Synthesis, characterization, and properties of poly(2- and 3-aminophenol) and poly(2- and 3-aminophenol)-Cu(II) materials

Summary Poly(2-aminophenol) and poly(3-aminophenol) were synthesized from the respective monomers by using CuCl₂ × 2H₂O and ammonium persulfate as oxidizing agents in HCl(aq). The materials were characterized by FT-IR, X- ray electron spectroscopy (XPS), electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spectroscopy, elemental analysis, thermal stability, and electrical conductivity. The poly(2-aminophenol) presented a higher copper(II) content than that of poly(3-aminophenol), moreover as shown by ESR measurements, Cu appears homogeneously dispersed in the former, poly(2-amino phenol), while it seems not to be the case in the latter. The electrical conductivity did not depend on the conditions of synthesis as well as of the hydroxyl groups position. The results indicate that the polymers have several branched rings and their thermal stability increased by the presence of the copper ions into the polymer matrix. Received: 7 August 2002/Revised version: 8 November 2002/ Accepted: 12 November 2002 Correspondence to B. L. Rivas     

The Mechanism of Copper(II)-catalysed Polymerization of 2,4,6-Tribromophenols

The copper(II )-catalysed polymerization of 2,4,6-tribromophenol and 2,4,6-tribromo-3-methylphenol by homogeneous and heterogeneous reaction was studied. The dependence of polymer yield and molecular weight on reaction time was investigated. The variance of bromide ion concentration in the polymerization mixture was measured continuously by a bromide ion selective electrode. The existence of phenoxy radical during the homogeneous polymerization process was confirmed by electron spin resonance measurements. A quinol ether equilibrium polymerization mechanism was proposed for the copper(II)-catalysed homogeneous polymerization of 2,4,6-tribromophenols. © of SCI.     

Synthesis and characterization of poly(vinyl 2,4,6‐trinitrophenylacetal) as a new energetic binder

Poly(vinyl alcohol) was modified by an aldehyde acetal reaction with 2,4,6‐trinitrophenylacetaldehyde to give a new energetic polymer poly(vinyl 2,4,6‐trinitrophenylacetal) (PVTNP). The structure of PVTNP was characterized by elemental analysis, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, and nuclear magnetic resonance spectra. The glass‐transition temperature of PVTNP was evaluated by differential scanning calorimetry (DSC), and the thermal stability of PVTNP was tested by differential thermal analysis (DTA) and thermogravimetric analysis (TGA). DSC traces showed that the PVTNP polymer had one single glass‐transition temperature at 105.3°C. DTA and TGA curves showed that the thermooxidative degradation of PVTNP in air was a three‐step reaction, and the percentage of degraded PVTNP reached nearly 100% at 650°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

新型salamo衍生物苦味酸铜(Ⅱ)配合物的合成与表征

以丙酮为溶剂,1,3-二胺氧丙烷双缩邻香草醛(H2L)与苦味酸铜反应,制备了一种新型salamo衍生物苦味酸铜(Ⅱ)配合物,其结构经元素分析,1HNMR,IR,TG-DTA及UV表征。结果表明,新型salamo衍生物是一种四齿配体,配合物的可能结构式为[Cu4L2(pic)4(H2O)2].2CH3COCH3.2H2O。     

Recent developments in the radiation grafting of N‐vinyl‐2‐pyrrolidone onto low‐density polyethylene with cinnamonitrile derivatives

The radiation‐induced graft polymerization of N‐vinyl‐2‐pyrrolidone onto low‐density polyethylene films was conducted with γ radiation by a simultaneous technique. The grafted copolymer was modified with cinnamonitrile or benzylidene malononitrile. The modified and grafted films were amidoximated with hydroxylamine hydrochloride in a basic medium. However, during amidoximation, the benzylidene malononitrile was cyclized to yield isoxazole ring through an addition to the nitrile group in its structure, whereas the nitrile groups of cinnamonitrile were converted into amidoxime groups. The swelling behavior of the grafted copolymers and copolymers grafted and modified either with cinnamonitrile or benzylidene malononitrile was studied. Amidoximated and grafted films and copolymer–metal complexes of Cu(II) were prepared and characterized. The effect of the isoxazole ring on polymeric materials was also investigated. These films were characterized with different analysis techniques, such as infrared, ultraviolet (UV), elemental analysis, energy‐dispersive spectroscopy, and electron spin resonance (ESR). The UV and ESR analyses revealed that the geometric structure of Cu(II) was square‐planar. Scanning electron microscopy was used to examine the grafted and modified films to determine the changes in the surface morphology. Morphological changes clearly appeared for both complexed and isoxazole films because of the increase in their crystallinity. The thermal stability of different films was investigated with thermogravimetric analysis. The improvement of the copolymer by modification with cinnamonitrile derivatives showed great promise for some practical applications, such as metal recovery by complexation or the use of isoxazole in medicine. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1189–1197, 2005     

