Liquid-phase Polymer-based Retention Research Articles

Arsenite retention properties of water‐soluble metal–polymers

AbstractThe properties of water‐soluble metal–polymers to retain As(III) from aqueous solution are investigated. Poly(acrylic acid)s with different tin contents are prepared. Amounts of 3, 5, 10, and 20 wt % of tin are added to the polymer. The metal compositions are evaluated by thermogravimetry (TG‐DSC) and atomic absorption spectroscopy. Structural properties are analyzed by infrared and 1H nuclear magnetic resonance spectroscopy, and X‐ray diffraction. Additionally, specific surface area was measured using CO2 as adsorbate. Arsenic retention properties are studied using the liquid‐phase polymer‐based retention (LPR) technique. The polymers can bind arsenic species from an aqueous solution in the pH range 4–8. The studies show that the retention capacity is a function of tin content and polymer concentration. At pH 8, the following mol ratios poly(AA)‐Sn : As(III) are analyzed: 600 : 1, 400 : 1, 200 : 1, 100 : 1, and 20 : 1. The highest retention, 80%, is obtained with poly(AA)‐Sn at 10 and 20 wt % of tin at mole ratios 400 : 1, and at nearly to 20 : 1 or 40 : 1 Sn‐As(III). The highest retention is observed at pH 8 and 4. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Metal ion interaction of water‐soluble copolymers containing carboxylic acid groups in aqueous phase by membrane filtration technique

AbstractThis article reports the synthesis of poly(N‐maleoylglycine‐co‐itaconic acid) by radical copolymerization under different feed mole ratios and its properties to remove various metal ions, such as Cu(II), Cr(III), Co(II), Zn(II), Ni(II), Pb(II), Cd(II), and Fe(III), in aqueous phase with the liquid‐phase polymer‐based retention(LPR) technique. The interactions of inorganic ions with the hydrophilic water‐soluble polymer were determined as a function of pH and filtration factor. Metal ion retention was found to strongly depend on the pH. Metal ion retention increased as pH and MG content units in the macromolecular backbone increased. The copolymers were characterized by elemental analysis, FTIR, 1H‐NMR, and 13C‐NMR spectroscopy. Additionally, intrinsic viscosity, molecular weight, and polydispersity have been determined for the copolymers. Copolymer and polymer–metal complex thermal behavior was studied using differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques under nitrogen atmosphere. The thermal decomposition temperatures (TDT) were influenced by the copolymer composition. The copolymers present lower TDT than the polymer–metal complex with the same copolymer composition. All copolymers present a single Tg, indicating the formation of random copolymers. A slight deviation of the Tg for the copolymers and its complexes can be observed. The copolymer Tg is higher than the Tg value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

A novel polycondensate containing cyclodextrin and lactose: Synthesis, metal-complexing properties, and degradation

The synthesis and characterization of the novel water-soluble polycondensate from β-cyclodextrin triazine and d-lactose are described, which represents the first copolymer containing cyclodextrin and lactose in the main-chain. In addition, the metal complex forming properties of the novel polymer for different metal ions such as Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) were studied using the liquid-phase polymer-based retention (LPR) method and compared with those of β-cyclodextrin. According to the retention profiles obtained by the LPR method, all 10 metal ions investigated showed a strong interaction with this polymer. Finally, this polycondensate was shown to be microbiologically degradable with exponential microbial growth of 45 CFU (10 8 mL −1) by using conventional microbiological methods.

Synthesis and properties of hydrophilic polymers, part 11: Synthesis, biodegradability, and metal complexation of copolymers of ethylenediaminetetraacetic acid dianhydride and lactose

AbstractThe synthesis and characterization of poly(ethylenediaminetetraacetic acid‐co‐lactose) of high molar mass (132 kg mol−1) is described. The polycondensate with pendant carboxylic groups was shown to be hydrolytically and microbiologically degradable by using conventional microbiological methods. The metal complexing properties of the polyester were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) ions in aqueous solution using the liquid‐phase polymer‐based retention (LPR) method. In addition, the complexing capacity of the Cu(II)‐saturated copolymer was determined by TGA to be 182 mg g−1 polymer. According to the retention profiles determined as a function of filtration factor by using LPR in conjunction with inductively coupled plasma spectrometry, Cr(III) and Fe(III) showed a strong interaction with this polymer under these conditions, indicated by retention values of 100% at pH 5. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2932–2939, 2007

Water‐soluble polymer materials as complexing reagents for the separation of metal ions using membrane filtration

