Hydrolyzed collagen‐based hydrogel with salt and pH‐responsiveness properties

A novel hydrolyzed collagen‐based hydrogel has been prepared by grafting the binary mixture of acrylamide and 2‐acrylamido‐2‐methylpropanesulfonic acid onto the collagen backbone in the presence of a crosslinking agent. Its physicochemical properties in aqueous solution were studied. The effect of reaction variables on both gel content and swelling capacity was investigated to achieve a hydrogel with improved absorbency and gel content. The absorbency under load of optimized hydrogel was also investigated by using an absorbency under load tester at various applied pressures. The swelling ratio in various salt solutions was also determined and additionally, the swelling of hydrogels was measured in solutions with pH ranged 1–13. The synthesized hydrogel exhibited a pH‐responsiveness character so that a swelling‐collapsing pulsatile behavior was recorded at pH 2 and 8. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

New smart carrageenan‐based superabsorbent hydrogel hybrid: Investigation of swelling rate and environmental responsiveness

Synthesis of novel natural‐based superabsorbents with improved properties is of prime importance in many applications. In this article we report an efficient synthesis of new polysaccharide‐based superabsorbent hybrid composing carrageenan, acrylic acid, sodium acrylate, and 2‐hydroxyethyl acrylate through homogenous solution polymerization process. Infrared spectroscopy and thermogravimetric analysis (TGA) were carried out to confirm the chemical structure of the hydrogel. Moreover, morphology of the samples was examined by scanning electron microscopy (SEM). To deeper studies on the structure‐property relation in SAP hydrogels, three hydrogels with different acrylic acid/2‐hydroxyethyl acrylate (AA/HEA) weight ratios were synthesized and swelling capacity in various media was assessed. The hydrogel hybrid was also tested to be swollen and deswollen alternatively in 0.01 and 0.1 M sodium chloride solution. Moreover, the swelling‐deswelling capability of the hydrogel in alternatively changed methanol‐water mixtures was studied. Additionally, the swelling kinetics of the synthesized hydrogels were examined. The absorbency under load (AUL) of hydrogel was also investigated by using an AUL tester at various applied pressures. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

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     

Preparation and Swelling Behavior of Fast‐Swelling Superabsorbent Hydrogels Based On Starch‐g‐Poly(acrylic acid‐co‐sodium acrylate)

Summary: A novel fast‐swelling porous superabsorbent hydrogel was prepared by grafting acrylic acid onto corn starch through free‐radical polymerization in aqueous solution using N,N′‐methylenebisacrylamide as a crosslinker, ammonium persulfate as an initiator, sodium dodecyl sulfate and p‐octyl poly(ethylene glycol)phenyl ether as pore‐forming agents. The graft polymerization and surface morphology of the porous superabsorbents were characterized by FTIR and SEM. The results indicate that the porous superabsorbents were endowed with higher equilibrium water absorbency and faster swelling rate (they needed only 10 min to reach 90% of their equilibrium water absorbency) compared with the nonporous superabsorbents. The dewatering method employed had a significant influence on the swelling behavior of the superabsorbents and dewatering agents were useful to preserve the pores formed during the polymerization process.

The equilibrium water absorbency in distilled water, for the porous and non‐porous starch‐g‐poly(acrylic acid‐co‐sodium acrylate) superabsorbent hydrogels dried through different procedures.     

Preparation of acrylated agarose‐based hydrogels and investigation of their application as fertilizing systems

In this study, we attempt to synthesize novel acrylated agarose (ACAG)‐based hydrogels with three different crosslinking densities. Acrylate groups were inserted onto agarose (AG) backbone through homogeneous reaction of acrylic monomers with AG backbone. Hydrogels were synthesized through radical copolymerization of a mixture of acrylic acid and 2‐hydroxyethyl acrylate with ACAG in aqueous solution using ammonium persulfate as an initiator. Infrared spectroscopy (FTIR) was carried out to confirm the chemical structure of the hydrogel. Moreover, morphology of the samples was assessed by scanning electron microscopy. The equilibrium swelling capacities of synthesized hydrogels were evaluated in various conditions. The absorbency under load and dynamic swelling kinetics of the hydrogels were also studied. Finally, the hydrogels were loaded with potassium nitrate and their potential for controlled release of this salt was investigated by conductimetry. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Optimization of synthetic conditions of a novel collagen‐based superabsorbent hydrogel by Taguchi method and investigation of its metal ions adsorption

