WO2025217992A1 - 一种水凝胶材料及其制备方法与应用 - Google Patents

一种水凝胶材料及其制备方法与应用

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Publication number
WO2025217992A1
WO2025217992A1 PCT/CN2024/096499 CN2024096499W WO2025217992A1 WO 2025217992 A1 WO2025217992 A1 WO 2025217992A1 CN 2024096499 W CN2024096499 W CN 2024096499W WO 2025217992 A1 WO2025217992 A1 WO 2025217992A1
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Prior art keywords
hydrogel material
substrate
hydrogel
present
material according
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English (en)
French (fr)
Inventor
汤柳燕
王耀
许宝林
魏成梦
李峰
罗秋霞
卿宁
卢振品
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Wuyi University Fujian
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Wuyi University Fujian
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides
    • C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • the present invention belongs to the technical field of hydrogel materials, and in particular relates to a hydrogel material and a preparation method and application thereof.
  • hydrogel The concept of "hydrogel” was first proposed in 1894. Since then, hydrogels have developed rapidly, being widely studied and applied in fields ranging from drug delivery, tissue engineering, medical implants, wound dressings, and contact lenses to sensors, actuators, electronic devices, optical devices, batteries, water harvesters, and soft robotics. Furthermore, the controllable modification of hydrogels as functional coatings on substrate surfaces has become a promising and challenging topic, particularly in the electronics and medical fields.
  • An ideal method for preparing a hydrogel coating achieves two goals: achieving strong adhesion to the substrate and being able to adhere to substrates of any shape. Strong adhesion refers to the strong interaction between the hydrogel coating and the substrate surface, which allows the hydrogel coating to adhere well to the substrate and prevent it from falling off or breaking during actual use.
  • Currently available methods for preparing hydrogel coatings on the market such as surface bridging, hydrogel coating, surface initiation, and surface catalytic free radical polymerization, are limited by the use of specialized monomers, a single substrate, fixed substrate shape, and complex reaction conditions, and are unable to meet market demand. Therefore, new methods for preparing hydrogel coatings are urgently needed to meet current market demands.
  • the present invention aims to address at least one of the technical problems existing in the aforementioned prior art.
  • the present invention provides a hydrogel material, a preparation method, and applications thereof.
  • the hydrogel material exhibits high adhesion, and coating the hydrogel material on a substrate surface can improve the substrate's lubricity and antifouling properties.
  • the present invention also provides a method for preparing the hydrogel material.
  • the present invention also provides a coated product.
  • the present invention also provides an application.
  • a hydrogel material which includes the following raw materials: epoxy resin, curing agent, amino acid metal complex, glucose oxidase solution and precursor solution; the precursor solution includes glucose, cross-linking agent and monomer.
  • the mass ratio of the epoxy resin, curing agent, amino acid metal complex, precursor solution and glucose oxidase solution is (30-70): (30-70): (5-15): (5-15): 1.
  • the mass ratio of the epoxy resin, curing agent, amino acid metal complex, precursor solution and glucose oxidase solution is (40-60): (40-60): (8-12): (8-12): 1.
  • the mass ratio of the epoxy resin, the curing agent, the amino acid metal complex, the precursor solution and the glucose oxidase solution is 50:50:10:10:1.
  • the mass ratio of glucose, cross-linking agent and monomer is (80-120): (0.1-2): (80-200).
  • the mass ratio of glucose, cross-linking agent and monomer is (90-110): (0.2-1.6): (90-200).
  • the mass ratio of glucose, cross-linking agent and monomer is 100:(0.28-1.45):(92.1-198.75).
  • the concentration of glucose oxidase in the glucose oxidase solution is 0.05-0.1 wt %.
  • the concentration of glucose oxidase in the glucose oxidase solution is 0.08-0.1 wt %.
  • the solvent of the glucose oxidase solution comprises phosphate buffer.
  • the solvent of the precursor solution includes phosphate buffer.
  • the epoxy resin includes at least one of E-44, E-51, E-42, E-31, E-21, and E-20.
  • the curing agent comprises a polyamide curing agent.
  • the amino acid metal complex includes at least one of ferrous glycine, ferrous histidine, molybdenum lysine, cobalt tryptophan, copper cysteine, manganese cysteine, and nickel tyrosine.
  • the amino acid metal complex is ferrous glycinate.
  • the cross-linking agent includes N,N-methylbisacrylamide or ethylene glycol dimethacrylate.
  • the cross-linking agent is N,N-methylbisacrylamide.
  • the monomers include N-hydroxyethyl acrylamide, N,N-dimethylacrylamide At least one of amine, acrylic acid, poly(ethylene glycol) methacrylate, acrylamide and sodium alginate.
  • a method for preparing the hydrogel material according to the first aspect of the present invention comprising the following steps:
  • step S2 The mixed solution in step S1 and the precursor solution are mixed and reacted to obtain a hydrogel material.
  • the reaction time in step S2 is 10-70 min.
  • the reaction time in step S2 is 15-60 min.
  • a coated product comprises a substrate, and the hydrogel material according to the first aspect of the present invention coated on a surface of the substrate.
  • the substrate comprises at least one of metal, plastic, ceramic, glass, rubber and wood board.
