Preparation,characterization, and metal ion retention capacity of Co(II) and Ni(II) from poly(p‐HO‐ and p‐Cl‐phenylmaleimide‐co‐2‐hydroxypropylmethacrylate) using the ultra filtration technique

p‐Chlorophenylmaleimide and p‐hydroxyphenylmaleimide with 2‐hydroxypropyl methacrylate were synthesized by radical polymerization, and the metal ion retention capacity and thermal behavior of the copolymers were evaluated. The copolymers were obtained by solution radical polymerization with a 0.50 : 0.50 feed monomer ratio. The maximum retention capacity (MRC) for the removal of two metal ions, Co(II) and Ni(II) in aqueous phase were determined using the liquid‐phase polymer based retention technique. Inorganic ion interactions with the hydrophilic polymer were determined as a function of pH. The metal ion retention capacity does not depend strongly on the pH. Metal ion retention increased with an increase of pH for a copolymer composition 0.50 : 0.50. At different pH, the MRC of the poly(p‐chlorophenylmaleimide‐co‐2‐hydroxypropylmethacrylate) for Co(II) and Ni(II) ions varied from 44.1 to 48.6 mg/g and from 41.5 mg/g to 46.0 mg/g, respectively; while the MRC of poly(p‐hydroxyphenylmaleimide‐co‐2‐hydroxypropyl methacrylate) for Co(II) and Ni(II) ions varied from 28.4 to 35.6 mg/g and from 27.2 to 30.8 mg/g, respectively. The copolymers and copolymer–metal complexes were characterized by elemental analysis, FT‐IR, ¹H NMR spectroscopy, and thermal behavior. The thermal behavior of the copolymer and polymer–metal complexes were studied using differential scanning calorimetry and thermogravimetry techniques under nitrogen atmosphere. The thermal decomposition temperature and T_g were influenced by the binding‐metal ion on the copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Synthesis and characterization of hydrophilic copolymers of maleimide derivatives with 2‐hydroxyethyl methacrylate: electrochemical and thermal behavior

BACKGROUND: The high‐technology industries have been the driving force in the development of new synthetic polymers that combine thermal stability with specific functional properties. In this study p‐chlorophenylmaleimide, p‐hydroxyphenylmaleimide and p‐nitrophenylmaleimide (R‐PhMI) with 2‐hydroxyethyl methacrylate (HEMA) were synthesized by free radical polymerization to obtain hydrophilic polymers, in order to study the effect of the p‐chloroaryl, p‐hydroxyaryl or p‐nitroaryl group on the copolymer composition, electrochemical behavior and thermal properties. RESULTS: The thermal behavior was correlated with the copolymer composition and functional groups, maleimide derivatives, on the copolymers. Thermal decomposition temperature (TDT) and glass transition temperature (T_g) were influenced by the functional groups of R‐PhMI moiety on the copolymer. The polymers showed an electrochemically irreversible reduction process under the conditions tested. CONCLUSION: Poly[(p‐chloromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] copolymer shows a higher TDT than poly[(p‐hydroxymaleimide)‐co‐(2‐hydroxyethyl methacrylate)] or poly[(p‐nitromaleimide)‐co‐(2‐hydroxyethyl methacrylate)] (NPHE). T_g decreases in going from nitro to hydroxyl to chloro groups. The NPHE copolymer shows a lower stability, losing weight at 200 °C. The NPHE copolymer shows a well‐defined reduction wave which is similar to those of the other copolymers and it also shows an additional quasi‐reversible reduction wave corresponding to the nitrobenzene group. Copyright © 2009 Society of Chemical Industry     

Effect of the nature of crosslinking agent on the unusual metal ion specificity and selectivity of N,N‐bis(2‐aminoethyl)polyacrylamide

