Superabsorbent polymeric materials. XII. Effect of montmorillonite on water absorbency for poly(sodium acrylate) and montmorillonite nanocomposite superabsorbents

A series of novel xerogels based on sodium acrylate (NaA), montmorillonite (MMT), and N,N′‐methylene‐bisacrylamide (NMBA) were prepared by inverse suspension polymerization and water solution polymerization. The influences of pure MMT, intercalated MMT, the method of polymerization, and the content of the MMT in the copolymeric gels on the water absorbency and the initial absorption rate in deionized water and various salt solutions were investigated. Results showed that the water absorbency was increased by adding a small amount of the pure MMT into the copolymeric gels, but decreased by adding intercalated MMT into the gels. In addition, the water absorbency of the gels prepared by water solution polymerization was lower than that prepared by inverse suspension polymerization. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3422–3429, 2004     

Effect of intercalated hydrotalcite on swelling and mechanical behavior for poly(acrylic acid‐co‐N‐isopropylacrylamide)/hydrotalcite nanocomposite hydrogels

A series of nanocomposite hydrogels were prepared from acrylic acid (AA), N‐isopropylacrylamide (NIPAAm), and intercalated hydrotalcite (IHT) by photopolymerization. The influence of the intercalating content of 2‐acrylamido‐2‐methyl propane sulfonic acid (AMPS) in HT on the swelling and mechanical properties for poly(AA‐co‐NIPAAm)/IHT nanocomposite hydrogels was investigated. The results showed that the higher the content of the AMPS‐HT was, the higher the swelling ratio of the gels and the higher the content of the intercalating agent was, the lower swelling ratio. It was also demonstrated that the swelling ratio of the gel was not affected by the counterion in HT. The gel strength and crosslinking density were not enhanced by adding AMPS‐HT into the gel composition, but the maximum effective crosslink density and shear modulus of the nanocomposite hydrogels were increased with an increase of the content of the intercalating agent in HT. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1572–1580, 2005     

Superabsorbent polymeric materials. XIII. Effect of oxyethylene chain length on water absorbency for the sodium acrylate and poly(ethylene glycol) methyl ether acrylate (PEGMEAn) copolymeric gels

In a previous study, we prepared a series of xerogels based on sodium acrylate (NaA) and 2‐hydroxyethyl methacrylate (HEMA, OE = 1) or poly(ethylene glycol) methacrylate (PEGMA, OE = 6) with different oxyethylene (OE) units. The effect of the contents of HEMA and PEGMA in the copolymeric gel on the swelling behavior in deionized water and various saline solutions was studied. Their results showed that the water absorbencies for these two series gels were effectively improved by adding a small amount of HEMA or PEGMA. In this article, a series of novel xerogels based on NaA and hydrophilic monomer poly(ethylene glycol) methyl ether acrylate (PEGMEA_n), which was synthesized from acryloyl chloride and poly(ethylene glycol) monomethyl ether with three oxyethylene (OE = 9, 16, 45) chain lengths, were prepared by inverse suspension polymerization. The effects of OE chain length in the copolymeric gel on the water absorption behavior and initial absorption rate for the present xerogels were investigated. Results showed that adding a small amount of PEGMEA_n could effectively increase the water absorbency of the gels. In addition, the water absorbency decreased with an increase of the OE chain length in PEGMEA_n. The initial absorption rate for the present copolymeric gels increased with increasing OE chain length in PEGMEA_n and the content of PEGMEA_n in the copolymeric gels. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 927–934, 2006     

Preparation of acrylic acid and AMPS cointercalated layered double hydroxide and its application for superabsorbent

