Synthesis,characterization, and swelling behaviors of chitosan‐g‐poly(acrylic acid)/poly(vinyl alcohol) semi‐IPN superabsorbent hydrogels

A series of granulated semi‐interpenetrating polymer network (semi‐IPN) superabsorbent hydrogels composed of chitosan‐g‐poly(acrylic acid) (CTS‐g‐PAA) and poly(vinyl alcohol) (PVA) were prepared by solution polymerization using ammonium persulfate (APS) as an initiator and N,N′‐methylenebisacrylamide (MBA) as a crosslinker. The effects of reaction conditions such as the concentration of MBA, the weight ratio of AA to CTS, and the content of PVA on water absorbency were investigated. Infrared (IR) spectra and differential scanning calorimetry (DSC) analyses confirmed that AA had been grafted onto CTS backbone, and PVA semi‐interpenetrating into CTS‐g‐PAA networks. SEM analyses indicated that CTS‐g‐PAA/PVA has improved porous surface and PVA was uniformly dispersed in CTS‐g‐PAA network. The semi‐IPN hydrogel containing 10 wt% PVA shows the highest water absorbency of 353 and 53 g g^?1 in distilled water and 0.9 wt% NaCl solution, respectively. Swelling behaviors revealed that the introduction of PVA could improve the swelling rate and enhance the pH stability of the superabsorbent hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

Study on superabsorbent composite—VII. Effects of organification of attapulgite on swelling behaviors of poly(acrylic acid‐co‐acrylamide)/sodium humate/organo‐attapulgite composite

A novel multifunctional superabsorbent composite from acrylic acid (AA), acrylamide (AM), sodium humate (SH) and organo‐attapulgite (organo‐APT), PAA‐AM/SH/organo‐APT, was synthesized by aqueous solution 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 FT‐IR. The effects of organo‐APT (HDTMA‐APT) content in the superabsorbent composite and organification degree of it on water absorbency of the superabsorbent composite were studied. The effects of incorporated HDTMA‐APT on swelling rate, water absorbency in various saline solutions and reswelling capability of the superabsorbent composite were also investigated. The results indicate that organification of APT had a remarkable influence on swelling behaviors of the superabsorbent composites. Comparing with the composite doped with APT, water absorbency for the composite incorporated with 10 wt% HDTMA‐APT was enhanced from 996 to 1282 g g^?1 in distilled water and from 63 to 68 g g^?1 in 0.9 wt% NaCl solution, respectively. The superabsorbent composite acquired its highest water absorbency when the organification degree of APT was 8.02 wt%. Water absorbency of the composites in various saline solutions decreased with the increasing concentration, especially for the multivalent cations. In addition, swelling rate and reswelling capability of the superabsorbent composite were also improved by introducing HDTMA‐APT into the composite compared with that of incorporating APT. Copyright © 2006 John Wiley & Sons, Ltd.     

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.     

Syntheses and properties of superabsorbent composites based on natural guar gum and attapulgite

Utilization of raw materials available in nature and their application to derive other useful products without any adverse impact on the environment has long been a desired goal. In this work, guar gum (GG) and attapulgite (APT) clay were used as raw materials for preparing guar gum‐g‐poly(acrylic acid)/attapulgite (GG‐g‐PAA/APT) superabsorbent composites through the graft copolymerization of GG, partially neutralized acrylic acid (AA) and APT in aqueous solution. The effects of reaction conditions such as concentrations of the initiator and crosslinker, APT content, etc. on water absorbency were investigated. The composite prepared under optimal conditions gave the best absorption of 529 g/g sample in distilled water and 61 g/g sample in 0.9 wt% NaCl solution. Swelling behaviors revealed that the superabsorbent composites retained a high water absorbency over a wide pH range of 4–11, and the developed composites also exhibited improved reswelling and water‐retention capabilities. The superabsorbent composites can be utilized as eco‐friendly water‐manageable materials for agricultural and horticultural applications. Copyright © 2008 John Wiley & Sons, Ltd.     

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.     

Synthesis of bio‐based internal and external cross‐linkers based on tannic acid for preparation of antibacterial superabsorbents

Recent researches focus on the synthesis of new cross‐linkers from natural resources. In the current work, functionalized tannic acid was employed as a replacement of petroleum‐based cross‐linkers because of its outstanding biochemical properties. Alkene‐ and epoxy‐functionalized tannic acids were synthesized as internal and external cross‐linkers, respectively. Cross‐linker structures were characterized with Ft‐IR and ¹HNMR analysis. Different amounts, as well as different numbers of alkene functional group, were incorporated during the superabsorbent synthesis. Moreover, the internal cross‐linked superabsorbent was surface cross‐linked with different amounts of epoxy‐functionalized tannic acid and increased the absorbency under load about 10 g g^?1. Free absorption properties in water and saline solution, absorbency under load, and rheological properties of superabsorbents were investigated. In addition, the antibacterial activity of the internal and external cross‐linked superabsorbent was studied against Escherichia coli and Staphylococcus aureus bacteria via different methods and compared with that of conventional superabsorbent.     

