CN112920427A - Anti-fatigue hydrogel and preparation method and application thereof - Google Patents

Anti-fatigue hydrogel and preparation method and application thereof Download PDF

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CN112920427A
CN112920427A CN202110106029.8A CN202110106029A CN112920427A CN 112920427 A CN112920427 A CN 112920427A CN 202110106029 A CN202110106029 A CN 202110106029A CN 112920427 A CN112920427 A CN 112920427A
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hydrogel
fatigue
freezing
precursor
preparation
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CN112920427B (en
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刘吉
张宽
陈兴梅
薛羽
张加俊
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Southern University of Science and Technology
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Abstract

The invention provides an anti-fatigue hydrogel and a preparation method and application thereof. The preparation method comprises the following steps: (1) directionally freezing and drying the precursor solution to obtain a hydrogel precursor; (2) soaking the hydrogel precursor obtained in the step (1) in water to obtain the anti-fatigue hydrogel; the preparation method further comprises a step of regulating and controlling the crystal domain, and the method for regulating and controlling the crystal domain comprises the following steps: adding any one or the combination of at least two of crystal nucleus into the precursor solution, applying external field force in the directional freezing process or carrying out temperature-controlled quenching treatment on the hydrogel precursor. The anti-fatigue hydrogel provided by the invention has better toughness and fatigue resistance, is suitable for long-time use, has a simple preparation method and a wide application system, and can be used for large-scale production of the anti-fatigue hydrogel.

Description

Anti-fatigue hydrogel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of hydrogel, and particularly relates to anti-fatigue hydrogel and a preparation method and application thereof.
Background
Hydrogels are aggregates of water molecules and polymer networks, are recognized as ideal materials for artificial tissues, drug delivery and biological research models, and have been widely used in advanced fields such as medical devices and bioelectronic devices in recent years, including wearable hydrogel electronics, oral hydrogel devices, stretchable hydrogel optical fibers, hydrogel adhesives, hydrogel soft robots, and the like. The development of the functional hydrogel is helpful for promoting a man-machine co-fusion technology by combining the rapid development of a plurality of fields such as artificial intelligence, robots, big data, intelligent medical treatment and the like, and provides powerful support for the development of new biological electronics, the development of personalized medical instruments, rehabilitation treatment and the like. Therefore, the development of hydrogel material system applicable to medical devices and bioelectronics has become one of the most advanced and valuable researches in multiple cross-fields of materials, machinery, chemistry, mechanics and biomedicine in recent years.
Although hydrogel material systems have a wide development prospect in the above-mentioned new scientific and technological fields, many challenges still face practical applications, such as low mechanical strength, poor toughness, easy fatigue fracture during long-term use, and the like. Over the last decade, researchers have developed a variety of high-toughness hydrogel systems, such as two-network hydrogels, nano-and micro-composite hydrogels, hydrogels based on dynamic host-guest interactions, as well as triblock copolymers and hydrophobically-associated hydrogels, among others.
For example, CN109485877A discloses a high temperature resistant high toughness organic hydrogel and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out polymerization reaction on 2-acrylamide-2-methylpropanesulfonic acid, N' -methylene bisacrylamide, an initiator and a reducing agent in an aqueous solution system to obtain single-network hydrogel; dipping the single-network gel into a solution containing acrylamide, N' -methylene bisacrylamide and a photoinitiator, and carrying out photoinitiated polymerization to obtain a double-network hydrogel; and (3) soaking the double-network hydrogel in a lithium chloride/ethylene glycol mixed solution until the mass balance is achieved, so as to obtain the organic hydrogel. CN104448161A discloses a modified gelatin nano-microsphere crosslinked organic composite hydrogel and a preparation method thereof, wherein the preparation method comprises the following steps: preparing modified gelatin nano microspheres by a two-step solvent removal method, respectively dissolving acrylamide monomers and the modified gelatin nano microspheres in deionized water, and stirring for 5-30 min in an inert atmosphere; adding a catalyst, stirring for 5-10 min in an inert atmosphere, and then adding an initiator; carrying out free radical polymerization reaction for 12-48 h at the temperature of-40 ℃; and soaking the reaction product in deionized water at 20 ℃, replacing the deionized water every 5-8 hours, and continuing for 48-72 hours to obtain the organic composite hydrogel. CN107417855A discloses an organic-inorganic hybrid emulsion particle toughened hydrophobically associating hydrogel and a preparation method thereof, which comprises the steps of preparing organic-inorganic hybrid emulsion particles and organic-inorganic hybrid emulsion particle toughened hydrophobically associating hydrogel. The inorganic core of the hybrid emulsion particle is silicon dioxide, and the organic shell is self-polymerization or copolymer of butyl acrylate, hexyl methacrylate, octyl methacrylate or lauryl methacrylate and styrene, acrylonitrile or methyl methacrylate.
These high-toughness hydrogel materials dissipate energy through the introduction of dynamic bonds, so that the hydrogel has higher toughness. However, under cyclic load, the mechanical properties of the high-toughness hydrogel are sharply reduced, and the toughening mechanism gradually fails, so that the high-toughness material also gradually fails in the dynamic load process. Therefore, how to obtain a hydrogel which has better mechanical properties and fatigue resistance and is suitable for long-term use has become a problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an anti-fatigue hydrogel and a preparation method and application thereof. The preparation method adopts a directional freezing process and regulates and controls the crystal domain in the hydrogel, so that the prepared anti-fatigue hydrogel has an ordered oriented structure and a proper nanocrystalline domain, can effectively improve the toughness strength and the anti-fatigue performance of the hydrogel, and is suitable for long-time use.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing an anti-fatigue hydrogel, comprising the steps of:
(1) directionally freezing and drying the precursor solution to obtain a hydrogel precursor;
(2) soaking the hydrogel precursor obtained in the step (1) in water to obtain the anti-fatigue hydrogel;
the preparation method further comprises a step of regulating and controlling the crystal domain, and the method for regulating and controlling the crystal domain comprises the following steps: adding any one or the combination of at least two of crystal nucleus into the precursor solution, applying external field force in the directional freezing process or carrying out temperature-controlled quenching treatment on the hydrogel precursor.
