CN115975319B - High self-adhesion polyvinyl alcohol-based hydrogel and preparation and molding method thereof - Google Patents
High self-adhesion polyvinyl alcohol-based hydrogel and preparation and molding method thereof Download PDFInfo
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- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 8
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- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004971 Cross linker Substances 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- LJAGLQVRUZWQGK-UHFFFAOYSA-N oxecane-2,10-dione Chemical compound O=C1CCCCCCCC(=O)O1 LJAGLQVRUZWQGK-UHFFFAOYSA-N 0.000 claims description 2
- ZJHUBLNWMCWUOV-UHFFFAOYSA-N oxocane-2,8-dione Chemical compound O=C1CCCCCC(=O)O1 ZJHUBLNWMCWUOV-UHFFFAOYSA-N 0.000 claims description 2
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- 108010004563 mussel adhesive protein Proteins 0.000 abstract description 4
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- Medicinal Preparation (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a high self-adhesion polyvinyl alcohol-based hydrogel and a preparation and molding method thereof, which are characterized in that the invention is based on the research and development of wearable devices such as a wearable sensor, a skin fuel cell and the like, and the invention breaks through the traditional preparation methods of hydrogels such as a freeze-thawing method, a boric acid crosslinking method and the like based on the polyvinyl alcohol hydrogel with good biocompatibility, high mechanical strength, water content similar to human tissues, elastic modulus and the like, and uses a hybrid of high self-adhesion Polydopamine (PDA) with mussel adhesive protein structure and Graphene Oxide (GO) as a crosslinking agent to form a multi-crosslinking network structure by utilizing covalent/non-covalent interaction between the GO-PDA hybrid crosslinking agent and CPVA molecules, thereby obtaining the high self-adhesion polyvinyl alcohol-based hydrogel, endowing the high self-adhesion polyvinyl alcohol-based hydrogel with excellent adhesion to various material substrates such as human skin, stretchable flexibility, conductivity and high sensing sensitivity, and shows good application prospect in the field of the wearable devices.
Description
Technical Field
The invention relates to a high self-adhesive polyvinyl alcohol-based hydrogel and a preparation and molding method thereof, belonging to the field of polymer processing.
Background
The adhesive polymer hydrogel has high water content, good mechanical flexibility, a structure similar to that of natural soft tissues, and can be firmly adhered to various solid surfaces, so that the adhesive polymer hydrogel can be widely applied as a wearable sensor, a skin fuel cell, a tissue sealant, a wound dressing, a transdermal drug delivery patch and the like, and can be perfectly adhered to the skin surface of a human body under the condition of not needing external auxiliary adhesive means, thereby being beneficial to meeting the complex curvature change of the skin and remarkably improving the working efficiency and stability of the wearable device.
The Poly Dopamine (PDA) similar to the mussel adhesive protein structure is rich in various functional groups such as quinolyl, catechol, amino and the like, can realize firm adhesion on the surfaces of various organic and inorganic materials, and can be introduced into a polymer hydrogel network to obtain the simulated mussel adhesive hydrogel capable of being adhered to the surface of human skin; however, for adhesive hydrogels prepared based on chemical synthetic materials such as polyacrylamide or polyacrylic acid, residual toxic monomers can cause skin allergy and generate inflammatory reaction, and for adhesive hydrogels prepared based on natural biological materials such as polysaccharide, protein, hyaluronic acid and the like, toughness and adhesive strength are weak, so that the application of the adhesive hydrogels in wearable devices is limited. Polyvinyl alcohol (PVA) is a polyhydroxy water-based polymer, PVA hydrogel is a porous material with a three-dimensional network structure, which is formed by PVA molecules through physical or chemical crosslinking in water solution, has water content and elastic modulus similar to human tissues, good biocompatibility, high mechanical strength, low friction coefficient and the like, and hydroxyl groups existing on the molecular structure can form stronger interaction with a substrate, so that the porous material has good adhesiveness; however, the conventional PVA hydrogel preparation methods, such as a freeze-thawing method and a boric acid crosslinking method, consume a large number of hydroxyl groups on the molecular chain during the crosslinking process, so that the adhesiveness of the gel is weakened; meanwhile, in the preparation process of the mussel-like adhesive hydrogel, PDA molecules are mostly added into a polymer gel matrix in a direct mixing mode, and the PDA molecules are easy to lose in the preparation and use processes due to weaker interaction with matrix molecules, so that the adhesiveness of the obtained gel is still lower, and therefore, the development of a wearable device with high self-adhesiveness and stretchable flexibility is urgently needed.
