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WO2025030644A1 - Viscosity-adjustable hydrogel material, and preparation method therefor and use thereof - Google Patents

Viscosity-adjustable hydrogel material, and preparation method therefor and use thereof Download PDF

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Publication number
WO2025030644A1
WO2025030644A1 PCT/CN2023/120704 CN2023120704W WO2025030644A1 WO 2025030644 A1 WO2025030644 A1 WO 2025030644A1 CN 2023120704 W CN2023120704 W CN 2023120704W WO 2025030644 A1 WO2025030644 A1 WO 2025030644A1
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parts
weight
viscosity
hydrogel material
adjustable
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Chinese (zh)
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孙洪岩
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to CN202380044152.9A priority Critical patent/CN119325491A/en
Publication of WO2025030644A1 publication Critical patent/WO2025030644A1/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/02Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075Macromolecular gels
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02Inorganic compounds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38Cellulose; Derivatives thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/06Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised 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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24Homopolymers or copolymers of amides or imides
    • C08J2333/26Homopolymers or copolymers of acrylamide or methacrylamide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02Polyalkylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/17Amines; Quaternary ammonium compounds
    • C08K5/18Amines; Quaternary ammonium compounds with aromatically bound amino groups

Definitions

  • the present application belongs to the technical field of self-repairing materials, and specifically relates to a viscosity-adjustable hydrogel material and a preparation method and application thereof.
  • Hydrogel is a hydrophilic polymer with a three-dimensional network structure synthesized from natural or synthetic materials. Due to the presence of hydrophilic groups such as -NH2 , -COOH, and -OH, the hydrogel network can form hydrogen bonds with water molecules, allowing the hydrogel to absorb and retain a large amount of water. Hydrogels are not only highly flexible, but also have a soft rubber consistency similar to living tissue, making them ideal substances or carriers for various applications.
  • Hydrogel is a gel material formed by physical or chemical cross-linking. Different cross-linking methods and matrix materials can give hydrogels adjustable physical and chemical properties. The large amount of water filled in its three-dimensional network structure helps to maintain good affinity between the hydrogel and the organism.
  • hydrogels when hydrogels are used in the human body, in addition to their own ability to promote wound healing and anti-inflammatory effects and to play a therapeutic role in diseases such as tumors, they can also be used as carriers of proteins, nucleic acids and small molecule drugs.
  • As an intelligent drug delivery system it can realize the controlled release process of substances in the human body, solve the problem of drugs being easily enzymatically or hydrolyzed, and thus improve the stability of drug delivery.
  • Biocompatible hydrogels allow electronic devices to directly contact human skin and can even be safely implanted in the body for long-term use, with minimal inflammatory or immune response to host tissues.
  • the intrinsic weight and flexibility of hydrogels can alleviate the discomfort caused by foreign devices that are worn or implanted in the human body for a long time, achieve continuous and persistent monitoring of healthcare sensing applications, and meet the basic requirements of the next generation of intelligent monitoring systems for continuous and long-term monitoring.
  • biodegradable and renewable natural materials can eventually return to nature after their service, avoiding the damage caused by the large-scale application of flexible electronics.
  • hydrogel As a new functional material, hydrogel has the characteristics of high water absorption and retention, biocompatibility, flexibility, etc. It can be endowed with specific properties through the selection of different materials and means of modification and compounding. Therefore, hydrogel and its derivatives have high research value and are increasingly widely used in various fields.
  • CN115286731A discloses an external light-cured medical hydrogel and a preparation method thereof, wherein the medical hydrogel is obtained by subjecting a pre-gel light-cured solution to ultraviolet light curing reaction.
  • CN110240712A discloses a high-stretch, high-viscosity, self-healing double-network hydrogel for tissue adhesion and a preparation method and application thereof, wherein the above hydrogels are only viscous and cannot achieve adjustable and coexistent properties of stickiness and non-stickiness, and have poor biocompatibility.
  • hydrogel materials exist in only one state, sticky or non-sticky, which cannot be adjusted.
  • the sticky and non-sticky properties of the same hydrogel material cannot be adjusted and coexist, which limits its application.
  • the hydrogel will freeze and cannot be restored after dehydration after thawing.
  • the biocompatibility of the hydrogel is poor. Therefore, it is an issue that cannot be ignored to develop a hydrogel material with adjustable and coexistent sticky and non-sticky properties, antifreeze and moisture retention, self-healing, biocompatibility and elasticity, which is suitable for biomedical materials and flexible electronic devices.
  • the present application provides a viscosity-adjustable hydrogel material, a preparation method and application thereof, which achieves the characteristics of adjustable and coexistent viscosity and non-viscosity by regulating with different chemical components, and at the same time has antifreeze and moisture retention, self-healing, biocompatibility and flexibility.
  • the present application provides a viscosity adjustable hydrogel material, wherein the raw materials for preparing the viscosity adjustable hydrogel material include the following components in parts by weight: 10 to 30 parts by weight of monomer, 1 to 20 parts by weight of cross-linking agent, 0.1 to 5 parts by weight of long-chain polymer, 0.01 to 5 parts by weight of dopamine hydrochloride, 0.01 to 5 parts by weight of clay and 50 to 90 parts by weight of water.
  • the viscosity-adjustable hydrogel material provided by the present application is an interpenetrating network flexible elastic hydrogel material, which forms a gel by reacting a monomer with a cross-linking agent, and the long-chain polymer can improve the overall flexibility and viscosity of the hydrogel material in the form of an interpenetrating network; dopamine hydrochloride can self-polymerize into polydopamine, which can also improve the overall viscosity of the hydrogel material and increase the self-healing performance in the form of an interpenetrating network; clay can be used to improve the strength of the hydrogel material; through the selection of chemical components and the regulation of dosage, the viscosity-adjustable hydrogel material provided by the present application can achieve the regulation of sticky and non-sticky properties, that is, a viscous hydrogel material can be obtained, and also a non-sticky hydrogel material can be obtained.
  • a hydrogel material with one side being sticky and the other side being non-sticky can be obtained, thereby achieving compatibility and coexistence of sticky and non-sticky hydrogel materials.
  • the added amount of the monomer can be 10 to 30 parts by weight, for example, it can be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight or 30 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the amount of the cross-linking agent added can be 1 to 20 parts by weight, for example, 1 part by weight, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight or 20 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the addition amount of the long-chain polymer can be 0.1 to 5 parts by weight, for example, it can be 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the added amount of dopamine hydrochloride can be 0.01 to 5 parts by weight, for example, it can be 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the added amount of the clay can be 0.01 to 5 parts by weight, for example, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the amount of water added can be 50 to 90 parts by weight, for example, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight or 90 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the monomer includes any one of acrylamide, methacrylamide or hydroxyethyl methacrylate, or a combination of at least two of them.
  • the monomer comprises acrylamide.
  • the cross-linking agent includes polyethylene glycol diacrylate and/or N,N'-methylenebisacrylamide.
  • the cross-linking agent comprises polyethylene glycol diacrylate.
  • the number average molecular weight of the polyethylene glycol diacrylate is 600-1000.
  • the long-chain polymer includes polyethylene oxide and/or hydroxyethyl cellulose.
  • the average molecular weight of the polyethylene oxide is 100,000 to 8,000,000, for example, 100,000, 500,000, 1,000,000, 1,500,000, 2,000,000, 2,500,000, 3,000,000, 3,500,000, 4,000,000, 5,000,000, 6,000,000, 7,000,000 or 8,000,000, as well as specific values between the above values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific values included in the range.
  • the viscosity of the hydroxyethyl cellulose is 100-6400 mPa.s, for example, it may be 100 mPa.s, 500 mPa.s, 1000 mPa.s, 1500 mPa.s, 2000 mPa.s, 3000 mPa.s, 4000 mPa.s, 5000 mPa.s, 6000 mPa.s or 6400 mPa.s, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the clay includes any one of lithium magnesium silicate, carbon fibers, silver nanoparticles, silicon dioxide nanoparticles or graphene oxide, or a combination of at least two thereof.
  • the particle size of the silver nanoparticles is 10 to 100 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the particle size of the silicon dioxide nanoparticles is 10 to 500 nm, for example, 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm, as well as specific point values between the above point values, are limited to space and for the sake of simplicity. Please do not exhaustively list the specific point values included in the stated range.
  • the raw materials for preparing the adjustable viscosity hydrogel material also include 10 to 50 parts by weight of a moisturizer, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the humectant includes polyols.
