树脂吸附率提高到57%.     

Chelation ion‐exchange study of copolymer resin derived from 8‐hydroxyquinoline 5‐sulphonic acid,oxamide, and formaldehyde

Copolymers (8‐HQ5‐SAOF) were synthesized by the condensation of 8‐hydroxyquinoline 5‐sulphonic acid (8‐HQ5‐SA) and oxamide (O) with formaldehyde (F) in the presence of acid catalyst. Four different copolymers were synthesized by using varied molar proportion of the reacting monomers. Copolymer resin composition has been determined on the basis of their elemental analysis and average molecular weights of these resins were determined by conductometric titration in nonaqueous medium. Viscometric measurement in dimethyl sulphoxide (DMSO) has been carried out with a view to ascertain the characteristic functions and constants. Electronic spectra, FTIR, and proton nuclear magnetic resonance spectra were studied to elucidate the structures. The newly synthesized copolymer proved to be a selective chelating ion‐exchange copolymer for certain metals. The chelating ion‐exchange properties of this synthesized copolymer was studied for different metal ions such as Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, and Pb²⁺. A batch equilibrium method was used in the study of the selectivity of metal ion uptake involving the measurements of the distribution of a given metal ion between the copolymer sample and a solution containing the metal ion only for representative copolymer 8‐HQ5‐SAOF‐I due to economy of space. The study was carried out over a wide pH range, shaking time, and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe³⁺, Cu²⁺, and Ni²⁺ ions than for Co²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ ions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of chelating resins with amino moieties and application on removal of copper(II) from EDTA complexes

Strong‐field ligands (amino moieties) are introduced into a hydrogel resin to obtain a chelating resin via inversion suspension polymerization. The characteristics of chelating copolymers are measured by using Fourier transform IR spectroscopy (FTIR), elemental analysis (EA), and scanning electron microscopy (SEM). After chelating copolymers adsorb cupric ions, the absorption peak of stretch N? H is shifted to higher frequency because of a coordination reaction from the FTIR spectra. Furthermore, the mechanism of metal complex adsorption on the chelating copolymer is that the strong‐field chelating ligand decomposes the bonding of the metal complexes and recoordinates the cupric ion to a chelating polymer, which is examined via FTIR, SEM with EA, and ionic chromatography analysis. The maximum adsorption capacity of cupric ions is 1.08 mmol/g and the adsorption capacity increases with the increase of the pH of the solution. The stability constant of the Cu chelating copolymer is 10^18.72, and it can have competition adsorption with EDTA in aqueous solution. These amino chelating copolymers can be used not only to recover metal ions but also to move anion pollution in wastewater. It is interesting that parts of the cupric ions adsorbed on the chelating copolymer are reduced into cupreous ions and/or copper atoms after electron spectroscopy for chemical analysis measurement. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2457–2468, 2005     

Removal and recovery of gallium and indium lons in acidic solution with chelating resin containing aminomethylphosphonic acid groups

Removal and recovery of gallium and indium ions in acidic solution with the macroreticular chelating resin containing aminomethylphosphonic acid groups was investigated. The resin (RMT-P) exhibited high affinity for gallium and indium ions in sulfuric acid solution. In the column method, gallium and indium ions in sulfuric acid solution (0.05 or 0.5 mol/dm³) were favorably adsorbed on the RMT-P when the solution containing 27.6 mg/dm³ of gallium ion or 51.4 mg/dm³ of indium ion was passed through the RMT-P column at a space velocity of 15 h^?1. The gallium and indium ions adsorbed were eluted by allowing 1 mol/dm³ sodium hydroxide or 4 mol/dm³ hydrochloric acid to pass through the column. The proposed resin appears to be useful for the recovery of gallium and indium ions in sulfuric acid solution.     

