CN114031790A - Anti-drag type quick self-healing hydrogel and preparation method thereof - Google Patents
Anti-drag type quick self-healing hydrogel and preparation method thereof Download PDFInfo
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910021538 borax Inorganic materials 0.000 claims description 61
- 239000004328 sodium tetraborate Substances 0.000 claims description 61
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 61
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 51
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 41
- 238000002156 mixing Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000006136 alcoholysis reaction Methods 0.000 claims description 11
- 238000000748 compression moulding Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 6
- 230000035876 healing Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 2
- -1 biomedicine Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 238000003825 pressing Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 210000000845 cartilage Anatomy 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000008113 selfheal Nutrition 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
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- C08J3/00—Processes of treating or compounding macromolecular substances
- 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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- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C—CHEMISTRY; METALLURGY
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/02—Polyalkylene oxides
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
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Abstract
The invention discloses a drag reduction type quick self-healing hydrogel and a preparation method thereof. The friction test shows that the hydrogel has low friction coefficient, and the minimum friction coefficient reaches 0.092. The hydrogel can realize self-healing after healing in air for 30 seconds, and shows excellent self-healing characteristics underwater. The anti-drag self-healing hydrogel has important application prospect in the fields of flexible robots, intelligent materials, biomedicine, oil gas chemical industry and the like due to the low friction and self-healing characteristics.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to a drag-reduction type quick self-healing hydrogel and a preparation method thereof.
Background
When one object and another object move or have a tendency to move relatively in a tangential direction of the contact surfaces, a force exists between the contact surfaces that resists the relative movement, which is called a frictional force. This phenomenon between the contact surfaces is known as "rubbing", in which one or both surfaces are gradually worn, thus requiring a lubricated condition to minimize shear stresses between the opposing surfaces. This reduction in shear stress is characterized by a coefficient of friction (COF). The friction and wear associated with frictional contact accounts for about 23% of the global energy consumption each year, thus reducing friction is of great significance for energy conservation and green development.
Hydrogels are widely used in the field of water lubrication and friction, such as artificial cartilage, due to their good wettability, sensitivity, low friction and biocompatibility. Polyvinyl alcohol (PVA) hydrogel, like cartilage, has a porous structure and good hydrophilicity. During wear in a wet environment, water stored in the pores is squeezed out by an external load, forming a fluid lubrication, thereby achieving a low coefficient of friction. The PVA hydrogel has good friction characteristics, so the PVA hydrogel has good application prospect in engineering lubrication and great research value.
Disclosure of Invention
The invention aims to provide a resistance-reducing type quick self-healing hydrogel and a preparation method thereof.
In order to achieve the aim, the invention provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) adding polyethylene oxide (PEO) into a borax solution to prepare a borax/PEO aqueous solution;
(2) adding the borax/PEO aqueous solution into the PVA aqueous solution under a stirring state, stirring for 20-40 min, and then performing compression molding to obtain the hydrogel.
Further, the weight average molecular weight of PEO is 150000-670000.
Further, the borax solution is prepared by ultrasonically stirring borax in deionized water, and the concentration of the borax solution is 1.3-1.4 wt%.
Furthermore, the mass ratio of the polyethylene oxide to the borax in the borax/PEO aqueous solution is 0.5-1.5: 0.7.
Further, the preparation method of the PVA aqueous solution comprises the following steps: mixing polyvinyl alcohol and deionized water, and stirring for 3-5 h at 90-100 ℃.
Furthermore, the concentration of the PVA aqueous solution is 10-20 wt%, wherein the weight-average molecular weight of the polyvinyl alcohol is 40000-110000, and the alcoholysis degree is 99%.
