Poly(N-vinylpyrrolidone)-grafted poly(N-isopropylacrylamide) copolymers: Synthesis, characterization and rapid deswelling and reswelling behavior of hydrogels

Poly(N-isopropylacrylamide)-block-poly(N-vinylpyrrolidone) diblock copolymer (PNIPAAm-b-PVPy) was successfully synthesized via sequential reversible addition-fragmentation chain transfer/macromolecular design via the interchange of xanthate (RAFT/MADIX) process, in which the chain transfer agent of xanthate was in situ afforded via the reaction of isopropylxanthic disulfide (DIP) with 2,2-azobisisobutylnitrile (AIBN). The RAFT/MADIX technique was employed to prepare the poly(N-vinylpyrrolidone)-grafted poly(N-isopropylacrylamide) copolymers (PNIPAAm-g-PVPy) with N,N-methylenebisacrylamide as the crosslinking agent. The comb-like PNIPAAm-g-PVPy copolymer networks with PVPy as the pendent chains were characterized by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and small angle X-ray scattering (SAXS). The hydrogel behavior of PNIPAAm-g-PVPy networks was investigated in terms of swelling, deswelling and reswelling tests. With the inclusion of PVPy chains, the swelling ratios of the hydrogels were significantly enhanced compared to the control PNIPAAm hydrogel. It is found that the PVPy-modified PNIPAAm hydrogels displayed faster response to the external temperature changes than the control PNIPAAm hydrogel. The improved thermoresponsive properties of hydrogels are ascribed to the formation of the comb-like architectures in the copolymer networks.     

Investigation of mechanical and thermodynamic properties of pH‐sensitive poly(N,N‐dimethylaminoethyl methacrylate) hydrogels prepared with different crosslinking agents

pH‐sensitive poly(N,N‐dimethylaminoethyl methacrylate) hydrogels were synthesized by free‐radical crosslinking polymerization using two different crosslinking agents; tetraethylene glycol dimethacrylate (TEGMA) and N,N′‐methylenebis(acrylamide) (BAAm). The influence of the polymerization factors such as the type of the crosslinking agent and the gel preparation concentration on the swelling behavior, the gel strength, the effective crosslinking density and the average chain length between the crosslink points for the resulting hydrogels was investigated. The results of the equilibrium swelling measurements in water showed that the linear swelling ratio of the resulting hydrogels increases with increasing gel preparation concentration. The swelling ratio of PDMAEMA hydrogels crosslinked with BAAm is larger than those for hydrogels crosslinked with TEGMA over the entire range of the polymer network concentration. The hydrogels exhibit very sharp pH‐sensitive phase transition in a very narrow range of pH between 7.7 and 8.0. From the mechanical measurements, it was also found that the linear swelling ratio of resulting hydrogels depends on the crosslinking density and also the type of the crosslinker used in the preparation. The resulting hydrogels are thought to be good candidates for pH‐sensitive drug delivery systems. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

A systematic method of synthesizing composite superabsorbent hydrogels from crosslink copolymer for removal of textile dyes from water

A systematic method was employed to synthesize several hydrogels by crosslink copolymerization of acrylamide (AM), hydroxyl ethylmethacrylate (HEMA) and N,N’-methylenebisacrylamide (NMBA) at varied operating conditions. Composite hydrogels were also prepared by in situ incorporation of varied amounts of sodium aluminosilicate filler to the monomer mixtures at optimum operating conditions. These hydrogels were used for removal of rhodamine B and methyl violet dye from water at low (0.5–3 mg/L) and high concentration (50–500 mg/L) ranges. The composite hydrogels showed much higher dye adsorption than the unfilled hydrogels. Kinetic, adsorption and thermodynamic parameters for dye adsorption were also evaluated.     

