Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

Metal ion adsorption behavior of poly[3‐(dimethylamine)propyl acrylate] and poly[3‐(dimethylamine)propylacrylate‐co‐acrylic acid] resins

Two resins were synthesized by radical polymerization using N,N′‐methylene‐bis‐acrylamide and ammonium persulfate as the crosslinking reagent and initiator, respectively. The yields were 98%. The resins were characterized by FTIR and UV‐Vis spectroscopy. Sorption behavior of resins toward Hg(II), Cd(II), Zn(II), Pb(II), and Cr(III) ions was studied at different pHs depending on the metal ion. Both resins showed selective sorption to Hg(II) ions at pH 2 from a mixture of all ions.The elution of Hg(II) bound to the resins was also investigated using perchloric acid at different concentrations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1251–1256, 2002; DOI 10.1002/app.10455     

Studies on poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) and its metal complexes

8‐Hydroxy‐4‐azoquinolinephenylmethacrylate (8H4AQPMA) was prepared and polymerized in ethyl methyl ketone (EMK) at 65°C using benzoyl peroxide as free radical initiator. Poly(8‐hydroxy‐4‐azoquinolinephenylmethacrylate) poly(8H4AQPMA) was characterized by infrared and nuclear magnetic resonance techniques. The molecular weight of the polymer was determined by gel permeation chromatography. Cu(II) and Ni(II) complexes of poly(8H4AQPMA) were prepared. Elemental analysis of polychelates suggests that the metal‐ligand ratio is about 1 : 2. The polychelates were further characterized by infrared spectra, X‐ray diffraction, spectral studies, and magnetic moments. Thermal analyses of the polymer and polychelates were carried out in air. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1516–1522, 2006     

Some Mechanical Properties of Poly[(acrylic acid)‐co‐(itaconic acid)] Hydrogels

Two series of hydrogels of poly[(acrylic acid)‐co‐(itaconic acid)] have been prepared by copolymerization in solution using tetrafunctional N,N′‐methylenebisacrylamide (NMBA) as cross‐linker. The resulting polymer was swollen in water at 298 K to yield homogenous transparent hydrogels. These hydrogels were characterized in terms of swelling and compression‐strain measurements. The influence of the comonomer composition and concentration of cross‐linking agent on volumetric swelling and the mechanical properties of these hydrogels were investigated. Inefficient cross‐linking is indicated by the small values of ν_e relative to the theoretical cross‐linking densities.

Dependence of measured affective cross‐linking density (ν_e) on the theoretical cross‐linking density (ν_t) for acrylic acid/itaconic acid hydrogels prepared at a fixed composition of AA80/AI20 wt.‐%, but at different concentrations of NMBA.     

The structure characterization of thermosensitive poly(N‐isopropylacrylamide‐co‐2‐hydroxypropyl methacrylate) hydrogel

The goal of this work was to investigate a possible way of crosslinking polymer chains and the potential formation of intramolecular hydrogen bonds in thermosensitive poly(N‐isopropylacrylamide‐co‐2‐hydroxypropyl methacrylate) (p(NIPAM‐HPMet)) hydrogels obtained by radical polymerization. The chemical structure of the synthesized hydrogels was investigated by Fourier transform infrared (FTIR) spectroscopy and XRD. The FTIR spectrum confirmed the presence of hydrogen bonds formed between the chains in the copolymer. XRD analysis confirmed the amorphous ? crystalline structure of the copolymer. A three‐glass transition and two melting temperatures were detected by DSC. It was found that the addition of HPMet increased the glass transition and melting temperatures of the p(NIPAM‐HPMet) copolymer. The swelling transport mechanism of p(NIPAM‐HPMet) changed from non‐Fickian at 20 °C to case III or zero‐order time‐independent kinetics characterized by a linear mass uptake with time with increasing temperature at 40 °C. © 2013 Society of Chemical Industry     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Nonionic water‐soluble polymer: Preparation,characterization, and application of poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) as a polychelatogen