  • the present application uses the humectant to impart antifreeze and moisturizing properties to the hydrogel material.
  • the polyol comprises glycerol and/or ethylene glycol.
  • the raw materials for preparing the adjustable viscosity hydrogel material also include 0.2 to 2 parts by weight of an initiator, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight or 2 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.
  • the initiator includes any one of a photoinitiator or a thermal initiator, and a photoinitiator is more preferred.
  • the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl-1-propanone and/or 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.
  • the viscosity-adjustable hydrogel material provided in the present application can initiate polymerization in different ways by selecting an initiator.
  • a photoinitiator can initiate polymerization by ultraviolet light irradiation
  • a thermal initiator can initiate polymerization by heating.
  • the present application provides a method for preparing the viscosity-adjustable hydrogel material as described in the first aspect, the preparation method comprising the following steps:
  • the monomer, the cross-linking agent, the long-chain polymer, the dopamine hydrochloride, the clay and the water are mixed to obtain the hydrogel solution precursor; the hydrogel solution precursor is reacted in the presence of the initiator to obtain the hydrogel material.
  • the mixed material also includes a moisturizer.
  • the mixing temperature is 25-60°C, for example, it can be 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the initiator is a photoinitiator, and the reaction is carried out under ultraviolet light.
  • the reaction time is 1 to 5 min, for example, it can be 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min or 5 min, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the reaction temperature is 18-35°C, for example, it can be 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 28°C, 30°C, 32°C, 34°C or 35°C, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.
  • the preparation method specifically comprises the following steps:
  • hydrogel solution precursor (1) mixing monomers, a cross-linking agent, a long-chain polymer, dopamine hydrochloride, a humectant, clay and water to obtain a hydrogel solution precursor;
  • step (3) The reaction system obtained in step (2) is reacted under ultraviolet light to obtain the hydrogel material.
  • the present application provides an application of the viscosity-adjustable hydrogel material as described in the first aspect in biomedical materials or flexible electronic devices.
  • the viscosity-adjustable hydrogel material provided in this application can easily achieve the compatibility and regulation of the two properties of the hydrogel material surface, sticky and non-sticky, through the selection of chemical components and the regulation of dosage, and at the same time has antifreeze and moisture retention, self-healing properties, biocompatibility and flexibility.
  • This application designs and optimizes the raw materials for preparing the viscosity-adjustable hydrogel, and the viscosity-adjustable hydrogel material can be cut and left to stand for 48 hours to achieve self-healing; the adhesion of the viscosity hydrogel material can be as high as 60N/m; it has good antifreeze properties when frozen at -18°C for 24 hours, and there is no ice on the surface; the mass reduction rate is as low as 3.8% when left to stand for 7 days at room temperature, and it has good moisture retention.
  • FIG. 1 is a photograph of the self-healing performance test of the viscosity-adjustable hydrogel material provided in Example 3.
  • FIG2 is a photograph showing the self-healing performance test of the hydrogel material provided in Comparative Example 1.
  • FIG3 is a photograph of the viscoelastic tensile test of the viscosity-adjustable hydrogel material provided in Example 1.
  • FIG. 4 is a comparative diagram of the adhesion of the viscosity-adjustable hydrogel materials provided in Example 1 and Example 2.
  • FIG. 5 is a bar graph showing the biocompatibility test of the viscosity-adjustable hydrogel material provided in Example 1.
  • Polyethylene glycol diacrylate number average molecular weight 1000, purchased from Aladdin Chemical Reagent;
  • a viscosity-adjustable hydrogel material The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 20 parts by weight of acrylamide, 1 part by weight of polyethylene glycol diacrylate, 3 parts by weight of polyethylene oxide, 2 parts by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.01 parts by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
  • a method for preparing a hydrogel material with adjustable viscosity comprising the following steps:
  • step (2) adding 2-hydroxy-2-methyl-1-phenyl-1-propanone to the hydrogel solution precursor obtained in step (1), continuing to stir for more than 10 minutes to obtain a reaction system, and then pouring it into a mold;
  • step (3) The reaction system obtained in step (2) is reacted under ultraviolet light for 2 minutes to obtain the viscosity-adjustable hydrogel material.
  • a viscosity-adjustable hydrogel material The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 15 parts by weight of acrylamide, 5 parts by weight of polyethylene glycol diacrylate, 0.5 parts by weight of polyethylene oxide, 0.01 parts by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.1 parts by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
  • a method for preparing a hydrogel material with adjustable viscosity which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this example, and the remaining process parameters and steps are the same as those in Example 1. same.
  • a viscosity-adjustable hydrogel material The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 25 parts by weight of acrylamide, 1 part by weight of polyethylene glycol diacrylate, 3 parts by weight of polyethylene oxide, 1 part by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.01 part by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
  • a method for preparing a hydrogel material with adjustable viscosity which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this example, and the remaining process parameters and steps are the same as those in Example 1.
  • a viscosity-adjustable hydrogel material The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 30 parts by weight of acrylamide, 1 part by weight of polyethylene glycol diacrylate, 1 part by weight of polyethylene oxide, 0.01 part by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.1 part by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.
  • a method for preparing a hydrogel material with adjustable viscosity which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this example, and the remaining process parameters and steps are the same as those in Example 1.
  • a hydrogel material which is different from Example 3 only in that the raw materials for preparing the hydrogel material do not contain 1 part by weight of dopamine hydrochloride, and the other raw materials are the same as those in Example 3.
  • a method for preparing a hydrogel material which differs from Example 3 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this comparative example, and the remaining process parameters and steps are the same as those in Example 3.
  • a hydrogel material which is different from Example 1 only in that glycerin is not added to the raw materials for preparing the hydrogel material, the added amount of water is 100 parts by weight, and the other raw materials are the same as those in Example 1.
  • a method for preparing a hydrogel material which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this comparative example, and the remaining process parameters and steps are the same as those in Example 1.
  • Adhesion test Using the peeling test method, a PET film or fiber cloth is attached to the surface of a 5 ⁇ 1.5 ⁇ 0.1 cm hydrogel and then peeled off with a certain force. The greater the peeling force, the stronger the adhesion of the hydrogel sample.
  • Viscoelastic tensile test Two hydrogel sections of 3 ⁇ 2 ⁇ 0.2 cm in size were partially overlapped with each other to a length of 1 to 2 cm. The two ends were then fixed and stretched. The length of the hydrogel at the maximum tensile deformation was measured to obtain the maximum tensile length increment.
  • Freeze resistance test A hydrogel sample of 4 ⁇ 4 cm and 1 mm thick was placed in a refrigerator and frozen at -18°C for 24 h. After taking it out, observe whether there is ice on the surface.
  • Moisture retention test A hydrogel sample with a diameter of 13 cm and a thickness of 4 cm and a certain mass was left standing at room temperature for 7 days and then tested for quality.
  • Figure 1 is a photograph of the self-healing performance test of the hydrogel material provided in Example 3; Figure 1 shows that the hydrogel material provided in Example 3 can achieve self-healing after being cut, and can still maintain good flexibility after self-healing.
  • Figure 2 is a photograph of the self-healing performance test of the hydrogel material provided in Example 1; Figure 2 shows that the hydrogel material provided in Example 1 has no self-healing performance because dopamine hydrochloride is not added.
  • Figure 3 is a photograph of the viscoelastic tensile test of the viscosity-adjustable hydrogel material provided in Example 1; Figure 3 shows that the hydrogel material provided in Example 1 has good viscoelastic tensile properties, and the stretched length can reach 800% of the original length.
  • Figure 4 is a comparison diagram of the adhesion of the viscosity-adjustable hydrogel materials provided in Example 1 and Example 2; Figure 4 shows that the viscosity-adjustable hydrogel material provided in this application is generally By regulating the amount of raw materials used in the preparation, the viscosity and non-stickiness of the hydrogel material can be regulated.
  • Figure 5 is a bar graph of the biocompatibility test of the viscosity-adjustable hydrogel material provided in Example 1; it can be seen from Figure 5 that the viscosity-adjustable hydrogel material provided in Example 1 still has a relative stability of up to 95% even after 120 hours, indicating that the hydrogel material provided in this example has good biocompatibility. It can be seen from Table 1 that the viscosity-adjustable hydrogel material provided in the present application has good antifreeze properties.
  • the mass reduction rate of the viscosity-adjustable hydrogel material provided in the present application was 3.8%, which is lower than 76.4% of Comparative Example 2, indicating that the viscosity-adjustable hydrogel material provided in the present application has good moisture retention.

