Novel hydrogels based on itaconic acid and citraconic acid: Synthesis,metal ion binding,and swelling behavior

Several copolymer hydrogels were prepared from radical copolymerization of 2‐hydroxypropyl methacrylate (HPMA) with itaconic acid (IA) and also with citraconic acid (CA) by using different feed ratios. The copolymers were characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy as well as by thermal analysis. The swelling process of the different hydrogels immersed in water at different pH has been studied, and also the swelling of the hydrogels loaded with metal ions (Pb²⁺, Cd²⁺) was investigated. The metal‐binding properties were studied by using the liquid‐phase polymer‐based retention technique, including studies on the influence of pH on the binding process. The efficiency of these hydrogels for the recovery of metal ions in solution was determined by atomic absorption spectroscopic analysis. The thermal characteristics of these copolymers were studied by using differential scanning calorimetry and thermogravimetric analysis in nitrogen atmosphere. Accordingly, the gels loaded with metal ions showed a slight increase of the thermal decomposition temperature when compared with the pristine gels. The copolymer gel HPMA‐co‐CA showed a single glass transition temperature, whereas for the copolymer systems, HPMA‐co‐IA, only the copolymers loaded with Cd²⁺ ions showed a glass transition temperature. The morphology of film produced from the copolymers was investigated by scanning electron microscopy, revealing generally smooth surfaces. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A facile preparation of pH‐temperature dual stimuli‐responsive supramolecular hydrogel and its controllable drug release

A series of pH‐temperature dual stimuli‐responsive random copolymers poly[N,N‐dimethylaminoethyl methacrylate‐co‐poly(poly(ethylene glycol) methyl ether methacrylate][poly(DMAEMA‐co‐MPEGMA)] were synthesized by free radical polymerization. The supramolecular hydrogel was formed by pseudopolyrotaxane, which was prepared with the host‐guest interactions between α‐cyclodextrin (α‐CD) and poly(ethylene glycol) (PEG) side chains. Fourier transform infrared (FT‐IR), nuclear magnetic resonance (¹H NMR), and X‐ray diffraction (XRD) confirmed the structures of the hydrogels. The pH‐temperature dual stimuli responsive properties of the hydrogels were characterized by rheometer. Finally, the controllable drug release behavior of the hydrogel, which was used 5‐fluorouracil (5‐Fu) as the model drug, was investigated at different temperatures and different pH values. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43279.     

Crosslinked poly(vinyl alcohol)/carboxymethyl chitosan hydrogels for removal of metal ions and dyestuff from aqueous solutions

Hydrogels composed of poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCh) were synthesized via ultraviolet (UV) irradiation that can be used in several industrial fields. Several analysis tools were used to characterize the physical and thermal properties of CMCh/PVA hydrogels namely FT‐IR, scanning electron microscope (SEM), XRD, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). TGA results showed that CMCh/PVA hydrogels are thermally more stable than CMCh and their thermal stability increases as PVA content increases in the hydrogel. Also, DSC results showed that CMCh/PVA hydrogels are at least partial miscible blends. Moreover, the swelling behavior of the CMCh/PVA hydrogels was studied in different buffered solutions and in different salt solutions at various concentrations. CMCh/PVA hydrogels swell much more than CMCh especially at alkaline pH. Both metal and dye uptake were studied for CMCh/PVA hydrogels. The hydrogels adsorb much more dyestuff and metal ions like Cu²⁺, Cd²⁺, and Co²⁺ than CMCh itself. Much dyestuff and metal ions are adsorbed by the hydrogels as PVA content increases in the hydrogel. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Competitive removal of nickel (II), cobalt (II), and zinc (II) ions from aqueous solutions by starch‐graft‐acrylic acid copolymers

Graft copolymerization of acrylic acid (AA) onto starch was carried out with ceric ammonium nitrate as initiator under nitrogen atmosphere. The grafting percentages (GP%) of starch‐graft‐acrylic acid (St‐g‐AA) copolymers were determined. The effect of GP% of St‐g‐AA copolymers on the competitive removal of Co²⁺, Ni²⁺, Zn²⁺ ions from aqueous solution was investigated at different pH (2, 4, 6). The concentrations of each ion in aqueous solution 5 mmol/L. Effects of various parameters such as treatment time, initial pH of the solution and grafting percentage of starch graft copolymers were investigated. Metal ion removal capacities of St‐g‐AA copolymers increased with GP% of the copolymers and pH. The results show that the removal of metal ions followed as given in the order Co²⁺ > Ni²⁺ > Zn²⁺. In this study, metal ion removal capacities were determined by atomic absorption spectrophotometer (AAS). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Facile preparation and characterization of sodium alginate/graphite conductive composite hydrogel

