Thermosensitive poly(n‐isopropylacrylamide) hydrogels bonded on cellulose supports

A two‐step initiation and polymerization process was developed for the preparation of two series of hydrogel–cellulose composites with distinctively different morphologies and swelling behaviors. Hydroentangled cotton cellulose fibers were optimally initiated in 20 mM aqueous ammonium cerium(IV) nitrate for 15 min and then polymerized in aqueous solutions of N‐isopropylacrylamide (NIPAAm) monomer and N,N′‐methylene bisacrylamide (BisA) crosslinker. The extents of hydrogels on the cellulose solids could be controlled by variations in the concentrations of the monomer and crosslinker as well as the NIPAAm/BisA solution‐to‐solid ratios. The two series of hydrogel–cellulose composites formed were hydrogel‐covered/filled cellulose (I) and cellulose‐reinforced hydrogel (II) composites. Series I composites were synthesized with NIPAAm/BisA solutions below the liquid saturation level of the cellulose; this led to pore structures (size and porosity) that depended on both the extent and swelling of the grafted hydrogels. Series II composites were polymerized in the presence of excessive NIPAAm/BisA solutions to produce cellulose solids completely encapsulated in the hydrogels. All the cellulose‐supported hydrogels exhibited lower extents of phase transition over a wider temperature range (28–40°C) than the free poly(N‐isopropylacrylamide) hydrogels (32°C). These findings demonstrate that hydrogels can be used to control the pore structure of cellulose and can be supported with cellulose fibers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 999–1006, 2003     

Preparation and swelling properties of glycoside-bearing hydrogels by gamma-ray radiation to glycoside-bearing polymer aqueous solutions

γ-Ray radiation on poly(glucosyloxyethyl methacrylate) [poly(GEMA)] and poly(glucosyloxyethyl acrylate) [poly(GEA)] aqueous solutions without any crosslinkers gives glycoside-bearing hydrogels in a high yield. The degree of the swelling ratios of each obtained hydrogel in water was decreased with an increase in the total radiation dose to each polymer solution. In order to clarify the formation mechanism of obtained poly(GEMA) hydrogel by γ-ray radiation, the swelling properties of each hydrogel were also compared with those of poly(GEA) under various conditions. Poly(GEMA) in an organic solvent, N,N-dimethylformamide and dimethylsulfoxide, was not gelled by γ-ray radiation, although poly(GEA) was gelled under these conditions. These results suggest that the radiation formation mechanism of the poly(GEMA) hydrogels is different from that of the poly(GEA) hydrogels. In addition, the radiolysis of water is necessary in order to form the hydrogels for poly(GEMA). Next, we predicted the radiation formation mechanism of the poly(GEMA) hydrogels by the crosslinking between the glucoside moieties in poly(GEMA). © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 965–972, 1998     

Preparation and swelling characterization of poly (n‐isopropylacrylamide)‐based porous hydrogels

Nine different poly(n‐isopropylacrylamide)‐based hydrogels, including nonionic, cationic, and anionic hydrogels, were synthesized in with and without the addition of pore‐forming agents. The synthesized hydrogels were characterized with dry gel density measurements, scanning electron microscopy observations, and the determination of the swelling ratio swelling kinetics. All the results showed that the cationic hydrogels had faster swelling kinetics than the anionic and nonionic hydrogels. The addition of pore‐forming agents (NaHCO₃ and carboxymethylcellulose) during the synthesis process led to porous hydrogels with lower dry densities, swelling ratios, and swelling kinetic parameter values. An empirical equation was developed to successfully correlate the swelling kinetic parameter with the hydrogel swelling ratio. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3651–3658, 2004     

Network parameters and volume phase transition behavior of poly(N‐isopropylacrylamide) hydrogels

