Preparation and properties of superabsorbent containing starch and sodium humate

Starch and sodium humate were utilized as raw material for synthesizing starch‐g‐poly(acrylic acid)/sodium humate (St‐g‐PAA/SH) superabsorbent by graft copolymerization reaction of starch (St) and acrylic acid (AA) in the presence of sodium humate (SH) in aqueous solution. The effect of weight ratio of AA to St, initial monomer concentration, neutralization degree of AA, amount of crosslinker, initiator and SH on water absorbency of the superabsorbent were studied. The swelling rate and swelling behavior in NaCl solution as well as reswelling ability of the superabsorbent were systematically investigated. The results showed that the superabsorbent synthesized under optimal conditions with SH content of 7.7 wt% and St content of 11.5 wt% exhibits water absorbency of 1100 g/g in distilled water and 86 g/g in 0.9 wt% NaCl solution, respectively. Introducing SH into the St‐g‐PAA polymeric network can improved the swelling rate and reswelling capability of the superabsorbent. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,characterization and water absorbency properties of poly(acrylic acid)/sodium humate superabsorbent composite

A novel poly(acrylic acid)/sodium humate superabsorbent composite was synthesized by aqueous solution polymerization of acrylic acid using N, N′‐methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator in the presence of sodium humate. The effects on water absorbency such as initial monomer concentration, degree of neutralization of acrylic acid, amount of crosslinker, initiator and sodium humate, etc. were investigated. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with a sodium humate content of 20% exhibited an absorption of 1268 g H₂O/g sample and 93 g H₂O/g sample in distilled water and in 0.9 wt% NaCl solution, respectively. Swelling rate and water retention tests were also carried out. The results show that sodium humate, as a kind of functional filler, can enhance comprehensive properties of superabsorbent composite and reduce the product cost significantly. Copyright © 2005 John Wiley & Sons, Ltd.     

Study on superabsorbent composite XVI. Synthesis, characterization and swelling behaviors of poly(sodium acrylate)/vermiculite superabsorbent composites

A series of superabsorbent composites were synthesized by copolymerization reaction of partially neutralized acrylic acid on unexpanded vermiculite (UVMT) micropowder using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator in aqueous solution. And the samples were further characterized by means of fourier-transform spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) and thermogravimetric analysis (TGA). The effects of vermiculite content on water absorbency were studied. Swelling behaviors of the superabsorbent composites in various cationic salt solutions (NaCl, CaCl₂ and FeCl₃), anionic salt solutions (NaCl, Na₂SO₄ and Na₃PO₄) and pH solutions were also systematically investigated. Results obtained showed that the equilibrium water absorbency increased with increasing UVMT content and the concentration of 20 wt.% clay gave the best absorption (1232 g/g in distilled water and 89 g/g in 0.9 wt.% NaCl). Data achieved also suggested that the water absorbency in various saline solutions decreased with an increase in the ionic strengths of these solutions. And it was found that at a higher ionic strength (>1 × 10⁻³ M), the water absorbency in monovalent cationic solutions was higher than those in multivalent cationic solutions. However, at the same ionic strength (>1 × 10⁻³ M), the effect of three anionic salt solutions on the swelling has the following order: NaCl < Na₂SO₄ < Na₃PO₄.     

Fabrication and properties of a novel superabsorbent composite based on coco peat and poly (acrylic acid) cross‐linked trimethylolpropane trimaleate under ultraviolet irradiation

