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     

Preparation and slow‐release property of a poly(acrylic acid)/attapulgite/sodium humate superabsorbent composite

A novel poly(acrylic acid)/attapulgite (APT)/sodium humate (SH) superabsorbent composite was synthesized through the graft copolymerization reaction of acrylic acid on APT micropowder and SH with N,N′‐methylene bisacrylamide as a crosslinker and ammonium persulfate as an initiator in an aqueous solution. Various effects on the water absorbency, including the amounts of the crosslinker, initiator, APT, and SH, were investigated. The superabsorbent composite was characterized with Fourier transform infrared spectroscopy and scanning electron microscopy. The superabsorbent composite synthesized under optimal synthesis conditions with an APT concentration of 20% and an SH concentration of 20% exhibited absorption of 583 g of H₂O/g of sample and 63 g of H₂O/g of sample in distilled water and in a 0.9 wt % NaCl solution, respectively. The slow‐release property of SH from the superabsorbent composite into water was measured, and a test of the water retention of the superabsorbent composite in soil was also carried out experimentally with and without the superabsorbent composite. The results showed that the superabsorbent composite had not only good water retention but also an additional slow‐release property of SH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 37–45, 2007     

Study on superabsorbent composites. XVIII. Preparation,characterization, and property evaluation of poly(acrylic acid‐co‐acrylamide)/organomontmorillonite/sodium humate superabsorbent composites

A series of novel multifunctional poly (acrylic acid‐co‐acrylamide) (PAA‐AM)/organomontmorillonite (O‐MMT)/sodium humate (SH) superabsorbent composites were synthesized by the graft copolymerization reaction of partially neutralized acrylic acid and acrylamide on O‐MMT micropowder and SH with N,N′‐methylene bisacrylamide as a crosslinker and ammonium persulfate as an initiator in an aqueous solution. The superabsorbent composites were characterized by means of Fourier transform infrared spectroscopy, X‐ray diffraction, scanning electron microscopy, and thermogravimetric analysis. The effect of the relative weight ratio of SH to O‐MMT on the water absorbency was studied, and the results indicated that the best water absorbency of 591 g/g in distilled water was obtained when an O‐MMT content of 20 wt % and an SH content of 30 wt % were incorporated. The superabsorbent composite possessed a good capacity for water retention; even after 30 days, 24.4 wt % of water could still be saved by the sand soil containing 1.0 wt % superabsorbent composite. The results from this study show that the water absorbency of a superabsorbent composite is improved by the simultaneous introduction of O‐MMT and SH into a PAA‐AM network in comparison with the incorporation of only O‐MMT or SH. Also, in comparison with PAA‐AM/MMT/SH, an appropriate amount of O‐MMT can benefit the developed composites with respect to their water absorbency, salt resistance, and capacity for water retention in sand soil. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Utilization of starch and montmorrilonite for the preparation of superabsorbent nanocomposite

Starch and montmorrilonite (MMT) were used as raw materials for synthesizing starch‐graft‐poly[acrylamide (AM)–acrylic acid (AA)]/MMT superabsorbent nanocomposite by graft and intercalation copolymerization reaction of starch, AM, and AA in the presence of organic MMT micropowder in aqueous solution. Major factors affecting water absorbency such as weight ratio of monomers to starch, weight ratio of AM to AA, neutralization degree of AA, amount of crosslinker, initiator, and MMT were investigated. The superabsorbent nanocomposite synthesized under optimal synthesis conditions exhibits absorption of 1120 g H₂O/g sample and 128 g H₂O/g sample in deionized water and in 0.9 wt % NaCl solution, respectively. IR spectra showed that the graft copolymerization between  OH groups on MMT and monomers took place during the reaction, and that crystal interlayer was pulled open in the superabsorbent nanocomposite. X‐ray diffraction analysis showed that the crystal interlayer of MMT was pulled open to 2.73 nm, and thus formed nanometer exfoliation composite material. Thermogravimetric analysis showed that starch‐graft‐poly (AM–AA) superabsorbent nanocomposite (8 wt % MMT) has good thermal stability. This superabsorbent nanocomposite with excellent water absorbency and water retention, being biodegradable in nature, economical and environment friendly, could be especially useful in industry, agricultural, and horticultural applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

Synthesis and properties of a poly(acrylic acid)/montmorillonite superabsorbent nanocomposite

