Adsorption and desorption properties of grafted polyethylene films modified with polyethylenimine chains

The chelating membranes for adsorption of metal ions were prepared by the bonding of linear and branched polyethylenimines (LPEI and BPEI) on the glycidyl methacrylate (GMA) photografted porous polyethylene (pPE) (pPE‐g‐PGMA) films. The adsorption and desorption properties of LPEI and BPEI‐bonded pPE‐g‐PGMA (LPEI‐(pPE‐g‐PGMA) and (BPEI‐(pPE‐g‐PGMA)) films to Cu²⁺ ions were investigated as a function of the grafted amount, amount of bonded PEI, molecular mass of PEI, pH value, and temperature. The amounts of LPEI and BPEI bonded to the pPE‐g‐PGMA films increased over the reaction time, and the bonding of LPEI and BPEI offered the water‐absorptivity to the pPE‐g‐PGMA films. The amount of adsorbed Cu²⁺ ions at pH 5.0 had the maximum value at the grafted amount of 10 mmol/g for the (LDPEI‐(pPE‐g‐PGMA) and (BPEI‐(pPE‐g‐PGMA) films with a constant amount of bonded PEI. The amount of adsorbed Cu²⁺ ions for the LPEI‐(pPE‐g‐PGMA) films was higher than that for the BPEI‐(pPE‐g‐PGMA) films. The amount of Cu²⁺ ions desorbed from the LPEI‐(pPE‐g‐PGMA) and BPEI‐(pPE‐g‐PGMA) films increased with an increase in the HCl concentration. The quantities of Cu²⁺ ions of about 100% were desorbed in the aqueous HCl solutions of more than 0.1M for the LPEI‐(pPE‐g‐PGMA) films and more than 0.05M for the BPEI‐(pPE‐g‐PGMA) films. The amounts of adsorbed Cu²⁺ ions were almost the same in each adsorption process at pH 5.0. This indicates that the LPEI‐(pPE‐g‐PGMA) and BPEI‐(pPE‐g‐PGMA) films can be applied to a repeatedly generative chelating membrane for adsorption and desorption of metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5965–5976, 2006     

Synthesis of monodisperse nonporous crosslinked poly(glycidyl methacrylate) particles with metal affinity ligands for protein adsorption

Monodisperse nonporous crosslinked poly(glycidyl methacrylate) (PGMA) particles with immobilized metal affinity ligands were prepared for selective recovery of proteins. The PGMA particles, with an average size of 2.2 µm, were prepared by a simple dispersion polymerization of glycidyl methacrylate (GMA) and ethylene glycol dimethacrylate (EGDMA). The particles were characterized by scanning electron microscopy (SEM) and Fourier‐transform infrared spectroscopy (FTIR). The epoxy groups of the particles were modified with the metal chelating agent iminodiacetic acid (IDA), which forms metal–IDA chelates at the active sites. After charging with copper ions, the particles were used to recover a model protein, bovine hemoglobin (BHb), in a batchwise manner. The particles had the adsorption capacity of 218.7 mg g⁻¹ with little nonspecific adsorption. The adsorption behavior could be described with the Langmuir equation. The effect of pH on the adsorption was also studied. Regeneration of the metal‐chelated particles was easily performed with 50 mmol L⁻¹ ethylenediaminetetraacetic acid (EDTA), followed by washing with water and reloading with Cu²⁺. The particles could be very useful as an affinity separation adsorbent. Copyright © 2005 Society of Chemical Industry     

Adsorption of Pb2+, Cu2+ and Co2+ by polypropylene fabric and polyethylene hollow fiber modified by radiation-induced graft copolymerization

