金属离子印迹聚合物的研究进展

金属离子印迹聚合物因其可实现自身的印迹,可用于环境重金属污水处理;通过金属离子与生物大分子的螯合配位作用,实现对药物、蛋白质等生物大分子的印迹,在环境分析和生物医药领域有着广泛的应用前景.本文着重介绍了离子印迹聚合物的来源、制备原理、制备条件的优化和选择、制备方法及其应用.     

Equilibrium and kinetics of heavy metal ion exchange

Ion exchange has a great potential to remove heavy metals from industrial wastewaters or heavy metal-containing sludge. In order to design and operate heavy metal removal processes, the equilibrium relationship between ions and resin must be known a prior. A series of ion-exchange equilibrium tests of Cu²⁺/H⁺, Zn²⁺/H⁺, and Cd²⁺/H⁺ systems using Amberlite IR-120 were performed. The equilibrium data were analyzed by the Langmuir isotherm, Freundlich isotherm, and selectivity coefficient approaches. The thermodynamic parameters such as Gibbs free energy change, enthalpy change, and entropy change were calculated. By comparison of the selectivity coefficients, the affinity sequence to IR-120 is Cu²⁺ > Zn²⁺ > Cd²⁺ > H⁺. Moreover, in order to understand the heavy metal extraction kinetics in the presence of Amberlite IR-120, the ion-exchange kinetics was also studied. The ion-exchange kinetic data were regressed by the pseudo first-order, second-order models, and a reversible reaction model. The activation energies calculated from the rate coefficients at different temperatures are 15.41, 7.04, and 17.01 kJ/mol for copper, zinc, and cadmium, respectively. Although the pseudo first- and second-order models are easier to use for data analysis, the resultant model parameters depend on operating conditions. The reversible reaction model is capable to predict the effects of resin to solution ratio, initial heavy metal concentration, and temperature on the ion-exchange kinetic curves.     

N,N′-methylene-bis-acrylamide-crosslinked polyacrylamides as supports for dithiocarbamate ligands for metal ion complexation

The complexation behaviour of dithiocarbamate functions supported on polyacrylamides with varying extents (2-20 mol%) of N,N′-methylene-bis-acrylamide (NNMBA) crosslinks was investigated. The crosslinked polyacrylamides were prepared by the free radical solution polymerization of the monomers in water at 80°C using potassium persulphate as initiator. The dithiocarbamate ligands were introduced by polymer-analogous reaction involving transamidation with ethylenediamine and dithiocarbamylation with carbon disulphide and alkali. The complexation behaviour of these dithiocarbamate resins with the ligand functions in different macromolecular environments were investigated towards Co(II), Ni(II), Cu(II), Zn(II) and Hg(II) ions by a batch equilibration technique. The metal ion intake varied with the extent of the NNMBA-crosslinking. Thus the 8% crosslinked system has the highest complexation capacity. The values for metal ion intake followed the order Hg(II)> Cu(II)> Zn(II)> Ni(II)> Co(II). The time-course of complexation, the possibility of recycling and the swelling characteristics of the uncomplexed and complexed resins were considered, and IR characterization and thermal studies were undertaken. The swelling values of the complexed resins are lower than those of the uncomplexed resins. The thermal stability of dithiocarbamates varied with the extent of NNMBA-crosslinks and with the metal ion.     

Effect of hydrogen‐bonding in the development of high‐affinity metal ion complexants: Polymer‐bound phosphorylated cyclodextrin

In a series of phosphorylated polyols bound to a polystyrene support, the position of the FTIR band assigned to hydrogen bonding between the  OH and phosphoryl oxygen correlates with the affinity of that phosphoryl oxygen for metal ions. Polymer with phosphorylated β‐cyclodextrin (pCD) ligands is now reported as a further test of this correlation. The metal ion affinity is probed with the uranyl ion. pCD is the most red‐shifted of a series of five phosphorylated polyols: the strongest polyol had been phosphorylated pentaerythritol (pPE) with a band at 873 cm⁻¹; pCD has a band at 868 cm⁻¹. Consistent with the FTIR bands, pCD has a significantly higher affinity for the uranyl ion than pPE: the percents complexed from a 10⁻⁴M uranyl solution in a background of 1.0N HNO₃, HCl, and H₂SO₄ are 94.7%, 90.5%, and 93.6%, respectively, for pCD and 68.6%, 52.1%, and 40.1%, respectively, for pPE. This further supports the hypothesis that the strong complexing ability of phosphorylated polyols is due to activation of the phosphoryl oxygen through hydrogen bonding between the PO and the  OH groups within the polyol. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Heavy metal removal by ion exchanger based on hydroxyethyl cellulose

