CN111333872B - Preparation method of anti-freezing organic-hydrogel with reversible adhesion and self-healing performance - Google Patents
Preparation method of anti-freezing organic-hydrogel with reversible adhesion and self-healing performance Download PDFInfo
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- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
The invention discloses a preparation method of an anti-freezing organic-hydrogel with reversible adhesion and self-healing performance. The organic hydrogel prepared by the invention has the performances of reversible adhesion, high stretchability, self-healing property, high moisture retention, frost resistance, transparency and the like, and is simple in preparation process, low in raw material cost, high in preparation efficiency and suitable for industrial production. The method has potential application prospects in the aspects of reversible adhesion devices, flexible electronic devices, supercapacitors, transparent electrodes and the like. The preparation process adopted by the invention comprises the following steps: preparing a polyvinyl alcohol (PVA) solution; (2) preparing a PVA/monomer pre-gel solution; and (3) ultraviolet irradiation gelation of the pre-gel solution.
Description
Technical Field
The invention relates to the technical field of preparation of reversible adhesion high-performance gel materials, in particular to a preparation method of anti-freezing organic-hydrogel with reversible adhesion and self-healing performance.
Background
The hydrogel is a high polymer material which is composed of a cross-linked polymer network and water and has unique soft and wet properties, and has wide application prospects in the fields of biomedicine, cosmetology, flexible electronic devices and the like. Hydrogels present significant problems during use. Mainly comprises the following steps:
(1) Volatilization and freezing of water in the hydrogel network can cause the gel to lose flexibility and conductivity;
(2) The existing construction method of the adhesive hydrogel mainly introduces Polydopamine (PDA) component into the hydrogel component. Although this is a commonly used method, functional groups in PDA are easily oxidized, resulting in a decrease in the adhesiveness of hydrogel with time, which is not favorable for long-term use of the gel material;
(3) The introduction of the conductive filler such as MXene, carbon nanotubes and graphene in the composite gel can greatly reduce the transparency of the gel material, and limit the application of the gel material in the fields of transparent electrodes and the like.
The developed organic/hydrogel material with reversible adhesion, ultra-long stretchability, transparency, conductivity and self-healing has wide market application prospect in the fields of flexible electronic devices, soft robots, wearable equipment, biological medicines, artificial skin, wound auxiliary materials and the like.
Disclosure of Invention
The invention provides a preparation method of anti-freezing organic-hydrogel with reversible adhesion and self-healing performance, which is a 'one-pot' method for forming gel, has the advantages of low raw material price, simple operation, stability, high efficiency and the like, and has intrinsic reversible adhesion, ultra-long stretchability, transparency, conductivity, self-healing performance, freezing resistance and long-term moisture retention performance.
In order to solve the problems in the prior art, the technical scheme of the invention is as follows: the preparation method of the anti-freezing organic-hydrogel with reversible adhesion and self-healing performance is characterized by comprising the following steps:
1) Preparation of polyvinyl alcohol (PVA) solution: weighing 5.3-17.6 g of PVA, adding 100mL of deionized water, heating at 89-100 ℃ for 1-3 h, and dissolving to prepare 5-15 wt% PVA solution;
2) Preparation of PVA/monomer pre-gel solution: according to PVA solution, H 2 SO 4 Sequentially adding raw materials, acrylic Acid (AA), an organic solvent, acrylamide (Am), an inorganic salt, a photoinitiator and glutaraldehyde, and stirring and mixing uniformly to obtain a pre-gel solution;
3) Ultraviolet light gelation of the pre-gel solution: and adding the uniformly mixed pre-gel solution into a mold, performing gelation by ultraviolet irradiation, and demolding to obtain the organic hydrogel film.
Further, in step 2):
PVA solution with the concentration of 5-15wt% is added in 6mL;
the adding amount of AA and Am is 15-24 wt% of the total amount, and the molar ratio of AA to Am is 1;
the content of the organic solvent is 5 to 46 weight percent of the total amount;
H 2 SO 4 the concentration is 10wt%, and the dosage is 0.15-0.25 mL;
the concentration of the inorganic salt is 0.1-0.5 mol/L;
the concentration of the glutaraldehyde aqueous solution is 5wt%, and the dosage is 1-1.2 mL;
the thickness of the gel is 1-3mm.