Cation-exchange adsorbents were prepared by radiation-induced grafting of glycidyl methacrylate (GMA) onto polypropylene (PP) fabric and polyethylene (PE) hollow fiber and subsequent phosphonation of epoxy groups of poly(GMA) graft chains. The adsorption characteristics of Pb²⁺, Cu²⁺ and Co²⁺ for the two cation-exchange adsorbents were studied. In the grafting of GMA onto PP fabric, the degree of grafting (%) increased with an increase in reaction time, reaction temperature, and pre-irradiation dose. The maximum grafting yield was observed around 60% GMA concentration. In 50, 130 and 250% GMA-grafted PP fabric, the content of phosphoric acid was 1.52, 3.40 and 4.50 mmol/g at 80 °C in the 85 % phosphoric acid aqueous solution for 24 h, respectively. The adsorption of Pb²⁺, Cu²⁺ and Co²⁺ by PP fabric adsorbent was enhanced with an increased phosphoric acid content The order of adsorption capacity of the PP fabric adsorbent was Pb²⁺>Co²⁺>Cu²⁺. In adsorption of Pb²⁺, Cu²⁺ and Co²⁺ by PE hollow fiber, the amount of Pb²⁺ adsorbed by the PE hollow fiber adsorbent containing 1.21 mmol/g of -PO₃H wasca. 54.4 g per kg. The adsorption amount of Cu²⁺ and Co²⁺ in the same PE hollow fiber wasca. 21.0 g per kg andca. 32.1 g per kg, respectively. The order of adsorption of the PE hollow fiber adsorbent was Pb²⁺>Co²⁺>Cu²⁺.     

Preparation of gel resins and removal of copper and lead from water

A series of gel resins were prepared by polymerizing glycidyl methacrylate (GMA) and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) and functionalizing with ammonia (NH₃) and tetraethylenepentamine (TEPA). The aminated gel resins were then used as an adsorbent for the removal of heavy metal ions (Cu²⁺ and Pb²⁺). These gel resins containing amino groups and chelating amino groups had excellent adsorptive properties for Cu²⁺ and Pb²⁺. The adsorption process reached equilibrium in 40 min, and the adsorption capacities of Cu²⁺ and Pb²⁺ were 75.0 mg g^?1 and 266.6 mg g^?1 for the NH₃‐aminated gel resins and 57.5 mg g^?1 and 330.6 mg g^?1 for the TEPA‐aminated gel resins, respectively. After five adsorption–desorption processes, the adsorption capacities only decreased slightly. Thus, these aminated gel resins can be used as effective adsorbents for aqueous heavy metal ions (Cu²⁺ and Pb²⁺). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44466.     

Adsorption and desorption of copper(II) from solutions on new spherical cellulose adsorbent

An investigation was conducted on the adsorption and desorption of copper(II) from aqueous solutions with a new spherical cellulose adsorbent containing the carboxyl anionic group. Various factors affecting the adsorption were optimized. The adsorption of Cu²⁺ ions on the adsorbent was found to be dependent on the initial time and pH, the concentration, and the temperature. The adsorption process follows both Freundlich and Langmuir adsorption isotherms and was found to be endothermic (ΔH = 23.99 kJ/mol). The Cu²⁺ ions adsorbed on the adsorbent can be recovered with a NaOH or HCl aqueous solution. The maximum percentage of recovery is about 100% when 2.4 mol/L HCl solution is used. In addition, only 7.2% of the adsorption capacity is lost after 30 replications of the adsorption and desorption. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 478–485, 2002; DOI 10.1002/app.10114     

Adsorption and desorption properties of cationic polyethylene film gels to organic anions and their regeneration