This article reports the cointercalation of acrylic acid (AA) and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) in the interlayer region of Mg₂Al layered double hydroxide (LDH) and the application of this inorganic–organic composite material in the field of water superabsorbent. The monomers of AA and AMPS were cointercalated into galleries of Mg₂Al−LDH (denoted as AA−AMPS/LDH) with various molar ratios by ion‐exchange method, which was confirmed by powder X‐ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), and elemental analysis. The polymer‐based superabsorbent was prepared through in situ free‐radical aqueous copolymerization of AA and AMPS, with AA−AMPS/LDH as additive, N,N′‐methylenebisacrylamide (NMBA) as crosslinker and potassium persulfate (KPS) as initiator. The composition of this poly(AA‐co‐AMPS)/LDH was demonstrated as a good water superabsorbent. The LDH content, water absorbency, thermal stability, and swelling rate of this superabsorbent were also investigated in detail. Results showed that the incorporation of a 5 wt % AA−AMPS/LDH into polymer matrix increased its water absorbency significantly by 27.7% (in water) and by 51.5% (in 0.9 wt % NaCl solution). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of hydrotalcite on the swelling and mechanical behaviors for the hybrid nanocomposite hydrogels based on gelatin and hydrotalcite

A series of hybrid nanocomposite hydrogels, based on gelatin and intercalated hydrotalcite (IHT), crosslinked with glutaraldehyde, was prepared in this study. The microstructures of the IHT and sample gels were identified by X‐ray diffraction (XRD). Swelling behaviors and physical properties of these hybrid gels were investigated. XRD results indicated that exfoliation of IHT was achieved in the hybrid nanocomposite gels. The results indicated that adding a small amount of IHT could effectively decrease the swelling ratio of the hybrid gels, but adding excess IHT could increase the swelling ratio of the nanocomposite hybrid gels. The crosslinking densities (ρ_x) of the present gels varied with IHT content and swelling ratio of the gels. The drug release behaviors of these gels were also investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 500–507, 2006     

Studies on poly(acrylic acid)/attapulgite superabsorbent composite. I. Synthesis and characterization

A novel poly(acrylic acid)/attapulgite superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) on attapulgite micropowder using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator in aqueous solution. The effects on water absorbency of such factors as reaction temperature, initial monomer concentration, degree of neutralization of AA, amount of crosslinker, initiator, and attapulgite were investigated. These crosslinked superabsorbent composites were characterized by thermogravimetetric analysis and scanning electron microscopy. The graft copolymerization reaction of AA on attapulgite micropowder was characterized by FTIR. The water absorbencies for these superabsorbent composites in water and saline solutions were investigated and water‐retention tests were carried out. Results obtained from this study show that the water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% exhibited an absorption of 1017 g H₂O/g sample and 77 g H₂O/g sample in distilled water and in 0.9 wt % NaCl solution, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1596–1603, 2004     

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     

Super alcohol-absorbent gels of sulfonic acid-contained poly(acrylic acid)

Alcohol-specific superabsorbing gels (super-alcogels) based on non-neutralized acrylic acid (AA, 60–94 mol%) and 2-acrylamido-2-methylpropane sulfonic acid (AMPS) were prepared via solution polymerization in water. Polyethylene glycol dimethacrylate and potassium persulfate were used as crosslinker and initiator, respectively. Characterization of samples was performed using FTIR, ¹H-NMR and thermomechanical analyses. Glass transition temperature and modulus of dried samples were found to be directly changed with their AA content. The gels exhibited enormous ability for absorbing and retaining a variety of mono- and poly-hydric alcohols. For example, in lieu of one gram of a typical sample composing 25 mol% AMPS, its absorption capacity was measured to be 53.0 g methanol, 42.1 g ethanol, 12.1 g n-propanol, 3.4 g iso-propanol, 41.2 g ethylene glycol, 20.7 g propylene glycol, 37.8 g 1,3-propanediol and 32.9 g glycerol. The absorbencies were superior to those of a known commercial poly(AA) sample, Carbopol. The alcohol absorbency was improved with increase of AMPS incorporated. It was recognized to be dependant on the alcohol characteristics such as H-bonding ability, OH/C ratio, electronic features (e.g. dielectric constant), steric hindrance of the neighboring groups of the solvent OH group, as well as the solvent viscosity. Normal phase transitions were observed in the gel swelling behavior in the alcohol-water binary mixtures. Rheological measurements of the water-swollen gel showed that more AMPS content resulted in gels with inferior storage modulus. All the empirical observations were discussed based on the related physicochemical principles.     