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Abstract

Provided in the present application are a viscosity-adjustable hydrogel material, and a preparation method therefor and the use thereof. The preparation raw materials of the viscosity-adjustable hydrogel material comprise the following components in parts by weight: 10-30 parts of a monomer, 1-20 parts of a cross-linking agent, 0.1-5 parts of a long-chain polymer, 0.01-5 parts of dopamine hydrochloride, 0.01-5 parts of clay and 50-90 parts of water. By means of selection of chemical components and regulation of the amounts thereof, the viscosity-adjustable hydrogel material provided in the present application can easily realize the compatibility and regulation of surface adhesive and non-adhesive properties of the hydrogel material, and also has an anti-freezing moisture retention property, a self-healing property, biocompatibility, flexibility and elasticity, such that same can be applied to biomedical materials or flexible electronic devices.

Description

一种粘性可调水凝胶材料及其制备方法和应用A viscosity adjustable hydrogel material and its preparation method and application 技术领域Technical Field

本申请属于自修复材料技术领域,具体涉及一种粘性可调水凝胶材料及其制备方法和应用。The present application belongs to the technical field of self-repairing materials, and specifically relates to a viscosity-adjustable hydrogel material and a preparation method and application thereof.

背景技术Background Art

水凝胶是一种由天然或合成材料合成的具有三维网络结构亲水聚合物。由于-NH2、-COOH、-OH等亲水基团的存在,水凝胶网络内部可以和水分子形成氢键,使得水凝胶能够吸收并保留大量的水分。水凝胶不仅具有高度的灵活性,还具有类似于活组织的软橡胶稠度,成为各种应用的理想物质或载体。通过改性改变和优化水凝胶原有的性能或通过复合使其具备新的优良性能,比如良好的生物相容性、可降解性和抗菌消炎的性能等,并且使其物理性质、化学性质和结构易于调控,在生物医学材料和柔性电子器件等多个方面,取得了重大突破,具有诱人的应用前景。Hydrogel is a hydrophilic polymer with a three-dimensional network structure synthesized from natural or synthetic materials. Due to the presence of hydrophilic groups such as -NH2 , -COOH, and -OH, the hydrogel network can form hydrogen bonds with water molecules, allowing the hydrogel to absorb and retain a large amount of water. Hydrogels are not only highly flexible, but also have a soft rubber consistency similar to living tissue, making them ideal substances or carriers for various applications. By modifying and optimizing the original properties of hydrogels or by compounding them to give them new excellent properties, such as good biocompatibility, degradability, and antibacterial and anti-inflammatory properties, and making their physical properties, chemical properties, and structures easy to regulate, major breakthroughs have been made in many aspects such as biomedical materials and flexible electronic devices, and they have attractive application prospects.

水凝胶是通过物理或化学交联形成的一种凝胶材料,不同的交联方式及基质材料能赋予水凝胶可调控的理化性质,其三维网络结构中所填充的大量水分有助于保持水凝胶与生物体间良好的亲和性。在生物医学材料领域,当水凝胶用于人体时,除了自身促伤口愈合、消炎的能力和发挥对肿瘤等疾病的治疗功效外,还能用作蛋白质、核酸及小分子药物的载体,作为智能给药系统,在人体内实现物质控释过程,解决药物易被酶解或水解的问题从而提高给药稳定性。Hydrogel is a gel material formed by physical or chemical cross-linking. Different cross-linking methods and matrix materials can give hydrogels adjustable physical and chemical properties. The large amount of water filled in its three-dimensional network structure helps to maintain good affinity between the hydrogel and the organism. In the field of biomedical materials, when hydrogels are used in the human body, in addition to their own ability to promote wound healing and anti-inflammatory effects and to play a therapeutic role in diseases such as tumors, they can also be used as carriers of proteins, nucleic acids and small molecule drugs. As an intelligent drug delivery system, it can realize the controlled release process of substances in the human body, solve the problem of drugs being easily enzymatically or hydrolyzed, and thus improve the stability of drug delivery.

高分子包含丰富的活性基团,提供了足够的分子修饰和改造空间来设计和构建三维交联网络,包括与人体组织顺应的机械性能、增强的导电性和灵敏度、自粘附、自愈合以及可3D打印等,满足了柔性传感材料的多功能集成和器件加工工艺需求。生物相容的水凝胶允许电子设备直接接触人体皮肤,甚至可以安全地植入体内长时间使用,对宿主组织的炎症或免疫反应最小。在柔性电子器件中,水凝胶的内在重量和灵活性可以缓解用于长期佩戴或植入人体的外来设备所带来的不适,实现对医疗保健传感应用的连续和持久的监测,满足下一代智能监护系统需实现连续和长期监测的基本要求。同时,可生物降解和可再生的天然材料最终可以在它们服役后回归自然,避免了因柔性电子大量应用而产 生电子垃圾堆积的环境问题。Polymers contain abundant active groups, which provide sufficient molecular modification and transformation space to design and construct three-dimensional cross-linked networks, including mechanical properties that conform to human tissue, enhanced conductivity and sensitivity, self-adhesion, self-healing, and 3D printing, etc., which meet the multifunctional integration and device processing requirements of flexible sensing materials. Biocompatible hydrogels allow electronic devices to directly contact human skin and can even be safely implanted in the body for long-term use, with minimal inflammatory or immune response to host tissues. In flexible electronic devices, the intrinsic weight and flexibility of hydrogels can alleviate the discomfort caused by foreign devices that are worn or implanted in the human body for a long time, achieve continuous and persistent monitoring of healthcare sensing applications, and meet the basic requirements of the next generation of intelligent monitoring systems for continuous and long-term monitoring. At the same time, biodegradable and renewable natural materials can eventually return to nature after their service, avoiding the damage caused by the large-scale application of flexible electronics. Environmental problems caused by the accumulation of electronic waste.

水凝胶作为新型功能材料,具有高吸水保水性、生物相容性、柔韧等特点,通过不同材料的选择以及改性、复合等手段可赋予其特定性能。因此,水凝胶及其衍生物具有较高的研究价值,在各个领域应用越来越广泛。As a new functional material, hydrogel has the characteristics of high water absorption and retention, biocompatibility, flexibility, etc. It can be endowed with specific properties through the selection of different materials and means of modification and compounding. Therefore, hydrogel and its derivatives have high research value and are increasingly widely used in various fields.