According to the invention, the anti-fatigue hydrogel with the ordered orientation structure can be prepared by adopting a directional freezing process, and meanwhile, the prepared anti-fatigue hydrogel has the ordered orientation structure and the appropriate size nanocrystalline domain by regulating and controlling the crystalline domain of the hydrogel, so that the toughness strength and the anti-fatigue threshold of the anti-fatigue hydrogel are further improved.
The precursor solution in the step (1) needs to be placed in a mold for freeze drying, the mold is prepared by adopting a 3D printing technology, and the 3D printing technology comprises any one or a combination of at least two of fused deposition molding, ink direct writing, laser sintering, digital light processing, electron beam melting molding, layered entity manufacturing, powder bonding and light curing molding; the shape of the die is designed by three-dimensional design software, and the three-dimensional design software comprises any one or the combination of at least two of SolidWorks, 3D Studio Max, CINEMA 4D, Maya, Rhinocero, Google Sketchup, CATIA, Unigraphics NX, AutoCAD, Pro/Engineer, Cimatron, LightWave 3D, Poser, FormZ or Blender.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the object and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
As a preferred technical scheme of the invention, the precursor in the precursor solution comprises any one or a combination of at least two of polyethylene glycol, polyvinyl alcohol polymer, polyacrylamide polymer, polyacrylic acid polymer, cellulose compound, lignin, sodium alginate, agar, cyclodextrin, collagen, chitosan, hyaluronic acid or polypeptide compound.
Preferably, the mass percentage of the precursor in the precursor solution is 0.5-50%, for example, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50%.
Preferably, the solvent of the precursor solution is water or an organic solvent.
Preferably, the organic solvent is selected from any one of methanol, ethanol, acetone, dimethyl sulfoxide, dichloromethane, glycerol, tetrahydrofuran or ethyl acetate or a combination of at least two of the above.
As a preferred embodiment of the present invention, the precursor solution further includes an inorganic filler.
Preferably, the inorganic filler is selected from any one of hydroxyapatite, graphene oxide, carbon nanotubes, carbon black, ceramic particles, silica, metal powder or clay powder or a combination of at least two of the same.
Preferably, the inorganic filler content in the precursor solution is 0.5 to 50% by mass, and may be, for example, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or the like.
As a preferred technical scheme of the invention, the cold source for directional freezing is carried out in the presence of a cold source.
Preferably, the temperature of the cold source is-196-0 ℃, and can be-196 ℃, 180 ℃, 160 ℃, 140 ℃, 120 ℃, 100 ℃, 80 ℃, 60 ℃, 40 ℃, 20 ℃ or 0 ℃ for example.
Preferably, the freezing rate in the directional freezing process is 0.001 to 1mm/s, and may be, for example, 0.001mm/s, 0.005mm/s, 0.01mm/s, 0.02mm/s, 0.05mm/s, 0.1mm/s, 0.2mm/s, 0.3mm/s, 0.4mm/s, 0.5mm/s, 0.6mm/s, 0.7mm/s, 0.8mm/s, 0.9mm/s, 1mm/s, or the like.
Preferably, the time of the directional freezing is 1-60 min, for example, 1min, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.
Preferably, the direction of the directional freezing is any one or any two of three directions perpendicular to each other.
In a preferred embodiment of the present invention, the drying method is freeze drying.
Preferably, the freeze-drying time is 1 to 48 hours, and for example, the freeze-drying time may be 1 hour, 2 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 27 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, 46 hours, 48 hours, or the like.
In a preferred embodiment of the present invention, the temperature of the immersion in water in the step (2) is 0 to 100 ℃, and may be, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Preferably, the immersion time in water is 1 to 48 hours, and for example, the immersion time can be 1 hour, 2 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 27 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, 46 hours or 48 hours.
In a preferred embodiment of the present invention, the crystal nuclei are selected from inorganic substances and/or organic substances.
Preferably, the inorganic substance is selected from any one or a combination of at least two of talcum powder, calcium oxide, carbon black, calcium carbonate, mica or kaolin.
Preferably, the organic substance is selected from any one of or a combination of at least two of metal carboxylate salts, metal phosphate salts, sorbitolidene derivatives and polyvinyl derivatives.
Preferably, the external field force comprises vibration and/or agitation.
Preferably, the frequency of the vibration is 100 to 400Hz, such as 100Hz, 120Hz, 150Hz, 170Hz, 200Hz, 230Hz, 250Hz, 270Hz, 300Hz, 330Hz, 360Hz, or 400 Hz.
Preferably, the rotation speed of the stirring is 500 to 3000rpm, for example, 500rpm, 800rpm, 1000rpm, 1200rpm, 1500rpm, 1700rpm, 2000rpm, 2200rpm, 2500rpm, 2700rpm, 3000rpm, or the like may be used.