Radical/Addition polymerization silicone hydrogels with simultaneous interpenetrating hydrophilic/hydrophobic networks

Transparent silicone hydrogels with interpenetrating hydrophilic/hydrophobic networks were simultaneously synthesized on the basis of the radical polymerization of the methacrylic monomer of 3‐methacryloxypropyl tris(trimethylsiloxy) silane (TRIS)/N,N‐dimethylacrylamide (DMA) and the addition polymerization of hydroxyl‐grafted polysiloxane (HPSO)/isophorone diisocyanate. The curing temperature was set at 80°C by a differential scanning calorimetry study. The polymerization process was studied by in situ Fourier transform infrared spectroscopy. The results indicate that the curing time was about 4.5 min, and the addition polymerization had a faster rate than radical polymerization. Then, the radical polymerization rate increased rapidly, and this led to instant curing. The interpenetrating polymer network (IPN) silicone hydrogels were characterized by swelling kinetics and dynamic mechanical thermal analysis. The results show that all of the hydrogels reached swelling equilibrium at about 4 h in water, and the IPN silicone hydrogels with a hydrophobic network of HPSO indicated a slower water transport than that of the copolymerization hydrogel of DMA and TRIS. The hydrophobic network was finely dispersed in the hydrophilic network, and the increasing hydrophobic network of HPSO decreased the glass‐transition temperature of the IPN silicone hydrogels. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41399.     

Effect of Potassium Methacrylate Content on Synthesis,Swelling, and Diffusion Characteristics of Acrylamide/Potassium Methacrylate Hydrogels

ABSTRACT

Hydrogels based on acrylamide (AAM) and potassium methacrylate (KMA) were synthesized by simultaneous free radical polymerization in aqueous solution using the redox initiator ammonium persulfate (APS) and N,N,N′N′-tetramethylethylenediamine (TMEDA) at room temperature. Eight different compositions of KMA hydrogels were prepared at a fixed concentration of N,N′,-methylenebisacrylamide (MBA) or diallyl phthalate (DP) as crosslinking agents. For all the AAM-KMA hydrogels, the percentage of swelling, swelling kinetics, and diffusion characteristics were investigated. It was found that higher swelling percentage values were obtained for hydrogels crosslinked with DP than for the conventional crosslinker MBA. The de-swelling characteristics of hydrogels were also studied in detail. The power law relationship of hydrogels was evaluated in saline solutions. Hydrogels formation was confirmed by IR spectroscopy. The thermal characteristics of these hydrogels were studied by using differential scanning calorimeter (DSC) and thermogravimetric analyzer (TGA) and revealed that MBA crosslinked AAM-KMA hydrogels show higher glass transition temperature (Tg) as well as higher decomposition temperatures (Td) than DP crosslinked AAM-KMA hydrogels. It is further confirmed from the studies that the DP crosslinked hydrogels have good swelling as well as de-swelling and salinity characteristics.     

Unusual swelling behavior of polymer-clay nanocomposite hydrogels

The swelling behavior and the elastic properties of nanocomposite hydrogels have been investigated. The hydrogels were prepared by free-radical polymerization of the monomers acrylamide (AAm), N,N-dimethylacrylamide (DMA), and N-isopropylacrylamide (NIPA) in aqueous clay suspensions at 21 °C. Laponite with a radius of gyration in distilled water of 20 nm was used as clay particles in the hydrogel preparation. The reactions with AAm monomer were carried out in the presence of the chemical crosslinker N,N′-methylenebis(acrylamide) (BAAm). It was found that the volume of nanocomposite hydrogels immersed in water rapidly increases and attains a maximum value after about one day. Surprisingly, further increase in the swelling time results in the deswelling of the gels until they reach a limiting swelling ratio after about 5 days. This unusual swelling behavior is observable only when the clay concentration in the hydrogel is above the overlap threshold c^∗. Swelling measurements combined with the elasticity tests show that the effective crosslink density first decreases, but then increases with increasing time of swelling of the hydrogels. The results were explained in terms of the rearrangements of the highly entangled polymer chains and clay particles during the gel volume change.     

Poly(ethylene oxide)-grafted poly(N-isopropylacrylamide) networks: Preparation, characterization and rapid deswelling and reswelling behavior of hydrogels

Poly(ethylene oxide)-grafted poly(N-isopropylacrylamide) networks (PNIPAAm-g-PEO) were prepared via the reversible addition-fragmentation chain transfer polymerization (RAFT) of N-isopropylacrylamide with trithiocarbonate-terminated poly(ethylene oxide) and N,N′-methylenebisacrylamide as the chain transfer agent and the crosslinking agent, respectively. It was found that the PNIPAAm-g-PEO copolymer networks were microphase-separated and that PEO microdomains were dispersed in the PNIPAAm matrix. The hydrogel behavior of the PNIPAAm-g-PEO networks was investigated using swelling, deswelling and reswelling tests. The PNIPAAm-g-PEO hydrogels displayed faster responses to external temperature changes than did the control PNIPAAm hydrogel.     