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.     

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.     

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.     

Synthesis and Properties of a Superabsorbent Polymer Prepared by Copolymerization of Sodium Acrylate with Sodium 1‐(Acryloyloxy)propan‐2‐yl Phosphate

A novel monomer, 1‐(acryloyloxy)propan‐2‐yl phosphoryl dichloride, was synthesized and characterized in this work. Thereafter, the monomer was neutralized with sodium hydroxide and copolymerized with sodium acrylate to obtain a superabsorbent polymer. The superabsorbent polymer was then modified to improve its swelling properties (i.e., the water absorbency under load, the hydrogel strength, the resilience and the dispersion). Both single factor and orthogonal design experiments were adopted to obtain optimal conditions. The superabsorbent polymer prepared under the optimal conditions showed improved water absorbency in physiological saline [17 g · g^?1 under load (P = 2 × 10³ Pa) and 65 g · g^?1 at atmospheric pressure] and other swelling properties, such as hydrogel strength, resilience and dispersion, also improved.

     

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.     

Synthesis and polymerization of 5‐(methacrylamido)tetrazole,a water‐soluble acidic monomer

The reaction of methacryloyl chloride with 5‐aminotetrazole gave the polymerizable methacrylamide derivative 5‐(methacrylamido)tetrazole ( 4 ) in one step. The monomer had an acidic tetrazole group with a pK_a value of 4.50 ± 0.01 in water methanol (2:1). Radical polymerization proceeded smoothly in dimethyl formamide or, after the conversion of monomer 4 into sodium salt 4‐Na , even in water. A superabsorbent polymer gel was obtained by the copolymerization of 4‐Na and 0.08 mol % N,N′‐methylenebisacrylamide. Its water absorbency was about 200 g of water/g of polymer, although the extractable sol content of the gel turned out to be high. The consumption of 4‐Na and acrylamide (as a model compound for the crosslinker) during a radical polymerization at 57 °C in D₂O was followed by ¹H NMR spectroscopy. Fitting the changes in the monomer concentration to the integrated form of the copolymerization equation gave the reactivity ratios r _4‐Na = 1.10 ± 0.05 and r_acrylamide = 0.45 ± 0.02, which did not differ much from those of an ideal copolymerization. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4333–4343, 2002     

Highly absorbing superabsorbent polymer

Acrylic acid (AA)–acrylamide (AM) based superabsorbent polymers (SAP) were synthesized by inverse suspension polymerization using potassium‐persulfate as the initiator, N,N′‐methylene bisacrylamide (BIS) as a crosslinker, sorbitan monostearate (Span 60) as the dispersant, cyclohexane as the solvent, and bis(methacryloylamino)‐azobenzene as the hydrophobic surface crosslinker. The influence of the polymerization parameters on the properties of the SAPs, water absorption (Q), morphology of the SAPs, swelling kinetics, salt resistance, and the reversibility of water absorption were investigated. The prepared SAPs have excellent water absorption, rapid water uptake, and good resistance to NaCl solutions. Furthermore, they show better reversible water uptake than the previously reported SAPs. The average water absorbency is 2800 g/g and 181 g/g of liquid absorbance in 0.025M NaCl solution. The initial water uptake rate is 1357 g/g/min and the reversibility of water absorption is 200 g/g in the repeated fourth cycle. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1357–1364, 2008     

Modification of polysulfones by click chemistry: Amphiphilic graft copolymers and their protein adsorption and cell adhesion properties

Well‐defined amphiphilic graft copolymer with hydrophobic polysulfone (PSU) backbone and hydrophilic poly(acrylic acid) (PAA) side chains were synthesized and characterized. For this purpose, commercially available PSU was converted to azido‐functionalized polymer (PSU‐N₃) by successive chloromethylation and azidation processes. Independently, poly(tert‐butyl acrylate) (PtBA) with an alkyne‐end‐group is obtained by using suitable initiator in atom transfer radical polymerization (ATRP). Then, this polymer was successfully grafted onto PSU‐N₃ by click chemistry to yield polysulfone‐graft‐poly(tert‐butyl acrylate), (PSU‐g‐PtBA). Finally, amphiphilic polysulfone‐graft‐poly(acrylic acid), (PSU‐g‐PAA), membranes were obtained by hydrolyzing precursor the PSU‐g‐PtBA membranes in trifluoroacetic acid. The final polymer and intermediates at various stages were characterized by ¹H NMR, FTIR, GPC, and SEM analyses. Protein adsorption and eukaryotic and prokaryotic cell adhesion on PSU‐g‐PAA were studied and compared to those of PSU‐g‐PtBA and unmodified PSU. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Study on superabsorbent of maleic anhydride/acrylamide semi‐interpenetrated with poly(vinyl alcohol)

