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).     

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.     

Preparation and performance of nanocomposite hydrogels based on different clay

To look for economic substitute of Laponite, two kinds of clay minerals purchased in China were chosen to prepare nanocomposite hydrogels. Structure, morphology, temperature-sensitivity and swelling behavior were investigated by XRD, SEM, DSC and gravimetric method. In comparison with hydrogel cross-linked by Laponite XLG, the hydrogel with hectorite (Lvjie trademark) or montmorillonite (G-105) as cross-linker exhibited higher swelling ratios as well as faster response rate. In the case of temperature-sensitivity, the volume phase transition temperature (VPTT) of the hydrogels cross-linked by hectorite (Lvjie trademark) and montmorillonite (G-105) was 31–33 °C, slightly different from hydrogels with Laponite XLG. The hydrogel with montmorillonite (G-105) was brown and fragile. The hectorite (Lvjie trademark) appeared as optimal substitute of Laponite in hydrogels because the prepared hydrogel exhibited high swelling ratio, rapid response rate, excellent thermal responsibility, good dispersion in hydrogel matrix and high storage modulus.     

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.     

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.     

High tensibility and pH-responsive swelling of nanocomposite hydrogels containing the positively chargeable 2-(dimethylamino)ethyl methacrylate monomer

Positively chargeable nanocomposite hydrogels (NC gels) were synthesized by in situ copolymerization of acrylamide (AM) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) in an aqueous suspension of hectorite clay Laponite XLS. The stability of the Laponite suspension containing DMAEMA was monitored by its transmittance, viscosity and zeta potential. The polymerization was initiated either by redox or UV radiation to fabricate the NC gels. Elongation at break and tensile strength decreased with increasing DMAEMA content in monomers up to 17 mol%. As expected from the protonation of DMAEMA, the NC gels containing more than 5 mol% DMAEMA showed pH-responsive swelling; the gels were swollen at pH < 4 and shrunken at pH > 4. In comparison with the redox-initiated NC gels, the UV-initiated NC gels possessed a more homogeneous structure with higher transmittance, better mechanical properties, and a larger equilibrium swelling ratio at pH < 4.     

Adjusting Some Properties of Poly(methacrylic acid) (Nano)Composite Hydrogels by Means of Silicon-Containing Inorganic Fillers

The present work aims to show how the main properties of poly(methacrylic acid) (PMAA) hydrogels can be engineered by means of several silicon-based fillers (Laponite XLS/XLG, montmorillonite (Mt), pyrogenic silica (PS)) employed at 10 wt% concentration based on MAA. Various techniques (FT-IR, XRD, TGA, SEM, TEM, DLS, rheological measurements, UV-VIS) were used to comparatively study the effect of these fillers, in correlation with their characteristics, upon the structure and swelling, viscoelastic, and water decontamination properties of (nano)composite hydrogels. The experiments demonstrated that the nanocomposite hydrogel morphology was dictated by the way the filler particles dispersed in water. The equilibrium swelling degree (SDe) depended on both the pH of the environment and the filler nature. At pH 1.2, a slight crosslinking effect of the fillers was evidenced, increasing in the order Mt < Laponite < PS. At pH > pKa_MAA (pH 5.4; 7.4; 9.5), the Laponite/Mt-containing hydrogels displayed a higher SDe as compared to the neat one, while at pH 7.4/9.5 the PS-filled hydrogels surprisingly displayed the highest SDe. Rheological measurements on as-prepared hydrogels showed that the filler addition improved the mechanical properties. After equilibrium swelling at pH 5.4, G’ and G” depended on the filler, the Laponite-reinforced hydrogels proving to be the strongest. The (nano)composite hydrogels synthesized displayed filler-dependent absorption properties of two cationic dyes used as model water pollutants, Laponite XLS-reinforced hydrogel demonstrating both the highest absorption rate and absorption capacity. Besides wastewater purification, the (nano)composite hydrogels described here may also find applications in the pharmaceutical field as devices for the controlled release of drugs.     

