Improved mechanical and swelling behavior of the composite hydrogels prepared by ionic monomer and acid-activated Laponite

A composite hydrogel (CH) with much improved mechanical and swelling properties was prepared using an ionic monomer and acid-activated Laponite XLS which was used as a cross-linking agent. Addition of acid-activated clay solved the gelation problem when ionic monomers were added to clay mineral dispersions. Reaction of Laponite XLS with sulfuric acid yielded amorphous silica. A dispersion of the acid-activated Laponite and the monomers was used to synthesize composite hydrogels by in-situ polymerization. The FT-IR spectra and rheological results of the composite hydrogels demonstrated the formation of a network. The equilibrium swelling ratios of composite hydrogels (> 6000 g/g) were more than 18 times larger than traditional organic cross-linked hydrogels. The moduli G′ and G″ in the observed frequency range were about 4 and 10 times larger than those of organic cross-linked hydrogel (OR gel). The improvement in both the equilibrium swelling ratio and mechanical strength was attributed to the homogeneous cross-linked network structure.     

聚(N-异丙基丙烯酰胺)/海藻酸钠/黏土复合水凝胶的制备及其性能

以无机黏土为交联剂制备了聚（N-异丙基丙烯酰胺）/海藻酸钠/黏土（PINPA/SA/clay）复合水凝胶,通过红外光谱、X射线衍射和SEM对凝胶的结构和形态进行了表征,并研究了凝胶的溶胀动力学和力学性能。结果表明：黏土的结晶结构已被破坏,黏土规整的片层被剥离并在凝胶中无序分布,起到交联剂的作用;随黏土含量的增加,凝胶网络交联密度增加,孔洞的孔径减小,溶胀速度下降。另外,PINPA/SA/clay凝胶显示了良好的力学性能,断裂伸长率超过1000%。     

通过RAFT聚合方法合成具有高强度和高溶胀率的纳米水凝胶

为了得到具有高强度和高溶胀率的纳米水凝胶(NCgels),N-异丙基丙烯酰胺通过可逆加成断裂链转移(RAFT)聚合的方法,插层在含有质量分数为0.25%～15%的可扩展的有机化的蒙脱土(Clay-S)层间并交联。结果表明,与传统水凝胶相比,该水凝胶的强度和溶胀性能得到了很大提高,并且对温度的变化具有较快的响应速率。以质量分数为5%的蒙脱土,链转移剂的质量分数为0.5%制备的纳米水凝胶为例,该水凝胶在20℃的溶胀率为450,而传统水凝胶在相同温度时的溶胀率仅为20;该水凝胶在1min内失去75%的水,在4min内失去约90%的水,而传统水凝胶在15min内仅失去66%左右的水。     

Network chain density and relaxation of in situ synthesized polyacrylamide/hectorite clay nanocomposite hydrogels with ultrahigh tensibility

Nanocomposite hydrogels (NC gel) D-AM and S-AM were synthesized through in situ polymerization of acrylamide (AM) with hectorite clays of Laponite RD and RDS, respectively. The tensile performance of the NC gel was observed at different crosshead speeds and all of the NC gels exhibited an extremely high tensibility, e.g., the elongation at break even higher than 4000%, except for two samples with the lowest Laponite content of 1 w/v%. Strong tensile hysteresis was observed in the elongation-reversion curve, indicating a slow relaxation in the NC gels. Dynamic moduli G′ and G″ within linear viscoelasticity illustrated that the network structure was formed in these gels with the junction of Laponite platelets. The Laponite RD showed stronger gelation capability than the tetrasodium pyrophosphate modified Laponite RDS. The relaxation modulus G(t) for the NC gels was found to be similar to the slow rubber relaxation with the critical exponent n of about 0.16, much lower than 0.66-0.71 for the critical gel at the sol-gel transition. In comparison, the chemically cross-linked hydrogel showed almost no relaxation during the same time interval. The effective network chain density of the NC gel was determined from equilibrium shear modulus, which was evidently lower than that of the chemically cross-linked hydrogels. The present results reveal that the high deformability of these NC gels comes from their low effective network chain density with moderate relaxation.     

Nanocomposite Hydrogels with High Mechanical Strength and High Swelling Ratio by RAFT Polymerization

Nanocomposite hydrogels (NC gels) have been prepared based on poly(N-isopropylacrylamide) (PNIPAM) containing 0.25-15 wt% of the expandable synthetic hectorite Laponite XLS (Clay-S) by reversible addition fragmentation chain transfer (RAFT) polymerization. The swelling behaviors were investigated and the hydrogels by RAFT polymerization (RAFT gels) showed accelerated shrinking kinetics and higher swelling ratio comparing with conventional hydrogels (CGel). This could be attributed to the presence of dangling chains mainly caused by chain transfer reagent (CTA), which could retard the crosslinking reaction rate greatly. Furthermore, the NC gels have stronger mechanical strength than CGel. The presence of Clay-S does not affect the value of the lower critical solution temperature (LCST).     