CN115286731A公开了一种外光固化医用水凝胶及其制备方法,所述医用水凝胶通过预凝胶光固化溶液经过紫外光固化反应后获得。CN110240712A公开了一种组织粘合用的高拉伸、高粘性、自愈合双网络水凝胶及其制备方法和应用,上述水凝胶均只具有粘性,无法实现粘与非粘特性可调控及两种特性共存,且生物相容性较差。CN115286731A discloses an external light-cured medical hydrogel and a preparation method thereof, wherein the medical hydrogel is obtained by subjecting a pre-gel light-cured solution to ultraviolet light curing reaction. CN110240712A discloses a high-stretch, high-viscosity, self-healing double-network hydrogel for tissue adhesion and a preparation method and application thereof, wherein the above hydrogels are only viscous and cannot achieve adjustable and coexistent properties of stickiness and non-stickiness, and have poor biocompatibility.

现有技术中,水凝胶材料只存在粘或非粘其中一种状态,不可调控,未能实现同一水凝胶材料粘与非粘特性可调控及共存的特征,使其在应用方面受到单一性限制;其次在0℃以下使用时水凝胶会结冰,解冻后脱水无法复原,同时水凝胶的生物相容性较差。因此,开发一种具有粘性与非粘性可调控及共存、抗冻保湿性、自愈合、生物相容性和柔弹性的水凝胶材料,以适用于生物医学材料及柔性电子器件是一个不容忽视的问题。In the prior art, hydrogel materials exist in only one state, sticky or non-sticky, which cannot be adjusted. The sticky and non-sticky properties of the same hydrogel material cannot be adjusted and coexist, which limits its application. Secondly, when used below 0°C, the hydrogel will freeze and cannot be restored after dehydration after thawing. At the same time, the biocompatibility of the hydrogel is poor. Therefore, it is an issue that cannot be ignored to develop a hydrogel material with adjustable and coexistent sticky and non-sticky properties, antifreeze and moisture retention, self-healing, biocompatibility and elasticity, which is suitable for biomedical materials and flexible electronic devices.

发明内容Summary of the invention

本申请提供了一种粘性可调水凝胶材料及其制备方法和应用,通过采用不同的化学成分调控,使其实现粘与非粘性可调控及共存的特点,同时具有抗冻保湿性、自愈合、生物相容性和柔弹性。The present application provides a viscosity-adjustable hydrogel material, a preparation method and application thereof, which achieves the characteristics of adjustable and coexistent viscosity and non-viscosity by regulating with different chemical components, and at the same time has antifreeze and moisture retention, self-healing, biocompatibility and flexibility.

第一方面,本申请提供一种粘性可调水凝胶材料,所述粘性可调水凝胶材料的制备原料按照重量份包括如下组分:单体10~30重量份、交联剂1~20重量份、长链高分子0.1~5重量份、盐酸多巴胺0.01~5重量份、粘土0.01~5重量份和水50~90重量份。In a first aspect, the present application provides a viscosity adjustable hydrogel material, wherein the raw materials for preparing the viscosity adjustable hydrogel material include the following components in parts by weight: 10 to 30 parts by weight of monomer, 1 to 20 parts by weight of cross-linking agent, 0.1 to 5 parts by weight of long-chain polymer, 0.01 to 5 parts by weight of dopamine hydrochloride, 0.01 to 5 parts by weight of clay and 50 to 90 parts by weight of water.

本申请提供的粘性可调水凝胶材料是一种互穿网络柔弹性水凝胶材料,通过单体与交联剂反应形成凝胶,长链高分子可通过互穿网络的形式提高水凝胶材料整体的柔韧性及粘性作用;盐酸多巴胺可自聚合为聚多巴胺,同样可通过互穿网络的形式提高水凝胶材料整体的粘性和增加自愈合性能;通过粘土可提高水凝胶材料的强度;通过化学组分的选择和用量调控,本申请提供的粘性可调水凝胶材料可实现粘与非粘特性的调控,即可得到粘性水凝胶材料,也可得 到非粘性水凝胶材料,在粘性水凝胶材料表面覆盖一层不粘水凝胶材料,即可得到一面粘一面不粘的水凝胶材料,可实现水凝胶材料粘与非粘性的兼容和共存。The viscosity-adjustable hydrogel material provided by the present application is an interpenetrating network flexible elastic hydrogel material, which forms a gel by reacting a monomer with a cross-linking agent, and the long-chain polymer can improve the overall flexibility and viscosity of the hydrogel material in the form of an interpenetrating network; dopamine hydrochloride can self-polymerize into polydopamine, which can also improve the overall viscosity of the hydrogel material and increase the self-healing performance in the form of an interpenetrating network; clay can be used to improve the strength of the hydrogel material; through the selection of chemical components and the regulation of dosage, the viscosity-adjustable hydrogel material provided by the present application can achieve the regulation of sticky and non-sticky properties, that is, a viscous hydrogel material can be obtained, and also a non-sticky hydrogel material can be obtained. By coating the surface of the sticky hydrogel material with a layer of non-sticky hydrogel material, a hydrogel material with one side being sticky and the other side being non-sticky can be obtained, thereby achieving compatibility and coexistence of sticky and non-sticky hydrogel materials.

所述粘性可调水凝胶材料的制备原料中,单体的添加量可以为10~30重量份,例如可以为10重量份、11重量份、12重量份、13重量份、14重量份、15重量份、16重量份、17重量份、18重量份、19重量份、20重量份、22重量份、24重量份、26重量份、28重量份或30重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。In the preparation raw materials of the viscosity adjustable hydrogel material, the added amount of the monomer can be 10 to 30 parts by weight, for example, it can be 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, 28 parts by weight or 30 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

所述交联剂的添加量可以为1~20重量份,例如可以为1重量份、2重量份、4重量份、6重量份、8重量份、10重量份、12重量份、14重量份、16重量份、18重量份或20重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。The amount of the cross-linking agent added can be 1 to 20 parts by weight, for example, 1 part by weight, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight or 20 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

所述长链高分子的添加量可以为0.1~5重量份,例如可以为0.1重量份、0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份或5重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。The addition amount of the long-chain polymer can be 0.1 to 5 parts by weight, for example, it can be 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

所述盐酸多巴胺的添加量可以为0.01~5重量份,例如可以为0.01重量份、0.05重量份、0.1重量份、0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份或5重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。The added amount of dopamine hydrochloride can be 0.01 to 5 parts by weight, for example, it can be 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

所述粘土的添加量可以为0.01~5重量份,例如可以为0.01重量份、0.05重量份、0.1重量份、0.5重量份、1重量份、1.5重量份、2重量份、2.5重量份、3重量份、3.5重量份、4重量份、4.5重量份或5重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。The added amount of the clay can be 0.01 to 5 parts by weight, for example, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 parts by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight or 5 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

所述水的添加量可以为50~90重量份,例如可以为50重量份、55重量份、60重量份、65重量份、70重量份、75重量份、80重量份、85重量份或90重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。 The amount of water added can be 50 to 90 parts by weight, for example, 50 parts by weight, 55 parts by weight, 60 parts by weight, 65 parts by weight, 70 parts by weight, 75 parts by weight, 80 parts by weight, 85 parts by weight or 90 parts by weight, as well as specific points between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

以下作为本申请的优选技术方案,但不作为对本申请提供的技术方案的限制,通过以下优选的技术方案,可以更好的达到和实现本申请的目的和有益效果。The following are preferred technical solutions of the present application, but are not intended to limit the technical solutions provided by the present application. Through the following preferred technical solutions, the objectives and beneficial effects of the present application can be better achieved and realized.

作为一个优选的技术方案,所述单体包括丙烯酰胺、甲基丙烯酰胺或甲基丙烯酸羟乙酯中的任意一种或至少两种的组合。As a preferred technical solution, the monomer includes any one of acrylamide, methacrylamide or hydroxyethyl methacrylate, or a combination of at least two of them.

优选地,所述单体包括丙烯酰胺。Preferably, the monomer comprises acrylamide.