Preferably, the temperature-controlled quenching temperature is 25-300 ℃, for example, 25 ℃, 50 ℃, 75 ℃, 100 ℃, 125 ℃, 150 ℃, 175 ℃, 200 ℃, 225 ℃, 250 ℃, 275 ℃ or 300 ℃.
It should be noted that the temperature for temperature-controlled quenching of the hydrogel precursor should be comparable to the glass transition temperature of the hydrogel precursor, so as to facilitate the generation of crystal domains.
Preferably, the temperature-controlled quenching time is 5-1440 min, for example, 5min, 30min, 60min, 120min, 180min, 240min, 300min, 360min, 450min, 550min, 640min, 750min, 840min, 950min, 1080min, 1200min, 1340min, 1440min, and the like.
As a preferred technical scheme of the invention, the preparation method specifically comprises the following steps:
(1) directionally freezing the precursor solution at-196-0 ℃ for 1-60 min, and freeze-drying for 1-48 h to obtain a hydrogel precursor; the directional freezing direction is any one or any two of three mutually perpendicular directions, and the freezing rate of the directional freezing is 0.001-1 mm/s;
(2) soaking the hydrogel precursor obtained in the step (1) in water at 0-100 ℃ for 1-48 h to obtain the anti-fatigue hydrogel;
the preparation method further comprises a step of regulating and controlling the crystal domain, and the method for regulating and controlling the crystal domain comprises the following steps: adding any one or the combination of at least two of crystal nucleus into the precursor solution, applying external field force in the directional freezing process or carrying out temperature-controlled quenching treatment on the hydrogel precursor.
In a second aspect, the present invention provides an anti-fatigue hydrogel prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a use of the fatigue-resistant hydrogel according to the second aspect in the field of bioelectronic devices or personalized medicine.
Compared with the prior art, the invention has at least the following beneficial effects:
the method adopts a directional freezing process and regulates and controls the crystal domain in the hydrogel, so that the prepared hydrogel has an ordered orientation structure and a nano crystal domain with proper size, the toughness strength and the fatigue resistance of the hydrogel can be effectively improved, the hydrogel is suitable for long-time use, and the toughness strength parallel to the orientation is 9.2-1270.8 kJ/m2The toughness strength perpendicular to the orientation is 0.2-74.1 kJ/m2The fatigue threshold parallel to the orientation is 21.1 to 3609.2J/m2The fatigue threshold value perpendicular to the orientation is 2.5 to 750.6J/m2. The preparation method provided by the invention has simple process steps, is suitable for large-scale production and preparation of various anti-fatigue hydrogels, and the toughness strength of the prepared anti-fatigue polyvinyl alcohol hydrogel parallel to the orientation is 1270.8kJ/m2The tenacity perpendicular to the orientation was 74.1kJ/m2Fatigue threshold parallel to orientation is 3609.2J/m2The fatigue threshold perpendicular to the orientation is 750.6J/m2Has excellent toughness, fatigue resistance and anisotropy.
Drawings
FIG. 1 is a schematic diagram of the preparation of an anti-fatigue hydrogel by a one-way freezing process in examples 1-3 and 5-15;
FIG. 2 is a schematic diagram of the preparation of an anti-fatigue hydrogel by the two-way freezing process in example 4;
FIG. 3 is a scanning electron microscope image of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1, wherein (a) is a scanning electron microscope image parallel to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel, and (b) is a partial magnified view of the microtopography of the fatigue-resistant polyvinyl alcohol hydrogel within the dashed-line frame in (a);
FIG. 4 is another SEM image of the fatigue-resistant PVA hydrogel provided in example 1, wherein (a) is a SEM image perpendicular to the orientation of the fatigue-resistant PVA hydrogel, and (b) is a partial magnified view of the microtopography of the fatigue-resistant PVA hydrogel within the dashed-line box in (a);
FIG. 5 is a strain-stress plot of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1;
FIG. 6 is a graph of the test results of the modulus of rupture and the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1;
FIG. 7 is a graph of the results of testing the elongation at break versus the orientation of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1;
FIG. 8 is a graph of fatigue threshold results for the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1;
the heat-conducting material comprises a 1-cold source, 2-precursor solution, 3-anti-fatigue hydrogel, 4-crystal domain, 5-precursor random chain segment, 6-solid precursor solvent, 7-inorganic filler and 8-heat-conducting substrate.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sources of some of the components in the examples and comparative examples are as follows:
polyacrylic acid: aldrich, CAS number 9003-01-4;
polyvinyl alcohol: sigma, CAS number 9002-89-5;
polyethylene glycol: adamas, CAS number 25322-68-3;
sodium alginate: adamas, CAS number 9005-38-3;
polyacrylamide: adamas, CAS number 9003-05-8;
lignin: TCI, CAS number 8061-51-6;
and (3) chitosan: adamas, CAS number 9012-76-4;
hydroxyapatite: nanjing Xiancheng nanomaterial science and technology Co., Ltd, CAS number 1306-06-5;
carbon black: adamas, CAS number 7440-44-0;
graphene: chinese institute of Oncology organic chemistry, Inc., TNGO.
Example 1
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a preparation method thereof, where the preparation process is shown in fig. 1, and the preparation method is as follows:
(1) establishing a model of a unidirectional freezing process in SolidWorks software, manufacturing a mold by adopting a high-temperature melt extrusion method, placing a 10 mass percent aqueous solution of polyvinyl alcohol into the mold, performing unidirectional freezing for 30min along the Z-axis direction at 0 ℃, and freeze-drying for 24h to obtain a polyvinyl alcohol hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 0.08 mm/s;
(2) and (2) quenching the polyvinyl alcohol hydrogel precursor obtained in the step (1) at the temperature of 100 ℃ for 90min, and soaking the polyvinyl alcohol hydrogel precursor in water for 24h at the temperature of 50 ℃ to obtain the anti-fatigue polyvinyl alcohol hydrogel.
