Preparation of a starch‐graft‐acrylamide/kaolinite superabsorbent composite and the influence of the hydrophilic group on its water absorbency

A novel starch‐graft‐acrylamide/kaolinite superabsorbent composite with water absorbency 4000 times (g ) was synthesized by a graft copolymerization reaction among acrylamide, potato starch and kaolinite ultrafine powder, followed by saponification with NaOH. The influence of the hydrophilic group on water absorbency was investigated. It was found that the combined absorbent effect of —CONH₂, —COONa and —COOH groups was superior to that of a single group, and the composite with the molar ratio of 8:6:3 for the —CONH₂, —COONa and —COOH groups exhibits the highest water‐absorbent ability. Copyright © 2003 Society of Chemical Industry     

Study on starch-graft-acrylamide/mineral powder superabsorbent composite

A novel starch-graft-acrylamide/mineral powder superabsorbent composite with water absorbency about 4000 times is synthesized by graft-copolymerization reaction among acrylamide, potato starch and mineral ultrafinepowder, followed by hydrolysis with sodium hydroxide. It is found that the composite doped with kaolinite powder possess higher water absorbency than those doped with bentonite or sercite powder, since the kaolinite powder can moderately disperse in the water and cross-link with acrylamide and starch. By controlling the amount of NaOH and reaction time during saponification process, the hydrophilic groups on the composite can be adjusted, it is found that the collaborative absorbent effect of −CONH₂, −COONa and −COOH groups is superior to that of single −CONH₂, −COONa or −COOH group. By the IR characterization, the polymerization reaction mechanism and structure of the composite is supposed, the mineral ultrafinepowder as a cross-linking point play an important role in the formation of network structure of the superabsorbent composite.     

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     

Study on superabsorbent composite. XV. Effects of ion‐exchanged attapulgite on water absorbency of superabsorbent composites

A series of superabsorbent composite, polyacrylamide/attapulgite, from acrylamide (AM) and ion‐exchanged attapulgite (APT) was prepared by aqueous polymerization, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The effects of ion‐exchanged APT on water absorbency of superabsorbent composites in distilled water and in 0.9 wt% NaCl solution were studied. The result indicates that higher cation‐exchange capacity (CEC) and lower specific surface area (SSA) of APT treated with various anions are of benefit for improving water absorbency in distilled water. The effects of AlCl₃ solution concentration and Al³⁺‐exchanged APT content on water absorbency of the composite were also investigated. The concentration of AlCl₃ solution has a great influence on water absorbency of the superabsorbent composite. Al³⁺‐exchange of APT could also enhance reswelling ability of the corresponding composite, which indicates that Al³⁺‐exchange of APT could improve gel strength and gives a direct evidence for its acting as an inorganic assistant crosslinker in the polymeric network. POLYM. COMPOS., 28:208–213, 2007. © 2007 Society of Plastics Engineers     

Study on superabsorbent composite. VIII. Effects of acid‐ and heat‐activated attapulgite on water absorbency of polyacrylamide/attapulgite

A novel superabsorbent composite, polyacrylamide/attapulgite, from acrylamide (AM) and attapulgite (APT), was prepared by free‐radical polymerization, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The effects of hydrochloric acid (HCl) concentration, acidification time, and acidification temperature while acidifying APT and temperature and APT heat‐activation on water absorbency of the superabsorbent composite in distilled water and in 0.9 wt % NaCl solution were studied. The water absorbency first decreases with increasing the HCl concentration while acidifying APT, and then increases with further increasing the HCl concentration. Prolongation of acidification time is of benefit to the increase of water absorbency. At a given HCl concentration, water absorbency for the composite increases with increasing acidification temperature. An important increase in water absorbency was observed after incorporating heat‐activated APT into the polymeric network, reaching a maximum of 1964 g g^?1 with the APT heat‐activated at 400°C. Acid‐ and heat‐activation can influence chemical composition, crystalline structure, cation exchange capacity (CEC), and specific surface area of APT according XRF, XRD, FTIR analysis, and physicochemical properties test, and then on water absorbency of corresponding PAM/APT superabsorbent composite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2419–2424, 2007     

Study on superabsorbent composites. IX: Synthesis,characterization and swelling behaviors of polyacrylamide/clay composites based on various clays

