Metal ion sorption properties of water-insoluble resins based on sodium styrene sulfonate and different comonomers

A set of water-insoluble resins based on sodium styrene sulfonate and different comonomers were synthesized. The resins poly(mono-2-(methacryloyloxy)ethyl succinate-co-sodium 4-styrene sulfonate) P(MOES-co-SSNa), poly(2-acrylamido glycolic acid-co-sodium 4-styrene sulfonate) P(AGA-co-SSNa), poly(acrylamide-co-sodium 4-styrene sulfonate) P(AAm-co-SSNa), and poly(2-(dimethylamine)ethyl acrylate-co-sodium 4-styrene sulfonate) P(DMAEA-co-SSNa) were synthesized by solution radical polymerization. The metal ion retention properties were studied by batch procedure for Cd(II), Zn(II), Pb(II), and Hg(II). Resins performance was compared with a poly(sodium 4-styrene sulfonate) (PSSNa) resin in order to evaluate the effect of comonomer on sorption properties. The effect of pH, time, temperature, and maximum retention capacity were studied. In addition, sorption experiments were carried out under competitive ion conditions to study the selectivity of resins. The resins P(AAm-co-SSNa) and P(AGA-co-SSNa), showed the most important differences compared with PSSNa resin, the former present higher sorption and the latter presented selectivity for Hg(II) at pH 2.     

Synthesis,characterization and polychelatogenic properties of poly[(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid)‐co‐(methacrylic acid)]

Poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid), poly(methacrylic acid), and five copolymers of poly[(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)‐co‐(methacrylic acid)] were synthesized by radical polymerization and obtained in yields >97%. The polymers were characterized by FT‐IR, [¹H]NMR, and [¹³C]NMR and studied by means of the Liquid‐phase Polymer‐based Retention (LPR) technique. The metal ion retention ability of the copolymers for Cu(II), Cd(II), Co(II), Hg(II), Ni(II), Zn(II), Cr(III) and Ag(I) was investigated at different pH values because of their environmental and analytical interest. The retention profiles of the copolymers were compared with those of the corresponding homopolymers and retention of metal ions was found to increase with increasing pH. © 2001 Society of Chemical Industry     

Metal‐ion‐retention properties of the poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine) resin

The water‐insoluble resin poly(2‐acrylamido‐2‐methyl‐1‐propanosulfonic acid‐co‐4‐vinyl pyridine), through a radical polymerization solution, was synthesized with ammonium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinking reagent. The metal‐ion‐retention properties were studied by batch and column equilibrium procedures for the following metal ions: Hg(II), Cu(II), Cd(II), Zn(II), Pb(II), and Cr(III). These properties were investigated under competitive and noncompetitive conditions. The effects of the pH, maximum retention capacity, and regeneration capacity were studied. The resin showed a high retention ability for Hg(II) ions at pH 2.0. The retention of Hg(II) ions from a mixture of ions was greater than 90%. The resin showed a high selectivity for Hg(II) with respect to other metal ions. The Hg(II)‐loaded resin was able to be recovered with 4M HClO₄. The retention capacity was kept after four cycles of adsorption and desorption. The retention properties for Hg(II) were very similar with the batch and column methods. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3556–3562, 2003     

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     

Poly(sodium 4-styrene sulfonate) and poly(2-acrylamidoglycolic acid) nanocomposite hydrogels: montmorillonite effect on water absorption,thermal, and rheological properties

A systematic study of water absorbency, thermal, and rheological properties was performed on nanocomposite hydrogels of poly(sodium 4-styrene sulfonate) (PSSNa) and poly(2-acrylamide glycolic acid) (PAAG). Montmorillonite was used as clay filler and was previously modified to hydrogel synthesis by addition of (3-acrylamide propyl)trimethylammonium chloride. Syntheses were carried out by in situ radical polymerization, using N,N-methylen-bis-acrylamide as crosslinker reagent. Nanocomposites showed an exfoliated morphology, confirmed by transmission electron microscopy and X-ray diffraction. The water absorption capacity (WAC) of unloaded PSSNa hydrogel was three times higher than for PAAG; due to clay addition, absorption capacity increased for PSSNa nanocomposites and decreased for PAAG. Finally, rheological properties of nanocomposite hydrogels were studied by both dynamic oscillatory test and shear creep analysis. Results showed improvements on mechanical properties, such as yield point, elastic recovery, and storage modulus as consequence of montmorillonite addition.     