Disclosure of Invention
The invention aims to provide a high self-adhesive polyvinyl alcohol-based hydrogel and a preparation and molding method thereof, which are characterized in that the invention is based on PVA hydrogel with good biocompatibility, high mechanical strength, water content similar to human tissues, elastic modulus and the like aiming at research and development of wearable devices such as wearable sensors, skin fuel cells and the like, breaks through the traditional preparation methods of hydrogels such as a freezing-thawing method, a boric acid crosslinking method and the like, introduces Carboxyl (CPVA) on a PVA molecular chain, takes a hybrid of high self-adhesive Polydopamine (PDA) with mussel adhesive protein structure and Graphene Oxide (GO) as a crosslinking agent, utilizes covalent/non-covalent interaction between the GO-PDA hybrid crosslinking agent and CPVA molecules to form a multi-crosslinking network structure, and obtains the high self-adhesive PVA-based hydrogel, thereby endowing the high self-adhesive PVA-based hydrogel with excellent adhesiveness, tensile flexibility, conductivity and high sensitivity to various material substrates such as human skin and the like.
The aim of the invention is achieved by the following technical measures, wherein the raw material fractions are parts by weight, except for the specific description.
The preparation method of the high self-adhesive polyvinyl alcohol-based hydrogel comprises the following steps:
preparation of GO-PDA hybrid crosslinker
Dispersing 1 part of Graphene Oxide (GO) and 1-50 parts of dopamine hydrochloride (DA) in 100-5000 parts of deionized water by ultrasonic, reacting for 30min-5h at room temperature, centrifuging, washing, and drying for later use;
preparation of Gao Zinian-based polyvinyl alcohol hydrogels
Dissolving 20 parts of polyvinyl alcohol (PVA) in 100-5000 parts of dimethyl sulfoxide, adding 1-10 parts of cyclic anhydride and 0.1-5 parts of triethylamine, reacting for 1-15 hours at 30-100 ℃, then cooling to room temperature, pouring the obtained product into acetone for precipitation, soaking, washing and drying to obtain carboxylated polyvinyl alcohol (CPVA); wherein, the polymerization degree of the polyvinyl alcohol is 400-3000, and the alcoholysis degree is 75-99%; the cyclic anhydride is any one of maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, azelaic anhydride and phthalic anhydride;
dissolving 20 parts of CPVA in 100-5000 parts of deionized water at 90 ℃ to obtain a solution (1); dispersing 1-10 parts of dopamine hydrochloride (DA) and 0.1-5 parts of GO-PDA in 10-100 parts of deionized water in an ultrasonic manner, adjusting the pH value to 8.5 by using NaOH to form a GO-PDA hybrid cross-linking agent solution, and marking the GO-PDA hybrid cross-linking agent solution as a solution (2); 1-10 parts of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 1-10 parts of N-hydroxysulfosuccinimide (NHS) are added into the solution (1) for activation, then the mixture is uniformly mixed with the solution (2), poured into a mould and crosslinked at room temperature, and the CPVA/GO-PDA high self-adhesive hydrogel is prepared.
The adhesive strength of the high self-adhesive polyvinyl alcohol-based hydrogel prepared by the invention to metal, rubber and pigskin can reach 150-210kPa, 150-200kPa and 30-60kPa respectively, the elongation at break can reach 1000-1500%, the strain sensitivity (GF) can reach 5-10, the micro deformation can be monitored, and the resistance change signals can be accurately and stably output and identified.