Swelling behavior of semi‐interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylamide‐co‐sodium methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(vinyl alcohol) (PVA) and poly(acrylamide‐co‐sodium methacrylate) poly(AAm‐co‐SMA) were prepared by the semi IPN method. These IPN hydrogels were prepared by polymerizing aqueous solution of acrylamide and sodium methacrylate, using ammonium persulphate/N,N,N¹,N¹‐tetramethylethylenediamine (APS/TMEDA) initiating system and N,N¹‐methylene‐bisacrylamide (MBA) as a crosslinker in the presence of a host polymer, poly(vinyl alcohol). The influence of reaction conditions, such as the concentration of PVA, sodium methacrylate, crosslinker, initiator, and reaction temperature, on the swelling behavior of these IPNs was investigated in detail. The results showed that the IPN hydrogels exhibited different swelling behavior as the reaction conditions varied. To verify the structural difference in the IPN hydrogels, scanning electron microscopy (SEM) was used to identify the morphological changes in the IPN as the concentration of crosslinker varied. In addition to MBA, two other crosslinkers were also employed in the preparation of IPNs to illustrate the difference in their swelling phenomena. The swelling kinetics, equilibrium water content, and water transport mechanism of all the IPN hydrogels were investigated. IPN hydrogels being ionic in nature, the swelling behavior was significantly affected by environmental conditions, such as temperature, ionic strength, and pH of the swelling medium. Further, their swelling behavior was also examined in different physiological bio‐fluids. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 302–314, 2005     

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 performance of thermosensitive poly(N‐isopropylacrylamide) hydrogels by frontal photopolymerization

In this study, frontal photopolymerization was applied to the fabrication of thermosensitive poly(N‐isopropylacrylamide) (PNIPAm) hydrogels. The influence of experimental conditions and reactant components on the feature of the polymerization front was investigated. The morphology of the samples indicated the successful preparation of PNIPAm hydrogels. The mechanical properties and thermal stability of the obtained hydrogels are discussed. The results indicated that the performance of the hydrogels is related to their microstructure and the type of crosslinkers. The swelling behavior and drug delivery ability were determined under different temperature conditions. The hydrogels exhibit a classical thermoresponsive behavior, which was also demonstrated by the DSC results. Therefore, frontal photopolymerization can be an alternative method for the preparation of PNIPAm hydrogels under mild conditions. © 2019 Society of Chemical Industry     

Radiation polymerization and concentration separation of P(NIPA‐co‐AMPS) hydrogels

Extraction or concentration with temperature‐sensitive hydrogels is a novel separation technology. In this study, N‐isopropylacrylamide (NIPA) was synthesized by acrylonitrile and isopropanol. Poly(N‐isopropylacrylamide) (PNIPA) and copolymer of NIPA and 2‐acrylamide‐2‐methylpropane sulfonate [P(NIPA‐co‐AMPS)] hydrogels were prepared by radiation polymerization. Dependence of their swelling behavior on temperature was studied. Effects of radiation dose on polymerization, feed composition on thermoresponse, electrolyte on relative swelling ratio, and swelling and deswelling kinetics were investigated. The experimental results showed that P(NIPA‐co‐AMPS) hydrogels with low content of AMPS/NIPA (1–5 %), prepared at a radiation dose‐rate of 1 kGy/h and total dose of 30–40 kGy, could enhance the swelling ratio of PNIPA hydrogels significantly and raise the phase‐transition temperatures. P(NIPA‐co‐AMPS) hydrogels produced under optimum conditions were used to concentrate aqueous bovine serum albumin (BSA, M = 69 000 g mol^?1) solution. When aqueous BSA concentration was below 5 %, the separation efficiency was more than 80 % with low cost and low energy consumption. Copyright © 2005 Society of Chemical Industry     