Equilibrium swelling behavior and elastic properties of polymer–clay nanocomposite hydrogels

Nanocomposite hydrogels were prepared by free‐radical polymerization of the monomers acrylamide (AAm), N,N‐dimethylacrylamide (DMA), and N‐isopropylacrylamide (NIPA) in aqueous clay dispersions at 21°C. Laponite XLS was used as clay nanoparticles in the hydrogel preparation. The hydrogels based on DMA or NIPA monomers exhibit much larger moduli of elasticity compared with the hydrogels based on AAm monomer. Calculations using the theory of rubber elasticity reveal that, in DMA‐clay or NIPA‐clay nanocomposites, both the effective crosslink density of the hydrogels and the functionality of the clay particles rapidly increase with increasing amount of Laponite up to 10% (w/v). The results suggest that DMA‐clay and NIPA‐clay attractive interactions are stronger than AAm‐clay interactions due to the formation of multiple layers on the nanoparticles through hydrophobic associations. It was also shown that, although the nanocomposite hydrogels do not dissolve in good solvents such as water, they dissolve in dilute aqueous solutions of acetone or poly(ethylene oxide) of molecular weight 10,000 g/mol, demonstrating the physical nature of the crosslink points. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

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.     

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.     

Nanoclay Reinforced Self‐Cross‐Linking Poly(N‐Hydroxyethyl Acrylamide) Hydrogels with Integrated High Performances

Despite recent significant progress in fabricating tough hydrogels, it is still a challenge to realize high strength, large stretchability, high toughness, rapid recoverability, and good self‐healing simultaneously in a single hydrogel. Herein, Laponite reinforced self‐cross‐linking poly(N‐hydroxyethyl acrylamide) (PHEAA) hydrogels (i.e., PHEAA/Laponite nanocomposite [NC] gels) with dual physically cross‐linked network structures, where PHEAA chains can be self‐cross‐linked by themselves and also cross‐linked by Laponite nanoplatelets, demonstrate integrated high performances. At optimal conditions, PHEAA/Laponite NC gels exhibit high tensile strength of 1.31 MPa, ultrahigh tensile strain of 52.23 mm mm^?1, high toughness of 2238 J m^?2, rapid self‐recoverability (toughness recovery of 79% and stiffness recovery of 74% at room temperature for 2 min recovery without any external stimuli), and good self‐healing properties (strain healing efficiency of 42%). The work provides a promising and simple strategy for the fabrication of dual physically cross‐linked NC gels with integrated high performances, and helps to expand the fundamentals and applications of NC gels.     

Rheological properties of thermoresponsive nanocomposite hydrogels

Highly elastic and robust nanocomposite hydrogels based on N‐isopropylacrylamide (NIPAM) and cationic (3‐acrylamidopropyl) trimethylammonium chloride (AMPTMA) were synthesized by photopolymerization. Nanoscopic clay, laponite XLS, was added in the gels during the synthesis. The effect of a hydrophobic salt, lithium bis(trifluoromethane) sulfonimide (LiNTf₂), and clay content on the viscoelastic properties, swelling ratio, and stiffness of the nanocomposite hydrogels were investigated as a function of temperature. Synthetic clay served as a multifunctional cross‐linker, producing hydrogels with enhanced elastic properties. Anionic NTf₂ binds to the cationic comonomer units and significantly affected the viscoelasticity and thermal properties. DSC measurements showed that the volume phase transition temperature and its enthalpy changed with the clay content and with introducing the cationic comonomer (AMPTMA) in the PNIPAM network. With the addition of either laponite XLS or the comonomer and 5 mM solution of LiNTf₂, a fourfold and fivefold increase in elastic modulus was obtained, respectively, compared to that of the homopolymer PNIPAM hydrogel. With increasing the temperature from 20 to 45°C for the copolymer gel with 10% AMPTMA in 5 mM LiNTf₂, the elastic modulus grew 15 times larger. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43123.     