Further, the organic solvent is one or more of ethylene glycol, glycerol or sorbitol.
Further, the inorganic salt is one or more of potassium chloride, sodium chloride and lithium chloride.
Further, the photoinitiator is alpha-ketoglutaric acid, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl]-1-acetone with wavelength of 365nm and light intensity of 50-150 mW/cm 2 The irradiation time is 30-60 min.
Compared with the prior art, the invention has the following advantages:
1. the gel material has stable intrinsic reversible adhesion performance, the gel is double-network gel prepared by a one-pot method, the first network is a glutaraldehyde cross-linked PVA network, and the second network is a physically cross-linked poly (acrylic acid-co-acrylamide) network. Both networks contain a large number of polar groups, can form a large number of non-covalent interactions with the surface of a substrate and show reversible adhesion. Since these polar groups are chemically stable groups, they are not easily oxidized and thus can maintain adhesion for a long period of time. The gel medium adopts a water/organic solvent mixed solvent, so that the gel has the performance of non-volatilization and low-temperature non-freezing which is not possessed or not possessed by other adhesion devices.
2. The gel material in the invention adopts one or more mixed solvents of water and glycol, glycerol or sorbitol as a medium, has reversible adhesiveness at low temperature and high temperature, and still has high adhesiveness at the temperature of-20-80 ℃;
3. because various conductive nano seasonings are not introduced, inorganic salt is used as a conductive component, the gel material has high transparency in a visible light range;
4. the gel material can self-heal at the temperature of-20-80 ℃, and can automatically repair the damaged part after being damaged, recover the adhesion function and prolong the service life of the material;
5. the method adopted by the invention is 'one-pot' gelling, is convenient for large-scale industrial production, and has simple and reliable preparation technology and stable production performance. Because the raw material materials comprise a large amount of water, glycerol and a small amount of high molecules and monomers, the gel material has low cost, is green and pollution-free and has wide application prospect;
6. the introduction of glycol/water and glycerol/water binary solvent systems is an effective method for realizing the anti-freezing and long-term moisture retention performances of the hydrogel material, glycol and glycerol molecules can form hydrogen bonds with water molecules to inhibit the formation of ice crystals, and meanwhile, free water in the gel is reduced to inhibit the volatilization of water;
7. the proportion of the PVA network and the poly (acrylic acid-co-acrylamide) network can be regulated and controlled through the PVA content and the feeding ratio of acrylic acid/acrylamide, so that the regulation and control of the mechanical property and the adhesion of the gel are realized, and the maximum elongation can reach 2000%.
Drawings
FIG. 1 is a photograph of an organic/hydrogel physical object prepared according to the present invention;
FIG. 2 shows the transmittance test results of the organic/hydrogel prepared according to the present invention;
FIG. 3 shows the stress-strain test results of organic/hydrogel prepared according to the present invention;
FIG. 4 shows the results of adhesion strength test of organic/hydrogel prepared according to the present invention to glass;
FIG. 5 shows the results of adhesion strength tests of organic/hydrogel prepared according to the present invention to various substrates at various temperatures;
FIG. 6 shows the results of the humidity retention test of the organic/hydrogel prepared according to the present invention and the conventional hydrogel at room temperature;
FIG. 7 shows the results of rheological property tests of the organic/hydrogel and hydrogel prepared by the present invention at-20 deg.C to 100 deg.C;
FIG. 8 shows the results of organic/hydrogel conductivity tests in accordance with the present invention;
fig. 9 is a schematic view of a roller type reversible adhesion device using the organic/hydrogel assembly of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. In the following description, numerous specific details are set forth in order to provide a better understanding of the present application. However, those skilled in the art will readily recognize that some of the features may be omitted or replaced with other elements, materials, methods in different instances.