The microtopography parallel to the orientation of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1 was characterized by scanning electron microscopy (SEM, instrument model Merlin Zeiss) and is shown in fig. 3, where (b) is a partial magnified view of the microtopography of the fatigue-resistant polyvinyl alcohol hydrogel within the dashed box in (a). As can be seen from FIG. 3, the microstructure parallel to the orientation direction of the anti-fatigue polyvinyl alcohol hydrogel is a layered structure with a thickness of 100-200 nm.
The microstructure perpendicular to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1 was characterized by scanning electron microscopy (SEM, instrument model Merlin Zeiss) and is shown in fig. 4, where (b) is a partial magnified view of the fatigue-resistant polyvinyl alcohol hydrogel microstructure within the dashed box in (a). As can be seen from fig. 4, the micro-topography perpendicular to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel is a honeycomb.
The static tensile mechanical properties of the anti-fatigue polyvinyl alcohol hydrogel provided in example 1 were tested by an electronic universal tester (instrument model XLD-100E), and the strain-stress curve graph is shown in fig. 5, and it can be seen from fig. 5 that the mechanical strength of the anti-fatigue polyvinyl alcohol hydrogel in the parallel and perpendicular orientation directions has significant difference, and shows significant anisotropy. Wherein, the test conditions of the electronic universal tester are as follows: the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1 was stretched at room temperature with a mechanical sensor of 100N and a compression rate of 20mm/min until the displacement at one end of the hydrogel reached 80% of the original length of the hydrogel, and the test was stopped.
The results of the test of the breaking modulus and the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1 are shown in fig. 6, and it can be seen from fig. 6 that the breaking modulus parallel to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel is greater than the breaking modulus perpendicular to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel, indicating that the fatigue-resistant polyvinyl alcohol hydrogel exhibits significant anisotropy in the parallel and perpendicular orientation directions.
The test results of the elongation at break and the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel provided in example 1 are shown in fig. 7, and it can be seen from fig. 7 that the modulus at break parallel to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel is greater than the modulus at break perpendicular to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel, indicating that the fatigue-resistant polyvinyl alcohol hydrogel exhibits significant anisotropy in the parallel and perpendicular orientation directions.
By immersion-type cyclic mechanicsThe fatigue resistance of the anti-fatigue polyvinyl alcohol hydrogel provided in example 1 was tested with a tester (CellScale, model U-stretch), and the test result is shown in FIG. 8. As can be seen from FIG. 8, the fatigue threshold value T perpendicular to the orientation direction of the anti-fatigue polyvinyl alcohol hydrogel is shown0Is 34J/m2Fatigue threshold f parallel to the orientation direction of the fatigue-resistant polyvinyl alcohol hydrogel0Is 1340J/m2Further, the fatigue resistance of the fatigue-resistant polyvinyl alcohol hydrogel in both the parallel and perpendicular orientation directions is shown to be significantly anisotropic. The method for the fatigue resistance test comprises the following steps: deionized water is used as a soaking solution, a dog-bone-shaped sample with a notch is placed in the middle of a clamp (the notch occupies one fifth of the width), the strain amount of 1 → 1000 times of cyclic load is set as lambda (lambda is 1-3 and the like), the loading speed is 1mm/s, after the test is finished, the integral area of a strain-stress curve under 1000 times of loading is taken, the crack propagation rate (G) is calculated,
G=2×k×c×W,
where k is a function which varies with the stretching (k 3 x λ)-1/2λ is the maximum strain in the cyclic stretching process), c is the crack length, and W is the integral area of the strain-stress curve;
obtaining a G- (dc/dN) relation curve and a fatigue threshold value f according to the G and the crack length (dc/dN) under the unit cycle number0The intersection point of the fitting line before mutation of dc/dN and the fitting line after mutation of dc/dN is obtained.
Example 2
The embodiment provides an anti-fatigue polyacrylic acid hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 1, and the preparation method comprises the following steps:
(1) establishing a model of a one-way freezing process in 3D Studio Max software, manufacturing a mold by adopting a photocuring forming method, placing a polyacrylic acid aqueous solution with the mass percentage of 10% in the mold, performing one-way freezing for 60min along the Z-axis direction at the temperature of-196 ℃, and performing freeze drying for 48h to obtain a polyacrylic acid hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 0.05 mm/s;
(2) and (2) carrying out temperature-controlled quenching 1440min on the polyacrylic acid hydrogel precursor obtained in the step (1) at the temperature of 25 ℃, and then soaking the quenched polyacrylic acid hydrogel precursor in water for 48h at the temperature of 25 ℃ to obtain the anti-fatigue polyacrylic acid hydrogel.
Example 3
The embodiment provides an anti-fatigue polyethylene glycol hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 1, and the preparation method comprises the following steps:
(1) establishing a model of a unidirectional freezing process in CINEMA 4D software, manufacturing a mold by adopting a photocuring molding method, placing 25 mass percent of polyethylene glycol and 20 mass percent of hydroxyapatite in an ethanol solution in the mold, performing unidirectional freezing for 5min along the Z-axis direction at-100 ℃, and freeze-drying for 1h to obtain a polyethylene glycol hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 0.02 mm/s;
(2) and (2) quenching the polyethylene glycol hydrogel precursor obtained in the step (1) at the temperature of 150 ℃ for 100min, and soaking the polyethylene glycol hydrogel precursor in water for 1h at the temperature of 5 ℃ to obtain the anti-fatigue polyethylene glycol hydrogel.