单核镍(Ⅱ)配合物的合成、表征和性质

报道了配体N ,N—二 (2—苯并咪唑甲基 )亚胺 (简写为IDB)及含镍 (Ⅱ )单核配合物 [Ni(IDB) 2 ]·Cl2 ·2CH3CH2 OH·2H2 O(Ⅰ )的合成 ,对 (Ⅰ )进行了元素分析、摩尔电导、紫外—可见光谱、红外光谱、自旋共振谱和循环伏安研究。推测配合物 (Ⅰ )的中心离子镍 (Ⅱ )为六配位八面体结构。     

ESR studies on the dimer formation between copper ions in the poly(vinylimidazole) · copper(II) complex

Summary ESR studies were made on the poly (vinylimidazole)· copper(II) complex in a lower magnetic field near 1600 gauss. The absorption in this region was observed for the poly(vinylimidazole) · copper (II) complex system while no absorption was present for the imidazole· copper (II) complex. The result was interpreted in terms of the dipolar interaction between copper (II) ions in the polymeric complex system, where the copper (II) ions were put together on the polymeric ligand in a highly condensed state.     

New polymeric Schiff base and its metal complexes

A novel polymeric Schiff base was synthesized by the reaction of a Schiff base from 2,4‐dihydroxy benzaldehyde and aniline with acryloyl chloride and was polymerized in methyl ethyl ketone at 70°C with benzoyl peroxide as a free‐radical initiator. Polychelates were obtained in an alkaline solution of poly(2‐hydroxy‐4‐acryloyloxy‐N‐phenylbenzylidine) with aqueous solutions of metal ions such as Cu(II), Ni(II), Co(II), Ca(II), Cd(II), Mn(II), and Zn(II). The polymeric Schiff base and polychelates were characterized with elemental analysis and spectral studies. The elemental analysis of the polychelates suggested that the metal‐to‐ligand ratio was 1:2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polychelates of the Cu(II) complex were square‐planar, those of the Ni(II), Mn(II), and Co(II) complexes were octahedral, and those of the Ca(II), Cd(II), and Zn(II) complexes were tetrahedral. X‐ray diffraction studies revealed that the polychelates were highly crystalline. The thermal properties of the Schiff base and polychelates were also examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 494–500, 2004     

Studies on CoSalen immobilized onto N‐(4‐methylimidazole)‐chitosan

A chitosan (CS) derivative, N‐(4‐methylimidazole)‐chitosan (MIC), was synthesized, and a cobalt (II) complex of bis(salicylideneethylene diamine), (CoSalen), was immobilized on it. The structure of the polymer‐immobilized CoSalen was characterized by elemental analysis, IR, XPS, fluorescence and ESR spectroscopy. It was demonstrated that the immobilization of CoSalen was realized through the coordination of a nitrogen atom of the pendant group, imidazole in MIC, to the Co(II) in CoSalen. The immobilized polymer complex is more efficient than the corresponding monomeric complex in catalyzing the oxidation of DOPA using oxygen. The results may be attributed to a site isolation effect offered by the supporting polymer chain. A mechanism similar to that for enzymatic catalysis was proposed. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2431–2436, 2006     

Synthesis and structure of copper-DMPLED complex,a bifunctional ligand with positive charged pyridine rings

N,N^′-bis(3-hydroxy-1,2-dimethyl-5-hydroxymethyl-4-pyridyl-methyl)ethylenediamine-N,N^′-diacetic acid, DMPLED and its copper complex has been synthesized and characterized with FAB-MS, elemental analysis and X-ray diffraction. The polyhedra of the Cu complex is described as a Jahn–Teller distorted octahedron with two axes elongated (Cu–O(1), Cu–O(4) are 2.481(4) and 2.676(4) Å, respectively). Cu–O(7), Cu–O(8), Cu–N(1) and Cu–N(2) are 1.914(4), 1.929(4), 1.998(6) and 2.019(5) Å, respectively.     