Metal ion desorbed crosslinked N,N‐bis(2‐aminoethyl)polyacrylamides showed enhanced specificity for the desorbed metal ion, and these polymers selectively rebind the desorbed metal ion from a mixture of metal ions. For this, polyacrylamide with 8 mol % divinylbenzene (DVB) and N,N′‐methylene‐bisacrylamide (NNMBA) crosslinking were prepared by solution polymerization. Diethylenetriamino functions were incorporated into the polymers by polymer analogous reactions. The complexing ability of the amino polymers were investigated toward various transition metal ions like Co(II), Ni(II), Cu(II), and Zn(II). Polymeric ligand and metal complexes were characterized by various spectral methods. The removal of the metal ion from the polymer matrix resulted in a memory for the desorbed metal ion. On rebinding, these polymers specifically rebind the desorbed metal ion and from a mixture of metal ions, it showed selectivity to the desorbed metal ion. Thus, the Cu(II) desorbed polymer specifically and selectively rebind Cu(II) ion from a mixture of Cu(II) and other metal ion. This selectivity is higher in the rigid DVB‐crosslinked system, resulting from the high rigidity of the crosslinked matrix compared to the semirigid NNMBA‐crosslinked system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Metal ion retention using the ultrafiltration technique: Preparation,characterization of the water-soluble poly(1-vinyl-2-pyrrolidone-co-itaconic acid) and its metal complexes in aqueous solutions

Radical copolymerization of 1-vinyl-2-pyrrolidone with itaconic acid at different feed monomer ratios (75–25 mol %) were investigated. The copolymers were characterized by elemental analysis, Fourier transform infrared (FTIR), ¹H and ¹³C NMR spectroscopy. The copolymer composition was determined from elemental analysis and found to be statistical copolymers. Additionally, viscosimetric measurements, molecular weight, and polydispersity have been determined. The metal complexation of poly(1-vinyl-2-pyrrolidone-co-itaconic acid) for the metal ions such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) were investigated at pH 3, 5, and 7 in aqueous solution. The metal ion interaction with hydrophilic polymers was determined as a function of the pH and filtration factor. Poly(1-vinyl-2-pyrrolidone-co-itaconic acid) showed a high affinity for the metal ions at pH 5 and 7. The poly(NVP-co-IA), with a copolymer composition of 29 : 71 mol % (PVA-3), presented the highest metal ion retention values, particularly at higher pHs, at which the carboxylic acid groups are nonprotonated and could easily coordinate with the metal ions. According to the interaction pattern obtained, Cr(II), Zn(II), Pb(II), and Ni(II) formed the most stable complexes at pH 7. The thermal behaviors of the copolymer and polymer metal complex were characterized using differential scanning calorimetry (DSC) and thermogravimetry techniques under nitrogen atmosphere. The copolymers present high thermal stability and do not present glass transition in DSC curves between 25 and 500°C. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Novel hydrogels based on itaconic acid and citraconic acid: Synthesis,metal ion binding,and swelling behavior

Several copolymer hydrogels were prepared from radical copolymerization of 2‐hydroxypropyl methacrylate (HPMA) with itaconic acid (IA) and also with citraconic acid (CA) by using different feed ratios. The copolymers were characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy as well as by thermal analysis. The swelling process of the different hydrogels immersed in water at different pH has been studied, and also the swelling of the hydrogels loaded with metal ions (Pb²⁺, Cd²⁺) was investigated. The metal‐binding properties were studied by using the liquid‐phase polymer‐based retention technique, including studies on the influence of pH on the binding process. The efficiency of these hydrogels for the recovery of metal ions in solution was determined by atomic absorption spectroscopic analysis. The thermal characteristics of these copolymers were studied by using differential scanning calorimetry and thermogravimetric analysis in nitrogen atmosphere. Accordingly, the gels loaded with metal ions showed a slight increase of the thermal decomposition temperature when compared with the pristine gels. The copolymer gel HPMA‐co‐CA showed a single glass transition temperature, whereas for the copolymer systems, HPMA‐co‐IA, only the copolymers loaded with Cd²⁺ ions showed a glass transition temperature. The morphology of film produced from the copolymers was investigated by scanning electron microscopy, revealing generally smooth surfaces. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and characterization of poly(1,3‐thiazol‐2‐yl‐carbomoyl) methyl methacrylate: Its metal complexes and antimicrobial activity studies