A series of novel poly(acrylic acid)/coco peat (PAA/CP) superabsorbent composites were prepared via the ultraviolet irradiation copolymerization of acrylic acid monomer (PAA) and coco peat cellulose (CP) in the presence of the cross‐linker trimethylolpropane trimaleate. The physico‐chemical structures of obtained PAA/CP were characterized by Fourier transform infrared spectroscopy, thermogravimetry/derivative thermogravimetry, X‐ray diffraction, and scanning electron microscopy, respectively. The critical parameters of affecting the water absorbency of PAA/CP, including the cross‐linker level, amount of CP and reaction time, were studied in detailed. The experimental results showed that the PAA/CP samples exhibited the maximum swelling value of 523.09 g/g in distilled water and 40.52 g/g in 0.9 wt % NaCl solution. The swelling behaviors of PAA/CP were significantly relied on the concentration of salt solution and the pH of external solution. The effect of ions species on the swelling performance was in the order: Na⁺ > Ca²⁺ > Fe³⁺ , and in pH 2.2 and 7.2 aqueous solutions PAA/CP composites displayed better pH‐responsiveness and reversible on‐off switching characteristics. Urea, as an agrochemical model, was loaded into PAA/CP substrate to supply with nitrogen nutrient. The test of their loading and releasing diffusion performance of urea suggested that the urea loading percentage of PAA/CP was remarkably dependent on the concentration of aqueous urea solutions and the release of urea from loaded PAA/CP samples in water followed a non‐Fickian mechanism. Owing to their considerable good water absorption capacity, slow urea release, economical and environment‐friendly merits, PAA/CP composites could be exploited for the agriculture applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Preparation,swelling behaviors and application of polyacrylamide/attapulgite superabsorbent composites

A series of superabsorbent composites, polyacrylamide/attapulgite (PAMA), were prepared from acrylamide (AM) and attapulgite micropowder in aqueous solution, using N,N′‐methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator and then saponified with sodium hydroxide solution. This paper focuses on swelling behaviors of the PAMA superabsorbent composites in various saline solutions. The results indicate that saline solutions can weaken the swelling abilities of the PAMA compsites greatly. Water absorbency of the PAMA composites with 20 and 40 wt% attapulgite in aqueous chloride salt solutions has the following order: Li⁺ = Na⁺ = K⁺, Mg²⁺ > Ca²⁺ = Ba²⁺ all through the range of concentration investigated. However, swelling properties of the composites are complicated in CuCl_2(aq), AlCl_3(aq) and FeCl_3(aq) solutions and are related to saline solutions concentration. The deswelling behavior of PAMA composites is more obvious in univalent chloride salt solutions than in divalent and trivalent ones. The influence of kind and valence of anions on swelling ability of the composites is limited and almost the same. Moreover, reswelling capability, practical water retention ability in sand soil of the composites and the effect of pH on water absorbency of the PAMA composites were investigated. The PAMA composite shows good water retention and reswelling ability in sand soil, and may be used as a recyclable water‐managing material for the renewal of arid and desert environment. Copyright © 2006 John Wiley & Sons, Ltd.     

Preparation and swelling behavior of amphoteric superabsorbent composite with semi-IPN composed of poly(acrylic acid)/Ca-bentonite/poly(dimethyldiallylammonium chloride)

Amphoteric superabsorbent composite with semi-interpenetrating polymer networks (semi-IPN) composed of poly(acrylic acid) (PAA)/Ca-bentonite/poly(dimethyldiallylammonium chloride) (PDMDAAC) was prepared by a combination of intercalative polymerization and a sequential IPN method and the effects of reaction parameters on the swelling capacity were studied. PDMDAAC was used as a polycation to modify bentonite and form semi-IPN with lightly crosslinked PAA. FTIR and TG were used to characterize the amphoteric superabsorbent composites with semi-IPN. The thermal stability of the product was not degraded as in the case of using small molecular surfactant to modify bentonite. The contents of carboxylic groups and nitrogen had been determined. This indicated that the product with certain content of carboxylic groups and nitrogen is inclined to exhibit excellent swelling capacity. The presence of PDMDAAC improved the swelling capacity. The resulting amphoteric superabsorbent composite showed excellent swelling capacity of 1578 g/g in distilled water and 136 g/g in 0.9 wt% NaCl solution. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis and properties of clay-based superabsorbent composite