A novel biopolymer‐based superabsorbent hydrogel was synthesized through chemical crosslinking by graft copolymerization of partially neutralized acrylic acid onto the hydrolyzed collagen, in the presence of a crosslinking agent and a free radical initiator. The Taguchi method, a robust experimental design, was employed for the optimization of the synthesis reaction based on the swelling capacity of the hydrogels. This method was applied for the experiments and standard L₁₆ orthogonal array with three factors and four levels were chosen. The critical parameters that have been selected for this study are crosslinker (N,N′‐methylene bisacrylamide), initiator (potassium persulfate), and monomer (acrylic acid) concentration. From the analysis of variance of the test results, the most effective factor to control equilibrium swelling capacity was obtained and maximum water absorbency of the optimized final product was found to be 500 g/g. The surface morphology of the gel was examined using scanning electron microscopy. Furthermore, the sorption capacity of the hydrogel toward bivalent metal ions was evaluated. Therefore, the hydrogel may be considered as a candidate to develop as an efficient biopolymer‐based chelating hydrogel for water treatment. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4878–4885, 2006     

Synthesis and characterization of functionalized acrylic‐acrylamide‐based superabsorbent gels

We have synthesized series of superabsorbent polymers (SAPs) by solution free radical polymerization of acrylic acid (AA), acrylamide (AM) with different functional monomers (FM). Three functional monomers including zwitterionic monomer [3‐(methacryloylamino) propyl] dimethyl (3‐sulfopropyl) ammonium (MPDSA), cationic monomer (3‐acrylamidopropyl) trimethylammonium chloride (APTAC) and anionic monomer 2‐acrylamidoglycolic acid monohydrate (AGAM) were selected to provide different charged groups on the superabsorbents. The effect of reaction parameters, such as degree of neutralization, content of initiator and crosslinker on the swelling capacity were assessed. The water absorbency of the superabsorbent were characterized in the distilled water, 0.9 wt % NaCl solution and the mixed solution containing 60 mg L^?1 CaCl₂ and 30 mg L^?1 MgCl₂, respectively. In addition, the swelling rate and water retention capacity in the soil were also investigated. Finally, the mechanism of different absorbency induced by the variety kinds of functional monomers was studied by XPS and FTIR, and tentative interpretation was presented as well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and swelling properties of a pH‐ and temperature‐dual responsive hydrogel by inverse microemulsion polymerization

A novel pH‐ and temperature‐dual responsive hydrogel was synthesized by inverse microemulsion polymerization, using itonic acid (IA) as pH‐responsive monomer, N‐isopropylacrylamide (NPAM) as thermo‐responsive monomer and acrylamide (AM) as the nonionic hydrophilic monomer. Factors affecting water and salt absorption, as well as swellability of the dual responsive hydrogels, such as IA/NPAM mass ratio and crosslinker amount, were investigated. pH‐ and temperature‐sensitivity and dynamic viscoelasticity behaviors of the dual responsive hydrogels were also studied. The dual responsive responsive hydrogels showed suitable water and salt absorbency, remarkable pH‐, and temperature‐sensitivity, adjustable swellability and enhanced viscoelastic behaviors under high stress. Water absorbency and pH‐sensitivity increased while salt absorbency and temperature‐ sensitivity decreased with increasing IA/NIPAM mass ratio. Both water absorbency and salt absorbency increased first with crosslinker amount increased to 0.2 wt %, and then decreased with increasing crosslinker amount. Temperature‐induced shrinkage range of the dual responsive hydrogels was higher and broader than that of the conventional poly(N‐isopropylacrylamide) hydrogel. TEM indicated that the as‐synthesized hydrogel particles were regular and spherical‐like in shape and had the mean particle size of 49nm in the range of 30–78 nm. FTIR indicated the structure of the dual responsive hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42139.     

