Hyperbranched polyglycerol/poly(acrylic acid) hydrogel for the efficient removal of methyl violet from aqueous solutions

Hydrogels were synthesized from hyperbranched polyglycerol (HPG) and acrylic acid through free‐radical polymerization with HPG as the crosslinker. The HPG/poly(acrylic acid) (PAA) hydrogel could absorb cationic dyes in aqueous solutions because of the existence of a porous structure and the large numbers of hydroxyl and carboxylic groups. With methyl violet chosen as a model compound, the HPG/PAA hydrogel reached a maximum adsorption of 394.12 mg/g at a feed concentration of 1 g/L. The highest removal ratio of 98.33% was observed at a feed concentration of 50 mg/L. The effects of the pH, contact time, and feed concentration on the dye adsorption were investigated. The dye adsorption data fit well with the pseudo‐second‐order and Langmuir models. We believe that the HPG/PAA hydrogels could perform well in appropriate applications in the removal of cationic dyes from aqueous solutions because of their high adsorption capacity and environmental friendliness. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42951.     

Grafting of poly (methyl acrylate) onto sulfite pulp fibers and its effect on water absorbance

To prepare super water absorbent hydrogels of wood cellulose fibers, poly (methyl acrylate) (PMA) was copolymerized onto softwood sulfite pulp fibers using free radical initiator followed by alkaline hydrolysis. Ceric ammonium nitrate (CAN) was used as the free radical initiator. Effects of various parameters such as fiber concentration, monomer/pulp (M/pulp) ratio, CAN concentration, and reaction time on the grafting yield and on other grafting parameters were investigated. The graft conversion was the same from low to medium fiber concentration. The amount of initiator required was found to be independent of fiber concentration to achieve maximum grafting yield. Different fiber fractions (classified based on their length) have no effect on the grafting yield. The evidence of graft copolymerization was determined by using ATR‐IR spectroscopy. The X‐ray diffraction (XRD) analysis shows that grafting takes place both in amorphous and crystalline regions of cellulose fibers and the decrease in crystallinity of the grafted fibers with an increase in grafting yield was confirmed. The surface morphology of the PMA‐g‐cellulose was characterized by scanning electron microscopy (SEM). The water retention value of the hydrolyzed grafted pulp was determined based on a centrifugation technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Water‐absorptive blend fibers of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol)

Through the addition of N‐hydroxymethyl acrylamide as a potential crosslinker, water‐absorptive blend fibers of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol) with three‐dimensional network structures were prepared with heat‐crosslinking technology after fiber formation. Fourier transform infrared, scanning electron microscopy, dynamic mechanical analysis, and thermogravimetry were used to analyze the structures and properties of the fibers. The tensile behavior and absorbent capacities of the fibers were also studied. The results showed that there were lots of chemical crosslinking points in the fibers, the compatibility of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol) was perfect, and the tensile properties of the fibers could be improved effectively through stretching in a vapor bath. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3353–3357, 2006     

N-异丙基丙烯酰胺pH敏感型水凝胶的制备及对甲基紫吸附性能研究

以N-异丙基丙烯酰胺和海藻酸钠(SA)为主要原料,制备了具有pH敏感型的智能水凝胶。探究了不同海藻酸钠、引发剂、交联剂等配比的凝胶在不同pH值环境下的溶胀性能,并对制备的凝胶进行甲基紫的吸附性能测试。结果表明:碱性条件下,凝胶溶胀度随SA用量的增加而增大,酸性条件下则相反;凝胶的溶胀度随交联剂用量的增加而减小;引发剂用量为3%时凝胶的溶胀度较高;凝胶在适宜条件下对甲基紫溶液有良好的吸附性能。     

Reuse of a waste adsorbent poly(AAc/AM/SH)‐Cu superabsorbent hydrogel,for the potential phosphate ion removal from waste water: Matrix effects,adsorption kinetics,and thermodynamic studies

