WO2021129079A1 - 一种可用于铁质炊具的石墨烯改性水性不粘涂料的制备方法 - Google Patents

一种可用于铁质炊具的石墨烯改性水性不粘涂料的制备方法 Download PDF

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WO2021129079A1
WO2021129079A1 PCT/CN2020/122073 CN2020122073W WO2021129079A1 WO 2021129079 A1 WO2021129079 A1 WO 2021129079A1 CN 2020122073 W CN2020122073 W CN 2020122073W WO 2021129079 A1 WO2021129079 A1 WO 2021129079A1
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graphene
zinc
preparation
water
temperature resistant
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French (fr)
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钱涛
刘海龙
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杭州吉华高分子材料股份有限公司
钱涛
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Priority to KR1020217040525A priority Critical patent/KR102459441B1/ko
Publication of WO2021129079A1 publication Critical patent/WO2021129079A1/zh

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    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • 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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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    • 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
    • C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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    • 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
    • C09D7/61—Additives non-macromolecular inorganic
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the invention relates to the field of polymer materials, in particular to a method for preparing graphene modified water-based non-stick coatings that can be used for iron cookware.
  • the protective ability of the coating depends more on its own resistance to penetration and barrier to corrosive media. It has also become an urgent need to improve the anti-corrosion performance of non-stick coatings applied to iron cookware.
  • Graphene is a two-dimensional honeycomb lattice structure composed of a single layer of carbon atoms densely packed. In single-layer graphene, each carbon atom forms a bond with surrounding carbon atoms through sp 2 hybridization to form a regular hexagon. It is precisely because of the special structure of graphene that it has high thermal stability, chemical stability and excellent resistance to permeation. It can effectively block the passage of gas atoms such as water and oxygen. Good physical barrier function.
  • each layer can still maintain the characteristics of two-dimensional graphene, it has The graphene sheets with ⁇ - ⁇ interaction are prone to agglomeration, the specific surface area of the sheet is sharply reduced, and the barrier and protection performance of the substrate is significantly reduced.
  • the electrochemical properties in the graphene layer are not affected. Will accelerate the electrochemical corrosion of metals.
  • Multilayer graphene is susceptible to damage and produces structural defects. From the perspective of electrochemical potential, damaged graphene acts as a positive electrode (C element) in the metal corrosion process, which will accelerate local electrochemical corrosion, especially when the Slight cracks or scratches appear in the coating, the corrosion rate of the exposed area is greatly accelerated, and the strength and toughness of the metal are reduced. Therefore, in order for graphene to give full play to its anti-corrosion properties in coatings, it must first solve the problem of its dispersion in resin and maintain the stability of the graphene structure.
  • the present invention provides a method for preparing graphene-modified water-based non-stick coatings that can be used for iron cookware.
  • the present invention first processes the multilayer graphene so that the sheets are filled with elemental zinc. Then, the tetraethyl orthosilicate reaction is used for in-situ coating modification to form zinc-containing graphene with an inorganic ceramic network.
  • the inorganic ceramic network After the inorganic ceramic network is obtained, it is mixed and reacted with tetraethyl orthosilicate and fluorine-containing emulsion to form an organic-inorganic interpenetrating network structure, so that the zinc-containing graphene is locked in the pores of the network structure, and the obtained graphite is prepared
  • the graphene structure in the olefin-modified water-based non-stick coating will not be destroyed, and once electrochemical corrosion of the galvanic cell occurs, elemental zinc can be used as a sacrificial electrode to delay the corrosion of the substrate.
  • the zinc-containing coating has certain antibacterial properties.
  • a method for preparing graphene-modified water-based non-stick coating for iron cooking utensils including the following steps:
  • Pre-dispersion of graphene The multilayer graphene is dispersed in water through a pre-dispersion process to form a graphene slurry with a mass fraction of 0.5-25%.
  • Tetraethyl acid adjust the pH to 1-4, stir and react for 2-5h at 200-300rpm at 40-80°C, and then filter to obtain the zinc-containing graphene modified in situ by the inorganic ceramic network; multilayer graphene, zinc and normal
  • the mass ratio of tetraethyl silicate is 30-5:10-2:1.