Synthesis of AA‐based superabsorbent interpenetrated with sodium PVA sulfate

An interpenetrating network of acrylic acid (AA)‐based superabsorbents and sodium PVA sulfate (SPS) were prepared by copolymerizing AA and N,N′‐methylene bisacrylamide as a crosslinking monomer in a solution of SPS with KPS, a radical initiator. The SPS was prepared through the sulfation of the hydroxyl groups of PVA with DMF‐SO₃ complex in DMSO. The AA‐based superabsorbent interpenetrated with SPS (SA‐IP‐SPS) showed superior properties such as higher water and saline absorbency, absorbency under load (AUL), and water retention value (WRV) compared with AA‐based superabsorbent due to the interpenetrated SPS. The maximum water and saline absorbency of SA‐IP‐SPS was 1753 and 125.6 g/g, respectively. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2525–2532, 2000     

Hydrogel composites based on linear low‐density polyethylene‐g‐poly (acrylic acid)/Kaolin or halloysite nanotubes

Two series of superabsorbent hydrogel composites were prepared using waste linear low‐density polyethylene, acrylic acid, and two types of clays including kaolin and halloysite nanotube (HNT) through emulsion polymerization. The effects of the clay content on Water absorbency were investigated to obtain a high swelling capacity. The prepared samples were characterized using FTIR, SEM, thermogravimetric analysis, XRD, solid‐state ¹³C Nuclear Magnetic Resonance spectroscopy, and ²⁹Si NMR. SEM characterization of the samples showed that the hydrogel composites have more pores and a higher swelling ratio than the clay‐free hydrogels. The hydrogel composite containing kaolin had higher water absorbency compared to the hydrogel composites with HNT. The swelling behavior of the hydrogel composite was investigated in various saline solutions. The hydrogel composite containing 5 wt % kaolin had the highest water absorbency (760 g/g in distilled water). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40101.     

Modified carrageenan. 4. Synthesis and swelling behavior of crosslinked κC‐g‐AMPS superabsorbent hydrogel with antisalt and pH‐responsiveness properties

To synthesize a novel biopolymer‐based superabsorbent hydrogel, 2‐acrylamido‐2‐methylpropanesulfonic acid (AMPS) was grafted onto kappa‐carrageenan (κC) backbones. The graft copolymerization reaction was carried out in a homogeneous medium and in the presence of ammonium persulfate (APS) as an initiator, N,N,N′,N′‐tetramethyl ethylenediamine (TMEDA) as an accelerator, and N,N′‐methylene bisacrylamide (MBA) as a crosslinker. A proposed mechanism for κC‐g‐AMPS formation was suggested and the hydrogel structure was confirmed using FTIR spectroscopy. The affecting variables on swelling capacity, i.e., the initiator, the crosslinker, and the monomer concentration, as well as reaction temperature, were systematically optimized. The swelling measurements of the hydrogels were conducted in aqueous solutions of LiCl, NaCl, KCl, MgCl₂, CaCl₂, SrCl₂, BaCl₂, and AlCl₃. Due to the high swelling capacity in salt solutions, the hydrogels may be referred to as antisalt superabsorbents. The swelling of superabsorbing hydrogels was measured in solutions with pH ranging 1 to 13. The κC‐g‐AMPS hydrogel exhibited a pH‐responsiveness character so that a swelling–deswelling pulsatile behavior was recorded at pH 2 and 8. The overall activation energy for the graft copolymerization reaction was found to be 14.6 kJ/mol. The swelling kinetics of the hydrogels was preliminarily investigated as well. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 255–263, 2005     

Synthesis and superswelling behavior of carboxymethylcellulose–poly(sodium acrylate‐co‐acrylamide) hydrogel

