Physicochemical modification of hydroxylated polymers to develop thermosensitive double network hydrogels

Due to the unique biophysicochemical characteristics of synthesized superhydrophilic poly[N-[tris(hydroxymethyl)methyl] acrylamide] (PTHMMA) and poly(vinyl alcohol) (PVA), in this study, we investigated the preparation of physically and chemically crosslinked thermosensitive double network (DN) hydrogels with superior mechanical properties. The effect of the combination of PTHMMA with PVA was further explored experimentally and theoretically. Moreover, adjusting the lower critical solution temperature (LCST) of PTHMMA/PVA DN hydrogels in the phosphate buffer was achieved by chemical alteration and crosslinking of water-soluble polymers. Changing the composition and the extent of ether/acetal linkages altered the LCST based on hydrophilic/hydrophobic composition, which decreased the complexity of adjusting hydrogels' temperature sensitivity. PTHMMA-comprising hydrogels were found to have non-Fickian and super case ΙΙ transport characters. Moreover, the construction of shrunken PVA at high temperature was tailored by introducing PTHMMA into the network to permit a relaxed drug release of indomethacin (IND) at 37°C and pH 7.4. Finally, the tensile strength, the equilibrium water content, thermo-sensitivity, and cell viability behaviors suggest that these materials can be tailored for potential applications as biomaterials.     

Synthesis of multifunctional high strength,highly swellable,stretchable and self‐healable pH‐responsive ionic double network hydrogels

The multifunctional double network (DN) soft hydrogels reported here are highly swellable and stretchable pH‐responsive smart hydrogel materials with sufficient strength and self‐healing properties. Such multifunctional hydrogels are achieved using double crosslinking structures with multiple physical and chemical crosslinks. They consist of a copolymer network of acrylamide (AM) and sodium acrylate (Na‐AA) and other reversible network of poly(vinyl alcohol)–borax complex. They were characterized by Fourier transform IR analysis and studied for their hydrogen bonding and ionic interaction. The degree of equilibrium swelling was observed to be as high as 5959% (at pH 7.0) for a hydrogel with AM/Na‐AA = 25/75 wt% in the network (GS‐6 sample). The highest degree of swelling was observed to be 6494% at pH 8.5. The maximum tensile strength was measured to be 1670, 580 and 130 kPa for a DN hydrogel (GS‐2 sample: AM/Na‐AA =75/25 wt% with 20, 40 and 60 wt% water content, respectively). The self‐healing efficiency was estimated to be 69% for such a hydrogel. These multifunctional DN hydrogels with amalgamation of many functional properties are unique in hydrogel materials and such materials may find applications in sensors, actuators, smart windows and biomedical applications. © 2018 Society of Chemical Industry     

Facile synthesis of extremely biocompatible double‐network hydrogels based on chitosan and poly(vinyl alcohol) with enhanced mechanical properties

An easy and ecofriendly method for designing double‐network (DN) hydrogels based on chitosan and poly(vinyl alcohol) (PVA) with high mechanical performance is described. When covalent bonds in the networks are used as crosslinking agents in the achievement of a higher mechanical strength, the irreversible deformation of these hydrogels after a large force is applied is still one of the most important obstacles. To overcome this problem, we used physical crosslinking for both networks. The mechanical strength, surface morphology, and cytotoxicity of the films were studied by tensile testing, scanning electron microscopy analysis, and an MTT assay. The synthesized chitosan–PVA DN hydrogels showed a large improvement in the tensile strength to 11.52 MPa with an elongation of 265.6%. The surface morphologies of the films demonstrated the effective interactions between the two networks and a suitable porosity. Also, because of the use of a natural polymer and honey as a plasticizer, the cell culture indicated that the synthesized DN hydrogels had good biocompatibility (with 327.49 ± 11.22% viability) and could be used as capable biomaterials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45752.     

A novel designed high strength and thermoresponsive double network hydrogels cross-linked by starch-based microspheres