  • the metal includes but is not limited to iron, copper and aluminum.
  • the plastic includes but is not limited to acrylic.
  • the rubber includes but is not limited to silicone.
  • the thickness of the hydrogel material coated on the surface of the substrate is 150-600 ⁇ m.
  • the adhesion strength of the hydrogel material coated on the surface of the substrate is 80-700 kPa.
  • a use of the hydrogel material according to the first aspect of the present invention in improving the lubricity and/or antifouling properties of a substrate is proposed.
  • the hydrogel material provided by the present invention can generate a universal hydrogel coating with high adhesion in situ on the substrate surface by separately immobilizing ferrous glycine and glucose oxidase on the surface of a substrate attached to an epoxy resin, and then reacting with a precursor solution.
  • This invention provides a theoretical basis and technical support for the controllable modification of hydrogels as functional coatings on material surfaces;
  • the hydrogel material provided by the present invention uses epoxy resin as the bottom layer.
  • the epoxy resin reacts with other raw materials through the large number of epoxy groups it carries to form a polymer network, which then reacts with the surface of the substrate to form a polymer network.
  • the adhesion of the hydrogel to the substrate surface is greatly improved;
  • the preparation method provided by the present invention has mild reaction conditions, does not require nitrogen filling of the precursor solution, is applicable to various substrates of various shapes, and is suitable for a variety of monomers;
  • the coated product provided by the present invention can improve the lubricity and antifouling properties of the substrate surface by coating the above-mentioned hydrogel material on the surface, and can be widely used in actual production.
  • FIG1 is a SEM result of a cross section of a hydrogel coating of a coated product in a test example of the present invention. wherein the scale bar is 10 ⁇ m;
  • FIG2 is a graph showing the test results of the hydrogel coating thickness of coated products prepared on different substrates in a test example of the present invention.
  • FIG3 is a graph showing the test results of the hydrogel coating thickness of the coating products prepared from different polymeric monomers in the test examples of the present invention.
  • FIG4 is a graph showing the FTIR results of coating products prepared from different polymeric monomers in a test example of the present invention
  • FIG4 is a graph showing the FTIR spectrum of a hydrogel coating prepared from AA+PEGMA, PEGMA monomer, and AA monomer
  • FIG4 is a graph showing the FTIR spectrum of a hydrogel coating prepared from HEAA+SA, HEAA monomer, and SA monomer;
  • FIG5 is a graph showing the adhesion strength test results of hydrogel coatings of coated products prepared with different polymeric monomers in a test example of the present invention
  • FIG5 is an adhesion test curve
  • FIG5 is an adhesion strength calculated based on the curve in FIG5;
  • FIG6 is a graph showing the test results of the lubricity of the hydrogel coating in a test example of the present invention.
  • FIG7 is a graph showing the test results of the anti-biological contamination property of the hydrogel coating in the test examples of the present invention.
  • This embodiment provides a hydrogel material, and the preparation method of the hydrogel specifically includes the following steps:
  • step 1) The mixed solution obtained in step 1) and the precursor solution obtained in step 2) were mixed and reacted for 15 minutes to obtain the PHEAA hydrogel material.
  • This embodiment provides a hydrogel material.
  • the preparation method of the hydrogel material is the same as that of Example 1, except that 92.1 parts by mass of HEAA in step 2) is replaced with 106.6 parts by mass of acrylamide (AM) and the amount of MBAA is adjusted to 0.32 parts by mass to prepare a PAM hydrogel material.
  • AM acrylamide
  • This embodiment provides a hydrogel material.
  • the preparation method of the hydrogel material is the same as that of Example 1, except that 92.1 parts by mass of HEAA in step 2) is replaced with 149.7 parts by mass of N,N-dimethylacrylamide (DMAA) and the amount of MBAA is adjusted to 0.74 parts by mass to prepare a PDMAA hydrogel material.
  • DMAA N,N-dimethylacrylamide
  • This embodiment provides a hydrogel material.
  • the preparation method of the hydrogel material is the same as that of Example 1, except that 92.1 parts by mass of HEAA in step 2) is replaced with 33.15 parts by mass of acrylic acid (AA) and 165.6 parts by mass of poly(ethylene glycol) methacrylate (PEGMA), and the amount of MBAA is adjusted to 0.99 parts by mass to prepare a PAA-PEGMA hydrogel material.
  • This embodiment provides a hydrogel material.
  • the preparation method of the hydrogel material is the same as that of Example 1, except that 92.1 parts by mass of HEAA in step 2) is replaced with 115.13 parts by mass of HEAA and 30 parts by mass of sodium alginate (SA), the amount of MBAA is adjusted to 1.45 parts by mass, and the reaction time in step 3) is adjusted to 60 min to prepare a PHEAA-SA hydrogel material.
  • This embodiment provides a coated product, which is composed of an acrylic substrate (25 mm ⁇ 50 mm) and the hydrogel material provided in Example 1.
  • the specific preparation method of the coated product includes the following steps:
  • step 4 Taking 10 parts by mass of the precursor solution obtained in step 3), placing the substrate covered with GOD obtained in step 2) into the precursor solution and reacting for 15 minutes, thereby obtaining a coated product coated with a high-adhesion universal hydrogel material.