In summary, the invention has the following advantages:
1. the drag-reduction type quick self-healing hydrogel prepared by the invention has excellent low friction performance, and the material can quickly self-heal after being damaged;
2. the preparation method provided by the invention is simple and convenient, the materials are simple and easy to obtain, and the nano-composite material is nontoxic and has good biocompatibility, can be used in the fields of biomedicine, self-repairing lubrication devices and the like, and has wide application prospect;
3. according to the invention, on the basis of PVA hydrogel, a dynamic cross-linking structure is introduced to endow the hydrogel with a self-repairing function, and meanwhile, a lubricating function is provided by combining a polymer molecular brush on the surface, so that the double functions of low friction and self-repairing of the hydrogel material are realized.
Drawings
FIG. 1 is a graph comparing the sliding of the drag-reducing type rapid self-healing hydrogel prepared in example 1 with a conventional PVA hydrogel on a glass plate and a silicone plate;
wherein FIG. 1(a) is a glass plate having an inclination angle of 10 °; FIG. 1(b) is a silica gel plate with an inclination angle of 20 °;
FIG. 2 is a point line graph of the friction coefficient and the friction coefficient of the drag-reducing type rapid self-healing hydrogel prepared in examples 1 to 3 and a conventional PVA hydrogel;
FIG. 3 is a stress-strain diagram before and after self-healing of the drag-reducing rapid self-healing hydrogel prepared in examples 1 to 3.
Detailed Description
The principles and features of this invention are described below in conjunction with embodiments, which are included to explain the invention and not to limit the scope of the invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) mixing 12.5g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% with 50g of deionized water, and heating and stirring at 95 ℃ for 4 hours to prepare a transparent PVA aqueous solution with the weight percent of 20;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 1.25g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 3.75 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 2
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) mixing 12.5g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% with 50g of deionized water, and heating and stirring at 95 ℃ for 4 hours to prepare a transparent PVA aqueous solution with the weight percent of 20;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 0.83g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 2.97 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 3
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) mixing 12.5g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% with 50g of deionized water, and heating and stirring at 95 ℃ for 4 hours to prepare a transparent PVA aqueous solution with the weight percent of 20;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 0.625g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 2.58 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 4
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 8.82g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99 percent is mixed with 50g of deionized water, and the mixture is heated and stirred for 4 hours at the temperature of 95 ℃ to prepare a 15 weight percent transparent PVA aqueous solution;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 1.25g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 3.75 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 5
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) mixing 5.556g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% with 50g of deionized water, and heating and stirring at 95 ℃ for 4 hours to prepare a 10 wt% transparent PVA aqueous solution;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 1.25g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 3.75 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3Of siliconAnd (3) putting a 5kg weight in a rubber mold, pressing for 6 hours and forming to obtain the product.
Example 6
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 8.82g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99 percent is mixed with 50g of deionized water, and the mixture is heated and stirred for 4 hours at the temperature of 95 ℃ to prepare a 15 weight percent transparent PVA aqueous solution;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 0.83g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 2.97 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 7
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 8.82g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99 percent is mixed with 50g of deionized water, and the mixture is heated and stirred for 4 hours at the temperature of 95 ℃ to prepare a 15 weight percent transparent PVA aqueous solution;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 0.625g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 2.58 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 8
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) mixing 5.56g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% with 50g of deionized water, and heating and stirring at 95 ℃ for 4 hours to prepare a 10 wt% transparent PVA aqueous solution;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 0.83g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 2.97 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Example 9
The embodiment provides a preparation method of a drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) mixing 5.56g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% with 50g of deionized water, and heating and stirring at 95 ℃ for 4 hours to prepare a 10 wt% transparent PVA aqueous solution;
(2) weighing 0.7g of borax and 50g of deionized water, mixing, uniformly stirring, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax to obtain a 1.38 wt% aqueous solution;
(3) adding 0.625g of polyethylene oxide with the molecular weight of 300000 into the borax water solution prepared in the step (2), and stirring for 10min until the polyethylene oxide is completely dissolved to prepare a 2.58 wt% borax/PEO water solution;
(4) mixing the PVA aqueous solution prepared in the step (1) and the borax/PEO aqueous solution prepared in the step (3) in equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) placing the pre-hydrogel into a size of 40 × 8 × 3mm3And pressing for 6 hours by applying a weight of 5kg to the silica gel mold to obtain the product.