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     

Superabsorbent polymeric materials VII: Swelling behavior of crosslinked poly[sodium acrylate‐CO‐trimethyl methacrylamido‐propyl ammonium iodide] in aqueous salt solutions

A series of xerogels based on sodium acrylate (SA), cationic comonomer trimethyl methacrylamidopropyl ammonium iodide (TMMAAI), and N,N‐methylene‐bis‐acrylamide (NMBA) were prepared by inverse suspension polymerization. The water absorbency and the swelling behavior for these highly absorbent polymers in deionized water and various saline solutions were investigated. Results indicated that the water absorbency increased when a small amount of TMMAAI monomer was introduced into the SA gel. The water absorbency decreased with increase in TMMAAI content, but the contrary result was observed for initial absorption rate. Moreover, with more crosslinking agent, the water absorbency was lower. Finally, the adsorption of copper ion by these gels was also investigated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1749–1759, 2000     

Synthesis of poly(AA‐co‐AM) superabsorbent composites by reinforcement of halloysite nanotubes

A novel poly(acrylic acid‐co‐acrylamide)/halloysite nanotubes [PAA‐AM/HNTs] superabsorbent composite was synthesized by free radical polymerization with using HNTs as an inorganic additive. The composite was characterized by Fourier transform infrared spectroscopy, scanning electron microscope, and thermogravimetric analysis. The results revealed that HNTs and PAA‐AM were combined well together to form a porous structure with a pore size of about 10 μm, and HNTs were uniformly distributed in the composite. The thermal stability was improved by adding HNTs in the composite. The influences of contents of initiator and halloysite, neutralization degree of AA, and molar ratio of AM to AA on water absorbency were investigated. The water absorbency and the water retention capacity were improved after adding HNTs into PAA‐AM. The composite containing 10% HNTs had the highest water absorbency of 1276 g/g in distilled water. Moreover, PAA‐AM/HNTs composite also had a high swelling rate within 60 min and could maintain 78% initial swelling capability after five reswelled test. The substantial enhancement of swelling properties enables PAA‐AM/HNTs suitable for numerous practical applications. POLYM. COMPOS., 36:229–236, 2015. © 2014 Society of Plastics Engineers     

Superabsorbent polymeric materials X: Effect of degree of neutralization on swelling behavior of crosslinked poly(sodium acrylate) in aqueous salt solutions

A series of xerogels based on different degrees of neutralizations (DN) of acrylic acid (AA) and N,N-methylene-bis-acrylamide (NMBA) were prepared by inverse suspension polymerization. The influence of the DN values of AA on water absorbency and swelling behavior for these highly absorbent polymers in deionized water and various saline solutions were investigated. Results indicate that the equilibrium-water absorbency (Q_eq) increases with an increase in the DN of AA until the DN value reaches 95% and then decreases at 100% of the DN value. However, the initial absorption rate for these gels decreases with an increase in the DN value of AA in both deionized water and 0.9 wt% NaCl solution. The adsorption of copper ions by these gels was also investigated.     

Synthesis and Swelling Behavior of Superabsorbents Cross-Linked with N-Maleyl Chitosan

A kind of superabsorbent based on the monomers maleic anhydride (MA) and acrylic acid (AA) was prepared by solution polymerization using ammonium peroxodisulfate (AP) and sodium bisulfite (NaHSO₃) as initiator, and N-maleyl chitosan (N-MACH) as cross-linker. Effects of process parameters such as the amount of cross-linker, mass ratio of MA to AA, and neutralization degree of AA on the water absorbency of superabsorbents are discussed. The results indicated the water absorbency of superabsorbents increased and then decreased with the increase of MA content, the amount of the N-MACH cross-linker, and the neutralization degree of AA. Under the optimal conditions, the water absorbency of superabsorbents could reach l560.42 g/g and 83.7 g/g in distilled water and in 0.9% NaCl solution, respectively. In addition, to enhance the water absorbency of superabsorbents in 0.9% NaCl solution, polyvinyl alcohol (PVA) was introduced as interpenetrating polymer in the network and 2-acrylamido-2-methyl propane sulfonic acid (AMPS) was introduced as comonomer. It was proved that PVA and AMPS could effectively improve the water absorbency of superabsorbents both in distilled water and 0.9% NaCl solution.     

