Chelating resins VI: Chelating resins of formaldehyde condensed phenolic Schiff bases derived from 4,4′‐diaminodiphenyl ether with hydroxybenzaldehydes—synthesis,characterization, and metal ion adsorption studies

Phenolic Schiff bases derived from o‐, m‐, and p‐hydroxybenzaldehydes and 4, 4′‐diaminodiphenyl ether were subjected to polycondensation reaction with formaldehyde. The resins were found to form polychelates readily with several metal ions. The materials were characterized by elemental analysis, GPC, IR, UV‐Vis, ¹H‐NMR, XRD, and thermal analyses like TG, DTG, and DSC studies. The ¹H‐NMR spectra of the resins provided evidence of polycondensation with well‐defined peaks for bridging methylene and terminal methylol functions. The metal‐ligand bonds were registered in the IR spectra of the polychelates. The thermal analysis data provided the kinetic parameters like activation energy, frequency factor, and entropy changes associated with the thermal decomposition. These data indicated the resins to be more stable than the polychelates. The DSC and XRD data indicated that the incorporation of metal ions significantly enhanced the crystallinity of the polymers. The resins could adsorb several metal ions from dilute aqueous solutions. Adsorption characteristics of the resins towards Cu(II) and Ni(II) were studied spectrophotometrically both in competitive and noncompetitive conditions. The effects of pH, contact time, quantity of the sorbent, concentration of the metal ions in a suitable buffer medium were studied. The resins were found to be selective for Cu(II) leading to its separation from a mixture of Cu(II) and Ni(II). © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 967–981, 2000     

Synthesis of resin IV: Salicylic acid,diaminonaphthalein, and formaldehyde terpolymer and its ion exchange

This article reports the synthesis, characterization, and ion exchange properties of a terpolymer. The terpolymer resin salicylic acid‐diaminonaphthalein‐formaldehyde (SDNF) was synthesized by the condensation of salicylic acid and diaminonaphthalein with formaldehyde in the presence of a hydrochloric acid catalyst. Terpolymer resin was characterized by elemental analysis, infrared (IR) spectroscopy, nuclear magnetic resonance spectroscopy, and UV–Visible spectral studies. The number average molecular weight of the resin was determined by nonaqueous conductometric titration. Chelation ion exchange properties have also been studied for Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺ ions employing a batch equilibrium method. It was employed to study the selectivity of metal ion uptake involving the measurements of distribution of a given metal ion between the polymer sample and a solution containing the metal ion. The study was carried out over wide pH range and in a media of various ionic strengths. The terpolymer showed 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     

Adsorption behavior and separation of vanadium(V), molybdenum(VI), and rhenium(VII) ions on crosslinked polymers containing acrylic acid derivative moieties

The radical polymerization of [2‐(acryloyloxy)ethyl]trimethylammonium methyl sulfate and [3‐(methacryloylamino)propyl]trimethylammonium chloride by using ammonium peroxydisulfate as initiator and N,N′‐methylene‐bis‐acrylamide as crosslinker agent at 70°C for 17 h was carried out. The crosslinker agent in the feed ranged between 2 and 6 mol %. The resins were completely insoluble in water and characterized by elemental analysis and FTIR spectroscopy. The metal ion binding capacity of these resins with V(V), Mo(VI), and Re(VII) were investigated using the batch equilibrium type. The pH, but not the crosslinking percentage in the feed, influenced the retention capacity of the resin, particularly for V(V) and Re(VII). Thus, at pH 1 only < 15% of V(V) was retained, but at pH 3 higher than 97% of V(V) was adsorbed. The resin–ion equilibrium was achieved between 15 min and 2 h depending on the resin, ion, and crosslinking degree. According to the pH, it is possible separate Re(VII) and Mo(VI) from V(V) at pH 1.0. To reuse the resins, the ions were stripped by using HCl, H₂SO₄, and Na₂CO₃ at different concentrations. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 369–376, 1999     