Example 4
The embodiment provides an anti-fatigue sodium alginate hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 2, and the preparation method comprises the following steps:
(1) establishing a model of a bidirectional freezing process in SolidWorks software, manufacturing a mold by adopting a laser sintering method, placing 50 mass percent of sodium alginate and 50 mass percent of carbon black aqueous solution in the mold, performing bidirectional freezing for 60min along the X-axis and Z-axis directions at the temperature of-196 ℃, and freeze-drying for 12h to obtain a sodium alginate hydrogel precursor; the cold source 1 of the bidirectional freezing is liquid nitrogen, the freezing rate of an X axis is 0.05mm/s, and the freezing rate of a Z axis is 0.07 mm/s;
(2) and (2) quenching the sodium alginate hydrogel precursor obtained in the step (1) at the temperature of 300 ℃ for 5min, and soaking the sodium alginate hydrogel precursor in water for 1h at the temperature of 10 ℃ to obtain the anti-fatigue sodium alginate hydrogel.
Example 5
The embodiment provides an anti-fatigue polyacrylamide hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 1, and the preparation method comprises the following steps:
(1) establishing a model of a unidirectional freezing process in SolidWorks software, manufacturing a mold by adopting a high-temperature melt extrusion method, placing a methanol solution of 15 mass percent of polyacrylamide and 10 mass percent of graphene in the mold, performing unidirectional freezing for 30min along the Z-axis direction at-180 ℃, and freeze-drying for 48h to obtain a polyacrylamide hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 0.001 mm/s;
(2) and (2) soaking the polyacrylamide hydrogel precursor obtained in the step (1) in water at 25 ℃ for 12h to obtain the anti-fatigue polyacrylamide hydrogel.
Example 6
The embodiment provides an anti-fatigue lignin hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 1, and the preparation method comprises the following steps:
(1) establishing a model of a one-way freezing process in SolidWorks software, manufacturing a mold by adopting a high-temperature melt extrusion method, placing lignin with the mass percentage of 11% and an ethyl acetate solution of graphene with the mass percentage of 5% in the mold, performing one-way freezing for 1min along the Z-axis direction at the temperature of-196 ℃, and performing freeze drying for 1h to obtain a lignin hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 1 mm/s;
(2) and (2) soaking the lignin hydrogel precursor obtained in the step (1) in water at 10 ℃ for 1h to obtain the anti-fatigue lignin hydrogel.
Example 7
The embodiment provides an anti-fatigue chitosan hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 1, and the preparation method comprises the following steps:
(1) establishing a model of a unidirectional freezing process in SolidWorks software, manufacturing a mold by adopting a high-temperature melt extrusion method, placing a tetrahydrofuran solution of chitosan with the mass percentage of 8% in the mold, performing unidirectional freezing for 60min along the Z-axis direction at the temperature of-196 ℃ and the vibration frequency of 400rpm, and performing freeze drying for 24h to obtain a chitosan hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 0.5 mm/s;
(2) and (2) soaking the chitosan hydrogel precursor obtained in the step (1) in water at 100 ℃ for 12h to obtain the anti-fatigue chitosan hydrogel.
Example 8
The embodiment provides an anti-fatigue polyethylene glycol hydrogel and a preparation method thereof, wherein the preparation process is shown in fig. 1, and the preparation method comprises the following steps:
(1) establishing a model of a unidirectional freezing process in SolidWorks software, manufacturing a mold by adopting a high-temperature melt extrusion method, placing 0.5 mass percent of polyethylene glycol and 0.5 mass percent of silicon dioxide aqueous solution into the mold, performing unidirectional freezing for 20min along the Z-axis direction at the temperature of minus 20 ℃ and the stirring speed of 1500rpm, and freeze-drying for 24h to obtain a polyethylene glycol hydrogel precursor; the cold source 1 of the unidirectional freezing is liquid nitrogen, and the freezing rate of the unidirectional freezing is 0.8 mm/s;
(2) and (2) soaking the polyethylene glycol hydrogel precursor obtained in the step (1) in water at 25 ℃ for 12h to obtain the anti-fatigue polyethylene glycol hydrogel.
Example 9
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the freezing rate of the unidirectional freezing in step (1) is 0.001mm/s, and the other conditions are the same as example 1.
Example 10
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the freezing rate of the unidirectional freezing in step (1) is 1mm/s, and the other conditions are the same as example 1.
Example 11
This example provides a polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the freezing rate of the unidirectional freezing in step (1) is 0.0005mm/s, and the other conditions are the same as example 1.
Example 12
This example provides a polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the freezing rate of the unidirectional freezing in step (1) is 1.2mm/s, and the other conditions are the same as example 1.
Example 13
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which is different from example 1 only in that the time for temperature controlled quenching in step (2) is 1440min, and the other conditions are the same as example 1.
Example 14
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the time for temperature controlled quenching in step (2) is 5min, and other conditions are the same as example 1.
Example 15
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the time for temperature controlled quenching in step (2) is 4min, and other conditions are the same as example 1.
Example 16
This example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that the time for temperature controlled quenching in step (2) is 1500min, and the other conditions are the same as example 1.