An investigation was undertaken on the adsorption and desorption properties of 2‐(dimethylamino)ethyl methacrylate grafted polyethylene (PE‐g‐PDMAEMA) films to anionic dye anions with one to three sulfonic groups in response to pH and temperature changes. The amounts of dye anions adsorbed on the PE‐g‐PDMAEMA films passed through the maximum values at about pH 3 because of an increase in the protonation of dimethylamino groups caused by a decrease in the pH value. The amounts of adsorbed dye anions decreased below pH 3 because the ionic strength increased with the addition of HCl to adjust the initial pH values of the aqueous dye solutions. The amounts of adsorbed dye anions decreased with an increase in the number of sulfonic groups in the dye molecules at the same pH value because electrostatic repulsion was generated between free sulfonic groups of the dye anions adsorbed onto the PE‐g‐PDMAEMA films and free dye anions in the medium. A large number of dye anions adsorbed were desorbed from the PE‐g‐PDMAEMA film with initial pH values above 11.0. The cyclic processes of adsorption at pH 3.0 and desorption at pH 11.0 were repeated without considerable fatigue. The PE‐g‐PDMAEMA films showed practically regenerative adsorption and desorption behavior in response to the pH changes. In addition, when the dye‐anion‐adsorbed PE‐g‐PDMAEMA films were alternately immersed in water at two different temperatures, dye anions were desorbed in water at higher temperatures without any chemical agents because of the deprotonation of dimethylamino groups and thermosensitive contraction of grafted PDMAEMA chains. These results indicate that PE‐g‐PDMAEMA films can be applied as regenerative ion‐exchange membranes for adsorption and desorption processes of anionic compounds in response to the pH and temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 381–391, 2006     

Improved synthesis of a branched poly(ethylene imine)‐modified cellulose‐based adsorbent for removal and recovery of Cu(II) from aqueous solution

This study focuses on an improved synthesis of a branched poly (ethylene imine) (PEI)‐modified cellulose‐based adsorbent (Cell‐g‐PGMA‐PEI). We aim to improve the adsorbent capacity by reducing side reaction of epoxide ring opening during graft copolymerization of glycidyl methacrylate (GMA) onto cellulose which increases the content of epoxy groups, anchors to immobilize branched PEI moieties. FTIR spectra provided the evidence of successful graft copolymerization of GMA onto cellulose initiated by benzoyl peroxide (BPO) and modification with PEI. The amount of epoxy groups of Cell‐g‐PGMA was 4.35 mmol g^?1 by epoxy titration. Subsequently, the adsorption behavior of Cu(II) on cell‐g‐PGMA‐PEI in aqueous solution has been investigated. The data from the adsorption kinetic experiments agreed well with pseudo‐second‐order model. The adsorption isotherms can be interpreted by the Langmuir model with the maximum adsorption capacity of 102 mg g^?1 which was largely improved compared with the similar adsorbent reported. The dynamic adsorption capacity obtained from the column tests was 119 mg g^?1 and the adsorbent could be regenerated by HCl of 0.1 mol L^?1. Results indicate that the novel pathway for the synthesis of Cell‐g‐PGMA‐PEI exhibits significant potential to improve the performance of adsorbents in removal and recovery of Cu(II) from aqueous solution. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Stability constants of polymer‐bound iminodiacetate‐type chelating agents with some transition‐metal ions

A chelating vinyl monomer, glycidyl methacrylate (GMA)–iminodiacetic acid (IDA), was formed by the reaction between GMA and IDA. Three polymeric chelating agents, PGMA–IDA, PGMA–IDA‐co‐methyl acrylate (MA), and PGMA–IDA‐co‐acrylamide (AAm), were also synthesized. Acid dissociation constants and stability constants of these chelating agents with Ni(II), Zn(II), and Co(II) were determined by means of potentiometric titration and ultraviolet–visible spectrophotometry, respectively. The values of K_a1 and K_a2 of all the polymeric chelating agents were smaller than those of GMA–IDA. The stability constants of all the polymeric chelating agents were larger than those of GMA–IDA. Increasing the MA content within PGMA–IDA‐co‐MA affected the stability constant only slightly. A proper molar ratio of AAm in PGMA–IDA‐co‐AAm, stability constants was 30–60 times greater than that of GMA–IDA. However, as the molar content of AAm increased, the stability constant of PGMA–IDA‐co‐AAm decreased. The results obtained in the polymer system are explained in terms of the polymer's stereo and entanglement structure, the neighboring effect, and the hydrophobic/hydrophilic nature of MA or AAm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1986–1994, 2002     