  • the present invention exhausts the air in the interlayer gaps of the multi-layer graphene through vacuuming and inert gas replacement to prevent the elemental zinc generated in the gaps from being oxidized, and then pressurizes to fill the zinc salt
  • elemental zinc is generated between the layers under the action of the reducing agent to achieve the molecular level mixing of elemental zinc and graphene, and then fixed in the inorganic ceramic network structure formed by tetraethylorthosilicate.
  • the electrochemical electrons that can only be conducted in the graphene layers are transferred to the zinc that acts as a sacrificial anode throughout the graphene layers. Conduction reduces the effect of electrochemical corrosion.
  • Metal cookware is often exposed to acid, salt and other media during use, especially iron cookware.
  • a layer of electrochemical corrosion electrolyte solution is formed, which forms countless tiny galvanic cells with the iron and a small amount of carbon in the iron substrate. In these galvanic cells, iron is the negative electrode and carbon is the positive electrode.
  • Multi-layer graphene modified coating is directly used. Multi-layer graphene is easily damaged and produces structural defects. From the perspective of electrochemical potential Look, the damaged graphene acts as a positive electrode (C element) in the metal corrosion process, which will accelerate local electrochemical corrosion, especially when the coating has slight cracks or scratches, the corrosion rate of the exposed area is greatly accelerated, and the metal is reduced. The strength and toughness of the performance.
  • C element positive electrode
  • the zinc-containing graphene in the present invention is uniformly dispersed in the non-stick coating, firstly strengthens the tightness between the non-stick resins, effectively fills the gaps in the non-stick resin, and constitutes a good shielding effect, effectively It eases the entry of electrolyte solution and improves the corrosion resistance of the non-stick coating.
  • the graphene structure fixed by the inorganic ceramic network structure is not easily damaged, and even if it is affected by electrochemical corrosion, the elemental zinc between the graphene layers can be As a sacrificial pole, it delays the corrosion of the substrate, and the zinc-containing coating has certain antibacterial properties.
  • the tetraethyl orthosilicate must be added in two parts, the first time is to form an inorganic ceramic network, and the second time is to realize the formation of an inorganic-organic interpenetrating network. Therefore, the special structure required by the present invention can be formed only by adding tetraethyl orthosilicate in two stages.
  • the multilayer graphene is commercially available graphene, and the number of layers is 10-50.
  • the pre-dispersion process is ultrasonic or grinding or adding a dispersant or a combination thereof.
  • the zinc salt is one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate and zinc carbonate.
  • the reducing agent is one or more of sodium citrate, sodium borohydride, glucose and ascorbic acid.
  • the fluorine-containing emulsion is one or more of PTFE, FEP, ECTFE, PCTFE and PFA.
  • the bonding resin is one or more of PES, PAI, PI and PPS.
  • the high temperature resistant pigments and fillers include high temperature resistant pigments and high temperature resistant fillers, the high temperature resistant pigments are inorganic high temperature resistant pigments or organic high temperature resistant pigments or a combination thereof, and the high temperature resistant fillers are ceramic powders. Or silicon carbide or a combination thereof.
  • the auxiliary agent is one or more of a dispersing agent, a leveling agent, a defoaming agent and a thickening agent.
  • the water is distilled water, ultrapure water or deionized water.
  • the present invention first uses vacuum-passing inert gas replacement to exhaust the air in the gaps between the multilayer graphene layers, and then pressurizes to fill the zinc salt into the gaps between the graphene layers, and in-situ reduction between the layers generates elemental substances Zinc realizes the molecular level mixing of graphene and elemental zinc between layers.
  • the present invention adopts the reaction of tetraethyl orthosilicate to form an inorganic ceramic network to realize the package modification of zinc-containing graphene, which not only avoids graphene agglomeration, but also realizes the structural protection of zinc-containing graphene.
  • the present invention is mixed and reacted with tetraethyl orthosilicate and fluorine-containing emulsion to form an organic-inorganic interpenetrating network structure, so that the zinc-containing graphene is locked in
  • the elemental zinc between the graphene layers can be used as a sacrificial anode to delay the corrosion of the substrate, and the zinc-containing coating has certain antibacterial properties.