Synthesis and characterization of porous poly(methacrylic acid‐co‐triethylene glycol dimethacrylate) by seed emulsion polymerization

Porous poly(methacrylic acid‐co‐triethylene glycol dimethacrylate) (poly MAA‐co‐3G) particles in the size range of 10–40 μm were prepared via seed emulsion polymerization. Mixtures of linear polymer, solvent, and/or nonsolvent were used as inert diluents. The prepared porous polymer was converted using hydroxylamine hydrochloride and sodium methoxide into the corresponding poly(hydroxamic acid). The surface area of the porous copolymer particles was determined colorimetrically. The effect of the diluent type and concentration on the surface area of the prepared porous polymer was examined. The metal ion absorption capacity of the resin toward the different metal ions was examined using an atomic absorption spectrophotometer. The thermal stability of the polymers was examined by thermal gravimetric analysis. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1209–1215, 2000     

Synthesis and characterization of a cation‐exchange resin based on vinylpyrrolidone‐co‐divinylbenzene: Effect of nature and amount of diluent on different resin properties

Fundamental studies regarding the synthesis of a porous copolymer synthesized from 1‐vinyl‐2‐pyrrolidone and divinylbenzene in the presence of different diluents were carried out. A series of porous copolymer resins was synthesized by suspension polymerization using the following diluents: dimethylphthalate (DMT), diethylphthalate, dibutylphthalate, and bis‐2‐ethyl hexylphthalate [dioctylphthalate (DOT)]. It was observed that the porosity of resin increases with increase in length of the methylene group in the phthalate ester of DMT to DOT. In another series of experiments the amount of solvent was increased from 30 to 60% while the crosslinkage was kept constant at 30% and the diluent used was DOT. It was observed that the porosity of resins increased as the fraction of solvent increased. However, surprisingly, the Na⁺ capacity did not show any appreciable change by varying the amount or nature of diluent, remaining approximately 4 meq/g. The resin remained mechanically strong despite higher porosity. The mechanical strength also did not show any significant change by varying the diluent or amount of diluent. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3917–3920, 2004     

Analytical applications of newly synthesized copolymer resin derived from p‐aminophenol,dithiooxamide, and formaldehyde

A copolymer resin (p‐APDF) has been synthesized using the monomers p‐aminophenol, dithiooxamide, formaldehyde in 1 : 1 : 2M proportions in the presence of 2M HCl as catalyst. The structure of p‐APDF copolymer has been elucidated on the basis of elemental analysis and various physicochemical techniques, i.e., UV‐visible, FTIR, and ¹H‐NMR spectroscopy. The number average molecular weight of copolymer resin was determined by nonaqueous conductometric titration in DMF. Viscosity measurement were carried out in DMF indicate normal behavior. The prepared resin proved to be a selective ion exchange resin for some metal ions. The chelating ion exchange properties of this resin was studied for Fe(III) and Cu(II), Ni(II), Co(II), Zn(II), Cd(II), Pb(II) ions. A batch equilibrium method was used to study selectivity of metal ion uptake over a wide pH range and in media of various ionic strength. The resin showed a higher selectivity for Fe(III), Ni(II), Cu(II) ions than for Co(II), Pb(II), Zn(II), and Cd(II) ions. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

丙烯酰胺-丙烯酸-丙烯羟肟酸共聚物乳液脱除电镀废水中的重金属离子

采用反相乳液聚合法合成了丙烯酰胺(AM)-丙烯酸(AA)- 丙烯羟肟酸(AHA)共聚物乳液。考察了该共聚物配方中丙烯羟肟酸用量、共聚物乳液的投量和pH值对电镀废水中重金属离子的脱除效果。结果表明：pH=10,丙烯羟肟酸在共聚物乳液中的用量≥15%,共聚物乳液的投量为20～30 mg/L时,脱除电镀废水中重金属离子的效果最好,Cr、Cu、Ni和Zn等重金属离子的脱去率≥99.5%,处理后的水中每种重金属离子浓度≤0.2 mg/L。     

Studies on poly(styrene‐co‐maleic anhydride)‐modified polyesteramide‐based anticorrosive coatings synthesized from a sustainable resource

