Sorption equilibrium of Cr(VI) ions by strong base anion exchangers with pyridine structures

Chromate sorption on pyridine strong base anion exchangers with different functional groups (methyl, ethyl, and butyl groups), at the quaternary nitrogen atoms, was studied as a function of various initial concentrations (100–1500 mg Cr/L) and counterion type. The studied resins in the Cl^?[ form have higher Cr(VI)‐retention capacities than those in the SO form. The pyridine strong base anion exchangers showed a selectivity reversal for the sulfate and chromate anions compared to that of the commercial resins. The alkyl substituent length of the quaternary nitrogen atoms exerted a substantial influence on the Cr(VI)‐retention capacity values for the resins in the Cl^? form; the chromate anions preferred resins with methyl functional groups, that is, resins with a greater hydrophilic structure. For the resins in the SO form the length of the substituent at the quaternary nitrogen atom had only a negligible influence on their Cr(VI)‐retention values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1957–1963, 2004     

Column adsorption of chromium(VI) by strong alkaline anion‐exchange fiber

The removal of chromium(VI) from saturated sodium chloride (NaCl) solution by strong alkaline anion‐exchange fiber (SAAEF) was achieved with column experiments. Factors affecting the adsorption, such as the pH value, loading density, flow rate, and operational temperature, were investigated. The results show that Cr(VI) removal was remarkably pH dependent. The optimal operational conditions were as follows: pH value = 2.0, loading density = 0.12–0.19 g/cm³, room temperature, and flow rate = 6–12 BV/h. The SAAEF column could be regenerated completely by 2% NaOH in saturated NaCl or 2% KOH in 15% KCl as an eluent. Cr(VI) was recycled as Na₂Cr₂O₇ and K₂Cr₂O₇, respectively. The desorption rate of Cr(VI) reached 98.09%. The adsorption ability of the SAAEFs was stable after repeated use. Overall, the results indicate that SAAEF proved to be an effective material for the adsorption of high concentrations of Cr(VI) from a saturated NaCl solution. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

A mild and clean synthesis of alkyl azides from alkyl halides mediated by poly(4‐vinylpyridine)‐supported sodium azide under nonaqueous conditions

Alkyl halides were efficiently converted to their corresponding alkyl azides under mild nonaqueous conditions with a polymer‐supported azide as a new polymeric reagent at room temperature at high yields and purities. All of the byproducts were removed by filtration, and pure products were obtained by the evaporation of the solvent. The spent polymeric reagent could usually be removed quantitatively and regenerated. The regenerated polymeric reagent could be reused several times. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation and adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly(aryl ether ketone)s with bromomethyl groups: Synthesis and quaternary amination

A series of bromomethylated poly(arylene ether ketone)s (PAEKs) with different contents of bromine tethered to the benzyl groups were successfully synthesized and characterized in this work. For this purpose, poly(arylene ether ketone) with 3,3′,5,5′‐tetramethyl‐4,4′‐dihydroxybipheny moiety (PAEK‐TM) was prepared by the aromatic nucleophilic polycondensation, and then the PAEK‐TM has benzylic methyl groups that were converted to bromomethyl groups by a radical reaction using N‐bromosuccinimide. Then, the bromomethylbenzyl groups in the membrane was converted to quaternary ammonium moieties in TMPAEK‐NOH. ¹H‐NMR measurements were used to characterize and confirm the structures of the resulting PAEK‐x‐BrTM and TMPAEK‐NBr derivatives (x refers to the molar percentage of bromine introduced per repeating units). TGA analysis showed that PAEK‐x‐BrTM exhibited a very low‐decomposition temperature at about 200°C corresponding to the C Br bond cleavage. The hydroxide conductivity of TMPAEK‐NOH membrane was 8 mS cm⁻¹ at room temperature, while the water uptake of TMPAEK‐NOH membrane was 22.3% at 20°C and 32.6% at 60°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Morphological study on the reactivity of styrene‐divinylbenzene copolymers in a chloromethylation reaction