A novel superabsorbent composites based on acrylic acid, acrylamide, and inorganic clay mineral-attapulgite were synthesized through a solution polymerization to improve water and saline absorbencies. The superabsorbent composite was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The effects of saline solutions, amount of initiator, crosslinker and attapulgite on the water absorbency of superabsorbent composites were investigated. The water retention test of superabsorbent composites were also carried out. The superabsorbent composite exhibited improved water and saline absorbencies compared with that of crosslinked poly(acrylic acid-co-acrylamide) superabsorbent polymer. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% reaches more than 1400 g H₂O/g and 110 g H₂O/g in distilled water and 0.9% NaCl solution, respectively.     

Acrylamide–itaconic acid superabsorbent polymers and superabsorbent polymer/mica nanocomposites

Superabsorbent polymer acrylamide (AM)/itaconic acid (IA) and its nanocomposite were synthesized by redox polymerization in an aqueous solution of both monomers with mica used as an inorganic additive. The influences of IA concentration, mica content, and crosslinker concentration on the water absorption and physical properties of the superabsorbent polymer and its nanocomposite were examined. Water absorbency in artificial urine by the synthesized copolymers, and the gel strength of the superabsorbent copolymers and their nanocomposites, were tested with loads of 0.28 or 0.70 psi. Transmission electron micrographs and X‐ray diffraction confirmed that the polymer chains were successfully intercalated into the silicate layers in the mica. The water absorbency and the artificial urine absorbency of the composite with an AM‐to‐IA mole ratio of 95:5, 0.2% mol N‐MBA, and 5% w/w mica were 748 ± 5 and 76 ± 2 g g^?1, respectively, whilst the neat copolymer achieved only 640 ± 7 and 72 ± 2 g g^?1 in water and artificial urine, respectively. The viscoelastic behavior suggested that the swollen gel of the nanocomposites exhibited mechanical stability and elasticity. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and properties of macroporous superabsorbent composite

A fast swelling macroporous superabsorbent composite was prepared by the copolymerization of partially neutralized acrylic acid, 2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid (AMPS), and attapulgite (APT) using N, N′‐methylenebisacrylamide (NNMBA) and trihydroxymethyl propane glycidol ether as crosslinking agents. For fast swelling rate (SR), sodium bicarbonate, polyethylene glycol (PEG), and sodium carboxymethylcellulose (CMC) were introduced into the reaction system as foaming agent and stabilizers. Furthermore, the copolymer was surface‐crosslinked with glycerine and sodium silicate, and then blended with aluminum sulfate and sodium carbonate. The influences of the amount of NNMBA, trihydroxymethyl propane glycidol ether, PEG, CMC and sodium bicarbonate, and reaction temperature on water absorbence both under atmospheric pressure and load, and on the SR were investigated. The water absorbence of the sample in 0.9 wt% NaCl aqueous solution under atmospheric pressure and certain load (P ≈ 2 × 10³ Pa) could reach 54 and 8 g.g^?1, respectively, and the SR could reach 0.471 ml g^?1 s^?1. The excellent strength, resilience, and the dispersion of swollen hydrogel were also observed for the sample. Moreover, the surface morphology of macroporous superabsorbent composite was characterized using scanning electron microscope. Copyright © 2009 John Wiley & Sons, Ltd.     

Preparation and properties of diatomite composite superabsorbent

A novel diatomite composite superabsorbent was synthesized by solution polymerization of partially neutralized acrylic acid and diatomite, using N,N′-methylenebisacrylamide as a crosslinking agent and hydrogen peroxide and L -ascorbic acid as a redox initial system. The influences of some reaction conditions, such as diatomite content, neutralization degree of acrylic acid, amount of initiator, amount of crosslinking agent, monomer concentration, and the reaction temperature on swelling characteristic were investigated. The water absorbency of the sample prepared at optimum conditions was 99 g/g in 0.9 wt% NaCl solution. The results of swelling rate measurement showed that diatomite composite superabsorbent had better swelling rate than that of poly(sodium acrylate) prepared in the same conditions. Other properties, i.e. water retention, reswelling ability and resistance to salt, were also examined. Copyright © 2007 John Wiley & Sons, Ltd.     

