Redox Sorption and Recovery of Silver Ions as Silver Nanocrystals on Poly(aniline‐co‐5‐sulfo‐2‐anisidine) Nanosorbents

Poly[aniline(AN)‐co‐5‐sulfo‐2‐anisidine(SA)] nanograins with rough and porous structure demonstrate ultrastrong adsorption and highly efficient recovery of silver ions. The effects of five key factors—AN/SA ratio, Ag^I concentration, sorption time, ultrasonic treatment, and coexisting ions—on Ag^I adsorbability were optimized, and AN/SA (50/50) copolymer nanograins were found to exhibit much stronger Ag^I adsorption than polyaniline and all other reported sorbents. The maximal Ag^I sorption capacity of up to 2034 mg g^?1 (18.86 mmol g^?1) is the highest thus far and also much higher than the maximal Hg‐ion sorption capacity (10.28 mmol g^?1). Especially at ≤2 mM Ag^I, the nanosorbents exhibit ≥99.98 % adsorptivity, and thus achieve almost complete Ag^I sorption. The sorption fits the Langmuir isotherm well and follows pseudo‐second‐order kinetics. Studies by IR, UV/Vis, X‐ray diffraction, polarizing microscopy, centrifugation, thermogravimetry, and conductivity techniques showed that Ag^I sorption occurs by a redox mechanism mainly involving reduction of Ag^I to separable silver nanocrystals, chelation between Ag^I and ? NH? /? N?/? NH₂/ ? SO₃H/? OCH₃, and ion exchange between Ag^I and H⁺ on ? SO₃^?H⁺. Competitive sorption of Ag^I with coexisting Hg, Pb, Cu, Fe, Al, K, and Na ions was systematically investigated. In particular, the copolymer nanoparticles bearing many functional groups on their rough and porous surface can be directly used to recover and separate precious silver nanocrystals from practical Ag^I wastewaters containing Fe, Al, K, and Na ions from Kodak Studio. The nanograins have great application potential in the noble metals industry, resource reuse, wastewater treatment, and functional hybrid nanocomposites.     

Phosphorylated polyacrylonitrile‐based electrospun nanofibers for removal of heavy metal ions from aqueous solution

The phosphorylated polyacrylonitrile‐based (P‐PAN) nanofibers were prepared by electrospinning technique and used for removal of Cu²⁺, Ni²⁺, Cd²⁺, and Ag⁺ from aqueous solution. The morphological and structural properties of P‐PAN nanofibers were characterized by scanning electron microscope and Fourie transform infrared spectra. The P‐PAN nanofibers were evaluated for the adsorption capacity at various pH, contact time, and reaction temperature in a batch system. The reusability of P‐PAN nanofibers for the removal of heavy metal ions was also determined. Adsorption isotherms and adsorption kinetics were also used to examine the fundamental adsorption properties. It is found that the P‐PAN nanofibers show high efficiency, and the maximal adsorption capacities of metal ions as calculated from the Langmuir model were 92.1, 68.3, 14.8, and 51.7 mg/g, respectively. The kinetics of the heavy metal ions adsorption were found to follow pseudo‐second‐order rate equation, suggesting chemical adsorption can be regarded as the major factor in the adsorption process. Sorption/desorption results reveal that the obtained P‐PAN nanofibers can remain high removal efficiency after four cycles.     

Uranium and lead adsorption onto bentonite and zeolite modified with polyacrylamidoxime

Polyacrylonitrile (PAN) and bentonite (B)/zeolite (Z)-PAN composites were prepared by direct polymerization of acrylonitrile (AN) and AN adsorbed onto B and Z. PAN and the composites were subjected to amidoximation procedure to obtain polyacrylamidoxime (PAO), B-PAO and Z-PAO compositions. The structural features were evaluated by FT-IR, XRD and SEM analysis. The adsorption dependency of the materials on ion concentration, temperature and time were investigated for Pb²⁺ and UO₂ ²⁺. The adsorption capacities of B/Z-PAO composites were higher than those of pure PAO. The values of enthalpy and entropy changes were positive. The kinetics of the adsorption was well defined by the pseudo second order rate model. For the use of 1 M HCl as a regenerative effluent, the composites were reusable for five sequential treatments without any change in their structures whereas PAO completely gelled in the first use.     

