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

The 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     

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. © 2000 Society of Chemical Industry     

Poly(N,N′-dimethylacrylamide-co-acrylic acid): Synthesis,characterization, and application for the removal and separation of inorganic ions in aqueous solution

The synthesis of poly (N,N′-dimethylacrylamide-co-acrylic acd) under different feed molar ratios was carried out by radical polymerization. Both homopolymers were also synthesized to compare the metal ion binding abilities. All polymers were water-soluble and were characterized by FTIR, ¹H-NMR, ¹³C-NMR, and TGA. The metal complexing properties for the metals Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Pb(II), Hg(II), Cr(III), and Fe(III) in the aqueous phase were investigated using the liquid-phase polymer-based retention (LPR) method. The metal ion interactions with the hydrophilic polymer were determined as a function of pH and the filtration factor. According to the interaction pattern obtained, the metal ions form the most stable complexes with the copolymer poly(N,N′-dimethylacrylamide-co-acrylic acid) within the pH range 5–7. Hg(II) was not retained at all the pH ranges investigated. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 93–100, 1998     

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     

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 (10⁸ mL⁻¹) by using conventional microbiological methods.     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

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

This 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 T_g, indicating the formation of random copolymers. A slight deviation of the T_g for the copolymers and its complexes can be observed. The copolymer T_g is higher than the T_g value for the polymer–metal complexes. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Poly[acrylamide-co-1-(2-hydroxyethyl)aziridine]: An efficient water-soluble polymer for selective separation of metal ions

Poly[acrylamide-co-1-(2-hydroxyethyl)aziridine], obtained by spontaneous copolymerization, which contains different types of ligand groups as tertiary amines and hydroxyl and amide groups, was tested as a polychelatogen using the liquid-phase polymer-based retention (LPR) technique. The metal ion retention ability of this polymer was found to depend on the pH and it showed a high selectivity to copper(II) at pH 5. The maximum capacity of Cu(II) was determined at pH 5 by using the enrichment variant of LPR. The retention capacities of the polymer with Cu(II), Cd(II), Co(II), Cr(III), Ni(II), Pb(II), Zn(II), and Fe(II) were studied at different pH and the results are compared with those of branched polyethylenimine and poly[1-(2-hydroxyethyl)aziridine] homopolymers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 817–824, 1998     

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     

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     

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     

Nonionic water‐soluble polymer: Preparation,characterization, and application of poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) as a polychelatogen

The free‐radical copolymerization of water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) was carried out with a feed monomer ratio of 75:25 mol %, and the total monomer concentration was 2.67M. The synthesis of the copolymer was carried out in dioxane at 70°C with benzoyl peroxide as the initiator. The copolymer composition was obtained with elemental analysis and ¹H‐NMR spectroscopy. The water‐soluble polymer was characterized with elemental analysis, Fourier transform infrared, ¹H‐ and ¹³C‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymer were performed. The thermal behavior of the copolymer and its complexes were investigated with differential scanning calorimetry (DSC) and thermogravimetry techniques under a nitrogen atmosphere. The copolymer showed high thermal stability and a glass transition in the DSC curves. The separation of various metal ions by the water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) reagent in the aqueous phase with liquid‐phase polymer‐based retention was investigated. The method was 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/metal‐ion complex formed. Poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) could bind metal ions such as Cr(III), Co(II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) in aqueous solutions at pHs 3, 5, and 7. The retention percentage for all the metal ions in the polymer was increased at pH 7, at which the maximum retention capacity could be observed. The interaction of inorganic ions with the hydrophilic polymer was determined as a function of the pH and filtration factor. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 178–185, 2006     

Application of a synthetic water-soluble poly(N-maleyl glycine-co-acrylamide) as polychelatogen for inorganic ions in aqueous solutions

Summary The water-soluble poly(N-maleyl glycine-co-acrylamide) (P(MG-co-Am)) reagent with strong complexing properties for the inorganic ions Cr(III), Co(II), Zn(II), Ni(II), Cu(II), Cd(II), Pb(II), Hg(II), As(V), and Se(IV) was investigated in aqueous phase in conjunction with membrane filtration using the Liquid-phase Polymer-based Retention (LPR) technique. The P(MG-co-Am) was shown to be useful for retention of different inorganic ions and their separation from elements not bound to the polymeric reagent. The inorganic ion interaction with the hydrophilic polymer was determined as a function of pH and filtration factor. At higher pH, the copolymer can be applied to the separation and preconcentration of most of the inorganic ions. Viscosimetric measurements of the copolymers were performed in the presence of metal ions at different pH values. Received: 8 July 1998/Revised version: 23 October 1998/Accepted: 27 October 1998     

Cetylpyridinium chloride-modified poly(ethyleneimine) for the removal and separation of inorganic ions in aqueous solution