Separation of metal ions by water‐insoluble polymers containing sulfonic/sulfonate groups

A water‐insoluble polymer, poly(sodium 4‐styrene sulfonate), was synthesized by radical polymerization at different amounts (2, 4, 6, and 8 mol %) of crosslinking reagent (CR). At the lowest CR level (2 mol %), only a water‐soluble polymer is obtained, and consequently it could not be studied as resin. The polymerization yield ranged from 82.6 to 91.6%. The resin is characterized by FTIR spectroscopy, thermal analysis, and scanning electron microscopy. The metal ion affinity is studied for the cations: Hg(II), Cd(II), Zn(II), Pb(II), Cr(III), and Al(III) with a batch equilibrium procedure under different experimental conditions. The metal ion affinity increased as the pH increased. At pH 5, the resin showed an affinity greater than 97% for all metal ions. Hg(II) showed the highest retention value at pH 2. The maximum retention capacity is determined at optimum pH for Hg(II), Cd(II), Pb(II), and Zn(II). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4328–4333, 2006     

Structural effects of type of intercalant in poly (4‐vinylpyridine) nanocomposites: compatible homopolymer or block copolymer

4‐vinylpyridine monomer was mixed with organophilic montmorillonite (MMT) clay and polymerized in the presence of free‐radical initiator. MMT clay was rendered organophilic by means of ion‐exchanging sodium cations for low‐molecular‐weight quaternized poly(4‐vinylpyridine) (P4VP) homopolymer and diblock copolymers of styrene and quaternized 4‐vinylpyridine (SVP) with different sequence lengths. The swelling behaviour of the MMT clay was studied by X‐ray diffraction (XRD). After the cation exchange, the resulting organophilic clays showed an expansion of interlayer distance indicating the nanoscale ordering of intercalant polymer and MMT layers. The nanocomposite materials, when moulded, exhibited improved thermal stability and dynamic mechanical properties compared with neat P4VP. The composite, having longer ionic segments in its organophilic MMT, showed exfoliated nanocomposite structure as well as higher stiffness and damping properties at higher temperatures even for MMT loading as low as 2 wt%. Copyright © 2006 Society of Chemical Industry     

Water‐insoluble polymers with ability to remove metal ions

Crosslinked poly[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide‐co‐2‐acrylamido glycolic acid [P(MAAPDSA‐co‐AGCO)] was synthesized by radical polymerization and tested as an adsorbent under competitive and noncompetitive conditions for Cu(II), Cd(II), Hg(II), Zn(II), Pb(II), and Cr(III) by batch and column equilibrium procedures. The resin–metal ion equilibrium was achieved before 1 h. The resin showed a maximum retention capacity value for Hg(II) at pH 2 of 1.084 meq/g. The recovery of the resin was investigated at 20°C under different concentrations of HNO₃ and HClO₄. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3679–3685, 2004     

Montmorillonite clay nanocomposites based on vinyl pyridine‐styrene‐butadiene terpolymer (VPR)/acrylonitrile‐butadiene rubber (NBR) blend

This study describes a novel route to synthesize vinyl pyridine‐styrene‐butadiene terpolymer rubber (VP rubber) montmorillonite clay nanocomposites by latex blending technique. The pyridine moiety of the VP rubber was modified with methyl iodide to form the pyridinium ion during latex blending. Cation exchange reaction of the pyridinium ion of the VP rubber latex with sodium montmorillonite occurred during latex stage mixing which helped to form VP rubber‐montmorillonite clay nanocomposites. Coagulation of the latex‐clay slurry produced nanocomposites master batch. The master batch was compounded with acrylonitrile butadiene rubber (NBR). Fourier Transform Infrared Spectroscopy (FTIR) confirmed the modification of the pyridine moiety of VP rubber. Wide angle X‐ray diffraction (WAXD), scanning electron microscopy‐energy dispersive X‐ray spectrophotometry (SEM‐EDS) and transmission electron microscopy (TEM) provided the evidences of formation of nanocomposite. Remarkable improvements in the mechanical properties were found by addition of small amount of modified clay. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Trace metal ion retention properties of crosslinked poly(4‐vinylpyridine) and poly(acrylic acid)