Sorption of Cr(III)‐containing cations on strongly basic anion exchangers

It is shown that strongly basic anion exchangers AV‐17 and Varion‐AD in definite conditions are able to retain Cr(III)‐containing ions from Cr(III) sulfate solution. It is found that the sorption of Cr(III)‐containing ions on the polymers is essentially dependent on the pH, temperature, and Cr(III) sulfate concentration. The maximum temperature dependence of sorption was found to be about 60°C. The sorption isotherms are well described by Langmuir's equations. The sorption kinetics is determined by the diffusion of Cr(III)‐containing ions into polymer's phase. It is assumed that the Cr(III)‐containing ions are retained through formation, in polymer's phase, of the jarosite‐type mineral compounds: R₄N[Cr₃(OH)₆(SO₄)₂], H₃O[Cr₃(OH)₆(SO₄)₂], and K[Cr₃(OH)₆(SO₄)₂]. For comparison of sorptional capacities, the sorption of Cr(III)‐containing ions was determined on different cation and anion exchangers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3978–3985, 2006     

Sorption of Zn(II) and Pb(II) ions in the presence of the biodegradable complexing agent of a new generation

The macroporous chelating ion exchangers containing different functional groups i.e. Purolite S-920, Purolite S-930 and Lewatit TP-208 have been used in the sorption process of Zn(II) and Pb(II) ions. The effect of the presence of biodegradable, environmentally friendly aminopolycarboxylate chelating agent, trisodium salt of methylglycinediacetic acid (MGDA) on its sorption capacity was also examined. The investigations were carried out by the static method. Besides the effect of initial concentration of Zn(II) and Pb(II) and the complexing agent the research concerns the influence of solution pH, phase contact time on effectiveness of sorption. The equilibrium and kinetics of Zn(II)–MGDA and Pb(II)–MGDA complexes sorption were obtained and fitted using the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D–R) models as well as the pseudo first and pseudo second order kinetic models. The intraparticle diffusion model was also used. The results showed that the sorption processes of Zn(II) and Pb(II) complexes with MGDA on Purolite S-920, Purolite S-930 and Lewatit TP-208 followed well the pseudo second order kinetics.     

Thermal,catalytic, antimicrobial,and chelating aspects of phenolic resin and its polychelates with f‐block elements

The polymeric ligand (resin) was synthesized by condensation of 2‐hydroxy‐4‐ethoxybenzophenone with ethane diol in the presence of polyphosphoric acid as a catalyst at 145°C for 10 h. The synthesized resin was used to study its ion exchange efficiency and to synthesize its polychelates with 4f‐block elements. The resin and its polychelates were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR, NMR, and thermogravimetric analyses. The molecular weight was determined using number–average molecular weight (M_n ) by a vapor pressure osmometry (VPO) method. Ion‐exchange studies at various concentrations of different electrolytes, pH, and rate have been carried out for f‐block elements. Antimicrobial activity of all polychelates and catalytic activity of selected polychelates in organic synthesis have been studied. It is observed that resin can be used as an ion‐exchanger and polychelates are found to be an efficient catalysts and antimicrobial agents. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies on poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) and its metal complexes

8‐Hydroxy‐4‐azoquinolinephenylmethacrylate (8H4AQPMA) was prepared and polymerized in ethyl methyl ketone (EMK) at 65°C using benzoyl peroxide as free radical initiator. Poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) poly(8H4AQPMA) was characterized by infrared and nuclear magnetic resonance techniques. The molecular weight of the polymer was determined by gel permeation chromatography. Cu(II) and Ni(II) complexes of poly(8H4AQPMA) were prepared. Elemental analysis of polychelates suggests that the metal‐ligand ratio is about 1 : 2. The polychelates were further characterized by infrared spectra, X‐ray diffraction, spectral studies, and magnetic moments. Thermal analyses of the polymer and polychelates were carried out in air. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1516–1522, 2006     

