Collagen-g-poly(Sodium Acrylate-co-Acrylamide)/sodium montmorillonite superabsorbent nanocomposites: synthesis and swelling behavior

Nanocomposite superabsorbents were synthesized by graft copolymerization of mixture of acrylamide (AAm) and acrylic acid (AA) onto collagen using potassium persulfate (KPS) as a free radical initiator and methylenebisacrylamide (MBA) as a crosslinker. Nanoclay sodium montmorillonite (MMt) was introduced as filler into superabsorbent. The chemical structure of the Collagen-g-poly(Sodium Acrylate-co-Acrylamide)/MMt nanocomposite was characterized by means of FTIR spectroscopy, XRD patterns, and TGA thermal methods. Morphology of the sample was examined by scanning electron microscopy (SEM). The effects of reaction variables were systematically optimized to achieve a superabsorbent with swelling capacity as high as possible. Under the optimized conditions concluded, the maximum swelling capacity in distilled water was 950 g/g. Dewatering of nanocomposite and clay-free superabsorbent revealed that inclusion of nanoclay into superabsorbents can improve water retention of superabsorbent under heating. The swelling ratio in various salt solution and kinetic of dewatering was also determined and additionally, the swelling of nanocomposite superabsorbent was measured in solution with pH ranged 1–13. The synthesized nanocomposite exhibited a pH-responsive characteristic.     

Swelling study of superabsorbent PAA‐co‐PAM/clay nanohydrogel

A series of superabsorbent composites were prepared from acrylic acid (AA), acrylamide (AM), and Cloisite® 30B by aqueous solution polymerization technique using ammonium peroxodisulfate (APS) as initiator. The interaction of the organically modified nanoclay with PAA‐co‐PAM copolymer was verified by FTIR, whereas the morphology of the composite was studied by Scanning Electron Microscopy (SEM). The water absorbency in deionized water and saline water of the synthesized nanohydrogels was measured by calculating their percentage swelling ratio. The effects of copolymerization, monomer ratio, clay content, and temperature on the water absorbency were studied. The results indicated a considerable increase in swelling ratio by proper monomer proportion and incorporation of optimum clay percentage into the copolymer matrix. It was found that the nanohydrogel acquired highest water absorbency with 2% clay loading. The reswelling ability and water retention capacity of the PAA‐co‐PAM hydrogel and PAA‐co‐PAM/clay nanohydrogel were also measured. The water absorbency was found to increase after each reswelling for which it may be useful as recyclable superabsorbent material. The results of water retention capacity of the nanohydrogel were also encouraging and find application in agriculture, especially in drought‐prone areas. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis,characterization, and swelling behavior of alginate‐g‐poly(sodium acrylate)/kaolin superabsorbent hydrogel composites

A novel superabsorbent composite based on sodium alginate and the inorganic clay kaolin was synthesized via the graft copolymerization of acrylic acid (AA) in an aqueous medium with methylene bisacrylamide (MBA) as a crosslinking agent and ammonium persulfate (APS) as an initiator. The effects of reaction variables, such as the MBA, AA, and APS concentrations and the alginate/kaolin weight ratio, on the water absorbency of the composite were systematically optimized. Evidence of grafting and kaolin interactions was obtained by a comparison of the Fourier transform infrared spectra of the initial substrates with that of the superabsorbent composite, and the hydrogel structure was confirmed with scanning electron microscopy. The results indicated that with an increasing alginate/kaolin weight ratio, the swelling capacity and gel content increased. The effects of various salt media were also studied, along with the swelling kinetics. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Semi‐IPN carrageenan‐based nanocomposite hydrogels: Synthesis and swelling behavior

Inclusion of nano‐clays into hydrogels is an efficient approach to produce nanocomposite hydrogels. The introduction of nano‐clay into hydrogels causes an increase in water absorbency. In the present work, Nanocomposite hydrogels based on kappa‐carrageenan were synthesized using sodium montmorillonite as nano‐clay. Acrylamide and methylenebisacrylamide were used as monomer and crosslinker, respectively. The structure of nanocomposite hydrogels was investigated by XRD and SEM techniques. Swelling behavior of nanocomposite hydrogels was studied by varying clay and carrageenan contents as well as methylenebisacrylamide concentration. An optimum swelling capacity was achieved at 12% of sodium montmorilonite. The swollen nanocomposite hydrogels were used to study water retention capacity (WRC) under heating. The results revealed an increase in WRC due to inclusion of sodium montmorilonite clay. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A new composite sorbent for water and dye uptake: Highly swollen acrylamide/2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid/clay hydrogels crosslinked by 1,4‐butanediol dimethacrylate

