Synthesis of copolymers containing opposite charged comonomers and their interactions with metal ions

Radical polymerization was used to synthesize three copolymers of [3‐(methacryloylamino)propyl]trimethylammonium chloride and methacrylic acid [P(MPTA‐co‐MA)]; three copolymers of MPTA and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid [P(MPTA‐co‐APSA)], which had different feed monomer mole ratios but a constant total number of moles (0.03 mol); and the homopolymers poly(MPTA), poly(MA), and poly(APSA). The yields for all homopolymers and copolymers were over 70 and 90%, respectively. All products were dissolved in water, purified, and fractioned by an ultrafiltration membrane with different exclusion limits of the molecular weight (3,000, 10,000, 30,000, and 100,000 g mol^?1). All fractions were lyophilized. The polymeric materials were characterized by FTIR and ¹H‐NMR spectroscopy. The metal ion interaction with the hydrophilic polymers was determined as a function of the pH and the filtration factor. It was dependent on the pH, type of ligand group, and charge of the metal ion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1715–1721, 2003     

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

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

The 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 of water-soluble polymers containing sulfonic acid and amine moieties for the recovery of metal ions using ultrafiltration

Copolymers from 2-acrylamido-2-methyl-propane sulfonic acid (APSA) and N-acryloyl-N-methyl piperazine (AP) were synthesized by radical polymerization with ammonium peroxydisulfate as the initiator. The copolymerization yield ranged between 93 and 95%. The copolymers were completely water soluble, and were characterized by FTIR and NMR spectroscopy. The copolymer composition was determined from elemental analysis through the S/C ratio. The binding capacity for metal ion was studied by the LPR technique at different pH and filtration factors. The retention depended strongly on the pH and on the copolymer composition. With increasing pH and increasing content of APSA units in the copolymer, the metal ion retention increased. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 22–30, 2001     

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid): Synthesis,characterization, and retention properties for environmentally impacting metal ions

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Cr³⁺, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd²⁺ to 0.34 for Ag⁺. The antibacterial activity of Ag⁺, Cu²⁺, Zn²⁺, and Cd²⁺ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd²⁺ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Poly(ethylene‐alt‐maleic acid) as complexing reagent to separate metal ions using membrane filtration

Commercial, water‐soluble poly(ethylene‐alt‐maleic anhydride), P(E‐alt‐MAn), was quantitatively hydrolyzed by 0.2M NaOH to yield poly(ethylene‐alt‐maleic acid), P(E‐alt‐MAc). The polymer structure is confirmed by FT‐IR spectroscopy. As the pH increases, metal ion affinity increases because the majority of the functional groups are present as carboxylate anions, which can form more stable complexes at a higher pH. By increasing the filtration factor, Z, metal ion affinity does not significantly decrease, which means that the ligand–metal interaction is strong and cannot be destroyed by washing with water at the filtration cell's pH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2057–2061, 2006     

Functional water‐soluble polymers: polymer–metal ion removal and biocide properties

Water‐soluble polymers have attracted much interest due to their potential applications in environmental protection engineering to remove harmful pollutants and in biomedicine in the areas of tissue engineering, within‐body implants or other medical devices, artificial organ prostheses, ophthalmology, dentistry, bone repair, and so on. In this review, particular emphasis is given to the ability of water‐soluble polymers with amine, amide, carboxylic acid, hydroxyl and sulfonic acid functional groups to remove metal ions by means of the liquid‐phase polymer‐based retention (LPR) technique that combines the use of water‐soluble polymers and ultrafiltration membranes. The second part is dedicated to showing the potential application of functional water‐soluble polymers and their polymer–metal complexes as biocides for various bacteria. These polymers and polymer–metal complexes show an efficient bactericide activity, especially to Gram‐negative bacteria, Staphylococcus aureus reaching concentrations lower than 4 µg mL^?1. This activity depends on polymer size, type of metal ion, contact time and concentration of polymer and metal ion. The discussion reveals that in the case of the LPR process the efficiency of metal ion removal depends strongly on the type of polymer functional group and the feed pH value. In general, two mechanisms of ion entrapment are suggested: complex formation and electrostatic interaction. In the case of the medical use of water‐soluble polymers and their complexes with metal ions, the review documents the unique bactericide properties of the investigated species. The polymer‐metal ion complexes show a reduced genotoxic activity compared with free metal ions. Copyright © 2009 Society of Chemical Industry     

Ultrafiltration of metal ions by water‐soluble chelating poly(N‐acryloyl‐N‐methylpiperazine‐co‐N‐acetyl‐α‐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     

Novel water‐soluble acryloylmorpholine copolymers: Synthesis,characterization, and metal ion binding properties

Poly(4‐acryloylmorpholine), poly(4‐acryloylmorpholine‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The water‐soluble polymers obtained, containing tertiary amino, amide, and sulfonic acid groups, were investigated, in view of their metal binding properties, as polychelatogens by using the liquid‐phase polymer‐based retention technique, under different experimental conditions. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), Cd(II), Pb(II), Zn(II), Cr(III), and Al(III). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 180–185, 2006     

