The ring‐opening polymerization of D,L‐lactide catalyzed by new complexes of Cu,Zn, Co,and Ni Schiff base derived from salicylidene and L‐aspartic acid

D ,L ‐lactide (LA) was first successfully ring‐opening polymerized in melt by Schiff base complexes K[ML]nH₂O [M = Cu(II), Zn(II), Co(II), Ni(II); n = 2, 2, 3, 3.5; H₃L = L‐aspartic acid‐salicylidene Schiff base], which were prepared by Schiff base ligand derived from salicylidene and L‐aspartic acid and corresponding acetates. The effects of various complexes, the molar ratio of K[ML]nH₂O/LA, the polymerization temperature, and time were studied in detail. The results show that all complexes studied have the ability to initiate the ring‐opening polymerization of D ,L ‐lactide in melt. More than 90% high polymerization conversion and narrow molecular weight distribution (MWD) can be obtained very easily. However, the Ni(II) complex shows better catalytic property than other complexes on the polymerization and the molecular weight (MW) of poly(D ,L ‐lactide) (PLA) produced. With a rise in temperature and a prolongation of time, the MW of PLA decreased remarkably. The MW of PLA prepared by all complexes is not very high, which might be related to the crystalline water of complexes. X‐ray study indicated that PLA produced by Ni(II) complex is an amorphous polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3312–3315, 2002     

Oxidation of styrene over polymer‐ and nonpolymer‐anchored Cu(II) and Mn(II) complex catalysts

Catalytic oxidation of styrene was investigated over polymer‐ and nonpolymer‐anchored Cu(II) and Mn(II) complex catalysts prepared by schiff base tridentate ligands. The effect of temperature, styrene to H₂O₂ mole ratio and catalyst amount on the catalytic activity and product selectivity was investigated. Further, the catalysts were characterized by various techniques, such as elemental analysis, atomic absorption spectroscopy (AAS), FTIR, FE‐SEM, EDAX, TGA, and UV–vis spectrophotometer. The elemental analysis, EDAX and AAS results confirmed the formation of Cu(II) and Mn(II) complexes, and it was found that the metal loading in the polymer‐anchored complex catalysts were in the range of 0.53–3.74 %. FTIR results showed the co‐ordination bond formation between the polymer ligands and metal ion. The catalytic data showed that, over all the catalysts, the main reaction products were benzaldehyde, styrene oxide, and benzoic acid. The polymer‐anchored complex catalysts were found to be much more active when compared with nonpolymer‐anchored catalysts. The maximum conversion of styrene (92.3%) was obtained over PS‐[Cu(Hfsal‐aepy)Cl] catalyst with benzaldehyde selectivity to 69% at the styrene to H₂O₂ mole ratio of 1 : 4 at 75°C. Although the PS‐[Mn(Hfsal‐aepy)Cl] catalyst was less active, it was highly selective to benzaldehyde. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Intercalative redox polymerization and characterization of poly(n‐vinyl‐2‐pyrrolidinone) in the gallery of vermiculite: A novel inorganic–organic hybrid material

In this article we present the synthesis of poly(N‐vinyl‐2‐pyrrolidinone) (PNVP)–vermiculite hybrid material and its characterization by various spectroscopic techniques, X‐ray diffraction (XRD), and thermal analysis. The polymer was synthesized by intercalative redox polymerization of the monomer at 110°C, using copper (II) ion‐exchanged vermiculite. XRD analysis following intercalative polymerization indicates the presence of two prominent peaks with corresponding d (002) spacing of 14.3 (intercalated) and 9.9 (not intercalated) Å, suggesting the formation of a partially intercalated hybrid material. Electron spin resonance studies of the intercalated material show values of “g” different from that of the Cu (II)‐ion‐exchanged vermiculite, indicating that polymer formed in the gallery of vermiculite complexes with the unreacted Cu (II). Thermogravimetric analysis indicates the amount of polymer in the gallery spacing to be ≈20 mass %, which is confirmed by I₂ labeling of the PNVP in the nanocomposite, followed by UV spectroscopy. The IR absorption peaks corresponding to PNVP, along with the XRD and thermal analysis data confirms that the gallery expansion is due to the formation of a partially intercalated inorganic‐organic hybrid material. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1825–1830, 2000     

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, and adsorption behavior of aminophosphinic grafted on poly(styrene‐Co‐divinylbenzene) for divalent metal ions in aqueous solutions