Conductive composite hydrogels based on sodium alginate (SA) and graphite were fabricated by a facile method via dispersing homogeneously conductive graphite into SA hydrogel matrix. The hydrogel was formed by in situ release of Ca²⁺ from Ca–EDTA, thus eliminating the multistep reactions and tedious purification compared to the previous work. Raman spectra, scanning electron microscopy (SEM), X‐ray diffraction (XRD), and thermogravimetric analysis (TGA) were used to characterize the structure, crystalline nature, and thermostability of SA/graphite composite hydrogels. The SA/graphite composite hydrogels exhibited the improved network and layer‐type structure. The thermal stability of the hydrogel decreased slightly after the graphite was incorporated into the SA hydrogel matrix regardless of the content of graphite. The enhanced mechanical strength of SA/graphite composite hydrogel was achieved via increasing the f value (i.e., [Ca²⁺]/[COO^‐ in alginate]) and lowering graphite content. The conductivity of the composite hydrogels could be varied in a broad range, reaching up to 10⁻³ S/cm, mainly depending on the content of graphite and the f value. POLYM. COMPOS., 37:3050–3056, 2016. © 2015 Society of Plastics Engineers     

Synthesis and swelling properties of a pH‐ and temperature‐dual responsive hydrogel by inverse microemulsion polymerization

A novel pH‐ and temperature‐dual responsive hydrogel was synthesized by inverse microemulsion polymerization, using itonic acid (IA) as pH‐responsive monomer, N‐isopropylacrylamide (NPAM) as thermo‐responsive monomer and acrylamide (AM) as the nonionic hydrophilic monomer. Factors affecting water and salt absorption, as well as swellability of the dual responsive hydrogels, such as IA/NPAM mass ratio and crosslinker amount, were investigated. pH‐ and temperature‐sensitivity and dynamic viscoelasticity behaviors of the dual responsive hydrogels were also studied. The dual responsive responsive hydrogels showed suitable water and salt absorbency, remarkable pH‐, and temperature‐sensitivity, adjustable swellability and enhanced viscoelastic behaviors under high stress. Water absorbency and pH‐sensitivity increased while salt absorbency and temperature‐ sensitivity decreased with increasing IA/NIPAM mass ratio. Both water absorbency and salt absorbency increased first with crosslinker amount increased to 0.2 wt %, and then decreased with increasing crosslinker amount. Temperature‐induced shrinkage range of the dual responsive hydrogels was higher and broader than that of the conventional poly(N‐isopropylacrylamide) hydrogel. TEM indicated that the as‐synthesized hydrogel particles were regular and spherical‐like in shape and had the mean particle size of 49nm in the range of 30–78 nm. FTIR indicated the structure of the dual responsive hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42139.     

Heavy metal sensors and sequestrating agents based on polyaromatic copolymers and hydrogels

A series of readily available, amphiphilic pyrene‐ and perylene‐containing fluorescent materials, derived from the co‐polymerisation of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid with acrylate esters, can be used to detect heavy metal ions in the micromolar concentration range in aqueous solutions. The incorporation of these amphiphilic copolymers into semi‐interpenetrating hydrogels also resulted in the irreversible removal of divalent Co²⁺, Ni²⁺, Cu²⁺ and Pb²⁺ ions from aqueous solutions at neutral pH.     

Synthesis and characterization of novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels

Novel pH‐sensitive chitosan‐poly(acrylamide‐co‐itaconic acid) hydrogels were prepared by free radical copolymerization of acrylamide and itaconic acid (IA) in chitosan solution. The hydrogels were characterized using Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry and the swelling ratios of the hydrogels in water (pH 6.8) and pH 1.2. The influence of composition on the thermal properties of the hydrogels was assessed. The glass transition temperatures of the samples increased with IA content, ranging from 110 to 136 °C. Swelling of the hydrogels was found to obey second‐order kinetics with respect to the remnant swelling, indicating that diffusion is controlled by the relaxation of chains. The equilibrium swelling degree was strongly dependent on pH and composition. At both pH values the highest water uptake was obtained for the IA‐free sample M1. From the equilibrium swelling results the average molar mass between crosslinks, M_c, and the crosslink density of the chitosan‐poly(acrylamide‐co‐itaconic acid) samples were calculated. The results evidenced the reinforcing effect of IA on the hydrogel structure. It is concluded that these highly swellable pH‐sensitive hydrogels can be useful for applications in biomedicine and pharmacy. © 2013 Society of Chemical Industry     