Poly(1,3‐thiazol‐2‐yl‐carbomoyl) methyl methacrylate [poly(TCMMA)] is prepared in dimethyl sulfoxide using 2,2′‐azobisisobutyronitrile as an initiator at 60°C. Poly(TCMMA) is characterized by IR and ¹H‐NMR spectroscopic techniques. Cadmium(II), copper(II), and nickel(II) chelates of poly(TCMMA) were synthesized. An elemental analysis of the polychelates suggests a metal/ligand ratio of 1:2. The polychelates are further characterized by IR and magnetic susceptibility measurements. The thermal properties of the polymer and metal chelates are also discussed. The molecular weights of the poly(TCMMA) are determined by the gel permeation chromatography technique. The antimicrobial activities of the polymer and metal chelates are tested against Staphylococcus aureus COWAN I (bacteria), Escherichia coli ATCC 25922 (bacteria), Listeria monocytogenes SCOTTA (bacteria), Bacillus subtilis LMG (bacteria), Enterobacter aeroginosa CCM 2531 (bacteria), Klebsiela pneumania FMCS (bacteria), Candida albicans CCM 314 (Mayo yeast), and Saccharamyces cerevisiae UGA 102 (Mayo yeast). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3244–3251, 2003     

Metal‐ion‐retention properties of the poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine) resin

The water‐insoluble resin poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine), through a radical polymerization solution, was synthesized with ammonium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinking reagent. The metal‐ion‐retention properties were studied by batch and column equilibrium procedures for the following metal ions: Hg(II), Cu(II), Cd(II), Zn(II), Pb(II), and Cr(III). These properties were investigated under competitive and noncompetitive conditions. The effects of the pH, maximum retention capacity, and regeneration capacity were studied. The resin showed a high retention ability for Hg(II) ions at pH 2.0. The retention of Hg(II) ions from a mixture of ions was greater than 90%. The resin showed a high selectivity for Hg(II) with respect to other metal ions. The Hg(II)‐loaded resin was able to be recovered with 4M HClO₄. The retention capacity was kept after four cycles of adsorption and desorption. The retention properties for Hg(II) were very similar with the batch and column methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3556–3562, 2003     

New antimicrobial polyurea: Synthesis,characterization, and antibacterial activities of polyurea‐containing thiosemicarbazide–metal complexes

A novel class of polymer–metal complexes was prepared by the condensation of a polymeric ligand with transition‐metal ions. The polymeric ligand was prepared by the addition polymerization of thiosemicarbazides with toluene 2,4‐diisocyanate in a 1 : 1 molar ratio. The polymeric ligand and its polymer–metal complexes were characterized by elemental analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, and ¹³C‐NMR and ¹H‐NMR spectroscopy. The geometries of the central metal ions were determined by electronic spectra (UV–visible) and magnetic moment measurement. The antibacterial activities of all of the synthesized polymers were investigated against Bacillus subtilis and Staphylococcus aureus (Gram positive) and Escherichia coli and Salmonella typhi (Gram negative). These compounds showed excellent antibacterial activities against these bacteria with the spread plate method on agar plates, and the number of viable bacteria were counted after 24 h of incubation period at 37°C. The antibacterial activity results revealed that the Cu(II) chelated polyurea showed a higher antibacterial activity than the other metal‐chelated polyureas. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Nickel(II) complexes bearing the bis(β‐ketoamino) ligand for the copolymerization of norbornene with a higher 1‐alkene