A series of clay-based superabsorbent composite from acrylamide (AM) and various clays, such as attapulgite, kaolinite, mica, vermiculate and Na⁺-montmorillonite, was prepared by free-radical aqueous polymerization, using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator, and then saponified with sodium hydroxide solution. In this paper, the reaction mechanism and thermal stability of the superabsorbent composites incorporated with various clays were characterized by FTIR, XRD and TGA, respectively. The effects of clay kind and clay content on equilibrium water absorbency of these composites were also investigated and compared. In addition, the influences of clay kind on comprehensive swelling behaviors of the PAM/clay superabsorbent composites were studied. The results indicated that the introduced clays could influence physicochemical properties of obtained superabsorbent composites. Mica could improve thermal stability of corresponding superabsorbent composites to the highest degree comparing with the other clays. The PAM/clay superabsorbent composites incorporated with 10 wt% clay of various kinds were all endowed with equilibrium water absorbency of more than 1300 g g⁻¹. The equilibrium water absorbency decreases with increasing clay content and correlates with the kind of clay. Attapulgite-based superabsorbent composite was endowed with higher water absorbency in univalent cationic saline solution, however, the vermiculite- and the kaolinite-based ones acquired the highest water absorbency in CaCl₂ and FeCl₃ aqueous solution, respectively. Moreover, the superabsorbent composites incorporated with Na⁺-montmorillonite have higher swelling rate and that of doped with mica was endowed with higher reswelling capability.     

Superabsorbent composite. XIII. Effects of Al3+‐attapulgite on hydrogel strength and swelling behaviors of poly(acrylic acid)/Al3+‐attapulgite superabsorbent composites

Al³⁺‐attapulgite (Al³⁺‐APT) was prepared by treating attapulgite (APT) with AlCl₃ aqueous solution of various concentrations. The poly(acrylic acid)/Al³⁺‐attapulgite (PAA/Al³⁺‐APT) superabsorbent composite was prepared by reaction of partly neutralized acrylic acid, and Al³⁺‐APT in aqueous solution using N, N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. The surface morphology of the composite was investigated by SEM, and the Al³⁺‐APT composite generated a relatively planar surface comparing the nature APT. The effects of Al³⁺‐APT on hydrogel strength and swelling behaviors, such as equilibrium water absorbency, swelling rate, and reswelling capability, of the superabsorbent composites were also studied. The hydrogel strength and reswelling capability were improved, however, the equilibrium water absorbency and swelling rate decreased with increasing AlCl₃ solution concentration. The equilibrium water absorbency firstly increased, and then decreased with increasing Al³⁺‐APT content. The results indicate that Al³⁺‐APT acts as an assistant crosslinker in the polymeric network, which has great influences on hydrogel strength and swelling behaviors of the PAA/Al³⁺‐APT superabsorbent composites. POLYM. ENG. SCI., 47:619–624, 2007. © 2007 Society of Plastics Engineers.     

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,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     

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     

Synthesis and properties of poly(sodium acrylate‐co‐2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid)/attapulgite as a salt‐resistant superabsorbent composite

A novel salt‐resistant superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid (AMPS) and attapulgite (APT). To enhance the swelling rate (SR) of the copolymer, sodium bicarbonate was used as a foaming agent in the course of copolymerization. Furthermore, for improving the properties of swollen hydrogel, such as strength, resilience and dispersion, the copolymer was surface‐crosslinked with glycerine and sodium silicate, and then the surface‐crosslinked copolymer was blended with aluminum sulfate and sodium carbonate in post treatment process. The influences of some reaction conditions, such as amount of AMPS, APT, and initiator, and neutralization degree of acrylic acid on water absorbency in 0.9 wt% NaCl aqueous solution both under atmospheric pressure (WA) and load (WA_P, P ≈ 2 × 10³ Pa) were investigated. In addition, the effect of them on SR was also studied. The WA and WA_P of the superabsorbent composite prepared under optimal conditions in 0.9 wt% NaCl aqueous solution were 52 g·g^?1 and 8 g·g^?1, respectively. Besides, the SR was fast, and it could reach 0.393 mL·(g·s)^?1. Moreover, the swollen hydrogel possessed excellent salt resistance, hydrogel resilience and dispersion. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers     