  • This embodiment provides a coating product, which is composed of a silicone substrate and the hydrogel material provided in Example 1.
  • the specific preparation method is the same as that of Example 6, except that the acrylic substrate is replaced by a silicone substrate.
  • This embodiment provides a coated product, which is composed of a glass substrate and the hydrogel material provided in Example 1.
  • the specific preparation method is the same as that of Example 6, except that the acrylic substrate is replaced by a glass substrate.
  • This embodiment provides a coated product, which is composed of an iron substrate and the hydrogel material provided in Example 1.
  • the specific preparation method is the same as that of Example 6, except that the acrylic substrate is replaced by the iron substrate.
  • This embodiment provides a coated product, which is composed of a copper substrate and the hydrogel material provided in Example 1.
  • the specific preparation method is the same as that of Example 6, except that the acrylic substrate is replaced by a copper substrate.
  • This embodiment provides a coated product, which is composed of an aluminum substrate and the hydrogel material provided in Example 1.
  • the specific preparation method is the same as that of Example 6, except that the acrylic substrate is replaced by an aluminum substrate.
  • This embodiment provides a coated product, which is composed of an acrylic substrate and the hydrogel material provided in Example 2.
  • the specific preparation method is the same as that of Example 6.
  • This embodiment provides a coated product, which is composed of an acrylic substrate and the hydrogel material provided in Example 3.
  • the specific preparation method is the same as that of Example 6.
  • This embodiment provides a coated product, which is composed of an acrylic substrate and the hydrogel material provided in Example 4.
  • the specific preparation method is the same as that of Example 6.
  • This embodiment provides a coated product, which is composed of an acrylic substrate and the hydrogel material provided in Example 5.
  • the specific preparation method is the same as that of Example 6.
  • This embodiment provides a coated product, which is composed of a 50 mm ⁇ 20 mm ⁇ 1 mm PVC substrate and the hydrogel material provided in Example 1.
  • the specific preparation method is the same as that in Example 6; the only difference is that the acrylic substrate is replaced with a PVC substrate, and the reaction time in step 4) is 45 minutes.
  • This embodiment provides a coated product, which is composed of a 50 mm ⁇ 20 mm ⁇ 1 mm PVC substrate and the hydrogel material provided in Example 2.
  • the specific preparation method is the same as that in Example 12; the only difference is that the acrylic substrate is replaced with a PVC substrate, and the reaction time in step 4) is 45 minutes.
  • This embodiment provides a coated product, which is composed of a 50 mm ⁇ 20 mm ⁇ 1 mm PVC substrate and the hydrogel material provided in Example 3.
  • the specific preparation method is the same as that in Example 13; the only difference is that the acrylic substrate is replaced with a PVC substrate, and the reaction time in step 4) is 45 minutes.
  • This embodiment provides a coated product, which is composed of a 50 mm ⁇ 20 mm ⁇ 1 mm PVC substrate and the hydrogel material provided in Example 4.
  • the specific preparation method is the same as that in Example 14; the only difference is that the acrylic substrate is replaced with a PVC substrate, and the reaction time in step 4) is 45 minutes.
  • This embodiment provides a coated product, which is composed of a 50 mm ⁇ 20 mm ⁇ 1 mm PVC substrate and the hydrogel material provided in Example 5.
  • the specific preparation method is the same as that of Example 15; the only difference is that the acrylic substrate is replaced with a PVC substrate.
  • This embodiment provides a coated product, which is composed of a glass substrate and the hydrogel material provided in Example 4.
  • the specific preparation method is the same as that of Example 14, except that the acrylic substrate is replaced by a glass substrate.
  • This test example tested multiple characterization parameters of the hydrogel materials in the coated products prepared in Examples 6-20, including scanning electron microscopy (SEM) microstructure, thickness of the hydrogel materials on different substrate surfaces, thickness of the hydrogel materials with different raw material ratios, Fourier transform infrared spectroscopy (FTIR) characterization, and adhesion strength.
  • SEM scanning electron microscopy
  • FTIR Fourier transform infrared spectroscopy
  • Example 6 The coated product prepared in Example 6 was frozen with liquid nitrogen and then broken, and dried in a vacuum freeze dryer for 12 hours.
  • the cross section of the hydrogel coating was observed and photographed using a SEM. The results are shown in FIG1 .
  • the hydrogel coating is tightly bonded to the substrate, and part of the hydrogel extends into the epoxy/ferrous glycine/glucose oxidase layer.
  • the surface hydrogel coating is firmly attached to the substrate by bonding with the epoxy/ferrous glycine/glucose oxidase layer.
  • the thickness of the hydrogel on the surface of the coated products prepared in Examples 6-11 was measured using a polarizing microscope, and the results are shown in FIG2 .
  • the substrates used for the coated products prepared in Examples 6-11 are shown in Table 1 .
  • the thickness of the resulting hydrogel coating is relatively stable, basically maintained at 400-500 ⁇ m, indicating that the hydrogel material provided by the present invention can be successfully coated on the surfaces of various substrates and is suitable for wide application in actual production.