Polyesteramide (PEA) coating resin, synthesized from linseed oil, a sustainable resource, was found to show improved physicomechanical and acid‐resistance properties. To further improve these properties in terms of alkali resistance, scratch hardness, and thermal stability and to reduce the baking temperature, we have attempted to incorporate styrene into the polymer backbone through its copolymer with maleic anhydride. The structural elucidation of modified PEA resin (SCPEA) was carried out by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopes. The physicomechanical and chemical‐resistance properties were investigated by standard methods and thermal stability was investigated by thermogravimetric analysis method. A comparative study of these properties of PEA and SCPEA was carried out. It was observed that the SCPEA showed better properties than the reported one. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2538–2544, 2004     

Preparation of Chelating Resins Containing a Pair of Neighboring Carboxylic Acid Groups and the Adsorption Characteristics for Heavy Metal Ions

Abstract

For the functional enhancement of chelating resins containing carboxylic acids, copolymer beads were prepared by suspension polymerization of styrene (St), methyl methacrylate (MMA), and divinylbenzene (DVB) in the presence of toluene as diluent. The phenyl rings of the beads were directly chloromethylated, and the carboxylic ester groups of the beads were converted into hydroxymethyl groups by reduction followed by chlorination to give chloromethyl groups, respectively. The chelating resins containing a pair of neighboring carboxylic acid groups (NCAGs) were obtained by the alkylation of chloromethyl groups in copolymer beads with diethyl malonate in the presence of sodium hydride followed by hydrolysis using aqueous alkali solution. Accordingly, the structural effects of the resins on the adsorption of heavy metal ions were investigated. Poly(St‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, and Cu²⁺, whereas poly(MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Cu²⁺, Cd²⁺, and Co²⁺. On the other hand, poly(St‐co‐MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, Co²⁺, and Cu²⁺: a synergistic effect on the adsorption of heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, and Co²⁺ was observed. The adsorption ability of poly(St‐co‐MMA‐co‐DVB)‐based chelating resin among three kinds of chelating resins was relatively good.     

ACID/BASE AND METAL UPTAKE PROPERTIES OF CHELATING AND WEAK BASE RESINS

Purolite's weakly basic experimental resins with diethanolamine, morpholine, 2-vinylpyridine, mono-and bispicolylamine functionalities were evaluated with respect to their hydrogen, Zn, Ni, Cu and Cd uptake, and compared with Purolite's commercial chelating iminodiacetate, aminophosphonate and hydroxamic acid resins. Special attention was paid to the resin performances in acidic solutions. In general, diethanolamine, morpholine and 2-vinylpyridine resins took up these metals poorly. Only cadmium was retained in acidic solutions, probably as negatively charged chloride complexes. The chelating resins, with their weakly acidic groups, did not function in acidic solutions but worked well at pH 4 and above. The only resin that efficiently removed metals from acidic solutions was the bispicolylamine resin. Metal uptake values on this resin did not change appreciably in the pH range between 1 and 6. Maximum uptake values ranged between 0.6 and 1.7 mmol/g, being highest for copper and lowest for nickel. Acid/base properties of the weakly basic resins did not correlate with their capability to take up metals from solution: the results obtained did not support the initial assumption that the weaker the resins are the better they take up metals in acidic solutions.     

Resin I: Synthesis,characterization, and ion‐exchange properties of terpolymer resins derived from 2,4‐dihydroxypropiophenone,biuret, and formaldehyde