Metal ion binding capability of the water‐soluble poly(vinyl phosphonic acid) for mono‐, di‐, and trivalent cations

A water‐soluble polymer containing phosphonic acid groups was investigated as a polychelatogen by using the liquid‐phase polymer‐based retention technique (LPR) under different experimental conditions. The maximum retention capacity of this polymer was determined at different pHs and polymer–metal ion ratios. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), and Cr(III). The maximum retention capacity values of the divalent metal ions were very similar and higher than those for the trivalent cations, indicating that the polymer–metal ion interaction was basically through electrostatic type. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2917–2922, 2004     

Polyelectrolyte‐assisted removal of metal ions with ultrafiltration

The water‐soluble polymers poly(styrene sulfonic acid‐co‐maleic acid) and poly(acrylic acid‐co‐maleic acid) were investigated with respect to their metal‐ion‐binding ability with ultrafiltration. The studied metal ions included Ag(I), Cu(II), Ni(II), Co(II), Ca(II), Mg(II), Pb(II), Cd(II), Zn(II), Al(III), and Cr(III) ions. The retention properties of the polyelectrolytes for the metal ions depended strongly on the ligand type. As for the carboxylate ligands, with increasing concentration and pH, the metal‐binding affinity increased. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1091–1099, 2005     

Water‐soluble copolymers of 1‐vinyl‐2‐pyrrolidone and acrylamide derivatives: synthesis,characterization, and metal binding capability studied by liquid‐phase polymer‐based retention technique

Radical copolymerizations of 1‐vinyl‐2‐pyrrolidone with acrylamide and N,N′‐dimethylacrylamide at different feed ratios were investigated. The copolymers were characterized by Fourier transform infrared spectroscopy, ¹H NMR, and ¹³C NMR spectroscopy. The copolymer composition was determined from the ¹H NMR spectra and found to be statistical. The metal complexation of poly(acrylamide‐co‐1‐vinyl‐2‐pyrrolidone) and poly(N,N′‐dimethylacrylamide‐co‐1‐vinyl‐2‐pyrrolidone) for the metal ions Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Pb(II), Fe(III), and Cr(III) were investigated in an aqueous phase. The liquid‐phase polymer‐based retention method is based on the retention of inorganic ions by soluble polymers in a membrane filtration cell and subsequent separation of low‐molecular compounds from the polymer complex formed. The metal ion interaction with the hydrophilic polymers was determined as a function of the pH and the filtration factor. Poly(N,N‐dimethylacrylamide‐co‐1‐vinyl‐2‐pyrrolidone) showed a higher affinity for the metal ions than poly(acrylamide‐co‐1‐vinyl‐2‐pyrrolidone). According to the interaction pattern obtained, Cr(III) and Cu(II) formed the most stable complexes at pH 7. Pb(II) and Zn(II) were not retained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 741–750, 1999     

Use of Poly(methyl methacrylate-co-methacrylic acid) Membranes in the Ultrafiltration of Aqueous Fe3+ Solutions by Complexing with Poly(vinyl pyrrolidone) and Dextran

Abstract

In this study water soluble complexible polymers, poly(vinyl pyrrolidone) (PVP) and dextran, were used for the ultrafiltration (UF) of aqueous Fe⁺³ solutions by using poly(methyl methacrylate-co-methacrylic acid) (PMMA-co-MA) membranes. Effects of polymer concentration and pH on the volume collected in the filtration of Fe⁺³ solutions and percent retentions (R%) were examined. It was determined that increase in polymer concentration decreased the permeability of PMMA-co-MA membrane and pH increased the retention of Fe³⁺ solutions. R% for Fe³⁺ solutions were obtained as 62% and 48% with PVP and dextran respectively at pH 3.0, for a filtration period of 80 minutes and retention for Fe³⁺ solution without using any complex forming polymer was found as 14%. Membranes were characterized by AFM analysis and contact angle measurements.     

Water‐soluble amine and imine polymers with the ability to bind metal ions in conjunction with membrane filtration

The commercial polymers poly(ethylene imine) (PEI), poly(ethylene imine epichlorohydrin), and poly(dimethylamine‐co‐epichlorohydrin) were purified and fractionated by ultrafiltration. Their metal‐ion‐binding properties with respect to different ligand groups and the effect of the concentration on the retention properties were investigated. The amine ligands of the polymers formed the most stable complexes with the metal ions. In general, there was an effect of the pH and polymer fraction size on the retention properties. As the pH and polymer fraction size increased, the affinity to bind metal ions also increased. PEI had the highest metal‐retention values, particularly at higher pHs, at which the amine groups were nonprotonated and could coordinate easily with the metal ions. Only Pb(II) was poorly retained. The affinity for all the metal ions, except Pb(II), increased significantly at pH 5. The metal‐ion retention decreased quickly as the filtration factor increased, except for Cu(II), Co(II), Ni(II), Cd(II), and Zn(II) ions, which were retained by over 40% at a filtration factor of 4. For other metal ions such as Pb(II), Ca(II), and Mg(II), only 10% remained bound to the polymer. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 222–231, 2005     