The first embodiment is as follows:
a method for preparing organic/hydrogel with intrinsic reversible adhesion, ultra-long stretchability, transparency and conductivity, comprising the steps of:
step 1) preparation of polyvinyl alcohol (PVA) aqueous solution: weighing 11.1g of PVA in a round-bottom flask, adding 100g of deionized water, sealing and swelling for 24h, then installing a condensing device, heating and stirring at 90 ℃ for 2h to dissolve the PVA to obtain a PVA solution with the concentration of 10 wt%;
step 2) preparation of PVA/monomer pre-gel solution: 6mL of 10wt% PVA aqueous solution and 0.2mL of 10wt% H were sequentially added to the round-bottom flask 2 SO 4 3.15g AA,9mL glycerol, 2.82g Am,0.6015g KCl,0.05g alpha-ketoglutaric acid, 1mL 5wt% aqueous solution of glutaraldehyde;
step 3) ultraviolet light gelation of the pre-gel solution: adding the uniformly mixed PVA/monomer pre-gel solution into a mold (composed of a tetrafluoroethylene plate, a glass plate and a silicon rubber interlayer and having a thickness of 3 mm), and using the PVA/monomer pre-gel solution with a wavelength of 365nm and a light intensity of 50mW/cm 2 And (4) irradiating by ultraviolet light for 40min, and demolding to obtain the organic/hydrogel. The hydrogel obtained is a colorless transparent flexible material, see fig. 1 and fig. 2.
Example two:
a method for preparing organic/hydrogel with intrinsic reversible adhesion, ultra-long stretchability, transparency and conductivity, comprising the steps of:
step 1) preparation of polyvinyl alcohol (PVA) aqueous solution: weighing a certain amount of 5.3g of PVA in a round-bottom flask, adding 100g of deionized water, sealing and swelling for 24h, then installing a condensing device, heating and stirring at 90 ℃ for 2h to dissolve the PVA to obtain a PVA solution with the concentration of 5 wt%;
step 2) preparation of PVA/monomer pre-gel solution: 6mL of a 5wt% aqueous PVA solution and 0.2mL of a 10wt% H solution were sequentially added to the round-bottom flask 2 SO 4 3.16g of AA,9mL of glycerol, 2.82g of am,0.6015g of KCl,0.05g of alpha-ketoglutaric acid, and 1mL of 5wt% glutaraldehyde aqueous solution;
step 3) ultraviolet light gelation of the pre-gel solution: adding the uniformly mixed PVA/monomer pre-gel solution into a mold (consisting of a tetrafluoroethylene plate, a glass plate and a silicon rubber interlayer and having the thickness of 3 mm), and using the PVA/monomer pre-gel solution with the wavelength of 365nm and the light intensity of 70mW/cm 2 And (3) irradiating for 30min by ultraviolet light, and demolding to obtain the organic/hydrogel.
The elongation at break of the organic/hydrogel is 3250%, the strength is 50kPa, and the organic/hydrogel has ultralong tensile property and higher mechanical strength.
The organic/hydrogel has adhesion strength of 10kPa to glass and high moisture retention.
The organic/hydrogel can maintain mechanical flexibility, conductivity and self-healing property at the temperature of-20-80 ℃.
Example three:
a method for preparing organic/hydrogel with intrinsic reversible adhesion, ultra-long stretchability, transparency and conductivity, comprising the steps of:
step 1) preparation of polyvinyl alcohol (PVA) aqueous solution: weighing 11.1g of PVA in a round-bottom flask, adding 100g of deionized water, sealing and swelling for 24h, then installing a condensing device, heating and stirring at 90 ℃ for 2h to dissolve the PVA to obtain a 10wt% PVA solution;
step 2) preparation of PVA/monomer pre-gel solution: 6mL of 10wt% PVA water were sequentially added to the round-bottom flaskSolution, 0.2mL of 10wt% H 2 SO 4 3.15g AA,9mL glycerol, 5.64g Am,0.6015g KCl,0.05g alpha-ketoglutaric acid, 1mL 5wt% aqueous solution of glutaraldehyde;
step 3) ultraviolet light gelation of the pre-gel solution: adding the uniformly mixed PVA/monomer pre-gel solution into a mold (consisting of a tetrafluoroethylene plate, a glass plate and a silicon rubber interlayer and having the thickness of 3 mm), and using the PVA/monomer pre-gel solution with the wavelength of 365nm and the light intensity of 100mW/cm 2 And (4) irradiating for 25min by using ultraviolet light, and demolding to obtain the organic/hydrogel.
The elongation at break of the organic/hydrogel is more than 800%, the strength is 350kPa, and the organic/hydrogel has ultralong tensile property and higher mechanical strength. The organic/hydrogel can maintain mechanical flexibility, conductivity and self-healing property at the temperature of-20-80 ℃.