The most commonly applied methods for the treatment of used adsorbents is to recover them in acid/alkaline medium or direct enflame them. This work dealt with a new potential and economic method to utilize a waste adsorbent. Poly(AAc/AM/SH) superabsorbent hydrogels have proved to be a good adsorbent for Cu²⁺ ions and after adsorption the hydrogels were recovered in acid medium. In this report, the Cu²⁺ ion adsorbed hydrogel has not undergone any regeneration process and applied directly to phosphate ion adsorption. The Cu²⁺ ions‐loaded poly(AAc/AM/SH) hydrogels, were stable within a wide pH range and suitable for phosphate ion adsorption. The factors affecting the phosphate adsorption, such as pH, ionic strength, contact time, temperature, initial concentration of the phosphate ion, and coexisting ions were systematically investigated. The phosphate adsorption was highly pH dependent; and the maximum adsorption of 87.62 mg/g was achieved at pH 6.1. The adsorption data fitted the Langmuir adsorption isotherm better than the Freundlich isotherm. The concomitant anions show profounder adverse influence on phosphate ion adsorption of poly(AAc/AM/SH)‐Cu hydrogel and the effect follows the order citrate > sulfate > bicarbonate > chloride > nitrate. The thermodynamic parameters including ΔH°, ΔG°, and ΔS° for the adsorption processes of phosphate ions on the gel were also evaluated, and the negative ΔG° and ΔH° confirmed that the adsorption process was spontaneous and exothermic. The adsorption kinetic results suggest that the adsorption process was well described by the pseudo second‐order kinetic model. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Equilibrium adsorption isotherm and controlled release of antibiotic drug chloroamphenicol from poly(2‐vinyl pyridine/acrylic acid) hydrogels prepared by gamma radiation

High water sorption of 2‐vinyl pyridine (2‐VP)/acrylic acid (AAc) hydrogel were prepared by free‐radical polymerization in aqueous solution of 2‐VP with AAc as comonomer. The amount of ionic monomer (AAc), the irradiation dose of prepared hydrogel, the pH, and the concentration of drug play an important factor on loading, adsorption, and releasing of water‐soluble chloroamphenicol drug. As a result of dynamic swilling tests, the effect of relative content of AAc on the swelling showed that it allowed a non‐Fickian type of water diffusion. The adsorption of the drug onto (2‐VP/AAc) hydrogels was studied by Freundlish adsorption isotherm. The drug concentrations showed an influence on the adsorption of drug which increased with increasing AAc content. From Freundlish adsorption isotherm, the empirical constants, k and n, can be evaluated and showed the ability of hydrogel to be loaded by the drug and the affinity of the drug to be uptake onto the hydrogel respectively. FTIR, TGA, and SEM techniques were used to study the characterization of hydrogel (2‐VP/AAc). Additionally, the release of the drug loaded from hydrogel discs was studied microbiologically to show that hydrophilic structure of the hydrogel has an antimicrobial effect as a dehydration of cytoplasm and unbalance of the cell wall functions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of a superabsorbent from an ultraviolet‐irradiated waste nameko mushroom substrate and poly(acrylic acid)

To better use the waste nameko mushroom substrate (WNMS) and prevent its pollution into the environment, a novel superabsorbent polymer was synthesized via the UV irradiation copolymerization of acrylic acid and WNMS in the presence of an initiator (dimethoxy‐2‐phenylacetophenone and ammonium persulfate) and crosslinker N,N′‐methylenebisacrylamide. The factors that had an influence on the water absorbency of the superabsorbent polymer were investigated and optimized. Under the optimized conditions, WNMS–poly(acrylic acid) was obtained. Its swelling behaviors, which followed the pseudo‐second‐order swelling kinetic model, were investigated in distilled water (1701 g/g) and a 0.9 wt % NaCl solution (388 g/g). The water absorbency was 1011 g/g in a 0.1 wt % urea solution and 80% amount of urea diffused into the gels. The urea diffusion followed a Fickian diffusion mechanism. Moreover, the product showed excellent water retention capabilities under the condition of high temperature or high pressure. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40471.     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Small‐angle neutron scattering of poly(styrene)/poly(acrylic acid–ethyl acrylate) copolymers: The effect of the degree of hydrolysis of the poly(acrylic acid–ethyl acrylate) block

We report the results of systems based on polystyrene‐poly(ethyl acrylate) (PEA) diblocks, which self‐assemble in aqueous solutions to form spherical micelles. Previous work has shown that the rheological properties of these solutions, in particular the gel–liquid transition, can be tuned through the use of a simple hydrolysis reaction to convert PEA to poly(acrylic acid) (PAA). We studied the effect of the extent of hydrolysis on the self‐assembly and micellar interactions. Small‐angle neutron scattering (SANS) spectra were fit with a variety of models to determine the micelle structure. As more PEA was converted to PAA (i.e., as the corona became more charged and more hydrophilic), the micellar aggregation number decreased, analogous to observations of other polymeric micelles. This effect could impact the gel–liquid transition and rheology in this system and in similar micellar block copolymer gels. Finally, our SANS spectra qualitatively agreed with predictions for attractive colloidal glasses, confirming the idea that the elasticity of these gels arises from the jamming of micelles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 490–497, 2004     