Characterization of plasticized maize starch/chitosan blends irradiated with an electron beam

Plasticized maize starch/Schiff base modified chitosan (PLST/MCS) blend films were prepared by solution casting and then irradiating to various doses using an electron beam. The effect of electron beam irradiation on the structure–property behavior of each blend was characterized by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), mechanical measurements, and scanning electron microscopy (SEM). PLST/MCS blends loaded with Cu(II) were also investigated using electron spin resonance (ESR) and infrared spectroscopy (FTIR). The results of thermogravimetric analysis (TGA), in terms of weight loss and rate of decomposition, indicated that the thermal stabilities of the PLST/CS blends were higher than that of pure PLST, particularly at >350 °C, which was thought to be due to a cyclization process upon ammonia removal. Electron beam irradiation slightly affected the thermal stability of the blends up to 50 kGy. The IR spectra indicated that there was a shift in the carbonyl bands upon the chelation of copper ion with the polymer. The IR spectra also exhibited a narrowing in the bands at 3600–3200 cm⁻¹ due to the coordination of the NH₂ and OH groups with copper ions. The ESR results revealed that Cu(II) uptake occurred through coordination with lone pairs of electrons on NH₂ and OH in PLST/CS blends.     

Synthesis,Characterization, Crystal Structure and Antimicrobial Evaluation of a Novel –M–X–M–X– Type Infinite Chain 1D Cu(II) Complex with Eflornithine Hydrochloride Hydrate as Ligand

A novel –M–X–M–X– type infinite chain 1D copper(II) complex of Eflornithine, Dichloro-[2-amino-5-ammonio-2-(difluoromethyl)pentanoate]copper(II) hydrate, [Cu(C₆H₁₂F₂N₂O₂)Cl₂]·H₂O 1 has been synthesized and characterized by elemental analysis, spectroscopic techniques (UV/Vis and FT-IR), TGA and X-ray diffraction. Single-crystal X-ray diffraction analysis of the complex 1 showed the structure to be monoclinic with space group Cc, a = 13.1295(15) Å, b = 12.1859(14) Å, c = 8.1927(9) Å, β = 118.359(3) Å, V = 1153.5(2) Å³, Z = 4. The complex exhibits a quadratic planar coordination of the Cu-atom. The Cu(II) centre is coordinated by two chloride atoms, an oxygen atom of the carboxyl- and a nitrogen atom of the amino-group, respectively, forming a quadratic planar geometry. The terminal amino group of the ligand is protonated to form NH₃ ⁺ while the carboxylic moiety is deprotonated to form Zwitterionic eflornithine ligand, with the coordination of the metal at the nitrogen atom of the second amino group. The compound has –M–X–M–X– infinite 1D chain polymeric structure. Two neigbouring Cu(EFL)Cl chain units are bridged by an Cl^? ion, forming a –Cu–Cl–Cu–Cl– linear chain structure along C-axis. The antibacterial activities of the complex on Escherichia coli (E. coli), Staphylococcus aureus (S. aureus) and Pseudomonas aeruginosa (P. aeruginosa) were investigated and found to be active at higher concentration than the parent ligand.     

Syntheses and structures of a phenoxo-bridged copper(II) distorted cubane and related complexes with 2-hydroxy-N-(2-pyridylalkyl)benzamide ligands

Two new pyridylalkylamide ligands containing phenol groups appended to the amide, 2-hydroxy-N-(2-pyridylmethyl)benzamide (HL^PhOH) and 2-hydroxy-N-(2-pyridylethyl)benzamide (HL^PhOH′), were synthesized. Copper(II) complexes of these ligands were synthesized and characterized by X-ray crystallography, ESI-MS, FTIR, UV/Vis, and EPR spectroscopy. When basic Et₃N was used to deprotonate the ligands, tetracopper(II) [Cu₄(L^PhO)₄] (1) or dicopper(II) [Cu₂(L^PhO′)₂(CH₃OH)₂] (3) were formed. When base was not used, mononuclear [Cu(HL^PhOH)₂Cl₂] (2) resulted. Complex 1 possesses a distorted cubane-like structure, with the ligands bridging via the phenoxo oxygen atoms, and the copper atoms possessing a distorted square planar geometry. The ligands in dimeric complex 3 also bridge between copper(II) atoms via the phenoxo oxygen atoms, and the copper atoms are square pyramidal. Monomeric 2 is a tetragonally distorted six-coordinate species with pyridyl N atoms and chloride ligands in the equatorial plane, and long interactions with the amide carbonyl O atoms in the axial positions.     