Thermosensitive hydrogels were prepared by free radical polymerization in aqueous solution from N‐isopropylacrylamide (NIPA) monomer and N,N‐methylenebis(acrylamide) (MBAAm) crosslinker. The swelling equilibrium of the hydrogels in deionized water was investigated as a function of temperature and MBAAm content. The results indicated that the swelling behavior and temperature sensitivity of the hydrogels were affected by the amount of MBAAm content. The average molecular mass between crosslinks and polymer–solvent interaction parameter (χ) of the hydrogels were determined from equilibrium swelling values. The swelling variations were explained according to swelling theory based on the hydrogel chemical structure. The swelling equilibrium of the hydrogels was also investigated as a function of temperature in aqueous solutions of the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyltrimethylammonium bromide (DTAB). In deionized water, the hydrogels showed a discontinuous volume phase transition at 32°C. In SDS and DTAB solutions, the equilibrium swelling ratio and the volume phase transition temperature (lower critical solution temperature) of the hydrogels increased, which is ascribed to the conversion of nonionic PNIPA hydrogel into polyelectrolyte hydrogels because of binding of surfactant molecules through the hydrophobic interaction. Additionally, the amount of free SDS and DTAB ions was measured at different temperatures by a conductometric method; it was found that the electric conductivity of the PNIPA–surfactant systems depended strongly on both the type and concentration of surfactant solutions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1756–1762, 2006     

Dynamic swelling behavior of pH‐sensitive anionic hydrogels used for protein delivery

There have been many attempts to use anionic hydrogels as oral protein delivery carriers because of their pH‐responsive swelling behavior. The dynamic swelling behavior of poly(methacrylic acid‐co‐methacryloxyethyl glucoside) and poly(methacrylic acid‐g‐ethylene glycol) hydrogels was investigated to determine the mechanism of water transport through these anionic hydrogels. The exponential relation M_t/M_∞ = ktⁿ (where M_t is the mass of water absorbed at time t and M_∞ is the mass of water absorbed at equilibrium) was used to calculate the exponent (n) describing the Fickian or non‐Fickian behavior of swelling polymer networks. The mechanism of water transport through these gels was significantly affected by the pH of the swelling medium. The mechanism of water transport became more relaxation‐controlled in a swelling medium of pH 7.0, which was higher than pK_a of the gels. The experimental results of the time‐dependent swelling behaviors of the gels were analyzed with several mathematical models. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1606–1613, 2003     

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) hydrogels: Interactions with surfactants

Poly(N‐isopropylacrylamide‐co‐sodium acrylate) [poly(NIPAM‐co‐SA)] hydrogels were modified with three different kind of surfactants (cationic, anionic, and nonionic) to study the effect on the swelling properties. The structural variation of the surfactant‐modified hydrogels was investigated in detail. The interaction between the surfactants and the hydrogel varies and strictly depends on the surfactant type. The variation in thermal stability of the modified surfactant hydrogels was investigated and compared with unmodified hydrogel. Further, the hydrogel swelling/diffusion kinetic parameters were investigated and diffusion of water into hydrogel was found to be of the non‐Fickian transport mechanism. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3423–3430, 2007     

Synthesis and network parameters of hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) hydrogels

Hydrophobic poly(N‐[3‐(dimethylaminopropyl)]methacrylamide‐co‐lauryl acrylate) [P(DMAPMA‐co‐LA)] hydrogels with different LA content were synthesized by free‐radical crosslinking copolymerization of corresponding monomers in water by using N,N‐methylenebis(acrylamide) as the crosslinker, ammonium persulfate as the initiator, and N,N,N′,N′‐tetramethylethylenediamine as the activator. The swelling equilibrium of the hydrogels was investigated as a function of temperature and hydrophobic comonomer content in pure water. An interesting feature of the swelling behavior of the P(DMAPMA‐co‐LA) hydrogels with low LA content was the reshrinking phase transition where the hydrogels swell once and collapse as temperature was varied in the range of 30–40°C. The average molecular mass between crosslinks (M?_c) and polymer–solvent interaction parameter (χ) of the hydrogels were calculated from equilibrium swelling values. The enthalpy (ΔH) and entropy (ΔS) changes appearing in the χ parameter for the hydrogels were determined by using the Flory–Rehner theory based on the phantom network model of swelling equilibrium. The positive values for ΔH and ΔS indicated that the hydrogels had a positive temperature‐sensitive property in water, that is, swelling at a higher temperature and shrinking at a lower temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4159–4166, 2006     