Mesoporous hollow silicon spheres modified with manganese ion sieve: Preparation and its application for adsorption of lithium and rubidium ions

In this work, mesoporous hollow silicon spheres modified with 3‐aminopropyl‐ triethoxysilane (APTES) of loaded hydrogen manganese oxide lithium ion sieve (APTES/HMO‐ HS) was prepared. The structure and morphology of as‐prepared APTES/HMO‐HS were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray photoelectron spectroscopy, transmission electron microscopy and nitrogen adsorption‐desorption measurements. The Brunner‐Emmet‐Teller (BET) surface areas, pore diameters and pore volumes of APTES/HMO‐HS decreased gradually, while the Li:Mn:Si molar ratios range from 1:1:50 to 1:1:10. The obtained hierarchical porous APTES/50HMO‐HS has a high specific surface area (557.1694 m² g^‐1). The lithium and rubidium ions solutions were used to measure the adsorption performance of the APTES/HMO‐HS adsorbent. The pseudo‐first‐order and pseudo‐second‐order kinetics, Langmuir and Freundlich isotherms of APTES/HMO‐HS were investigated; suggesting that the adsorption kinetics can be described by the pseudo‐second‐order kinetic model and the adsorption isotherms well fits the Langmuir isotherm equation. The obtained results show that the prepared APTES/HMO‐HS exhibits excellent abilities to simultaneously and selectively recover Li⁺ and Rb⁺ (11.22 mg·g^‐1 and 8.31 mg·g^‐1) and have a promising application in the simultaneous adsorption of lithium and rubidium ions.     

Atom transfer radical polymerization with activators regenerated by electron transfer of acrylonitrile from silica nanoparticles,and adsorption properties of the resin for Hg2+ after amidoximation with hydroxylamine

Polyacrylonitrile (PAN) was grafted from surfaces of chloro‐modified silica‐gel with their surface chlorines as initiation sites, using an iron (III)‐mediated surface‐initiated atom transfer radical polymerization (ATRP) with activators regenerated by electron transfer (SI‐ARGET ATRP) method. The graft reaction exhibits first‐order kinetics with respect to the polymerization time in the low‐monomer‐conversion stage. The conversion of monomer (C%) and the percentage of grafting (PG%) increased with increasing of the polymerizing time and reached 23 and 730% after a polymerizing time of 24 hr, respectively. Hydroxylamine (NH₂OH·HCl) was used to modify the cyano groups of SG‐g‐PAN to obtain amidoxime (AO) groups. The AO SG‐g‐PAN was used to remove Hg²⁺. The adsorption kinetics indicated that the pseudo‐second‐order model was more suitable to describe the adsorption kinetics of AO SG‐g‐PAN for Hg²⁺. The adsorption isotherms demonstrated that Langmuir model was much better than Freundlich model to describe the isothermal process. Copyright © 2010 John Wiley & Sons, Ltd.     

A Dual‐Surface Amidoximated Halloysite Nanotube for High‐Efficiency Economical Uranium Extraction from Seawater

By chemical cross‐linking the amidoxime group onto dual‐surfaces of natural ore materials, namely halloysite nanotubes (HNTs), an efficient adsorbent, AO‐HNTs, is developed. AO‐HNTs show high uranium adsorption capacity of 456.24 mg g^?1 in 32 ppm uranium‐spiked simulated seawater. In natural seawater, AO‐HNTs reach the high uranium extraction capacity of 9.01 mg g^?1 after 30 days’ field test. The dual‐surface amidoximated hollow nanotubular AO‐HNTs exhibit more coordination active sites for uranium adsorption, which is attributed to the high and fast uranium adsorption capacity. Because of the stable natural ore structure, AO‐HNTs also show long service life. Benefiting from the low cost of HNTs, the cost for uranium extraction from seawater is close to the uranium price in the spot uranium market, suggesting that AO‐HNTs could be used for economical extraction of uranium from the oceans.     

