Synthesis and superswelling behavior of carboxymethylcellulose–poly(sodium acrylate‐co‐acrylamide) hydrogel

In this paper, attention is paid to synthesis and swelling behavior of a superabsorbent hydrogel based carboxymethylcellulose (CMC) and polyacrylonitrile (PAN). The physical mixture of CMC and PAN was hydrolyzed in NaOH solution to yield hydrogel, CMC–poly(NaAA‐co‐AAm). During alkaline hydrolysis, the nitrile groups of PAN were completely converted to a mixture of hydrophilic carboxamide and carboxylate groups followed by in situ crosslinking of the grafted PAN chains. A proposed mechanism for hydrogel formation was suggested and the structure of the product was established using FTIR spectroscopy. The reaction variables affecting the swelling capacity of the hydrogel were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Swelling measurements of the synthesized hydrogels in various chloride salt solutions indicated a swelling‐loss with increase in the ionic strength of the salt solutions. The pH of the various solutions also affected the swelling of the superabsorbent. Furthermore, the present hydrogels showed a pH‐reversible property. Finally, the swelling kinetics of synthesized hydrogels with various absorbent particle sizes was briefly examined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

A convenient one‐step preparation of chitosan‐poly(sodium acrylate‐co‐acrylamide) hydrogel hybrids with super‐swelling properties

Hydrogel hybrids were conveniently prepared from alkaline hydrolysis of chitosan–poly(acrylonitrile) mixture under highly practical conditions. The reaction of chitosan alkoxide anions with nitrile groups of poly(acrylonitrile) (PAN) forms crosslinking points and results in a three‐dimensional network with superswelling ability in aqueous media. The hydrogel hybrid was identified using FTIR spectroscopy. The PAN content of the hydrolyzing feed affects proportionally the swelling capacity of the hydrogel hybrid. The swelling properties (capacity and rate) of the ampholytic hydrogel were investigated preliminarily. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1615–1619, 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 water absorbency of a novel poly(acrylate‐co‐acrylamide)/vermiculite superabsorbent composite

A novel poly(acrylate‐co‐acrylamide)/expanded vermiculite (EVMT) superabsorbent composite was synthesized by aqueous solution polymerization method. The water absorbency of the superabsorbent composite still reaches 850 g/g when 50 wt % EVMT is added, which is significant in decreasing the production cost of the superabsorbent composites. By controlling the molar ratio of acrylic acid monomer and acrylamide monomer, and neutralization degree of acrylic acid, the hydrophilic groups on the composite can be adjusted, and it is found that the collaborative absorbent effect of ? CONH₂, ? COOK, and ? COOH groups is superior to that of single ? CONH₂, ? COOK, or ? COOH group. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 735–739, 2007     

Preparation and properties of porous poly(sodium acrylate‐co‐acrylamide) salt‐resistant superabsorbent composite

A novel semi‐interpenetrating polymer networks (semi‐IPNs) porous salt‐resistant superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid and acrylamide using polyethylene glycol as semi‐IPNs composite, N,N′‐methylenebisacrylamide, triene propanol phosphate, and trihydroxymethyl propane glycidol ether as crosslinking agents, methanol, propanol, and butanol as foaming agents, and L ‐ascorbic acid and peroxide hydrogen as initiators. To improve the properties of swollen hydrogel, such as strength, resilience, permeabilities, and dispersion, the copolymer was surface‐crosslinked, and then blended with aluminum sulfate, sodium carbonate, and sodium 1‐octadecanol phosphate in the course of post treatment. The influences of reaction conditions on properties of superabsorbent composite were investigated and optimized, and the water absorbency of superabsorbent composite prepared at optimal conditions in 0.9 wt% NaCl aqueous solution under atmospheric pressure and certain load (P ≈ 2 × 10³ Pa) were 61 g g^?1 and 16.7 g g^?1, respectively. Moreover, the swelling rate reached 22.003 × 10^?3 g (g s)^?1. And the excellent hydrogel properties, such as hydrogel strength, resilience, permeabilities, and dispersion were also obtained. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Investigation of pH sensitivity of poly(acrylic acid‐co‐acrylamide) hydrogel

It was found that the upper critical solution temperature (UCST) of poly(acrylic acid‐co‐acrylamide) hydrogel decreases with increase in pH. The UCST of samples equilibrated in a buffer at pH 2.5 was 33.7 °C, whereas it shifted to below 0 °C when swollen in buffers above pH 10. FT‐IR showed that COOH group of acrylic acid ionized gradually in alkaline media. The morphology change of the hydrogel swollen in different buffers was studied by environmental scanning electron microscopy (ESEM). ESEM images showed that the pore size of the sample increased with increase in pH, and in strongly basic media the three‐dimensional network was replaced by a ‘sausage‐like’ or ‘desert‐like’ structure. A study of the pH‐dependent release of cefazolin sodium was also carried out. Copyright © 2003 Society of Chemical Industry     