A new kind of nanocomposite double network (DN) hydrogels consisting of starch-based microspheres cross-linked oligo (ethylene glycol) methyl ether methacrylate) (POEGMA) as soft network and diethylene glycol dimethacrylate (DEGMA) cross-linked poly(2-(2-methoxyethoxy) ethyl methacrylate (PMEO₂MA) as brittle network (named POEGMA/PMEO₂MA DN hydrogels) were synthesized by a two-step free radical polymerization. The chemical structure of DN hydrogels was characterized by ¹H NMR, the temperature sensitive properties were measured by the lower critical solution temperature (LCST) tested by UV-Vis spectrophotometer as a function of temperature, the mechanical properties were measured by tensile test. The LCST showed only one transition at 20.2 °C measured by the transmittance variation as a function of the ambient temperature from 5 to 70 °C. The fracture toughness and the hysteresis behaviors were also tested and showed that they were affected by the content of starch-based microspheres cross-linker in the soft POEGMA network, the content of small-molecular cross-linkers and monomer concentration in the brittle PMEO₂MA network. They are related to perfect network and physical adherence and entanglements between microspheres and the networks brought by AAS microspheres, the increment of “sacrifice bond” brought by DEGMA and polymer chains entanglement brought by MEO₂MA. These studies will provide theoretical support for the future research of DN hydrogel and macromolecular microspheres cross-linked hydrogel.     

Chitosan-based double network hydrogels with self-healing and dual-responsive shape memory abilities

Chitosan-based single network hydrogels with imine bonds have excellent self-healing capability, while poor mechanical properties limit their applications. Here, chitosan-polyacrylamide-based double network hydrogels were prepared via in situ free-radical polymerization of acrylamide in the presence of N-carboxyethyl chitosan (CEC) and dibenzaldehyde-terminated telechelic poly(ethylene glycol), which had excellent mechanical properties, self-healing, and dual-responsive shape memory abilities. The maximum tensile strength and elongation at break could reach 460 kPa and 4600%, respectively. Meanwhile, owing to the reversibility of imine bonds, elongation and strength at break of hydrogels could heal by 84.2 and 93.2% under alkali stimulation at 35 °C, respectively. Furthermore, the hydrogels also had good shape memory abilities for pH-stimuli responsiveness of the imine bonds and metal ions stimuli responsiveness of CEC. The prepared chitosan-based functional hydrogels have great potential application prospects in tissue scaffolds, actuators, and wearable devices. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48247.     

Highly Stretchable,Strain-Sensitive,and Antifreezing Macromolecular Microsphere Composite Starch-Based Hydrogel

Starch-based hydrogel is widely used as an excellent biocompatibility and biodegradability material. However, due to the disadvantages of poor mechanical properties, brittleness, and low stretchability attribute that remains a challenge to prepare multifunctional starch hydrogel integrating high stretchability, strength, and conducting capacity. In this study, macromolecular microspheres with various wettability are successfully incorporated into the hydrogel prepared using the carboxymethyl starch and polyacrylamide cross-linked by Fe³⁺ and covalent cross-linker, respectively. The obtained double-network (DN) hydrogel performs good mechanical properties (the fracture stress 483 ± 38 kPa and the elongation at break 1615 ± 25%). Impressively, the obtained DN hydrogels by solvent soaking still maintain excellent mechanical strength and flexibility at −40 °C. Furthermore, it can be assembled to be a resistance-type strain sensor to detect multiscale strain. Therefore, the strategy can shed light on the preparation of multifunctional starch-based hydrogel for broad applications.     

Ultrastretchable,Super Tough,and Rapidly Recoverable Nanocomposite Double‐Network Hydrogels by Dual Physically Hydrogen Bond and Vinyl‐Functionalized Silica Nanoparticles Macro‐Crosslinking

It remains a challenge to develop tough hydrogels with recoverable or healable properties after damage. Herein, a new nanocomposite double‐network hydrogel (NC‐DN) consisting of first agar network and a homogeneous vinyl‐functionalized silica nanoparticles (VSNPs) macro‐crosslinked polyacrylamide (PAM) second network is reported. VSNPs are prepared via sol‐gel process using vinyltriethoxysilane as a silicon source. Then, Agar/PAM‐SiO₂ NC‐DN hydrogels are fabricated by dual physically hydrogen bonds and VSNPs macro‐crosslinking. Under deformation, the reversible hydrogen bonds in agar network and PAM nanocomposite network successively break to dissipate energy and then recombine to recover the network, while VSNPs in the second network could effectively transfer stress to the network chains grafted on their surfaces and maintain the gel network. As a result, the optimal NC‐DN hydrogels exhibit ultrastretchable (fracture strain 7822%), super tough (fracture toughness 18.22 MJ m^‐3, tensile strength 431 kPa), rapidly recoverable (≈92% toughness recovery after 5 min resting at room temperature), and self‐healable (can be stretched to 1331% after healing) properties. The newly designed Agar/PAM‐SiO₂ NC‐DN hydrogels with tunable network structure and mechanical properties by multi‐bond crosslinking provide a new avenue to better understand the fundamental structure‐property relationship of DN hydrogels and broaden the current hydrogel research and applications.     