Chemical treatments on the cuticle layer enhancing the uranium(VI) uptake from aqueous solution by amidoximated wool fibers

Urea, sodium hydroxide and sodium sulfide were used to treat the cuticle layer of wool before graft copolymerization and amidoximation to enhance the uranium uptaking capacity of amidoximated wool fiber based adsorbent (Wool-g-AOs). The wool-g-AOs were used for recovery of U(VI) from aqueous solutions. The simulated nuclear industry effluent was used for investigating the selectivity and industrial applicability of Wool-g-AOs. The adsorption of uranium(VI) on Wool-g-AOs was pH dependent. The Langmuir model fitted well with the equilibrium data. Kinetic data were fitted well to pseudo second order model.

     

A novel green biosorbent from chitosan modified by sodium phytate for copper (II) ion removal

A novel kind of adsorbent bead was prepared from chitosan (CS) by ionic‐linked with sodium phytate (SP) and then covalent cross‐linked with epichlorohydrin (ECH) by nonsolvent‐induced phase separation. The structure of the beads was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The adsorption properties of the beads for Cu(II) ions under different adsorption conditions were investigated. The maximum adsorption capacity of Cu(II) ions was 177.1 mg g⁻¹ at the conditions of pH of 5.2, temperature of 50°C, and initial Cu(II) ion concentration of 728.3 mg L⁻¹. The adsorption isotherm of Cu(II) ions on the CS/SP/ECH beads was well correlated with the Langmuir isotherm model, and the whole adsorption process could be better followed the pseudo‐second‐order kinetic model. Moreover, the CS/SP/ECH beads still exhibited good adsorption capacity even after the 15th regeneration cycles.     

Adsorption of cinnabarinic acid from culture fluid with magnetic microbeads

In this study, antimicrobial pigment cinnabarinic acid (CA) was produced from Pycnoporus cinnabarinus in laboratory‐scale batch cultures. Magnetic poly(ethylene glycol dimethacrylate‐N‐methacryloyl‐l‐tryptophan methyl ester) [m‐poly(EGDMA‐MATrp)] beads (average diameter = 53–103 µm) were synthesized by copolymerizing of N‐methacryloyl‐l‐tryptophan methyl ester (MATrp) with ethylene glycol dimethacrylate (EGDMA) in the presence of magnetite (Fe₃O₄) and used for the adsorption of CA. The m‐poly(EGDMA‐MATrp) beads were characterized by N₂ adsorption/desorption isotherms (Brunauer Emmet Teller), X‐ray photoelecron spectroscopy, scanning electron microscopy, infrared spectroscopy, thermal gravimetric analysis, electron spin resonance and swelling studies. The efficiency of m‐poly(EGDMA‐MATrp) beads for separation of CA from culture fluid was evaluated. The effects of pH, initial concentration, contact time and temperature on adsorption were analyzed. The maximum CA adsorption capacity of the m‐poly(EGDMA‐MATrp) beads was 272.9 mg g⁻¹ at pH 7.0, 25 °C. All the isotherm data can be fitted with the Langmuir, Freundlich and Dubinin–Radushkevich isotherm models. The adsorption process obeyed pseudo‐second‐order kinetic model. Thermodynamic parameters ΔH = 5.056 kJ mol⁻¹, ΔS = 52.44 J K⁻¹ mol⁻¹ and ΔG = −9.424 kJ mol−¹ to ‐11.27 kJ mol−¹ with the rise in temperature from 4 to 40 °C indicated that the adsorption process was endothermic and spontaneous. Copyright © 2015 John Wiley & Sons, Ltd.     