Styrene‐divinylbenzene (S‐DVB) copolymers with different kinds of porous structures were synthesized by aqueous suspension polymerization using n‐heptane as the pore forming agent. The amount of this solvent (monomer dilution degree) and the DVB content in the organic phase were varied. The combination of three different dilution degree values and three DVB contents yielded three series of copolymers with a variety of porous structures. The three series were composed by copolymers with pore diameters (D) in the following ranges: D < 500 Å, 500 < D < 1000 Å, and D > 1000 Å, respectively. The effect of synthesis conditions on the pore size distribution and on the copolymer matrix rigidity was evaluated. These copolymers were submitted to a chloromethylation reaction with a paraformaldehyde/gaseous HCl mixture in the presence of zinc chloride as a Lewis acid catalyst and 1,2‐dichloroethane as solvent. The effect of the copolymer porosity on the chloromethylation reaction extension was evaluated. It was possible to observe that a gel copolymer with a high swelling capacity in the reaction medium achieved the same chloromethylation yield observed for a high porous copolymer. This result thus indicates that, in the case of the chloromethylation reaction studied here, the high swelling capacity of the gel copolymer can counterbalance its limited surface area, turning this type of polymer structure as reactive as a macroporous one. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Production of microporous resins for heavy‐metal removal. II. Functionalized polymers

Ion‐exchange polymers were used successfully in water‐treatment operations. In this study, three ion‐exchange resins based on 4‐vinylpyridine and divinylbenzene functionalized with N‐oxide groups were obtained. Their ion‐adsorption properties were measured in solutions containing chromium at concentrations of 4 and 500 ppm with column and batch equilibrium techniques. The removal efficiency of the chromium ions with HCl was observed to increase after the protonation of the N‐oxide groups. The resins could be reused after 10 cycles with the metal removal efficiency maintained at higher than 95%. These studies evidenced a strong correlation between the morphology and ionic group content in the resin and its chromium ion sorption capability. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation and characterization of high efficiency ion‐exchange crosslinked acrylic fibers

Commercial acrylic fiber samples were first pretreated with hydrazine under various concentrations to give crosslinked structure. Then, the crosslinked fiber samples with different degree of crosslinking were treated with hydroxylamine hydrochloride to develop ion‐exchange fibers. These fibers contain amidoxime, amine, amide, and hydrazide groups simultaneously. The effects of reaction conditions on physical properties, thermal characteristics, surface morphology, ion adsorption quantity, and reusability were investigated. The results show that by increasing the reaction time, temperature, and concentration of hydroxylamine hydrochloride, the content of amidoxime groups in all samples were increased, but with noncrosslinked fibers noticeable drop in the mechanical properties were observed, while in crosslinked sample prepared under optimum conditions of reaction, good ion adsorption capacity with keeping mechanical properties was achieved. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2202–2209, 2006     

Novel grafted nafion membranes for proton‐exchange membrane fuel cell applications

Novel poly(glycidyl methacrylate)‐grafted Nafion–phosphoric acid membranes for direct‐oxidation methanol fuel cells were prepared with a potassium persulfate chemical initiation system for the first time. The introduced epoxy groups were converted to amine groups through a reaction with ethylenediamine, which consequently doped with phosphoric acid ( PO₃H) groups. The latter significantly contributed to enhancing the ion‐exchange capacity, mechanical properties, and thermal stability. Factors affecting the modification steps were studied. Changes in the chemical and morphological structure were verified through Fourier transform infrared spectroscopy, TGA, and scanning electron microscopy characterization. Various grafting percentages (GP%'s) up to 32.31% were obtained. As a result, the thickness of the grafted membranes increased. Furthermore, the methanol permeability of the modified membranes was reduced with increasing grafted polymer content compared with that of the Nafion membrane. An 83.64% reduction in the methanol permeability was obtained with a polymer grafted content of 18.27%. Finally, the efficiency factor for all of the modified Nafion membranes was enhanced compared with that of Nafion. A fourfold improvement was obtained with membranes with a GP% of 18.27% as a maximum value. Such promising results nominate the used technique as a one for the improvement of Nafion membrane efficiency. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mesoporous silica as smart lubrication containers applied to self-lubricating polyurethane materials

Self-lubricating composite with stimuli-responsive properties attracts great interest in recent years. Herein, mesoporous silica (MS) as oil-laden containers is explored to achieve self-lubricating feature. The as-prepared MS possesses a high Brunauer-Emmett-Teller (BET) surface area (1,542.35 m²/g), which satisfies the criterion for construction of ideal repository for storing enough liquid lubricants. In addition, the thermal stimuli-responsiveness behavior of the oil-laden mesoporous silica (OMS) for lubrication has been investigated by thermogravimetric analyzer tester. As expected, an excellent tribological performance (friction coefficient and wear rate decreased by 63.29 and 82.63%) is obtained by adding 10 wt% OMS into the polyurathene matrix, showing great promise for self-lubricating application.     