聚环氧乙烷对PAMPS/PAM双网络水凝胶结构和性能的影响

采用紫外光引发聚合制备了含聚环氧乙烷（PEO）的聚(2-丙烯酰胺-2-甲基丙磺酸)(PAMPS）/聚丙烯酰胺（PAM）双网络（DN）水凝胶。使用扫描电子显微镜（SEM）观察了PAMPS单网络水凝胶的结构;测定了PEO改性前后双网络水凝胶的压缩及拉伸性能。PEO改性DN凝胶的第一网络网孔上由于PEO片晶结构引起不同程度的褶皱,这种褶皱起支撑作用;PEO的分子量达到5万时,褶皱的支撑作用最佳,DN凝胶的力学性能最佳;DN凝胶的力学性能随PEO加入量先提高后下降,在PEO加入量为0.1%时,PEO片晶结构加固了DN凝胶的物理交联点,力学性能达到最大,压缩应力达到31.6 MPa;加入更多的PEO阻碍了第一网络的凝胶化,造成网络结构的不连续,从而使DN凝胶的力学性能下降。     

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.     

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     

Autonomic self-healing in covalently crosslinked hydrogels containing hydrophobic domains

Self-healing hydrogels suffer from low mechanical strength due to their reversible breakable bonds which may limit their use in any stress-bearing applications. This deficiency may be improved by creating a hybrid network composed of a combination of a physical network formed via reversible crosslinks and a covalent network. Here, we prepared a series of hybrid hydrogels by the micellar copolymerization of acrylamide with 2 mol % stearyl methacrylate (C18) as a physical crosslinker and various amounts of N,N′-methylenebis(acrylamide) (BAAm) as a chemical crosslinker. Rheological measurements show that the dynamic reversible crosslinks consisting of hydrophobic associations surrounded by surfactant micelles are also effective within the covalent network of the hybrid hydrogels. A significant enhancement in the compressive mechanical properties of the hybrid gels was observed with increasing BAAm content. The existence of an autonomous self-healing process was also demonstrated in hybrid gels formed at low chemical crosslinker ratios. The largest self-healing efficiency in hybrids was observed in terms of the recovered elastic modulus, which was about 80% of the original value.     

Robust hydrogel of regenerated cellulose by chemical crosslinking coupled with polyacrylamide network

Regenerated cellulose/polyacrylamide (RC/PAAm) double network (DN) hydrogels are composed of cellulose crosslinked by epichlorohydrin (ECH) and chemical-crosslinked PAAm. The prepared RC/PAAm DN hydrogels present enhanced strength, good shape recovery property, excellent energy dissipation properties, decreased equilibrium water content, and low equilibrium swelling ratio (SR). The compressive strength and modulus of RC/PAAm hydrogel are about 4.3 and 11.5 times compared to that of RC hydrogel, respectively. Intriguingly, the chemical crosslinking between ECH and cellulose chains could increase the distance between cellulose chains. Consequently, the increasing molar ratio of ECH to glucose leads to larger SRs and decreased mechanical strength of the hydrogels. Additionally, higher PAAm contents lead to more densely crosslinked networks, and thus decreasing the SRs and improving the mechanical strength of the hydrogels. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47811.     

Conductive double-network hydrogel for a highly conductive anti-fatigue flexible sensor

Improving the mechanical properties of hydrogels is a prime example of their large-scale, diverse applications. Herein, we report a one-pot method for preparing a double network system hydrogel where the polyvinyl alcohol served as the first polymer backbone, acrylamide as the second network, and N, N′-Methylenebisacrylamide as the cross-linker, and the prepared hydrogels presented excellent mechanical properties with 1168% tensile strain and 598 kPa compressive strength. Through the metal–ligand bonds, an electrolyte solution containing Cu²⁺ was introduced into the hydrogel, which exhibits higher water retention than other electrolyte-containing hydrogels. Specially, the hydrogel was able to retain water for 8 h under extreme dry conditions at 60°C. The GF value was calculated to be 0.124 when the strain was 0%–64.2%. Furthermore, the hydrogel flexible sensor can detect changes in ambient temperature. When the ambient temperature rises, its relative resistance also tends to rise. In conclusion, this hydrogel sensor offers great potential applications in flexible sensors.     