A novel type of highly swollen hydrogels based on acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) crosslinked by 1,4‐butanediol dimethacrylate (BDMA) was prepared by free radical solution polymerization in aqueous media. Water uptake and dye sorption properties of polyelectrolyte AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were investigated as a function of composition to find materials with swelling and sorption properties. FTIR analyses were made. Swelling experiments were performed in water and dye solution at 25°C, gravimetrically. Highly swollen AAm/AMPS and AAm/AMPS/Bent hydrogels were used in experiments on sorption of water‐soluble monovalent cationic dye such as Lauths violet “LV, (Thionin).” Swelling of AAm/AMPS hydrogels was increased up to 1,920–9,222% in water and 867–4,644% in LV solutions, while AAm hydrogels swelled 905% in water and swelling of AAm/AMPS/Bent hydrogels was increased up to 2,756–10,422% in water and 1,200–3,332% in LV solutions, while AAm/Bent hydrogels swelled 849% in water. Some swelling kinetic and diffusional parameters were found. Water and LV diffusion into hydrogels was found to be non‐Fickian in character. For sorption of cationic dye, LV into AAm/AMPS and AAm/AMPS/Bent hydrogel was studied by batch sorption technique at 25°C. The amount of the dye sorbed per unit mass removal effiency and partition coefficient of the hydrogels was investigated. The influence of AMPS content in the hydrogels to sorption was examined. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Carrageenan‐g‐poly(acrylamide)/poly(vinylsulfonic acid,sodium salt) as a novel semi‐IPN hydrogel: Synthesis,characterization, and swelling behavior

A semi‐interpenetrating polymer network (semi‐IPN) hydrogel based on kappa‐carrageenan (κC) and poly (vinylsulfonic acid, sodium salt) (PVSA) was prepared by graft copolymerization of acrylamide (AAm) using methylenebisacrylamide (MBA) as a crosslinking agent and ammonium persulfate (APS) as an initiator. FTIR spectroscopy was used for confirming the structure of the final product. It was found that the chemical composition of the Semi‐IPN hydrogel is equal to the initial homopolymers and monomer feed compositions. The swelling capacity of the hydrogel was shown to be affected by the MBA, APS, and AAm concentration as well as κC/PVSA weight ratio. The swelling behavior of the hydrogel was also investigated in various pHs and salt solutions. Since the highly swelling biopolymer‐based hydrogel exhibits low salt‐sensitivity, it may be referred to as an anti‐salt superabsorbent hydrogel. The swelling kinetics of the superabsorbent hydrogels was studied as well. POLYM. ENG. SCI., 47:1388–1395, 2007. © 2007 Society of Plastics Engineers     

Effect of sodium montmorillonite nanoclay on the water absorbency and cationic dye removal of carrageenan-based nanocomposite superabsorbents

Nanocomposite superabsorbents were synthesized by simultaneously solution copolymerization of acrylamide (AAm) and sodium acrylate (Na-AA) in the presence of carrageenan biopolymer and sodium montmorillonite (Na-MMt) nanoclay. Potassium persulfate (KPS) and methylenebisacrylamide (MBA) were used as initiator and crosslinker, respectively. The structure and morphology of the nanocomposites were investigated using XRD, FTIR, scanning electron microscopy (SEM), and TEM techniques. The influence of nanoclay and carrageenan contents as well as monomer weight ratios on the degree of swelling of nanocomposites was studied. The optimum water absorbency was obtained at 10 wt% of clay, 10 wt% of carrageenan, and 1:1 of monomers weight ratio. The obtained nanocomposites were examined to remove of crystal violet (CV) cationic dye from water. The effect of carrageenan and clay content on the speed of dye adsorption revealed that while the rate of dye adsorption is enhanced by increasing the clay content up to 14 wt% of clay, it was decreased as the carrageenan increased in nanocomposite composition. The results showed that the pseudo-second-order adsorption kinetic was predominated for the adsorption of CV onto nanocomposites. The experimental equilibrated adsorption capacity of nanocomposites was analyzed using Freundlich and Langmuir isotherm models. The results corroborated that the experimental data fit the Freundlich isotherm the best.     

