CN114015079A - Polyvinyl alcohol-based piezoelectric active hydrogel and preparation and forming method thereof - Google Patents
Polyvinyl alcohol-based piezoelectric active hydrogel and preparation and forming method thereof Download PDFInfo
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- CN114015079A CN114015079A CN202111525569.6A CN202111525569A CN114015079A CN 114015079 A CN114015079 A CN 114015079A CN 202111525569 A CN202111525569 A CN 202111525569A CN 114015079 A CN114015079 A CN 114015079A
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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
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—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 a halogen; Derivatives of such polymers
- C08J2327/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- 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
- C08J2427/00—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 a halogen; Derivatives of such polymers
- C08J2427/02—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—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 a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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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
- C08J2429/00—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
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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Abstract
The invention discloses a polyvinyl alcohol (PVA) -based piezoelectric active hydrogel and a preparation and forming method thereof, which are characterized in that polyvinylidene fluoride (PVDF) with excellent piezoelectric property is selected and compounded with PVA, and a high-efficiency preparation and forming method of freeze thawing, solvent replacement, annealing and swelling is established through research so as to greatly enhance the intermolecular interaction of PVA/PVDF in the gel forming process and promote the formation of PVDF high-voltage electrical beta crystal, thereby endowing the PVA gel with excellent piezoelectric functional property and having better application prospect in the field of biomedical engineering.
Description
Technical Field
The invention relates to a polyvinyl alcohol-based piezoelectric active hydrogel and a preparation and forming method thereof, belonging to the field of polymer processing.
Background
The piezoelectric material is a material which can induce the surface of the material to generate charge in proportion or generate geometric strain corresponding to an applied electric field by applying mechanical stress, and the formed positive (reverse) piezoelectric effect enables the material to be widely applied to various fields of medical treatment, military, electronics, energy sources and the like as a mechanical energy-electric energy transducer, a sensor, a driver and the like. Piezoelectricity can be found in different parts of the human body, such as bones, tendons, ligaments, skin, dentin, collagen and the like, so that research and application of piezoelectric materials are of great significance for healing and repairing human tissues, particularly skin and skeletal muscles.
The polyvinyl alcohol (PVA) hydrogel has a three-dimensional network structure, no toxicity, no side effect, excellent biocompatibility and chemistryThe PVA hydrogel material has the advantages of stable property, excellent flexibility and high elasticity, high water absorption, easy processing and wide application prospect in the field of biomedical engineering, and few research reports on the PVA hydrogel material with piezoelectric activity at present: wangwnjiang, China geological university (Beijing), 2020, prepared a piezoelectric power generation composite hydrogel by a tape casting method with PVA as a matrix and LiCl as a filler, and studied Li+The polarization capability in PVA hydrogel and the influence factors influencing the polarization, the dielectric constant and the loss of the composite gel are increased along with the increase of the content, the thickness and the water content of LiCl, and the power generation performance is enhanced after high-pressure polarization. PVA hydrogel materials with high piezoelectric activity are still to be researched and developed.
Disclosure of Invention
The invention aims to provide a polyvinyl alcohol (PVA) -based piezoelectric active hydrogel and a preparation and forming method thereof, aiming at the defects of the prior art, and the preparation and forming method is characterized in that polyvinylidene fluoride (PVDF) with excellent piezoelectric property is selected and compounded with PVA, and a high-efficiency preparation and forming method of freeze thawing, solvent replacement, annealing and swelling is established through research so as to greatly enhance the intermolecular interaction of the PVA/PVDF in the gel forming process and promote the formation of PVDF high-voltage electrical beta crystal, thereby endowing the PVDF with excellent piezoelectric functional property.
The aim of the invention is achieved by the following technical measures, wherein the raw material fractions are parts by weight except for special specifications.