Terpolymers (2,4‐DHPBF) were synthesized by the condensation of 2,4‐dihydro‐xypropiophenone, biuret, and formaldehyde in the presence of acid catalyst with varying the molar ratio of reacting monomers. Terpolymer composition has been determined on the basis of their elemental analysis and their number–average molecular weight of these resin were determined by conductometric titration in nonaqueous medium. The viscosity measurements were carried out in N,N‐dimethyl formamide which indicate normal behavior. IR spectra were studied to elucidate the structure. The terpolymer resin has been further characterized by UV–visible and ¹H‐NMR spectra. The newly synthesized terpolymers proved to be selective chelating ion‐exchange terpolymers for certain metals. The chelating ion‐exchange properties of this terpolymer was studied for Fe (III), Cu (II), Hg (II), Cd (II), Co (II), Zn (II), Ni (II), and Pb (II) ions. A batch equilibrium method was employed in the study of the selectivity of metal ion uptake involving the measurement of the distribution of a given metal ion between the terpolymer sample and a solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The terpolymer showed a higher selectivity for Fe (III), Hg (II), Cd (II), and Pb (II) ions than for Cu (II), Co (II), Zn (II), and Ni (II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Resin. III. Synthesis,characterization, and ion-exchange properties of a 2,2′-dihydroxybiphenyl–formaldehyde copolymer resin

A 2,2′-dihydroxybiphenyl–formaldehyde copolymer, synthesized by the condensation of 2,2′-dihydroxybiphenyl with CH₂O in the presence of an acid catalyst, proved to be a selective chelating ion-exchange copolymer for certain metals. The chelating ion-exchange properties of this copolymer were studied for Fe(III), Cu(II), Ni(II), Zn(II), Cd(II), and Pb(II) ions. A batch equilibrium method was employed in the study of the selectivity of metal ion uptake, involving the measurements of the distribution of a given metal ion between the copolymer sample and the solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe(III), Cu(II), and Ni(II) ions than for Co(II), Zn(II), Cd(II), and Pb(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chelation ion‐exchange properties of copolymer resin derived from 4‐hydroxyacetophenone,oxamide, and formaldehyde

A copolymer (4‐HAOF) prepared by condensation of 4‐hydroxyacetophenone and oxamide with formaldehyde in the presence of an acid catalyst proved to be a selective chelating ion‐exchange copolymer for certain metals. Chelating ion‐exchange properties of this copolymer were studied for Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Hg²⁺ ions. A batch equilibrium method was employed in the study of the selectivity of metal‐ion uptake involving the measurements of the distribution of a given metal ion between the copolymer sample and a solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe³⁺ ions than for Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Ni²⁺, and Hg²⁺ ions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 787–790, 2003     

Synthesis of porous poly(hydroxamic acid) from poly(ethyl acrylate-co-divinylbenzene)

Summary Porous poly(hydroxamic acid) resins were prepared by suspension polymerization of poly(ethyl acrylate-co-divinylbenzene) followed by the reaction with hydroxylamine via nucleophilic substitution. Various degree of dilution and crosslinking ratio were applied to obtain suitable material for use as a chelating polymer. The effects of degree of dilution and crosslinking ratio on the surface morphology, hydroxamic acid group content, and apparent density were investigated in detail.     

Water‐based crosslinkable coatings via miniemulsion polymerization of acrylic monomers in the presence of unsaturated polyester resin

Hybrid miniemulsion polymerization was performed with a three‐component acrylic system of methyl methacrylate, butyl acrylate, and acrylic acid in the presence of a Bayer® Roskydal TPLS2190 unsaturated polyester resin. Latexes were obtained in which the polyester resin was grafted to the acrylic polymer, forming a water‐based crosslinkable coating. Grafting between the resinous component and the acrylic polymer is a feature different from the work of others who have attempted to combine the properties of both systems in water‐based blends. Both emulsions and latexes were shelf‐stable for over 6 months, shear‐stable, and resistant to at least one freeze/thaw cycle. Resin‐to‐monomer ratios were studied as high as 1 : 1 (wt : wt), and total emulsion solids, as high as 45%. Monomer droplet and latex particle sizes were similar, suggesting evidence of the preponderance of droplet nucleation. A high level of crosslinking (>70%) during polymerization was observed in this particular hybrid system in contrast to those involving alkyd or polyurethane resins (<5%). Films, both homogeneous and hard, were achieved with exceptional adhesion. Electron microscopy showed the hybrid particle morphology to have internal domains of polyester resin in an acrylic matrix. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 916–927, 2000