A promising porous polymer-nanoclay hydrogel nanocomposite as water reservoir material: synthesis and kinetic study

A porous hydrogel nanocopmposite based on biodegradable salep and montmorillonite (MMT) was synthesized by in-situ free radical graft polymerization of salep chains with acrylic acid (AA) monomers. The chemical structure and morphological properties of the prepared hydrogels was evaluated by FTIR spectroscopy, X-ray diffraction and SEM techniques. The effect of reaction variables such as crosslinker, initiator, monomer and clay contents on equilibrium water absorption capacity and swelling kinetic of hydrogel were investigated and optimized. Swelling behavior of the hydrogels in various pH and saline solutions was also studied. Incorporation of MMT into hydrogel matrix caused the formation of porous hydrogel network. These porous structures resulted in higher water uptake capacity and swelling rate in hydrogel nanocomposite in comparison to neat hydrogel sample. Moreover, hydrogel nanocomposite sample exhibited proper salt and pH-sensitive behavior. High swelling capacity and rate, porosity, salt and pH sensitivity make hydrogel nanocomposite a profitable candidate in agricultural and horticultural applications, such as water reservoir system.     

High clay content nanocomposite hydrogels with surprising mechanical strength and interesting deswelling kinetics

A series of high hectorite content nanocomposite Poly (N-isopropylacrylamide), (PNIPAAm), hydrogels have been successfully synthesized by choosing a special kind of hectorite (Laponite XLS) modified by tetrasodium pyrophosphate. It was found that these hydrogels show surprising mechanical properties (i.e. tensile strength: 1 MPa, elongation at break: 1400%) and complicated deswelling behavior, which are due to the high clay content of the hydrogels and ionic dispersant contained in Laponite XLS, respectively.     

Mechanically strengthened double network composite hydrogels with high water content: a preliminary study

A novel poly[(1,2-ethylenediamino) (2-hydroxy-1,3-propanedily) chloride]/ Laponite/polyacrylic acid (PEDAECH/Laponite/PAA) hydrogel was synthesized by two-step solution polymerization combining nanocomposite (NC) strategy with double network (DN). The structural characteristics of resulting hydrogels were investigated by Fourier Transform infrared spectrum (FTIR) and Transmission Electron Microscopy (TEM). A core shell structure was observed in PEDAECH/Laponite composite. The swelling and mechanical strength of the resulting hydrogels were measured when PEDAECH/Laponite composite dose varied. The novel hydrogel achieved a high compressive stress of 148.0 KPa even in higher water content of 98.7% when the PEDAECH/Laponite composite dose is 0.05 ml, the dose of AA was 3.6 ml, N, N??-methylenebisacrylamide (MBAM) dose was 0.04 wt% (based on the weight of AA) and reaction temperature was 0 °C, Based on the cyclic compression studies, there is a small decline in the maximum stress of the hydrogels at the fixed strain of 45% even under three cyclic compressions.     

Novel metronidazole-loaded hydrogel as a gastroretentive drug delivery system

A metronidazole-loaded hydrogel was synthesized by free radical polymerization using dimethylaminoethyl methacrylate (DMAEMA) monomer and triethyleneglycol dimethacrylate (TEGDA) and methylene bisacrylamide (MBA) as cross-linkers. The DMAEMA hydrogels were cross-linked with 5 and 10% MBA or with 0.1, 0.5, 1 and 4% TEGDA as cross-linking agents. Ammonium persulfate and tetramethyl ethylene diamine were used as initiator and catalyst, respectively. The prepared hydrogels were characterized, and the effect of cross-linking agent content on the swelling behavior and in vitro drug release of hydrogels was investigated. The results of X-ray diffractometry, differential scanning calorimetry and Fourier transform infrared spectroscopy studies indicated that the prepared hydrogels possessed an amorphous morphology and there was not any interaction between the hydrogel polymers and metronidazole as drug, which resulted in the dependence of drug release on the physicochemical characteristics of hydrogel such as swelling, polymer erosion, and surface morphology. According to the results, the hydrogel containing 0.5% TEGDA which was prepared by freeze-drying method exhibited a porous structure with a high swelling ratio and displayed a sustained and complete drug release. It could be concluded that the hydrogel developed by this facile method is a good candidate with a potential for use in gastroretentive drug delivery systems.     