作为一个优选的技术方案,所述交联剂包括聚乙二醇二丙烯酸酯和/或N,N’-亚甲基双丙烯酰胺。As a preferred technical solution, the cross-linking agent includes polyethylene glycol diacrylate and/or N,N'-methylenebisacrylamide.

优选地,所述交联剂包括聚乙二醇二丙烯酸酯。Preferably, the cross-linking agent comprises polyethylene glycol diacrylate.

优选地,所述聚乙二醇二丙烯酸酯的数均分子量为600~1000。Preferably, the number average molecular weight of the polyethylene glycol diacrylate is 600-1000.

作为一个优选的技术方案,所述长链高分子包括聚环氧乙烷和/或羟乙基纤维素。As a preferred technical solution, the long-chain polymer includes polyethylene oxide and/or hydroxyethyl cellulose.

优选地,所述聚环氧乙烷的平均分子量为100000~8000000,例如可以为100000、500000、1000000、1500000、2000000、2500000、3000000、3500000、4000000、5000000、6000000、7000000或8000000,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。Preferably, the average molecular weight of the polyethylene oxide is 100,000 to 8,000,000, for example, 100,000, 500,000, 1,000,000, 1,500,000, 2,000,000, 2,500,000, 3,000,000, 3,500,000, 4,000,000, 5,000,000, 6,000,000, 7,000,000 or 8,000,000, as well as specific values between the above values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific values included in the range.

优选地,所述羟乙基纤维素的粘度为100~6400mPa.s,例如可以为100mPa.s、500mPa.s、1000mPa.s、1500mPa.s、2000mPa.s、3000mPa.s、4000mPa.s、5000mPa.s、6000mPa.s或6400mPa.s,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。Preferably, the viscosity of the hydroxyethyl cellulose is 100-6400 mPa.s, for example, it may be 100 mPa.s, 500 mPa.s, 1000 mPa.s, 1500 mPa.s, 2000 mPa.s, 3000 mPa.s, 4000 mPa.s, 5000 mPa.s, 6000 mPa.s or 6400 mPa.s, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.

作为一个优选的技术方案,所述粘土包括硅酸镁锂、碳纤维、银纳米粒子、二氧化硅纳米粒子或氧化石墨烯中的任意一种或至少两种的组合。As a preferred technical solution, the clay includes any one of lithium magnesium silicate, carbon fibers, silver nanoparticles, silicon dioxide nanoparticles or graphene oxide, or a combination of at least two thereof.

优选地,所述银纳米粒子的粒径为10~100nm,例如可以为10nm、20nm、30nm、40nm、50nm、60nm、70nm、80nm、90nm或100nm,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。Preferably, the particle size of the silver nanoparticles is 10 to 100 nm, for example, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.

优选地,所述二氧化硅纳米粒子的粒径为10~500nm,例如可以为10nm、50nm、100nm、150nm、200nm、250nm、300nm、350nm、400nm、450nm或500nm,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申 请不再穷尽列举所述范围包括的具体点值。Preferably, the particle size of the silicon dioxide nanoparticles is 10 to 500 nm, for example, 10 nm, 50 nm, 100 nm, 150 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm or 500 nm, as well as specific point values between the above point values, are limited to space and for the sake of simplicity. Please do not exhaustively list the specific point values included in the stated range.

作为一个优选的技术方案,所述粘性可调水凝胶材料的制备原料按照重量份还包括保湿剂10~50重量份,例如可以为10重量份、15重量份、20重量份、25重量份、30重量份、35重量份、40重量份、45重量份或50重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。As a preferred technical solution, the raw materials for preparing the adjustable viscosity hydrogel material also include 10 to 50 parts by weight of a moisturizer, for example, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight or 50 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

优选地,所述保湿剂包括多元醇,本申请通过保湿剂赋予水凝胶材料抗冻保湿性。Preferably, the humectant includes polyols. The present application uses the humectant to impart antifreeze and moisturizing properties to the hydrogel material.

优选地,所述多元醇包括甘油和/或乙二醇。Preferably, the polyol comprises glycerol and/or ethylene glycol.

作为一个优选的技术方案,所述粘性可调水凝胶材料的制备原料按照重量份还包括引发剂0.2~2重量份,例如可以为0.2重量份、0.4重量份、0.6重量份、0.8重量份、1重量份、1.2重量份、1.4重量份、1.6重量份、1.8重量份或2重量份,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。As a preferred technical solution, the raw materials for preparing the adjustable viscosity hydrogel material also include 0.2 to 2 parts by weight of an initiator, for example, 0.2 parts by weight, 0.4 parts by weight, 0.6 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight or 2 parts by weight, as well as specific values between the above points. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific points included in the range.

优选地,所述引发剂包括光引发剂或热引发剂中的任意一种,进一步优选光引发剂。Preferably, the initiator includes any one of a photoinitiator or a thermal initiator, and a photoinitiator is more preferred.

优选地,所述光引发剂包括2-羟基-2-甲基-1-苯基-1-丙酮和/或2,4,6(三甲基苯甲酰基)二苯基氧化膦。Preferably, the photoinitiator comprises 2-hydroxy-2-methyl-1-phenyl-1-propanone and/or 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide.

本申请提供的粘性可调水凝胶材料,可通过引发剂的选择来进行不同方式的引发聚合,例如选用光引发剂可通过紫外光照射引发聚合,选用热引发剂可通过加热方式引发聚合。The viscosity-adjustable hydrogel material provided in the present application can initiate polymerization in different ways by selecting an initiator. For example, a photoinitiator can initiate polymerization by ultraviolet light irradiation, and a thermal initiator can initiate polymerization by heating.

第二方面,本申请提供一种如第一方面所述的粘性可调水凝胶材料的制备方法,所述制备方法包括如下步骤:In a second aspect, the present application provides a method for preparing the viscosity-adjustable hydrogel material as described in the first aspect, the preparation method comprising the following steps:

将单体、交联剂、长链高分子、盐酸多巴胺、粘土和水混合,得到水凝胶溶液前驱体;所述水凝胶溶液前驱体在引发剂的存在下进行反应,得到所述水凝胶材料。The monomer, the cross-linking agent, the long-chain polymer, the dopamine hydrochloride, the clay and the water are mixed to obtain the hydrogel solution precursor; the hydrogel solution precursor is reacted in the presence of the initiator to obtain the hydrogel material.

作为一个优选的技术方案,所述混合的物料还包括保湿剂。As a preferred technical solution, the mixed material also includes a moisturizer.

优选地,所述混合的温度为25~60℃,例如可以为25℃、30℃、35℃、40℃、45℃、50℃、55℃或60℃,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。 Preferably, the mixing temperature is 25-60°C, for example, it can be 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C or 60°C, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.

优选地,所述引发剂为光引发剂,所述反应在紫外光照下进行。Preferably, the initiator is a photoinitiator, and the reaction is carried out under ultraviolet light.

优选地,所述反应的时间为1~5min,例如可以为1min、1.5min、2min、2.5min、3min、3.5min、4min或5min,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。Preferably, the reaction time is 1 to 5 min, for example, it can be 1 min, 1.5 min, 2 min, 2.5 min, 3 min, 3.5 min, 4 min or 5 min, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.

优选地,所述反应的温度为18~35℃,例如可以为18℃、19℃、20℃、21℃、22℃、23℃、24℃、25℃、26℃、28℃、30℃、32℃、34℃或35℃,以及上述点值之间的具体点值,限于篇幅及出于简明的考虑,本申请不再穷尽列举所述范围包括的具体点值。Preferably, the reaction temperature is 18-35°C, for example, it can be 18°C, 19°C, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 28°C, 30°C, 32°C, 34°C or 35°C, as well as specific point values between the above point values. Due to space limitations and for the sake of brevity, this application no longer exhaustively lists the specific point values included in the range.

