Physicochemical studies of crosslinked thiolated polyvinyl alcohol hydrogels

This study is related to the post-crosslinking of thiolated polyvinyl alcohol (TPVA) hydrogels using three crosslinkers, sodium trimetaphosphate (STMP), boric acid (BA) and glyoxal (GLY) under alkaline conditions. The crosslinking reaction was carried out under different conditions: crosslinker nature, crosslinker content and crosslinking time. The influence of different crosslinkers on the physicochemical and structural characteristics of TPVA was evaluated. The three reagents used for crosslinking presented different action mode on hydrogels. The optimized crosslinking conditions were the crosslinker content is 0.1 % (w/v) at crosslinking time of 30 min. The results showed that the STMP-crosslinked TPVA had the maximum thiol content and swelling ability. All crosslinked TPVA samples were stable in different pH media. The involvement of thiol and other relevant groups after crosslinking in the different crosslinked TPVA samples was confirmed by attenuated total reflectance-infrared spectra. The microanalysis of elements present in the crosslinked samples were analyzed by energy-dispersive X-ray microanalysis.     

Preparation and Evaluation of Functionalized Poly(vinyl alcohol)-Based Hydrogels for Arsenite Removal from Water

Cross-linked thiolated polyvinyl alcohol (TPVA) hydrogels were synthesized by a two-step functionalization process, i.e., esterification and cross-linking of polyvinyl alcohol (PVA) hydrogel. PVA was esterified with thioglycolic acid and was subsequently cross-linked with sodium trimeta phosphate (STMP). The cross-linked TPVA was utilized as chelating material for arsenite As(III) binding. Atomic absorption spectroscopy (AAS) was used to detect and monitor As(III) concentration in water. Various parameters affecting the arsenic removal process were investigated. It was observed that the cross-linked TPVA behaves as an excellent chelating material for As(III). A maximum removal efficiency of 94% was achieved under our experimental conditions. To investigate the interaction of As(III) with functional groups before and after the removal process, attenuated total reflectance-infrared (ATR) was used. The microanalysis of elements present in samples was carried out by energy dispersive X-ray microanalysis. The material showed good regeneration ability along with antimicrobial activity against both bacterial and fungal strains.     

Pervaporation separation of aqueous mixtures using crosslinked poly(vinyl alcohol), I. Characterization of the reaction between PVA and amic acid

For the purposes of new membrane material development for pervaporation separation based on crosslinked polyvinyl alcohol (PVA), IR spectroscopy and DSC were used to characterize the crosslinking reaction and the imidization of the (PVA)-amic acid system. The IR spectra and the thermal analysis were performed on specimens that had been reacted for several different times at 150°C. The crosslinking reaction between the hydroxy groups of PVA and the carboxylic groups of amic acid was faster than the imidization of the amic acid. The best reaction times were about 30 min for the crosslinking reaction and 90 min for the imidization. The effects of the reaction time and the amic acid content on the thermal and mechanical properties have also been investigated.     

Fast responsive poly(acrylic acid‐co‐N‐isopropyl acrylamide) hydrogels based on new crosslinker

Novel dual temperature‐ and pH‐sensitive poly(acrylic acid‐co‐N‐isopropylacrylamide), AA/NIPAAm, hydrogels were successfully prepared by chemical crosslinking with crosslinkers. Copolymers of AA/NIPAAm were crosslinked in the presence of different mol % of N,N‐methylene bisacrylamide (MBA) and melamine triacrylamide (MAAm) as crosslinkers by bulk radical polymerization. The resultant xerogels were characterized by extracting the soluble fractions and measuring the equilibrium water content. Lower critical solution transition temperatures (LCST) were measured by DSC. The properties of crosslinked AA/NIPAAm series are evaluated in terms of compositional drift of polymerization, heterogeneous crosslinking, and chemical structure of the relevant components. Soluble fractions of the crosslinked networks were reduced by varying the MAAm and MBA concentrations. The influence of environmental conditions such as temperature and pH on the swelling behavior of these polymeric gels was investigated. The swelling behaviors of the resulting gels show pH sensitivity. The prepared MAAm type AA/NIPAAm hydrogels exhibited a more rapid deswelling rate than MBA type AA/NIPAAm hydrogels in ultra pure water in response to abrupt changes from 20°C to 50°C. The results of this study provide valuable information regarding the development of dual stimuli‐sensitive hydrogels with fast responsiveness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