The invention has the following advantages:
the invention prepares a high self-adhesion polyvinyl alcohol-based hydrogel, which has the following characteristics:
due to the conventional PVA hydrogel preparation methods, such as freeze-thawing method, boric acid crosslinking method, during crosslinking
Consuming a large number of hydroxyl groups on the molecular chain, thereby weakening the adhesiveness of the gel; the invention breaks through the traditional PVA hydrogel preparation method, and constructs the PVA-based nano composite hydrogel with a multi-crosslinking network structure by taking the GO-PDA as a hybridization crosslinking point in a PVA composite system by introducing Carboxyl (CPVA) on a PVA molecular chain and creatively taking a hybrid of high self-adhesive Polydopamine (PDA) with a mussel adhesive protein structure and Graphene Oxide (GO) as a crosslinking agent and utilizing amidation reaction between the carboxyl on the CPVA molecular chain and amino on the PDA molecular chain, and the physical crosslinking effect of hydrogen bonding and the like by taking the GO as a crosslinking center in the system; because the composite system contains a large number of functional groups such as carboxyl, hydroxyl, catechol, quinolyl, amino and the like, the interaction sites between the composite system and the substrate material are increased
Strong, the adhesive strength is obviously increased;
in the preparation process of the mussel-like adhesive hydrogel, PDA molecules are mostly added into a polymer gel matrix in a direct mixing mode, and the PDA molecules are easy to lose in the preparation and use processes due to weaker interaction with matrix molecules, so that the adhesion of the obtained gel is still lower; the invention forms a multi-crosslinking network structure by utilizing covalent/non-covalent interaction between the GO-PDA hybrid crosslinking agent and CPVA molecules, thereby bonding the PDA molecules into the PVA molecular crosslinking network, effectively solving the problem that the PVA molecules are easy to fall off and lose in the preparation and use processes, and obtaining the high self-adhesive PVA base
A hydrogel;
grafting Dopamine (DA) to GO layer using Graphene Oxide (GO) high enhancement effect and excellent conductivity
And (3) researching and preparing the GO-PDA hybrid cross-linking agent to form a brick mud structure, uniformly dispersing the brick mud structure in a CPVA matrix, and forming the CPVA/GO-PDA nano composite hydrogel with a multi-cross-linked network structure through intermolecular physical-chemical action, so that the hydrogel is endowed with excellent toughness, conductivity and high sensing sensitivity, and has a good application prospect in the field of wearable devices.
Detailed Description
The present invention is described in detail below by way of examples, which are necessary to be pointed out herein for further illustration only and are not to be construed as limiting the scope of the invention, as those skilled in the art may make numerous insubstantial improvements and adaptations of the invention based on the foregoing disclosure.
Example 1
1g of Graphene Oxide (GO) and 10g of dopamine hydrochloride (DA) are ultrasonically dispersed in 1000g of deionized water, reacted for 1h at room temperature, and then centrifuged, washed and dried for later use.
Dissolving 20g of polyvinyl alcohol (PVA) with the polymerization degree of 1700 and the alcoholysis degree of 88% in 1000g of dimethyl sulfoxide, adding 5g of maleic anhydride and 0.5g of triethylamine, reacting for 10 hours at 50 ℃, then cooling to room temperature, pouring the obtained product into acetone for precipitation, soaking, washing and drying to obtain carboxylated polyvinyl alcohol (CPVA);
20g CPVA was dissolved in 2000g deionized water at 90℃and designated solution (1); dispersing 2g of dopamine hydrochloride (DA) and 1g of GO-PDA in 80g of deionized water in an ultrasonic manner, adjusting the pH value to 8.5 by using NaOH to form a GO-PDA hybrid cross-linking agent solution, and marking the GO-PDA hybrid cross-linking agent solution as a solution (2); 2g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 5-g N-hydroxy thiosuccinimide (NHS) are added into the solution (1) for activation, then the mixture is uniformly mixed with the solution (2), poured into a mould and crosslinked at room temperature, and the CPVA/GO-PDA high self-adhesive hydrogel is prepared.
Example 2
1g of Graphene Oxide (GO) and 5g of dopamine hydrochloride (DA) are ultrasonically dispersed in 500g of deionized water, reacted for 2 hours at room temperature, and then centrifuged, washed and dried for later use.