Effect of the intercalation agent content of montmorillonite on the swelling behavior and drug release behavior of nanocomposite hydrogels

A series of novel dual functional nanocomposite hydrogels were prepared from N‐isopropylacrylamide (NIPAAm), acrylic acid (AA) that is neutralized 50 mol % by sodium hydroxide (SA50), and montmorillonite (MMT). MMT was intercalated with three different contents of intercalation agent of (3‐acrylamidopropyl) trimethyl ammonium chloride (TMAACl). Investigation of the effect of intercalated MMT with three contents of intercalation agent (TMAACl) in the present nanocomposite hydrogels on the swelling and drug release behaviors is the main purpose in this study. The microstructure was identified by X‐ray diffraction (XRD). Results showed that the swelling ratio for the present nanocomposite hydrogels decreased with an increase in the content of the intercalation agent. The gel strength of the present gels did not change obviously with an increase in the content of intercalation agent. XRD results indicated that exfoliation of MMT was achieved in the dry and swollen gel state. Finally, the drug release behaviors for these gels were accessed also. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 74–82, 2004     

Uptake of zinc,nickel, and chromium by N-isopropyl acrylamide polymer gels

Pure N-isopropyl acrylamide (NIPA) polymer gel and NIPA copolymers containing 2-acrylamido-2-methylpropane sulfonic acid (AMPS), 2-acetamidoacrylic acid (AAA), and acrylic acid (AA) were prepared and evaluated with respect to their capability for taking up zinc, nickel, and chromium ions from solutions. AAA-containing NIPA gels were found to take up these metal ions most efficiently. Titration of these gels verified the strong acidic nature of the AMPS–NIPA gel and the weakly acidic nature of the AA–NIPA and AAA–NIPA gels. The ion-exchange capacities, derived from the titration curves, were, however, rather low in all cases. NIPA gels are known to collapse at temperatures about 32°C. This, however, was found to have no effect on the ion-exchange behavior of the gels. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68:355–362, 1998     

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(acrylic acid)/sodium humate superabsorbent composite for agricultural use

A novel poly (acrylic acid)/sodium humate superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) on sodium humate micropowder using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and potassium peroxydisulfate (KPS) as an initiator in aqueous solution. The effects on water absorbency of factors such as reaction temperature, initial monomer concentration, and degree of neutralization of AA, amount of crosslinker, initiator, and sodium humate were investigated. The superabsorbent composite was characterized by scanning electron microscopy, and the graft copolymerization reaction of AA on sodium humate micropowder was characterized by IR spectroscopy. Results obtained from this study show that the water absorbency of the superabsorbent composite synthesized under optimal conditions for synthesis with a sodium humate content of 5.3% exhibited absorption of 684 g H₂O/g sample in distilled water. Water‐retention in soil is enhanced by the use of the superabsorbent composite. The effect of superabsorbent composite on the growth of corn is reported. The superabsorbent composite may be of use as water management materials for agriculture purposes in desert and drought‐prone areas. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5137–5143, 2006     

Electrolyte and pH responsive surfactant association in ionic semi‐interpenetrating networks containing cellulose or chitin synthesized in lithium chloride–N,N‐dimethylacetamide