Trace metal ion retention properties of crosslinked poly(4‐vinylpyridine) and poly(acrylic acid)

The crosslinked resins poly(4‐vinylpiridine) (PVPy) and poly(acrylic acid) (PAA) were obtained by radical polymerization. PVPy shows monodentate ligands and PAA at basic pH is basically as acrylate anion, which can contain end‐carboxylates groups or form a bridge acting as mono‐ or bidentate ligands. The retention properties for trace metal ions from saline aqueous solutions and natural seawaters of these two resins were investigated by Batch equilibrium procedure. The metal ions studied were Cu(II), Pb(II), Cd(II), and Ni(II). The following effects were studied: pH, contact time, amount of the adsorbent, temperature, and salinity. The resin PVPy showed a high affinity for Cd(II) and PAA for Cu(II) and Cd(II). The metal ions were determined in the filtrate by atomic absorption spectrometry. By the treatment of the loaded resin with 4M HNO₃, it was possible to remove completely the Cu(II) ions. The retention properties of the resins were studied for trace metal ions present in the natural seawaters. Both resins showed a high affinity for Cd(II) when the natural seawater contained Cu(II) and Cd(II). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2908–2916, 2004     

Arsenite retention properties of water‐soluble metal–polymers

The 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     

Infrared spectroscopy and electrical properties of ternary poly(acrylic acid)–metal–poly(acrylamide) complexes

Fourier transform infrared spectroscopy (FTIR) and electrical measurements were used for the characterization of the interpolymer complexation between poly(acrylic acid) (PAA) and poly(acrylamide) (PAAm) and also the ternary PAA–metal–PAAm complexes. The interpolymer complexes were prepared by adjusting the pH value of the mixture solutions at different PAA weight fractions (W_PAA). The ternary complexes were prepared by mixing metal chloride solutions (such as ErCl₃ and LaCl₃) with different concentrations to PAA–PAAm mixtures and adjusting the pH value for different W_PAA. It was found that the IR spectra of the interpolymer complexes showed absorption bands at shifted positions and of intensities different from those of the parent polymers. Also, the examination of the spectra of the ternary metal–polymer complexes revealed that they depend on the nature, lency, ionic radius, and concentration of the added metal chlorides. Analysis of the electrical results showed that the electrical conductivity of the interpolymer complexes are always lower than those of PAA and PAAm, which was attributed to the decrease in the mobility of the polymer chains as a result of the complexation. Also, the conductivity of the ternary metal complexes showed a dependence on the properties of the additives and were found to decrease with increasing their concentrations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2699–2705, 2002     

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     

Selective retention properties to silver(I) and mercury(II) ions of poly(4‐vinylpyridine) methyl iodide studied by the liquid‐phase polymer‐based retention technique

The retention of various metal ions by water‐soluble poly(4‐vinylpyridine) methyl iodide in conjunction with ultrafiltration membrane 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‐molecular weight species from the polymer metal ion complex formed. It is shown that the polychelatogen can bind silver(I) and mercury(II) ions in aqueous solution at pH 1. At higher pH, the water‐soluble polymer can be applied to the separation and preconcentration of silver metal ions. Therefore, this polychelatogen is highly selective to Hg(II) at pH 1 with respect to metal ions such as Cd(II) and Zn(II). © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2578–2582, 2001     

Poly(sodium 4‐styrene sulfonate) and poly(2‐acrylamido glycolic acid) polymer–clay ion exchange resins with enhanced mechanical properties and metal ion retention

This research presents the synthesis of novel nanocomposite ion exchange resins based on poly(sodium 4‐styrene sulfonate) and poly(2‐acrylamido glycolic acid). Nanocomposites were synthesized by in situ radical polymerization using organic modified montmorillonite as filler and different clay contents. Loaded resins showed improvements in mechanical properties compared with unloaded resins: specifically, when the nominal montmorillonite content was 2.5 wt%, poly(sodium 4‐styrene sulfonate) nanocomposite increased its shear modulus from 323 to 910 Pa and doubled its elastic recovery ratio, and the yield point was almost 20 times higher than for unloaded resins. In the case of metal ion retention, the effect of pH and clay content were studied for Cd(II), Pb(II), Cu(II), Cr(III) and Al(III) by a batch procedure. Results showed high efficiency, reaching over 80% after only 1 h of contact. Poly(2‐acrylamido glycolic acid) presented a higher pH dependence than poly(sodium 4‐styrene sulfonate). In addition, it was observed that montmorillonite contributes to retention capacity from the increase in distribution coefficients for loaded resins compared with unloaded resins. Copyright © 2011 Society of Chemical Industry