Effect of synthesis composition on the swelling pressure of polymeric hydrogels

This paper focuses on the determination of the swelling pressure of polymeric hydrogels by variation of the composition of the monomer mixture used for synthesis via free radical polymerization. The method used is based on the principle of determining the swelling pressure at a given final volume of swelling. Data for different types of low swollen hydrogels based on weakly crosslinked poly(acrylic acid)/poly(sodium acrylate) copolymers are presented for swelling in deionised water. For polymer volume fractions ?_P between 0.03 and 0.30, swelling pressures p in the range of 0.20-4.23 MPa were obtained. No effect on the swelling pressure could be found by variation of monomer concentration and crosslinker content. In contrast, the content of sodium acrylate had an effect on the swelling pressure. The results are discussed based on the effect of counterion condensation.     

Swelling and auramine-<Emphasis Type="Italic">O</Emphasis> adsorption of carboxymethyl cellulose grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels

Carboxymethyl cellulose (CMC) grafted poly(methyl methacrylate)/Cloisite 30B nanocomposite hydrogels were prepared for adsorptive removal of auramine-O (as a cationic dye model) from wastewater. For the synthesis of nanocomposite hydrogel by free radical polymerization method, potassium persulfate (KPS), methyl methacrylate (MMA), N,N′-methylene bisacrylamide (MBA) and Cloisite 30B were used as initiator, monomer, cross-linker and nano-filler, respectively. The nanocomposite hydrogels were characterized by FTIR, TGA, SEM and XRD techniques. The FTIR results showed that the monomer was grafted onto carboxymethyl cellulose chains successfully. Swelling behavior of nanocomposite hydrogel as a function of KPS, MBA, MMA concentration and CMC/Cloisite 30B weight ratio was studied by Taguchi method using Minitab 16 software. According to ANOVA results, the most effective factor of equilibrium swelling of nanocomposite hydrogel was CMC/Cloisite 30B weight ratio. Addition of Cloisite 30B to hydrogel up to a certain amount improved swelling, though its high amount decreased swelling. The effects of pH and ionic strength on swelling of optimum hydrogels were investigated. Maximum swelling of nanocomposite hydrogel occurred at pH 7.0. The kinetic data of adsorption fitted well to pseudo-second-order model. The best isotherm for investigation of adsorption mechanism was Langmuir model suggesting the formation of a monolayer on the adsorbent surface. FTIR results, before and after auramine-O adsorption, showed that complexation is the main mechanism of adsorption. High adsorption capacity of nanocomposite hydrogels made them more efficient in wastewater treatment application.     

Effect of hydrophobic polystyrene microphases on temperature-responsive behavior of poly(N-isopropylacrylamide) hydrogels

Reversible addition-fragmentation chain transfer polymerization was employed to prepare the crosslinked poly(N-isopropylacrylamide)-graft-polystyrene networks (PNIPAAm-g-PS). Due to the immiscibility of PNIPAAm with PS, the crosslinked PNIPAAm-g-PS copolymers displayed the microphase-separated morphology. While the PNIPAAm-g-PS copolymer networks were subjected to the swelling experiments, it is found that the PS block-containing PNIPAAm hydrogels significantly exhibited faster response to the external temperature changes according to swelling, deswelling, and reswelling experiments than the conventional PNIPAAm hydrogels. The improved thermo-responsive properties of hydrogels have been interpreted on the basis of the formation of the specific microphase-separated morphology in the hydrogels, i.e., the PS blocks pendent from the crosslinked PNIPAAm networks were self-assembled into the highly hydrophobic nanodomains, which behave as the microporogens and thus promote the contact of PNIPAAm chains and water. The self-organized morphology in the hydrogels was further confirmed by photon correlation spectroscopy (PCS). The PCS shows that the linear model block copolymers of PNIPAAm-g-PS networks were self-organized into micelle structures, i.e., the PS domains constitute the hydrophobic nanodomains in PNIPAAm-g-PS networks.     