Removal of heavy metal ions from aqueous solutions by radiation‐induced chitosan/(acrylamidoglycolic acid‐co‐acrylic acid) magnetic nanopolymer

An effective method was developed to isolate toxic heavy metal ions from the aqueous solution by the magnetic nanopolymers. The magnetic sorbent was prepared with radiation‐induced crosslinking polymerization of chitosan (CS), 2‐acrylamido‐glycolic acid (AMGA), and acrylic acid (AAc), which stabilized by magnetite (Fe₃O₄) as nanoparticles. The formation of magnetic nanoparticles (MNPs) into the hydrogel networks was confirmed by Fourier transform infrared spectroscopy, X‐ray diffraction, transmission electron microscopy, and Scanning electron microscopy, which revealed the formation of MNPs throughout the hydrogel networks. The swelling behavior of the hydrogels and magnetic ones was evaluated at different pH values. The adsorption activity for heavy metals such as Cu²⁺ and Co²⁺ by nonmagnetic and magnetic hydrogels, Fe₃O₄/CS/(AMGA‐co‐AAc), in terms of adsorption amount was studied. It was revealed that hydrogel networks with magnetic properties can effectively be used in the removal of heavy metal ions pollutants and provide advantageous over conventional ones. POLYM. ENG. SCI., 55:1441–1449, 2015. © 2015 Society of Plastics Engineers     

Synthesis and characterization of salep sulfate and its utilization in preparation of heavy metal ion adsorbent

A multicomponent polysaccharide obtained from dried tubers of certain natural terrestrial orchids was chemically modified by sulfonation using chlorosulfonic acid–dimethylformamide (HClSO_3–DMF) complex as a reagent. For a structural characterization of salep sulfate ¹H nuclear magnetic resonance (NMR), Fourier transform infrared (FTIR) spectra, and Thermogravimetric analysis (TGA) curves were recorded. The sulfate content of modified salep was determined using elemental analysis. This modified biopolymer was used to prepare a new environment‐friendly heavy metal ion adsorbent, salep sulfate‐graft‐polyacrylic acid hydrogel (SS‐g‐PAA). Swelling rate and equilibrium water absorbency in various pH and saline solutions were investigated to study the effect of salep sulfate on swelling behavior of the hydrogel. In addition, the effect of sulfate content on heavy metal ion adsorption from aqueous solution was investigated. The results show that SS‐g‐PAA can effectively remove heavy metal ions (Co²⁺, Zn²⁺, Cu²⁺) from aqueous solution and swelling behavior of the hydrogels highly dependent on the amount of sulfate group on corresponding modified polysaccharide. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3001–3008, 2013     

Formation of thermosensitive water‐soluble copolymers with phosphinic acid groups and the thermosensitivity of the copolymers and copolymer/metal complexes

Thermosensitive and water‐soluble copolymers were prepared through the copolymerization of acryloyloxypropyl phosphinic acid (APPA) and N‐isopropyl acrylamide (NIPAAm). The thermosensitivity of the copolymers and copolymer/metal complexes was studied. The APPA–NIPAAm copolymers with less than 11 mol % APPA moiety had a lower critical solution temperature (LCST) of approximately 45°C, but the APPA–NIPAAm copolymers with greater than 21 mol % APPA moiety had no LCST from 25 to 55°C. The APPA–NIPAAm copolymers had a higher adsorption capacity for Sm³⁺, Nd³⁺, and La³⁺ than for Cu²⁺, Ni²⁺ and Co²⁺. The APPA–NIPAAm (10:90) copolymer/metal (Sm³⁺, Nd³⁺, or La³⁺) complexes became water‐insoluble above 45°C at pH 6–7, but the APPA–NIPAAm (10:90) copolymer/metal (Cu²⁺,Ni²⁺, or Co²⁺) complexes were water‐soluble from 25 to 55°C at pH 6–7. The temperature at which both the APPA–NIPAAm copolymers and the copolymer/metal complexes became water‐insoluble increased as the pH values of the solutions increased. The APPA–NIPAAm copolymers were able to separate metal ions from their mixed solutions when the temperature of the solutions was changed; this was followed by centrifugation of the copolymer/metal complexes after the copolymers were added to the metal solutions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 116–125, 2004     