In the present work, two novel aminophosphinic acid ligands grafted on poly(styrene‐1%divinylbenzene) (St‐1%DVB) have been synthesized by reacting polymer precursors bearing primary amino groups with benzaldehyde (or propionaldehyde) and phenylphosphinic acid by the “one‐pot” Kabatachnik‐Fields reaction. The resins functionalized with aminophosphinic pendant groups were characterized by means of Fourier transform infrared spectroscopy (FTIR), thermal analysis, energy dispersive X‐ray microanalysis (EDX), and Scanning electron microscopy (SEM) imaging. Its adsorption capacity for divalent metal ions such as Cu(II) and Ni(II) were investigated. The adsorption procedure of Cu(II) and Ni(II) ions on polymer‐grafted aminophosphinic acid ligands was carried out by batch experiments. The result also shows that the adsorption process was best described by a pseudo‐second‐order kinetic equation and by the Langmuir adsorption isotherm. The best maximum adsorption capacity was obtained for resin with aminobenzylphosphinic acid groups [1.46 mg Cu(II)/g and 1.36 mg Ni(II)/g]. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synthesis of poly[N′‐(2‐cyanoacetyl)acrylohydrazide] and its copolymers with styrene and N‐phenylacrylamide: Characterization,complexation, thermal stability,swelling, and morphology

N′‐(2‐cyanoacetyl)acrylohydrazide (CAH) was obtained with the treatment of 2‐cyanoacetohydrazide with acryloyl chloride in acetonitrile. The obtained acrlyoyl derivative was transferred to the corresponding polymer, poly[N′‐(2‐cyanoacetyl)acrylohydrazide] (PCAH), through treatment with 2,2′‐azobisisobutyronitrile at 75°C. Copolymers with styrene or N‐phenyl acrylamide monomers were synthesized with different ratios. The structures of these polymers were characterized with elemental analysis and spectral data. The morphology, metal uptake, and ion selectivity of the polymers were studied. In addition, the swelling behavior of the polymer and metallopoymer complexes at different times of drying was also investigated. Thermogravimetric analysis of the polymer and polymer complexes under air reflected that PCAH–Pb was the most stable, followed by PCAH, PCAH–Hg, PCAH–Cu, PCAH–Ni, and PCAH–Co. A similar stability with little difference was reported under nitrogen. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of the nature of the crosslinking agent on the metal‐ion complexation characteristics of 4 mol % DVB‐ and NNMBA‐crosslinked polyacrylamide‐supported glycines

Metal‐ion complexation behavior of glycine functions supported on divinylbenzene (DVB)‐ and N,N′‐methylene bisacrylamide (NNMBA)‐crosslinked polyacrylamide was carried out toward Co(II), Ni(II), Cu(II), and Zn(II) ions. The polymeric ligands and the derived metal complexes were characterized by IR, UV, and EPR spectra and by SEM. The metal‐ion complexation of the rigid DVB‐crosslinked system is lower than that of the semirigid NNMBA‐crosslinked system. The glycine ligands renervated after the desorption of the metal ions showed an unusual specificity toward the desorbed metal ion. The low degree of crosslinking makes the desorption process simple and shows fast rebinding kinetics. The metal‐ion‐desorbed polymeric ligands would have pockets or holes characteristic of the desorbed metal ion, resulting in its specific rebinding. The rigidity of the crosslinking also determines the kinetics of metal‐ion rebinding. The specificity and selectivity characteristics of the crosslinked polymeric ligand was found to be increased as the crosslinking agent changes from semirigid NNMBA to rigid and hydrophobic DVB. Thus, copper‐desorbed resins showed an increased specificity toward copper ions and selectively binds copper ions from a mixture of copper and cobalt ions. The metal‐ion specificity and selectivity characteristics of the metal‐ion‐desorbed system is exploited for the concentration of desorbed metal ions from a mixture of metal ions. The resin is amenable for a continuous process and can be regenerated several times. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3432–3444, 1999     

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     

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     

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.     