Dye removal by a novel hydrogel‐clay nanocomposite with enhanced swelling properties

Acrylamide (AAm)‐2‐acrylamide‐2‐methylpropanesulfonic acid sodium salt (AMPSNa) hydrogel and AAm‐AMPSNa/clay hydrogel nanocomposite having 10 w% clay was prepared by in situ copolymerization in aqueous solution in the presence of a crosslinking agent (N,N′‐methylenebisacrylamide (NMBA)). Swelling properties and kinetics of the hydrogel samples were investigated in water and aqueous solutions of the Safranine‐T (ST) and Brilliant Cresyl Blue (BCB) dyes. The swelling and diffusion parameters were also calculated in water and dye solutions. It was observed that the AAm‐AMPSNa/clay hydrogel nanocomposite exhibits improved swelling capacity compared with the AAm‐AMPSNa hydrogel. It was also found that the diffusion mechanisms show non‐Fickian character. Adsorption properties of the hydrogel samples in the aqueous solution of ST and BCB dyes were also investigated. Clay incorporation into the hydrogel structure increased not only the adsorption capacity but also the adsorption rate. Adsorption capacity values of the hydrogel nanocomposite were found to be 484.2 and 494.2 mg g^?1 for the ST and BCB dyes, respectively. It was seen that the adsorption of dyes by the hydrogel nanocomposite completed in 10 min while the AAm‐AMPSNa hydrogel adsorbed dyes approximately in 90 min. Adsorption data of the samples were modelled by the pseudo‐first‐order and pseudo‐second‐order kinetic equations in order to investigate dye adsorption mechanism. It was found that the adsorption kinetics of hydrogel nanocomposite followed a pseudo‐second‐order model. Equilibrium isotherms were analyzed using the Langmuir and Freundlich isotherms. It was seen that the Langmuir model fits the adsorption data better than the Freundlich model. Copyright © 2008 John Wiley & Sons, Ltd.     

Use of metal composite MOF‐5‐Ag2O‐NPs as an adsorbent for the removal of Auramine O dye under ultrasound energy conditions

In this work, MOF‐5 composited with Ag₂O nanoparticles was prepared and characterized via X‐ray diffraction, field emission‐scanning electron microscopy, energy‐dispersive spectroscopy and FT‐IR analysis. This new material was subsequently employed for removing basic yellow dye [Auramine O (AO)] from aqueous solution under ultrasound irradiation. Several experiments were designed by central composite design in which operational parameters such as such as pH, MOF‐5‐Ag₂O mass and initial concentration of AO involved in the process were optimized. The significance of individual parameters and their possible interactions were investigated using analysis of variance (anova ). The optimum values of 6, 0.025 g and 6 mg l^?1 were obtained for the pH, MOF‐5‐Ag₂O‐NPs mass and the initial concentrations of AO, respectively, with desirability of 1.0. At such conditions, the efficiency for the removal of AO was found to be 89.45%. Various isotherm models for fitting the experimental equilibrium data were studied, and it was found that the Langmuir model has the highest efficiency for correlation of experimental equilibrium data, so that the monolayer adsorption capacity of MOF‐5‐Ag₂O for successful removal of AO was 260.70 mg g^?1 at optimal conditions.     

Adsorption of UO2+2 by polyethylene adsorbents with amidoxime,carboxyl, and amidoxime/carboxyl group

The polyethylene (PE) adsorbents were prepared by a radiation-induced grafting of acrylonitrile (AN), acrylic acid (AA), and the mixture of AN/AA onto PE film, and by subsequent amidoximation of cyano groups of poly-AN graft chains. With an increase of AA composition in AN/AA monomer mixture, the water uptake of the grafted polyethylene film increased. In AN/AA mixture, the maximum adsorption of UO²⁺₂ was observed in the adsorbent with a ratio of AN/AA (50/50, mol%) in copolymer. The amidoxime, carboxyl, and amidoxime/carboxyl groups onto PE acted as a chelating site for the selected UO²⁺₂. The complex structure of polyethylene with three functional groups and UO²⁺₂ was confirmed by Fourier Transform Infrared (FTIR) spectroscopy.     