Semi‐interpenetrating networks (SIPNs) of N,N‐dimethylacrylamide (DMAm)–N,N‐dimethylamino‐ethylacrylamide (DMAEAm), or N,N‐dimethylacrylamide (DMAm)–2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) containing cellulose or chitin were synthesized in 9% LiCl–N,N‐dimethylacetamide (DMAc). The SIPNs were formulated to contain (1, 2, or 5% w/w) cellulose or 0.8% w/w chitin. Control systems (without polysaccharide) were also synthesized in 9% LiCl–DMAc. An acrylamide (Am)–AMPS hydrogel was synthesized for comparison with the SIPN composites. The swelling behavior of these materials was investigated as a function of pH (DMAEAm‐containing networks) or electrolyte concentration (AMPS‐containing networks). The DMAm–AMPS materials were found to have higher equilibrium water content (EWC) values in deionized water than the DMAm–DMAEAm materials. The EWC of the DMAm–DMAEAm materials was largest between pH 4 and 5 due to the protonation of the tertiary amine, with the chitin‐containing material exhibiting the largest EWC. The DMAm–AMPS materials exhibited a decrease in EWC values with an increase in electrolyte concentration. Polymer–surfactant interactions were shown to exist for surfactants of opposite charge of the ionic mer units incorporated into the polymeric network. Surfactant sequestration by the polysaccharide‐containing materials was greater than that of the control gels; however, the rates of surfactant binding were lower. Release of the bound surfactant was achieved by the disruption of the charge–charge interactions by changing the pH of the medium (DMAEAm‐containing networks) or by the addition of electrolyte (AMPS‐containing networks). The DMAm–DMAEAm SIPNs released only 4% of the surfactant originally sequestered. By contrast, the DMAm–AMPS SIPNs released approximately 80%. The control Am–AMPS hydrogel–surfactant complex collapsed in the presence of electrolyte, and no surfactant was released from the complex. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 989–998, 1999     

Synthesis,characterization and swelling behaviors of hydroxyethyl cellulose‐g‐poly(acrylic acid)/attapulgite superabsorbent composite

In this work, a series of novel hydroxyethyl cellulose‐ g‐poly(acrylic acid)/attapulgite (HEC‐g‐PAA/APT) superabsorbent composites were prepared through the graft polymerization of hydroxyethyl cellulose (HEC), partially neutralized acrylic acid (AA), and attapulgite (APT) in aqueous solution, and the composites were characterized by means of Fourier‐transform spectroscopy, scanning electron microscopy, and transmission electronmicroscopy. The effects of polymerization variables including concentrations of the initiator and crosslinker and APT content on water absorbency were studied, and the swelling properties in various pH solutions as well as the swelling kinetics in various saline solutions were also systematically evaluated. Results showed that the introduction of 5 wt% APT into HEC‐g‐PAA polymeric network could improve both water absorbency and water absorption rate of the superabsorbent composites. In addition, the superabsorbent composites retained high water absorbency over a wide pH range of 4–10, and the swelling kinetics of the superabsorbent composites in CaCl₂ and FeCl₃ solutions exhibited a remarkable overshooting phenomenon. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

Swelling behavior and determination of diffusion characteristics of acrylamide–acrylic acid hydrogels

In this study, a random copolymer of acylamide and acrylic acid [poly(AAm‐co‐AA)] was prepared by a redox copolymerization method of their aqueous solutions. The effects of initial AAm/AA mole ratio, PEG 4000 content, and N,N′‐methylenebisacrylamide concentration on swelling behavior were investigated in water. Average molecular weights between crosslinks, percentage swelling, swelling equilibrium values, and diffusion/swelling characteristics (i.e., the structure of network constant, the type of diffusion, the initial swelling rate, swelling rate constant) were evaluated for every hydrogel systems. The hydrogels showed mass swelling capabilities in the range 789–1040% (for AAm/AA hydrogels), 769–930% (for AAm/AA hydrogels in the presence of PEG 4000), and 716–1040% (for AAm/AA hydrogels containing different concentrations of the crosslinker). The swelling capabilities of the hydrogels decreased with the increasing AA, PEG 4000, and crosslinker concentrations. The diffusion of water into AAm/AA hydrogels was found to be a non‐Fickian type. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1289–1293, 2004