Antibody purification using porous metal–chelated monolithic columns

A novel monolithic material was developed to obtain efficient and cost‐effective purification of IgG from human plasma. The porous monolith was obtained by bulk polymerization in a glass tube of 2‐hydroxyethyl methacrylate (HEMA) and N‐methacryloyl‐(L )‐histidine methyl ester (MAH). The poly(HEMA‐MAH) monolith had a specific surface area of 214.6 m²/g and was characterized by swelling studies, porosity measurement, FTIR, scanning electron microscopy, and elemental analysis. Then the monolith was loaded with Cu²⁺ ions to form the metal chelate. Poly(HEMA‐MAH) monolith with a swelling ratio of 74% and containing 20.9 μmol MAH/g was used in the adsorption/desorption of IgG from aqueous solutions and human plasma. The maximum adsorption of IgG from an aqueous solution in phosphate buffer was 10.8 mg/g at pH 7.0. Higher adsorption was obtained from human plasma (up to 104.2 mg/g), with a purity of 94.1%. It was observed that IgG could be repeatedly adsorbed and desorbed with the poly(HEMA‐MAH) monolith without significant loss of adsorption capacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 395–404, 2006     

Preparation of aminoalkyl celluloses and their adsorption and desorption of heavy metal ions

Aminoalkyl celluloses (AmACs) were prepared from 6-chlorodeoxycellulose and aliphatic diamines H₂N(CH₂)_mNH₂ (m = 2, 4, 6, 8). Their adsorption and desorption of divalent heavy metal ions such as Cu²⁺, Mn²⁺, Co²⁺, Ni²⁺ and their mixtures were also investigated in detail. Adsorption of metal ions on AmACs was remarkably affected by the pH of the solution, the metal ion and its initial concentration, and also the number of methylene units in the diamines. No adsorption of metal ions occurred on AmACs in strongly acidic solutions. However, metal ions were adsorbed rapidly on AmACs from weakly acidic solutions and the amount of adsorption increased with increasing pH. The effectiveness of AmACs as adsorbents decreased with increasing length of the methylene moiety, and AmACs from ethylenediamine (m = 2) was most effective. The adsorption of metal ions on AmACs was in the order Cu²⁺ > Ni²⁺ > Co²⁺ > Mn²⁺. Accordingly, their behavior followed the Irving-Williams series and Cu²⁺ ions were preferentially adsorbed from solutions containing metal ion mixtures. The adsorbed ions were easily desorbed from the AmACs by stirring in 0.1 M HCl.     

Immobilized metal ions cellophane–PGMA‐grafted membranes for affinity separation of β‐galactosidase enzyme. I. Preparation and characterization

Immobilized Cu²⁺ ions affinity cellophane–poly(glycidyl methacrylate) (PGMA)‐grafted membranes have been prepared through three steps. The first step was introducing of epoxy groups to its chemical structure through grafting process with PGMA. Factors affecting the grafting process have been studied and grafting percentage (GP) up to 233% has been obtained. The second step was converting the introduced epoxy groups to sulfonic ones. It was found that maximum amount of sulfonic groups (2.7 mmol/g) was obtained with minimum GP (46.08%). The third and last step was the immobilization of Cu²⁺ ions into sulfonated grafted membranes obtained from the previous step. Maximum amount of immobilized Cu²⁺ ions was found to be 60.9 ppm per gram of polymer. The verification of the grafting and sulfonation steps has been performed through characterization of the obtained membranes using FTIR, TGA, and EDAX analysis. Finally, Cu²⁺‐immobilized membranes have been evaluated in separation of β‐galactosidase (β‐Gal) enzyme from its mixture with bovine serum albumin (BSA) in different pH medium. Maximum protein adsorption, for both proteins, has been obtained at pH range 4–4.5; as 90 and 45% for β‐Gal and BSA, respectively. The results showed high affinity toward β‐Gal separation although BSA concentration (0.5%) is 20‐folds of β‐Gal (0.025%). © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Highly porous,water-swellable,and reusable chelating polymeric gels for heavy metal ion removal from aqueous waste