A Facile Strategy for Synergistic Integration of Dynamic Covalent Bonds and Hydrogen Bonds to Surmount the Tradeoff between Mechanical Property and Self-Healing Capacity of Hydrogels

The self-healable hydrogels have attracted increasing attention due to their promising potential for ensuring the durability and reliability of hydrogels. However, they still face a serious challenge to achieve a positive balance between mechanical and healing performance, especially for the room-temperature autonomous self-healable hydrogels. Herein, a simple but efficient strategy to fabricate a kind of dynamic boronate and hydrogen bonds dual-crosslinked double network (DN) hydrogel based on a UV-initiated one-pot in situ polymerization of N-acryloyl glycinamide (NAGA) in polyvinyl alcohol-borax slime is reported. The obtained PN-x/PB hydrogels, especially with high content of PNAGA, are shown to possess high mechanical strength, high toughness, and fatigue-resistance properties as well as excellent self-healability at room temperature (nearly 88% self-healing efficiency based on the strain compression test), due to the dynamic DN structure, and the combination of the adaptable and reconfigurable dynamic boronate bonds and hydrogen bonds. Considering the easily available materials and simple preparation process, this novel strategy should offer not only a kind of dynamic DN hydrogel with robust mechanical performance and high self-healing capability, but also enrich the methodological toolbox for synergistic integration of dynamic covalent bonds and hydrogen bonds to surmount the tradeoff between mechanical properties and self-healing capacity of hydrogels.     

Super tough double network hydrogels and their application as biomaterials

The double network (DN) technique, developed by authors’ group, provides an innovative and universal pass way to fabricate hydrogels with super high toughness comparable to rubbers. The excellent mechanical performances of DN hydrogels originate from the specific combination of two networks with contrasting structures. The first brittle network serves as sacrificial bonds, which breaks into small clusters to efficiently disperse the stress around the crack tip into the surrounding damage zone, while the second ductile polymer chains act as hidden length, which extends extensively to sustain large deformation. Based on the principle of DN hydrogel, the author’s group recently has developed several novel systems and techniques, which has greatly expanded the practical accessibility of DN technique for practical use. The DN principle and the DN gel have already attracted much attention in the soft matter community. Inspired by the DN principle, many research groups have also designed and developed some innovative hydrogels with large enhancement in their mechanical strength and toughness. Some tough hydrogels fabricated by the DN technique also exhibit good biocompatibility and low friction resistance with promising prospective in industrial and medicine fields, especially for load-bearing artificial soft tissues such as artificial cartilage. In this feature article, we address the major concept and toughening mechanism of DN gel, then we describe some recent novel hydrogel systems based on the DN concept, and finally the applicability of DN gel as soft biomaterials is discussed.     

Agar/PAAc-Fe<Superscript>3+</Superscript> hydrogels with pH-sensitivity and high toughness using dual physical cross-linking

As promising structural materials, various tough hydrogels have been developed recently by incorporating various kinds of bonds. An important challenge is to use dual physical cross-linking to develop both toughness and self-recovery in a single material. Here we report smart, strain-responsive hydrogels composed of a fully physically linked agarose/poly(acrylic acid)-ferric ion (agar/PAAc-Fe³⁺) double network (DN) with high toughness and pH-sensitivity. These hydrogels were fabricated in a one-pot reaction to generate dual physical cross-linking through, first, a hydrogen-bonded cross-linked agarose network, and, second, a physically linked PAAc-Fe³⁺ network via Fe³⁺ coordination interactions. The DN hydrogels possessed high toughness, with breaking strain of 1130%, fast self-recovery properties in ambient conditions (100% recovery in 30 min) and self-healing properties (the healed hydrogels can be manually stretched up to 700% of their original length after self-healing for 60 h from the cut-off state). In addition, the hydrogels exhibited pH-sensitivity due to the dissociation of ionic coordinate bonds between –COO^? ions of the PAAc chains and Fe³⁺ ions. Double-layer hydrogel strips with two different concentrations of PAAc formed a “C”-shaped material when initially immersed in pH 7 solution and then soaked in a pH 3 solution. These characteristics make the hydrogels attractive candidates for tissue engineering, soft actuators and flexible electronics.     

A novel fabrication method of temperature-responsive poly(acrylamide) composite hydrogel with high mechanical strength