Efficient Removal of Cobalt(II) and Strontium(II) Metals from Water using Ethylene Diamine Tetra‐acetic Acid Functionalized Graphene Oxide

Graphene oxide (GO) with high specific surface area was prepared and functionalized with ethylene diamine tetra‐acetic acid (EDTA). The as‐prepared GO and the functionalized one (GO‐EDTA) were characterized using high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FT‐IR), X‐ray diffraction (XRD), and Raman spectroscopy. The as‐prepared and EDTA funcationalized GO were applied as adsorbent to remove strontium(II) and cobalt(II) from water. The results indicated that the prepared materials are efficient adsorbents for strontium(II) and cobalt(II) removal. The adsorption of Co^II and Sr^II under effects of contact time, temperature, and pH was investigated It is concluded that the maximum adsorption capacities of GO for Co^II and Sr^II were about 168 and 140 mg · g^–1, whereas of GO‐EDTA the values were about 197 and 158 mg · g^–1, respectively. It is indicated that pH 6 and temperature 40 °C are the best condition for Co^II and Sr^II removal from water. The application of Langmuir and Freundlich isotherms indicated that Langmuir isotherm is best fit for Co^II and Sr^II equilibrium adsorption. Adsorption kinetics were studied by applying pseudo first‐order, pseudo second‐order, and intraparticle diffusion models on the experimental data. The results proved that pseudo second‐order model is the best represented adsorption kinetics. Appling the intraparticle diffusion regressions on the experimental data indicated that intraparticle diffusion involved in adsorption process, which was not the only rate‐controlling step.     

Chitosan as a biosorbent for adsorption of iron (II) from fracking wastewater

In this work, porous chitosan (CS) was investigated as a biosorbent for the removal of iron (II) from the synthetic fracking wastewater. The underlying problem with the production water from fracking industries is that it contains iron (II) up to 55 mg/L, which needs to be eliminated. Porous CS had a specific surface area of 1.05 m²/g with the average pore diameter of 319 A, as determined by using Brunauer‐Emmett‐Teller surface area analysis. The kinetics, isotherms, and thermodynamic analysis confirm that the porous CS can be a potential candidate for iron (II) removal. Both the pseudo‐first‐order model and pseudo‐second‐order model have good fit on iron (II) adsorption with the porous CS. Kinetic studies revealed that the CS‐iron (II) adsorption system was controlled by intraparticle diffusion. The monolayer adsorption capacity of the porous CS from Langmuir model was found to be 51.81 mg/g. The experimental data were fitted against common adsorption isotherms and yielded excellent fits in the following order: Langmuir > Temkin > Freundlich > Dubinin‐Radushkevich isotherms. Thermodynamic studies revealed that the adsorption of iron (II) onto porous CS was feasible and spontaneous. The adsorption process is endothermic, and the entropy is the driving force.     

Preparation of Fluorescent Thiol Group‐Functionalized Silica Microspheres for the Detection and Removal of Silver Ions in Aqueous Solutions