The free‐radical copolymerization of water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) was carried out with a feed monomer ratio of 75:25 mol %, and the total monomer concentration was 2.67M. The synthesis of the copolymer was carried out in dioxane at 70°C with benzoyl peroxide as the initiator. The copolymer composition was obtained with elemental analysis and ¹H‐NMR spectroscopy. The water‐soluble polymer was characterized with elemental analysis, Fourier transform infrared, ¹H‐ and ¹³C‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymer were performed. The thermal behavior of the copolymer and its complexes were investigated with differential scanning calorimetry (DSC) and thermogravimetry techniques under a nitrogen atmosphere. The copolymer showed high thermal stability and a glass transition in the DSC curves. The separation of various metal ions by the water‐soluble poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) reagent in the aqueous phase with liquid‐phase polymer‐based retention was investigated. The method was based on the retention of inorganic ions by this polymer in a membrane filtration cell and subsequent separation of low‐molar‐mass species from the polymer/metal‐ion complex formed. Poly(1‐vinyl‐2‐pyrrolidone‐co‐hydroxyethylmethacrylate) could bind metal ions such as Cr(III), Co(II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) in aqueous solutions at pHs 3, 5, and 7. The retention percentage for all the metal ions in the polymer was increased at pH 7, at which the maximum retention capacity could be observed. The interaction of inorganic ions with the hydrophilic polymer was determined as a function of the pH and filtration factor. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 178–185, 2006     

Synthesis and properties of chitosan‐modified poly(acrylic acid)

Potassium persulfate (K₂S₂O₈) was used to initiate the polymerization of acrylic acid (AA) monomer in a chitosan (CS) solution. Both a poly(acrylic acid) (PAA) homopolymer and a CS‐co‐PAA copolymer were produced. When the amount of AA was increased from 5 to 40 g with 5 g of CS, the total monomer conversion was found to increase from 89 to 98% after 2 h of reaction at 70°C. In addition, the percentage of reacted AA monomer being converted to the CS‐co‐PAA copolymer (copolymerization efficiency) and the weight composition of the PAA portion in the copolymer (copolymer composition) both increased with the amount of AA added. The structures and properties of the synthesized CS‐modified PAA polymers were studied. In Fourier transform infrared spectra, the formation of a polyelectrolyte complex between CS chains and PAA chains could be observed. From the thermograms obtained via differential scanning calorimetry, we found that the presence of rigid CS chains increased the glass‐transition temperature of PAA. Thermogravimetric analysis revealed three stages of degradation of the synthesized CS‐modified PAA polymers. The swelling ratio of the CS‐modified PAA polymers depended on the pH value and had a maximum value in a buffer solution at pH 7. This was due to the changes in the morphological structure with the pH value. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Studies of poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) and its metal complexes

Poly(8‐hydroxy‐4‐azoquinolinephenol‐formaldehyde) resin (8H4AQPF) was prepared by condensing 8‐hydroxy 4‐azoquinoline phenol with formaldehyde (1 : 1 mol ratio) in the presence of oxalic acid. Polychelates were obtained when the DMF solution of poly(8H4AQPF) containing a few drops of ammonia was treated with the aqueous solution of Cu(II) and Ni(II) ions. The polymeric resin and polymer–metal complexes were characterized with elemental analysis and spectral studies. The elemental analysis of the polymer–metal complexes suggested that the metal‐to‐ligand ratio was 1 : 2. The IR spectral data of the polychelates indicated that the metals were coordinated through the nitrogen and oxygen of the phenolic ? OH group. Diffuse reflectance spectra, electron paramagnetic resonance, and magnetic moment studies revealed that the polymer–metal complexes of the Cu(II) complexes were square planar and those of the Ni(II) complexes were octahedral. X‐ray diffraction studies revealed that the polymer metal complexes were crystalline. The thermal properties of the polymer and polymer–metal complexes were also examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1506–1510, 2006     

Synthesis,characterization, and metal complexation of poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) as polychelatogens in aqueous solution