In the present work, ion exchange resin based on hydroxyethyl cellulose has been synthesized to remove the heavy metals, such as iron, cobalt, copper, and zinc from their aqueous solutions. The conditions in the column and batch modes were investigated for this purpose. The resin, having an average swelling percentage of 75.94 and an exchange capacity of 2.57 meq g⁻¹ resin, is being introduced as a new ion exchange resin in the heavy metal removal process. An investigation of the column operations using aqueous solutions of heavy metal ions indicated that the resin prepared has some advantages, including high total exchange capacity and good chemical stability. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3501–3506, 1999     

Preparation and metal ion adsorption properties of the resin containing sulfonic acid groups

In this study, we explored a new ion exchange material synthesized by radical polymerization of styrene and 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid by using 2,2′‐azo‐isobutyronitrile (1 mol %) and divinylbenzene (0.5 mol %) as initiator and crosslinking reagents, respectively. The resin was obtained from a large excess (90%) of styrene in the feed. The yield was 72.3%. The resin was completely insoluble in water and characterized by elemental analysis, FTIR spectroscopy, scanning electron microscopy, and thermal analysis. The metal ion retention capability was investigated for Ag(I), Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III). The effect of pH, time, and resin/metal ion mol ratio on the metal ion retention was studied. Selectivity of the resins from a mixture of metal ions and the maximum retention capacity at optimum pH were also determined. The recovery of the resin by using 1 and 4 M HClO₄ and HNO₃ demonstrated that it is possible to recover the resin above 80%. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1230–1235, 2003     

Kinetics of metal ion exchange in iminodiacetic resins at low concentrations

The kinetics of metal exchange processes with iminodiacetic chelating resin, which occurs with metal concentration change, has been studied. Mechanisms of rate control were analyzed, and diffusivities determined from experiments in batch solutions with decreasing metal concentrations, following the unreacted core model. Metal exchange in binary and ternary systems are analyzed and diffusivity variations of these systems discussed in terms of reaction fronts. The influence of temperature was also studied and energies of activation determined.     

A new functionalized reduced graphene oxide adsorbent for removing heavy metal ions in water via coordination and ion exchange

ABSTRACT

Heavy metal ion pollution has become a serious problem. In this paper, a new type of adsorbent, reduced graphene oxide grafted by 4-sulfophenylazo groups (RGOS), was synthesized to adsorb heavy metal ions in an aqueous solution via two kinds of adsorption modes, ion exchange and coordination. The maximum adsorption capacities of the RGOS for Pb(II), Cu(II), Ni(II), Cd(II) and Cr(III) were 689, 59, 66, 267 and 191 mg/g, respectively. Adsorption equilibrium time of RGOS for heavy metal ions is no more than 10 min. Adsorption mechanism was supposed based on elemental analyses, adsorption data, and Fourier transform infrared spectra.     

树脂吸附结合还原络合法去除盐酸中的铁离子

研究D201强碱性阴离子交换树脂（Cl型）吸附结合还原络合法进行盐酸除铁离子精制的过程,最佳试验条件为：采用D201强碱性阴离子交换树脂（Cl型）,还原剂硫代硫酸钠加入量1%（相对树脂质量,下同）,螯合剂EDTA加入量0.5%;在该条件下进行盐酸除铁离子精制,铁离子质量浓度降至0.1 mg/L以下。     

Synthesis and adsorption properties of magnetic resin microbeads with amine and mercaptan as chelating groups