具有各向异性结构的聚乙烯醇水凝胶的制备及性能表征

首先对聚乙烯醇（PVA）水溶液进行定向冷冻-解冻制备出具有各向异性结构的PVA水凝胶,然后采用⁶⁰Co-γ射线对其进行辐射交联以提高其热稳定性和力学性能。扫描电子显微镜（SEM）结果显示PVA水凝胶保持了各向异性的微观结构,在平行冷冻方向上具有相对规整的取向结构,在垂直冷冻方向上呈现均匀孔洞结构。热稳定性测试结果表明：辐射剂量在30~70 kGy范围内、定向冷冻次数为1次的PVA水凝胶在60℃热水浴中保持凝胶状态长达10 h以上。对辐射交联PVA水凝胶进行拉伸力学性能测试,凝胶具有各向异性的拉伸性能,且拉伸强度和弹性模量均有提高,辐射剂量为10 kGy、定向冷冻次数为3次的PVA水凝胶（DFT-RC-3-10）在垂直定向冷冻方向上的拉伸强度和弹性模量分别为0.86和0.10 MPa。     

Study on a new polymer/graphene oxide/clay double network hydrogel with improved response rate and mechanical properties

pH‐ and temperature‐responsive double network hydrogels (DN hydrogels) were prepared by using poly (N‐isopropylacrylamide) (PNIPAM) as a tightly crosslinked network (1st network), polyacrylic acid (PAA) as a loosely crosslinked network (2nd network), with clay and graphene oxide as effective crosslinkers and reinforcing fillers. The structure and morphology of the hydrogels were characterized by SEM, FTIR, DSC, and TGA. The synergetic effects of clay, GO and DN structure on various physical properties were investigated. With the increasing of crosslinking densities, the swelling ratios of DN hydrogels gradually decreased by increasing the contents of graphene oxide and PAA. While the DN hydrogels had much better mechanical properties than that of the conventional chemically cross‐linked PNIPAM hydrogels. POLYM. ENG. SCI., 55:1361–1366, 2015. © 2015 Society of Plastics Engineers     

Hydrogels reinforced with nanoclays with improved response rate

Two series of semiinterpenetrating networks (SIPN) based on linear hydrophilic poly(vinyl alcohol) (PVA) and thermo‐responsive poly(N‐isopropylacrylamide) (PNIPA), physically crosslinked with inorganic clay, are presented. The hydrogels with different crosslinking densities were prepared by varying the content of clay from 1 to 6 wt % and contained linear interpenetrant, PVA in the range of 0.5–1.5 wt %. The effect of clay content on swelling/deswelling behavior and phase transition in PNIPA gels, as well as the feasibility of reinforcing the gels with high molecular weight PVA, were analyzed. The thermal response of hydrogels, followed by DSC, confirmed that the insertion of hydrophilic PVA did not have a significant effect on the onset of the volume phase transition temperature, while the response was faster. The equilibrium degree of swelling of SIPNs and PNIPA hydrogels was in the range of 9–79 and decreased with increasing content of clay. The internal morphology and surface wettability of the hydrogels were investigated by scanning electron microscope analysis and contact angle measurements, respectively. The network structural parameters of the PNIPA and SIPN nanocomposites hydrogels, such as the average molecular weight between crosslinks, M_c, and effective crosslinking density, N_e, were determined by dynamic mechanical analysis. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44535.     