  • the thickness of the hydrogel on the surface of the coated products prepared in Example 6 and Examples 12-15 was measured using a polarizing microscope, and the results are shown in FIG3 .
  • the formulas of the precursor solutions used in the coated products prepared in Example 6 and Examples 12-15 are shown in Table 2.
  • the above monomers can be used to successfully prepare hydrogel coatings, and the thickness of the coating varies slightly with the monomer structure.
  • the FTIR spectrum shows that 1250 cm -1 is the in-plane bending of CO stretching and OH coupling on PAA, 1110 cm -1 is the CO stretching peak of PEGMA, 1542 cm -1 is the NH bending vibration (amide II) of HEAA, and 1050 cm -1 is the COC stretching of SA.
  • the above results confirm that the present invention successfully prepares a coated product coated with a hydrogel layer using polymerized monomers AA+PEGMA and HEAA+SA.
  • the coated products prepared in Examples 16-20 were aged for 3 h at room temperature, and then the adhesion strength of the gel coating was tested by lap shear test using an electronic universal testing machine. The hydrogel coating was pulled at a speed of 5 mm/min. The layers were bonded until failure, and the bonding strength was calculated by dividing the maximum strength by the bonding area.
  • the formulas of the precursor solutions used in the coating products prepared in Examples 16-20 are shown in Table 3. The results are shown in FIG5 .
  • the hydrogel coatings prepared using different polymer monomers have different adhesions, among which the adhesion strength of the PDMAA hydrogel coating reaches 686 kPa, indicating that the high-adhesion general-purpose hydrogel material prepared using the present invention has higher adhesion.
  • Example 12 The coated product prepared in Example 12 was used as the test group, and the acrylic substrate was used as the control group.
  • the test group and the control group were placed horizontally on the laboratory table and formed a 5° tilt angle with the laboratory. Then, a 50g weight was placed at one end of each group. The results are shown in Figure 6.
  • Bovine serum was used as a biofouling agent, and the coated products prepared in Example 8 and Example 21 were used as a test group, and the glass substrate was used as a control group to conduct an anti-biological contamination test.