Strengthening mechanism of poly(acrylamide)/graphene oxide/laponite dual nanocomposite hydrogels

Laponite or graphene oxide (GO) is usually used as a multifunctional crosslinker or a nanofiller to improve the nanocomposite gel strength. To explore the strengthening mechanism of GO/Laponite‐based dual nanocomposite hydrogels, we synthesized a dual nanocomposite hydrogel through in situ polymerization of acrylamide (AM) in the dispersion of GO and Laponite. The interactions between GO and Laponite were confirmed by rheological test. GO and Laponite nanosheets were exfoliated well and dispersed uniformly in the hydrogels at low concentration of GO. Crosslinking network and thermal behaviors were investigated with respect to the concentration of GO and Laponite. The gel exhibited a high mechanical strength of 391 kPa with extensibility of 1420% and a high toughness of 2.58 MJ/m³, which was expected to be applied in biological engineering field. GO is not a much more effective agent than Laponite due to formation of GO aggregates in high concentration of GO. This work provides a guidance for the synthesis of tough dual nanocomposite hydrogels. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44963.     

Preparation of hydrogels composed of poly(vinyl alcohol) and polyethyleneimine and their electrical response

Semi‐ and full‐interpenetrating polymer network (IPN) hydrogels composed of poly(vinyl alcohol) and polyethyleneimine (PEI) were prepared to investigate the bending behavior under the electric response. To find out the characteristics of the hydrogel in the medium, swelling ratio, and rate and water state of the hydrogels were measured. The swelling ratio of the semi‐IPN hydrogels increased with PEI content in the matrix, whereas that of full‐IPN hydrogels dramatically decrease with increase of PEI contents in the hydrogels. In the water state of hydrogel, the bound water and free water of semi‐IPN hydrogels increased with PEI weight ratio. The full‐IPN hydrogels show the lower free water content in comparison with the semi‐IPN hydrogel. The IPN hydrogels exhibited bending angle change in response to external stimulus such as voltage, the bending angle increased with PEI concentration. In addition, the repeated bending behaviors according to the magnitude of the applied electric field revealed that the bending angle is reversible without collapse of formation of hydrogel in all samples. Thus, the hydrogels will be useful as novel modulation systems in the field of artificial organ and matrix for drug delivery. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and dual response of ionic nanocomposite hydrogels with ultrahigh tensibility and transparence

Ionic nanocomposite hydrogels cross-linked by hectorite Laponite XLS with high tensile strength and ultrahigh tensibility were successfully synthesized for the first time via in situ copolymerization of N-isopropylacrylamide (NIPAm) and sodium methacrylate (SMA). The pH and temperature response, transparency, and mechanical properties of the ionic hydrogels were investigated. The results showed that the addition of only 2 mol% of SMA endowed the nanocomposite hydrogels with pH response, while the temperature response remained in the whole pH range. All the as-prepared hydrogels, even with 10 mol% of SMA, demonstrated transparency higher than 75%. The tensile strength evidently decreased from 60 kPa to 45 kPa when the SMA content was higher than 6 mol%. The elongation at break increased with increasing SMA content and 2800% was achieved for the sample containing 10 mol% of SMA. The effective network chain density was estimated from the tensile stress at elongation of 200% and the equilibrium storage modulus. The low chain density was the intrinsic origin of the ultrahigh tensibility for these ionic NC gels. This work provides a new way to prepare dual responsive hydrogels with ultrahigh tensibility and high transparency.     

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。     

Water sorption behavior of CMC/PAM hydrogels prepared by γ-irradiation and release of potassium nitrate as agrochemical

Novel types of highly swelling CMC/PAM hydrogels have been prepared by grafting cross-linked polyacrylamide (PAM) chains onto carboxymethylcellulose (CMC) via a free radical polymerization method using γ-irradiation. The prepared CMC/PAM hydrogels were characterized by FT-IR spectral analysis. The AM content and irradiation dose had a direct effect on gel content of CMC/PAM hydrogels and inverse effect on their swelling ratio. The hydrogels showed enormous swelling in aqueous medium and displayed swelling characteristics which were highly dependent on the chemical composition of the hydrogel, pH and ionic strength of the medium in which the hydrogel was immersed. The results were supported by morphological properties of CMC/PAM hydrogels by using SEM. The kinetics of water uptake and the water transport mechanism were studied as a function of the CMC/AM ratio into the prepared hydrogel. The release rate of potassium nitrate entrapped within the CMC/PAM matrix increased by enhancing its loading %, and decreased with lowering AM content and irradiation dose.     