The crosslinked resins poly(4‐vinylpiridine) (PVPy) and poly(acrylic acid) (PAA) were obtained by radical polymerization. PVPy shows monodentate ligands and PAA at basic pH is basically as acrylate anion, which can contain end‐carboxylates groups or form a bridge acting as mono‐ or bidentate ligands. The retention properties for trace metal ions from saline aqueous solutions and natural seawaters of these two resins were investigated by Batch equilibrium procedure. The metal ions studied were Cu(II), Pb(II), Cd(II), and Ni(II). The following effects were studied: pH, contact time, amount of the adsorbent, temperature, and salinity. The resin PVPy showed a high affinity for Cd(II) and PAA for Cu(II) and Cd(II). The metal ions were determined in the filtrate by atomic absorption spectrometry. By the treatment of the loaded resin with 4M HNO₃, it was possible to remove completely the Cu(II) ions. The retention properties of the resins were studied for trace metal ions present in the natural seawaters. Both resins showed a high affinity for Cd(II) when the natural seawater contained Cu(II) and Cd(II). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2908–2916, 2004     

Novel water‐soluble acryloylmorpholine copolymers: Synthesis,characterization, and metal ion binding properties

Poly(4‐acryloylmorpholine), poly(4‐acryloylmorpholine‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) were synthesized by radical polymerization. The water‐soluble polymers obtained, containing tertiary amino, amide, and sulfonic acid groups, were investigated, in view of their metal binding properties, as polychelatogens by using the liquid‐phase polymer‐based retention technique, under different experimental conditions. The metal ions investigated were Ag(I), Cu(II), Co(II), Ni(II), Cd(II), Pb(II), Zn(II), Cr(III), and Al(III). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 180–185, 2006     

Synthesis and application of polymer–clay nanocomposite‐supported dichromate oxidizing agent

A hybride polymer–clay nanocomposite supported dichromate reagents was prepared. Direct interaction of poly(styrene‐co‐N‐methyl‐4‐vinylpyridinium) iodide with sodium montmorillonite (MMT) through ion exchange between sodium cations in MMT and pyridinium ions in the copolymer afforded a polymer–clay nanocomposite (3). The resulting nanocomposite was reacted with potassium dichromate to form the nanocomposite‐supported reagents (4). The structure of the resulting nanocomposite was characterized by elemental analysis, infrared spectroscopy, X‐ray diffraction and transmission electron microscopy. The dispersion of the MMT particles in the polymer matrix was confirmed using scanning electron microscopy. X‐ray mapping for silicon in the nanocomposite revealed uniform distribution of Si in the polymer matrix. The effectiveness of these materials has been tested for oxidation of saturated primary, secondary and benzylic alcohols to their corresponding aldehydic and ketonic compounds in addition to oxidation of quinol to the corresponding quinone. Importantly, there is almost no formation of side‐product of this process. POLYM. COMPOS., 36:2066–2075, 2015. © 2014 Society of Plastics Engineer     

Metal ion retention properties of poly(acrylic acid) and poly[N‐3‐(dimethylamino)propyl acrylamide‐co‐acrylic acid]

The crosslinked resins poly(acrylic acid) (PAA) and poly[N‐3‐(dimethylamino)propyl acrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] are obtained by radical polymerization and characterized by FTIR spectroscopy. PAA at basic pH exists basically as an acrylate anion that may contain end carboxylate groups or form bridges acting as mono‐ or bidentate ligands. P(NDAPA‐co‐AA) presents three potential ligand groups in its structure: carboxylic acid, amide, and amine. The trace metal ion retention properties of these two resins is compared by using the batch equilibrium procedure. The metal ions are contained in saline aqueous solutions and are found in natural seawater. The retention of Cu(II), Pb(II), Cd(II), and Ni(II) metal ions is studied under competitive and noncompetitive conditions. The effects on the pH, contact time, amount of adsorbent, temperature, and salinity are investigated. The PAA resin presents a high affinity (>80%) for Cu(II) and Cd(II) ions. The P(NDAPA‐co‐AA) resin shows a high affinity for Pb(II) and Cd(II) ions. With 4M HNO₃ it is possible to completely recover the PAA resin charged with Cu(II) ions and the P(NDAPA‐co‐AA) resin charged with Pb(II) ions. The two resins show a high affinity for Cd(II) ions from the seawater containing Cu(II) and Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1385–1394, 2005     