Study on superabsorbent composite. III. Swelling behaviors of polyacrylamide/attapulgite composite based on acidified attapulgite and organo-attapulgite

A novel kind of salt-resistant superabsorbent composite, polyacrylamide/attapulgite, from acrylamide (AM) and attapulgite (APT) was prepared by free-radical aqueous polymerization, using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The organification of APT with hexadecyltrimethyl ammonium bromide (HDTMABr) was proved by FTIR and XRD. The effects of acidified APT (H⁺-APT), organo-APT (HDTMABr-APT) and the content of APT in the superabsorbent composite on the water absorbency and the initial swelling rate for the superabsorbent composite in distilled water and in various saline solutions were studied. The effects of incorporated HDTMABr-APT and H⁺-APT on the reswelling ability of the superabsorbent composites were investigated. The results indicate that the incorporation of APT had remarkable influence on the improvement of water absorbency and swelling rate of the composites. Comparing with the composite doped with H⁺-APT, the water absorbency for the composite doped with 10 wt% HDTMABr-APT was enhanced from 2140 g g⁻¹ to 2800 g g⁻¹ in distilled water and from 100 g g⁻¹ to 121 g g⁻¹ in 0.9 wt% NaCl solution, respectively. The water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, the reswelling ability of the superabsorbent composites is also improved evidently by adding a small amount of HDTMABr-APT into the composite, comparing with that of incorporated with H⁺-APT.     

Study on superabsorbent composite. IV. Effects of organification degree of attapulgite on swelling behaviors of polyacrylamide/organo-attapulgite composites

A novel kind of superabsorbent composite, polyacrylamide/organo-attapulgite, from acrylamide (AM) and attapulgite (APT) was prepared by aqueous polymerization, using N,N′-methylenebisacrylamide (MBA) as a crosslinker and ammonium persulfate (APS) as an initiator. APT was organified with five different degree of hexadecyltrimethyl ammonium bromide (HDTMABr), and the organification degree of APT was proved by FTIR, TGA and XRD. The effects of organification degree of APT on water absorbency and swelling rate of the superabsorbent composite in distilled water and in various saline solutions were investigated in this study. The effect of organification degree on reswelling ability of the superabsorbent composites was also investigated. The results indicate that the organification degree of APT had remarkable influence on swelling behaviors of the superabsorbent composites. The superabsorbent composite acquired its highest water absorbency when the organification degree of APT is 8.02 wt.%.     

Preparation of composites and nanocomposites based on bentonite and poly(sodium acrylate). Effect of amount of bentonite on the swelling behaviour

A series of composite and nanocomposite hydrogels were synthesized by copolymerization reaction of partially neutralized acrylic acid (SA) on bentonite micropowder (BT) using N,N′-methylenebisacrylamide (MBA) as a crosslinker and potassium persulfate (I) as an initiator in aqueous solution. The influences of Na⁺-BT, organoBT (O-BT), and the content of the BT in the copolymeric gels on the swelling behaviour in deionized water and saline solution (0.2 wt.% NaCl_(aq)) were investigated. Results showed that the equilibrium swelling (W_∞) was decreased by adding a small amount of the BT, however, at higher BT contents, the W_∞ increased with the increase of the amount of clay. It was found that a concentration of 14 wt.% Na⁺-BT gave the best results absorption (955 g/g). Moreover, the amount of swelling for these absorbents in saline solution was smaller than that in deionized water. These hydrogels were characterized by X-ray diffraction and scanning electron microscopy. Finally, the thermogravimetric analysis indicated that introduction of clay to the polymer network resulted in an increase in thermal stability.     