AbstractThe commercial, water‐soluble poly(sodium anetole sulfonate) (PAnS), poly(sodium vinylsulfonate) (PVS), and poly(sodium 4‐styrene sulfonate) (PStyS) were investigated as metal ion binding reagents using the liquid‐phase‐polymer‐based retention (LPR) technique. The retention profiles of the following metal ions: Co(II), Ni(II), Ca(II), Mg(II), Pb(II), Cd(II), Zn(II), Cr(III), and Cu(II) were obtained by the LPR technique at pH 3, 5, and 7, and by changing the filtration factor Z from 0 to 10. As the pH increased, the affinity towards the metal ions increased slightly. By increasing the filtration factor Z, the affinity for the metal ions did not decrease significantly. This means that the ligand–metal interaction was strong, and it is not possible to break it by washing with water at the same pH of the filtration cell. Copyright © 2006 John Wiley & Sons, Ltd.

Poly(2-acrylamido glycolic acid): A water-soluble polymer with ability to interact with metal ions in homogenous phase

A water-soluble polymer, poly(2-acrylamido glycolic acid) was obtained by radical polymerization and characterized by FT-IR, 1H NMR, and 13C NMR spectroscopy. The metal ion retention properties were investigated through the liquid-phase polymer based retention (LPR) technique at different pHs and filtration factor Z. The affinity of the ligand groups for the metal ions depends strongly on the pH. At lower pH, the retention is lower than 50%, which increased as the pH increased. At pH 5, the polymer showed a high affinity and selectivity for Pb(II), and at pH 7 the P(AGA) formed stable complexes with Cu(II), Co(II), Ni(II), Cd(II), and Pb(II). Of the three potential ligand groups, amide, hydroxyl, and carboxylate groups, the carboxylate groups form the more stable complexes with the metal ions.

Retention properties of arsenate anions of water‐soluble polymers by a liquid‐phase polymer‐based retention technique

AbstractThe retention properties of arsenic ions from an aqueous solution by water‐soluble cationic polymers and cationic–anionic copolymers were investigated. Poly[(3‐methacryloylamine)propyl]trimethylammonium chloride [P(ClMPTA)] and poly[(3‐methacryloylamine)propyl]trimethylammonium chloride–co–acrylic acid [P(ClMPTA‐co‐AA] were synthesized by radical polymerization. The copolymers were prepared with feed mole ratios of ClMPTA to AA of 1 : 1, 1 : 2, and 2 : 1. The copolymer compositions were evaluated by FTIR spectroscopy, TG‐DSC, and elemental analysis. The liquid‐phase polymer‐based retention (LPR) technique was used. This technique consists of retention of arsenate anions by the quaternary ammonium salt of a water‐soluble polymer in a filtration membrane cell. It was shown that the polymers could bind H2AsO species from an aqueous solution more selectively at pHs of 6 and 8, than at a pH of 4. An increase in the polymer concentration was associated with increased retention capacity but not linearly. At the highest concentration the influence of pH was better observed. Investigation of copolymers showed the concerted action of polycations and polyanions on the ability to retain arsenic. At the lowest pH, the role of ionic strength of the media had a remarkable effect on the retention ability, independently of copolymer composition. At a pH of 6 a copolymer polycation/polyanion composition of 2 : 1 had the highest selective effect. At a pH of 8, a nonequimolar copolymer composition showed the same efficiency for the retention of arsenate species. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2677–2684, 2006

ERROR SIMULATION IN THE DETERMINATION OF THE FORMATION CONSTANTS OF POLYMER-METAL COMPLEXES (PMC) BY THE LIQUID-PHASE POLYMER-BASED RETENTION (LPR) TECHNIQUE

The Liquid-phase polymer-based retention (LPR) technique allows calculating the formation constant of polymer-metal ion complexes (Kf). The dependence of the relative error in Kf (eK) on the error in the total retention coefficient a (ea) has been searched and it was found that its influence is higher as a increases, so that its measurement must be performed with higher precision. In addition, ea is higher for high a values due to the stronger influence of errors in the measurements of the different magnitudes that allow its calculation. In order to achieve a measurement of Kf with a relative error lower than 7 %, the experimental a found should not exceed the value 0.4 when relative errors for the independent variables ranging between 2 % and 5 % are considered

Interactions of polyelectrolytes bearing carboxylate and/or sulfonate groups with Cu(II) and Ni(II)

The interactions between the water-soluble polyelectrolytes poly(acrylic acid) (PAA) and poly(vinyl sulfonic acid) (PVS), and Cu(II) and Ni(II) are studied by the liquid-phase polymer-based retention (LPR) technique. Assuming a Ni(II)–PVS interaction of electrostatic nature, the nature of the Ni(II)–PAA interaction is found to be electrostatic, while Cu(II)–PAA interactions imply the formation of coordinative bonds. The charge related formation constants for the systems Ni(II)–PAA, Ni(II)–PVS, and Cu(II)–PVS are found to be 57.57×10 2, 43.4×10 2, and 60.5×102 M −1, respectively in a 0.010 M NaNO 3 aqueous solution at pH 5, and 1.4×10 2 for both systems containing Ni(II) and 1.3×10 2 M −1 for the system Cu(II)–PVS in a 0.10 M NaNO 3 aqueous solution at pH 5.