We carried out the free‐radical copolymerization of N‐phenylmaleimide with acrylic acid and acrylamide with an equimolar feed monomer ratio. We carried out the synthesis of the copolymers in dioxane at 70°C with benzoyl peroxide as the initiator and a total monomer concentration of 2.5M. The copolymer compositions were obtained by elemental analysis and ¹H‐NMR spectroscopy. The hydrophilic polymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, ¹H‐NMR spectroscopy, and thermal analysis. Additionally, viscosimetric measurements of the copolymers were performed. Hydrophilic poly(N‐phenylmaleimide‐co‐acrylic acid) and poly(N‐phenylmaleimide‐co‐acrylamide) were used for the separation of a series of metal ions in the aqueous phase with the liquid‐phase polymer‐based retention method in the heterogeneous phase. The method is based on the retention of inorganic ions by the polymer in conjunction with membrane filtration and subsequent separation of low‐molecular‐mass species from the formed polymer/metal‐ion complex. The polymer could bind several metal ions, such as Cr(III), Co (II), Zn(II), Ni(II), Cu(II), Cd(II), and Fe(III) inorganic ions, in aqueous solution at pH values of 3, 5, and 7. The interaction of the inorganic ions with the hydrophilic polymer was determined as a function of pH and a filtration factor. Hydrophilic polymeric reagents with strong metal‐complexing properties were synthesized and used to separate those complexed from noncomplexed ions in the heterogeneous phase. The polymers exhibited a high retention capability at pH values of 5 and 7. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Adsorption of cationic dyes on poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbents

Inverse suspension polymerization was carried out to synthesize poly(acrylic acid‐co‐sodium acrylate‐co‐acrylamide) superabsorbent polymers (SAPs) crosslinked with ethylene glycol dimethacrylate (EGDMA). The equilibrium swelling capacities of the SAPs, determined by swelling them in DI water, were found to vary with the acrylamide (AM) content. The SAPs were used to adsorb four cationic dyes (Acriflavine, Auramine‐O, Azure‐I and Pyronin‐Y). The effect of AM content in the SAPs on the adsorption of the cationic dyes was investigated. Different initial concentrations of Azure‐I were used with the same amount of the SAP to explore the effect of initial dye concentration on the adsorption. The effect of the adsorbent amount was investigated by taking different amounts of SAP with a fixed initial concentration of Acriflavine. The kinetics of the dye adsorption was modeled by a first order model and the equilibrium amount of the dye adsorbed, adsorption rate coefficients, removal efficiency and partition coefficients were determined. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and Swelling Properties of Temperature‐Sensitive Semi‐Interpenetrating Polymer Networks Composed of Poly[(N‐tert‐butylacrylamide)‐co‐acrylamide] and Hydroxypropyl Cellulose

Summary: Temperature‐responsive hydrogels based on linear HPC and crosslinked P(NTBA‐co‐AAm) were prepared by the semi‐IPN technique. The structure of these semi‐IPN hydrogels was investigated by FT‐IR spectroscopy. An increase in normalized band ratios (A₂₉₈₀/A₁₆₆₅) was observed with increasing HPC content in the initial mixture. The swelling kinetics and water transport mechanism of these semi‐IPN hydrogels were examined and their temperature responsive behaviors were also investigated by measuring equilibrium swelling ratios and pulsatile swelling experiments. The results showed that these semi‐IPN hydrogels underwent a volume phase transition between 18 and 22 °C irrespective of the amounts of MBAAm and HPC. However, below the volume phase transition temperature, their equilibrium swelling ratios were affected by the amount of MBAAm and HPC. The pulsatile swelling experiments indicated that the lower the MBAAm and the higher HPC contents in semi‐IPN hydrogels the faster the response rate temperature change.

Equilibrium swelling ratios of the semi‐IPN P(NTBA‐co‐AAm)/HPC hydrogels in water shown as a function of temperature.     

Grafting of acrylic acid‐co‐itaconic acid onto ePTFE and characterization of water uptake by the graft copolymers

Expanded polytetrafluoroethylene, ePTFE, is an attractive material for use as the implant in facial reconstruction surgery because it is bioinert; however, its low surface energy does not facilitate a strong interfacial bond with bone and thus for some applications the surfaces need to be modified to enhance their bone‐integration properties. The surface modification of ePTFE membranes with copolymers of acrylic acid (AA) and itaconic acid (IA) using in situ gamma radiation induced grafting has been studied. Solutions with AA mole fractions ranging from 0.4 to 1.0 have been investigated. Graft yields of 35–50% with water uptakes of greater than 300% were obtained using 3 mol L^?1 aqueous solutions of the monomers and a total incident dose of 10 kGy. The grafts were characterized by Fourier transform infrared and X‐ray photoelectron spectroscopy analyses and the compositional microstructure of the grafted copolymers was investigated. The water uptake by the grafted membranes displayed a complex dependence on polymer chemistry and topology. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41482.     