Synergistic strengthening of composite films by crosslinking graphene oxide reinforcement and poly(vinyl alcohol) with dicarboxylic acids

High‐strength plastic materials with excellent biodegradability, non‐toxicity and economically wide availability are in high demand. Herein, we demonstrate graphene oxide (GO) composite of poly(vinyl alcohol) (PVA) as a potential bioplastic material by chemical crosslinking. For a potential bioplastic material, PVA has to be addressed for its high water absorbing capacity along with improvement in tensile strength and thermal stability. These issues were addressed by enhancing the interfacial binding between PVA and GO, covalent bonds between the two being introduced by crosslinking with dicarboxylic acids, namely succinic acid (SuA) and adipic acid (AdA). Crosslinking of neat PVA with dicarboxylic acids also resulted in enhanced swelling resistance and thermal stability. The greatest improvement in tensile strength and swelling resistance was observed for a GO crosslinked with diacids due to the synergistic effect of reinforcement and crosslinking. Improvements of 225 and 234% in the tensile strength of PVA (31.19 MPa) were observed for 5% GO–PVA samples crosslinked with 6.25 mmol AdA and 7.5 mmol SuA, respectively. For the same samples, water uptake was 44 and 29%, respectively, compared to the non‐crosslinked PVA (359%). © 2017 Society of Chemical Industry     

Hydrogels of starch/carboxymethyl cellulose crosslinked with sodium trimetaphosphate via reactive extrusion

Hydrogels are materials with advantages in specific applications, such as, retention of food active compounds. This work aims to develop starch (S)/carboxymethyl cellulose (CMC) hydrogels with porous structure, using reactive extrusion to promote crosslinking with sodium trimetaphosphate (STMP). The expansion, porosity, degree of substitution, gel fraction, swelling properties, and FTIR are studied, comparing S, S/CMC, S/STMP, and S/CMC/STMP formulations. Samples containing STMP present the same degree of substitution (0.050 ± 0.001). Higher porosity and percentage of open pores are observed in the mixed hydrogel (S/CMC/STMP). Crosslinking increase the swelling capacity at pH 7, and this property, just like the gel fraction, are sensitive to pH variations. The hydrogel S/CMC present the highest swelling rate compared with the other samples, suggesting strong interaction between components. The reactive extrusion process is efficient to produce starch and starch/CMC hydrogels crosslinked with STMP and the overall results demonstrate the advantages of the mixed hydrogel.     

Crosslinked poly(vinyl alcohol)/carboxymethyl chitosan hydrogels for removal of metal ions and dyestuff from aqueous solutions

Hydrogels composed of poly(vinyl alcohol) (PVA) and carboxymethyl chitosan (CMCh) were synthesized via ultraviolet (UV) irradiation that can be used in several industrial fields. Several analysis tools were used to characterize the physical and thermal properties of CMCh/PVA hydrogels namely FT‐IR, scanning electron microscope (SEM), XRD, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). TGA results showed that CMCh/PVA hydrogels are thermally more stable than CMCh and their thermal stability increases as PVA content increases in the hydrogel. Also, DSC results showed that CMCh/PVA hydrogels are at least partial miscible blends. Moreover, the swelling behavior of the CMCh/PVA hydrogels was studied in different buffered solutions and in different salt solutions at various concentrations. CMCh/PVA hydrogels swell much more than CMCh especially at alkaline pH. Both metal and dye uptake were studied for CMCh/PVA hydrogels. The hydrogels adsorb much more dyestuff and metal ions like Cu²⁺, Cd²⁺, and Co²⁺ than CMCh itself. Much dyestuff and metal ions are adsorbed by the hydrogels as PVA content increases in the hydrogel. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Pullulan–STMP hydrogels: a way to correlate crosslinking mechanism,structure and physicochemical properties

Rheological and swelling properties of hydrogels based on pullulan crosslinked with sodium trimetaphosphate (STMP) are explained according to various polymer and crosslinking agent concentrations using ³¹P-nuclear magnetic resonance study. This method has allowed determining the amount of all the species present in the medium when varying both pullulan and STMP concentrations. We have clearly demonstrated with a good agreement by both ³¹P-NMR and rheology that a critical STMP concentration occurs which is function of pullulan concentration. This typical crosslinking agent concentration delimitates the maximum of gel structure together with the minimum of swelling.     