Absorbency and adsorption of poly(acrylic acid‐co‐acrylamide) hydrogel

Poly(acrylic acid‐co‐acrylamide) (PAAAM) hydrogels have been prepared from partly neutralized acrylic acid (AA) and acrylamide (AM) by solution polymerization, and their absorbency and adsorption in both CuCl₂ and FeCl₃ solutions have been investigated. PAAAM hydrogels and their complexes with Cu²⁺ or Fe³⁺ have been characterized by FTIR. The absorbency of PAAAM in both CuCl₂ and FeCl₃ solutions increases initially and then decreases as the absorbing time increases. The adsorption of PAAAM in both CuCl₂ and FeCl₃ solutions can be described by the pseudo‐second order chemisorption kinetics proposed by Ho and McKay, and the equilibrium uptake of Cu²⁺ on PAAAM can well be fit with the Langmuir adsorption isotherm. However, the equilibrium uptake of Fe³⁺ on PAAAM increases as the initial Fe³⁺ concentration increases for Fe³⁺ concentration smaller than 5.625 × 10^?3 mol/L, and then decreases with Fe³⁺ concentration. The largest uptakes for Cu²⁺ and Fe³⁺ are 247 and 173 mg/g, respectively. The results also show that the uptake of Cu²⁺ and Fe³⁺ on PAAAM increases remarkably when pH of the solution is changed from 2.3 to 4.2 and from 1.0 and 2.1, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characteristic of electric stimuli responsive hydrogel composed of polyvinyl alcohol/poly (sodium maleate‐co‐sodium acrylate)

Maleic anhydride was used to preparare polyvinyl alcohol/poly (sodium maleate‐co‐sodium acrylate) hydrogels (PVA/poly(SMA‐SAA)) by a repeated frost‐defrost process because of its higher charge density and potential electric stimuli sensitivity. The bending angle was measured in a noncontact electric field using carbon as plate electrodes. It was found that the bending angle was dependent on various factors, including composition of hydrogel, concentration of NaCl solution, types of electrolyte solution, and electric voltage. It exhibited that the bending angle increased when the concentration of NaCl solutions and the electric voltages increased. An abnormal bending direction was observed, and it was affected not only by the kinds of hydrogels, but also by the exterior variations. The hydrogel showed good reversibility in on‐off electric field and could be a candidate for practical application. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Radiation initiated synthesis,characterization, and swelling behavior of poly (acrylic acid-co-acrylamide)/starch grafted hydrogel

The powerful waves of ultrasound are used in polymerization reactions in the absence of initiator. In the present research, the hydrogel was obtained by water-soluble acrylic monomers, starch, and the crosslinking agent of methylene bis acrylamide dissolved in water/glycerol dual. The hydrogel is formed by these waves only in viscous environments such as glycerol, heat, or initiator is not required. In the presence of ultrasound, the time of product formation is reduced to a few minutes. Moreover, the resulting hydrogels have more uniform microscopic structure and are more swollen. The structure of the grafted hydrogel was examined meanwhile the hydrogel swelling in three environments of pure water, saltwater, and under pressure was measured. It was found that the grafted hydrogel has double swelling rate in the pure. Also, after loading the ciprofloxacin into the synthesized hydrogel, this drug is released 99% in initial 20 min. 0.1 g starch in 1.5 g acrylic hydrogel has the most drug release. The high swelling capacity in the pH ranges of 5–9 shows the extension of drug application in acidic or alkaline environments, and also after several using the gel and the capacity of water absorbency, which was about 70% of its initial water, indicates the perfect reusability capacity of the gel.     