作为一个优选的技术方案,所述制备方法具体包括如下步骤:As a preferred technical solution, the preparation method specifically comprises the following steps:

(1)将单体、交联剂、长链高分子、盐酸多巴胺、保湿剂、粘土和水混合,得到水凝胶溶液前驱体;(1) mixing monomers, a cross-linking agent, a long-chain polymer, dopamine hydrochloride, a humectant, clay and water to obtain a hydrogel solution precursor;

(2)在步骤(1)得到的水凝胶溶液前驱体中加入光引发剂,得到反应体系;以及(2) adding a photoinitiator to the hydrogel solution precursor obtained in step (1) to obtain a reaction system; and

(3)步骤(2)得到的反应体系在紫外光照下进行反应,得到所述水凝胶材料。(3) The reaction system obtained in step (2) is reacted under ultraviolet light to obtain the hydrogel material.

第三方面,本申请提供一种如第一方面所述的粘性可调水凝胶材料在生物医学材料或柔性电子器件中的应用。In a third aspect, the present application provides an application of the viscosity-adjustable hydrogel material as described in the first aspect in biomedical materials or flexible electronic devices.

与现有技术相比,本申请具有以下有益效果:Compared with the prior art, this application has the following beneficial effects:

本申请提供的粘性可调水凝胶材料,通过化学组分的选择和用量调控,可轻松实现水凝胶材料表面粘与非粘两种特性的兼容与调控,同时具有抗冻保湿性、自愈合性能、生物相容性和柔弹性。本申请通过粘性可调水凝胶制备原料的设计和优化,将粘性可调水凝胶材料切分后静置48h,即可实现自愈合;粘性水凝胶材料的粘附力可高达60N/m;在-18℃冷冻24h,表面无冰块,具有良好的抗冻性;室温下静置7天质量减少率低达3.8%,具有良好的保湿性。The viscosity-adjustable hydrogel material provided in this application can easily achieve the compatibility and regulation of the two properties of the hydrogel material surface, sticky and non-sticky, through the selection of chemical components and the regulation of dosage, and at the same time has antifreeze and moisture retention, self-healing properties, biocompatibility and flexibility. This application designs and optimizes the raw materials for preparing the viscosity-adjustable hydrogel, and the viscosity-adjustable hydrogel material can be cut and left to stand for 48 hours to achieve self-healing; the adhesion of the viscosity hydrogel material can be as high as 60N/m; it has good antifreeze properties when frozen at -18℃ for 24 hours, and there is no ice on the surface; the mass reduction rate is as low as 3.8% when left to stand for 7 days at room temperature, and it has good moisture retention.

附图说明BRIEF DESCRIPTION OF THE DRAWINGS

图1是实施例3提供的粘性可调水凝胶材料自愈合性能测试照片。FIG. 1 is a photograph of the self-healing performance test of the viscosity-adjustable hydrogel material provided in Example 3.

图2是对比例1提供的水凝胶材料自愈合性能测试照片。FIG2 is a photograph showing the self-healing performance test of the hydrogel material provided in Comparative Example 1.

图3是实施例1提供的粘性可调水凝胶材料粘弹拉伸性测试照片。FIG3 is a photograph of the viscoelastic tensile test of the viscosity-adjustable hydrogel material provided in Example 1.

图4是实施例1和实施例2提供的粘性可调水凝胶材料的粘附性对比图。 FIG. 4 is a comparative diagram of the adhesion of the viscosity-adjustable hydrogel materials provided in Example 1 and Example 2.

图5是实施例1提供的粘性可调水凝胶材料的生物相容性测试柱状图。FIG. 5 is a bar graph showing the biocompatibility test of the viscosity-adjustable hydrogel material provided in Example 1.

具体实施方式DETAILED DESCRIPTION

下面结合附图并通过具体实施方式来进一步说明本申请的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本申请,不应视为对本申请的具体限制。The technical solution of the present application is further described below in conjunction with the accompanying drawings and through specific implementation methods. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

下述实施例和对比例中部分组分来源如下所述:The sources of some components in the following examples and comparative examples are as follows:

(1)聚乙二醇二丙烯酸酯:数均分子量1000,购自阿拉丁化学试剂;(1) Polyethylene glycol diacrylate: number average molecular weight 1000, purchased from Aladdin Chemical Reagent;

(2)聚环氧乙烷:平均分子量1000000,购自合肥巴斯夫生物科技有限公司。(2) Polyethylene oxide: average molecular weight 1,000,000, purchased from BASF Biotechnology Co., Ltd., Hefei.

实施例1Example 1

一种粘性可调水凝胶材料,所述粘性可调水凝胶材料的制备原料按照重量份包括如下组分:丙烯酰胺20重量份、聚乙二醇二丙烯酸酯1重量份、聚环氧乙烷3重量份、盐酸多巴胺2重量份、甘油50重量份、硅酸镁锂0.01重量份、水50重量份和2-羟基-2-甲基-1-苯基-1-丙酮0.2重量份。A viscosity-adjustable hydrogel material. The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 20 parts by weight of acrylamide, 1 part by weight of polyethylene glycol diacrylate, 3 parts by weight of polyethylene oxide, 2 parts by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.01 parts by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.

一种粘性可调水凝胶材料的制备方法,所述制备方法包括如下步骤:A method for preparing a hydrogel material with adjustable viscosity, the preparation method comprising the following steps:

(1)将本实施例提供的粘性可调水凝胶材料的制备原料丙烯酰胺、聚乙二醇二丙烯酸酯、聚环氧乙烷、盐酸多巴胺、甘油、硅酸镁锂和水混合,混合温度为40℃,并搅拌24h得到水凝胶溶液前驱体;(1) Mixing the raw materials for preparing the adjustable viscosity hydrogel material provided in this embodiment, acrylamide, polyethylene glycol diacrylate, polyethylene oxide, dopamine hydrochloride, glycerol, lithium magnesium silicate and water, at a mixing temperature of 40° C., and stirring for 24 hours to obtain a hydrogel solution precursor;

(2)在步骤(1)得到的水凝胶溶液前驱体中加入2-羟基-2-甲基-1-苯基-1-丙酮,继续搅拌10min以上,得到反应体系,然后倒入模具;(2) adding 2-hydroxy-2-methyl-1-phenyl-1-propanone to the hydrogel solution precursor obtained in step (1), continuing to stir for more than 10 minutes to obtain a reaction system, and then pouring it into a mold;

(3)步骤(2)得到的反应体系在紫外光照下进行反应,反应的时间为2min,得到所述粘性可调水凝胶材料。(3) The reaction system obtained in step (2) is reacted under ultraviolet light for 2 minutes to obtain the viscosity-adjustable hydrogel material.

实施例2Example 2

一种粘性可调水凝胶材料,所述粘性可调水凝胶材料的制备原料按照重量份包括如下组分:丙烯酰胺15重量份、聚乙二醇二丙烯酸酯5重量份、聚环氧乙烷0.5重量份、盐酸多巴胺0.01重量份、甘油50重量份、硅酸镁锂0.1重量份、水50重量份和2-羟基-2-甲基-1-苯基-1-丙酮0.2重量份。A viscosity-adjustable hydrogel material. The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 15 parts by weight of acrylamide, 5 parts by weight of polyethylene glycol diacrylate, 0.5 parts by weight of polyethylene oxide, 0.01 parts by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.1 parts by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 parts by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.

一种粘性可调水凝胶材料的制备方法,其与实施例1的区别仅在于步骤(1)的制备原料为本实施例提供的制备原料,其余工艺参数与步骤均与实施例1相 同。A method for preparing a hydrogel material with adjustable viscosity, which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this example, and the remaining process parameters and steps are the same as those in Example 1. same.