  • the anti-biological contamination test specifically included the following steps:
  • the hydrogel material prepared by the present invention has excellent anti-biological contamination ability. Coating the hydrogel material on the surface of the substrate can significantly reduce the adsorption of proteins on the coating surface, thereby improving the anti-biological contamination ability of the coated product.
  • the hydrogel material provided by the present invention is suitable for wide application in antibacterial or antibacterial materials.

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Abstract

本发明公开了一种水凝胶材料及其制备方法与应用，所述水凝胶材料包括以下原料：环氧树脂、固化剂、氨基酸金属配合物、葡萄糖氧化酶溶液和前驱体溶液；所述前驱体溶液包括葡萄糖、交联剂和单体。本发明提供的水凝胶材料具有高附着力，因此能够牢固结合在基材表面，还能够提高基材的润滑性和防污效果。

Description

一种水凝胶材料及其制备方法与应用 技术领域
本发明属于水凝胶材料技术领域，具体涉及一种水凝胶材料及其制备方法与应用。
背景技术
“水凝胶”这一概念在1894年首次被提出，在此之后，水凝胶的发展极其迅速，从药物传递、组织工程、医疗植入物、伤口敷料、隐形眼镜到传感器、执行器、电子设备、光学设备、电池、水采集器和软机器人等等领域中被广泛研究和应用。同时，水凝胶作为功能涂层在基板表面的可控修饰已经成为一个前途与挑战兼具的课题，尤其是在电子领域和医疗领域。
理想的水凝胶涂层制备方法达到以下两个目标：实现与基体的强附着力以及能在任意形状基体上进行附着。强附着力是指水凝胶涂层与基体表面有较强的相互作用，是为了让水凝胶涂层很好的同基体贴合在一起，在实际应用中不至于发生脱落或断裂。现在市面上已有的水凝胶涂层制备方法，如表面桥接法、水凝胶涂料法、表面引发法、表面催化引发的自由基聚合法等，这些方法受限于特种单体、单种基材、基材形状固定、反应条件复杂等问题，还无法满足市场需求，因此，迫切需要新的水凝胶涂层制备方法以适应目前市场需求。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出一种水凝胶材料及其制备方法与应用，所述水凝胶材料具有高附着力，将所述水凝胶材料涂覆在基材表面能够提高基材的润滑性和防污效果。
本发明还提出一种上述水凝胶材料的制备方法。
本发明还提出一种涂覆产品。
本发明还提出一种应用。
根据本发明的第一方面，提出了一种水凝胶材料，所述水凝胶材料包括以下原料：环氧树脂、固化剂、氨基酸金属配合物、葡萄糖氧化酶溶液和前驱体溶液；所述前驱体溶液包括葡萄糖、交联剂和单体。
在本发明的一些实施方式中，所述环氧树脂、固化剂、氨基酸金属配合物、前驱体溶液和葡萄糖氧化酶溶液的质量比为(30-70)：(30-70)：(5-15)：(5-15)：1。
在本发明的一些优选的实施方式中，所述环氧树脂、固化剂、氨基酸金属配合物、前驱体溶液和葡萄糖氧化酶溶液的质量比为(40-60)：(40-60)：(8-12)：(8-12)：1。
在本发明的一些更优选的实施方式中，所述环氧树脂、固化剂、氨基酸金属配合物、前驱体溶液和葡萄糖氧化酶溶液的质量比为50：50：10：10：1。
在本发明的一些优选的实施方式中，所述葡萄糖、交联剂和单体的质量比为(80-120)：(0.1-2)：(80-200)。
在本发明的一些更优选的实施方式中，所述葡萄糖、交联剂和单体的质量比为(90-110)：(0.2-1.6)：(90-200)。
在本发明的一些更优选的实施方式中，所述葡萄糖、交联剂和单体的质量比为100：(0.28-1.45)：(92.1-198.75)。
在本发明的一些优选的实施方式中，所述葡萄糖氧化酶溶液中葡萄糖氧化酶的浓度为0.05-0.1wt％。
在本发明的一些更优选的实施方式中，所述葡萄糖氧化酶溶液中葡萄糖氧化酶的浓度为0.08-0.1wt％。
在本发明的一些实施方式中，所述葡萄糖氧化酶溶液的溶剂包括磷酸盐缓冲液。
在本发明的一些实施方式中，所述前驱体溶液的溶剂包括磷酸盐缓冲液。
在本发明的一些实施方式中，所述环氧树脂包括E-44、E-51、E-42、E-31、E-21和E-20中的至少一种。
在本发明的一些实施方式中，所述固化剂包括聚酰胺固化剂。
在本发明的一些实施方式中，所述氨基酸金属配合物包括甘氨酸亚铁、组氨酸亚铁、赖氨酸钼、色氨酸钴、半胱氨酸铜、半胱氨酸锰和酪氨酸镍中的至少一种。
在本发明的一些优选的实施方式中，所述氨基酸金属配合物为甘氨酸亚铁。