Swelling properties of CMC‐g‐poly (AAm‐co‐AMPS) superabsorbent hydrogel

A series of biopolymer‐based superabsorbent hydrogels based on carboxymethyl cellulose has been prepared by free‐radical graft copolymerization of acrylamide and 2‐acrylamido‐2‐methylpropan sulfonic acid (AMPS) in aqueous solution using methylenebisacrylamide as a crosslinking agent and ammonium persulfate as an initiator. The effect of variables on the swelling capacity such as: acrylamide/AMPS weight ratio, reaction temperature, and concentration of the initiator and crosslinker were systematically optimized. The results indicated that with increasing the amount of AMPS, the swelling capacity is increased. FT‐IR spectroscopy and scanning electron microscope analysis were used to confirm the hydrogel structure. Swelling measurements of the synthesized hydrogels in different salt solutions indicated considerable swelling capacity. The absorbency under load of the superabsorbent hydrogels was determined by using an absorbency under load tester at various applied pressures. A preliminary swelling and deswelling behaviors of the hydrogels were also studied. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Behaviors of polyelectrolyte AAm/AMPS/bentonite composite hydrogels in uptake of uranyl ions from aqueous solutions

Uranyl ion (UO₂²⁺) sorption properties of polyelectrolyte composite hydrogels made by the polymerization of acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) were investigated as a function of composition to find materials with swelling and uranyl ion sorption properties. Highly swollen AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with AMPS as co‐monomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of AMPS content in hydrogels was examined. Uranyl ion adsorption from aqueous solutions was studied by batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of AMPS on the uranyl ion adsorption were examined. Finally, adsorption capacity (the amount of sorbed uranyl ion per gram of dry hydrogel) (q) was calculated to be 0.67 × 10⁻³–2.11 × 10⁻³ mol uranyl ion per gram for the hydrogels. Removal effiency of uranyl ions (RE%) was changed range 9.05–29.92%. The values of partition ratio (K_d) of uranyl ions was calculated to be 0.10–0.43 for AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

壳聚糖接枝PAAm半互穿网络凝胶的性能

以过硫酸钾(KPS)为自由基引发剂,在壳聚糖(CS)上接枝共聚了聚丙烯酰胺(PAAm).以亚甲基双丙烯酰胺(MBA)或甲醛为交联剂,并研究了试验因素,如交联剂浓度和单体比率对水凝胶溶胀能力的影响.试验表明水凝胶具有离子强度敏感性、pH敏感性和温度敏感性.这种可随外界因素响应及"开关"的性质,使此类智能水凝胶有望成为生物制品载体,例如药物载体.     

微波辐射APT–g-PAMPS高吸水性树脂的制备及性能

以凹凸棒黏土(APT)和2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为原料,过硫酸钾(KPS)为引发剂,N,N'-亚甲基双丙烯酰胺(NMBA)为交联剂,采用微波辐射法接枝共聚合成了APT-g-PAMPS耐盐性复合高吸水性树脂,用FTIR和XRD对复合吸水性树脂的结构进行了表征。考察了微波功率和时间及APT用量对树脂吸水倍率的影响,测定了不同APT用量高吸水性树脂的吸水速率、保水性能及反复吸水性能。FTIR和XRD结果显示,APT和有机单体之间发生了接枝共聚反应,其反应仅在APT的表面进行,单体并没有插入到APT的层间。结果表明,微波功率为195 W,辐射时间为2.5 min,w(APT)=5%时,树脂在去离子水和生理盐水中的吸水倍率分别为987g/g和102 g/g。该复合高吸水性树脂具有较快的吸水速率、较强的保水性能和较好的反复吸水性能。在体系中引入适量APT能够显著提高复合吸水树脂的吸水能力和耐盐性能,同时能明显加快树脂的吸水速率和提高树脂的保水性能。     

An amphoteric hydrogel: Synthesis and application as an internal curing agent of concrete

A new crosslinked amphoteric hydrogel (PAC) was synthesized and evaluated as an internal curing agent of concrete. PAC was prepared from acrylamide (AM) and 4‐(2‐((carboxylatomethyl)dimethylammonio)ethoxy)?4‐oxobut‐2‐enoate (CMD) through free‐radical polymerization by using ammonium persulfate (APS) as an initiator and methylene‐bisacrylamide (MBA) as a crosslinker. The structure of the prepared polymer was verified by the IR spectra. The effects of the polymerization variables on the swelling capacity of PAC were investigated. The water absorbency of PAC was found to increase with increasing CMD/AM ratio, reach a maximum value, and decrease afterword. Increase of either APS or MBA content decreased the water absorbency. The highest water absorbency of PAC hydrogel (P7) achieved in deionized water, 0.1M NaCl solutions and 0.1M CaCl₂ solutions, was 306 g/g, 32 g/g, and 22 g/g, respectively. Compared with a commercial acrylate‐based hydrogel 283HA, P7 was less sensitive to the existence of Ca²⁺ ions in cement pore solutions, and more effective in reducing the cracking tendency of cement pastes. Finally, mortars incorporated with proper amounts of P7 showed smaller drying shrinkage and higher compressive strength than that without hydrogel present. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42175.     