A novel bis(β‐ketoamino)Ni(II) complex catalyst, Ni{CF₃C(O)CHC[N(naphthyl)]CH₃}₂, was synthesized, and the structure was solved by a single‐crystal X‐ray refraction technique. The copolymerization of norbornene with higher 1‐alkene was carried out in toluene with catalytic systems based on nickel(II) complexes, Ni{RC(O)CHC[N(naphthyl)]CH₃}₂(R?CH₃, CF₃) and B(C₆F₅)₃, and high activity was exhibited by both catalytic systems. The effects of the catalyst structure and comonomer feed content on the polymerization activity and the incorporation rates were investigated. The reactivity ratios were determined to be r_1‐octene = 0.009 and r_norbornene = 13.461 by the Kelen–Tüdõs method for the Ni{CH₃C(O)CHC[N(naphthyl)]CH₃}₂/B(C₆F₅)₃ system. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of ¹H‐NMR and ¹³C‐NMR. The thermogravimetric analysis results showed that the copolymers exhibited good thermal stability (decomposition temperature, T_dec > 400°C), and the glass‐transition temperature of the copolymers were observed between 215 and 275°C. The copolymers were confirmed to be noncrystalline by wide‐angle X‐ray diffraction analysis and showed good solubility in common organic solvents. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis,characterization, and catalytic behavior of copper complexes with fluorosubstituted β‐ketoimine ligands

A series of β‐ketoimine ligands with various fluorine substitutions on the N‐aryl ring and the corresponding copper complexes were synthesized. The fluorosubstituents exerted significant effects on the structures and catalytic activities of the copper complexes. X‐ray diffraction revealed that the copper(II) central ions were coordinated by two trans‐oriented β‐ketoimino ligands with delocalized double bonds. Complex 2b (with mono‐o‐fluorosubstitution on the N‐aryl moiety) adopted a central symmetric square planar structure, whereas complex 2f (with bis‐o‐fluorosubstitution) had a distorted square planar structure with a dihedral angle of 28.2°. The Cu? N bond length in 2f was appreciably shorter than that in 2b . When activated by modified methylaluminoxane, the copper complexes effectively polymerized methyl acrylate. Furthermore, substitution with more fluorine atoms resulted in a higher activity. The catalytic activity of the pentafluorosubstituted complex 2h reached 57.5 kg (mol of Cu)^?1·h^?1 under optimized conditions; this was the highest value reported up to this point for copper complexes in acrylic monomer polymerization. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41178.     

Synthesis,characterization, and catalytic study of polymeric metal complexes derived from divalent transition metal ions with 2,4‐dihydroxy benzophenone and 2,4‐dihydroxy acetophenone

The polymeric metal complexes of poly (3‐hydroxy‐4‐((Z)‐1‐(phenylimino)ethyl)phenyl‐3‐methylbut‐2‐enoate) designated as [poly(3H4‐1PEPMB)] and poly (3‐hydroxy‐4‐((Z)‐phenyl(phenylimino)methyl)phenyl‐3‐methylbut‐2‐enoate designated as [poly(3H4‐PPMPMB)] containing Cu(II), Ni(II), Co(II), Cd(II), Mn(II), Ca(II), and Zn(II) ions were synthesized. The ploymer ligands and metal complexes were charcterized by Fourier transform infrared, nuclear magnetic resonance (NMR), thermogravimetric analysis, differential scanning calorimeter (DSC), and X‐ray diffraction (XRD) techniques. The XRD study of the complexes revealed highly crystalline nature of polychelates. The polymeric complexes were active for the oxidation of aldehyde group. The oxidation activity of Cu (II) complex of poly (3H4‐1PEPMB) was studied for the oxidation of benzaldehyde and its derivaties to corresponding carboxylic acids. The oxidation products were confirmed by GC‐MS analysis. The oxidation of aldehydes was quantitative with 100% selectivity for benzioc acid. Thermal analysis of complexes indicated reasonably good thermal stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis,characterization, ion‐exchange,and antimicrobial study of poly[(2‐hydroxy‐4‐methoxybenzophenone) propylene] resin and its polychelates with lanthanides (III)