Properties of highly water-absorptive hydroxyethylcellulose graft copolymers: Viscoelasticity and moisture sorption

The viscoelasticity of the hydrogels, the moisture sorption, and the characteristics of the sorbed water of highly water-absorptive hydroxyethylcellulose (HEC) graft copolymers [e.g., HEC graft copolymers containing partially hydrolyzed polyacrylamide (HEC-P-Hyd-PAM), etc.] were investigated in comparison with commercial absorbents. The viscosity (η) and the rigidity (G) of the dispersions of their hydrogels were, respectively, proportional to the second to the sixth powers and the fifth to the seventh powers of their concentrations (η = KC^2–6 and G = K′C^5–7). With respect to the characteristics of the sorbed water, the conductivity of 0.1 N KCI in the hydrogels of the HEC water, absorbents was about 11.8 mS/cm, which was almost the same as that of 0.1 N KCI in pure water, and the water absorbency of dry matter (soybean seeds) in their hydrogels was almost the same as that in pure water. These results suggest that most of the sorbed water in the HEC super water absorbents behaves like free water. The maximum volume of sorbed moisture in a monolayer fashion (V_m) of HEC-P-Hyd-PAM analyzed using the Brunauer-Emmett-Teller equation was about 0.21 g/g (1.2 mol water/polymer repeat unit), and there was no cluster water at 92% relative humidity or below as a result of applying the cluster function concept. © 1995 John Wiley & Sons, Inc.     

Synthesis and properties of starch-graft-acrylic acid/Na-montmorillonite superabsorbent nanocomposite hydrogels

The graft copolymerization of acrylic acid (AA) onto starch was carried out with monomer/starch weight ratio = 1.5. Cerium ammonium nitrate (CAN) and N,N′-methylenebis acrylamide (NMBA) were used as initiator and crosslink agent, respectively. Na-montmorillonite was used as nanoparticles. Starch-graft-acrylic acid/Na-MMT (S-g-AA/MMT) nanocomposite hydrogels were characterized by X-ray diffraction (XRD) and FTIR analysis. The effect of Na-MMT content in nanocomposite hydrogels on the swelling behavior was investigated. Increasing the Na-MMT/monomers ratio up to 1% causes an increment in water absorbency, which indicates that Na-MMT can improve the ability of water absorbency but further increase of Na-MMT causes a decrease in water absorbency. In addition, we describe the removal of safranine T from aqueous solutions using S-g-AA/MMT nanocomposite hydrogels. Effects of various parameters such as treatment time, initial dye concentration, and amount of the Na-MMT were investigated. The Freundlich equations were used to fit the equilibrium isotherms. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoreversible hydrogels. XVIII. Synthesis,swelling characteristics,and diffusion behaviors of porous,ionic, thermosensitive hydrogels

Porous, ionic, thermosensitive hydrogels were prepared from N‐isopropylacrylamide, a cationic monomer [trimethyl (acrylamido propyl) ammonium iodide (TMAAI)], an anionic monomer [acrylic acid (AA)], a zwitterionic monomer [N′,N′‐dimethyl (acrylamido propyl) ammonium propane sulfonate], or a nonionic monomer [poly(ethylene glycol) methyl ether acrylate], and a pore‐forming agent [poly(ethylene glycol) (PEG)] of different molecular weights. Some fundamental properties and dynamic swelling kinetic parameters and solute permeation for these porous gels were investigated. The results showed that the gel containing the cationic monomer TMAAI had a higher equilibrium swelling ratio. The diffusion coefficients showed that the swelling rates for the gels with the anionic monomer AA and PEG with a higher molecular weight (20,000) were faster. The results showed that the fast swelling–deswelling behavior for the porous structure gels was due to them being more available than the gels with long hydrophilic side chains. In addition, the interactive force between the solutes and gels and the solute permeation through the porous gels were investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2214–2223, 2003     