Example four:
a method for preparing organic/hydrogel with intrinsic reversible adhesion, ultra-long stretchability, transparency and conductivity, comprising the steps of:
step 1) preparation of polyvinyl alcohol (PVA) aqueous solution: weighing 11.1g of PVA in a round-bottom flask, adding 100g of deionized water, sealing and swelling for 24h, then installing a condensing device, heating and stirring at 90 ℃ for 2h to dissolve the PVA to obtain a 10wt% PVA solution;
step 2) preparation of PVA/monomer pre-gel solution: 6mL of 10wt% PVA aqueous solution and 0.2mL of 10wt% H were sequentially added to the round-bottom flask 2 SO 4 3.15g AA,9mL glycerol, 8.46g am,0.6015g KCl,0.05g alpha-ketoglutaric acid, 1mL 5wt% aqueous solution of glutaraldehyde;
step 3) ultraviolet light gelation of the pre-gel solution: adding the uniformly mixed PVA/monomer pre-gel solution into a mold (consisting of a tetrafluoroethylene plate, a glass plate and a silicon rubber interlayer and having the thickness of 3 mm), and using the PVA/monomer pre-gel solution with the wavelength of 365nm and the light intensity of 100mW/cm 2 And (4) irradiating for 25min by using ultraviolet light, and demolding to obtain the organic/hydrogel.
The elongation at break of the organic/hydrogel is more than 800%, the strength is 350kPa, and the organic/hydrogel has ultralong tensile property and higher mechanical strength. The organic/hydrogel can maintain mechanical flexibility, conductivity and self-healing property at the temperature of-20-80 ℃.
Example five:
a method for preparing organic/hydrogel with intrinsic reversible adhesion, ultra-long stretchability, transparency and conductivity, comprising the steps of:
step 1) preparation of polyvinyl alcohol (PVA) aqueous solution: weighing 11.1g of PVA in a round-bottom flask, adding 100g of deionized water, sealing and swelling for 24h, then installing a condensing device, heating and stirring at 90 ℃ for 2h to dissolve the PVA to obtain a PVA solution with the concentration of 10 wt%;
step 2) preparation of PVA/monomer pre-gel solution: 6mL of 10wt% PVA aqueous solution and 0.2mL of 10wt% H were sequentially added to the round-bottom flask 2 SO 4 3.15g AA,9mL glycerol, 2.82g Am,0.6015g KCl,0.05g alpha-ketoglutaric acid, 1mL glutaraldehyde aqueous solution with the concentration of 5 wt%;
step 3) ultraviolet light gelation of the pre-gel solution: adding the uniformly mixed PVA/monomer pre-gel solution into a mold (consisting of a tetrafluoroethylene plate, a glass plate and a silicon rubber interlayer and having a thickness of 1 mm), and using the PVA/monomer pre-gel solution with a wavelength of 365nm and a light intensity of 100mW/cm 2 And (5) irradiating for 25min by using ultraviolet light, and demolding to obtain the organic/hydrogel.
The organic/hydrogel can keep mechanical flexibility, conductivity and self-healing property within the temperature range of-20 ℃ to 80 ℃, as shown in figure 5, the organic/hydrogel has adhesion effect on glass, wood and copper sheets at different temperatures, the adhesion force on the glass and the wood is larger than 19kPa, and the adhesion force on the copper sheet is larger than 20kPa.
The following tests were performed using the organic/hydrogel prepared in example one:
detecting the mechanical property of the organic/hydrogel:
the prepared organic/hydrogel was cut into a 30mm × 10mm × 3mm sample, stretched at a speed of 20mm/min with a universal tensile machine, and a stress-strain curve was recorded. The detection result is shown in figure 3, and the detection result shows that the breaking elongation can reach 2000%, the strength is more than 300kPa, and the ultra-long tensile property and the high mechanical strength are realized.
Organic/hydrogel adhesion performance testing:
the prepared organic/hydrogel was cut into 20mm × 10mm × 3mm sample strips (area is denoted as S), adhered between two glass plates, time-shear force was applied to both ends of the glass plates, the stress-strain curve was recorded to obtain the maximum stress (F), and the adhesive strength was calculated according to the formula F/S. As a result of the examination, referring to FIG. 4, it can be seen that the adhesion strength of the organic/hydrogel to glass can be up to 16.261kPa, and the adhesion strength increases with the increase of the adhesion time. As shown in FIG. 5, the gel still had high adhesion at-18 ℃ and 80 ℃.