Comparison the properties of PVA/Na+‐MMT nanocomposite hydrogels prepared by physical and physicochemical crosslinking

A novel physicochemical crosslinked nanocomposite hydrogel based on polyvinyl alcohol (PVA) and natural Na‐montmorillonite (Na⁺‐MMT) was synthesized by chemical crosslinking of nanocomposite hydrogel followed by a freezing‐thawing process. The effects of physical crosslinking, as well as physicochemical crosslinking, on the structure, morphology, and properties (thermal, mechanical, swelling, and deswelling) of nanocomposite hydrogels were investigated and compared with each other. The structure and morphology of nanocomposites were studied by Fourier transform infrared, X‐ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy techniques. The thermal and mechanical properties of nanocomposites that were affected by physical and physicochemical crosslinking were evaluated by thermogravimetric analysis, differential scanning calorimeter, dynamic mechanical analysis, hardness test, and Water vapor transmission rate (WVTR) experiments. The results showed that the physicochemical crosslinking of a PVA nanocomposite leads to a reduction in crystallinity and melting temperature, as well as an increase in the Hardness and WVTR compared to a physically crosslinked PVA nanocomposite hydrogel. The swelling and deswelling experiments were performed using a gravimetric method, and it was shown that controlled crosslinking of PVA nanocomposite hydrogel with glutaraldehyde causes the swelling ratio to increase and the cumulative amount of water loss to decrease. The swelling (sorption) and deswelling (desorption) kinetics data for physically and physicochemical crosslinking of nanocomposite hydrogels were fitted with a fickian model. It is concluded that through control crosslinking of PVA nanocomposite can lead to a hydrogel with higher swelling capacity than that is in conventional PVA nanocomposite hydrogel. POLYM. COMPOS., 37:897–906, 2016. © 2014 Society of Plastics Engineers     

Influence of Natural Crosslinkers on Chitosan Hydrogels for Potential Biomedical Applications

Chitosan (CH) is a very well-known biopolymer that has been widely used for the development of biomaterials with a wide range of applications in the biomedical field, such as the preparation of hydrogels, owing to its outstanding anti-inflammatory, antibacterial and antifungal properties, biocompatibility and biodegradability, although they present limited mechanical properties. Chemical crosslinking is one of the most recurrent strategies for the reinforcement of these structures and, above all, crosslinking with natural-origin compounds that do not compromise their biocompatibility is considered a hot topic in this research field. D-fructose (F), obtained from the hydrolyzation and further isomerization of starch, an abundant raw material and genipin (G), which is extracted from the fruits of Gardenia jasminoides Ellis are used as natural crosslinkers. Chitosan-based hydrogels crosslinked with each crosslinking agent are prepared and characterized through Fourier transform infrared (FTIR) spectroscopy, crosslinking and swelling degree determination, rheological, microstructural, and biological studies. The results demonstrate that crosslinking with G is more beneficial for chitosan-based hydrogels since these samples showed more compact structures and better rheological performance. Additionally, excellent biological in vitro behavior due to the crosslinking with G, unlike that of F.     

Preparation and characterization of films based on crosslinked blends of gum acacia,polyvinylalcohol, and polyvinylpyrrolidone-iodine complex

In an attempt to develop iodine-release systems based on polymeric blend for biomedical applications, our research group prepared blends of gum acacia (GA), polyvinylalcohol (PVA), and polyvinylpyrrolidone-iodine (PVP-I) complex. The blends of GA/PVA and GA/PVA/PVP-I prepared from the aqueous solutions of the polymers were crosslinked with glutaraldehyde to increase the water resistance of the films and to improve their thermal and mechanical properties. The crosslinked GA/PVA and GA/PVA/PVP-I blend films were characterized by FTIR spectroscopy, DSC, and TGA. The swelling behavior of the prepared blends was investigated and crosslinked GA/PVA blend films were found to be pH sensitive. The properties of PVP-I containing blends differed from those prepared without it probably due to the formation of an intermolecular interaction between PVP-I and the hydroxy-polymers. The results indicated that after crosslinking the blends showed improvement in water resistance, thermal, and mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Zwitterionic hydrogels crosslinked with novel zwitterionic crosslinkers: Synthesis and characterization