  • the synthesis method of the present invention is simple, convenient, and easy to industrialize.
  • the obtained coating has good adhesion with the coating substrate after film formation. It is used on iron cookware and has anti-heat accumulation, anti-corrosion, good antibacterial properties and good durability. , Non-sticky and other advantages.
  • Figure 1 is a schematic diagram of the reaction principle of the present invention.
  • a method for preparing graphene-modified water-based non-stick coating for iron cooking utensils including the following steps:
  • Pre-dispersion of graphene The multilayer graphene is dispersed in water through a pre-dispersion process to form a graphene slurry with a mass fraction of 0.5-25%.
  • the multilayer graphene is commercially available graphene, and the number of layers is 10-50.
  • the pre-dispersion process is ultrasonic or grinding or adding a dispersant or a combination thereof.
  • Tetraethyl acid adjust the pH to 1-4, stir and react for 2-5h at 40-80°C, 200-300rpm, and then filter to obtain in-situ modified zinc-containing graphene of inorganic ceramic network; multilayer graphene, zinc and normal
  • the mass ratio of tetraethyl silicate is 30-5:10-2:1.
  • the zinc salt is one or more of zinc sulfate, zinc chloride, zinc acetate, zinc nitrate and zinc carbonate.
  • the reducing agent is one or more of sodium citrate, sodium borohydride, glucose and ascorbic acid.
  • the fluorine-containing emulsion is one or more of PTFE, FEP, ECTFE, PCTFE and PFA.
  • the bonding resin is one or more of PES, PAI, PI and PPS.
  • the high temperature resistant pigments and fillers include high temperature resistant pigments and high temperature resistant fillers, the high temperature resistant pigments are inorganic high temperature resistant pigments or organic high temperature resistant pigments or a combination thereof, and the high temperature resistant filler is ceramic powder or silicon carbide or a combination thereof.
  • the auxiliary agent is one or more of dispersing agent, leveling agent, defoaming agent and thickening agent.
  • the water is distilled water, ultrapure water or deionized water.
  • Pre-dispersion of graphene The multi-layer graphene is pre-dispersed in water through an ultrasonic dispersion process to form a graphene slurry with a mass fraction of 5%.
  • the reaction was stirred at 300 rpm for 3 hours and then filtered to obtain zinc-containing graphene modified in situ by the inorganic ceramic network; the mass ratio of multilayer graphene, zinc and tetraethyl orthosilicate was 10:2:1.
  • Example 1 The only difference from Example 1 is that only the water-based non-stick coating is prepared without the addition of graphene, zinc and tetraethyl orthosilicate.
  • the specific solution is: adding PES, carbon black, silicon carbide, dispersant, fluid to the PTFE emulsion A leveling agent, a thickening agent and water are used to obtain a water-based non-stick coating.
  • the materials and composition are the same as those in Example 1.
  • step 2 the graphene slurry is modified with a conventional silane coupling agent and does not contain zinc.
  • the specific solution is: the graphene slurry prepared in step 1) is combined with KH560 After blending, 200rpm mechanical stirring and room temperature reaction for 2h, silane coupling agent modified graphene was obtained; the mass ratio of multilayer graphene to KH560 was 5:1.
  • Other materials and composition are the same as in Example 1.
  • Example 1 The only difference from Example 1 is that elemental zinc is not generated in the graphene sheet in step 2), and is not a molecular-level mixing.
  • the specific solution is: blending the graphene slurry prepared in step 1) with zinc sulfate, Add sodium citrate dropwise. After the addition is complete, the temperature is raised to 50°C, and the reaction is stirred at 10rpm for 60min. Tetraethyl orthosilicate is added to adjust the pH to 4, and the reaction is stirred at 80°C, 300rpm for 2h, and then filtered to obtain a ceramic network.
  • Modified zinc-containing graphene the mass ratio of multilayer graphene, zinc and tetraethylorthosilicate is 5:2:1.
  • Example 1 The only difference from Example 1 is that only tetraethyl orthosilicate is added in step 2), but not in step 3), and other materials and compositions are consistent with the embodiment.