Superhydrophobic polyurethane and silica nanoparticles coating with high transparency and fluorescence

A superhydrophobic surface was prepared by spin‐coating trimethylsiloxane functionalized SiO₂ (TMS‐SiO₂) solutions onto a precoated polyurethane (PU) layer. The superhydrophobic coatings showed high stability with time, and the prepared coatings remained superhydrophobicity even after 6 months. Furthermore, the as‐prepared surface showed high transparency with a transmittance above 70% in visible light region (400–800 nm). The transition of the composite surface from superhydrophobicity to hydrophilicity can be achieved by increasing the drying temperature. More interestingly, the surface showed excellent fluorescent property by the incorporation of fluorescent Europium (Eu) complex into the surface and without deteriorating the superhydrophobic and transparent properties. It was believed that the superhydrophobic surface with multifunction would broaden the applications of superhydrophobic materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Competitive adsorption of uranyl ions in the presence of Pb(II) and Cd(II) ions by poly(glycidyl methacrylate) microbeads carrying amidoxime groups and polarographic determination

The adsorption capacity of UO in the presence of Pb(II) and Cd(II) ions was investigated with amidoximated poly(glycidyl methacrylate) (PGMA) microbeads with an average size of 135 μm packed in a glass column (0.5‐cm i.d. and 20‐cm length, flow rate = 3 mL/min) under competitive conditions. A differential pulse polarography technique was used for the determination of trace quantities of uptaken elements by the measurement of the reduction peak currents at ?200/?950, ?400, and ?600 mV (vs a saturated calomel electrode) for UO, Pb(II), and Cd(II) ions, respectively. When only UO was found in the eluate, its adsorption was 85.3% from a 50 μM initial solution. However, when there was UO with binary systems of Pb(II) or Cd(II), it was 78.2 and 76.3%, respectively. On the other hand, in a ternary mixture of UO with Pb(II) and Cd(II), the adsorption was found to be 75.2% with the same initial concentration. According to the results, the competitive adsorption studies showed that these amidoximated PGMA microbeads had good adsorption selectivity for UO with the coexistence of Pb(II) and Cd(II) ions. The ionic strength of the solution also influenced the UO adsorption capacity of the amidoximated PGMA microbeads. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4168–4172, 2007     

A simple postsulfonation of poly(arylene ether sulfone) Radel® R

Commercially available Radel® R, a poorly acid resistant biphenol‐based poly(arylene ether sulfone), was successfully sulfonated by a simple and rapid postsulfonation reaction using oleum as the sulfonating agent. Polymer degradation due to contact with acid could easily be minimized by adjusting reaction conditions. The suitable reaction conditions, when the 1 : 3 molar ratio of the polymer to the sulfonating agent was used, were: 10% of oleum in chloroform, 10% concentration of Radel® R in chloroform, and temperature between 0 and 50°C. Under these conditions, the reaction was complete within 45 min. Thermal properties, degradation characteristics and the viscosity of the postsulfonated polymer are reported. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Modification of silica gel,cellulose, and polyurethane with a sterically hindered N‐halamine moiety to produce antimicrobial activity

The sterically hindered amine monomer 4‐[3‐triethoxysilylpropoxyl]‐2,2,6,6‐tetramethylpiperidine has been synthesized and covalently bonded to the surfaces of silica gel particles and cellulose (cotton) and copolymerized in a polyurethane coating formulation. Upon exposure to dilute sodium hypochlorite (household bleach), a very stable N‐Cl bond is formed in situ at the hindered amine nitrogen site. This source of oxidative chlorine provides an antimicrobial function to the silica gel, cotton, and polyurethane. Stability, regenerability, and biocidal efficacy data are presented. The new N‐halamine materials were remarkably effective against Staphylococcus aureus and Escherichia coli O157 : H7 in brief periods of contact. The materials should find application in water treatment and medical applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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     

Antimicrobial silica and sand particles functionalized with an N‐halamine acrylamidesiloxane copolymer

