CN114031790B - Drag-reduction type rapid self-healing hydrogel and preparation method thereof - Google Patents
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910021538 borax Inorganic materials 0.000 claims description 70
- 239000004328 sodium tetraborate Substances 0.000 claims description 70
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 70
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 48
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 48
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 238000006136 alcoholysis reaction Methods 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000035876 healing Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 238000005461 lubrication Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 4
- 210000000845 cartilage Anatomy 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 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
- 230000009977 dual effect Effects 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
- 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
- 230000035945 sensitivity Effects 0.000 description 1
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- 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
- 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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- 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
- 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
-
- 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
- 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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- C—CHEMISTRY; METALLURGY
- 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 drag-reduction type quick self-healing hydrogel and a preparation method thereof. The friction test shows that the friction coefficient of the hydrogel is low, 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 under water. The drag-reduction self-healing hydrogel has important application prospects in the fields of flexible robots, intelligent materials, biological medicines, oil-gas chemical industry and the like due to low friction and self-healing characteristics.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to drag-reduction type quick self-healing hydrogel and a preparation method thereof.
Background
When one object and another object move in a tangential direction of the contact surfaces or have a tendency to move relative to each other, a force is present between the contact surfaces that resists their relative movement, and this force is called a friction force. This phenomenon between the contact surfaces is known as "friction" in which one or both surfaces are progressively worn and therefore require a state of lubrication to minimize shear stress between the opposing surfaces. This reduction in shear stress is characterized by a coefficient of friction (COF). Friction and wear associated with frictional contact each year account for about 23% of the global energy consumption, thus reducing friction, and having 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) hydrogels, similar to cartilage, have a porous structure and good hydrophilicity. During wear in a wet environment, water stored in the pores is squeezed out by external load, forming fluid lubrication, thereby achieving a low friction coefficient. The PVA hydrogel has good friction characteristics, so that the PVA hydrogel has good application prospect in engineering lubrication and has great research value.
Disclosure of Invention
The invention aims to provide drag-reduction type quick self-healing hydrogel and a preparation method thereof.
In order to achieve the above purpose, the invention provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) Adding polyethylene oxide (PEO) into borax solution to prepare borax/PEO water solution;
(2) Adding borax/PEO aqueous solution into PVA aqueous solution under stirring, stirring for 20-40 min, and pressing to form to obtain hydrogel.
Further, the PEO has a weight average molecular weight of 150000 ～ 670000.
Further, the borax solution is prepared by ultrasonic stirring of borax in deionized water, and the concentration of the borax solution is 1.3-1.4 wt%.
Further, the mass ratio of polyethylene oxide to 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 with deionized water, and stirring for 3-5 h at 90-100 ℃.
Further, the concentration of the PVA aqueous solution is 10 to 20wt%, wherein the weight average molecular weight of the polyvinyl alcohol is 40000 to 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 be quickly self-repaired after being damaged;
2. the preparation method provided by the invention is simple and convenient, the materials are simple and easy to obtain, the material is nontoxic, the material has good biocompatibility, the material can be used in the fields of biomedicine, self-repairing lubrication devices and the like, and the material 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 simultaneously, a polymer molecular brush on the surface is combined to provide a lubricating function, so that the dual functions of low friction and self-repairing of the hydrogel material are realized.
Drawings
FIG. 1 is a comparative graph of drag reducing fast self-healing hydrogels prepared in example 1 versus conventional PVA hydrogels sliding on glass and silica gel plates;
wherein FIG. 1 (a) is a glass plate having an inclination angle of 10 °; FIG. 1 (b) shows a silica gel plate with an inclination angle of 20 °;
FIG. 2 is a plot of the coefficient of friction and the coefficient of friction plot of the drag reducing fast self-healing hydrogels prepared in examples 1-3 with conventional PVA hydrogels;
FIG. 3 is a stress-strain diagram of the drag reducing rapid self-healing hydrogel prepared in examples 1-3 before and after self-healing.
Detailed Description
The principles and features of the present invention are described below in connection with the following examples, which are set forth to illustrate, but are not to be construed as limiting the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 12.5g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 20wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 1.25g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 3.75;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 2
The embodiment provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 12.5g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 20wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 0.83g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 2.97;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 3
The embodiment provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 12.5g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 20wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 0.625g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 2.58;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 4
The embodiment provides a preparation method of 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% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 15wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 1.25g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 3.75;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 5
The embodiment provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 5.556g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% is mixed with 50g of deionized water, and heated and stirred for 4 hours at 95 ℃ to prepare a 10wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 1.25g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 3.75;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 6
The embodiment provides a preparation method of 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% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 15wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 0.83g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 2.97;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 7
The embodiment provides a preparation method of 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% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 15wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 0.625g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 2.58;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 8
The embodiment provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 5.56g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 10wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 0.83g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 2.97;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Example 9
The embodiment provides a preparation method of drag-reduction type quick self-healing hydrogel, which comprises the following steps:
(1) 5.56g of polyvinyl alcohol with molecular weight of 88000 and alcoholysis degree of 99% and 50g of deionized water are mixed, heated and stirred for 4 hours at 95 ℃ to prepare a 10wt% transparent PVA aqueous solution;
(2) Weighing 0.7g of borax and 50g of deionized water, mixing uniformly, and putting into an ultrasonic machine for ultrasonic treatment for 5min to completely dissolve the borax, so as to prepare 1.38wt% borax aqueous solution;
(3) Adding 0.625g of polyethylene oxide with a molecular weight of 300000 into the borax water solution prepared in the step (2), stirring for 10min to completely dissolve, and preparing into a borax/PEO water solution with a weight percent of 2.58;
(4) Mixing the PVA aqueous solution prepared in the step (1) with the borax/PEO aqueous solution prepared in the step (3) in an equal volume, and slowly stirring for 1h to form pre-hydrogel;
(5) Placing the pre-hydrogel into a container of 40×8X3mm 3 And applying a weight of 5kg to press for 6 hours to form the silica gel mold.