Sequestration and removal of heavy metal ions from aqueous solutions pose multiple challenges. Ease of synthesis, high adsorption capacity and ease of regeneration are important considerations in the design of polymeric adsorbent materials developed for this purpose. To meet this objective, a new approach was used to design and synthesize a highly porous polystyrene-based resin (IDASR15) bearing iminodiacetate functional groups in every repeat unit by free radical polymerization with N, N'-methylenebisacrylamide as crosslinker followed by base hydrolysis. The physiochemical chemical properties of the resin were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, equilibrium swelling value (ESV) and thermogravimetric analysis. Metal uptake capacity of IDASR15 towards low concentrations of various toxic heavy metal ions such as Cu²⁺, Cd²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, Co³⁺, Cr³⁺, Fe²⁺, Fe³⁺, and Al³⁺ were investigated from their aqueous solution by batch method and found to be 0.943–2.802 mmol/g. The maximum capacity was 2.802 mmol/g obtained for Cu²⁺ ion at pH 5. The potential for regeneration and reuse has been demonstrated with Cu²⁺ ion by batch and column methods. The reported results suggest that IDASR15 is a highly efficient and porous complexing agent for commonly found toxic metal ions in aqueous streams with a high ESV of 68.55 g of water/1.0 g of IDASR15. It could also be reused ~99.5% of adsorption efficiency which is very promising and holds significant potential for waste-water treatment applications.     

A chelating cellulose adsorbent for the removal of Cu(II) from aqueous solutions

Regenerated cellulose wood pulp was grafted with the vinyl monomer glycidyl methacrylate (GMA) using ceric ammonium nitrate as initiator and was further fuctionalised with imidazole to produce a novel adsorbent material, cellulose‐g‐GMA‐imidazole. All cellulose, grafted cellulose and functionalized cellulose grafts were physically and chemically characterized using a number of analytical techniques, including elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, differential thermal analysis, and scanning electron microscopy. The cellulose‐g‐GMA material was found to contain 1.75 mmol g^?1 epoxy groups. These epoxy groups permitted introduction of metal binding functionality to produce the cellulose‐g‐GMA‐imidazole final product. Following characterization, a series of adsorption studies were carried out on the cellulose‐g‐GMA‐imidazole to assess its capacity in the removal of Cu²⁺ ions from solution. Cellulose‐g‐GMA‐imidazole sorbent showed an uptake of ～70 mg g^?1 of copper from aqueous solution. The adsorption process is best described by the Langmuir model of adsorption, and the thermodynamics of the process suggest that the binding process is mildly exothermic. The kinetics of the adsorption process indicated that copper uptake occurred within 30 min and that pseudo‐second‐order kinetics best describe the overall process. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 2006     

Preparation of iminodiacetic acid-type composite chelating material IDAA-PGMA/SiO2 and preliminary studies on adsorption behavior of heavy metal ions and rare earth ions

A kind of iminodiacetic acid (IDAA)-type composite chelating materials was prepared by first graft polymerization and subsequent polymer reaction. Monomer glycidyl methacrylate (GMA) was grafted on micron-sized silica gel particles in the manner of “graft through” in a solution polymerization system, resulting in the grafted particles poly(glycidyl methacrylate) (PGMA)/silicon dioxide (SiO₂). Subsequently, the ring-opening reaction of the epoxy groups of the grafted PGMA was carried out with IDAA as reaction reagent, resulting in the bonding of IDAA groups onto PGMA/SiO₂ and obtaining the composite chelating material IDAA-PGMA/SiO₂ particles. The effects of the main factors on the graft polymerization of GMA and the bonding reaction of IDAA were examined emphatically, and the adsorption behavior of IDAA-PGMA/SiO₂ particles toward several kinds of heavy metal ions and rare earth ions was preliminarily explored. The experiments results show that: (a) to obtain the grafted particles PGMA/SiO₂ with high grafting degree, in the graft polymerization step, the reaction temperature and the used amount of initiator should be controlled. The suitable temperature is 70°C and the appropriate used amount of initiator is 1.4 % of the monomer mass. Under the optimal conditions, the grafted degree of PGMA can reach 17.50 g/100 g. (b) It is feasible to introducing of IDAA groups onto PGMA/SiO₂ particles via ring-opening reaction of epoxy groups of the grafted PGMA under alkaline conditions, and the bonding rate of IDAA group can get up to 70% based on epoxy groups of the grafted PGMA. (c)The composite chelating material IDAA-PGMA/SiO₂ possesses very strong chelating adsorption ability for heavy metal ions, and especially toward Pb²⁺ ion, the adsorption capacity can reach 24 g/100 g. (d) The adsorption ability of IDAA-PGMA/SiO₂ for rare earth ions is weaker than that for heavy metal ions. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Porous magnetic chelator support for albumin adsorption by immobilized metal affinity separation