Removal properties of crosslinked poly(2‐acrylamido glycolic acid) for trace heavy metal ions: Effect of pH,temperature, contact time,and salinity on the adsorption behavior

Crosslinked poly(2‐acrylamido glycolic acid) resin was synthesized by radical polymerization. This resin contains three potential ligand groups and was studied as an adsorbent of trace heavy metal ions from a saline aqueous solution and sea water by using the Batch equilibrium procedure. Adsorption characteristics of the resin toward Cu(II), Ni(II), Cd(II), and Pb(II) were studied spectrophotometrically, both in competitive and noncompetitive conditions. The effect of pH, contact time, amount of sorbent, temperature, and salinity were studied. The resin showed a high affinity particularly for Ni(II). It was possible to remove completely Ni(II) and Pb(II) from the resin by 4M HNO₃. The retention properties of the resin were also investigated for Cu(II) contained in natural sea waters. The retention behavior was similar to that of the synthetic metal ion aqueous solution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2614–2621, 2003     

Designing of fullers‐earth‐containing poly(vinyl alcohol)‐g‐poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) nanocomposites: Swelling and deswelling behaviors

In this study, polymer–clay nanocomposites (PCNs) composed of poly(vinyl alcohol)s (PVAs), poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid), and fullers earth were prepared by the effective dispersal of inorganic nanoclays in the organic PVA matrix via in situ free‐radical polymerization with potassium persulfate as an initiator and N,N‐methylene bisacrylamide as a crosslinker. The monomer, 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid, was grafted onto the PVA backbone, and at the same time, fullers earth layers were intercalated and exfoliated into the grafted copolymer, especially at a low or moderate loading of the fullers earth. The synthesized PCN materials were characterized by Fourier transform infrared spectroscopy and wide‐angle X‐ray diffraction techniques. The morphological features of the synthesized materials were studied by scanning electron microscopy; this revealed that the swelling ratio of this nanocomposite increased with increasing fullers earth content. The X‐ray diffraction results indicated that the fullers earth was exfoliated in the nanocomposite matrix, and its introduction into the polymer matrix enhanced the percentage crystallinity of the polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(sodium 4-styrenesulfonate)–metal ion interactions

The metal ion-binding properties of poly(sodium 4-styrenesulfonate) in conjunction with membrane filtration were investigated for Cu(II), Cd(II), Co(II), Cr(III), Hg(II), Ni(II), Pb(II), Zn(II), and Fe(II). Different experiments were carried out at different pH's, metal ion concentrations, polymer concentrations, and molecular weight fractions. Only Fe(II) and Cr(III) were retained at pH 1, which allows a selective separation of these metals from all the other metal ions. At pH 3 the retention ability of this polymer increased for all the metal ions. On the other hand, the metal ion-retention properties are dependent on the polymer/metal ratio. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 219–225, 1998     

Novel POBD‐modified organoclay and its polyimide nanocomposites for removal of the Co(II) ion