We demonstrate that silica microspheres can act as a sensitive fluorescent sensor and adsorbent of Ag⁺ in aqueous media. These thiol‐functionalized silica microspheres are doped with quantum dots (QDs) using organosilane chemistry in a one‐step preparation. Ligand exchange takes place between the thiolated organosilane and acid‐capped QDs, making the doping easy. Ag⁺ adsorption by the silica microspheres causes the decrease of fluorescence intensity of the QDs. The detection limit for Ag⁺ is found to be 10 μmol/L. The abundance of thiol groups on the surface of the microspheres could effectively remove Ag⁺ through strong interaction. When microspheres with a diameter of 1.1 μm are used as the adsorbents, the adsorption capacity for Ag⁺ reached 102 mg/g. This excellent adsorption ability is due to the abundance of thiol groups that act as the active sites, facilitating the adsorption of the massive metal ions on the surface of the microspheres. Furthermore, the adsorption isotherm data follows the Freundlich model. The structure and content of the silica microspheres were investigated by scanning and high‐resolution transmission electron microscopy, energy dispersive X‐ray spectroscopy, and Raman analysis, and the fluorescence properties were characterized by fluorescence microscopy.     

Hydroxyethyl Starch-g-Poly-(N,N-dimethylacrylamide-co-acrylic acid): An efficient dye removing agent

Hydroxyethyl Starch-g-Poly-(N,N-dimethylacrylamide-co-acrylic acid) was synthesized by solution polymerization technique using potassium peroxydisulfate (K₂S₂O₈) as the initiator at 90 °C. The synthesized graft copolymer was characterized by FTIR, NMR (both ¹H and ¹³C) Spectroscopy, molecular weight determination by GPC, TGA/DTG and SEM analysis. Biodegradation study was carried out by enzymatic hydrolysis. The number of carboxylic acid groups incorporated into the polymer was calculated by measuring neutralization equivalent (N.E) of the graft copolymer titrimetrically. The synthesized graft copolymer was used as the adsorbent for the removal of Malachite green, a cationic dye from its aqueous solution. The operating variables studied were the amount of adsorbent, solution pH, contact time, temperature and the initial dye concentration. The adsorption data were used to fit in the pseudo-first order and pseudo-second order rate equation in order to investigate the sorption mechanism. Equilibrium isotherm was analyzed using the Langmuir and the Freundlich isotherms. In the present investigation it was found that the adsorption kinetics followed a pseudo second order kinetics for the studied dye concentration range. The negative value of free energy change indicates the spontaneous nature of the adsorption and also suggesting a chemisorption process.     

Understanding the interactions in acrylic copolymer/1‐butyl‐3‐methylimidazolium chloride from solution rheology

The effects of the type and content of comonomers on the rheological properties of acrylic copolymers in 1‐butyl‐3‐methylimidazolium chloride ([BMIM]Cl) were explored. According to the de Gennes scaling law for solution, comparison of intrinsic viscosity and scaling analysis of the exponent in the specific viscosity‐ and relaxation time‐concentration power law indicated that solution of both polyacrylonitrile (PAN) homo‐polymer and copolymer poly(acrylonitrile‐co‐methyl acrylate) (poly(AN‐co‐MA)) in [BMIM]Cl behave in the same manner as neutral polymer in a θ‐solvent. However, [BMIM]Cl acts as a more good solvent for poly(acrylonitrile‐co‐acrylamide) (poly(AN‐co‐AM)). The dissolution and unique rheological behavior of such solutions have been attributed to the interactions between copolymer chains and [BMIM]Cl. The interactions between nitrile group (?C≡N) and 1‐butyl‐3‐methylimidazolium cation ([BMIM]⁺) should interrupt and break the dipolar‐dipolar interactions of PAN resulting in the subsequent dissolution of the polymer in [BMIM]Cl. Such interactions between ?C≡N and [BMIM]⁺ ion are still dominated by the solvating ability of poly(AN‐co‐MA) in [BMIM]Cl, even though carbonyl group (C=O) in MA repeating unit could coordinate to cation of the ionic liquid. The salvation capacity of [BMIM]Cl for poly(AN‐co‐AM) can be evidently improved due to the extra hydrogen bond interactions between ?NH₂ group of AM and anion of [BMIM]Cl. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation and adsorption properties of crosslinked polystyrene-supported low-generation diethanolamine-typed dendrimer for metal ions