Swelling–deswelling kinetics of ionic poly(acrylamide) hydrogels and cryogels

A series of ionic poly(acrylamide) (PAAm) gels was prepared by free‐radical crosslinking copolymerization of acrylamide and N,N′‐methylenebisacrylamide in aqueous solutions. The gels were prepared both below and above the bulk freezing temperature of the polymerization solvent water, which are called as the cryogels and the hydrogels, respectively. The deswelling behavior of swollen gels in acetone as well as the reswelling behavior of the collapsed gels in water were investigated. It was shown that the cryogels respond against the external stimuli much faster than the hydrogels. The interior morphology of the cryogel networks exhibits a discontinuity and a two‐phase structure, compared to the continuous morphology of the hydrogel networks. Introduction of the ionic units in the network chains further increased the response rate of the cryogels. In contrast to these advantages of cryogels, they exhibit lower swelling capacities than the conventional hydrogels. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 319–325, 2006     

快速响应聚(N-异丙基丙烯酰胺)水凝胶的制备及性能

以N-异丙基丙烯酰胺为单体、N,N′-亚甲基双丙烯酰胺为交联剂、过硫酸铵为引发剂、N,N,N,′N′-四甲基乙二胺为加速剂,在不同浓度的羧甲基纤维素的水溶液中,在低温下聚合/交联制备了一系列快速响应的温度敏感性聚(N-异丙基丙烯酰胺)水凝胶。用SEM观察了其表面形态,测定了不同温度下达到平衡时水凝胶的溶胀比,研究了水凝胶的去溶胀动力学。结果表明,与传统水凝胶相比,该水凝胶的溶胀性能有所提高,并且对温度的变化具有较快的响应速率。以质量分数为0.75%的羧甲基纤维素水溶液中制备的水凝胶为例,该水凝胶在20℃时的溶胀比为21.4,而传统水凝胶在相同温度时的溶胀比仅为12.9;该水凝胶在1 m in内失去60%的水,在4 m in内失去约80%的水,而传统水凝胶在15 m in内仅失去66%左右的水。     

Synthesis and swelling properties of the copolymer of acrylamide with anionic monomers

A series of novel superabsorbent copolymers of acrylamide (AM), sodium allylsulfonate (SAS), sodium acrylate (AA), and N,N′-methylenebisacrylamide (BisA) were synthesized using potassium persulfate (KPS)/N,N,N′,N′-tertramethylethylenediamine (TMEDA) as the initiator. The influences of synthetic variables (monomer concentration, temperature, initiator concentration, and pH) on the polymerization conversion (y°) and swelling properties were studied in detail. These gels should have potential application as water super-absorbents. © 1996 John Wiley & Sons, Inc.     

Reentrant phase transition and fast responsive behaviors of poly{N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels prepared in poly(ethylene glycol) solutions