Three magnetic chelating resins containing amino and mercapto groups were prepared by the suspended condensation polymerization of 2‐chloroethoxymethyl thiirane with diamines. The magnetic resins were microbeads whose diameter was in the range of 10 to 45 μm. The structure of the resins was characterized by XPS, IR, and elemental analysis. Their adsorption properties for Hg(II), Au(III), Pd(II), Pt(IV), Ag(I), Cu(II), Zn(II), and Pb(II) were investigated. The experimental results show the magnetic resins have high affinity for Hg(II) and noble metal ions. In the competitive adsorption, the resins predominantly adsorbed Hg(II) or Pd(II) in the coexistence of Cu(II), Zn(II), and Mg(II). Desorption of Pd(II) loaded on the resins was studied by using 2M hydrochloric acid solution containing 1% thiourea as desorbent. A high desorption ratio (up to 96.5%) was observed, and repeated adsorption/desorption operations showed the probability of repeated use of the magnetic resins. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1587–1592, 2001     

Study of ion solvation and ion association in polymer gel electrolyte with polyethylene oxide-co-polypropylene oxide as a plasticizer

Using a molal conductance method, ion solvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)–LiClO₄ gel electrolytes with amorphous ethylene oxide-co-propylene oxide (EO-co-PO, M̄_n = 1750) as the plasticizer were investigated. It was found that the fraction of solute existing as single ions (α_i) and ion pairs (α_p) decreases, while that of triple ions (α_t) increases linearly with increasing salt concentration. The dependence of these fractions on molecular weight of plasticizer was also examined. It was shown that α_i and α_t increase and α_p decreases with increasing molecular weight. The result of temperature dependence of these fractions was very interesting: when the temperature is lower than 55°C, α_i increases while α_p and α_t decrease with increasing temperature; however, when the temperature is higher than 55°C, the reverse is true.     

Synthesis of new chelating ion exchange resin with hydroxamic and amidoxime groups and study of its metal binding property

The synthesis of a new chelating ion exchanger with hydroxamic and amidoxime groups was performed by an aminolysis reaction of an ethylacrylate/acrylonitrile/divinylbenzene copolymer with hydroxylamine in the presence of sodium ethoxylate. We studied the retention property of the new resin for Pb(II), Cd(II), Cu(II), Ni(II), Zn(II), Mn(II), and Fe(III) metal cations from aqueous solutions. The retention capacity depends on the contact time, the pH of the solution, and the types of counterions of the metal cations. Competitive adsorptions of Pb(NO₃)₂ + Fe₂(SO₄)₃, Pb(NO₃)₂ + MnSO₄, Pb(NO₃)₂ + Cd(NO₃)₂, and Pb(NO₃)₂ + CuCl₂ on the new chelating ion exchanger were performed. The results showed that the resin preferentially retained the Pb(II) ions from the binary aqueous mixtures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2956–2962, 2003     

Ion exchange of alkali metal cations with an inorganic resin

A comparison of the ion exchange properties of the inorganic resin Isolute SCX-2 with alkali metal cations, including francium, to the organic Dowex 50X8 resin is presented. The purpose of this study was to investigate the ion exchange properties of the alkali metal cations with a resin containing a less hydrophobic backbone structure. It was found that the less hydrophobic Isolute SCX-2 resin had a smaller range of values for the distribution coefficients when exchanged with the alkali metals than Dowex 50X8.     

Preparation and characterization of silanized silica gel‐supported poly(acrylic acid) network polymer and study of its analytical application as selective extractor for lead ion

A novel silanized silica gel (SSG)‐supported poly(acrylic acid) network polymer (ion exchanger) has been synthesized and characterized for the study of its analytical applications. The chemical nature of the ion exchanger has been elucidated with the help of FTIR, NMR, TGA, DSC, and SEM. The immobilization of the polymer network on SSG has been studied. The optimum pH range for quantitative extraction of lead was found to be 4.5–6.0. The effects of pH and stripping agent on extraction and elution of Pb(II), respectively, have been investigated. Ion exchange and break through capacity of the exchanger have been determined at room temperature. Pb(II) has been extracted quantitatively from various environmental samples. A plausible mechanism for lead ion exchange has been suggested. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A study of the synthesis,kinetics, and characterization of reactive graft copolymers of poly(vinyl imidazole) and cellulose for use as supports in enzyme immobilization and metal ion uptake