实施例3Example 3

一种粘性可调水凝胶材料,所述粘性可调水凝胶材料的制备原料按照重量份包括如下组分:丙烯酰胺25重量份、聚乙二醇二丙烯酸酯1重量份、聚环氧乙烷3重量份、盐酸多巴胺1重量份、甘油50重量份、硅酸镁锂0.01重量份、水50重量份和2-羟基-2-甲基-1-苯基-1-丙酮0.2重量份。A viscosity-adjustable hydrogel material. The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 25 parts by weight of acrylamide, 1 part by weight of polyethylene glycol diacrylate, 3 parts by weight of polyethylene oxide, 1 part by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.01 part by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.

一种粘性可调水凝胶材料的制备方法,其与实施例1的区别仅在于步骤(1)的制备原料为本实施例提供的制备原料,其余工艺参数与步骤均与实施例1相同。A method for preparing a hydrogel material with adjustable viscosity, which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this example, and the remaining process parameters and steps are the same as those in Example 1.

实施例4Example 4

一种粘性可调水凝胶材料,所述粘性可调水凝胶材料的制备原料按照重量份包括如下组分:丙烯酰胺30重量份、聚乙二醇二丙烯酸酯1重量份、聚环氧乙烷1重量份、盐酸多巴胺0.01重量份、甘油50重量份、硅酸镁锂0.1重量份、水50重量份和2-羟基-2-甲基-1-苯基-1-丙酮0.2重量份。A viscosity-adjustable hydrogel material. The raw materials for preparing the viscosity-adjustable hydrogel material include the following components in parts by weight: 30 parts by weight of acrylamide, 1 part by weight of polyethylene glycol diacrylate, 1 part by weight of polyethylene oxide, 0.01 part by weight of dopamine hydrochloride, 50 parts by weight of glycerol, 0.1 part by weight of lithium magnesium silicate, 50 parts by weight of water and 0.2 part by weight of 2-hydroxy-2-methyl-1-phenyl-1-propanone.

一种粘性可调水凝胶材料的制备方法,其与实施例1的区别仅在于步骤(1)的制备原料为本实施例提供的制备原料,其余工艺参数与步骤均与实施例1相同。A method for preparing a hydrogel material with adjustable viscosity, which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this example, and the remaining process parameters and steps are the same as those in Example 1.

对比例1Comparative Example 1

一种水凝胶材料,其与实施例3的区别仅在于所述水凝胶材料的制备原料不加盐酸多巴胺1重量份,其余原料均与实施例3相同。A hydrogel material, which is different from Example 3 only in that the raw materials for preparing the hydrogel material do not contain 1 part by weight of dopamine hydrochloride, and the other raw materials are the same as those in Example 3.

一种水凝胶材料的制备方法,其与实施例3的区别仅在于步骤(1)的制备原料为本对比例提供的制备原料,其余工艺参数与步骤均与实施例3相同。A method for preparing a hydrogel material, which differs from Example 3 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this comparative example, and the remaining process parameters and steps are the same as those in Example 3.

对比例2Comparative Example 2

一种水凝胶材料,其与实施例1的区别仅在于所述水凝胶材料的制备原料不加甘油,水的添加量为100重量份,其余原料均与实施例1相同。A hydrogel material, which is different from Example 1 only in that glycerin is not added to the raw materials for preparing the hydrogel material, the added amount of water is 100 parts by weight, and the other raw materials are the same as those in Example 1.

一种水凝胶材料的制备方法,其与实施例1的区别仅在于步骤(1)的制备原料为本对比例提供的制备原料,其余工艺参数与步骤均与实施例1相同。A method for preparing a hydrogel material, which differs from Example 1 only in that the raw materials for preparation in step (1) are the raw materials for preparation provided in this comparative example, and the remaining process parameters and steps are the same as those in Example 1.

性能测试Performance Testing

(1)自愈合性能测试:将水凝胶切断后再拼接,静置48h后,拉伸>300%不断裂。 (1) Self-healing performance test: The hydrogel was cut and then spliced. After standing for 48 hours, it was stretched to more than 300% without breaking.

(2)生物相容性测试:MTT法评价材料对NIH3T3细胞毒性影响,分别在细胞培养过程中的24h、72h和120h进行测试,如果细胞存活率(相对稳定性)≥85%,可证明水凝胶材料具有生物相容性。(2) Biocompatibility test: The MTT method was used to evaluate the cytotoxicity of the material to NIH3T3 cells. The test was performed at 24 h, 72 h, and 120 h during the cell culture process. If the cell survival rate (relative stability) was ≥ 85%, it could be proved that the hydrogel material was biocompatible.

(3)粘附性测试:采用剥离测试法,将PET膜或纤维布贴附在5×1.5×0.1cm水凝胶表面,然后用一定的力量将其剥离,剥离的力量越大,说明水凝胶样品粘附力越强。(3) Adhesion test: Using the peeling test method, a PET film or fiber cloth is attached to the surface of a 5×1.5×0.1 cm hydrogel and then peeled off with a certain force. The greater the peeling force, the stronger the adhesion of the hydrogel sample.

(4)粘弹拉伸性测试:将两块3×2×0.2cm水凝胶部分叠加,叠加长度为1~2cm,然后固定两端进行拉伸,测量最大拉伸形变时的水凝胶长度,得到最大拉伸长度增量。(4) Viscoelastic tensile test: Two hydrogel sections of 3×2×0.2 cm in size were partially overlapped with each other to a length of 1 to 2 cm. The two ends were then fixed and stretched. The length of the hydrogel at the maximum tensile deformation was measured to obtain the maximum tensile length increment.

(5)抗冻性测试:将4×4cm,厚度为1mm的水凝胶样品放入冰箱,在-18℃条件下冷冻24h,取出后观察表面是否有冰块。(5) Freeze resistance test: A hydrogel sample of 4×4 cm and 1 mm thick was placed in a refrigerator and frozen at -18°C for 24 h. After taking it out, observe whether there is ice on the surface.

(6)保湿性测试:将直径为13cm,厚度为4cm,一定质量的水凝胶样品在室温环境下静置7天后测试质量。(6) Moisture retention test: A hydrogel sample with a diameter of 13 cm and a thickness of 4 cm and a certain mass was left standing at room temperature for 7 days and then tested for quality.

按照上述性能测试方法测试实施例1~4、对比例1~2得到的水凝胶材料的各项性能,测试结果如图1~4、表1所示。The various properties of the hydrogel materials obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were tested according to the above-mentioned performance testing method. The test results are shown in FIGS. 1 to 4 and Table 1.