Comparative example 1
The present comparative example provides an anti-fatigue polyvinyl alcohol hydrogel and a method of making the same, the method comprising:
(1) establishing a model in SolidWorks software, manufacturing a mold by adopting high-temperature melt extrusion, placing a polyvinyl alcohol aqueous solution with the mass percentage of 10% in the mold, freezing for 30min at the temperature of 0 ℃, and freeze-drying for 24h to obtain a polyvinyl alcohol hydrogel precursor;
(2) and (2) quenching the polyvinyl alcohol hydrogel precursor obtained in the step (1) at the temperature of 100 ℃ for 90min, and soaking the polyvinyl alcohol hydrogel precursor in water for 24h at the temperature of 50 ℃ to obtain the anti-fatigue polyvinyl alcohol hydrogel.
Comparative example 2
This comparative example provides an anti-fatigue polyvinyl alcohol hydrogel and a method for preparing the same, which are different from example 1 only in that step (2) is: soaking the polyvinyl alcohol hydrogel precursor obtained in the step (1) in water for 48h to obtain the anti-fatigue polyvinyl alcohol hydrogel; other conditions were the same as in example 1.
Comparative example 3
The present comparative example provides a polyacrylic acid hydrogel and a method for preparing the same, the method comprising:
establishing a model in SolidWorks software, manufacturing a die by adopting high-temperature melt extrusion, uniformly stirring and mixing an acrylic acid aqueous solution with the mass percentage of 5% and a photoinitiator I2959, placing the mixture into the die, curing the mixture for 10min in an ultraviolet curing line (400W, the strength is 100%), and then soaking the cured mixture into water at 25 ℃ for 24h to obtain the polyacrylic acid hydrogel; the mass ratio of the photoinitiator I2959 to the acrylic acid monomer is 1: 100.
Comparative example 4
The present comparative example provides a polyethylene glycol hydrogel and a method for preparing the same, the method comprising:
establishing a model in SolidWorks software, adopting high-temperature melt extrusion to manufacture a mold, placing an ethanol solution of polyethylene glycol with the mass percentage of 5% in the mold, freezing for 12 hours at the temperature of minus 20 ℃, then unfreezing for 3 hours at room temperature, circulating for five times, finally freeze-drying for 24 hours, and soaking the polyethylene glycol hydrogel in water for 24 hours at the temperature of 25 ℃ to obtain the polyethylene glycol hydrogel.
Comparative example 5
The comparative example provides a sodium alginate hydrogel and a preparation method thereof, wherein the preparation method comprises the following steps:
establishing a model in SolidWorks software, adopting high-temperature melt extrusion to manufacture a mold, placing an aqueous solution of sodium alginate with the mass percentage of 5% in the mold, freezing for 12 hours at the temperature of minus 20 ℃, then freeze-drying for 24 hours, and soaking the mold in a calcium chloride solution with the molar equivalent of 5M at the temperature of 25 ℃ for 24 hours to obtain the sodium alginate hydrogel.
Comparative example 6
The present comparative example provides a polyacrylamide hydrogel and a method of making the same, the method comprising:
establishing a model in SolidWorks software, manufacturing a mold by adopting high-temperature melt extrusion, uniformly stirring and mixing 5 mass percent of acrylamide aqueous solution and a photoinitiator I2959, placing the mixture into the mold, curing for 10min in an ultraviolet curing line (400W, the strength is 100%), and then soaking the mixture into water at 25 ℃ for 24h to obtain the polyacrylamide hydrogel; the mass ratio of the photoinitiator I2959 to the acrylamide is 1: 100.
Comparative example 7
The present comparative example provides a lignin hydrogel and a method of making the same, the method comprising:
establishing a model in SolidWorks software, manufacturing a mould by adopting high-temperature melt extrusion, placing an ethyl acetate solution of lignin with the mass percentage of 5% in the mould, freezing for 12 hours at the temperature of-20 ℃, then unfreezing for 3 hours at room temperature, circulating for five times, finally freeze-drying for 24 hours, and soaking the lignin hydrogel in water for 24 hours at the temperature of 25 ℃ to obtain the lignin hydrogel.
Comparative example 8
The present comparative example provides a chitosan hydrogel and a method for preparing the same, the method comprising:
establishing a model in SolidWorks software, adopting high-temperature melt extrusion to manufacture a mold, placing an acetic acid aqueous solution (pH is 3) of chitosan with the mass percentage of 2.5% in the mold, freezing at-20 ℃ for 12h, then freeze-drying for 24h, and soaking in a glutaraldehyde aqueous solution with the mass percentage of 5% at 25 ℃ for 24h to obtain the chitosan hydrogel.
The hydrogels provided in the above examples and comparative examples were tested for their performance, with the following test criteria:
toughness strength: the hydrogels provided in the above examples and comparative examples were stretched at 25 ℃ using an electronic universal tester (model XLD-100E) until they completely broke, resulting in a strain-stress curve, wherein the hydrogel samples were cut into dog-bone-shaped samples with a notch having a width (notch is one fifth of the width), and the test conditions were: the mechanical sensor is 100N, the compression speed is 20mm/min,
the toughness strength is S multiplied by L,
wherein S is the integrated area of the strain-stress curve (unit J/m)3) And L is the original length (m) of the hydrogel sample.