CMC-g-PAMPS/APT复合高吸水树脂的溶胀行为及热稳定性能

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为单体,凹凸棒黏土(APT)和羧甲基纤维素钠(CMC)为复合组分,采用微波辐射方法制备了CMC-g-PAMPS/APT环境友好复合高吸水性树脂。考察了APT用量对树脂吸水速率、保水性能和反复吸水性能的影响,利用XRD和TG等方法分析了该树脂的结构及其热稳定性能。结果表明,APT和CMC参与了接枝共聚反应,其反应仅在APT的表面进行,单体并没有插入到APT的层间。在APT质量分数为7.5%时,树脂的分解温度主要在250℃以上,具有良好的热稳定性。经过5次反复溶胀后,树脂的吸水倍率较不含APT的树脂提高了近42%。在体系中引入APT能显著提高树脂的吸水速率和保水性能。     

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     

Ethanol‐assisted dispersion of attapulgite and its effect on improving properties of alginate‐based superabsorbent nanocomposite

The dispersion of attapulgite (APT) as nanorod‐like single crystals is crucial to fully develop its functionality of one‐dimensional nanometer material as a filler of composite materials. In this study, APT was dispersed by the assistance of ethanol during the high‐pressure homogenization process to form individual nanorod‐like crystals. The dispersed APT was used to prepare new sodium alginate‐g‐poly(sodium acrylate‐co‐styrene)/attapulgite (NaAlg‐g‐P(NaA‐co‐St)/APT) superabsorbent nanocomposites. The effect of ethanol/water ratio on the dispersion of crystal bundles of APT was investigated by field emission scanning electron microscopy, and the results indicate that APT crystal bundles were effectively disaggregated in ν(CH₃CH₂OH) : ν(H₂O) ? 5 : 5 solution after homogenized at 50 MPa. The better dispersion of APT in NaAlg‐g‐P(NaA‐co‐St) matrix has clearly improved the gel strength (from 1300 Pa to 1410 Pa, ω = 100 rad/s), swelling capacity (442–521 g/g), swelling rate (3.3303–4.5736 g/g/s), and reswelling ability of the superabsorbent nanocomposite. Moreover, the nanocomposites showed fast swelling–deswelling responsive behavior in different saline solutions. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

CMC-g-PAA/APT/HA复合高吸水性树脂的制备与溶胀性能

以羧甲基纤维素(CMC)为基质,丙烯酸(AA)为单体,凹凸棒黏土(APT)和腐植酸(HA)为复合组分,采用水溶液聚合法制备了羧甲基纤维素接枝聚丙烯酸/凹凸棒黏土/腐植酸(CMC-g-PAA/APT/HA)环境友好复合高吸水性树脂,用红外光谱(FTIR)进行了结构表征。考查了APT和HA含量对树脂吸水倍率和吸水速率的影响,研究了树脂在不同pH溶液中的溶胀行为以及反复吸水性能。试验结果表明,APT和HA通过其表面的活性基团参与了接枝共聚反应,在体系中引入HA和APT能够显著提高复合高吸水性树脂的吸水能力。在HA含量为5%(质量分数),APT含量为30%(质量分数)时,树脂可达到最优吸蒸馏水倍率为582g/g。该复合高吸水性树脂在pH值在4～11范围内时具有较高的吸水性能,表现出优异的pH稳定性。经过5次反复溶胀后,该复合吸水树脂仍能达到424g/g的吸水倍率,较不含APT和HA样品提高了近44%。     

Studies on poly(acrylic acid)/attapulgite superabsorbent composites. II. Swelling behaviors of superabsorbent composites in saline solutions and hydrophilic solvent–water mixtures

The effect of the attapulgite content on the swelling for a series of poly(acrylic acid)/attapulgite superabsorbent composites in water was studied. The effects of the temperature and pH values on the water absorbency of the superabsorbent composites were investigated. The swelling behavior of the superabsorbent composites in various saline solutions was also investigated. The water absorbency in various salt solutions decreased with an increase in the ionic strength of the solutions. At a high ionic strength (>1 × 10^?3M), the water absorbency in monovalent cationic solutions was higher than that in multivalent cation solutions. This dramatic reduction of the water absorbency in multivalent cationic solutions of high ionic strength may have been due to the complexing ability of the carboxylate groups inducing the formation of intramolecular and intermolecular complexes, which resulted in an increased crosslink density of the network. The swelling behavior of the superabsorbent composites in mixtures of water and hydrophilic solvents, including methanol, acetone, ethanol, and dimethyl sulfoxide (DMSO), was also investigated. The water absorbency decreased with an increase in the concentration of any of the four organic solvents, and two transitions were observed in the superabsorbent composite/hydrophilic solvent–water mixture systems. The main transition for the four hydrophilic solvent–water mixtures was a collapse of the swollen gel (at 50–80% methanol, 30–80% acetone, 50–80% ethanol, and 50–80% DMSO). For the methanol–water system, the magnitudes of the first and second transitions for the poly(acrylic acid)/attapulgite superabsorbent composites containing lower proportions of attapulgite were larger than those for the superabsorbent composites with higher attapulgite contents. The effect of the mixture temperature on the water absorbency of the superabsorbent composites in 10 min was also reported. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1869–1876, 2004     