In this paper, attention is paid to synthesis and swelling behavior of a superabsorbent hydrogel based carboxymethylcellulose (CMC) and polyacrylonitrile (PAN). The physical mixture of CMC and PAN was hydrolyzed in NaOH solution to yield hydrogel, CMC–poly(NaAA‐co‐AAm). During alkaline hydrolysis, the nitrile groups of PAN were completely converted to a mixture of hydrophilic carboxamide and carboxylate groups followed by in situ crosslinking of the grafted PAN chains. A proposed mechanism for hydrogel formation was suggested and the structure of the product was established using FTIR spectroscopy. The reaction variables affecting the swelling capacity of the hydrogel were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. Swelling measurements of the synthesized hydrogels in various chloride salt solutions indicated a swelling‐loss with increase in the ionic strength of the salt solutions. The pH of the various solutions also affected the swelling of the superabsorbent. Furthermore, the present hydrogels showed a pH‐reversible property. Finally, the swelling kinetics of synthesized hydrogels with various absorbent particle sizes was briefly examined. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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 of poly(sodium acrylate‐co‐sodium 1‐(acryloyloxy) propan‐2‐yl phosphate) and comparative study on its swelling properties with poly(sodium acrylate) and poly(sodium acrylate‐co‐2‐hydroxypropyl acrylate)

A new superabsorbent copolymer, poly(sodium acrylate‐co‐sodium 1‐(acryloyloxy) propan‐2‐yl phosphate) [P(SA‐co‐SAPP)], was synthesized by a novel prepared monomer, 1‐(acryloyloxy) propan‐2‐yl phosphoryl dichloride. The swelling properties of the superabsorbent were investigated by comparison with poly(sodium acrylate) (PSA) and the copolymer of poly(sodium acrylate‐co‐2‐hydroxypropyl acrylate) [P(SA‐co‐HPA)]. The results showed that (1) the superabsorbent containing sodium 1‐(acryloyloxy) propan‐2‐yl phosphate had higher water absorbency at general testing conditions; (2) the swelling properties of P(SA‐co‐SAPP) and PSA were obviously influenced by pH of solutions, which were different from that of P(SA‐co‐HPA); (3) the swelling process and the saturated water absorbency of all superabsorbents were remarkably affected by cations, especially multivalent ones, while barely affected by anions. POLYM. ENG. SCI., 47:728–737, 2007. © 2007 Society of Plastics Engineers.     

Swelling behavior of poly(sodium acrylate)/kaoline superabsorbent composite

Using partly neutralized acrylic acid as monomer, kaoline ultrafine powder as filler and N,N′‐(dimethyl)acrylamide as crosslink agent, poly(sodium acrylate)/kaoline superabsorbent composite was synthesized by aqueous solution polymerization method. Using the superabsorbent composite as collagen, a hydrogel was prepared. The influence of the neutralization degree of superabsorbent collagen, the compositions, the concentration, and the pH value of exterior solution on the swelling behavior of the hydrogel was investigated. It was found that the swelling capability of the hydrogel depended on the groups on the collagen. The swelling capability of the hydrogel relied on the ionic intensity, molecular polarity, molecular volume, as well as the concentration of exterior solution. When the pH value of exterior solution was equal to seven, the hydrogel has a maximum swelling value of 800 times. POLYM. ENG. SCI. 46:324–328, 2006. © 2006 Society of Plastics Engineers     

Synthesis and swelling properties of protein‐poly(acrylic acid‐co‐acrylamide) superabsorbent composite

A novel superabsorbent polymer composite was synthesized by graft copolymerization of cottonseed protein and acrylic monomers in order to explore the new application of cottonseed protein in nonfood field. This composite was synthesized by solution based copolymerization, using partly neutralized acrylic acid, acrylamide and cottonseed protein as raw material, N,N‐methylene bisacrylamide as crosslinking agent, potassium persulphate and sodium sulfite as the initiators. The effects of the certain variables of the copolymerization on the water absorbency of the synthesized composite were measured. The chemical structure of the composite was characterized by means of Fourier transform infrared spectroscopy, differential scanning calorimetry and thermogravimetry analysis. The swelling properties of the composite were carried out under varying pH conditions. Further, the saline sensitivity, swelling kinetics and water retention ability of the composite was investigated. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

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.     