Cyclometalated N‐Heterocyclic Carbene‐Platinum Catalysts for the Enantioselective Cycloisomerization of Nitrogen‐Tethered 1,6‐Enynes

Platinum(II) complexes which combine six‐membered N‐heterocyclic carbene‐containing metallacyclic units and monodentate chiral phosphines have been prepared. The key step of their synthesis is the intramolecular oxidative addition of N‐2‐iodobenzylimidazolylidene‐platinum(0)‐diene complexes in the presence of the chiral phosphorus ligands. The platinum(II) metallacycles have been used as well‐defined pre‐catalysts for the enantioselective cycloisomerization of nitrogen‐tethered 1,6‐enynes into 3‐azabicyclo[4.1.0]hept‐4‐enes. High enantiomeric excesses have been obtained with either Monophos or phenyl‐Binepine based catalysts (ees=82–96%), although phenyl‐Binepine outperforms Monophos in these reactions. The absolute configuration of the final 3‐azabicyclo[4.1.0.]heptenes has been established by X‐ray diffraction studies. The method has been extended then to the cycloisomerization of dienynes with enantiotopic vinyl groups. An (S)‐phenyl‐Binepine‐platinum(II) complex allows total diastereoselectivity and high enantioselectivity levels to be attained in these reactions (ees up to 95%) which represent the first enantioselective desymetrizations achieved via enyne cycloisomerizations.     

Novel building blocks for oligonuclear copper complexes derived from β‐ketoenamines of histidine

Condensation products of L‐histidine with the 3‐oxoenolethers diethyl‐ethoxymethylene‐malonate ( 1 ) and ethyl‐ethoxymethylene‐cyanoacetate ( 2 ) react with copper(II) as di‐anionic ligands to give neutral 1:1 complexes Cu‐ His1 and Cu‐ His2 . Both complexes crystallize as oligonuclear units, even from strongly donating solvents like N‐methylimidazole (Meim) (Cu‐ His1 ) and pyridine (Cu‐ His2 ). X‐ray structure analyses show supramolecular structures, formed of two (Cu‐ His1 ) or four (Cu‐ His2 ) formula units of the complex, which arrange to macrocycles by means of intermolecular coordination of the imidazole‐N. Strong H‐bridges result in a face‐to‐face orientation of the hydrophilic sites of two great rings. ESI‐MS investigations in pyridine solution give evidence for the existence of dimeric, tetrameric and – in case of Cu‐ His2 – trimeric units, besides the monomeric adducts with one pyridine. In contrast to the dimeric or tetrameric (“cubane‐like”) copper(II) complexes of amino alcohols and their β‐ketoenamines, the complexes Cu‐ His1 and Cu‐ His2 show no significant spin coupling from room temperature down to 4 K. The complexes Cu‐ His1 and Cu‐ His2 give no electrochemically reversible Cu^II/I reduction in pyridine. However, the isolation of a stable diamagnetic copper(I) complex of the methylester derivative, Cu^I‐ HisMe1 , supports the assumption, that similar histidine‐derived copper complexes should display reversible redox behaviour and catalytic activity in reactions with O₂.     

Cationic Ruthenium‐Cyclopentadienyl‐Diphosphine Complexes as Catalysts for the Allylation of Phenols with Allyl Alcohol; Relation between Structure and Catalytic Performance in O‐ vs. C‐Allylation

A new catalytic method has been investigated to obtain either O‐ or C‐allylated phenolic products using allyl alcohol or diallyl ether as the allyl donor. With the use of new cationic ruthenium(II) complexes as catalyst, both reactions can be performed with good selectivity. Active cationic Ru(II) complexes, having cyclopentadienyl and bidentate phosphine ligands are generated from the corresponding Ru(II) chloride complexes with a silver salt. The structures of three novel (diphosphine)Ru(II)CpCl catalyst precursor complexes are reported. It appears that the structure of the bidentate ligand has a major influence on catalytic activity as well as chemoselectivity. In addition, a strong cocatalytic effect of small amounts of acid is revealed. Model experiments are described that have been used to build a reaction network that explains the origin and evolution in time of both O‐allylated and C‐allylated phenolic products. Some mechanistic implications of the observed structure vs. performance relation of the [(diphosphine)RuCp]⁺ complexes and the cocatalytic role of added protons are discussed.     

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     

1H NMR,thermal, and conductivity studies on PVAc based gel polymer electrolytes

The lithium‐ion conducting gel polymer electrolytes (GPE), PVAc‐DMF‐LiClO₄ of various compositions have been prepared by solution casting technique. ¹H NMR results reveal the existence of DMF in the gel polymer electrolytes at ambient temperature. Structure and surface morphology characterization have been studied by X‐ray diffraction analysis (XRD) and scanning electron microscopy (SEM) measurements. Thermal and conductivity behavior of polymer‐ and plasticizer‐salt complexes have been studied by differential scanning calorimetry (DSC), TG/DTA, and impedance spectroscopy results. XRD and SEM analyses indicate the amorphous nature of the gel polymer‐salt complex. DSC measurements show a decrease in T_g with the increase in DMF concentrations. The thermal stability of the PVAc : DMF : LiClO₄ gel polymer electrolytes has been found to be in the range of (30–60°C). The dc conductivity of gel polymer electrolytes, obtained from impedance spectra, has been found to vary between 7.6 × 10^?7 and 4.1 × 10^?4 S cm^?1 at 303 K depending on the concentration of DMF (10–20 wt %) in the polymer electrolytes. The temperature dependence of conductivity of the polymer electrolyte complexes appears to obey the VTF behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nickel and copper removal study from aqueous solution using new cationic poly[acrylamide/N,N‐DAMB/N,N‐DAPB] super absorbent hydrogel