Removal of metal ions by water-soluble polymacromonomers in conjunction with ultrafiltration membrane

The macromonomer polyethylene glycol methylether methacrylate was homo- and copolymerized with 2-acrylamido-2-methyl-1-propane sulfonic acid under three feed monomer ratios. The initiator used was ammonium peroxydisulfate (0.2 mol %). All the polymers were completely soluble in water. The copolymer composition was determined by elemental analysis. The metal ion interaction capability of the three polymers was investigated through the liquid-phase polymer-based retention (LPR) technique at different values of pH and filtration factor Z. The highest metal ion retention ability was observed at pH 5.0. The homopolymer showed a high selectivity for Ni(II) ions at pH 3.0. The copolymers (PEGMEM)1.51-co-(APSA)1.00 and (PEGMEM)1.00-co-(APSA)1.95 showed a high selectivity for Cr(III) ions at pH 3.0. The maximum retention capacity, in general, was similar for the homo- and copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2955–2960, 2004

Synthesis and properties of hydrophilic polymers. IX. Synthesis, biodegradability, and metal complexation of copolymers of ethylenediaminetetraacetic acid dianhydride and lactose

AbstractThe synthesis and characterization of poly(ethylenediaminetetraacetic acid‐co‐lactose) with pendant carboxylic groups of high molar mass (132 kg mol−1) is described. The polycondensate was hydrolytically and microbiologically degradable with conventional microbiological methods. The metal‐complexing properties of the polyester were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II), Pb(II), and Al(III) ions in aqueous solution with the liquid‐phase polymer‐based retention (LPR) method. In addition, the complexing capacity of the Cu(II)‐saturated copolymer was determined by thermogravimetric analysis to be 182 mg g−1 of polymer. According to the retention profiles determined as a function of the filtration factor with LPR in conjunction with inductively coupled plasma spectrometry, Cr(III) and Fe(III) showed a strong interaction with this polymer under these conditions, as indicated by retention values of about 100% at pH 5. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 650–657, 2003

PREPARATION, CHARACTERIZATION AND APPLICATION OF POLY(HYDROXYETHYL METHACRYLATE -co- ACRYLAMIDE) AS NON IONIC WATER-SOLUBLE POLYCHELATOGEN

The free radical copolymerization of soluble poly(hydroxyethyl methacrylate-co-acrylamide) was studied in the range 25 to 75 % in the feed. The copolymers compositions were determined from the N/C by elemental analysis. The r1 and r2 were determined by the Kelen Tudos method. The experimental data indicate random comonomer incorporation with alternanting tendency. The separation of various metal ions by the water-soluble poly(hydroxyethyl methacrylate-co-acryl amide) reagent in aqueous phase using the Liquid-phase Polymer-based Retention (LPR) was investigated. The method is based on the retention of inorganic ions by this polymer in a membrane filtration cell and subsequent separation of low-molar mass species from the polymer complex formed. It is shown that poly(HEMA-co-AAm) can bind metal ions : Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), Pb(II), Hg(II), and Fe(III) in aqueous solution at pH 3, 5, and 7. The inorganic ion interaction with the hydrophilic polymer was determined as a function of pH and filtration factor. In addition, the maximum capacity values of the copolymer for lead (II) were investigated at different pH

Poly(acrylic acid‐co‐vinylsulfonic acid): Synthesis, characterization, and properties as polychelatogen

AbstractThe synthesis of the water‐soluble poly(acrylic acid‐co‐vinylsulfonic acid) at different feed monomer ratios, while maintaining constant the total number of mol, was carried out by radical polymerization. The copolymers were characterized by FTIR and 1H‐NMR spectroscopies. The copolymer composition was determined by its sulfur content and by potentiometric titration. The metal ion binding properties for Ni(II) and Cu(II) in the aqueous phase were studied using the liquid‐phase polymer‐based retention (LPR) technique for two values of ionic strength. For comparison, the retention properties of both homopolymers were included. The complexing ability of the polymer was determined by the relative amount of carboxylic acid groups. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1698–1704, 2003