Synthesis and properties of biodegradable hydrogels of κ-carrageenan grafted acrylic acid-co-2-acrylamido-2-methylpropanesulfonic acid as candidates for drug delivery systems

Novel types of highly swelling hydrogels were prepared by grafting crosslinked polyacrylic acid-co-poly-2-acrylamido-2-methylpropanesulfonic acid (PAA-co-PAMPS) chains onto κ-carrageenan through a free radical polymerization method. Here, we propose a mechanism for κ-carrageenan-g-PAA-co-PAMPS formation and confirm the hydrogel structure using FTIR spectroscopy. The effect of grafting variables (i.e. concentration of methylenebisacrylamide (MBA), acrylic acid/-2-acrylamido-2-methylpropanesulfonic acid (AA/AMPS) weight ratio, ammonium persulfate (APS), κ-carrageenan, neutralization percent and reaction temperature) were systematically optimized to achieve a hydrogel with a maximum swelling capacity. The maximum water absorbency of the optimized final product was 1238 g/g, while poly-2-acrylamido-2-methylpropanesulfonic acid-g-κ-carrageenan and polyacrylic acid-g-κ-carrageenan hydrogels swelled to a range of 135–800 g/g. The swelling of superabsorbent hydrogels was measured in various solutions with pH values ranging from 1 to 13. In addition, the pH reversibility, on–off switching behavior and swelling kinetics in distilled water were preliminarily investigated.     

SYNTHESIS AND SWELLING BEHAVIOR OF SUPERABSORBENT POLYMERIC MATERIALS

A series of novel crosslinked copolymers based on the monomers acrylamide (AM), calcium acrylate (CA), and sodium methacrylate (SMA) were prepared by aqueous solution polymerization using ammonium persulfate (APS) as initiator and N, N-methylene-bis-acrylamide (MBA) as crosslinking agent. The synthetic variables monomer concentration, crosslinker concentration, initiator concentration were also studied. The experimental results of SAPs show good absorbency in both water and NaCl solutions. The copolymers were characterized by IR spectroscopy. The water retention of SAPs was studied in an oven at 60 and 100°C.     

Chitosan‐modified nanoclay–poly(AMPS) nanocomposite hydrogels with improved gel strength

BACKGROUND: Making (nano)composite structures is one of the efficient approaches for strengthening hydrogels extended in recent years. The present paper deals with the synthesis and properties of novel nanocomposite hydrogels based on 2‐acrylamido‐2‐methylpropane‐1‐sulfonic acid (AMPS). Initially, a bio‐modified clay, chitosan‐intercalated montmorillonite (chitoMMT), was prepared. Then, this was incorporated into the polymerization of AMPS in the presence of a macro‐crosslinker, i.e. poly(ethylene glycol) dimethacrylate, to yield super‐swelling nanocomposite hydrogels. The swelling capacity as well as some structural, rheological and thermomechanical properties of the hydrogels were studied and compared with those of the clay‐free counterpart. RESULTS: ChitoMMT exhibited no toxicity, which was confirmed using cell‐culture testing. A chitoMMT content of ca 6% was found to be the most favourable content of the bio‐modified clay for achieving a product with improved properties (i.e. the highest gel content, the highest gel strength and optimal thermal stability). Based on a dynamic mechanical thermal analysis study, an increased glass transition temperature (98.2 °C) and improved rubbery modulus (up to 238% higher than that of the clay‐free counterpart) were recorded. Thermogravimetric analysis verified that the thermal stability of nanocomposite samples was higher than that of clay‐free samples. CONCLUSION: Owing to the non‐toxicity of the incorporated chitoMMT, the strengthened hydrogels may be considered as potential candidates for bio‐applications. Copyright © 2009 Society of Chemical Industry     