Study on superabsorbent composite. XX. Effects of cation‐exchanged montmorillonite on swelling properties of superabsorbent composite containing sodium humate

In this work, the effects of different cation‐exchanged montmorillonite on water absorbency of poly(acrylic acid‐co‐acrylamide)/montmorillonite/sodium humate (PAA‐AM/MMT/SH) superabsorbent composite were systematically investigated under the same preparation conditions. The superabsorbents doped with different cation‐exchanged montmorillonite were characterized by Fourier‐transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy technologies. Swelling behaviors of developing superabsorbent composite in various cationic saline solutions (NaCl, CaCl₂, and FeCl₃) were also investigated. The water absorbencies of superabsorbent composite with 20 wt% MMT and 30 wt% SH are 638, 723, 682, and 363 g g⁻¹ in distilled water for incorporating natural Na⁺‐MMT, Li⁺‐exchanged MMT, Ca²⁺‐exchanged MMT, and Al³⁺‐exchanged MMT, respectively. The results showed that the cation‐exchange process had some obvious influences on final water absorbency of superabsorbent composite. NaCl, CaCl₂, and FeCl₃ solutions did not alter the swelling characteristics of the superabsorbent materials at a concentration of less than 0.01 mM, however, a concentration of greater than 0.1 mM caused a collapse in the swelling curves. The excellent swelling‐reswelling‐swelling behavior and lower swelling rate testified that Al³⁺‐exchanged MMT can act as an assistant crosslinker in the polymeric network. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Preparation and Swelling Behavior of a pH-Responsive Psyllium-g-Poly(acrylic acid)/Attapulgite Superabsorbent Nanocomposite

In this study, a series of psyllium-g-poly(acrylic acid)/attapulgite (PSY-g-PAA/APT) superabsorbent nanocomposites were prepared. The effects of the content of APT on equilibrium water absorption, swelling rate, and the swelling behaviors of the nanocomposites in various cationic saline solutions and different pH solutions were also systematically investigated. The nanocomposite containing 10 wt% APT gives the best water absorption of 568 g/g in distilled water and 64 g/g in 0.9 wt% NaCl solution. The excellent responsive properties and reversible On-Off switching characteristics can be observed in various pH buffer solutions.     

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     

Study on superabsorbent composite. XI. Effect of thermal treatment and acid activation of attapulgite on water absorbency of poly(acrylic acid)/attapulgite superabsorbent composite

The effect of acid activation and thermal treatment of attapulgite on water absorbency of superabsorbent composite were investigated. Under the same preparation conditions, superabsorbent composite prepared with natural attapulgite exhibited a water absorbency of 639 g/g and it merely kept 71% of its initial water absorbency after 5 times of swelling–deswelling–reswelling test. However, superabsorbent composites prepared with 2–10 M hydrochloric acid acidified attapulgite and 100–400°C thermal treated attapulgite respectively exhibited the water absorbency of 884–1,241 g/g and 701–1,515 g/g. Also, those superabsorbent composites can keep 87% and 85% of their initial water absorbency after 5 times of swelling–deswelling–reswelling test, respectively. These results showed that, compared with superabsorbent composite prepared with natural attapulgite, the comprehensive water‐absorbing properties of poly(acrylic acid)/ attapulgite superabsorbent composites were improved effectively by acid activation and thermal treatment of attapulgite. This improvement of water absorbencies and gel strength of superabsorbent composite may be due to synthetical factors such as changes in the crystalline structure and the specific surface area and improvement of the number and the activity of hydroxyl groups of attapulgite, which in turn influence the grafting efficiency of monomer, crosslinking density, and the structure of superabsorbent composite network. POLYM. COMPOS., 28:397–404, 2007. © 2007 Society of Plastics Engineers