Synthesis of superabsorbent starch‐graft‐poly(potassium acrylate‐co‐acrylamide) and its properties

The superabsorbent's ability to resist deformation and to resist deswelling under externally applied pressures is important in practical application. For instance, it is used in infant diapers, in soil for agriculture, and in forestry. In this article, we report on the synthesis of a superabsorbent/starch‐graft‐poly(potassium acrylate‐co‐acrylamide) by inverse suspension polymerization. The effects of reaction conditions, such as monomeric concentration, ratio of water to oil, reaction temperature, and obtaining spherical resin, were investigated. Experiments showed that the superabsorbent has a good compressive strength and keeps the shape of particles after absorbing water. After mixing with soil it does not become sticky, and the loose structure can better retain air. It is fit to retain water in soil. In addition, thermogravimetric analysis revealed the superior thermal stability of the grafted product and its large particle size also reduces risk of air pollution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1536–1542, 2003     

Synthesis,characterization, and swelling behavior of alginate‐g‐poly(sodium acrylate)/kaolin superabsorbent hydrogel composites

A novel superabsorbent composite based on sodium alginate and the inorganic clay kaolin was synthesized via the graft copolymerization of acrylic acid (AA) in an aqueous medium with methylene bisacrylamide (MBA) as a crosslinking agent and ammonium persulfate (APS) as an initiator. The effects of reaction variables, such as the MBA, AA, and APS concentrations and the alginate/kaolin weight ratio, on the water absorbency of the composite were systematically optimized. Evidence of grafting and kaolin interactions was obtained by a comparison of the Fourier transform infrared spectra of the initial substrates with that of the superabsorbent composite, and the hydrogel structure was confirmed with scanning electron microscopy. The results indicated that with an increasing alginate/kaolin weight ratio, the swelling capacity and gel content increased. The effects of various salt media were also studied, along with the swelling kinetics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characterization of dual responsive sodium alginate‐g‐poly(vinyl alcohol) hydrogel

Poly(vinyl alcohol) (PVA) was chosen as a controllable gelator to prepare sodium alginate (SA)‐based physically cross‐linked dual‐responsive hydrogel by three steps. First, polyvinyl acetate (PVAc) was grafted onto SA via radical copolymerization. Then, the copolymer was subsequently converted into SA‐g‐poly(vinyl alcohol) (SAPVA) by alcoholysis reaction. PVA content of SAPVA was tailored by controlling the graft percentage of PVAc, i.e. through varying the amount of vinyl acetate during copolymerization. Finally, SAPVA hydrogels were formed by freezing‐thawing cycles. The structure of the graft copolymers was verified with FTIR spectroscopy. X‐ray diffraction analysis results revealed that the crystallinity of SAPVA hydrogels depended on the PVA content of SAPVA. The swelling test showed that SAPVA hydrogels were pH‐responsive, and the swelling was reversible. SAPVA hydrogels also behaved electric‐responsive. In addition, the pH‐sensitivity of SAPVA hydrogels was able to be controlled with the composition of the hydrogels. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐sodium acrylate) superabsorbent polymers

A novel hydroxyethyl chitosan‐g‐poly(acrylic acid‐co‐Sodium Acrylate) (HECTS‐g‐(PAA‐co‐PSA)) superabsorbent polymer was prepared through graft copolymerization of acrylic acid and sodium acrylate onto the chain of hydroxyethyl chitosan. The structure of the polymer was characterized by FTIR. By studying the water absorption of the polymer synthesized under different conditions, the optimal conditions for synthesizing the polymer with the highest swelling ratio was defined. This superabsorbent polymer was further treated by the solvent precipitation method and by the freeze‐drying method. We found that the water absorption rate of the treated polymer was greatly increased and the microstructure of the treated polymer was changed from small pores to loose macro pores. The swelling processes of the polymers before and after modification fit first‐order dynamic processes. The amount of the residual acrylic acid was greatly decreased after treatments. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of bentonite–poly[(acrylic acid)‐acrylamide] water superabsorbent by photopolymerization

A novel bentonite–poly[(acrylic acid)‐acrylamide] superabsorbent composite with water and salt solution absorbencies of 450 and 108 times its own weight, respectively, was successfully synthesized by photopolymerization of acrylic acid with acrylamide in the presence of bentonite powder using 30 min of ultraviolet irradiation at room temperature. The results show a synergetic effect of Michler's ketone and benzophenone mixed photoinitiators on the water absorbency, and incorporation of bentonite below 10 wt% into the water superabsorbent can slightly increase the water and salt solution absorbencies, and improve water retention, as demonstrated using thermogravimetric analysis and differential scanning calorimetry. Fourier transform infrared spectroscopy allowed the determination of the structure of the bentonite composite superabsorbent. Copyright © 2006 Society of Chemical Industry     