Synthesis of hydrogels by polymerization of itaconic acid–choline chloride deep eutectic solvent

Itaconic acid (IA)–choline chloride (CC) deep eutectic solvents (DES) were prepared and characterized by NMR, TGA, and DSC. Poly(itaconic acid–co–bisacrylamide) hydrogels were synthesized by in situ polymerization‐crosslinking of the DES. For comparison, the hydrogels were also prepared in water under the same process conditions, that is, temperature, time, initial concentration of the monomer, the initiator, and N,N′‐methylenebisacrylamide (BAA) as the cross‐linking agent. Chemical structure of the polymers was proved by elemental analysis and FTIR. The values of insoluble gel fraction and water swelling of obtained hydrogels suggest that polymers prepared in DES have higher cross‐link density. Preliminary comparative studies of polymerization of IA in water and in DES medium indicated higher polymerization rate resulting from the presence of the choline salt, what might explain properties of the hydrogels prepared in DES. This study shows that DES can be used both as a solvent and catalyst in free‐radical polymerization processes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40608.     

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     

Preparation of a novel pH-sensitive hydrogel based on acrylic acid and polyhedral oligomeric silsesquioxane for controlled drug release of theophylline

Hydrogels based on pH-sensitive polymers are of great interest as potential biomaterials for the controlled delivery of drug molecules. In this study, a novel pH-sensitive copolymer hydrogel based on acrylic acid (AA) monomer by free-radical solution polymerization were synthesized with organic–inorganic cross-linking agent of octavinyl polyhedral oligomeric silsesquioxane (OVPOSS). And its properties were compared with conventional hydrogels using N,N′-methylenebisacrylamide (MBA) as cross-linking agent. The copolymers were characterized by Fourier transform infrared spectra and differential scanning calorimetry. The morphology after swelling was presented by scanning electron microscopy. Swelling behaviors in different pH and potential applications in controlled drug delivery of the hydrogels were also examined. The results showed that both hydrogels were pH sensitive. However, as the addition of OVPOSS limited the movement of the molecular chain segment, the swelling ratio and the drug-release rate of theophylline in SGF decreased obviously when using OVPOSS as cross-linking agent, comparing with P(MBA-co-AA) hydrogels. The results in this study suggested that P(OVPOSS-co-AA) could serve as potential candidate for theophylline drug delivery.     

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.     

Diels–Alder reaction in water for the straightforward preparation of thermoresponsive hydrogels

Because the properties and applications of hydrogels are determined by the formation principle and conditions of the hydrogels, novel methods for preparing hydrogels have increasingly triggered scientists' interest. Here the Diels–Alder reaction was applied to the preparation of hydrogels. For the resultant polymeric diene and dienophile, the Diels–Alder reaction could be performed in water. The gelation time was found to be closely related to the temperature. The gelation time decreased with the temperature increasing. Moreover, the hydrogels were stable in water, and the retro‐Diels–Alder reaction could be performed in N,N‐dimethylformamide easily. A study of the swelling ratio indicated that the hydrogels were responsive to the temperature. The hydrogel formation method described here provides several advantages, such as mild reaction conditions, no initiator or catalyst, a tunable gelation rate, and thermal reversibility, and it has great potential for the preparation of biomaterials. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Robust and thermo-response graphene–PNIPAm hybrid hydrogels reinforced by hectorite clay

Graphene oxide (GO) based hydrogels were proposed to be used as biomaterials and stimuli-response materials, but their poor mechanical properties restricted their applications. We enhanced GO–poly(N-isopropylacrylamide) (PNIPAm) hydrogels by hybrid with the hectorite clay through in situ polymerization for the first time. This clay was found to stabilize the GO in the aqueous suspension when a reducer was added in a redox initiating pair. These GO–clay–PNIPAm hybrid hydrogels exhibited a high mechanical strength and extensibility with the GO sheets as the cross-linker and with the hectorite clay as both the cross-linker and reinforcing agent. They were thermal-responsive with the volume phase transition at ∼34 °C. Reduction of the GO with l-ascorbic acid under environmental friendly conditions resulted in a high conductivity to the graphene–clay–PNIPAm hydrogels. These graphene–clay–PNIPAm hydrogels still had desirable mechanical properties. This finding has provided an easy method to prepare strong and stimuli-response graphene–polymer hydrogels to meet the demand for the newly developed soft matter.