Macroporous temperature‐sensitive poly {N‐[3‐(dimethylaminopropyl)] methacrylamide} hydrogels were synthesized by free‐radical crosslinking polymerization of the monomer N‐[3‐(dimethylaminopropyl)] methacrylamide and the crosslinker N,N′‐methylenebisacrylamide in aqueous solutions at 22°C. Poly(ethylene glycol) (PEG) with a molecular weight of 1000 g/mol was used as the pore‐forming agent during the polymerization reaction. The concentration of PEG in the polymerization solutions was varied between 0 and 18 wt %, whereas the crosslinker (N,N′‐methylenebisacrylamide) concentration was fixed at 2 wt % (with respect to the monomer). The effects of the PEG concentration on the thermo‐induced phase‐transition behavior and the chemical structure, interior morphology, and swelling/deswelling kinetics were investigated. Normal‐type hydrogels were also prepared under the same conditions without PEG. An interesting feature of the swelling behavior of both the normal‐type and macroporous hydrogels was the reentrant phase transition, in which the hydrogels collapsed once and reswelled as the temperature was continuously increased. Scanning electron micrographs revealed that the interior network structure of the hydrogels prepared in PEG solutions became more porous with an increase in the PEG concentration in the polymerization solution. This more porous matrix provided numerous water channels for water diffusion in or out of the matrix and, therefore, an improved responsive rate to external temperature changes during the deswelling and swelling processes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel biodegradable superabsorbent hydrogels derived from cotton cellulose and succinic anhydride: Synthesis and characterization

The synthesis of novel superabsorbent hydrogels was investigated with the reaction of cotton cellulose and succinic anhydride (SA) in the presence of 4‐dimethylaminopyridine as an esterification catalyst in a mixture of lithium chloride (LiCl) and N‐methyl‐2‐pyrrolidinone (NMP) or in a mixture of tetrabutylammonium fluoride (TBAF) and dimethyl sulfoxide (DMSO), followed by NaOH neutralization. Interestingly, a hydrogel was obtained without any crosslinking agent, and this indicated the partial formation of a diester between the cellulosic hydroxyl group and SA. The products obtained in LiCl/NMP exhibited superior absorbency to these obtained in TBAF/DMSO. The former absorbed an amount of water about 400 times its dry weight, and this was comparable to a conventional sodium polyacrylate superabsorbent hydrogel. Furthermore, in an aqueous NaCl solution, the absorbency of the product hydrogels was higher than that of the sodium polyacrylate superabsorbent hydrogel. The formed hydrogels biologically degraded almost completely after 25 days, and this showed their excellent biodegradability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3251–3256, 2006     

Compressive moduli and network parameters of N‐isopropylacrylamide hydrogels copolymerized by monoesters of itaconic acid and crosslinked with tetraallylammonium bromide

The present study focuses on the mechanical properties of hydrophilically or hydrophobically modified poly(N‐isopropylacrylamide) (PNIPAAm) hydrogels, and all discussions on their improved mechanical strengths are based on the conformational effects of hydrophobic side chains attached to the comonomers and the structural differences between the crosslinkers. Three different types of monoalkyl itaconates, bearing octyl (Oc), cetyl (Ce), and cyclohexyl (CH) groups as comonomers, were used to prepare the copolymeric PNIPAAm hydrogels crosslinked with N,N′‐methylenebisacrylamide (BIS) and tetraallylammonium bromide (TAB) as neutral tetrafunctional and ionic octafunctional crosslinkers, respectively. The most striking result is the compressive E modulus of TAB‐crosslinked PNIPAAm hydrogel containing 10 mol % of mOcI. It reaches nearly 1.0 MPa and is independent of the temperature and pH of the swelling/shrinking medium. The result was discussed in terms of the inter/intramolecular interactions between hydrophobic octyl groups adopting a rod‐like conformation in the case of 25 °C/distilled deionized water (DDW) and 37 °C/DDW combinations. Further, it was observed that the electrostatic repulsive forces between the carboxylate groups on mOcI units could be suppressed even at 37 °C and pH 9 due to the rod‐like conformations of C₈H₁₇ groups. Its micrographs under bright‐field and polarized light supported the presence of an ordered anisotropic phase and multiple associations of extended, hydrophobic side chains. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45039.     