A series of superabsorbents of maleic anhydride (MAH)/acrylamide (AM) interpenetrated with poly(vinyl alcohol) (PVA) were prepared by aqueous polymerization, using N,N‐methylenebiacrylamide (NNMBA) as a crosslinker and ammonium persulfate (APS) as an initiator. The samples were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and scanning electron microscope (SEM). The effects of reaction variables on the water absorbency of the superabsorbents in distilled water and in 0.9 wt% NaCl solution were investigated. In addition, the effect of the PVA content on the swelling rate and sensitivity to saline of the superabsorbents were also investigated. The results showed that the absorbency, both in 0.9 wt% NaCl solution and in distilled water, first decreased and then increased with increasing PVA content. Moreover, the resultant superabsorbent had a higher absorption rate and it became less sensitive to saline by incorporating certain amount of PVA into the network of the hydrogel. Copyright © 2009 John Wiley & Sons, Ltd.     

Frontal polymerization synthesis and characterization of Konjac glucomannan‐graft‐acrylic acid polymers

Konjac glucomannan‐graft‐acrylic acid polymers, used as superabsorbent polymers (SAPs), were synthesized by frontal polymerization (FP). The features of front propagation including front velocity and maximum temperature (T_max) were influenced by the amount of glucomannan, initiator, and environment temperature. The graft copolymer was characterized by FTIR, DSC, and SEM. The amount of crosslinking agent mainly determined the crosslinking degree of SAPs that would affect the water absorbency and microstructure. Water absorbency of SAP was also investigated and most of them displayed high water absorption rate. The aforementioned results allow us to conclude that FP can be considered as a promising method to fabricate SAP for its excellent advantages. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3391–3398, 2009     

Synthesis and Characterization of Montmorillonite-Graft-Acrylic Acid Superabsorbent by Using Glow-Discharge Electrolysis Plasma

Crosslinking graft polymerization of poly acrylic/montmorillonite superabsorbent composite in aqueous solution was prepared by using glow-discharge electrolysis plasma, in which acrylic acid and acid-activated montmorillonite were used as starting materials, N,N-methylenebisacrylamide as a crosslinking agent. To optimize the synthetic conditions, seven important parameters of the graft-polymerization were examined in detail, such as the discharge voltage, discharge time, the neutralization of acrylic acid, post polymerization temperature, amounts of crosslinking agent, montmorillonite and acrylic acid used in this study. The structure, thermal stability and morphology of product were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis, scanning electron microscopy, respectively. The absorbency of poly acrylic/montmorillonite superabsorbent was examined to yield the following results: 1,834 g/g for distilled water, 116 g/g for 0.05 mol/L and 75 g/g for 0.15 mol/L sodium chloride solution. Such excellent character could be important to use in many fields, for example, in agricultural and horticultural applications.     

Synthesis and properties of starch‐graft‐polyacrylamide/clay superabsorbent composite

A novel starch‐graft‐polyacrylamide/clay superabsorbent composite is synthesized by graft copolymerization reaction of acrylamide, potato starch and clay mineral micropowder, followed by hydrolysis with sodium hydroxide. The water absorbency of the composite reaches 4 000 g H₂O/g. The influence of kind and amounts of clay and of the crosslinker in the composite on the absorbent properties is discussed in this paper.     

3种丙烯酸系列高吸水树脂的吸水性能

采用反相悬浮聚合法合成了3种聚丙烯酸系列吸水树脂：聚丙烯酸钠(PAA)、丙烯酸-丙烯酰胺共聚物(P(AA/AM))和丙烯酸-马来酸酐共聚物(P(AA/MA))。 对3种树脂的吸水性、保水性、耐候性和耐电解质等性能进行测试比较。 结果表明,P(AA/MA)的吸水性能最优异,10 min内吸蒸馏水量可达3578.4 g/g;在一定的温度或压力范围内,3种树脂均有良好的保水性能,在不同温度下储存均能保持各自的吸水性;P(AA/MA)的耐电解质性能较为突出,吸生理盐水量可达107.2 g/g,其综合性能最好。     

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.%.