Synthesis,characterization, and metal ion uptake studies of chelating resins derived from formaldehyde/furfuraldehyde condensed phenolic schiff base of 4,4′‐diaminodiphenylmethane and o‐hydroxyacetophenone

The synthesis, characterization, and metal ion uptake studies of two chelating resins with multiple functional groups are reported. The chelating resins were synthesized by condensing a phenolic Schiff base derived from 4,4′‐diaminodiphenylmethane and o‐hydroxyacetophenone with formaldehyde or furfuraldehyde. The resins readily absorbed transition metal ions, such as Cu²⁺ and Ni²⁺, from dilute aqueous solutions. The Schiff base, resins, and metal polychelates were characterized by various instrumental techniques, such as elemental‐analysis, ultraviolet–visible spectroscopy proton and carbon‐13 nuclear magnetic resonance spectroscopy (¹H‐NMR and ¹³C‐NMR, respectively), X‐ray diffraction (XRD), and thermogravimetric–differential thermogravimetric analyses (TG–DTG). The ¹H‐NMR and ¹³C‐NMR studies were used to determine the sites for aldehyde condensation with the phenolic moiety. Fourier transform infrared data provided evidence for metal–ligand bonding. Thermogravimetric analysis was employed to compare the relative thermal stabilities of the resins and the polychelates. The TG data were fitted into different models and subjected to computational analysis to calculate the kinetic parameters. The XRD data indicate that the incorporation of metal ion into the resin matrix significantly enhanced the degree of crystallinity of the material. The extent of metal‐ion loading into the resins was studied in competitive and noncompetitive conditions, varying the time of contact, metal ion concentrations, and pH of the reaction medium in a suitable buffer medium. The furfuraldehyde‐condensed resin was more effective in removing metal ions than the formaldehyde‐condensed resins. The resins were selective for Cu²⁺, resulting in separation of Cu²⁺ and Ni²⁺ from the mixture at pH 5.89. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 570–581, 2003     

Preparation and adsorption properties of the chelating resins containing carboxylic,sulfonic, and imidazole groups

The crosslinked poly(1‐vinylimidazole‐co‐acrylic acid), P(VIm‐co‐AA), and poly(1‐vinylimidazole‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) P(VIm‐co‐APSA) were synthesized by radical polymerization and tested as adsorbents under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch equilibrium procedure. The resin–metal ion equilibrium was achieved before 1 h. The resin P(VIm‐co‐AA) showed a maximum retention capacity (MRC) value for Pb(II) at pH 3 and Hg(II) at pH 1 of 1.1 and 1.2 mEq/g, respectively, and the resin P(VIm‐co‐AA) showed at pH 3 the following MRC values: Hg(II) (1.5 mEq/g), Cd(II) (1.9 mEq/g), Zn(II) (2.7 mEq/g), and Cr(III) (2.8 mEq/g). The recovery of the resin was investigated at 25°C with 1 M and 4 M HNO₃ and 1 M and 4 M HClO₄. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2852–2856, 2003     

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     

Mn-SOD的纯化方法研究

以嗜热芽孢杆菌B．S110—2所产Mn—SOD为研究对象,对其纯化方法进行了研究,用碱处理的方法替代了传统的硫酸铵分级沉淀蛋白的方法;通过对金属螯合层析中二价金属离子的选择及洗脱液pH的选择,初步建立了一套适合分离纯化Mn-SOD的金属螯合层析体系,为实际生物产品的分离奠定了基础。     

Synthesis,characterization, and chelating properties of the polymacromonomer: Poly[(ethyleneglycol) methyl ether methacrylate]

The radical polymerization of the macromonomer poly(ethyleneglycol) methyl ether methacrylate with ammonium persulfate at 60°C was carried out. The polymer was completely soluble in water. Yield was 75%. The polymacromonomer was characterized by Fourier transform infrared, proton nuclear magnetic resonance (NMR), and ¹³C NMR spectroscopy. M_n, M_w, and the polydispersity were determined by gel permeation chromatography. The polymacromonomer showed a high thermal stability with a TDT_50% of 420°C. The metal ion binding capacity of this polychelatogen with respect to different metal ions was investigated through the liquid‐phase polymer‐based retention (LPR) technique. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2929–2934, 2002     