Magnetic poly(2‐hydroxyethylmethacrylate) (mPHEMA) beads are modified by iminodiacetic acid (IDA) to implify the reactive groups and subsequent binding of Cu²⁺ ions to form metal chelate. mPHEMA beads, in the size range of 80–120 μm, were produced by a modified suspension polymerization technique. mPHEMA beads were characterized by swelling tests, electron spin resonance (ESR), FTIR, and scanning electron microscopy (SEM). Important results obtained in this study are as follows. The swelling ratio of mPHEMA beads was 34%. The presence of magnetite particles in the polymeric structure was confirmed by ESR. FTIR data confirmed that the magnetic polymer beads were modified with functional groups IDA. The mPHEMA beads have a spherical shape and porous structure. The effect of pH and concentration of human serum albumin (HSA), on the adsorption of HSA to the metal‐chelated magnetic beads, were examined in a batch reactor. Most importantly, the magnetic beads had little nonspecific adsorption for HSA (0.5 mg/g) before introducing IDA groups. Cu²⁺ chelation increased the HSA adsorption up to 28.4 mg/g. Adsorption behavior can be described at least approximately with the Langmuir equation. Regeneration of the metal‐chelated magnetic beads was easily performed with 1.0M NaSCN, pH 8.0, followed by washing with distilled water and reloading with Cu²⁺. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2501–2510, 2004     

Metal recovery using immobilized cell suspension from a brewery

Lead, copper, and cadmium were adsorbed onto calcium alginate beads containing the cell suspension discarded from a brewery. In the cell suspension, there were many cells under lysis. The cell-suspension immobilized beads were prepared by adding 0.6% (w/v) sodium alginate into the cell suspension from the brewery and then making the cell suspension fall dropwise into the swirling 1% (w/v) calcium alginate solution. The dry weight of insoluble solid in the cell suspension was 96 g dry weight/l and the dry density of the bead containing cell suspension was 140 g dry weight/l of the bead. The specific metal uptake of the cell-suspension immobilized bead was 23.7 mg Pb²⁺, 14.3 mg Cu²⁺, and 13.4 mg Cd²⁺/g bead dry weight, respectively. The cell-suspension immobilized beads retained the initial metal-uptake capacity after 20 repeated batches of adsorption and desorption, but the fraction of metal desorbed from the beads by 1 M HCl solution was only 70% of the adsorbed metal. The beads, which had been contained for 14 successive days in the 0.5% (w/v) CaCl₂ solution at 4 °C just after 20 cycles of adsorption/desorption, retained the initial metal-uptake capacity after 30 repeated cycles, and more than 90% of the copper and cadmium adsorbed on the beads was desorbed by the 1 M HCl solution.     

Synthesis,characterization, and application of polyethersulfone bound‐iminodiacetic acid

A new method to introduce iminodiacetic acid (IDA) onto polyethersulfone (PES) matrix through chlorosulfonation was described in this work, and the prepared PES‐IDA was used as adsorbent for the removal of metal ions from aqueous solutions. Chlorosulfonic groups ( SO₂Cl) were introduced onto PES first, then IDA was grafted onto PES by using the interactions between the chlorosulfonic group and the imino group of IDA. The grafted IDA was characterized by fourier transform infrared measurement, X‐ray photoelectron spectroscopy analysis, and thermogravimetric analysis spectra. The adsorbed amounts by the PES‐IDA for Cu²⁺ and Ag⁺ were 3.44 mg/g and 7.09 mg/g, respectively. The PES‐IDA adsorbent may expand the usage of PES in purification fields and could make some potential contributions to the polymer‐based adsorbents. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption studies of Cu2+ onto poly (vinyl alcohol)/poly (acrylamide-co-N-isopropylacrylamide) core–shell nanogels synthesized through surfactant-free emulsion polymerization