High strength, stimuli-responsive poly(acrylamide) composite hydrogels (PAAm CH gels) were prepared by grafting polymerization of acrylamide (AAm) onto temperature-sensitive core–shell microgels. These microgels, composing of poly(N-isopropylacrylamide) as core and polyvinylamine (PVAm) as shell, were used as both initiator and crosslinker to form a robust three-dimensional network via bonding the poly(acrylamide) (PAAm) backbone. The CH gels exhibited a remarkably rapid shrinking rate and transmittance switch in response to the environmental temperature change, which the conventional chemically cross-linking PAAm hydrogels (PAAm OR) were short of. Even compared to the bulk PNIPAAm hydrogels (PNIPAAm OR) crosslinked with N,N′-methylenebisacrylamide (MBA), the CH gels were featured with faster responsive rate, which could be attributed to the formation of interconnected water transportation channels between the microspheres and PAAm gel matrix due to the fast shrinking of microgels. Moreover, the effects of microgel species and content on swelling and mechanical properties of CH gels were also systematically investigated. The results elaborated that the CH gels could be compressed almost 99% without breaking and completely recovered their original shape when the stress was removed. And the optimized compressive strength of CH gels could be up to 21.94 MPa. Based on the analysis of CH gel mechanical properties, the influence of microsphere content on effective network chains density of CH gels was discussed through rheology measurements. Finally, the essential reinforcement on mechanical properties was mainly contributed to the homogeneous microstructure of hydrogel network and the energy dissipation mechanism of microgels in gel matrix.     

Highly Mechanical and Fatigue‐Resistant Double Network Hydrogels by Dual Physically Hydrophobic Association and Ionic Crosslinking

Double network (DN) hydrogels with high strength and toughness are considered as promising soft materials. Herein, a dual physically cross‐linked hydrophobic association polyacrylamide (HPAAm)/alginate‐Ca²⁺ DN hydrogel is reported, consisting of a HPAAm network and a Ca²⁺ cross‐linked alginate network. The HPAAm/alginate‐Ca²⁺ DN hydrogel exhibits excellent mechanical properties with the fracture stress of 1.16 MPa (3.0 and 1.7 times higher than that of HPAAm hydrogel and HPAAm/alginate hydrogel, respectively), fracture strain of 2604%, elastic modulus of 71.79 kPa, and toughness of 14.20 MJ m^?3. HPAAm/alginate‐Ca²⁺ DN hydrogels also demonstrate self‐recovery, notch‐insensitivity, and fatigue resistance properties without any external stimuli at room temperature through reversible physical bonds consisting of hydrophobic association and ionic crosslinking. As a result, the dual physical crosslinking would offer an avenue to design DN hydrogels with desirable properties for broadening current applications of soft materials.     

A Dual‐Crosslinked Strategy to Construct Physical Hydrogels with High Strength,Toughness, Good Mechanical Recoverability,and Shape‐Memory Ability

A novel type of physical hydrogel based on dual‐crosslinked strategy is successfully synthesized by micellar copolymerization of stearyl methacrylate, acrylamide, and acrylic acid, and subsequent introduction of Fe³⁺. Strong hydrophobic associations among poly(stearyl methacrylate) blocks form the first crosslinking point and ionic coordination bonds between carboxyl groups and Fe³⁺ serve as the second crosslinking point. The mechanical properties of the hydrogel can be tuned in a wide range by controlling the densities of two crosslinks. The optimal hydrogel shows excellent mechanical properties (tensile strength of ≈6.8 MPa, elastic modulus of ≈8.0 MPa, elongation of ≈1000%, toughness of 53 MJ m^?3) and good self‐recovery property. Furthermore, owing to stimuli responsiveness of physical interaction, this hydrogel also shows a triple shape memory effect. The combination of two different physical interactions in a single network provides a general strategy for designing of high‐strength hydrogels with functionalities.     

Tough and recoverable triple‐network hydrogels based on multiple pairs of toughing mechanisms with excellent ionic conductivity as stable strain sensors

The emerging applications of hydrogels in flexible devices require it possess multifunctional properties including stable mechanical and functions under various deformations or external environments. Herein, a multifunctional polyvinyl alcohol/M‐alginate/PAM hydrogel with very excellent mechanical properties and sensing functions was fabricated by introducing multiple pairs of toughing mechanisms into triple network (TN). The multiple supramolecular physical networks work as sacrificial networks to toughen the materials when hydrogel deforms. The broken bonds can reform upon unloading endowing the recovery of hydrogels' properties and functions with the assistance of the elastic covalent network. The optimal TN hydrogels are extremely tough (a fracture strength of 512 kPa, a fracture toughness of 3 MJ/m³) and recoverable from fatigue damage (~77% toughness recovery after 5 min resting at room temperature). The presence of abundant ionic species endows the tough and recoverable TN hydrogels high ionic conductivity and high sensitivity as strain sensors. Moreover, such TN hydrogels with multi‐bond crosslinking in three networks can potentially guarantee stable mechanical and sensor functions under various deformations or external environments compared to the DN candidates. This work provides a simple strategy for fabricating multifunctional hydrogels with high stability to fulfill its flexible devices applications. POLYM. ENG. SCI., 59:1657–1666 2019. © 2019 Society of Plastics Engineers