A novel superabsorbent nanocomposite was synthesized through the intercalation polymerization of partially neutralized acrylic acid and a sodium‐type montmorillonite powder with N,N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate and sodium sulfite as a type of mixed redox initiator. The effects of such factors as the amounts of the sodium‐type montmorillonite, crosslinker, and initiator and neutralization degree on the water absorbency of the nanocomposite were investigated. The structure and micrographs of the superabsorbent were characterized with Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy. The results showed that the acrylic acid monomer was successfully intercalated into the montmorillonite layers and banded together with them. The montmorillonite layers were exfoliated and basically dispersed in the composite on a nanoscale after the polymerization. The water absorbency of the nanocomposite was much higher than that of pure poly(acrylic acid). The optimum absorbency of the nanocomposite in distilled water and saline water (NaCl concentration = 0.9%) was 1201 and 83 g/g, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5725–5730, 2006     

Study on superabsorbent composite XXV. Synthesis,characterization, and swelling behaviors of poly(acrylic acid‐co‐N‐acryloylmorpholine)/attapulgite superabsorbent composites

In this work, a novel poly(acrylic acid‐co‐N‐acryloylmorpholine)/attapulgite superabsorbent composite was prepared by graft copolymerization among acrylic acid, N‐acryloylmorpholine and attapulgite in aqueous solution, using N,N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. The result from FTIR spectra showed that  OH of attapulgite participated in graft copolymerization with acrylic acid and N‐acryloylmorpholine. Proper monomer ratio and atapulgite content could form a loose surface, and improve reswelling ability and initial swelling rate. The buffer action of the  COOH and  COO⁻ groups in the superabsorbent composite keeps the water absorbency a rough constant in the pH range of 4.4–9.6. Both polarity and structure of an organic solvent are responsible for the phase transition point of the superabsorbent composite. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

Synthesis and characterization of a salt‐resisting superabsorbent based on poly(acrylic acid) with sodium tungstate as a crosslinker

A novel salt‐resistant superabsorbent polymer was synthesized by solution polymerization from the monomer acrylic acid (AA) with potassium persulfate as the initiator. Sodium tungstate was first employed as a crosslinker in the preparation to achieve a better crosslinked polymer (WPAA). In addition to the xerogel WPAA, sodium hydroxide and tris(2‐hydroxyethyl)amine (TEA) were introduced for the preparation of WPAA–sodium and WPAA–TEA hydrogels, respectively. The effect on the water absorbency of factors such as the reaction temperature, degree of neutralization of AA, and amounts of the crosslinker sodium tungstate and the initiator were investigated. The crosslinked xerogels were characterized with infrared spectroscopy. These crosslinked superabsorbent composites with sodium tungstate were characterized with thermogravimetric analysis and scanning electron microscopy. The water absorbencies of these superabsorbent composites in water and saline solutions were investigated. Results obtained from this study showed that under the same synthesis conditions, in comparison with superabsorbent composites with an aluminum salt as a crosslinker and styrene as a graft copolymer, the salt resistance of the superabsorbent composite synthesized with sodium tungstate as a crosslinker was obviously enhanced. Moreover, the WPAA–TEA xerogel had absorbency values of 223.6 and 81.9 g/g for distilled water and a 0.9 wt % NaCl solution, respectively, and it showed better salt resistance and a better water‐absorbing rate than the WPAA–sodium xerogel because of the modification with triethanolamine. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

耐盐型丙烯酸-丙烯酰胺接枝共聚高吸水树脂的合成及其性能研究

采用溶液聚合法,以丙烯酸(AA)和丙烯酰胺(AM)为单体,N,N＇-亚甲基双丙烯酰胺(NMBA)为交联剂,过硫酸钾(KPS)为引发剂.合成出丙烯酸-丙烯酰胺接枝共聚高吸水树脂.探讨了单体比[m(丙烯酸):m(丙烯酰胺)]、交联剂和引发荆用量、单体中和度及聚合温度对树脂吸水率的影响.IR光谱表明,丙烯酸和丙烯酰胺发生了接...     