Superabsorbent hydrogel of acrylic acid/potassium acrylate copolymers by ultraviolet photopolymerization: Synthesis and properties

Synthesis of superabsorbent hydrogel (SAHG) of acrylic acid‐potassium acrylate copolymer by direct Ultraviolet (UV) photopolymerization is a new method. The effects of degree of neutralization of acrylic acid (AA), photoinitiators, crosslinking agents, and exposure time of UV light on water absorbent properties were investigated. The results showed that the water absorbency (Q) and the salt solution (NaCl, 0.9%) absorbency (Qs) of SAHG, based on Irgacure 651, are high, reaching about 1400 and 130 mL/g, respectively. UV absorption spectrum proved that peak of UV absorption of Irgacure 651 matched the UV light source we used. Among the crosslinking agents, N,N′‐methylene bisacrylamide is more efficient than others, because of its very small content and high Q. ¹³C NMR spectrometry was used to identify the mechanism of crosslinking reaction through esterification of hydroxyethyl acrylate (HEA) and 2‐hydroxypropyl acrylate (HPA) with carboxylic acid group in acrylic acid‐ammonium acrylate copolymerization, but efficiency of crosslinking reaction by esterification was lower than that of copolymerization of vinyl group in crosslinking agent. The Q of acrylic acid‐potassium acrylate copolymer of SAHG reaches 1592 mL/g under the following conditions: degree of neutralization of acrylic acid is 80%, content of Irgacure 651 is 0.25 wt %, content of HEA is 0.2 wt %, and exposure time is 10 min. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1181–1187, 2006     

Competitive adsorption of Ag (I) and Cu (II) by tripolyphosphate crosslinked chitosan beads

Alkalization of chitosan before crosslinking was applied in this study to enhance the adsorption capacity of the modified chitosan. Competitive adsorption of Ag (I) and Cu (II) from bimetallic solutions was studied using the newly synthesized tripolyphosphate crosslinked alkalized chitosan beads. Results indicated that alkalization before crosslinking helps to protect amine group from crosslinking and hence increases the uptake capacity and selectively of the synthesized beads toward Ag (I). The maximum uptakes of Ag (I) and Cu (II) were 82.9 and 15.5 mg g^?1, respectively, at room temperature with an initial concentration of each metal being 2.0 mM and the sorbent dosage of 1.0 g L^?1. The uptake of Ag (I) and Cu (II) by the beads can be better described by Langmuir isotherm and pseudo‐second rate equation. Analyses from FTIR and XPS confirmed that free amine, hydroxyl, and groups are involved in metal binding with amine and hydroxyl groups more selective to Ag (I). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42717.     

Graft copolymerization of methyl acrylate onto poly(vinyl alcohol) initiated by potassium diperiodatonickelate(IV)

The graft copolymerization of methyl acrylate onto poly(vinyl alcohol) (PVA) with a potassium diperiodatonickelate(IV) [Ni(IV)]–PVA redox system as an initiator was investigated in an alkaline medium. The grafting parameters were determined as functions of the temperature and the concentrations of the monomer and initiator. The structures of the graft copolymers were confirmed by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The Ni(IV)–PVA system was found to be an efficient redox initiator for this graft copolymerization. A single‐electron‐transfer mechanism was proposed for the formation of radicals and the initiation. Other acrylate monomers, such as methyl methacrylate, ethyl acrylate, n‐butyl acrylate, and n‐butyl methacrylate, were used as reductants for graft copolymerization. These reactions definitely occurred to some degree. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 529–534, 2003     

Preparation of Sodium carboxymethylcellulose/poly(methyl acrylate) IPN hydrogels and their application for adsorption

Sodium carboxymethylcellulose/poly(methyl acrylate) (NaCMC/PMA) interpenetrating polymer networks (IPNs) were prepared by fractional step in 40 wt % ethanol solution with N,N′‐methylenebisacrylamide as a crosslinker. Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimeter were used to characterize the NaCMC/PMA IPN hydrogels and confirm the IPN structure as well. Simultaneously, adsorption of the obtained IPN hydrogels to methylene blue (MB) was also investigated. It was observed that the adsorption of MB onto the hydrogels was mainly dependent on the initial concentration of MB and the pH of the solution. Adsorption rate of MB was much higher in the first 9 h than that in the following period and saturated adsorption amount of MB was 2370 mg/g at the initial MB concentration of 100 mg/L. Moreover, the adsorption capacity of the IPN hydrogels at the neutral pH condition is much higher than those at acid or alkaline pH conditions. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41101.     