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     

Poly(methacrylamide‐co‐acrylic acid) hydrogels for gastrointestinal delivery of theophylline. I. Swelling characterization

pH sensitive copolymeric hydrogels have been synthesized by free‐radical polymerization of methacrylamide and acrylic acid in aqueous medium. The gels were characterized by FTIR spectroscopy, thermogravimetric analysis, and swelling measurements. To determine the suitability of theses hydrogels for gastrointestinal oral delivery of model drug theophylline, their swelling behavior was investigated as a function of pH and various structural parameters such as the average molecular weight between crosslinks, crosslink density, and mesh size were calculated. Likewise initial, average and late time diffusion coefficients were also evaluated in simulating intestinal fluid of pH 6.8 at 37°C. The gel underwent sharp volume phase transition in the vicinity of pH 5.8. The mesh sizes of the hydrogel were between 8.4 and 9.2 Å in the collapsed state (pH range 1–2; SGF) and between 514 and 524 Å in the swollen state (pH range 7–8; SIF). The experimental data was found to fit well to Beren‐Hopfenberg equation thus suggesting that later part of swelling was chain relaxation controlled. The activation energy, as determined from Arrhenius equation was found to be 13.71 kJ mol^?1. Likewise, enthalpy of mixing was also evaluated using Gibbs‐Helmholtz equation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2995–3008, 2006     

Synthesis of water‐insoluble functional copolymers containing amide,amine, and carboxylic acid groups and their metal‐ion‐uptake properties

The crosslinked poly[N‐(3‐dimethylamino)propylmethacrylamide] [P(NDAPA)] and poly[N‐(3‐dimethylamino)propylmethacrylamide‐co‐acrylic acid] [P(NDAPA‐co‐AA)] were synthesized by radical polymerization. The resins were completely insoluble in water. The metal‐ion‐uptake properties were studied by a batch equilibrium procedure for the following metal ions: silver(I), copper(II), cadmium(II), zinc(II), lead(II), mercury(II), chromium(III), and aluminum(III). The P(NDAPA‐co‐AA) resin showed a lower metal‐ion affinity than P(NDAPA), except for Hg(II), which was retained at 71% at pH 2. At pH 5, the resin showed a higher affinity for Pb(II) (80%) and Cu(II) (60%), but its affinity was very low for Zn(II) and Cr(III). The polymer ligand–metal‐ion equilibrium was achieved during the first 20 min. By changing the pH, we found it possible to remove between 60 and 70% of Cd(II) and Zn(II) ions with (1M, 4M) HClO₄ and (1M, 4M) HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5232–5239, 2006     

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid): Synthesis,characterization, and retention properties for environmentally impacting metal ions

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Cr³⁺, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd²⁺ to 0.34 for Ag⁺. The antibacterial activity of Ag⁺, Cu²⁺, Zn²⁺, and Cd²⁺ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd²⁺ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Determination of swelling behavior and morphological properties of poly(acrylamide‐co‐itaconic acid) and poly(acrylic acid‐co‐itaconic acid) copolymeric hydrogels

Poly(acrylamide‐co‐itaconic acid) (PAAmIA) and poly(acrylic acid‐co‐itaconic acid) (PAAIA) copolymeric hydrogels were prepared with different compositions via free‐radical polymerization. Ethylene glycol dimethacrylate (EGDMA) was used as an original crosslinker for these monomers. Gelation percentages of the monomers were studied in detail and it was found that addition of IA into the monomer mixture decreased the gelation percentage. The variation in swelling values (%) with time, temperature, and pH was determined for all hydrogels. PAA, which is the most swollen hydrogel, has the swelling percentage value of 2000% at pH = 7.4, 37°C. Swelling behaviors were explained with detailed SEM micrographs, which show the morphologic differences between dry and swollen hydrogels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5994–5999, 2006