表1
Table 1

图1是实施例3提供的水凝胶材料自愈合性能测试照片;通过图1可以看出实施例3提供的水凝胶材料被切分后可以实现自愈合,并且自愈合后仍能保持良好的柔弹性。图2是对比例1提供的水凝胶材料自愈合性能测试照片;通过图2可以看出,对比例1提供的水凝胶材料由于不加盐酸多巴胺,因此没有自愈合性能。图3为实施例1提供的粘性可调水凝胶材料粘弹拉伸性测试照片;通过图3可以看出实施例1提供的水凝胶材料具有良好的粘弹拉伸性,拉伸长度可达原来长度的800%。图4为实施例1和实施例2提供的粘性可调水凝胶材料的粘附性对比图;通过图4可以看出,本申请提供的粘性可调水凝胶材料通 过制备原料用量的调控,可实现水凝胶材料粘性与非粘特性的调控。图5为实施例1提供的粘性可调水凝胶材料的生物相容性测试柱状图;通过图5可以看出实施例1提供的粘性可调水凝胶材料即使在120h后,相对稳定性仍高达95%,说明本实施例提供的水凝胶材料具有良好的生物相容性。通过表1可以看出,本申请提供的粘性可调水凝胶材料具有良好的抗冻性,进行保湿性测试时,本申请提供的粘性可调水凝胶材料的质量减少率为3.8%,低于对比例2的76.4%,说明本申请提供的粘性可调水凝胶材料具有良好的保湿性。Figure 1 is a photograph of the self-healing performance test of the hydrogel material provided in Example 3; Figure 1 shows that the hydrogel material provided in Example 3 can achieve self-healing after being cut, and can still maintain good flexibility after self-healing. Figure 2 is a photograph of the self-healing performance test of the hydrogel material provided in Example 1; Figure 2 shows that the hydrogel material provided in Example 1 has no self-healing performance because dopamine hydrochloride is not added. Figure 3 is a photograph of the viscoelastic tensile test of the viscosity-adjustable hydrogel material provided in Example 1; Figure 3 shows that the hydrogel material provided in Example 1 has good viscoelastic tensile properties, and the stretched length can reach 800% of the original length. Figure 4 is a comparison diagram of the adhesion of the viscosity-adjustable hydrogel materials provided in Example 1 and Example 2; Figure 4 shows that the viscosity-adjustable hydrogel material provided in this application is generally By regulating the amount of raw materials used in the preparation, the viscosity and non-stickiness of the hydrogel material can be regulated. Figure 5 is a bar graph of the biocompatibility test of the viscosity-adjustable hydrogel material provided in Example 1; it can be seen from Figure 5 that the viscosity-adjustable hydrogel material provided in Example 1 still has a relative stability of up to 95% even after 120 hours, indicating that the hydrogel material provided in this example has good biocompatibility. It can be seen from Table 1 that the viscosity-adjustable hydrogel material provided in the present application has good antifreeze properties. When the moisture retention test was performed, the mass reduction rate of the viscosity-adjustable hydrogel material provided in the present application was 3.8%, which is lower than 76.4% of Comparative Example 2, indicating that the viscosity-adjustable hydrogel material provided in the present application has good moisture retention.

申请人声明,本申请通过上述实施例来说明本申请的详细工艺流程,但本申请并不局限于上述详细工艺流程,即不意味着本申请必须依赖上述详细工艺流程才能实施。所属技术领域的技术人员应该明了,对本申请的任何改进,对本申请产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本申请的保护范围和公开范围之内。 The applicant declares that the present application uses the above-mentioned embodiments to illustrate the detailed process flow of the present application, but the present application is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present application must rely on the above-mentioned detailed process flow to be implemented. The technicians in the relevant technical field should understand that any improvement to the present application, the equivalent replacement of the raw materials of the present application product, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present application.

Claims (10)

一种粘性可调水凝胶材料,其制备原料按照重量份包括如下组分:单体10~30重量份、交联剂1~20重量份、长链高分子0.1~5重量份、盐酸多巴胺0.01~5重量份、粘土0.01~5重量份和水50~90重量份。A viscosity adjustable hydrogel material, the preparation raw materials of which include the following components in parts by weight: 10-30 parts by weight of monomer, 1-20 parts by weight of cross-linking agent, 0.1-5 parts by weight of long-chain polymer, 0.01-5 parts by weight of dopamine hydrochloride, 0.01-5 parts by weight of clay and 50-90 parts by weight of water. 根据权利要求1所述的粘性可调水凝胶材料,其中,所述单体包括丙烯酰胺、甲基丙烯酰胺或甲基丙烯酸羟乙酯中的任意一种或至少两种的组合。The viscosity-adjustable hydrogel material according to claim 1, wherein the monomer comprises any one of acrylamide, methacrylamide or hydroxyethyl methacrylate, or a combination of at least two of them. 根据权利要求1所述的粘性可调水凝胶材料,其中,所述交联剂包括聚乙二醇二丙烯酸酯和/或N,N’-亚甲基双丙烯酰胺;所述聚乙二醇二丙烯酸酯的数均分子量为600~1000。The viscosity-adjustable hydrogel material according to claim 1, wherein the cross-linking agent comprises polyethylene glycol diacrylate and/or N,N'-methylenebisacrylamide; and the number average molecular weight of the polyethylene glycol diacrylate is 600 to 1000. 根据权利要求1所述的粘性可调水凝胶材料,其中,所述长链高分子包括聚环氧乙烷和/或羟乙基纤维素;所述聚环氧乙烷的平均分子量为100000~8000000;所述羟乙基纤维素的粘度为100~6400mPa.s。The viscosity-adjustable hydrogel material according to claim 1, wherein the long-chain polymer comprises polyethylene oxide and/or hydroxyethyl cellulose; the average molecular weight of the polyethylene oxide is 100,000 to 8,000,000; and the viscosity of the hydroxyethyl cellulose is 100 to 6,400 mPa.s. 根据权利要求1所述的粘性可调水凝胶材料,其中,所述粘土包括硅酸镁锂、碳纤维、银纳米粒子、二氧化硅纳米粒子或氧化石墨烯中的任意一种或至少两种的组合;所述银纳米粒子的粒径为10~100nm;所述二氧化硅纳米粒子的粒径为10~500nm。The viscosity-adjustable hydrogel material according to claim 1, wherein the clay comprises any one of lithium magnesium silicate, carbon fiber, silver nanoparticles, silicon dioxide nanoparticles or graphene oxide, or a combination of at least two thereof; the particle size of the silver nanoparticles is 10 to 100 nm; and the particle size of the silicon dioxide nanoparticles is 10 to 500 nm. 根据权利要求1~5任一项所述的粘性可调水凝胶材料,其中,所述粘性可调水凝胶材料的制备原料按照重量份还包括保湿剂10~50重量份;所述保湿剂包括多元醇;所述多元醇包括甘油和/或乙二醇。The viscosity-adjustable hydrogel material according to any one of claims 1 to 5, wherein the raw materials for preparing the viscosity-adjustable hydrogel material further include 10 to 50 parts by weight of a humectant; the humectant includes a polyol; and the polyol includes glycerol and/or ethylene glycol. 根据权利要求1~5任一项所述的粘性可调水凝胶材料,其中,所述粘性可调水凝胶材料的制备原料按照重量份还包括引发剂0.2~2重量份;所述引发剂包括光引发剂或热引发剂中的任意一种,进一步优选光引发剂;所述光引发剂包括2-羟基-2-甲基-1-苯基-1-丙酮和/或2,4,6(三甲基苯甲酰基)二苯基氧化膦。The viscosity adjustable hydrogel material according to any one of claims 1 to 5, wherein the raw materials for preparing the viscosity adjustable hydrogel material further include 0.2 to 2 parts by weight of an initiator; the initiator includes any one of a photoinitiator or a thermal initiator, and a photoinitiator is further preferred; the photoinitiator includes 2-hydroxy-2-methyl-1-phenyl-1-propanone and/or 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide. 一种如权利要求1~7任一项所述的粘性可调水凝胶材料的制备方法,其包括如下步骤:A method for preparing the viscosity-adjustable hydrogel material according to any one of claims 1 to 7, comprising the following steps: 将单体、交联剂、长链高分子、盐酸多巴胺、粘土和水混合,得到水凝胶溶液前驱体;所述水凝胶溶液前驱体在引发剂的存在下进行反应,得到所述粘性可调水凝胶材料。The monomer, the cross-linking agent, the long-chain polymer, the dopamine hydrochloride, the clay and the water are mixed to obtain the hydrogel solution precursor; the hydrogel solution precursor is reacted in the presence of the initiator to obtain the viscosity-adjustable hydrogel material. 根据权利要求8所述的制备方法,其中,所述混合的物料还包括保湿剂;所述混合的温度为25~60℃;所述引发剂为光引发剂,所述反应在紫外光照下进行;所述反应的时间为1~5min。 The preparation method according to claim 8, wherein the mixed material also includes a moisturizer; the mixing temperature is 25 to 60°C; the initiator is a photoinitiator, and the reaction is carried out under ultraviolet light; and the reaction time is 1 to 5 minutes. 一种如权利要求1~7任一项所述的粘性可调水凝胶材料在生物医学材料或柔性电子器件中的应用。 A use of the viscosity-adjustable hydrogel material as claimed in any one of claims 1 to 7 in biomedical materials or flexible electronic devices.
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