Preparation of a novel bentonite intercalation composite by changing the chemical state of aluminum

A new environment-friendly bentonite intercalation composite was successfully obtained from alumina sol intercalation. This process used industrial grade pseudo boehmite as the aluminum source and provided with the advantage of zero emission of acidic wastewater. The bentonite intercalation composite was investigated by XRF, ICP, XRD, FT-IR, BET, and pyridine-FTIR. Results indicated that the basal spacing was enlarged from 14.72 to 15.60 Å; the specific surface area increased by 128%; and the total acid content increased from 65.32 to 245.76 μmol/g. The catalytic activity of this composite was tested by alkylation of aromatics with olefins. The results show that the weak Lewis acid generated by extra-framework aluminum and specific surface area play a decisive role, while weak Brønsted acid site is not the active site for this alkylation reaction.     

Needleless electrospinning of poly(acrylic acid) superabsorbent: Fabrication,characterization and swelling behavior

In this work, nanofibrous hydrogel has been fabricated from needleless electrospinning of Poly(acrylic acid) (PAA) in an aqueous solution with different concentrations. First, all solution samples were characterized for pH, surface tension, conductivity and viscosity. Next, electrospinnability of the PAA-water dope solution was investigated using the needleless electrospinning technique under constant conditions. Results indicated that the PAA-water solution was not electrospinnable. Therefore, the neutralization of carboxylic groups in the PAA chemical structure using the NaOH solution was investigated to enhance the PAA electrospinnability. Morphology observation revealed that the fiber diameters ranged from 40 to 250 nm and increased with increasing the solution concentrations. Increasing the neutralization degree (10%, 15% and 20% with 50 wt% NaOH solution) led to increase the dope viscosity and conductivity. The resultant nanofibers could be rendered water-insoluble by incorporating 1,4-butanediol diglycidyl-ether in the PAA-water dope solution, then heat-induced crosslinking was performed using a microwave at different curing times (1–5 min) and temperatures (45–105 °C). The nanofibrous hydrogel mat was then characterized by FTIR. The resulting nanofibrous hydrogel showed remarkable water absorption capacity up to 17,000% and 51,000% (within 15 min) in the standard saline solution and distilled water, respectively.     

Taguchi optimized synthesis of collagen-g-poly(acrylic acid)/kaolin composite superabsorbent hydrogel

A novel biopolymer-based hydrogel composite was synthesized through chemical crosslinking by graft copolymerization of partially neutralized acrylic acid onto the hydrolyzed collagen. The Taguchi method, a robust experimental design, was employed for the optimization of the synthesis based on the swelling capacity of the hydrogels. This method was applied for the experiments and standard L16 orthogonal array with five factors and four levels. In the synthesis of the composite superabsorbent, N,N′-methylene bisacrylamide (MBA) as crosslinker, ammonium persulfate (APS) as initiator, acrylic acid (AA) as monomer, neutralization percent (NU), and collagen/kaolin weight ratio were used as important factors. From the analysis of variance of the test results, the most effective factor controlling equilibrium swelling capacity was obtained and maximum water absorbency of the optimized final product was found to be 674 g/g. The surface morphology of the gel was examined using scanning electron microscopy. Furthermore in this research, swollen gel strength of composite SAPs already swollen under realistic conditions (saline solution absorbency under load) was determined.     