Fatigue threshold: the hydrogel provided by the above examples and comparative examples was subjected to fatigue resistance testing at 25 ℃ using a soak type cyclic mechanical tester (CellScale, model U-stretch), wherein the fatigue resistance testing method was to place a dog-bone-shaped sample with a notch in the middle of a jig (the notch occupies one fifth of the width) using deionized water as a soak solution, set the strain amount of 1 to 1000 cyclic loads to be λ (λ is 1 to 3, etc.), set the loading speed to be 1mm/s, after the test was finished, take the integral area of the strain-stress curve under 1000 loads, calculate the crack propagation rate (G),
G=2×k×c×W,
where k is a function which varies with the stretching (k 3 x λ)-1/2λ is the maximum strain in the cyclic stretching process), c is the crack length, and W is the integral area of the strain-stress curve;
obtaining a G- (dc/dN) relation curve and a fatigue threshold value f according to the G and the crack length (dc/dN) under the unit cycle number0The intersection point of the fitting line before mutation of dc/dN and the fitting line after mutation of dc/dN is obtained.
The results of the above property tests are shown in table 1 below:
TABLE 1
Figure BDA0002917689270000181
Figure BDA0002917689270000191
As can be seen from Table 1, the method adopts a directional freezing process and regulates and controls the crystal domain in the hydrogel, so that the prepared hydrogel has an ordered oriented structure and a nano crystal domain with a proper size, the toughness strength and the fatigue resistance of the hydrogel can be effectively improved, the hydrogel is suitable for long-time use, and the toughness strength parallel to the orientation is 9.2-1270.8 kJ/m2The toughness strength perpendicular to the orientation is 0.2-74.1 kJ/m2The fatigue threshold parallel to the orientation is 21.1 to 3609.2J/m2The fatigue threshold value perpendicular to the orientation is 2.5 to 750.6J/m2. The preparation method provided by the invention has simple process steps, is suitable for large-scale production and preparation of various anti-fatigue hydrogels, and the toughness strength of the prepared anti-fatigue polyvinyl alcohol hydrogel parallel to the orientation is up to 1270.8kJ/m2The tenacity perpendicular to the orientation was 74.1kJ/m2Fatigue threshold parallel to orientation is 3609.2J/m2The fatigue threshold perpendicular to the orientation is 750.6J/m2Has excellent toughness, fatigue resistance and anisotropy.
If the freezing rate of the oriented freezing is small (example 11) as compared with example 1, the toughness strength and fatigue resistance of the hydrogel obtained are poor, and the toughness strength parallel to the orientation is 918.4kJ/m2The tenacity perpendicular to the orientation was 10.6kJ/m2Fatigue threshold parallel to orientation is 1940.7J/m2Fatigue threshold perpendicular to orientation of 180.3J/m2(ii) a When the freezing rate of the directional freezing is high (example 12), the toughness strength and fatigue resistance of the hydrogel obtained are good and are close to those of the hydrogel obtained in example 10. Therefore, the toughness strength and the fatigue resistance of the prepared hydrogel are gradually enhanced along with the increase of the freezing rate of the directional freezing, and the influence of the freezing rate of the directional freezing on the toughness strength and the fatigue resistance is small after the freezing rate of the directional freezing reaches 1 mm/s.
Compared with example 1, if the time of temperature-controlled quenching is shorter in the step of regulating the crystal domain (example 15), the toughness strength and the fatigue resistance of the prepared hydrogel are poorer, and the toughness strength parallel to the orientation is as high as 680kJ/m2The tenacity perpendicular to the orientation was 30kJ/m2Fatigue threshold parallel to orientation is 1260.5J/m2Fatigue threshold perpendicular to orientation of 224.8J/m2(ii) a If the temperature-controlled quenching time is longer in the step of regulating the crystal domain (example 16), the toughness strength and the fatigue resistance of the prepared hydrogel are better, the toughness strength is closer to that of the fatigue-resistant hydrogel prepared in example 13, and the toughness strength parallel to the orientation is as high as 1274.2kJ/m2The tenacity perpendicular to the orientation was 74.8kJ/m2Fatigue threshold parallel to orientation is 3615.4J/m2Fatigue threshold perpendicular to orientation of 752J/m2. Therefore, along with the increase of the temperature-controlled quenching time, the toughness strength and the fatigue resistance of the prepared anti-fatigue hydrogel are gradually enhanced, and when the temperature-controlled quenching time reaches 1440min, the effect of prolonging the temperature-controlled quenching time on the toughness strength and the fatigue resistance of the anti-fatigue hydrogel is small, and the method is not beneficial to the large-scale production of the anti-fatigue hydrogel.
In comparison with example 1, if directional freezing was not performed during freezing (comparative example 1), the obtained hydrogel was inferior in toughness strength and fatigue resistance in the longitudinal and transverse directions, and its toughness strength parallel to the orientation was as high as 175kJ/m2Tenacity perpendicular to orientation of 154kJ/m2Fatigue threshold parallel to orientation is 1015.2J/m2Fatigue threshold perpendicular to orientation of 1000J/m2(ii) a If the crystal domain is not controlled during the preparation of the hydrogel (comparative example 2), the prepared hydrogel has poor toughness strength and fatigue resistance, and the toughness strength parallel to the orientation is 160.7kJ/m2The tenacity perpendicular to the orientation was 10.4kJ/m2Fatigue threshold parallel to orientation of 100J/m2Fatigue threshold perpendicular to orientation of 20.1J/m2. Therefore, the directional freezing and the regulation and control of crystal domains are realized in the process of preparing the anti-fatigue hydrogelThe toughness strength and fatigue resistance of fatigue resistant hydrogels are of critical importance.