Behavior of acrylic acid–itaconic acid hydrogels in swelling,shrinking, and uptakes of some metal ions from aqueous solution

An experimental research of the absorption properties of metal ions onto synthetic hydrogel obtained by solution polymerization of acrylic acid and itaconic acid in presence of N,N′‐methylenebisacrylamide as crosslinking agent was carried out. The swelling behavior in aqueous salt solutions was studied as a function of divalent cation concentration (Cu²⁺, Zn²⁺, Ni²⁺, Co²⁺, Cd²⁺, Pb²⁺, Hg²⁺) in the external solution ranging from 10^?5 to 1M, at 25°C. The ability of these hydrogels to bind cations was measured at different pH values and metal ion concentrations. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 530–536, 2003     

Synthesis and characterization of poly{N‐[3‐(dimethylamino) propyl] methacrylamide‐co‐itaconic acid} hydrogels for drug delivery

A novel pH‐sensitive hydrogel system composed of itaconic acid (IA) and N‐[3‐(dimethylamino) propyl] methacrylamide was designed. This system was prepared by aqueous copolymerization with N,N‐methylene bisacrylamide as a chemical crosslinker. The chemical structure of the hydrogels was characterized by Fourier transform infrared (FTIR) spectroscopy. The microstructure and morphology of the hydrogels were evaluated by X‐ray diffraction (XRD) and scanning electron microscopy (SEM). The SEM study of hydrogels on higher magnification revealed a highly porous morphology with uniformly arranged pores ranging from 40 to 200 μm in size. XRD analysis revealed the amorphous nature of the hydrogels, and it was found that an increase in the IA content in the monomer feed greatly reduced the crystallinity of the hydrogels. Swelling experiments were carried out in buffer solutions at different pH values (1.2–10) at 37°C ± 1°C to investigate their pH‐dependent swelling behavior and dimensional stability. An increase in the acid part (IA) increased the swelling ratio of the hydrogels. Temperature‐sensitive swelling of the hydrogels was investigated at 20–70°C in simulated intestinal fluid. The hydrogels swelled at higher temperatures and shrank at lower temperatures. 5‐Aminosalicylic acid (5‐ASA) was selected as a model drug, and release experiments were carried out under simulated intestinal and gastric conditions. 5‐ASA release from the poly N‐[3‐(dimethylamino) propyl] methacrylamide‐co‐itaconic acid‐80 (PDMAPMAIA‐80) hydrogel was found to follow non‐Fickian diffusion mechanism under gastric conditions, and a super case II transport mechanism was found under intestinal conditions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Removal of heavy metals from model wastewater by using carboxymehyl cellulose/2‐acrylamido‐2‐methyl propane sulfonic acid hydrogels

A series of functional copolymer hydrogels composed of carboxymethyl cellulose (CMC) and 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) were synthesized using γ‐radiations‐induced copolymerization and crosslinking. Preparation conditions were optimized, and the swelling characteristics were investigated. The ability of the prepared hydrogels to recover some toxic metal ions from their aqueous solutions was studied. The prepared hydrogel showed a great capability to recover metal ions such as: Mn⁺², Co⁺², Cu⁺², and Fe⁺³ from their solutions. The data revealed that the chelating ability of the prepared hydrogels is mainly dependent on their internal composition, in addition to the physical properties of the metal ion solution such as pH and metal ion concentration. The data show that the chelating ability of the prepared hydrogels increases by increasing the AMPS content in the hydrogel as well as the increment in the pH of the solution and the metal ion concentration. The prepared CMC/AMPS copolymer hydrogels are chemically stable enough to be reused for at least five times with the same efficiency. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Temperature/pH dual responsive OPGMA based copolymeric hydrogels prepared by gamma radiation: an optimisation study