智能型聚甲基丙烯酸凝胶的合成与表征

以甲基丙烯酸(MAA)为单体,过硫酸钾(KPS)为引发剂,无机纳米粒子Laponite或者N,N'-亚甲基双丙烯酰胺(BIS)为交联剂,通过原位自由基聚合的方法分别合成了纳米复合聚甲基丙烯酸凝胶和传统型聚甲基丙烯酸凝胶,并利用红外、流变、溶胀性能测试、剥离强度测试等手段对凝胶的性能进行了表征。比较了在不同单体(MAA)含量、体系pH值下,Laponite含量和BIS含量对物理交联法和化学交联法制备的凝胶的交联密度的影响,以及两种凝胶溶胀度随溶液pH值以及温度的变化关系。研究表明:增加单体MAA的含量、增加交联剂Laponite或BIS的含量,以及降低体系的pH值有利于凝胶网状结构的形成。化学交联的传统型聚甲基丙烯酸凝胶具有明显的pH敏感性和温度敏感性,而物理交联的纳米复合聚甲基丙烯酸凝胶具有良好的粘结性能。     

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.     

An inorganic cross-linked quadruple shape memory hydrogel with high mechanical performance

Shape memory hydrogels (SMHs) have been the subject of great interest in recent years. However, there were few reports on the simultaneous multiple shape memory and high mechanical performance. Therefore, a novel nanocomposite (NC) hydrogel poly (acrylic acid)/Chitosan/ Laponite (PAA/CS/Laponite) was developed by using Laponite as physical cross-linker. In order to achieve three temporary shapes, the PAA/CS/Laponite was soaked in iron chloride hexahydrate (FeCl₃), sodium hydroxide (NaCl) and sodium hydroxide (NaOH) respectively to (a) form metal coordination; (b) gain the chains entanglement of chitosan; (c) get the microcrystalline structure of chitosan. The maximum shape fixity ratio of PAA/CS/Laponite can reach 100% in 1 minute and it can be restored its original shape within 5 minutes. Moreover, PAA/CS/Laponite showed excellent mechanical performance. The maximum tensile and compressive strengths were 0.73 MPa and 13.1 MPa. By comparison with PAA/CS obtained from our previous work, the tensile strength, elongation at break and compressive strength increased by 2.21 times, 1.46 times, and 3.26 times respectively. Scanning electron microscopy (SEM) showed that the obtained sample has uniform honeycomb network structures which can effectively explain why the gel has strong mechanical performance. These characteristics make PAA/CS/Laponite have huge application potential in reality.     

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.     

Preparation and evaluation of thermo-reversible copolymer hydrogels containing chitosan and hyaluronic acid as injectable cell carriers

Poly(N-isopropylacrylamide) end-capped with a carboxyl group (PNIPAM-COOH) was grafted to chitosan for synthesizing thermo-reversible chitosan-g-poly(N-isopropylacrylamide) (CPN), which was further grafted with hyaluronic acid (HA) to form hyaluronic acid-g-CPN (HA-CPN). PNIPAM-COOH, CPN and HA-CPN formed injectable free-flowing aqueous solutions and exhibited reversible sol-to-gel phase transition (above 5% polymer concentration) at 30 °C. Chemical properties and temperature-dependent physical properties of the polymer hydrogels, such as rheological behavior, phase transition kinetics, and water content were characterized in detail. The mechanical stiffness of hydrogels increased with the presence of chitosan in the copolymer, but decreased after conjugation with HA. Chitosan and HA grafting also endowed higher water content and resistance to volume contraction during phase change of the copolymer solution. In vitro cell culture experiments with chondrocytes and meniscus cells in HA-CPN hydrogel showed beneficial effects on the cell phenotypic morphology, proliferation, and differentiation. Progressive tissue formation was demonstrated by monotonic increases in extracellular matrix contents and mechanical properties.     

Synthesis and characterization of thermoresponsive N-isopropylacrylamide/methacrylated pullulan hydrogels

Thermosensitive hydrogels were prepared by free radical polymerization starting from a methacrylated pullulan derivative (acting as the cross-linker) and using N-isopropylacrylamide (NIPAAM) as the monomer. Several hydrogels were obtained by changing the monomer to cross-linker ratio. A significant thermosensitivity was observed only when the molar amount of NIPAAM incorporated in the network was at least eight times higher that of methacrylate groups on pullulan. The hydrogel with high amount of NIPAAM deswells more than 80% after the T-jump. The lower critical solution temperature of thermosensitive hydrogels decreases with increasing amount of NIPAAM. The mechanical properties of the hydrogels are strongly affected by the percentage of incorporated NIPAAM and by the temperature.