在本发明的一些实施方式中，所述交联剂包括N,N-甲基双丙烯酰胺或二甲基丙烯酸乙二醇酯。
在本发明的一些优选的实施方式中，所述交联剂为N,N-甲基双丙烯酰胺。
在本发明的一些实施方式中，所述单体包括N-羟乙基丙烯酰胺、N,N-二甲基丙烯酰 胺、丙烯酸、聚(乙二醇)甲基丙烯酸酯、丙烯酰胺和海藻酸钠中的至少一种。
根据本发明的第二方面，提出了一种如本发明第一方面所述水凝胶材料的制备方法，所述制备方法包括以下步骤：
S1：将氨基酸金属配合物、环氧树脂、葡萄糖氧化酶溶液和固化剂混匀，得到混合液；
S2：将步骤S1所述混合液和前驱体溶液混匀，反应即得水凝胶材料。
在本发明的一些实施方式中，步骤S2中所述反应的时间为10-70min。
在本发明的一些优选的实施方式中，步骤S2中所述反应的时间为15-60min。
根据本发明的第三方面，提出了一种涂覆产品，所述涂覆产品包括基材，以及涂布于所述基材表面的如本发明第一方面所述的水凝胶材料。
在本发明的一些实施方式中，所述基材包括金属、塑料、陶瓷、玻璃、橡胶和木板中的至少一种。
在本发明的一些优选的实施方式中，所述金属包括但不限于铁、铜和铝。
在本发明的一些优选的实施方式中，所述塑料包括但不限于亚克力。
在本发明的一些优选的实施方式中，所述橡胶包括但不限于硅胶。
在本发明的一些实施方式中，所述涂布在所述基材表面的水凝胶材料的厚度为150-600μm。
在本发明的一些实施方式中，所述涂布在所述基材表面的水凝胶材料的黏附强度为80-700kPa。
根据本发明的第四方面，提出了如本发明第一方面所述的水凝胶材料在提高基材润滑性和/或防污性中的应用。
本发明至少具有以下有益效果：
1)本发明提供的水凝胶材料通过分别将甘氨酸亚铁和葡萄糖氧化酶固定在环氧树脂附着的基材表面，再同前驱体溶液反应，即可在基材表面原位生成具有高附着力的通用型水凝胶涂层，本发明为水凝胶作为功能涂层在材料表面的可控性修饰提供了理论依据和技术支持；
2)本发明提供的水凝胶材料采用环氧树脂作为底层，所述环氧树脂通过其携带的大量环氧基团与其他原料发生反应形成聚合物网络，该聚合物网络再与基材表面发生拓 扑粘附，使水凝胶在基材表面的附着力大大提升；
3)本发明提供的制备方法的反应条件温和，无需对前驱体溶液充氮，适用于多种形状的多种基材，并且多种单体都适用于该制备方法；
4)本发明提供的涂覆产品，通过在表面涂覆上述水凝胶材料，能够提高基材表面的润滑性和防污性，可广泛应用于实际生产。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明试验例中涂覆产品的水凝胶涂层横截面的SEM结果图；其中，比例尺为10μm；
图2为本发明试验例中对不同基材制得涂覆产品的水凝胶涂层厚度的检测结果图；
图3为本发明试验例中对不同聚合单体制得涂覆产品的水凝胶涂层厚度的检测结果图；
图4为本发明试验例中对不同聚合单体制得涂覆产品的FTIR结果图；其中，A图为AA+PEGMA制得的水凝胶涂层、PEGMA单体和AA单体的FTIR图谱，B图为HEAA+SA制得的水凝胶涂层、HEAA单体和SA单体的FTIR图谱；
图5为本发明试验例中不同聚合单体制得涂覆产品的水凝胶涂层的黏附强度检测结果图；其中，A图为附着力测试曲线，B图为根据A图中曲线计算得到的粘附强度；
图6为本发明试验例中对水凝胶涂层润滑性能的检测结果图；
图7为本发明试验例中对水凝胶涂层的抗生物污染性的检测结果图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
本实施例提供了一种水凝胶材料，该水凝胶的制备方法具体包括以下步骤：
1)按照质量份称取以下原料：50份环氧树脂E-44、50份固化剂605(购自米加占，货号610189137324)、1份葡萄糖氧化酶(GOD，购自上海阿拉丁生化科技股份有限公 司)溶液和10份甘氨酸亚铁；将上述原料混匀，得到混合液；GOD溶液是浓度为0.1wt％的PBS缓冲液(0.2M，pH＝5)；
2)称取92.1质量份N-羟乙基丙烯酰胺(HEAA)、0.28质量份N,N-甲基双丙烯酰胺(MBAA)和100质量份葡萄糖溶于1000质量份的PBS缓冲液中，得到前驱体溶液；
3)将步骤1)所得混合液和步骤2)所得前驱体溶液混匀，反应15min，即得PHEAA水凝胶材料。
实施例2
本实施例提供了一种水凝胶材料，该水凝胶材料的制备方法与实施例1相同，区别仅在于将步骤2)中92.1质量份HEAA替换为106.6质量份丙烯酰胺(AM)并将MBAA的用量调整为0.32质量份，制备得到PAM水凝胶材料。
实施例3
本实施例提供了一种水凝胶材料，该水凝胶材料的制备方法与实施例1相同，区别仅在于将步骤2)中92.1质量份HEAA替换为149.7质量份N,N-二甲基丙烯酰胺(DMAA)并将MBAA的用量调整为0.74质量份，制备得到PDMAA水凝胶材料。
实施例4
本实施例提供了一种水凝胶材料，该水凝胶材料的制备方法与实施例1相同，区别仅在于将步骤2)中92.1质量份HEAA替换为33.15质量份丙烯酸(AA)和165.6质量份聚(乙二醇)甲基丙烯酸酯(PEGMA)并将MBAA的用量调整为0.99质量份，制备得到PAA-PEGMA水凝胶材料。
实施例5
本实施例提供了一种水凝胶材料，该水凝胶材料的制备方法与实施例1相同，区别仅在于将步骤2)中92.1质量份HEAA替换为115.13质量份HEAA和30质量份海藻酸钠(SA)并将MBAA的用量调整为1.45质量份，且步骤3)的反应时间调整为60min，制备得到PHEAA-SA水凝胶材料。