Study on superabsorbent composites XIX. Synthesis, characterization and performance of chitosan-g-poly (acrylic acid)/vermiculite superabsorbent composites

A novel chitosan-g-poly (acrylic acid)/unexpanded vermiculite (CTS-g-PAA/UVMT) superabsorbent composite was prepared by graft polymerization among chitosan (CTS), acrylic acid (AA) and unexpanded vermiculite (UVMT) in aqueous solution. The effect of polymerization variables, including the content of crosslinker, initiator and UVMT, the weight ratio of AA to CTS, the reaction temperature, time and drying method, on water absorbency were studied. The swelling rate of the superabsorbent composite in distilled water was also investigated. The results from FTIR spectra showed that CTS and UVMT participated in graft polymerization reaction with AA. Introducing UVMT into the CTS-g-PAA polymeric network could form a loose and more porous structure by the SEM analysis, and the polymerization reaction is performed on the surface of UVMT micropowders from the results of XRD. The introduced UVMT enhanced the swelling rate and the water absorbency of CTS-g-PAA/UVMT superabsorbent composite.     

Influence of the COOH and COONa groups and crosslink density of poly(acrylic acid)/montmorillonite superabsorbent composite on water absorbency

A novel poly(acrylic acid)/montmorillonite superabsorbent composite with a water absorbency of 1100 times its own weight was synthesized by the graft copolymerization of acrylic acid with a cross‐linking agent in the presence of montmorillonite ultrafine powder. The influence of the amount of crosslinker and montmorillonite on water absorbency has been investigated. It was found that a crosslinker concentration of 0.03 wt% and 30 wt% montmorillonite gave the best results. The collaborative absorbent effect of sodium carboxylate and carboxylic acid groups was superior to that of sodium carboxylate or carboxylic acid groups alone, and the composite with a ratio of about 2/3 for sodium carboxylate to carboxyl acid groups possessed the highest water absorbence. © 2001 Society of Chemical Industry     

Waste polystyrene foam‐graft‐acrylic acid/montmorillonite superabsorbent nanocomposite

A novel superabsorbent nanocomposite based on partially neutralized acrylic acid, waste polystyrene foam, and sodium type montmorillonite (Na‐MMT) powder was synthesized through emulsion polymerization using N, N′‐methylenebisacrylamide as a crosslinker, 2,2′‐azo‐bisiso‐butyronitrile, ammonium persulfate, and sodium sulfite as mixed redox initiators. The effects of such factors as amount of Na‐MMT, crosslinker, initiator, and neutralization degree on water absorbency of the superabsorbent were investigated. The composites were characterized by Fourier transform infrared spectroscope, X‐ray diffraction, thermo gravimetric analysis, and scanning electron microscope. The results show that acrylic acid monomer successfully grafted onto the polystyrene chain, the layers of Na‐MMT were exfoliated and dispersed in the composite at nano size after copolymerization. The introduction of waste polystyrene foam in the composite increased the water absorbency rate. The addition of Na‐MMT not only enhanced the thermal stability of the composites but also increased its water absorbency, and the optimal water absorbencies of distilled water and saline water (w_NaCl = 0.9%) of the nanocomposites were more than 1180 g H₂O/g and 72.6 g H₂O/g, respectively. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 2341–2349, 2007     

GG-g-PAA/LOESS复合高吸水性树脂的制备与性能

以瓜尔胶(GG)、丙烯酸(AA)和黄土(LOESS)为原料,过硫酸铵(APS)为引发剂,N,N'-亚甲基双丙烯酰胺(MBA)为交联剂,采用水溶液聚合法制备了瓜尔胶接枝聚丙烯酸/黄土(GG-g-PAA/LOESS)复合高吸水性树脂。采用FTIR和SEM对其结构进行了表征,研究了LOESS的添加量对复合高吸水性树脂的溶胀能力和溶胀动力学的影响,考察了复合高吸水性树脂的保水性能、反复溶胀性以及在不同pH溶液中的吸水性能。结果表明,瓜尔胶、丙烯酸和LOESS发生了接枝共聚,体系中引入LOESS能够显著提高复合高吸水性树脂的吸水性能。当LOESS的质量分数为2%时,该树脂最高吸水倍率可达602 g/g,室温下6 d后,其保水率仍达28%,5次反复溶胀,吸水倍率仍能保持初始时的49%。此外,该复合高吸水性树脂还表现出优异的pH稳定性。     

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     

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     

Synthesis,swelling behaviors,and slow‐release characteristics of a guar gum‐g‐poly(sodium acrylate)/sodium humate superabsorbent