A new cationic poly[acrylamide/N,N‐diallyl morpholinium bromide/N,N‐diallyl piperidinium bromide] super absorbent hydrogels (H1–H7) were prepared via microwave irradiated free radical cyclopolymerization using different composition. By the swelling study, hydrogel H1 is found to bear good swelling properties amongst all prepared hydrogels. The hydrogel H1 has been characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscope (SEM), and TGA analysis. A batch system was applied to study the adsorption of Ni(II) and Cu(II) from aqueous solutions by hydrogel H1. The effect of treatment time, pH of the medium, amount of adsorbent doses, and initial feed concentration of metal ion on adsorption of Ni(II) and Cu(II) from their solution were also investigated. Adsorption of Ni(II) and Cu(II) increases with the increase in treatment time, adsorbent doses, and initial feed concentration and decreases with the increase in pH of the medium. The desorption of metal ions were carried out using 1N HCl and 0.5N H₂SO_4. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphological dependency of polymer electrolyte membranes on transient salt type: effects of anion species

Two types of transition metal salts, i.e. Cu(NO₃)₂ and CuCl₂, with different anion species were used to prepare various polyethersulfone‐based poly(N‐vinyl pyrrolidone) (PVP) composite membranes. The polymer crystallinity, strength of some of the bonds in the membrane structure and effects of anion species on the membrane morphology were investigated through X‐ray diffraction (XRD), scanning electron microscopy with energy‐dispersive X‐ray spectrometry (SEM‐EDX), Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy. The XRD results indicated an enhancement of the PVP crystallinity after addition of Cu(NO₃)₂. Moreover, addition of copper salt was accompanied by an increase of effective membrane distances. The FTIR analysis revealed that the nitrate ions might be better distributed than the other salt ions. The complexes created between them and carbonyl oxygens on the PVP chains were thus stronger. More powerful interactions caused a crystallinity enhancement following the addition of Cu(NO₃)₂. The SEM‐EDX experiment gave insight into the copper ion and carbonyl oxygen distributions in the membrane surface and active layer. The uniform distribution of copper ions resulted in a clear distribution of interchain interactions and complexes in the active layer structure and also caused structural order improvement. Copyright © 2010 Society of Chemical Industry     

Effect of the nature and degree of crosslinking on the catalase‐like activity of polystyrene‐supported schiff base‐metal complexes

Catalase‐like activity of the metal complexes of various crosslinked polystyrene‐supported Schiff bases were carried out and correlated with the nature and degree of crosslinking in the polymer support. Polystyrenes with 2–20 mol % ethyleneglycol dimethacrylate (EGDMA), 1,4‐butanediol dimethacrylate (BDDMA) and 1,6‐hexanediol diacrylate (HDODA) were used as polymer supports. functions of diethylenetriamine and salicylaldehyde were incorporated to the chloromethylpolystyrene by polymer analogous reactions and complexed with Fe(II), Fe(III), Co(II), Ni(II), and Cu(II) ions. The metal uptake decreased in the order: Cu(II) > Co(II) > Ni(II) > Fe(III) > Fe(II), and extent of metal uptake by the various crosslinked system varied with the nature and degree of the crosslinking agent. The polymeric ligands and the metal complexes were characterized by various analytical techniques. The catalytic activities of these metal complexes were investigated towards the decomposition reaction of hydrogen peroxide. Generally among the various metal complexes, the catalytic activities decreased in the order: Co(II) > Cu(II) > Ni(II) > Fe(III) ? Fe(II). With increasing rigidity of the crosslinking agent their catalytic activity also decreased. Of the various crosslinked systems, the catalytic activity decreased in the order: HDODA‐ > BDDMA‐ > EGDMA‐crosslinked system. Also, the catalytic activity is higher for low crosslinked systems and decreased further with increasing degree of crosslinking. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1271–1278, 2004     

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     

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