In continuation to our earlier work to use bioresource for developing alternate materials for use at the interface of biotechnology and polymer science, we have utilized pine needles as a renewable stock of cellulose to synthesize graft copolymers of vinyl imidazole. Kinetics of N‐VIm by simultaneous γ‐irradiation method has been investigated as a function of total dose, monomer concentration, and amount of water. Effect of water–methanol solvent composition on graft yields and polymerization kinetics has also been studied at the optimum grafting conditions of the total dose and monomer concentration. Effect of some additives such as ZnCl₂, Mohr salt, tetramethylethylene diamine, potassium persulfate, ammonium persulfate as grafting accelerators and promoters has also been studied. Graft copolymers have been characterized by elemental analysis, FTIR, and swelling studies. The graft copolymers have been used as supports for metal ions sorption, enzyme immobilization, and as potential biomimicking catalysts. Sorption behavior of Fe²⁺ ions and Cu²⁺ ions and the immobilization of bovine serum albumin and protease as a function of graft yield has been reported. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1522–1530, 2006     

Poly (styrene sulfonamides) with EDTA‐like chelating groups for removal of transition metal ions

Chlorosulfonated styrene–divinyl benzene (10%) resin beads (420–590 μm), when treated with an excess of triethylene tetramine (TETA), give a corresponding polymeric sulfonamide with three amine functions. The free amine functions of the resin were carboxymethylated almost quantitatively by reacting with 20% excess of potassium chloroacetate in aqueous solution. The resulting resin with iminoacetic acid functions showed rapid chelating abilities for transition metal ions such as Zn (II), Cd (II), Cu (II), Ni (II), Co (II), and Fe (III) ions. At the neutral pHs the chelating resin was able to reduce the metal ion concentrations lower than 1 ppm in about 15 min of the contacting time. Interestingly, when the resin was used in sodium form, metal binding capacities were higher than the theoretical capacity (1.66 mmol · g⁻¹), due to simultaneous precipitation of the transition metal hydroxides on bead particles. The resin samples loaded with metal ions can be regenerated more than 10 times by simple acid‐base treatments, without activity loss. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2749–2755, 2000     

Studies on syntheses and permeabilities of special polymer membranes: 50. Transport of metal ions against their concentration gradient through water-insoluble poly(styrene sulphonic acid) membrane

Water-insoluble cation exchange membranes were prepared by heat treating membranes made of poly(styrene sulphonic acid) and poly(vinyl alcohol). Transport of metal ions through the above cation exchange membrane against their concentration gradient was investigated under various conditions. The transport in this system, where one side of the membrane in a diaphragm cell was acidic and the other alkaline, was influenced significantly by the initial H⁺ ion concentration on the acidic side. The selectivity of metal ions in diffusive transport depended on the size of their hydrated ions and that in transport against their concentration gradient was due to the affinity between the metal ions and the carrier fixed to the membrane.     

Synthesis,characterization, and metal‐ion uptake studies of chelating resins derived from formaldehyde‐condensed azodyes of aniline and 4,4′‐diaminodiphenylmethane coupled with phenol/resorcinol

The diazonium salts of aniline and 4,4′‐diaminodiphenylmethane coupled with phenol and resorcinol were condensed with formaldehyde in alkaline media to yield polymeric resins. These polymers were found to readily react with metal ions like Cu²⁺ and UO, forming polychelates. The azodyes, resins, and polychelates were characterized by several instrumental techniques such as elemental analysis, FTIR, ¹H‐NMR, GPC, XRD, TG–DTG, and DSC studies. The chelating capacity of the resins toward Cu²⁺ and UO ions was studied by spectrophotometry. The extent of metal loading of the resins was studied by varying the time of contact, metal‐ion concentration, and pH of the reaction medium. The alkali and alkaline earth metal ions had little effect on the metal‐ion uptake behavior of the resins. The resin derived from the azodye of 4,4′‐diaminodiphenylmethane was found to be more efficient in removing the metal ions from solution than were the resins from aniline. The optimum conditions for effective separation of Cu²⁺ from UO were determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3128–3141, 2000