聚（N-异丙基丙烯酰胺）／海藻酸钠／粘土复合水凝胶的制备及溶胀动力学研究

以无机粘土为交联剂制备了聚（N-异丙基丙烯酰胺）／海藻酸钠／粘土（PINPA／SA／Clay）复合水凝胶,通过红外光谱、X射线衍射对凝胶的结构进行了表征,结果表明：粘土的结晶结构已被破坏,粘土规整的片层被剥离并在凝胶中无序分布,起到交联剂的作用;随粘土含量的增加,凝胶网络交联密度增加,溶胀速度下降。在不同温度下对不同粘土含量的凝胶进行了溶胀动力学测试,表明在低于其相转变温度时,凝胶的扩散类型为non－Fickian扩散。     

Mechanical properties and drug release rate of poly(vinyl alcohol)/poly(ethylene glycol)/clay nanocomposite hydrogels: Correlation with structure and physical properties

Poly(vinyl alcohol)/poly(ethylene glycol) hydrogels containing curcumin as a drug and the various amounts of a montmorillonite nanoclay are prepared using the freezing–thawing method. Nanoclay quantity influence on the physicomechanical properties and the drug release rate of the hydrogel as well as relationship between them is investigated. X-Ray diffraction and Atomic force microscopy analysis reveal the nanoclays have an intercalation structure in the hydrogel, and the hydrogel crystallization decreases with increasing the nanoclay inclusion. From the SEM micrographs observation, it was revealed that due to the presence of the nanoclay in the hydrogel, its porosity decreased. The naonoclay has an amount-depended dual effect on the hydrogel swelling. The swelling mechanism is a normal Fickian diffusion for all the hydrogel samples. Strong physical interactions between the nanoclays and the polymer chains in the nanocomposite hydrogels are evidenced by the rheological studies. These interactions lead to significant reinforcement of the hydrogel tensile strength, intensified by the nanoclay amount. Interestingly, the nanoclays show the capability of accelerating and, also, decelerating the drug release of the hydrogel. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47843.     

Swelling behavior and structural characteristics of polyvinyl alcohol/montmorillonite nanocomposite hydrogels

A series of nanocomposite hydrogels based on polyvinyl alcohol containing 0–10 wt % of the organically modified montmorillonite clay were prepared by freezing‐thawing cyclic method. The morphology of the nanocomposite hydrogels was observed by the scanning electron microscopy technique. The structural properties were determined by measuring the network mesh size, crosslinking density, and average molecular weight of polymer chains between crosslinks. The swelling behavior and the effect of swelling medium temperature on the swelling kinetics and characteristics of the nanocomposite hydrogels were also investigated. The results showed that two structural characteristics i.e., network mesh size and average molecular weight of polymer chains between crosslinks have inverse dependence on the clay loading level in the nanocomposite hydrogel, while crosslinking density shows completely direct dependence. Swelling measurements demonstrated a linear relation between the degree of swelling and the square root of immersion time at all swelling medium temperatures. The results indicated that the swelling characteristics of the nanocomposite hydrogels including the equilibrium degree of weight and volume swelling and the equilibrium water content were decreased by increasing the quantity of the clay incorporated into the hydrogel as well as by decreasing the temperature of swelling medium. While, the time required to reach to the equilibrium condition, as another swelling characteristic of the hydrogels, exhibited a completely opposite behavior. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

A transparent Laponite polymer nanocomposite hydrogel synthesis via in-situ copolymerization of two ionic monomers

The poor stability of clay dispersion in the presence of ionic species presents a challenge for preparing ionic clay polymer nanocomposite (CPN) transparent hydrogel with desired strength. The transparent and tough ionic hydrogels are highly demanded as potential material options for contact lens or ophthalmic implants. Here we reported an ionic CPN hydrogel with combined high transparency and mechanical properties synthesized via in-situ copolymerization of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) and acrylic acid (AA) in Laponite dispersion. The ionic transparent CPN can have strength of 189 kPa and a strain of 1780% which is likely a result of uniformly dispersed Laponite platelets in the structure. A synergistic interaction between acylamino and sulfonic acid functional groups was found to play a key role in the stable dispersion of Laponite. This work provided a new way to prepare transparent ionic CPN hydrogels.     

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.     

High-strength,ultrastretchable hydrophobic association hydrogel reinforced by tailored modified carboxymethyl cellulose

A new pathway to construct high-strength, ultrastretchable hydrogels based on tailored modified carboxymethyl cellulose (TMCMC)and hydrophobic association(HPA) system was investigated. TMCMC was prepared from degradation of carboxymethyl cellulose (CMC)/N,N′-methylene bisacrylamide (MBA) chemical cross-linked hydrogels. The residual double bonds of TMCMC, confirmed by ¹H-NMR and FTIR analysis, reacted with acrylamide in HPA to form TMCMC/HPA hydrogels, and the homogeneous and fine spatial network structure of TMCMC/HPA hydrogel could be observed by scanning electron microscopy. Rheological analysis revealed that the coexistence of physical and chemical crosslinking in TMCMC/HPA hydrogels. Further studies showed that TMCMC/HPA hydrogel with MBA content of 0.5 wt% has outstanding mechanical properties, and its fracture stress, elongation and tensile strength reach 1.17 MPa, 3717.05% and 15.68 MJ·m⁻³, respectively. Moreover, the hydrogel displayed good swelling resistance and stable strain electrical signal response.