Effect of N‐methylimidazole and 3,5‐dimethylpyrazole ligands on the polymerization of di(2,6‐dichlorophenolato) Cu(II)/Co(II) complexes in the solid state

The polymerization of 2,6‐dichlorophenol (DCPH) was achieved through the thermal decomposition of copper complexes of DCPH with N‐methylimidazole (NMIz) and 3,5‐dimethylpyrazole (DMPz) ligands. Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), mass spectrometry, ultraviolet–visible spectroscopy, diffuse reflectance spectroscopy, magnetic susceptibility balance, electron spin resonance, X‐ray analysis, and elemental analysis were used to characterize the complexes. The polymerization was achieved either in the solid state or in the melt. The structural analyses were performed with FTIR and NMR spectroscopy analyses. The glass‐transition temperatures were determined by DSC, and the intrinsic viscosities were determined by viscosimetry. The effects of the temperature and time on the conversion percentage and viscosity of the polymers were examined. Varying the decomposition temperature during a 3‐h scan showed that the DMPz complex of Cu decomposed at lower temperatures than the NMIz complex, whereas the NMIz complex yielded a higher conversion to the polymer. Complexes of DCPH with NMIz and DMPz ligands produced 1,2‐ and 1,4‐addition products, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3797–3805, 2004     

Synthesis,Characterization, and Applications of a New Chelating Resin Containing 4-2-(Thiazolylazo) Resorcinol (TAR)

A new phenol–formaldehyde based chelating resin containing 4-(2-thiazolylazo) resorcinol (TAR) functional groups has been synthesized and characterized by Fourier transform infrared spectroscopy and elemental analysis. Its adsorption behavior for Cu(II), Pb(II), Ni(II), Co(II), Cd(II), and Mn(II) has been investigated by batch and column experiments. The chelating resin is highly selective for Cu(II) in the pH range 2 ～ 3, whereas alkali metal and alkaline earth metal ions such as Na(I), Mg(II), and Ca(II) are not adsorbed even at pH 6. Quantitative recovery of most metal ions studied in this work except Co(II) is achieved by elution with 2M HNO₃ at a flow rate of 0.2 mL min^?1. A similar trend is observed for distribution coefficient values. The quantitative separations achieved on a mini-column of chelating resin include Cd(II) – Cu(II), Mn(II) – Pb(II), Co(II) – Cu(II), Mn(II) – Ni(II), and Mn(II) – Co(II) – Cu(II). The recovery of copper(II) is quantitative (98.0–99.0%) from test solutions (10–50 mg/L) by 1 mol/L HNO₃-0.01 mol/L EDTA. The chelating resin is stable in acidic solutions below 2.5 M HNO₃ or HCl as well as in alkaline solution below pH 11. The adsorption behavior of the resin towards Cu(II) was found to follow Langmuir isotherm and second order rate.     

Synthesis and characterization of novel aromatic poly(benzimidazole-amide)/Ag and Cu nanocomposites through transition metal complexation

A new thermally stable aromatic poly(benzimidazole-amide)s PBIAs was synthesized by low-temperature polycondensation of bis-benzimidazole diamines; 1,4-bis(5-amino-1H-benzimidazol-2-yl)benzene (3a) and 1,3-bis(5-amino-1H-benzimidazol-2-yl)benzene (3b) with two different diacid chlorides. Diamines 3a and 3b were prepared via direct condensation of 1,2-phenylene diamine and terephthalic or isophthalic acid in polyphosphoric acid in high yield. Chemical structures of synthesized monomers were confirmed by elemental analyses and spectroscopic methods. The structures of synthetized polymers were confirmed by FT-IR, ¹H-NMR, elemental and thermogravimetric analysis (TGA), X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). Thermal stability of the polymers was ascertained via 10 % weight loss temperatures in the range of 315–380 °C (inert atmosphere). Existence of benzimidazole moieties in polymer’s structure makes them suitable for easy coordination to Lewis acids or metallic ions, whereas the substitution of C–H or N–H protons allows for the synthesis of complex derivatives. As a result, a series of novel nanocomposites, via metal complexation of PBIA6a due to their great solubility with Ag⁺ or Cu²⁺ cations followed by reduction to metals by sodium borohydride (NaBH₄), was prepared. The resulting nanocomposites’ structures were confirmed by FT-IR, XRD, TGA, UV/vis, FE-SEM, TEM and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM–EDX). The FE-SEM, TEM and SEM–EDX results indicated that Cu and Ag particles were dispersed homogenously in nano scale in the polymer matrix.     