Test examples
1. The drag reducing fast self-healing hydrogel prepared in example 1 was slid over glass and silicone plates with conventional PVA hydrogels, the results being shown in fig. 1.
The drag-reduction type quick self-healing hydrogel prepared by the invention can slide on glass plates and silica gel plates with different inclination angles, and PVA hydrogel can not slide, which shows that the drag-reduction type quick self-healing hydrogel prepared by the invention can effectively increase the lubricating performance.
2. The friction coefficients of the drag-reducing fast self-healing hydrogels prepared in examples 1-3 and conventional PVA hydrogels were examined and the results are shown in FIG. 2.
The friction coefficients of the drag-reduction type quick self-healing hydrogel prepared by the invention are lower than those of the conventional PVA hydrogel, and the friction coefficients continuously decrease along with the increase of the content of polyethylene oxide, and the drag-reduction type quick self-healing hydrogel reaches the best when the content of the polyethylene oxide is 0.55wt% and the minimum friction coefficient is 0.092.
3. The self-healing ability of the drag-reducing rapid self-healing hydrogel prepared in examples 1 to 3 was examined within 30 seconds, and the results are shown in fig. 3, in which the hydrogel using dynamic borate bonds showed 85% healing efficiency after 30 seconds of healing in air, demonstrating that the drag-reducing rapid self-healing hydrogel prepared in the present invention has excellent self-healing properties. Meanwhile, the hydrogel has excellent self-healing characteristics under water, and can be applied to wide fields such as flexible robots, biomedicine and the like by combining the self-healing characteristics under various environments.
While specific embodiments of the invention have been described in detail, it should not be construed as limiting the scope of the patent. Various modifications and variations which may be made by those skilled in the art without the creative effort are within the scope of the patent described in the claims.
Claims (3)
1. The preparation method of the drag-reduction type quick self-healing hydrogel is characterized by comprising the following steps of:
(1) Adding polyethylene oxide into borax water solution to prepare borax/polyethylene oxide water solution; the borax aqueous solution is prepared by ultrasonic stirring of borax in deionized water, and the concentration of the borax aqueous solution is 1.3-1.4wt%;
(2) Mixing borax/polyethylene oxide aqueous solution and polyvinyl alcohol aqueous solution in equal volume under stirring, stirring for 1h, pouring into a silica gel mold, and pressing to form to obtain hydrogel;
wherein the weight average molecular weight of the polyethylene oxide is 150000-670000;
the mass ratio of polyethylene oxide to borax in the borax/polyethylene oxide aqueous solution is 0.5-1.5:0.7;
the concentration of the polyvinyl alcohol aqueous solution is 10-20wt%, wherein the weight average molecular weight of the polyvinyl alcohol is 40000-110000, and the alcoholysis degree is 99%.
2. The method for preparing the drag reducing type rapid self-healing hydrogel according to claim 1, wherein the method for preparing the polyvinyl alcohol aqueous solution comprises the following steps: and mixing the polyvinyl alcohol with deionized water, and stirring for 3-5 hours at the temperature of 90-100 ℃.
3. 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 1-2.
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| CN101480501A (en) * | 2009-01-07 | 2009-07-15 | 四川大学 | Substitute material for repairing articular cartilage and preparation method |
| CN102634042A (en) * | 2012-04-20 | 2012-08-15 | 浙江大学 | PVA (polyvinyl alcohol) composite aquagel with bioactivity and preparation method thereof |
| CN105885064A (en) * | 2016-04-18 | 2016-08-24 | 北京化工大学 | Toughened polyvinyl alcohol composite hydrogel and application thereof |
| CN106823019A (en) * | 2016-12-21 | 2017-06-13 | 南京大学 | A kind of selfreparing ultrasonic puncture polyvinyl alcohol hydrogel biomimetic material and its preparation method and application |
| CN110054856A (en) * | 2019-04-22 | 2019-07-26 | 常州大学 | The preparation method and applications of low temperature resistant self-healing hydrogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101480501A (en) * | 2009-01-07 | 2009-07-15 | 四川大学 | Substitute material for repairing articular cartilage and preparation method |
| CN102634042A (en) * | 2012-04-20 | 2012-08-15 | 浙江大学 | PVA (polyvinyl alcohol) composite aquagel with bioactivity and preparation method thereof |
| CN105885064A (en) * | 2016-04-18 | 2016-08-24 | 北京化工大学 | Toughened polyvinyl alcohol composite hydrogel and application thereof |
| CN106823019A (en) * | 2016-12-21 | 2017-06-13 | 南京大学 | A kind of selfreparing ultrasonic puncture polyvinyl alcohol hydrogel biomimetic material and its preparation method and application |
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