Poly (vinyl alcohol) (PVA) nanoparticle core and poly (acrylamide-co-N-isopropylacrylamide) P(AAm-co-NIPAm) hydrogel shell were fabricated to produce well-defined PVA/P(AAm-co-NIPAm) core–shell nanogels using Surfactant Free Emulsion Polymerization (SFEP). The nanogel was characterized by the FTIR, TEM TGA thermogram and SEM techniques. The adsorbent was utilized for Cu²⁺ removal from aqueous solution. Batch adsorption process indicated that 0.9 mol% PAAm nanogel exhibited higher adsorption affinity toward Cu²⁺. The kinetics parameters were investigated according to the pseudo-first-order, pseudo-second-order and intraparticle diffusion rate models. The adsorption equilibrium match with Langmuir adsorption isotherm rather than Freundlich isotherm. The Cu²⁺ loaded nanogels were effectively desorbed using 0.1 mol/l from HCl as stripping agent.     

A novel carbon aerogel prepared for adsorption of copper(II) ion in water

A novel carbon aerogel with network pore and surface group of hydroxyl was prepared from cellulose colloid, through sol-gel reaction, freeze-drying and carbonization. Surfactant like isooctyl alcohol ether phosphate was taken as structure inducer in sol-gel reaction, for construction of porous network in the prepared samples. Characteristic of a specific area about 725.12 m²/g and total pore volume about 0.64 cm³/g, the prepared cellulose-based carbon aerogel of CCA₂, has a maximum capacity about 55.25 mg/g for Cu²⁺ in neutral aqueous solution. Its adsorption equilibrium can be reached within 10 min in an aqueous solution of pH7.0 at 25?°C, while desorption of Cu²⁺ need about 1 h eluted by HCl or HNO₃ solution of 0.01 M. And regeneration of the carbon aerogel in adsorption of Cu²⁺ can be repeated for five times, remaining 96% adsorption capacity. It is also found in adsorption process the kinetics nicely follows pseudo-second-order rate expression, and the isotherm fits Langmuir model.     

Alanine containing porous beads for mercury removal from artificial solutions

N‐methacryloyl‐(L )‐alanine (MALA) was synthesized by using methacryloyl chloride and alanine as a metal‐complexing ligand or comonomer. Spherical beads with an average diameter of 150–200 μm were obtained by suspension polymerization of MALA and 2‐hydroxyethyl methacrylate (HEMA) conducted in an aqueous dispersion medium. Poly(HEMA–MALA) beads were characterized by SEM, swelling studies, surface area measurement, and elemental analysis. Poly(HEMA–MALA) beads have a specific surface area of 68.5 m²/g. Poly(HEMA–MALA) beads with a swelling ratio of 63%, and containing 247 μmol MALA/g were used in the removal of Hg²⁺ from aqueous solutions. Adsorption equilibrium was achieved in about 60 min. The adsorption of Hg²⁺ ions onto PHEMA beads was negligible (0.3 mg/g). The MALA incorporation into the polymer structure significantly increased the mercury adsorption capacity (168 mg/g). Adsorption capacity of MALA containing beads increased significantly with pH. The adsorption of Hg²⁺ ions increased with increasing pH and reached a plateau value at around pH 5.0. Competitive heavy metal adsorption from aqueous solutions containing Cd²⁺, Cu²⁺, Pb²⁺, and Hg²⁺ was also investigated. The adsorption capacities are 44.5 mg/g for Hg²⁺, 6.4 mg/g for Cd²⁺, 2.9 mg/g for Pb²⁺, and 2.0 mg/g for Cu²⁺ ions. These results may be considered as an indication of higher specificity of the poly(HEMA–MALA) beads for the Hg²⁺ comparing to other ions. Consecutive adsorption and elution operations showed the feasibility of repeated use for poly(HEMA–MALA) chelating beads. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1222–1228, 2006