Synthesis and water absorbency of crosslinked superabsorbent polymers

A series of novel copolymer superabsorbents based on monomer acrylamide (AM), potassium methacrylate (KMA), and 2‐hydroxyethyl methacrylate (HEMA) were prepared by copolymerization using ammonium persulfate (APS) as an initiator and N,N‐methylenebisacrylamide (MBA) as a crosslinking agent. The synthetic variables (the monomer concentration, crosslinker concentration, and initiator concentration) were also studied. The experimental results of superabsorbent polymers (SAPs) show a better absorbency in both water and NaCl solutions. The copolymers were characterized by IR spectroscopy. The water retention in the soil was enhanced using the above superabsorbents. The use of SAPs for the growth of groundnut plants was also investigated. SAPs can be considered for water‐managing materials for agriculture and horticulture purposes in desert and drought‐prone areas. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1795–1801, 2002     

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.     

Effects of modified vermiculite on the synthesis and swelling behaviors of hydroxyethyl cellulose-<Emphasis Type="Italic">g</Emphasis>-poly(acrylic acid)/vermiculite superabsorbent nanocomposites

A series of hydroxyethyl cellulose-g-poly(acrylic acid)/vermiculite (HEC-g-PAA/VMT) superabsorbent nanocomposites were prepared by radical solution polymerization among hydroxyethyl cellulose (HEC), partially neutralized acrylic acid (AA), raw vermiculite (RVMT), acidified vermiculite (AVMT) and organo-vermiculite (OVMT) in the presence of initiator ammonium persulfate (APS) and crosslinker N,N’-methylenebisacrylamide (MBA). FTIR results revealed that AA was grafted onto HEC backbone and VMT participated in polymerization. VMT was exfoliated during polymerization reaction and a nanocomposite structure was formed as shown by XRD and TEM analysis. Effects of VMT content, concentration of HCl solution and organification degree of OVMT on water absorbency were investigated and the swelling kinetics of the developed nanocomposites was also evaluated. Results showed that incorporation of VMT greatly enhanced the water absorbency, and the modified VMT by acidification and organification can improve the water absorbency more remarkably than raw one. OVMT can improve the swelling capabilities and swelling rate to the highest degree in contrast to RVMT and AVMT.     

Formulation design,optimization, characterization and swelling behaviour of a cationic superabsorbent based on a copolymer of [3‐(methacryloylamino)propyl]trimethylammonium chloride and acrylamide

A series of crosslinked copolymers with cationic nature have been prepared based on acrylamide (AAm) and [3‐(methacryloylamino)propyl]trimethyl ammonium chloride (MAPTAC) using N,N′ methylene‐bis‐acrylamide (MBA) as crosslinking agent. Taguchi's method has been employed for the purpose of formulation design and optimization as well as investigating the effects of various compositional parameters, such as total monomer concentration, cationic monomer and crosslinking agent concentration. The swelling behaviour of the synthesized gels in electrolyte solutions composed of ions with different valency has been studied and compared with an anionic‐based superabsorbent. The swelling capacity and absorbency were found to be enhanced with increase of the MAPTAC moieties of the copolymer chains, and therefore increase of their cationic character. All the cationic hydrogels prepared had greater swelling capacity, with less change in their swelling behaviour, when immersed into aqueous solutions containing multivalent cations. The anionic‐based hydrogels collapsed in similar ionic solutions with moderate‐to‐high ionic strength and did not show any tendency to re‐swell. The complex modulus (G*) of the crosslinked copolymers in the equilibrium swollen state was measured by rheomechanical spectroscopy and was correlated with the chemical composition of the network. Thermogravimetric analysis of the dry cationic superabsorbent showed more bound water but similar thermal behaviour to crosslinked polyacrylamide Copyright © 2003 Society of Chemical Industry     

Synthesis and investigation of swelling behavior of new agar based superabsorbent hydrogel as a candidate for agrochemical delivery

In this investigation a new type of superabsorbent hydrogel based on agar was prepared, and the effect of the feed ratio of some components (acrylic acid, MBA, APS and agar) on the swelling capacity of the hydrogel was systematically studied. Maximum water absorbency of the optimized final product was found to be 1,100 g/g in distilled water. The structure of the hydrogel was characterized by FT-IR method and morphology of the samples was examined by scanning electron microscopy (SEM). Swelling properties of optimized hydrogel sample in different swelling mediums were investigated. The optimum hydrogel were also loaded with potassium nitrate and its potential for controlled release of potassium was investigated by measuring conductivity in various conditions.