Superabsorbents used in agricultural and ecological projects with low‐cost, slow‐release fertilizers and environmentally friendly characteristics have been extensively studied. The use of a natural polymer as the matrix and then further polymerization with some functional material has become the preferred method. In this work, with natural guar gum (GG), partially neutralized acrylic acid, and sodium humate (SH) as the raw materials, ammonium persulfate as the initiator, and N,N′‐methylenebisacrylamide (MBA) as the crosslinker, GG‐g‐poly(sodium acrylate) (PNaA)/SH superabsorbents were synthesized through a solution polymerization reaction and were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, and thermogravimetric analysis. The effects of the SH content and MBA concentration on the water absorbency were investigated. The results showed that the introduction of SH into the GG‐g‐PNaA system could improve the water absorbency, swelling rate, pH‐resistant property, and reswelling capability, and the superabsorbent containing 15 wt % SH had the highest water absorbency of 532 g/g of sample in distilled water and 62 g/g of sample in a 0.9 wt % NaCl solution. The slow release in water and water retention in sandy soil tests revealed that the superabsorbent could act as a fertilizer as well as an effective water‐saving material for agricultural applications. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of superabsorbent based on the graft copolymerization of acrylic acid and acrylamide onto konjac glucomannan and its application in the water retention in soils

A new konjac glucomannan (KGM)-based superabsorbent polymer, KGM-g-poly(acrylic acid-co-acrylamide), was prepared by the free radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto KGM in the presence of N,N′-methylenebisacrylamide as a crosslinker with potassium persulfate as an initiator. The effects of reaction parameters, including the amount of crosslinking agent and initiator, the weight ratio of both (AA + AM) to KGM and AM to (AA + AM), neutralization degree of AA, bath temperature, and reaction time, on the water absorbency of the superabsorbent were investigated. The Fourier transform infrared spectroscopy was used to characterize the structures of the copolymer. The maximum water absorbency of the optimized product was 650 g/g for distilled water and 70 g/g for a 0.9 wt % aqueous NaCl solution. Furthermore, the water retention of the copolymer in soils was studied. The effect of the copolymers on the aggregate distribution of soils was also evaluated. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Superabsorbent composite XXII: Effects of modified sepiolite on water absorbency and swelling behavior of chitosan‐g‐poly(acrylic acid)/sepiolite superabsorbent composite

In this work, a series of chitosan‐g‐poly(acrylic acid)/sepiolite (CTS‐g‐PAA/ST) superabsorbent composites containing raw sepiolite, acid‐activated sepiolite, and cation‐exchanged sepiolite were synthesized by free‐radical graft polymerization in aqueous solution, using N,N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. The effects of raw sepiolite, acid‐activated sepiolite, and cation‐exchanged sepoilite on equilibrium water absorbency, swelling rate, and swelling behavior in different pH value solution of superabsorbent composites were systematically investigated. The results from FTIR spectra showed that chitosan and sepiolite participated in graft polymerization reaction with acrylic acid. The introduction of acid‐activated and cation‐exchanged sepiolite into chitosan‐g‐poly(acrylic acid) polymeric network could improve water absorbency and swelling rate compared with that of the raw sepiolite. All prepared samples have similar swelling behavior in different pH solutions and the equilibrium water absorbencies of samples keep roughly constant in the pH range from 4 to 12. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis and characterization of potassium humate–acrylic acid–acrylamide hydrogel

A novel potassium humate–acrylic acid–acrylamide (KHA–AA–AM) superabsorbent polymer was prepared from the reaction among leonardite potassium humate, acrylic acid and acrylamide by free radical initiating process using ammonium persulfate as the initiator and N, N′-methylene bisacrylamide as the crosslinker. Various effects of synthesis conditions on superabsorbent polymer were studied and the optimal reaction condition was obtained with crosslinker concentration 0.44–0.74 wt%, initiator concentration 1.12–2.22 wt%, n(KOH)/n(AA) 0.51–0.70, monomer concentration 10.95–12.59 wt%, graft reaction temperature 83 ± 1°C, monomer mole ratio of acrylic acid to acrylamide 1.42–2.30, and potassium humate content 17.54 wt%. Under the optimal conditions, the solution absorbency of KHA–AA–AM superabsorbent polymer to deionized water, tap water, 0.5% carbamide solution and 0.9% NaCl solution were 733–756, 161–284, 786–825, and 76–83 g/g, respectively.