The polymeric ligand (resin) was prepared from 2‐hydroxy‐4‐methoxybenzophenone with 1,3‐propane diol in the presence of polyphosphoric acid as a catalyst on constant heating at 160°C for 13 h. The poly[(2‐hydroxy‐4‐methoxybenzophenone) propylene] (HMBP‐PD) form 1 : 2 metal/ligand polychelates (metal–polymer complexes) with La(III), Pr(III), Nd(III), Sm(III), Gd(III), Tb(III), and Dy(III). The polymeric ligand and its polychelates (metal–polymer complexes) were characterized on the basis of elemental analyses, electronic spectra, magnetic susceptibilities, IR‐spectroscopy, NMR, and thermogravimetric analyses. The molecular weight was determined using number average molecular weight (M_n) by a vapor pressure osmometry (VPO) method. Activation energy ( E ) of the resin was calculated from differential scanning calorimetry (DSC). All the polychelates are paramagnetic in nature except La(III). Ion‐exchange studies at different electrolyte concentrations, pH, and rate have been carried out for lanthanides(III) metal ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Aerobic oxidative polymerization of 2,6‐dimethylphenol in water with a highly efficient copper(II)– poly(N‐vinylimidazole) complex catalyst

A Cu(II)–poly(N‐vinylimidazole) (PVI) complex was prepared and used to catalyze the oxidative polymerization of 2,6‐dimethylphenol (DMP) to form poly(2,6‐dimethyl‐1,4‐phenylene oxide) (PPO) in water. The stoichiometric ratio between imidazole groups in PVI and copper ions was found to be 4 when continuous variation analysis was applied. Compared with a conventional Cu(II)–low‐molecular‐weight ligand complex, a high catalytic efficiency was observed in the polymerization of DMP catalyzed by the Cu(II)–PVI complex. The influence of the Cu(II)–PVI complex concentration and imidazole/Cu(II) molar ratio on the oxidative polymerization of DMP was studied. Both the yield and molecular weight of PPO increased significantly with the catalyst concentration and decreased with the imidazole/Cu(II) molar ratio. The molecular weight of PVI also played an important role in the improvement of the catalytic efficiency. The high catalytic efficiency of the Cu(II)–PVI complex may have been due to the concentration effect of the catalyst and substrate. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Novel anionic polymerization of β-lactones mediated by alkali metal supramolecular complexes

The anionic polymerization of β-lactones mediated by supramolecular complexes of alkali metal alkoxides and naphthalenides is demonstrated. The novel chemistry of the initiation and the propagation steps of polymerization is discussed.     

Poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium): Synthesis,characterization, and its potential application for the removal of metal ions from aqueous solution

In the current study, poly(N‐vinylpyrrolidone‐co‐2‐acrylamido‐2‐methylpropanesulfonate sodium), poly(VP‐co‐AMPS), was prepared and used for the removal of Cu²⁺, Cd²⁺, and Ni²⁺ ions via a polymer‐enhanced ultrafiltration (PEUF) technique. The copolymer was synthesized by radical polymerization in an aqueous medium with a comonomer feed composition of 50:50 mol %. The molecular structure of the copolymer was elucidated by ATR‐FTIR and ¹H NMR spectroscopy, and the average molecular weight was obtained by GPC. The copolymer composition was determined to be 0.42 for VP and 0.58 for AMPS by ¹H NMR spectroscopy. The copolymer and homopolymers exhibited different retention properties for the metal ions. PAMPS exhibited a high retention capacity for all of the metal ions at both pH values studied. PVP exhibited selectivity for nickel ions. Poly(VP‐co‐AMPS) exhibited a lower retention capacity compared to PAMPS. However, for poly(VP‐co‐AMPS), selectivity for nickel ions was observed, and the retention of copper and cadmium ions increased compared to PVP. The homopolymer mixture containing PAMPS and PVP was inefficient for the retention of the studied metal ions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41272.