The purpose of this study was to attain oligo(propylene glycol) methacrylate (OPGMA) based hydrogels for different biomedical applications. Since the volume phase transition temperature (VPTT) of poly(oligo(propylene glycol) methacrylate) (POPGMA) homopolymer was below room temperature, it was necessary to tune the thermoresponsiveness and the VPTT to higher temperatures; radical copolymerisation of OPGMA with more hydrophilic and/or pH responsive monomers was used to adjust these values. A series of copolymeric hydrogels with different ratios of OPGMA, 2-hydroxyethyl methacrylate (HEMA) and itaconic acid (IA) was synthesised by gamma radiation. The swelling properties were preliminarily investigated over a wide pH (2.2–9.0) and temperature (4–80 °C) ranges. Additional characterization of their structure and properties was conducted by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The presented results revealed temperature/pH dual responsive P(OPGMA/IA) and P(OPGMA/HEMA/IA) copolymers with large diversity in swelling properties, as a result of the addition of OPGMA thermoresponsive units with a lower critical solution temperature (LCST) and IA pH responsive units. It was demonstrated that VPTT can be significantly shifted to higher (e.g. body) temperatures at higher pH values (pH ≥ 4) by increasing the IA content in the hydrogel composition. Due to the possibility of making dual responsive copolymers in the manner explained in this paper, OPGMA based hydrogels show potential for different biomedical applications.     

Spectroscopic and thermal studies of poly[(N‐vinylimidazole)‐co‐(maleic acid)] hydrogel and its quaternized form

BACKGROUND: In this study, poly[(N‐vinylimidazole)‐co‐(maleic acid)] (poly(VIm/MA)) hydrogels were prepared by γ‐irradiation of ternary mixtures of N‐vinylimidazole–maleic acid–water using a ⁶⁰Co γ‐source. Spectroscopic and thermal analyses of these hydrogels as a function of protonation showed that the results are consistent with the existence of an H‐bridged complex when the imidazole rings are partially protonated. Finally, the efficiency and binding trends of Cu²⁺, Co²⁺, Cd²⁺ and Pb²⁺ ions with both protonated and unprotonated poly(VIm/MA) hydrogels were determined. RESULTS: Gelation of 90% was reached at around 180 kGy dose at the end of irradiation. The poly(VIm/MA) hydrogels synthesized were further protonated in HCl solutions with different concentrations. Hydrogels originally showed 450% volumetric swelling; this ratio reached 1900% after protonation at pH = 5.0. Fourier transform infrared spectral changes in the ⁺N? H stretching region (3200–3600 and 1173 cm^?1) and the ring mode deformation at 915 cm^?1 are consistent with the formation of an H‐bridged complex between the protonated and unprotonated imidazole rings upon partial protonation. Similar changes were obtained from NMR spectra of both the protonated and unprotonated forms of the hydrogels. CONCLUSION: Protonated and unprotonated hydrogels have been used in heavy metal ion adsorption studies for environmental purposes. Adsorption decreased with decreasing pH value due to the protonation of the VIm ring. The adsorption of Me²⁺ ions decreased in the order Cu²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺, which is related to the complexation stability as well as the ionic radius of the metal ions. These results show that P(VIm/MA) hydrogels can be used efficiently to remove heavy metal ions from aqueous solutions. However, the protonated form is a bad choice for heavy metal ion adsorption due to electrostatic repulsion forces; it can nevertheless be assumed to be a good choice for anion adsorption from environmental waste water systems. Copyright © 2007 Society of Chemical Industry     

Dual Cross‐Linked Hydrogels with High Strength,Toughness, and Rapid Self‐Recovery Using Dynamic Metal–Ligand Interactions

A dual cross‐linking design principle enables access to hydrogels with high strength, toughness, fast self‐recovery, and robust fatigue resistant properties. Imidazole (IMZ) containing random poly(acrylamide‐co‐vinylimidazole) based hydrogels are synthesized in the presence of Ni²⁺ ions with low density of chemical cross‐linking. The IMZ‐Ni²⁺ metal–ligand cross‐links act as sacrificial motifs to effectively dissipate energy during mechanical loading of the hydrogel. The hydrogel mechanical properties can be tuned by varying the mol% of vinylimidazole (VIMZ) in the copolymer and by changing the VIMZ/Ni²⁺ ratio. The resultant metallogels under optimal conditions (15 mol% VIMZ and VIMZ/Ni²⁺ = 2:1) show the best mechanical properties such as high tensile strength (750 kPa) and elastic modulus (190 kPa), combined with high fracture energy (1580 J m^?2) and stretchability (800–900% strain). The hydrogels are pH responsive and the extent of energy dissipation can be drastically reduced by exposure to acidic pH. These hydrogels also exhibit excellent anti‐fatigue properties (complete recovery of dissipated energy within 10 min after ten successive loading–unloading cycles at 400% strain), high compressive strength without fracture (17 MPa at 96% strain), and self‐healing capability due to the reversible dissociation and re‐association of the metal ion mediated cross‐links.     