Dissolving 20g of polyvinyl alcohol (PVA) with the polymerization degree of 1500 and the alcoholysis degree of 99 percent in 2000g of dimethyl sulfoxide, adding 3g of glutaric anhydride and 1g of triethylamine, reacting for 7 hours at 60 ℃, then cooling to room temperature, pouring the obtained product into acetone for precipitation, soaking, washing and drying to obtain carboxylated polyvinyl alcohol (CPVA);
20g CPVA was dissolved in 3000g deionized water at 90℃and noted as solution (1); dispersing 5g of dopamine hydrochloride (DA) and 2g of GO-PDA in 50g of deionized water in an ultrasonic manner, adjusting the pH value to 8.5 by using NaOH to form a GO-PDA hybrid cross-linking agent solution, and marking the GO-PDA hybrid cross-linking agent solution as a solution (2); 5g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 3g N-hydroxysulfosuccinimide (NHS) are added into the solution (1) for activation, then the mixture is uniformly mixed with the solution (2), poured into a mould and crosslinked at room temperature, and the CPVA/GO-PDA high self-adhesive hydrogel is prepared.
Claims (1)
1. The preparation and molding method of the high self-adhesive polyvinyl alcohol-based hydrogel is characterized by comprising the following steps of: preparation of GO-PDA hybrid crosslinker
Dispersing 1 part of Graphene Oxide (GO) and 1-50 parts of dopamine hydrochloride (DA) in 100-5000 parts of deionized water by ultrasonic, reacting for 30min-5h at room temperature, centrifuging, washing, and drying for later use;
preparation of Gao Zinian-based polyvinyl alcohol hydrogels
Dissolving 20 parts of polyvinyl alcohol (PVA) in 100-5000 parts of dimethyl sulfoxide, adding 1-10 parts of cyclic anhydride and 0.1-5 parts of triethylamine, reacting for 1-15 hours at 30-100 ℃, then cooling to room temperature, pouring the obtained product into acetone for precipitation, soaking, washing and drying to obtain carboxylated polyvinyl alcohol (CPVA); wherein, the polymerization degree of the polyvinyl alcohol is 400-3000, and the alcoholysis degree is 75-99%; the cyclic anhydride is any one of maleic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, pimelic anhydride, azelaic anhydride and phthalic anhydride;
dissolving 20 parts of CPVA in 100-5000 parts of deionized water at 90 ℃ to obtain a solution (1); dispersing 1-10 parts of dopamine hydrochloride (DA) and 0.1-5 parts of GO-PDA in 10-100 parts of deionized water in an ultrasonic manner, adjusting the pH value to 8.5 by using NaOH to form a GO-PDA hybrid cross-linking agent solution, and marking the GO-PDA hybrid cross-linking agent solution as a solution (2); 1-10 parts of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (EDC) and 1-10 parts of N-hydroxysulfosuccinimide (NHS) are added into the solution (1) for activation, then the mixture is uniformly mixed with the solution (2), poured into a mould and crosslinked at room temperature, and the CPVA/GO-PDA high self-adhesive hydrogel is prepared.
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| CN105906744A (en) * | 2016-05-05 | 2016-08-31 | 四川大学 | Fusible self-repairing modified polyvinylalcohol elastomer and preparation method thereof |
| CN107840971A (en) * | 2017-10-27 | 2018-03-27 | 华南理工大学 | It is a kind of that from adhering to, wearable power is quick to sense composite aquogel and preparation method thereof |
| CN108530651A (en) * | 2018-01-25 | 2018-09-14 | 四川大学 | PH is sensitive, can self-healing, can cell adhesion medical aquogel and preparation method thereof |
| CN111333865A (en) * | 2020-03-20 | 2020-06-26 | 重庆石墨烯研究院有限公司 | Preparation method of high-strength wear-resistant polyvinyl alcohol hydrogel |
| CN113930037A (en) * | 2021-10-27 | 2022-01-14 | 苏州大学 | Filling type flexible strain sensing material and preparation method thereof |
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