实施例6
本实施例提供了一种涂覆产品，该涂覆产品由亚克力基材(25mm×50mm)和实施例1提供的水凝胶材料组成，该涂覆产品的具体制备方法包括以下步骤：
1)按照质量份称取以下原料：50份环氧树脂E-44、50份固化剂605(购自米加占， 货号610189137324)和10份甘氨酸亚铁；将上述原料混匀，将混合物均匀涂布在亚克力基材上，放入70℃烘箱烘干30min，得到预处理的基材；
2)称取1质量份葡萄糖氧化酶(GOD)溶于1000质量份的PBS缓冲液(0.2M，pH＝5)，得到GOD溶液；取1质量份GOD溶液滴在步骤1)所得预处理的基材上，静置1h，然后用PBS冲洗基板表面，得到覆盖有GOD的基材；
3)称取92.1质量份N-羟乙基丙烯酰胺(HEAA)、0.28质量份N,N-甲基双丙烯酰胺(MBAA)和100质量份葡萄糖溶于1000质量份的PBS缓冲液，得到前驱体溶液；
4)取10质量份步骤3)所得前驱体溶液，将步骤2)所得覆盖有GOD的基材放入到前驱体溶液中反应15min，即得涂覆有高附着通用型水凝胶材料的涂覆产品。
实施例7
本实施例提供了一种涂覆产品，该涂覆产品由硅胶基材和实施例1提供的水凝胶材料组成，具体制备方法与实施例6相同，区别仅在于将亚克力基材替换为硅胶基材。
实施例8
本实施例提供了一种涂覆产品，该涂覆产品由玻璃基材和实施例1提供的水凝胶材料组成，具体制备方法与实施例6相同，区别仅在于将亚克力基材替换为玻璃基材。
实施例9
本实施例提供了一种涂覆产品，该涂覆产品由铁基材和实施例1提供的水凝胶材料组成，具体制备方法与实施例6相同，区别仅在于将亚克力基材替换为铁基材。
实施例10
本实施例提供了一种涂覆产品，该涂覆产品由铜基材和实施例1提供的水凝胶材料组成，具体制备方法与实施例6相同，区别仅在于将亚克力基材替换为铜基材。
实施例11
本实施例提供了一种涂覆产品，该涂覆产品由铝基材和实施例1提供的水凝胶材料组成，具体制备方法与实施例6相同，区别仅在于将亚克力基材替换为铝基材。
实施例12
本实施例提供了一种涂覆产品，该涂覆产品由亚克力基材和实施例2提供的水凝胶材料组成，具体制备方法与实施例6相同。
实施例13
本实施例提供了一种涂覆产品，该涂覆产品由亚克力基材和实施例3提供的水凝胶材料组成，具体制备方法与实施例6相同。
实施例14
本实施例提供了一种涂覆产品，该涂覆产品由亚克力基材和实施例4提供的水凝胶材料组成，具体制备方法与实施例6相同。
实施例15
本实施例提供了一种涂覆产品，该涂覆产品由亚克力基材和实施例5提供的水凝胶材料组成，具体制备方法与实施例6相同。
实施例16
本实施例提供了一种涂覆产品，该涂覆产品由50mm×20mm×1mm的PVC基材和实施例1提供的水凝胶材料组成，具体制备方法与实施例6相同；区别仅在于将亚克力基材替换为PVC基材，且步骤4)的反应时间为45min。
实施例17
本实施例提供了一种涂覆产品，该涂覆产品由50mm×20mm×1mm的PVC基材和实施例2提供的水凝胶材料组成，具体制备方法与实施例12相同；区别仅在于将亚克力基材替换为PVC基材，且步骤4)的反应时间为45min。
实施例18
本实施例提供了一种涂覆产品，该涂覆产品由50mm×20mm×1mm的PVC基材和实施例3提供的水凝胶材料组成，具体制备方法与实施例13相同；区别仅在于将亚克力基材替换为PVC基材，且步骤4)的反应时间为45min。
实施例19
本实施例提供了一种涂覆产品，该涂覆产品由50mm×20mm×1mm的PVC基材和实施例4提供的水凝胶材料组成，具体制备方法与实施例14相同；区别仅在于将亚克力基材替换为PVC基材，且步骤4)的反应时间为45min。
实施例20
本实施例提供了一种涂覆产品，该涂覆产品由50mm×20mm×1mm的PVC基材和实施例5提供的水凝胶材料组成，具体制备方法与实施例15相同；区别仅在于将亚克力基材替换为PVC基材。
实施例21
本实施例提供了一种涂覆产品，该涂覆产品由玻璃基材和实施例4提供的水凝胶材料组成，具体制备方法与实施例14相同，区别仅在于将亚克力基材替换为玻璃基材。
试验例
本试验例测试了实施例6-20制备的涂覆产品中水凝胶材料的多项表征参数，包括扫描电镜(SEM)表征的显微结构、不同基材表面水凝胶材料的厚度、不同原料配比水凝胶材料的厚度、傅里叶红外光谱(FTIR)表征以及黏附强度，具体试验方法和试验结果如下：
1.利用SEM表征涂覆产品：
将实施例6制备得到的涂覆产品通过液氮冷冻后掰断，用真空冷冻干燥机干燥12h，利用SEM观察水凝胶涂层横截面并拍照，所得结果如图1所示。
由图1可知，水凝胶涂层与基材紧密结合，并且部分水凝胶延伸入环氧/甘氨酸亚铁/葡萄糖氧化酶层，表面水凝胶涂层通过与环氧/甘氨酸亚铁/葡萄糖氧化酶层结合而牢固附着在基材上。
2.检测不同基材制备得到的涂覆产品的水凝胶涂层厚度：
利用偏光显微镜检测实施例6-11制备得到的涂覆产品表面的水凝胶厚度，所得结果如图2所示；实施例6-11制得的涂覆产品所用基材如表1所示。
表1实施例6-11所得涂覆产品使用的基材
由图2可知，在不同种类基材表面涂覆本发明实施例1提供的水凝胶材料，所得水凝胶涂层的厚度比较稳定，基本维持在400-500μm，说明本发明提供的水凝胶材料能够成功涂覆在多种基材表面，适合广泛在实际生产中应用。
3.检测不同聚合单体制备得到的涂覆产品的水凝胶涂层厚度：