Two novel zwitterionic sulfobetaine dimethacrylate crosslinkersN,N-bis(methacryloxyethyl)-N-methyl-N-(3-sulfopropyl)ammonium (CL1) and N,N-bis(methacryloxyethyl)-N-methyl-N-(4-sulfobutyl)ammonium (CL2) betaines were synthesized and used for preparation of zwitterionic hydrogels formed from N-(methacryloxyethyl)-N,N-dimethyl-N-(3-sulfopropyl)ammonium betaine (SBDMA) via redox-initiated free-radical polymerization. The commercially available crosslinkers N,N′-methylene bisacrylamide (BIS) and ethylene glycol dimethacrylate (EDMA) were also used. Equilibrium water content, sorption degree, diffusion coefficient of water, state of water, degree of crosslinking and mechanical properties were determined for hydrogels crosslinked using different crosslinking conditions. A minor difference in the spacer length between the charged moieties in CL1 and CL2 crosslinkers, respectively, was shown to influence the hydrogel properties. The CL1 and CL2 crosslinkers with chemical structure similar to SBDMA resulted in hydrogels with higher stiffness, mechanical strength and crosslink density compared to hydrogels crosslinked by BIS and EDMA. This difference was assigned to suppression of the compositional drift during the hydrogel formation when crosslinkers with chemical structure similar to monomer were used. PolySBDMA hydrogels exhibited a low adhesion of RAT-2 fibroblasts-like cells.     

Pluronics as crosslinking agents for collagen: novel amphiphilic hydrogels

A series of Pluronic samples (L61, L121, F68, F108) were investigated as collagen crosslinking agents to determine their ability to improve the Young's modulus of a collagen hydrogel, while simultaneously serving as surfactants for single‐walled carbon nanotubes (SWNTs). The crosslinked collagen matrices were prepared by blending type I bovine collagen with either Pluronics or SWNTs dispersed in an aqueous Pluronic solution and crosslinked utilizing carbodiimide chemistry. The resulting material was a crosslinked collagen hydrogel with sufficient mechanical strength to be manipulated and transferred without damaging the matrix. Differential scanning calorimetry confirmed a change in the denaturation temperature for hydrogels prepared using Pluronic or Pluronic/SWNT solutions. Water uptake analysis confirmed the crosslinked matrices to be hydrogels. These collagen hydrogels produced with Pluronics as the crosslinking agents exhibited a Young's modulus 3 to 9 times greater than collagen hydrogels produced in the absence of any crosslinking agent, regardless of polymer molecular weight. However, non‐covalent incorporation of SWNTs was not found to affect the Young's modulus of the resulting collagen hydrogels at the incorporation levels achieved with the Pluronics surfactants. Copyright © 2010 Society of Chemical Industry     

Effects of crosslinking degree of poly(vinyl alcohol) hydrogel in aqueous solution: kinetics and mechanism of copper(II) adsorption

Recently, a renewed interest in hydrogels for heavy metal removal of wastewater has been growing because of embarking opportunities in industrial applications. One of the most interesting hydrogels potentially used as absorbent is poly(vinyl alcohol) (PVA), owing to its biocompatibility. In this study, the adsorption capacity of copper(II) ion onto PVA hydrogel (PVAH) adsorbents with different crosslinking degrees of 1, 3 and 5 % from aqueous solution was investigated. The PVAH adsorbents were prepared from PVA, using glutaraldehyde as a crosslinking agent. Their properties were determined by Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), and water absorption measurement. The results showed that PVA was crosslinked with glutaraldehyde. It exhibited an equilibrium swelling ratio in the range of 195–250 %, depending on the crosslinking degree with different PVAH structures defined from SEM micrographs. The adsorption capacity of copper(II) ion onto PVAH adsorbents was investigated and found that higher crosslinking degree decreased the absorption capacity. This behavior is due to the decrease in reactive sites, resulting in the decrease of interaction between copper(II) ion and PVA. Besides, the adsorption capacity also depended on contact time, pH and temperature. The adsorption process followed pseudo-second-order kinetic, having a 0.99 correlation coefficient. Intraparticle diffusion was confirmed by the adsorption mechanism controlled by particle and film diffusions.     