Synthesis of CdS nanoparticles dispersed within amphiphilic poly(urethane acrylate‐co‐styrene) films

CdS nanoparticles were prepared using amphiphilic urethane acrylate nonionomer (UAN) precursor chains having a poly(propylene oxide)‐based hydrophobic segment and a hydrophilic poly(ethylene oxide) segment. Cadmium salts were first dissolved in UAN/styrene solutions, and then the solutions were copolymerized to obtain poly(urethane acrylate‐co‐styrene) films containing dissolved cadmium salts. After reduction with H₂S gas, freestanding films containing CdS nanoparticles were obtained. Transmission electron microscopy images of the films showed that 9.67‐nm CdS nanoparticles were dispersed within the poly(urethane acrylate‐co‐styrene) matrix. The formation of CdS nanoparticles was also confirmed with UV absorption spectra and photoluminescence emission spectra of the films. Transmission electron microscopy and dynamic mechanical analysis measurements confirmed that hydrophilic/hydrophobic microphase separation in UAN/styrene solutions occurred during the dissociation of the cadmium salts, and the microphase‐separated structures were locked in by crosslinking copolymerization. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2357–2363, 2005     

Preparation of starch‐graft‐poly(acrylamide)/attapulgite superabsorbent composite

A novel starch‐graft‐poly(acrylamide)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of starch, acrylamide (AM), and attapulgite micropowder using N.N‐methylene‐bisacrylamide (MBA) as a crosslinker and ammonium persulphate (APS) as an initiator in aqueous solution, followed by hydrolysis with sodium hydroxide. The effects on water absorbency, such as amount of crosslinker, initiator, attapulgite, weight ratio of acrylamide to starch in the feed, gelatinization conditions of starch and molar ratio of NaOH to acrylamide, and so forth, were investigated. These superabsorbent composites were characterized by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The water absorbencies for these superabsorbent composites in water and saline solution were investigated, and water retention tests were carried out. Results obtained from this study showed that the water absorbency of superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% exhibit absorption of 1317 g H₂O/g sample and 68 g H₂O/g sample in distilled water and in 0.9 wt % NaCl solution, respectively. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1351–1357, 2005     

Superabsorbent polymeric materials. VI. Effect of sulfobetaine structure on swelling behavior of crosslinked poly(sodium acrylate‐co‐sulfobetaines) in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), N,N‐dimethyl(acrylamidopropyl) ammonium propane sulfonate (DMAAPS) or dimethyl(methacryloyloxy ethyl) ammonium propane sulfonate (DMAPS), and N,N′‐methylene bisacrylamide (NMBA) was prepared by inverse suspension polymerization. The water absorbencies or swelling kinetic behaviors for these xerogels in water or various saline solutions were investigated. The swelling behaviors of these absorbents were related to their chemical structures, their compositions, and the nature of external salt solutions. The water absorbencies of these two copolymeric gel series in deionized water or in various salt solutions would be improved effectively by copolymerizing SA with a small amount of zwitterionic monomer (DMAAPS or DMAPS). The water absorbency of the gel containing DMAPS is larger than that of the gel containing DMAAPS when the amount of zwitterionic monomer in the copolymeric gel is <0.8 mol %, but a contrary result is observed when the zwitterionic monomer content is >0.8 mol %. The tendency of the absorbency for these gels in dilute solution is in the order Cu²⁺ > Zn²⁺ > Co²⁺ > Ni²⁺ for CuCl₂, ZnCl₂, CoCl₂, and NiCl₂ aqueous solution, respectively. The absorbency and initial absorption rate for those gels are related with gel compositions and salt concentrations. Finally, the adsorption of cupric ion by these gels is also investigated. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1221–1232, 1999     

Synthesis of poly(sodium acrylate‐co‐sodium 1‐(acryloyloxy) propan‐2‐yl phosphate) and comparative study on its swelling properties with poly(sodium acrylate) and poly(sodium acrylate‐co‐2‐hydroxypropyl acrylate)

A new superabsorbent copolymer, poly(sodium acrylate‐co‐sodium 1‐(acryloyloxy) propan‐2‐yl phosphate) [P(SA‐co‐SAPP)], was synthesized by a novel prepared monomer, 1‐(acryloyloxy) propan‐2‐yl phosphoryl dichloride. The swelling properties of the superabsorbent were investigated by comparison with poly(sodium acrylate) (PSA) and the copolymer of poly(sodium acrylate‐co‐2‐hydroxypropyl acrylate) [P(SA‐co‐HPA)]. The results showed that (1) the superabsorbent containing sodium 1‐(acryloyloxy) propan‐2‐yl phosphate had higher water absorbency at general testing conditions; (2) the swelling properties of P(SA‐co‐SAPP) and PSA were obviously influenced by pH of solutions, which were different from that of P(SA‐co‐HPA); (3) the swelling process and the saturated water absorbency of all superabsorbents were remarkably affected by cations, especially multivalent ones, while barely affected by anions. POLYM. ENG. SCI., 47:728–737, 2007. © 2007 Society of Plastics Engineers.     