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

AbstractThe 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. Mn, Mw, and the polydispersity were determined by gel permeation chromatography. The polymacromonomer showed a high thermal stability with a TDT50% 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

Ultrafiltration of metal ions by water-soluble chelating poly(N-acryloyl-N-methylpiperazine-co-N-acetyl-?-aminoacrylic acid)

Water-soluble copolymers of N-acryloyl-N-methylpiperazine and N-acetyl-α-aminoacrylic acid were synthesized by radical polymerization. The copolymerization yield ranged between 60 and 97%. The FTIR and NMR spectra demonstrated that the copolymerization occurred. The copolymer composition was determined from 1H-NMR spectra by comparison of methyl groups from both moieties. The copolymers were richest in AAA units. The metal ion retention properties were investigated by the liquid-phase polymer-based retention (LPR) technique at different pH and filtration factors. The affinity for the metal ions depended on the copolymer composition, pH, and filtration factor. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2556–2561, 2002

A Novel Biodegradable Carboxy-Functional Lactose Copolymer

The synthesis of the first lactose main-chain copolymer was achieved by means of solution polyreaction of ethylenediaminetetraacetic acid dianhydride with D-lactose. The water-soluble carboxy-functional material based on EDTA with a high molar mass is shown to be biodegradable. The metal complexing properties of the polymer based on the liquid-phase polymer-based retention (LPR) method showed a strong interaction with Cr(III), Fe(III), and Sr(II) ions.

Synthesis, characterization and polychelatogenic properties of poly[(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid)‐co‐(methacrylic acid)

AbstractPoly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid), poly(methacrylic acid), and five copolymers of poly[(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐co‐(methacrylic acid)] were synthesized by radical polymerization and obtained in yields >97%. The polymers were characterized by FT‐IR, [1H]NMR, and [13C]NMR and studied by means of the Liquid‐phase Polymer‐based Retention (LPR) technique. The metal ion retention ability of the copolymers for Cu(II), Cd(II), Co(II), Hg(II), Ni(II), Zn(II), Cr(III) and Ag(I) was investigated at different pH values because of their environmental and analytical interest. The retention profiles of the copolymers were compared with those of the corresponding homopolymers and retention of metal ions was found to increase with increasing pH.© 2001 Society of Chemical Industry

Poly(N-acetyl-α-acrylic acid): Synthesis, Characterization and Chelation Properties through Liquid Phase Polymer-Based Retention Technique

The synthesis and characterization of the water-soluble poly(N-acetyl-α-acrylic acid) by radical polymerization were carried out. The polymer was characterized by Fourier Transform Infrared (FT-IR), 1H NMR and 13C NMR spectroscopies, and thermogravimetric analysis (TGA). The metal ion binding properties for the metals Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Pb(II), Hg(II), Cr(III) in the aqueous phase were studied using the liquid-phase polymer-based retention technique. The metal ion interactions with the hydrophilic polymer were determined as a function of pH and of the filtration factor. The polychelatogen showed a high affinity for metal ions and higher selectivity for Cr(III) at pH = 3.

Chelating properties of poly(N-acryloyl piperazine) by liquid-phase polymer-based retention (LPR) technique

The synthesis of poly(N-acryloylpiperazine) was carried out by radical polymerization giving a yield of 90%. The polymer was soluble in water and was characterized by FTIR, 1H NMR, 13C NMR spectroscopy, and TGA. The metal ability binding properties for the Ag(I), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Pb(II), and Cr(III) metal ions in the aqueous phase were investigated using the liquid-phase polymer-based retention (LPR) method. The metal ion interactions with the hydrophilic polymers were determined as a function of pH and filtration factor.

Part 8. Preparation, characterization and metal complexing of poly[(2-hydroxyethyl)-DL-aspartamide] in aqueous solution

Poly[(2-hydroxyethyl)-DL-aspartamide] was synthesized by polyreaction of aspartic acid and subsequent polymer-analogous functionalization with ethanolamine. The water-soluble polymer was characterized by FTIR, NMR, TGA and light-scattering measurements. The metal complexing properties of the polymer were studied for Cr(III), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Sr(II), Cd(II) and Pb(II) ions in aqueous solution using the liquid-phase polymer-based retention (LPR) method. According to the retention profiles of LPR, Cr(III), Fe(III), Cu(II) and Pb(II) showed a strong interaction with this polymer under these conditions, indicated by retention values of about 100%. In contrast, Co(II), Ni(II), Zn(II), Sr(II) and Cd(II) exhibited retention values of only 50-60% in dilute solution at pH 5.