A polyvinyl alcohol-based piezoelectric active hydrogel and a preparation method thereof comprise the following steps:
adding 10 parts of PVA into 50-300 parts of dimethyl sulfoxide (DMSO) and 10-50 parts of water, dissolving at 90 ℃, and adjusting the pH value to 6-8 by hydrochloric acid to obtain a solution I; adding 1-30 parts of PVDF into 5-300 parts of DMSO, and dissolving at 90 ℃ to obtain a solution II; uniformly mixing the solution I and the solution II, pouring the mixture into a mold, freezing the mixture for 10 to 30 hours at a temperature of between 18 ℃ below zero and 40 ℃ below zero, unfreezing the mixture for 4 to 20 hours, and freezing and unfreezing the mixture for 1 to 4 times to obtain gel containing a DMSO solvent, soaking the gel in distilled water, and changing the water for multiple times until no DMSO exists in the water to obtain PVA/PVDF hydrogel; further annealing the hydrogel at 50-150 ℃ for 3-30h, and then putting the hydrogel in distilled water for swelling for 4-20h to obtain PVA-based hydrogel with piezoelectric activity; wherein the polymerization degree of the PVA is 400-3000, and the alcoholysis degree is 75-99%.
The output voltage of the prepared polyvinyl alcohol-based piezoelectric active hydrogel can reach 4.0V, and the output current can reach 247.4 nA.
The invention has the following advantages:
the invention aims at the application requirement of polyvinyl alcohol (PVA) hydrogel in the field of biomedical engineering, and aims to prepare the PVA hydrogel with piezoelectric activity. Selecting polyvinylidene fluoride (PVDF) with excellent piezoelectricity, compounding the PVDF with PVA, researching and establishing a freeze-thaw-solvent replacement-annealing-swelling efficient preparation and forming method, preliminarily forming a gel sample containing a DMSO solvent in a freeze-thaw stage, and forming certain hydrogen bond action and microcrystals among PVA molecules and between the PVA molecules and PVDF molecules to form a physical cross-linking point; after the DMSO solvent is replaced by water, the hydrogen bond function and the crystallinity of the DMSO solvent are enhanced; and then annealing the composite material, further enhancing the intermolecular hydrogen bond action and the crosslinking degree of the composite system to form a three-dimensional network structure, greatly improving the intermolecular interaction of PVA/PVDF, and promoting the formation of PVDF high-voltage electrical beta crystal, thereby endowing PVA gel with excellent piezoelectric functional characteristics.
Detailed Description
The present invention is described in detail below by way of examples, it should be noted that the examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that those skilled in the art can make insubstantial modifications and adaptations of the present invention based on the above disclosure.
Example 1
Adding 5g of PVA into 25g of dimethyl sulfoxide (DMSO) and 5g of water, dissolving at 90 ℃, and adjusting the pH value to 6 by using hydrochloric acid to obtain a solution I; 0.5g PVDF is added into 2.5g DMSO and dissolved at 90 ℃ to obtain a solution II; uniformly mixing the solution I and the solution II, pouring the mixture into a mold, freezing the mixture for 10 hours at the temperature of-18 ℃, thawing the mixture for 4 hours, freezing and thawing the mixture for 1 time to obtain gel containing a DMSO solvent, soaking the gel in distilled water, and changing water for many times until no DMSO exists in the water to obtain PVA/PVDF hydrogel; the hydrogel was further annealed at 50 ℃ for 3h, and then swollen in distilled water for 4h to obtain a PVA-based hydrogel having piezoelectric activity.
Example 2
Adding 5g of PVA into 100g of dimethyl sulfoxide (DMSO) and 12.5g of water, dissolving at 90 ℃, and adjusting the pH value to 7 by using hydrochloric acid to obtain a solution I; adding 7.5g of PVDF into 50g of DMSO, and dissolving at 90 ℃ to obtain a solution II; uniformly mixing the solution I and the solution II, pouring the mixture into a mold, freezing the mixture for 20 hours at the temperature of minus 25 ℃, unfreezing the mixture for 10 hours, and freezing and unfreezing the mixture for 2 times to obtain gel containing a DMSO solvent, soaking the gel in distilled water, and changing the water for many times until no DMSO exists in the water to obtain PVA/PVDF hydrogel; the hydrogel was further annealed at 100 ℃ for 15h, and then placed in distilled water to swell for 10h, to obtain a PVA-based hydrogel having piezoelectric activity.