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composite: Preparation,swelling investigation and its application as a slow-release fertilizer

Sodium alginate-g-poly(acrylic acid-co-2-hydroxyethyl methacrylate)/montmorillonite superabsorbent composites (SACs) were prepared by graft copolymerization of acrylic acid (AA) and 2-hydroxyethyl methacrylate (HEMA) onto sodium alginate (Na-Alg) in the presence of montmorillonite (MMT) using N,N′-methylenebisacrylamide (MBA) as a crosslinker and potassium persulfate (KPS) as an initiator in aqueous solution. The composite structures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), Thermal Gravimetric Analysis (TGA) and Scanning Electron Microscope (SEM). The effect of % initiator, crosslinker amount and clay ratio on the swelling capacity was investigated. The results indicated that the highest swelling capacity of the composites in distilled water was 752 g/g by using 1.25% KPS and 0.06% MBA, 75% AA, 6.25% HEMA and 12.5% Na-Alg. Different samples were loaded with urea to evaluate their release potentials, and the release was studied by measuring the conductivity. The amount of urea release increased with increasing MMT amount.     

Preparation of sodium borosilicates using sodium silicate and boric acid

The gelling behaviour of an aqueous sodium silicate solution with boric acid was investigated for different initial compositions and solid sodium borosilicate samples were obtained by drying the gels at 100°C, 225°C and 450°C. The chemical composition, dissolution, pH, loose-packed bulk density, B.E.T. surface area, moisture, size distribution and XRD/IR patterns of the sodium borosilicate particles were determined. The minimum gelling times were observed at pH values between 9–10 and although no gels were obtained using HCl at pH = 11, the silicate solution was gelled with boric acid suggesting borate ions promote the formation of siloxane network and behave as a crosslinking agent.     

Preparation and properties of novel plastisols based on acrylic core-shell lattices

A series of core-shell lattices comprising a core portion of rubbery acrylic homo- or copolymers and a surrounding shell portion of glassy methyl methacrylate (MMA) homo- or copolymers were designed as plastisols for automotive underbody coatings. The lattices were synthesized by a semi-continuous seeded emulsion polymerization and characterized by using differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM). DSC investigations demonstrated that the incorporation of a hard segment of MMA into the core portion and strongly polar monomer methyl acrylic acid (MAA) or cross-linker allyl methacrylate (ALMA) into the shell portion resulted in an improvement of the glass transition temperatures. SEM micrographs verified that the latex particles were always spherical with regular structure throughout the polymerization stage. Novel plastisols were developed based on the abovementioned core-shell polymers with dioctyl phthalate (DOP) or tricresyl phosphate (TCP) plasticizers, whose core portions were compatible with the employed plasticizer and whose shell portions were incompatible with the plasticizer. Evaluation of the viscosity as a function of the storage time revealed that the storage stability of the plastisols could be obtained through incorporation of the strongly polar monomer MAA or the cross-linker ALMA into the shell portions. The mechanical properties of the plastigels were improved by incorporating MMA into the core portion or by incorporating MAA or ALMA into the shell portion of the lattices. A balance between the mechanical properties of plastigels and the storage stability of plastisols should be considered during selection of the monomers both for the core and shell.     

Preparation and characterization of poly(acrylic acid)‐iron rich smectite superabsorbent composites

A novel poly(acrylic acid)‐iron rich smectite (IRS) superabsorbent composite was synthesized by graft copolymerization reaction of acrylic acid (AA) in the presence of N,N‐methylenebisacrylamide (MBA) as a crosslinker. IRS was used to strengthen the hydrogel products in the polymerization process. Water absorbencies for these superabsorbent composites in water and saline solutions were investigated. IRS caused a reduced equilibrium swelling as low as 8–26%. However, grafted IRS particles resulted in improved gel strength as high as 66% compared to the IRS‐free sample. IRS modified superabsorbent hydrogel composites exhibited higher thermal stability compared to the IRS‐free sample. The pH dependent reversible swelling behavior of hydrogels was also investigated. It is found that the swelling process is pH dependent and reversible for synthesized superabsorbent. Superabsorbent hydrogel composites were characterized by thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). FTIR spectroscopy was confirmed grafting of acrylic chains onto the surface of IRS particles. From the standpoint of these results, these strengthened and thermostabilized hydrogels may be considered as good candidates for a controlled release study and agricultural applications. Copyright © 2007 John Wiley & Sons, Ltd.