The removal and separation of a series of ions by the water-soluble cetylpyridinium chloride-modified poly(ethyleneimine) (PEI-CPC) in conjunction with membrane filtration were investigated. The Liquid-Phase Polymer-Based Retention (LPR) method was applied to study the removal of the low-molecular species at different pH values and at several element concentrations. The study comprises aqueous solutions of the anions chromate and phosphate, and of the cations Cu(II), Zn(II), Co(II), Ni(II), Cr(III), Fe(III), Cd(II), Pb(II) and Sr(II). The results show that a high retention was attained in neutral solutions for both anions and also for most metal ions investigated. PEI-CPC exhibited good removing abilities for chromate and phosphate ions even at relatively high concentrations of anions (85 and 150 mg · L ^?1, respectively) and also for most of the metal ions studied. In the case of Cu(II), Ni(II), Cd(II), and Sr(II) ions, selective interactions were observed. The polymer reagent and its interaction products were characterized by IR, UV/VIS spectrometry, and viscometry. In addition, the interaction behaviour was investigated by the retention ability. A good correlation was found between the retention data and the IR and UV/VIS spectra of the interaction products of the polymer reagent with the metal ions.     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

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     

Crossflow filtration of iron(III), copper(II), and cadmium(II) aqueous solutions with alginic acid/cellulose composite membranes

The removal of Fe(III), Cu(II), and Cd(II) ions from aqueous solutions was investigated with a crossflow filtration technique. Alginic acid (AA)/cellulose composite membranes were used for retention. In the filtration of Fe(III) solutions, the effects of the crossflow velocity, applied pressure, AA content of the membranes, and pH on the retention percentage and the permeate flux were examined. The maximum retention percentage was found to be 89% for a 1 × 10^?4M Fe(III) solution at the flow velocity of 100 mL/min and the pressure of 60 kPa with 0.50% (w/v) AA/cellulose composite membranes at pH 3. Aqueous solutions of Cu(II) and Cd(II) were filtered at the flow velocity of 100 mL/min and pressure of 10 kPa. The effects of the AA content of the membranes and pH of the waste medium on the retention percentage and the permeate flux were determined. For 1 × 10^?4M Cu(II) and Cd(II) solutions, the maximum retention percentages were found to be 94 and 75%, respectively, at pH 7 with 0.50% (w/v) AA/cellulose composite membranes. When metal‐ion mixtures were used, the retention percentages of Fe(III), Cu(II), and Cd(II) were found to be 89, 48, and 10%, respectively, at pH 3 with 0.50% (w/v) AA/cellulose composite membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymer-Enhanced Crossflow Filtration for Removal of Fe(III), Cu(II), and Cd(II) Ions from Dilute Aqueous Solutions

Abstract

The removal of Fe(III), Cu(II), and Cd(II) ions from aqueous solutions was studied by polymer-enhanced crossflow filtration technique. Alginic acid polymer was used as complexing agents to enhance the retention. Alginic acid/cellulose composite membranes were used in the filtration. In the filtration of metal ion solutions the effects of alginic acid content of the membranes and pH on the percent retention and the permeate flux were examined. The maximum percent retention was found as 98% for 1 × 10^?4 M Fe(III) solution at the flow velocity of 100 mL/min, pH of 3.0, pressure of 60 kPa in the presence of alginic acid as complexing agent by using 0.25 (w/v)% alginic acid/cellulose composite membranes. For 1 × 10^?4 M Cu(II) and Cd(II) solutions the maximum percent retentions were found as 71% and 80% respectively using 0.50 (w/v)% Alginic acid/cellulose composite membranes when the filtration was carried out in the presence of alginic acid at pressure of 10 kPa, flow velocity of 100 mL/min and pH of 7.0.     

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     

Synthesis and characterization of a surface imprinting silica gel polymer functionalized with phosphonic acid groups for selective adsorption of Fe(III) from aqueous solution

A Fe(III) ion‐imprinted silica gel polymer functionalized with phosphonic acid groups (IIP‐PA/SiO₂) was prepared with surface imprinting technique by using Fe(III) ion as template ion, grafted silica gel as support, and vinylphosphonic acid as functional monomer. The polymer was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–Teller, and thermogravimetric analysis. The synthesized imprinted silica gel polymer was used as a sorbent for Fe(III) adsorption. The adsorption properties, such as the effect of solution pH, adsorption kinetic, adsorption isotherm, adsorption selectivity as well as the regeneration of sorbent were studied. The results showd that the prepared sorbent (IIP‐PA/SiO₂) had a short adsorption equilibrium time (12 min) and high adsorption capacity (29.92 mg g^?1) for Fe(III) at the optimal pH of 2.0. The selectivity coefficients of the sorbent for Fe(III) in presence of Cr(III), M_n (II), and Zn(II) were 51.76, 27.86, and 207. 76, respectively. Moreover, the adsorption capacity of the prepared sorbent did not decrease significantly after six repeated use. Thus, the prepared ion‐imprinted silica gel polymer was a promising candidate sorbent for the selective adsorption of Fe(III) from aqueous solutions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45165.