Simultaneous novel synthesis of conducting,nonconducting, and crosslinked polymers by microwave initiation

A novel synthesis of poly(dibromophenylene oxide) (P), conducting polymer (CP), and/or crosslinked polymer (CLP), and/or radical ion polymers (RIP) was achieved simultaneously from sodium 2,4,6‐tribromophenolate by microwave energy in a very short‐time interval. The synthesized polymers were characterized via elemental analysis, FTIR, ¹H NMR and ¹³C NMR, X‐ray diffraction spectroscopy, SEM, DSC, TGA, ESR, GPC, conductivity measurement, and light scattering. It was found that polymerization proceeds through both 1,2‐ and 1,4‐addition at equal rates. The effects of the energy and time on the % conversion and the polymer synthesis were investigated. The optimum condition for synthesis of P (the highest M_w, 2.97 × 10⁵ g/mol) and CP was 70 W for 5 min in 5 mL water and 100 W for 1 min in 0.5 mL water, having maximum values 23.6% and 27.2%, respectively. In addition, synthesis of CLP and RIP were achieved in 5 mL water at 350 W and 700 W at the end of 1 min, respectively. The direct synthesis of highly conducting polymer, with the conductivity of 1 S cm^?2 was achieved in the absence of applied doping process in a very short time sequence. P, CP, CLP, and RIP had fine granular, sponge‐like, dendrite, and coarse surface structures, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5427–5435, 2006     

Copper Ion Extraction by a Mixture of Fatty Hydroxamic Acids Synthesized from Commercial Palm Olein

Abstract

A mixture of fatty hydroxamic acids (FHA), synthesized from a commercial palm olein, was evaluated as an extractant for extraction of copper ion from aqueous media. The content of hydroxamic acid groups in the FHA, analyzed by elemental analysis, was 3.52 mmol/g. Copper extraction from aqueous media was studied by solvent extraction technique using octanol as an organic phase. The extraction of copper ion was through the formation of 1∶2 (Cu(II)∶FHA) complex, pH dependent and not affected by the presence of a large amount of Co(II), Ni(II), Cd(II) and Zn(II) ions.     

Separation and Recovery of Silver(I) Ions from Base Metal Ions by Melamine‐formaldehyde‐thiourea (MFT) Chelating Resin

Abstract

Melamine‐formaldehyde‐thiourea (MFT) chelating resin were prepared using melamine (2,4,6‐triamino‐1,3,5‐triazine), formaldehyde, and thiourea and this resin has been used for separation and recovery of silver(I) ions from copper(II) and zinc(II) base metals and calcium(II) alkaline‐earth metal in aqueous solution. The MFT chelating resin was characterized by elemental analysis and FT‐IR spectra. The effect of pH, adsorption capacity, and equilibrium time by batch method and adsorption, elution, flow rate, column capacity, and recovery by column method were studied. The maximum uptake values of MFT resin were found as 60.05 mg Ag⁺/g by batch method and 11.08 mg Ag⁺/g, 0.052 mg Zn²⁺/g, 0.083 mg Cu²⁺/g and 0.020 mg Ca²⁺/g by column method. It was seen that MFT resin showed higher uptake behavior for silver(I) ions than base and earth metals due to chelation.     

Investigation of novel polytriazole resins

2,4,6-Tri(4-propargyloxy-phenyl)pyridine(POPP) was made from 2,4,6-tri (4-hydroxyphenyl)pyridine(HPP) and propargyl bromide. The chemical structures of POPP and HPP were well characterized by means of FTIR, ¹H-NMR, ¹³C-NMR, and elemental analysis. Novel polytriazole resins (P-PTA resins) were prepared from POPP and azide compounds via 1, 3-dipolar cycloaddition reaction and characterized by solubility, FTIR, DSC, and TGA analyses. The P-PTA resins show good solubility in common solvents. The resins could be cured at 80 °C. The glass transition temperature (T_g) and the 5% weight loss temperature (T_d5) of the cured P-PTA-33 resin arrive at 310 and 365 °C in nitrogen atmosphere, respectively.