Two novel chelating resins, polystyrene supported G1.0 diethanolamine-typed dendrimer (PS-DEA) and G2.0 diethanolamine-typed dendrimer (PS-(DEA)₂), were prepared by anchoring low-generations diethanolamine-typed dendrimer into crosslinked polystyrene in this paper. Fourier transform-infrared spectra (FTIR), scanning electron microscopy (SEM) and elemental analysis were employed to character their structures. The results of adsorption for metal ions showed that the resins had good adsorption capacities for Cu²⁺, Ag⁺ and Hg²⁺, especially PS-DEA for Cu²⁺. The adsorption kinetics and adsorption isotherms of PS-DEA for Cu²⁺ and PS-(DEA)₂ for Hg²⁺ were studied. The results showed that the adsorption kinetics of the two resins can be modeled by pseudo second-order rate equation wonderfully and Langmuir and Freundlich equations could well interpret the adsorption of PS-(DEA)₂ for Hg²⁺ and PS-DEA for Cu²⁺, respectively. The adsorption mechanism of the resins for Cu²⁺ was confirmed by X-ray photoelectron spectroscopy (XPS).     

Iodide adsorption on the surface of chemically pretreated clinoptilolite

The possibility to use the monoionic Ag⁺-form (eventually Hg⁺- and Hg²⁺- forms) of clinoptilolite of domestic origin for radioactive iodide elimination from waters has been studied. The capacity of the monoforms of clinoptilolite towards iodide exceeds many times that of the capacity of clinoptilolite in natural form. Due to the low solubility product of AgI, Hg₂I₂ and HgI₂ iodides generate precipitates on the zeolite surface. Rtg analyses of the silver form of clinoptilolite after sorption of iodide demonstrate the formation of new crystals on the zeolite surface. The influence of interfering anions on the adsorption capacity of silver clinoptilolite towards iodide was investigated, too. Kinetic curves of iodide desorption from the surface of silver and mercury clinoptilolite were compared. Simultaneously, adsorption isotherms for the systems aqueous iodide solution/Ag^–, Hg-clinoptilolite were determined.     

Synthesis and metal complexation of dihydroxyphosphino‐functionalized crosslinked styrene/maleic anhydride copolymers

Crosslinked styrene (St)/maleic anhydride (MA) copolymers were synthesized, hydrolyzed with dicarboxylic acid, and converted to bear dihydroxyphosphino functionalities. The St–MA copolymers were prepared by azobisisobutyronitrile‐initiated polymerization in toluene at 90 °C in the presence of 2, 10, or 20% divinylbenzene crosslinker. The MA moiety was hydrolyzed into dicarboxylic acid to improve the hydrophilicity of the copolymers. The phenyl ring of St was phosphorylated with phosphorus trichloride in the presence of aluminum chloride and then hydrolyzed and oxidized with nitric acid at room temperature. The structures of the hydrolyzed and dihydroxyphosphino‐functionalized copolymers were confirmed by Fourier transform infrared spectroscopy and elemental analysis. The complexation behavior of these functionalized copolymers toward metal ions in 25 ppm aqueous solutions was observed over time periods of up to 7 h. The adsorption toward Pb(+2) was highest, followed by those of Cu(+2), Cr(+3), and Ni(+2). On the dihydroxyphosphino‐functionalized St–MA (20% divinylbenzene) copolymer, the adsorption of Pb(+2) showed a linear relationship with the concentrations and fit the Langmuir isotherm. The kinetics of Pb(+2) adsorption on this dihydroxyphosphino‐functionalized copolymer also fit the rate equation of the moving boundary model, t = [1 ? 3(1 ? X)^2/3 + 2(1 ? X)], where X is the fractional conversion. The metal‐ion adsorption kinetics of this copolymer appeared to be particle diffusion control, in which the moving boundary advanced from the surface toward the center. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 92–101, 2004