The monomer 2‐acrylamido‐2‐methyl‐1‐(5‐methylhydantoinyl)propane (HA) was copolymerized with 3‐(trimethoxysilyl)propyl methacrylate (SL) and covalently attached onto silica gel and sand particles. As a result HASL copolymer‐grafted silica gel and sand particles (HASL SGPs and SPs) were obtained. These two types of HASL SGPs and SPs provided excellent biocidal efficacy against Gram positive S. aureus and Gram negative E. coli O157:H7 bacteria when the copolymer‐grafted particles were exposed to dilute sodium hypochlorite (household bleach) solution. In a flowing water application, seven logs of bacteria were inactivated within 10 s of contact time with the particles packed into a column. The treated particles also exhibited good washing and storage stabilities. The chlorine loss during extensive flow could be recovered by further exposure to dilute bleach solution. The antimicrobial particles have potential application for use in inexpensive disinfecting water filters for slow water flows. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43413.     

Highly conductive polymer composites with excellent toughness,fluidity and temperature-independent conductivity

Conductive polymer composites of low melting point metal/ high melting point metal/polymer were prepared by melt mixing and investigated the effects of Sn-to-Cu content ratio on the microstructure and properties of Sn/Cu/PA6 ternary composites with a metal content of 53.3 vol %. The results show that Sn reacts with Cu to form intermetallic compounds during melting processing. When V_Sn/V_Cu is less than 1.5, the metal phase is a solid. However, if V_Sn/V_Cu is higher than 1.5, the metal phase is a suspension. As V_Sn/V_Cu increases, the morphology of metal phase changes from “islands” to physically continuous networks, and the Volume resistivity, impact strength and complex viscosity of the composites can reach 1.11 × 10⁻⁴ Ω cm, 3.8 kJ/m² and 2.4 × 10³ Pa s, respectively. Moreover, the resistivity of the composites with physically continuous networks is almost independent of temperature. The combination of low and high melt point metals can be considered as a useful strategy to prepare conductive polymer composites with high performance. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48820.     

Water-soluble polymeric chemosensor for detection of Cu2+ ions with high selectivity and sensitivity

Development of water-soluble chemosensors that are selective and sensitive to Cu²⁺ ions is of tremendous importance owing to their potential applications in biological systems. In the present work, we report the synthesis of a new water-soluble polymer containing pendant rhodamine units that are capable of highly selective and sensitive detection of Cu²⁺ ions in aqueous medium. Poly(2-pyrrolidinemethyl acrylate) was prepared using RAFT polymerization technique. The pyrrolidine nitrogen group in the polymer was subjected to Aza-Michael type addition with ethyl acrylate that was followed by covalent linking of rhodamine units to the polymer. This polymer was completely water-soluble and found to be capable of sensing Cu²⁺ ions in aqueous medium. Cu²⁺-induced opening of the spirolactam ring of the rhodamine units resulted in rapid and easily noticeable colour change, thus enabling a highly selective detection of Cu²⁺ in μmol range. The ability of these polymeric systems to detect Cu²⁺ ions in complete aqueous media has more importance than use of organic solvents to solubilize the polymer as reported previously, and thus opened a new window for application of these systems in the detection of copper ions in biological systems.     

Adsorption of Zn(II) by crosslinked acrylic copolymers with amine functional groups

Adsorption of Zn(II) ions from diluted aqueous solutions by the acrylic copolymer based on ethylacrylate : acrylonitrile : divinylbenzene matrix with different crosslinking degrees and ethylenediamine and triethylenetetramine functional groups was investigated. Adsorption experiments were carried out by batch method. The effects of the pH, initial concentration of zinc, time of contact, and the crosslinking degree of the copolymers were studied. On the basis of Langmuir and Freundlich isotherms, the parameters that characterize the adsorption were determined. The maximum Zn(II) retention capacity value (500 mg g^?1) was obtained for the acrylic copolymer with 2% crosslinking degree and ethylenediamine, as functional groups. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 803–808, 2004     

Imidazole functionalized polyaniline: Synthesis,characterization, and Cu (II) coordination studies

Polyaniline functionalized with imidazole as strategically designed receptor group in its backbone was synthesized for copper binding. The synthesized polymer has been characterized using FTIR, NMR, and UV‐Vis spectroscopic techniques. The addition of copper (II) to the polymer distinctly changes the properties such as crystallinity, molecular weight, aggregation, and electronic properties. XRD, DLS, SEM, and four‐point probe techniques have been used for study of these changes. It is observed that the secondary ion generated as a result of copper coordination results in the doping of the polyaniline backbone, which enhances the conductivity by one order of magnitude. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011