Synthesis and swelling properties of protein‐poly(acrylic acid‐co‐acrylamide) superabsorbent composite

A novel superabsorbent polymer composite was synthesized by graft copolymerization of cottonseed protein and acrylic monomers in order to explore the new application of cottonseed protein in nonfood field. This composite was synthesized by solution based copolymerization, using partly neutralized acrylic acid, acrylamide and cottonseed protein as raw material, N,N‐methylene bisacrylamide as crosslinking agent, potassium persulphate and sodium sulfite as the initiators. The effects of the certain variables of the copolymerization on the water absorbency of the synthesized composite were measured. The chemical structure of the composite was characterized by means of Fourier transform infrared spectroscopy, differential scanning calorimetry and thermogravimetry analysis. The swelling properties of the composite were carried out under varying pH conditions. Further, the saline sensitivity, swelling kinetics and water retention ability of the composite was investigated. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Superabsorbent polymeric materials. XI. Effect of nonionic monomers on the swelling behavior of crosslinked poly(sodium acrylate‐co‐nonionic monomers) in aqueous salt solutions

A series of xerogels based on sodium acrylate, nonionic monomers such as 2‐hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol) methacrylate (PEGMA), and N,N′‐methylene bisacrylamide were prepared by inverse suspension polymerization. The results indicate that the water absorbencies for these two gel series were effectively improved by the addition of a small amount of nonionic monomer (HEMA or PEGMA). The initial absorption rates in deionized water were faster for the PEGMA gels than for the HEMA gels. Scanning electron microscopy showed that the spherical particle size was smaller for the PEGMA gels than for the HEMA gels. In addition, the water absorbency of the gels in various salt solutions decreased with increasing ionic strength, especially for the multivalent salt solutions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3666–3674, 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     

Superabsorbent polymeric materials IX: Effect of cationic structure on swelling behavior of crosslinked poly(sodium acrylate‐co‐cationic monomers) in aqueous salt solutions

Two series of xerogels based on sodium acrylate (SA), trimethyl methacrylamidopropyl ammonium iodide (TMMAAI), trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N′‐methylene‐bis‐acrylamide (NMBA) as a crosslinker were prepared by inverse suspension polymerization. The water absorbency and swelling kinetic behavior for these xerogels in water or various saline solutions were investigated. The results showed that the swelling behaviors of these absorbents are related to their chemical structures, their compositions, and the type of external salt solutions. There would be effective improvement in the water absorbency of these two gel series by copolymerizing SA with a small amount of cationic monomer (TMMAAI or TMMAI). The initial absorption rates in deionized water were found to be faster for TM series gels than for TA series gels. The two series of superabsorbents had a tendency to absorb water in dilute nitrate aqueous solutions in the order: Fe³⁺, Ni²⁺, Ca²⁺, Cu²⁺, and Na⁺ for Fe(NO₃)₃, Ni(NO₃)₂, Ca(NO₃)₂, Cu(NO₃)₂, and NaNO₃ aqueous solution, respectively. The absorbency and initial absorption rate for these gels were related to the gel compositions and salt concentrations. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1827–1837, 2001     

Superabsorbent polymeric materials VIII: Swelling behavior of crosslinked poly[sodium acrylate‐co‐trimethyl methacryloyloxyethyl ammonium iodide] in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), cationic comonomer, trimethyl methacryloyloxyethyl ammonium iodide (TMMAI), and N,N‐methylene‐bis‐acrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency and the swelling behavior for these high absorbent polymers in deionized water and various saline solutions were investigated. Results indicated that the water absorbency for the present copolymer gel increased when a small amount of TMMAI monomer was introduced into the SA gel, then decreased with increase in TMMAI content. The water absorbency was 583 g H₂O/g for a gel sample in deionized water containing 2.5 × 10⁻³ molar fraction TMMAI. But a contrary result was observed for initial absorption rate, that is, the initial absorption rates increased with an increase of TMMAI in deionized water and 0.9 wt % NaCl solution. The absorbency in the chloride salt solution decreased with an increase in the ionic strength of the salt solution. Finally, the adsorption of copper ion by these gels was also investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1665–1674, 2001