3D gel printing of magnetic hydrogel scaffolds assisted by in-situ gelation in a water level-controlled crosslinker bath

Polyvinylalcohol/chitosan (PVA/CS) is an excellent dual-network hydrogel material, but some significant challenges remain in fabricating composites with specific structures. In this study, 3D gel printing (3DGP) combined with a water-level controlled crosslinker bath was proposed for the rapid in-situ prototyping of PVA/CS/Fe₃O₄ magnetic hydrogel scaffolds. Specifically, the PVA/CS/Fe₃O₄ hydrogels were extruded into the crosslinker water to achieve rapid in-situ gelation, improving the printability of hydrogel scaffolds. The effect of the PVA/CS ratio on the rheological and mechanical properties of dual-network magnetic hydrogels was evaluated. The printing parameters were systematically optimized to facilitate the coordination between the crosslinking water bath and printer. The different crosslinking water baths were investigated to improve the printability of PVA/CS/Fe₃O₄ hydrogels. The results showed that the printability of the sodium hydroxide (NaOH) crosslinker was significantly better than that of sodium tripolyphosphate (TPP). The magnetic hydrogels (PVA: CS= 1: 1) crosslinked by NaOH had better compressive strength, swelling rate, and saturation magnetization of 1.17 MPa, 92.43%, and 22.19 emu/g, respectively. The MC3T3-E1 cell culture results showed that the PVA/CS/Fe₃O₄ scaffolds promoted cell adhesion and proliferation, and the scaffolds crosslinked by NaOH had superior cytocompatibility. 3DGP combined with a water-level controlled crosslinker bath offers a promising approach to preparing magnetic hydrogel materials.     

Chitosan,itaconic acid and poly(vinyl alcohol) hybrid polymer networks of high degree of swelling and good mechanical strength

Chitosan is a biodegradable, non‐toxic, biocompatible polymer convenient for use in drug delivery. In this study, hybrid polymeric networks (HPNs) based on chitosan, itaconic acid and poly(vinyl alcohol) (PVA) were prepared and characterized. Chitosan was dissolved in itaconic acid in order to obtain ionic crosslinking with the dicarboxylic acid. In the second step, this chitosan/itaconic acid network was mixed with PVA and chemically crosslinked with glutaraldehyde. The chitosan/itaconic acid ratio was kept constant, while the concentrations of PVA and glutaraldehyde were varied. All samples were characterized using swelling studies, dynamic mechanical analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, X‐ray diffraction and scanning electron microscopy. The equilibrium degrees of swelling obtained for the HPNs were higher than most of the values reported for chitosan hydrogels obtained by dissolving chitosan in acetic acid or HCl aqueous solutions. This method of synthesis also resulted in hydrogels with better mechanical properties and thermal stability. By changing the PVA content and the degree of crosslinking, it is possible to finely tune the properties of the HPNs, which could make them suitable as potential matrices in controlled drug delivery. Copyright © 2010 Society of Chemical Industry     

Materials,preparation, and characterization of PVA/MMT nanocomposite hydrogels: A review

This article presents a review of studies on materials, preparation, properties, and characterization of polyvinyl alcohol (PVA) nanocomposite hydrogels. The structure and properties of Montmorillonite, the nanoclay used in the manufacture of PVA nanocomposites and techniques for making PVA nanocomposite hydrogels have been reviewed. The characterization techniques such as Fourier transform infrared spectroscopy (FT‐IR), Differential scanning calorimetry (DSC), Dynamic mechanical analysis (DMA), Scanning electron microscopy, Transmission electron microscopy (TEM), X‐ray diffraction (XRD) are also studied. The XRD patterns and TEM images have proven the intercalated and exfoliated structures of PVA nanocomposite hydrogels that is due to the presence of nanoclay layers. Investigation of FT‐IR spectra shows the bonding formation between OH and silanol groups of PVA and Montmorillonite. Also, the results of DSC and DMA indicated a decrease in crystallinity and the glass transition temperature of PVA by the incorporation of nanoclay, while the loss modulus is increased compared to that of pure PVA. POLYM. COMPOS., 38:1086–1102, 2017. © 2015 Society of Plastics Engineers