Preparation and Characterization of Poly(bisphenol A oxalate) and Studying its Chelating Behavior Towards Some Metal Ions

Abstract

Poly(bisphenol A oxalate) was synthesized by condensation polymerization of Bisphenol A and oxalyl chloride in dichloromethane under dry nitrogen atmosphere below 5°C. The resulting linear alternating polymer was characterized by inherent viscosity, FTIR, ¹H‐NMR, and ¹³C‐NMR. The thermal behavior of the polymer was evaluated by differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The chelating behavior of the synthesized polymer towards some divalent metal ions was studied by the batch equilibrium technique as a function of pH and contact time. The isothermal behavior and kinetics of the metal ions uptake onto the polymer were also investigated. The polymer showed high rates of metal ion uptake toward Pb(II), Cu(II), and Mg(II), but low rates toward Ni(II) and Cd(II) in the measurement of metal uptake. Interestingly, the polymer was found to selectively chelate Pb(II) and Mg(II) ions in the concentration variation isotherm experiments.     

Preparation,characterization, and adsorption properties of cellulose acetate‐polyaniline membranes

Four lots of cellulose acetate (CA) membranes, modified with polyacrylic acid, using various plasticizers, and coated with polyaniline (PANI) were prepared. The morphology of the membranes was evaluated by using scanning electron microscopy, and the membranes showed larger pore size when the plasticizers were used. The electrical conductivity of the modified membranes and coated with PANI increased by two orders of magnitude when the plasticizer triphenyl phosphate was used. The strain at break improved by an order of magnitude and the glass transition temperature (T_g) showed an average decrease of 36°C when the membranes were plasticized. Finally, these membranes were tested as ion‐exchange materials of a gold‐iodide complex. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Sorption equilibria and diffusion of toluene,methanol, and cyclohexane in/through elastomers

Molecular transport of toluene, methanol, and cyclohexane and their mixtures in Chemraz 505 elastomer has been investigated using gravimetric techniques for short and long time exposure in these solvents. The sorption–desorption results have been used to calculate the diffusion coefficients by solving Fick's equation under appropriate boundary conditions. The dependence of sorption, desorption, diffusion, and permeation on temperature and composition changes was also studied. The results are discussed in terms of possible interactions between Chemraz 505 polymer and the solvent molecules. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43449.     

Acrylic three‐dimensional networks. II. Behavior of different acrylic ion exchangers in the retention and elution processes of some metal cations

The retention process of the Cu(II) and Ni(II) cations from CuSO₄ and NiSO₄ aqueous solutions by eight acrylic ion exchangers was studied. Also, the elution process of these cations with 0.5 mol · L⁻¹ HCl solution was analyzed. The quantitative retention and elution as well as the development aspects of the two processes were observed by the column method. Seven ion exchangers contained weak base, weak acid, and amphoteric functional groups, these being known as chelating agents. Also, an ion exchanger with carboxylic groups, as a model, was taken in this study. The experiments show that the ion exchangers can be divided in three types as follows: (a) bad chelating agents; (b) chelating ion exchangers with the limited efficiency; (c) ion exchangers with good chelating properties and a high application efficiency; especially, the ion exchanger with hydroxamic functional groups is considered in this class. Also, the experimental data prove that, both for Cu(II) and Ni(II) cations, the volume of the purified effluent is higher than the HCl volume needs for their complete elution. This fact means concentration of the metal cations in the liquid phase. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1387–1394, 1999     