Antifouling and blood‐compatible poly(ether sulfone) membranes modified by zwitterionic copolymers via In situ crosslinked copolymerization

A novel and simple but practical method for the preparation of modified poly(ether sulfone) (PES) membranes was provided by the in situ crosslinked copolymerization of sulfobetaine methacrylate (SBMA) and sodium p‐styrene sulfonate (NaSS) in PES solution followed by a phase‐separation technique. Then, semi‐interpenetrating network membranes modified by the crosslinked copolymers of poly(sulfobetaine methacrylate‐co‐sodium p‐styrene sulfonate) [P(SBMA‐co‐NaSS)] were prepared. The SBMA‐containing copolymer‐modified membranes showed improved protein antifouling properties with flux recovery ratios above 90%. Furthermore, the anticoagulant properties of the NaSS‐containing copolymer‐modified membranes were obviously enhanced; their activated partial thromboplastin time could be prolonged to about 115 s. Thus, the P(SBMA‐co‐NaSS) zwitterionic copolymer‐modified membranes showed improved antifouling properties and blood compatibility and will provide wide choices for their specific applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41585.     

Ammonium nitrogen adsorption from aqueous solution by poly(sodium acrylate)s: Effect on the amount of crosslinker and initiator

In this work, we discuss the ammonium nitrogen adsorption and reusability from aqueous solution by using poly(sodium acrylate) (PANa) hydrogels (Polymers 1–6 ) under different amount of crosslinker and initiator. The PANa hydrogels were synthesized from the neutralized acrylic acid (AA) monomer via free radical thermal polymerization by using ammonium persulfate (APS) as an initiator and N,N′-methylene-bisacrylamide (MBA) as a crosslinker. These polymers exhibited glass transition temperatures (T_g) of 68–88°C and T_d values (5% weight loss temperature) in the range of 190–221°C under nitrogen atmosphere. The PANa hydrogels had swollen ratios ranging from 387 to 4,063%, related to the crosslinking density. The final equilibrium adsorption capacity of the polymers was in the range of 20–39 ppm with an initial ammonium nitrogen concentration of 100 ppm. Among them, Polymer 3 without MBA crosslinker displayed the highest swollen characteristic along with the most efficient adsorption capacity. In comparison, the as-prepared high crosslinking density hydrogels showed relative lower adsorption capability but higher reusability. The polymer composition in this work determines the ability to absorb and desorb ammonium nitrogen compound.     

Network characteristics of homopolymer and some copolymers of poly(2-hydroxyethyl methacrylate)

Soluble poly(2-hydroxyethyl methacrylate) and copolymers of 2-hydroxyethyl methacrylate with n-butyl acrylate and 2-hydroxypropyl acrylate of varying compositions were synthesised by solution polymerisation. The polymers were characterised by dilute solution viscometry and shear viscosity. Crosslinked membranes were prepared from these polymers by introducing crosslinks in solution state through the reaction with 1,6-hexamethylene diisocyanate at a number of different crosslinker concentrations. The membranes swollen in dimethylformamide and water were characterised by performing equilibirium swelling measurements and calculating polymer volume fraction, the molecular mass between crosslinks (M?^c) and equilibrium water content (EWC) at 25°C. The calculation of M?^c used an expression developed by Peppas & Lucht for equilibrium swelling. This is a modified equation of the original Flory–Rehner expression, that allows non-Gaussian distribution of chain lengths. The variation of M?^c with crosslinker concentration and copolymer composition is discussed in terms of structural and molecular characteristics of these highly crosslinked networks.     

Preparation and Swelling Behavior of Fast‐Swelling Superabsorbent Hydrogels Based On Starch‐g‐Poly(acrylic acid‐co‐sodium acrylate)

Summary: A novel fast‐swelling porous superabsorbent hydrogel was prepared by grafting acrylic acid onto corn starch through free‐radical polymerization in aqueous solution using N,N′‐methylenebisacrylamide as a crosslinker, ammonium persulfate as an initiator, sodium dodecyl sulfate and p‐octyl poly(ethylene glycol)phenyl ether as pore‐forming agents. The graft polymerization and surface morphology of the porous superabsorbents were characterized by FTIR and SEM. The results indicate that the porous superabsorbents were endowed with higher equilibrium water absorbency and faster swelling rate (they needed only 10 min to reach 90% of their equilibrium water absorbency) compared with the nonporous superabsorbents. The dewatering method employed had a significant influence on the swelling behavior of the superabsorbents and dewatering agents were useful to preserve the pores formed during the polymerization process.

The equilibrium water absorbency in distilled water, for the porous and non‐porous starch‐g‐poly(acrylic acid‐co‐sodium acrylate) superabsorbent hydrogels dried through different procedures.