If the polyacrylic acid hydrogel was prepared using the prior art (comparative example 3), the polyacrylic acid hydrogel prepared had inferior toughness strength and fatigue resistance, and had toughness strength parallel to the orientation of 3.9kJ/m, as compared to example 22The tenacity perpendicular to the orientation was 2.7kJ/m2Fatigue threshold parallel to orientation of 9.6J/m2Fatigue threshold perpendicular to orientation of 8.7J/m2And the difference between the toughness strength and the fatigue threshold value parallel to the orientation and the toughness strength and the fatigue threshold value vertical to the orientation is smaller, which indicates that the prepared polyacrylic acid has no anisotropy; similarly, when the corresponding hydrogels were prepared using the prior art (comparative examples 4 to 8), the hydrogels prepared were inferior in toughness strength and fatigue resistance and were not anisotropic, as compared to examples 3 to 7. The method adopts the directional freezing process and regulates and controls the size and distribution of the crystal domains in the hydrogel, so that the prepared hydrogel has an ordered oriented structure and a nano crystal domain with proper size, can effectively improve the toughness and fatigue resistance of the hydrogel, has obvious anisotropy and is suitable for long-term use.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. A preparation method of an anti-fatigue hydrogel is characterized by comprising the following steps:
(1) directionally freezing and drying the precursor solution to obtain a hydrogel precursor;
(2) soaking the hydrogel precursor obtained in the step (1) in water to obtain the anti-fatigue hydrogel;
the preparation method further comprises a step of regulating and controlling the crystal domain, and the method for regulating and controlling the crystal domain comprises the following steps: adding any one or the combination of at least two of crystal nucleus into the precursor solution, applying external field force in the directional freezing process or carrying out temperature-controlled quenching treatment on the hydrogel precursor.
2. The preparation method according to claim 1, wherein the precursor in the precursor solution comprises any one or a combination of at least two of polyethylene glycol, polyvinyl alcohol polymer, polyacrylamide polymer, polyacrylic acid polymer, cellulose compound, lignin, sodium alginate, agar, cyclodextrin, collagen, chitosan, hyaluronic acid or polypeptide compound;
preferably, the mass percentage of the precursor in the precursor solution is 0.5-50%;
preferably, the solvent of the precursor solution is water or an organic solvent;
preferably, the organic solvent is selected from any one of methanol, ethanol, acetone, dimethyl sulfoxide, dichloromethane, glycerol, tetrahydrofuran or ethyl acetate or a combination of at least two of the above.
3. The production method according to claim 1 or 2, characterized in that the precursor solution further includes an inorganic filler;
preferably, the inorganic filler is selected from any one of hydroxyapatite, graphene oxide, carbon nanotubes, carbon black, ceramic particles, silica, metal powder or clay powder or a combination of at least two of the same;
preferably, the mass percentage of the inorganic filler in the precursor solution is 0.5-50%.
4. The production method according to any one of claims 1 to 3, wherein the directional freezing is performed in the presence of a cold source;
preferably, the temperature of the cold source is-196-0 ℃;
preferably, the freezing rate of the directional freezing is 0.001-1 mm/s;
preferably, the directional freezing time is 1-60 min;
preferably, the direction of the directional freezing is any one or any two of three directions perpendicular to each other.
5. The method according to any one of claims 1 to 4, wherein the drying method is freeze-drying;
preferably, the freeze drying time is 1-48 h.
6. The method according to any one of claims 1 to 5, wherein the temperature of the immersion in water in the step (2) is 0 to 100 ℃;
preferably, the time for soaking in water is 1-48 h.
7. The method according to any one of claims 1 to 6, wherein the crystal nuclei are selected from inorganic and/or organic species;
preferably, the inorganic matter is selected from any one or a combination of at least two of talcum powder, calcium oxide, carbon black, calcium carbonate, mica or kaolin;
preferably, the organic matter is selected from any one or a combination of at least two of metal carboxylate salts, metal phosphate salts, sorbierite derivatives or polyvinyl derivatives;
preferably, the external field force comprises vibration and/or agitation;
preferably, the frequency of the vibration is 100-400 Hz;
preferably, the rotating speed of the stirring is 500-3000 rpm;
preferably, the temperature of the temperature-controlled quenching is 25-300 ℃;
preferably, the time of temperature-controlled quenching is 5-1440 min.
8. The method according to any one of claims 1 to 7, comprising in particular the steps of:
(1) directionally freezing the precursor solution at-196-0 ℃ for 1-60 min, and freeze-drying for 1-48 h to obtain a hydrogel precursor; the directional freezing direction is any one or any two of three mutually perpendicular directions, and the freezing rate of the directional freezing is 0.001-1 mm/s;
(2) soaking the hydrogel precursor obtained in the step (1) in water at 0-100 ℃ for 1-48 h to obtain the anti-fatigue hydrogel;
the preparation method further comprises a step of regulating and controlling the crystal domain, and the method for regulating and controlling the crystal domain comprises the following steps: adding any one or the combination of at least two of crystal nucleus into the precursor solution, applying external field force in the directional freezing process or carrying out temperature-controlled quenching treatment on the hydrogel precursor.
9. An anti-fatigue hydrogel produced by the production method according to any one of claims 1 to 8.
10. Use of the fatigue-resistant hydrogel according to claim 9 in a bioelectronic device or a personalized medical device.
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CN115197552B (en) * 2022-05-26 2024-02-13 中山大学南昌研究院 Porous material with multi-scale long-range ordered channel structure and preparation method and application thereof
CN117700824A (en) * 2024-02-06 2024-03-15 中山大学 Preparation method, product and application of super-structure porous multifunctional hydrogel
CN117700824B (en) * 2024-02-06 2024-04-23 中山大学 Preparation method, product and application of super-structure porous multifunctional hydrogel
CN118240395A (en) * 2024-05-28 2024-06-25 浙江大学 Lignin-based layered oriented aerogel and preparation method thereof

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