Synthesis and super-swelling behavior of a novel protein-based superabsorbent hydrogel

Summary In this work, we synthesize a novel protein-based superabsorbent hydrogel and study its swelling behavior. The crosslinking graft copolymerization of acrylic acid (AA) onto the hydrolyzed collagen as a protein backbone was carried out in a homogeneous medium. Potassium persulfate (KPS) as an initiator and N,N^′-methylene bisacrylamide (MBA) as a crosslinker were used. The product’s structure was established using FTIR spectroscopy. We were systematically optimized the certain variables of the graft copolymerization (i.e. the monomer, the initiator, and the crosslinker concentration) to achieve a hydrogel with maximum swelling capacity. Under this condition, maximum capacity of swelling in distilled water was found to be 920 g/g. Morphology of the optimized sample was examined by scanning electron microscopy (SEM). The swelling ratio in various salt solutions was also determined. Additionally, the swelling of superabsorbing hydrogels was measured in solutions with pH ranged from 1 to 13. The synthesized hydrogel exhibited a pH-responsiveness character so that a swelling-collapsing pulsatile behavior was recorded at pH 2 and 8.     

Hydrolyzed collagen‐grafted‐poly[(acrylic acid)‐co‐(methacrylic acid)] hydrogel for drug delivery

Hydrolyzed collagen‐grafted‐poly[(acrylic acid)‐co‐(methacrylic acid)] hydrogels were synthesized by solution polymerization and confirmed by infrared spectroscopy. From sequential univariate analysis, the optimal molar ratio of acrylic acid: methacrylic acid was 92:8 in the presence of N,N′‐methylenebisacrylamide, ammonium persulfate, and N,N,N′,N′‐tetramethylethylenediamine at 0.12, 0.015, and 0.2% mol of the monomers, respectively. The water absorbency of this hydrogel was both pH‐ and temperature‐dependent, but was higher in nonbuffered water than in boric acid/citric acid/phosphate buffer under the same conditions. The optimal hydrogel could swiftly swell and deswell in neutral and acid solutions, respectively. Its potential application in drug delivery was examined using insulin and methylene blue as model payload drugs. Loading in a 50% (v v^?1) ethanol solution gave a higher insulin loading level than in the buffer water. Insulin and methylene blue were both released at pH 6.8 but not at pH 1.2, but followed first order kinetics and the Higuchi equation, respectively. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45654.     

Synthesis of an alginate–poly(sodium acrylate‐co‐acrylamide) superabsorbent hydrogel with low salt sensitivity and high pH sensitivity

This article describes the synthesis and swelling behavior of a superabsorbing hydrogel based on sodium alginate (NaAlg) and polyacrylonitrile (PAN). The physical mixture of NaAlg and PAN was hydrolyzed with a solution of NaOH to yield an alginate–poly(sodium acrylate‐co‐acrylamide) [Alg–poly(NaAA‐co‐AAm)] superabsorbent hydrogel. A proposed mechanism for hydrogel formation was suggested, and the structure of the product was established with Fourier transform infrared spectroscopy. The effects of reaction variables were systematically optimized to achieve a hydrogel with a swelling capacity as high as possible. Under the optimized conditions concluded, the maximum capacity of swelling in distilled water was 610 g/g. The absorbency of the synthesized hydrogels was also measured in various salt solutions. The swelling ratios decreased with an increase in the ionic strength of the salt solutions. In addition, the swelling capacity was determined in solutions with pHs ranging from 1 to 13. The Alg–poly(NaAA‐co‐AAm) hydrogel exhibited pH responsiveness, so a swelling–deswelling pulsatile behavior was recorded at pHs 2 and 8. This on–off switching behavior made the hydrogel as a good candidate for the controlled delivery of bioactive agents. Finally, the swelling kinetics of the hydrogels with various particle sizes were preliminarily investigated as well. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2927–2937, 2006