Test examples
1. The drag-reducing type rapid self-healing hydrogel prepared in example 1 and a conventional PVA hydrogel were slid on a glass plate and a silica gel plate, and the results are shown in fig. 1.
The prepared anti-drag type quick self-healing hydrogel can slide on glass plates and silica gel plates with different inclination angles, but the PVA hydrogel can not slide, so that the anti-drag type quick self-healing hydrogel prepared by the invention can effectively improve the lubricating property.
2. The friction coefficients of the drag-reducing type rapid self-healing hydrogels prepared in examples 1 to 3 and the conventional PVA hydrogel were measured, and the results are shown in fig. 2.
The friction coefficient of the drag-reduction type quick self-healing hydrogel prepared by the invention is lower than that of the conventional PVA hydrogel, and the friction coefficient is continuously reduced along with the increase of the content of the polyethylene oxide, so that the best friction coefficient is achieved when the content of the polyethylene oxide is 0.55 wt%, and the minimum friction coefficient is 0.092.
3. The self-healing capability of the drag-reduction type rapid self-healing hydrogel prepared in examples 1 to 3 within 30s is detected, and the result is shown in fig. 3, and the hydrogel with dynamic borate bonds has 85% healing efficiency after healing in air for 30s, which proves that the drag-reduction type rapid self-healing hydrogel prepared by the invention has excellent self-healing performance. Meanwhile, the hydrogel can show excellent self-healing characteristics underwater, and can be applied to the wide fields of flexible robots, biomedicine and the like by combining the self-healing characteristics under various environments.
While the present invention has been described in detail with reference to the specific embodiments thereof, it should not be construed as limited by the scope of the present patent. Various modifications and changes may be made by those skilled in the art without inventive step within the scope of the appended claims.
Claims (7)
1. A preparation method of the drag reduction type quick self-healing hydrogel is characterized by comprising the following steps:
(1) adding polyethylene oxide into borax water solution to prepare borax/polyethylene oxide water solution;
(2) adding the borax/polyethylene oxide aqueous solution into the polyvinyl alcohol aqueous solution under a stirring state, stirring for 20-40 min, and then performing compression molding to obtain the hydrogel.
2. The method for preparing the drag-reducing type rapid self-healing hydrogel according to claim 1, wherein the polyethylene oxide has a weight average molecular weight of 150000 to 670000.
3. The method for preparing the drag-reducing type rapid self-healing hydrogel according to claim 1, wherein the borax solution is prepared by ultrasonically stirring borax in deionized water, and the concentration of the borax solution is 1.3 to 1.4 wt%.
4. The preparation method of the drag-reducing type rapid self-healing hydrogel according to claim 1, wherein the mass ratio of the polyethylene oxide to the borax in the borax/polyethylene oxide aqueous solution is 0.5-1.5: 0.7.
5. The method for preparing the drag-reducing type rapid self-healing hydrogel according to claim 1, wherein the method for preparing the aqueous solution of polyvinyl alcohol comprises the following steps: mixing polyvinyl alcohol and deionized water, and stirring for 3-5 h at 90-100 ℃.
6. The preparation method of the drag-reducing type rapid self-healing hydrogel according to claim 5, wherein the concentration of the aqueous solution of polyvinyl alcohol is 10 to 20 wt%, wherein the weight average molecular weight of polyvinyl alcohol is 40000 to 110000, and the alcoholysis degree is 99%.
7. The drag-reducing type rapid self-healing hydrogel prepared by the preparation method of the drag-reducing type rapid self-healing hydrogel according to any one of claims 1 to 6.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117141701A (en) * | 2023-09-20 | 2023-12-01 | 深圳市环境科学研究院 | Whale type ocean detection equipment and detection method thereof |
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