Example 3
Adding 5g of PVA into 150g of dimethyl sulfoxide (DMSO) and 25g of water, dissolving at 90 ℃, and adjusting the pH value to 6.5 by using hydrochloric acid to obtain a solution I; adding 15g of PVDF into 150g of DMSO, and dissolving at 90 ℃ to obtain a solution II; uniformly mixing the solution I and the solution II, pouring the mixture into a mold, freezing the mixture for 30 hours at the temperature of minus 40 ℃, unfreezing the mixture for 20 hours, freezing and unfreezing the mixture for 4 times to obtain gel containing a DMSO solvent, soaking the gel in distilled water, and changing the water for many times until no DMSO exists in the water to obtain PVA/PVDF hydrogel; the hydrogel was further annealed at 150 ℃ for 30h, and then placed in distilled water to swell for 10h, to obtain a PVA-based hydrogel having piezoelectric activity.
Claims (1)
1. The polyvinyl alcohol-based piezoelectric active hydrogel is characterized in that the preparation and forming method of the hydrogel comprises the following steps:
adding 10 parts of PVA into 50-300 parts of dimethyl sulfoxide (DMSO) and 10-50 parts of water, dissolving at 90 ℃, and adjusting the pH value to 6-8 by hydrochloric acid to obtain a solution I; adding 1-30 parts of PVDF into 5-300 parts of DMSO, and dissolving at 90 ℃ to obtain a solution II; uniformly mixing the solution I and the solution II, pouring the mixture into a mold, freezing the mixture for 10 to 30 hours at a temperature of between 18 ℃ below zero and 40 ℃ below zero, unfreezing the mixture for 4 to 20 hours, and freezing and unfreezing the mixture for 1 to 4 times to obtain gel containing a DMSO solvent, soaking the gel in distilled water, and changing the water for multiple times until no DMSO exists in the water to obtain PVA/PVDF hydrogel; further annealing the hydrogel at 50-150 ℃ for 3-30h, and then putting the hydrogel in distilled water for swelling for 4-20h to obtain PVA-based hydrogel with piezoelectric activity; wherein the polymerization degree of the PVA is 400-3000, and the alcoholysis degree is 75-99%.
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| CN202111525569.6A CN114015079B (en) | 2021-12-14 | 2021-12-14 | Polyvinyl alcohol-based piezoelectric active hydrogel and preparation and forming method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116531553A (en) * | 2023-05-04 | 2023-08-04 | 中山大学附属第一医院 | Piezoelectric hydrogel for repairing diabetic wound surface as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101111542A (en) * | 2004-10-12 | 2008-01-23 | 齐默有限公司 | Pva hydrogel |
| CN106668870A (en) * | 2016-12-28 | 2017-05-17 | 常州大学 | Preparation method for medicine-carrying polypyrrole/sodium alginate gel |
| CN106810704A (en) * | 2017-02-08 | 2017-06-09 | 郑州大学 | Polyvinyl alcohol hydrogel and its preparation method and application |
| CN113304324A (en) * | 2021-03-31 | 2021-08-27 | 西南交通大学 | Preparation method of piezoelectric hydrogel and product |
-
2021
- 2021-12-14 CN CN202111525569.6A patent/CN114015079B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101111542A (en) * | 2004-10-12 | 2008-01-23 | 齐默有限公司 | Pva hydrogel |
| CN106668870A (en) * | 2016-12-28 | 2017-05-17 | 常州大学 | Preparation method for medicine-carrying polypyrrole/sodium alginate gel |
| CN106810704A (en) * | 2017-02-08 | 2017-06-09 | 郑州大学 | Polyvinyl alcohol hydrogel and its preparation method and application |
| CN113304324A (en) * | 2021-03-31 | 2021-08-27 | 西南交通大学 | Preparation method of piezoelectric hydrogel and product |
Non-Patent Citations (1)
| Title |
|---|
| 崔晓彤: "PVA-HA/PAA 复合水凝胶的制备与性能表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116531553A (en) * | 2023-05-04 | 2023-08-04 | 中山大学附属第一医院 | Piezoelectric hydrogel for repairing diabetic wound surface as well as preparation method and application thereof |
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