Organic/hydrogel moisturizing performance test:
two gel sample strips of 50mm multiplied by 3mm are respectively taken, and the change of the gel weight along with time is recorded under the indoor environment, so that the moisture retention performance of the gel is evaluated. As seen in FIG. 6, the weight of the organic/hydrogel was almost unchanged compared to the hydrogel, indicating that it had good moisturizing properties. Further testing found that the organic/hydrogel remained electrically conductive and mechanically flexible after 5 months of storage.
And (3) detecting the freezing resistance and stability of the organic/hydrogel:
the anti-freezing performance and stability of the organic/hydrogel are detected by testing the dynamic mechanical performance evaluation of the gel under different temperature conditions. The detection result is shown in fig. 7, and it can be seen that the storage modulus of the hydrogel is greatly reduced near 0 ℃, which indicates that the free water in the hydrogel is frozen below 0 ℃, the gel is hardened and loses flexibility, and the hydrogel has no temperature resistance. The storage modulus of the organic/hydrogel remained nearly constant as the temperature increased from-20 ℃ to 100 ℃, indicating that it maintained good flexibility under both low and high temperature conditions.
As can be seen in fig. 8, when the organic/hydrogel is connected to the circuit as a length of wire, the LED lights up, indicating that the organic/hydrogel is conductive.
The organic/hydrogel prepared by the technology has good reversible adhesion, freezing resistance, long-term moisture retention, self-healing property, conductivity and other properties, and can be used in the aspects of flexible electronic reversible adhesion devices, strain sensors, stress sensors, supercapacitors and the like. The application in the reversible bonding device is described as an example. The reversible adhesion device is shaped as shown in the schematic diagram of fig. 9, and is assembled by cutting a gel sheet with a thickness of 2mm into a rectangular shape with a length of 25.12cm and a width of 20cm, and attaching the gel sheet to a roller with a diameter of 8cm and a length of 20cm, wherein the roller is made of glass or polypropylene material. The organic/hydrogel material in such a device can be recycled and reused after absorbing the debris by rinsing with water and air drying.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention.
Claims (1)
1. The preparation method of the anti-freezing organic-hydrogel with reversible adhesion and self-healing performance is characterized by comprising the following steps:
1) Preparing a polyvinyl alcohol (PVA) solution: weighing 5.3 to 17.6g of PVA, adding 100mL of deionized water, and heating at 89 to 100 ℃ for 1 to 3 hours to dissolve the PVA to prepare a PVA solution with the concentration of 5 to 15 wt%;
2) Preparation of PVA/monomer pre-gel solution: 10% by weight H in PVA solution 2 SO 4 Sequentially adding raw materials, acrylic acid AA, an organic solvent, acrylamide Am, an inorganic salt, a photoinitiator and a glutaraldehyde aqueous solution, and stirring and mixing uniformly to obtain a pre-gel solution;
3) Ultraviolet light gelation of the pre-gel solution: adding the uniformly mixed pre-gel solution into a mold, using ultraviolet light to gelatinize the pre-gel solution, and demolding to obtain an organic hydrogel film;
in the step 2):
the adding amount of a PVA solution with the concentration of 5 to 15wt% is 6mL;
the adding amount of AA and Am is 15 to 24wt% of the total amount, and the molar ratio of AA to Am is 1 to 3;
the content of the organic solvent is 5 to 46wt percent of the total amount;
H 2 SO 4 the dosage is 0.15 to 0.25mL;
the concentration of the inorganic salt is 0.1 to 0.5mol/L;
the concentration of the glutaraldehyde aqueous solution is 5wt%, and the dosage is 1 to 1.2mL;
the organic solvent is glycerol;
the inorganic salt is potassium chloride;
the photoinitiator is one of alpha-ketoglutaric acid, 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone;
in the step 3):
the wavelength is 365nm, and the light intensity is 50-150 mW/cm 2 Irradiating for 30min to 60 min; the gel thickness is 1-3mm.
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| CN113185715B (en) * | 2021-04-21 | 2022-12-16 | 华南理工大学 | Self-healing conductive polyvinyl alcohol-based hydrogel and preparation method and application thereof |
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