An organophilic clay has been obtained via cation exchange reaction between sodium montmorillonite and the hydrochloride salt of 2‐(5‐(3,5‐diaminophenyl)‐1,3,4‐oxadiazole‐2‐yl)pyridine, POBD. Thermogravimetric analysis (TGA) showed that thermal decomposition of the organophilic clay starts at about 350°C, which shows that it is quite thermally stable compared with conventional montmorillonite modified with aliphatic long chain surfactants. POBD‐modified organoclay almost quantitatively removed the Co(II) ion from aqueous solution at pH = 10.0 (Q_t = 3.00 mg g⁻¹, R = 98.2%). A series of polyimide/clay nanocomposite materials (PCNs) consisting of POBD and benzophenone‐3,3′,4,4′‐tetracarboxylic dianhydride, BTDA were also prepared by an in situ polymerization reaction via thermal imidization. POBD‐modified organoclay was used as a surfactant at different concentrations. Intercalation of polymer chains within the organoclay galleries was confirmed by WXRD. Both the glass transition temperature and thermal stability are increased with respect to pristine PI at low clay concentrations. At high clay loadings, the aggregation of organoclay particles results in a decrease in T_g and thermal stability. In the SEM images of PCN 1 and 3%, too many micro cracks are observed in the background, and a flower‐shape pattern spreads uniformly over the entire surface. The maximum Co(II) uptake capacity and efficiency were observed at pH 10.0 within a 40‐h period for both PI and PCN films. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Adsorption of poly (4‐sodium styrene sulfonate) on kaolinite clays

The adsorption of polymer on clay particles has great importance in many industrial applications. This work aimed to study the adsorption of anionic polymer, poly (4‐sodium styrene sulfonate), on kaolinite clay surfaces. Three different Egyptian kaolinite clay samples were used. The kaolinite clays were saturated with sodium or calcium cation. It was found that the Freundlich isotherm is applicable for this polymer adsorption on kaolinite. The parameters of the Freundlich equation are very close, indicating a comparable nature for the binding behavior between the different samples of kaolinite and the adsorbed polymer. The adsorption process was examined at different pH values (3, 6, and 9 ± 0.1) to cover the range below and above the point of zero charge of kaolinite surfaces. It was found that, below this point, the polymer adsorption increased, while above it the polymer adsorption decreased. The polymer adsorption on calcium kaolinite was higher than that of sodium kaolinite at the same pH value. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1712–1719, 2006     

Preparation and performance of a transparent poly(3,4‐ethylene dioxythiophene)–poly(p‐styrene sulfonate‐co‐acrylic acid sodium) film with a high stability and water resistance

Poly(p‐styrene sulfonate‐co‐acrylic acid sodium) (PSA) from the copolymerization of acrylic acid sodium and p‐styrene sulfonate monomers were used to dope poly(3,4‐ethylene dioxythiophene) (PEDOT) to generate PEDOT–PSA antistatic dispersions. Compared to those of the PEDOT–poly(p‐styrene sulfonate sodium) (PSS), the physical and electrical properties of the PEDOT–PSA conductive liquids were much better. The PEDOT–PSA films possessed a better water resistance without a decrease in the conductivity. The sheet resistance of the PEDOT–PSA–poly(ethylene terephthalate) (PET) films was about 1.5 × 10⁴ Ω/sq with a 100 nm thickness, the same as the PEDOT–PSS–PET films. The transmittance of the PEDOT–PSA–PET films exceeded 88%. Furthermore, the environmental dispersity of the PEDOT–PSA antistatic dispersion was apparently improved by the dopant PSA so that the stability was extraordinarily promoted. Meanwhile, the water resistances of the PEDOT–PSA–PET and PEDOT–PSA films were also enhanced. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45163.     

Poly(N-hydroxymethyl acrylamide-co-acrylic acid) and poly(N-hydroxymethyl acrylamide-co-acrylamidoglycolic acid): synthesis, characterization, and metal ion removal properties

Macroreticular chelating resins containing carboxylic groups, poly(N-hydroxymethyl acrylamide-co-acrylic acid) P(HMA-co-AA) and poly(N-hydroxymethyl acrylamide-co-2-acrylamido glycolic acid) P(HMA-co-AGA) were synthesized by solution radical polymerization with ammonium persulfate as initiator and N,N′-methylene-bis-acrylamide as cross-linking reagent. The polymerization yield was 98.9 and 91.9% for P(HMA-co-AA) and P(HMA-co-AGA), respectively. The retention properties were studied under competitive and noncompetitive conditions by batch equilibrium procedure for the following metal ions: Cd(II), Cr(III), Zn(II), Pb(II), and Hg(II). The effects of pH, time, temperature, and initial ion concentration on adsorption were investigated. The resins showed a significant ability to retain Pb(II), greater than 79%, at pH 5.