利用偏光显微镜检测实施例6和实施例12-15制备得到的涂覆产品表面的水凝胶厚度，所得结果如图3所示；实施例6和实施例12-15制得的涂覆产品所用前驱体溶液的配方如表2所示。
表2实施例6和实施例12-15所得涂覆产品使用的前驱体溶液的配方
由图3可知，采用以上单体均可成功制备水凝胶涂层，涂层的厚度随单体结构不同而略有差异。
4.利用FTIR表征涂覆产品：
采用傅立叶变换红外光谱(NicoletiS50，Thermo Fisher Scientific，美国)，在波长范围为400-4000cm-1下对冻干后的环氧/甘氨酸亚铁/葡萄糖氧化酶层和水凝胶涂层的化学结构进行了分析。
由图4可知，FTIR光谱显示1250cm-1处为PAA上C-O拉伸与O-H耦合的平面内弯曲，1110cm-1处为PEGMA的C-O拉伸峰，1542cm-1处为HEAA的N-H弯曲振动(酰胺II)和1050cm-1处SA的C-O-C拉伸，以上结果证实本发明利用聚合单体AA+PEGMA和HEAA+SA成功制备得到涂覆有水凝胶图层的涂覆产品。
5.检测不同聚合单体制备得到的涂覆产品的水凝胶涂层附着力：
将实施例16-20制得的涂覆产品置于室温条件下老化处理3h，再使用电子万能测试机，采用搭接剪切试验测试凝胶涂层的黏附强度，以5mm/min的速度拉动水凝胶涂 层，直到失效，通过计算最大强度除以粘合面积来计算粘合强度；实施例16-20制得的涂覆产品所用前驱体溶液的配方如表3所示；所得结果如图5所示。
表3实施例16-20所得涂覆产品使用的前驱体溶液的配方
由图5可知，采用不同聚合单体制备得到的水凝胶涂层具有不同的附着力，其中PDMAA水凝胶涂层的黏附强度达到686kPa，说明使用本发明制备得到的高附着通用型水凝胶材料具有更高的附着力。
6.检测水凝胶涂层的润滑能力：
将实施例12制得的涂覆产品作为试验组，亚克力基板作为对照组，将试验组和对照组水平放置在实验桌，并与实验室形成5°的倾斜角，然后在两组一端分别放置一个50g的砝码，所得结果如图6所示。
由图6可知，涂覆有涂层的试验组上砝码会滑落，而对照组上砝码保持不动。以上结果说明本发明提供的水凝胶材料具有优良的润滑性能，将该水凝胶材料涂覆在基材上能够减小基材表面的摩擦力。
7.检测水凝胶涂层的抗生物污染性能：
采用牛蛋白血清作为生物污染剂，将实施例8和实施例21制得的涂覆产品作为试验组，玻璃基板作为对照组，进行抗生物污染测试；所述抗生物污染测试具体包括以下步骤：
1)将100μL用磺基氰5.5染料标记的牛血清白蛋白(BSA-Cy5.5)涂于载玻片上，并分别涂在实施例8和实施例21制得的水凝胶涂层(尺寸：25mm×50mm)上；
2)静置4h后，将这些样品冲洗并用去离子水洗涤至少三次，以去除表面上未附着的BSA；
3)使用激光共聚焦显微镜观察涂层表面，采用image J自动识别蛋白所占据的涂层表面积占总涂层面积的百分比，进一步用于评估水凝胶涂层的抗生物污染性能，所得结果如图7所示。
由图7可知，本发明制备的水凝胶材料具有优良的抗生物污染能力，将该水凝胶材料涂覆在基材表面能够显著减少蛋白质对涂层表面的吸附，从而提高了涂覆产品的抗生物污染能力，本发明提供的水凝胶材料适合广泛应用于抑菌或抗菌材料中。
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种水凝胶材料，其特征在于，所述水凝胶材料包括以下原料：环氧树脂、固化剂、氨基酸金属配合物、葡萄糖氧化酶溶液和前驱体溶液；
    所述前驱体溶液包括葡萄糖、交联剂和单体。
  2. 根据权利要求1所述的水凝胶材料，其特征在于，所述环氧树脂、固化剂、氨基酸金属配合物、前驱体溶液和葡萄糖氧化酶溶液的质量比为(30-70)：(30-70)：(5-15)：(5-15)：1；
    优选地，所述葡萄糖、交联剂和单体的质量比为(80-120)：(0.1-2)：(80-200)；
    优选地，所述葡萄糖氧化酶溶液中葡萄糖氧化酶的浓度为0.05-0.1wt％。
  3. 根据权利要求1所述的水凝胶材料，其特征在于，所述环氧树脂包括E-44、E-51、E-42、E-31、E-21和E-20中的至少一种。
  4. 根据权利要求1所述的水凝胶材料，其特征在于，所述固化剂包括聚酰胺固化剂。
  5. 根据权利要求1所述的水凝胶材料，其特征在于，所述氨基酸金属配合物包括甘氨酸亚铁、组氨酸亚铁、赖氨酸钼、色氨酸钴、半胱氨酸铜、半胱氨酸锰和酪氨酸镍中的至少一种。
  6. 根据权利要求1所述的水凝胶材料，其特征在于，所述交联剂包括N,N-甲基双丙烯酰胺或二甲基丙烯酸乙二醇酯。
  7. 根据权利要求1所述的水凝胶材料，其特征在于，所述单体包括N-羟乙基丙烯酰胺、N,N-二甲基丙烯酰胺、丙烯酸、聚(乙二醇)甲基丙烯酸酯、丙烯酰胺和海藻酸钠中的至少一种。
  8. 一种如权利要求1-7任一项中所述水凝胶材料的制备方法，其特征在于，所述制备方法包括以下步骤：
    S1：将氨基酸金属配合物、环氧树脂、葡萄糖氧化酶溶液和固化剂混匀，得到混合液；
    S2：将步骤S1所述混合液和前驱体溶液混匀，反应即得水凝胶材料。
  9. 一种涂覆产品，其特征在于，所述涂覆产品包括基材，以及涂布于所述基材表面的如权利要求1-7任一项中所述的水凝胶材料。
  10. 如权利要求1-7任一项中所述的水凝胶材料在提高基材润滑性和/或防污性中的 应用。
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