Preparation,characterization, and water‐sorption study of polyvinyl alcohol based hydrogels with grafted hydrophilic and hydrophobic segments

The interpenetrating polymer network hydrogels based on poly(vinyl alcohol) were obtained by graft copolymerization of acrylamide and styrene onto polyvinyl alcohol in the presence of N,N′‐methylene bisacrylamide as a crosslinking agent. The hydrogels were characterized by optical microscopy, scanning electron microscopy, infrared spectral analysis, differential scanning calorimeter, and thermogravimetric analysis. The hydrogels showed enormous swelling in aqueous medium and displayed swelling characteristics, which were highly dependent on the chemical composition of the hydrogels and pH of the swelling medium. The kinetics of water uptake and the mechanisms of water transport were studied as a function of composition of the hydrogel and pH of the swelling medium. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1129–1142, 2005     

魔芋粉-丙烯酸-丙烯酰胺接枝共聚合成高吸水树脂

以魔芋粉,丙烯酸和丙烯酰胺等为原料,经接枝聚合合成了魔芋粉－丙烯酸－丙烯酰胺类超强吸水性树脂。讨论了引发剂,交联剂,丙烯酸,丙烯酰胺等用量以及反应时间和反应温度等因素对树脂吸水性能的影响。结果表明: 在魔芋粉与单体质量比为1:4,引发剂用量为0.35%（占单体的质量）,丙烯酸/丙烯酰胺（质量）为1:1,丙烯酸中和度为80% ,反应温度为55～65℃,交联剂用量为0.75%（占单体的质量）的条件下,制得的SAP吸去离子水可达720g/g,吸0.9%的NaCl溶液为110g/g。     

Influence of the initiator system on the spatial inhomogeneity in acrylamide‐based hydrogels

The effect of the initiator system used in the gel preparation on the spatial inhomogeneity in poly(acrylamide) (PAAm) and poly(N,N‐dimethylacrylamide) (PDMA) hydrogels was investigated by static light scattering and elasticity measurements. The hydrogels were prepared by free‐radical crosslinking copolymerization of the monomers acrylamide (AAm) or N,N‐dimethylacrylamide (DMA) with N,N′‐methylenebisacrylamide as a crosslinker. Two different redox‐initiator systems, ammonium persulfate (APS)–N,N,N′,N′‐tetramethylethylenediamine (TEMED) and APS–sodium metabisulfite (SPS), were used to initiate the gelation reactions. Compared to the APS–TEMED redox pair, no significant scattered light intensity rise was observed during the crosslinking polymerization reactions initiated by the APS–SPS system. It was found that both PAAm and PDMA gels are much more homogeneous when the APS–SPS redox pair was used as the initiator. The results are explained by the formation of shorter primary chains as well as the delay of the gel point in APS–SPS initiated gel formation reactions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3228–3237, 2007     

Smart carboxymethylchitosan hydrogels that have thermo‐ and pH‐responsive properties

Thermo‐responsive poly(N‐isopropylacrylamide) (poly(NIPAAm)) and pH‐responsive poly(N,N′‐diethylaminoethyl methacrylate) (poly(DEAEMA)) polymers were grafted to carboxymethylchitosan (CMC) via radical polymerization to form highly water swellable hydrogels with dual responsive properties. Ratios of CMC, NIPAAm to DEAEMA used in the reactions were finely adjusted such that the thermo and pH responsiveness of the hydrogels was retained. Scanning electron microscopy (SEM) indicated the formation of an internal porous structure for the swollen CMC hydrogels upon incorporation of poly(NIPAAm) and poly(DEAEMA). Effect of temperature and pH changes on water swelling properties of the hydrogels was investigated. It was found that the water swelling of the hydrogels was enhanced when the solution pH was under basic conditions (pH 11) or the temperature was below its lower critical solution temperature (LCST). These responsive properties can be used to regulate releasing rate of an entrapped drug from the hydrogels, a model drug, indomethacin was used to demonstrate the release. These smart and nontoxic CMC‐based hydrogels show great potential for use in controlled drug release applications with controllable on‐off switch properties. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41505.