硫代酰胺基螯合纤维的合成及其吸附性能研究

以腈纶为起始原料,分别经水合肼、乙二胺、二乙烯三胺预交联后,以N,N-二甲基甲酰胺作溶剂与硫化钠反应,合成了三种携硫代酰胺功能基可达6.8mmol/g(干纤维)的螯合功能纤维。探讨了溶剂、反应温度、反应时间、pH等对反应产物的影响,利用红外光谱、元素分析、热稳定分析、重量分析等对该螯合纤维的结构、性能等进行了表征,并就其对金属离子的吸附性能进行了研究。结果表明:螯合纤维对Au3+、Ag+、Pd2+等贵金属离子具有良好的吸附性,对Ag+的吸附容量可达1510mg/g(干纤维),对Au3+、Pd2+的吸附容量分别为800mg/g(干纤维)和21.2mg/g(干纤维)。     

Acrylic Homo- and Co-polymers Based on 2, 4-dichlorophenyl Methacrylate and 8-quinolinyl Methacrylate

The monomer 2, 4-dichlorophenyl methacrylate (2,4-DMA) was synthesized from 2, 4-dichlorophenol and characterized by conventional methods. The homopolymers of 2,4-dichlorophenyl methacrylate and its copolymers with 8-quinolinyl methacrylate (8-QMA) in different feed ratio were prepared by free radical polymerization using dimethyl formamide (DMF) as a solvent and 2,2-azobis iso butyronitrile (AIBN) as an initiator. The resulting polymers were characterized by using IR spectroscopy. Reactivity ratios of monomer were evaluated using UV-spectroscopy. Average molecular weights and polydispersity were determined by gel permeation chromatography (GPC). Solution viscosity was also obtained. The thermal analysis was carried out using TGA and DSC. The homo- and co-polymers were also tested for their antimicrobial properties against selected microorganism. The metal ion uptake capacity of synthesized copolymers was estimated by batch equilibration method using different metal ion solution under different experimental conditions. It is observed that due to the presence of pendant ester bound quinoline group, the copolymers are capable of adsorbing cations from their aqueous solution.     

Studies of poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) and its metal complexes

Poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) resin (8H4AQPF) was prepared by condensing 8‐hydroxy 4‐azoquinoline phenol with formaldehyde (1 : 1 mol ratio) in the presence of oxalic acid. Polychelates were obtained when the DMF solution of poly(8H4AQPF) containing a few drops of ammonia was treated with the aqueous solution of Cu(II) and Ni(II) ions. The polymeric resin and polymer–metal complexes were characterized with elemental analysis and spectral studies. The elemental analysis of the polymer–metal complexes suggested that the metal‐to‐ligand ratio was 1 : 2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polymer–metal complexes of the Cu(II) complexes were square planar and those of the Ni(II) complexes were octahedral. X‐ray diffraction studies revealed that the polymer metal complexes were crystalline. The thermal properties of the polymer and polymer–metal complexes were also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1506–1510, 2006     

Synthesis,characterization, and properties of a polyhedral oligomeric octadiphenylsulfonylsilsesquioxane

A novel polyhedral oligomeric octadiphenylsulfonylsilsesquioxane (ODPSS) was synthesized from octaphenylsilsesquioxane and benzenesulfonyl chloride via a Friedel–Crafts reaction with a high yield. ODPSS was identified by Fourier transform infrared spectroscopy, ¹H‐NMR, ¹³C‐NMR, ²⁹Si‐NMR, matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry (MALDI–TOF MS), wide‐angle X‐ray diffraction, and elemental analysis to be a kind of polyhedral oligomeric silsesquioxane of a T₈R₈ structure. ODPSS exhibited superior thermal stability according to thermogravimetric analysis. Its initial thermal decomposition temperature (T_onset) was at 491°C in air and 515°C in nitrogen. Thermal and mechanical properties of epoxy resin (EP) composites with ODPSS added were studied by differential scanning calorimetry and tensile testing. The results show that the incorporation of ODPSS at a low loading content not only improved the glass‐transition temperature of the EP composites but also enhanced their tensile strength. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40892.