Thermoplastic hydrogel based on pentablock copolymer consisting of poly(γ‐benzyl L‐glutamate) and poloxamer

A thermoplastic hydrogel based on a pentablock copolymer composed of poly(γ‐benzyl L ‐glutamate) (PBLG) and poloxamer was synthesized by polymerization of BLG N‐carboxyanhydride, which was initiated by diamine‐terminated groups located at the ends of poly(ethylene oxide) (PEO) chains of the poloxamer, to attain a new pH‐ and temperature‐sensitive hydrogel for drug delivery systems. Circular dichroism measurements in solution and IR measurements in the solid state revealed that the polypeptide block existed in the α‐helical conformation, as in the PBLG homopolymer. The intensity of the wide‐angle X‐ray diffraction patterns of the polymers depended on the poloxamer content in the copolymer and showed basically similar reflections to the PBLG homopolymer. The melting temperature (T_m) of the poloxamer in the copolymer was reduced with an increase of the PBLG block in comparison with the T_m of the poloxamer, which is indicative of a thermoplastic property. The water contents of the copolymers were dependent on the poloxamer content in the copolymers, for example, those for the GPG‐2 (48.7 mol % poloxamer) and GPG‐1 (57.5 mol % poloxamer) copolymers were 31 and 41 wt %, respectively, indicating characteristics of a polymeric hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2649–2656, 2003     

Rheological and thermal properties of saponified cassava starch‐g‐poly(acrylamide) superabsorbent polymers varying in grafting parameters and absorbency

Cassava starch‐graft‐poly(acrylamide) superabsorbent polymers (SAPs) with varying absorbencies were synthesized. Weight average molecular weight (M_w) of the hydrolyzed starch‐graft‐copolymers ranged from 1.6 × 10⁶ to 2.8 × 10⁶ g/mol, the largest being shown by the sample with highest percentage grafting. The storage (G′) and loss modulus (G″) of hydrogels were determined as a function of frequency. G″ was larger than G′ for the hydrogels with higher absorbencies and exhibited a liquid‐like behavior. However, hydrogels with lower absorbencies showed a reverse viscoelastic behavior. The viscosity of hydrogels determined using a Brookfield viscometer at different shear rates was found to be larger for the hydrogels with higher absorbencies. The melting temperature (T_m) and enthalpy change of fusion (ΔH_f) of the SAPs ranged from 149.7 to 177.7°C and 65 to 494.9 J/g, respectively and showed a positive correlation with grafting parameters and M_w. Heavy metal ion removal capacity of hydrogel followed the order Cu²⁺ > Pb²⁺ > Zn²⁺. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40368.     

Synthesis of the copolymer hydrogel κ‐carrageenan‐graft‐PAAm: Evaluation of its absorbent and adhesive properties

κ‐Carrageenan‐graft‐PAAm, a copolymer hydrogel of κ‐carrageenan (kC) and acrylamide (AAm), has been synthesized in aqueous medium at ～ pH 7 in the presence of the initiator potassium persulfate (KPS), using microwave irradiation. The reaction conditions were optimized by varying the concentration of AAm and KPS to obtain copolymer hydrogels having different nitrogen contents e.g., %N 6.35, 10.56, and 11.05. It was observed that copolymer hydrogel having %N 11.05 gives superior adhesive properties whereas copolymer hydrogel with %N 10.56 produces superior absorbent properties in the presence of optimized concentrations of AAm (0.87 and 1.1428 mol/L respectively) and KPS (0.022 and 0.0296 mol/L respectively). The product with %N 6.35 is a soft gel (2–5% gel in 1% KCl) exhibiting low gel strength (135 g cm^?2). The one with %N 10.56 showed superior swelling property and maximum swelling was observed in the alkaline pH (22 g/g). The swelling behaviors of the hydrogels were studied at different pHs (pH 1.2–12.5) as well as in 1% aqueous solutions of NaCl, KCl, and CaCl₂. The 5% dispersion of the hydrogel having %N 11.05 in water had good binding properties with papers, polyethylene sheets, and wood pieces. To evaluate the measure of adhesive property, the viscosity and solid and liquid weights of the applied adhesive were measured. Characterization of the copolymer hydrogels was done by TGA, X‐ray diffraction, ¹³C‐NMR, FT‐IR, elemental analyses, and rheological studies. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5144–5152, 2006