  • the graphene modified water-based non-stick coatings prepared in Examples 1-4 and Comparative Examples 1-4 were respectively coated on iron pans (thickness 15-20 ⁇ m), and then the hardness, heat buildup resistance and acid resistance were Tests for performance such as resistance, salt water resistance, antibacterial and non-stick properties, among which the hardness test is carried out according to GB/T 6739, the result is evaluated: paint film scratches; the heat accumulation test is carried out according to the induction cooker boiling water experiment, and the result is evaluated: boiled After water for 2 hours, observe with 4 times magnifying glass, the paint film has no cracks, wrinkles or peeling phenomenon; the acid resistance test is carried out according to the immersion method in GB/T 9274, the medium is 3% acetic acid solution, and the measurement is carried out according to GB /T 32095.2-2015 The surface abrasion resistance test is carried out after 5000 times.
  • the acid resistance of the coating after abrasion; the salt water resistance test is carried out according to the immersion method in GB/T 9274, and the medium is a NaCl solution with a mass fraction of 10%.
  • the acid resistance of the coating after abrasion after 5000 times of the plane abrasion resistance test carried out according to GB/T 32095.2-2015 was measured; the antibacterial resistance test was carried out according to ISO 22196-2011, and the result was evaluated: for Staphylococcus aureus and large intestine
  • the antibacterial efficacy value of bacilli is ⁇ 2; the non-stickiness test is carried out according to GB/T 32095.2-2015.
  • the result is evaluated: 10 fried eggs remain intact.
  • the test results are shown in Table 1.
  • comparative example 1 did not add graphene, zinc and tetraethyl orthosilicate, with low hardness, heat accumulation, poor acid and salt water resistance, severe corrosion on iron pans, and no antibacterial; while comparative example 2 added
  • the graphene directly modified by the silane coupling agent does not contain zinc.
  • the silane coupling agent can improve the dispersibility of the graphene and improve the hardness and heat resistance.
  • the graphene modified by the silane coupling agent The compactness of the coating is not good.
  • the graphene modified water-based non-stick coatings of Examples 1-4 have excellent hardness, heat accumulation resistance, acid resistance, salt water resistance, acid resistance after grinding, salt water resistance after grinding,
  • the antibacterial and non-stick properties indicate that the elemental zinc formed between graphene layers is mixed with graphene at the molecular level, and then the inorganic ceramic network formed by the reaction of tetraethylorthosilicate is used to coat and modify the zinc-containing graphene, which avoids graphite
  • the agglomeration of ene can protect the structure of zinc-containing graphene, and through the formation of a ceramic network, an organic-inorganic interpenetrating network structure is formed between the zinc-containing graphene and the fluorine-containing macromolecular chain, and the combination between the two It is more compact and has a synergistic effect of ceramic materials, zinc, graphen
  • raw materials and equipment used in the present invention are all commonly used raw materials and equipment in the field; the methods used in the present invention, unless otherwise specified, are all conventional methods in the field.

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PCT/CN2020/122073 2019-12-27 2020-10-20 一种可用于铁质炊具的石墨烯改性水性不粘涂料的制备方法 WO2021129079A1 (zh)

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CN114096020A (zh) * 2021-12-31 2022-02-25 烯泽韩力石墨烯应用科技(无锡)有限公司 抗菌型石墨烯ptc电热膜浆料及其制备方法和电热膜

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CN111100512B (zh) * 2019-12-27 2021-07-30 杭州吉华高分子材料股份有限公司 一种可用于铁质炊具的石墨烯改性水性不粘涂料的制备方法
CN112745759A (zh) * 2020-11-30 2021-05-04 哈尔滨理工大学 一种耐高温石墨烯自润滑水性防腐涂料的制备方法
CN114921145B (zh) * 2022-06-10 2023-07-18 洛阳大豫实业有限公司 一种改性石墨烯防腐涂料及其制备方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807845A (zh) * 2012-08-17 2012-12-05 叶全惠 一种薄层石墨烯层间包含金属颗粒的高导热散热材料的制备方法
CN103849092A (zh) * 2013-07-24 2014-06-11 广科工业股份有限公司 复合材料微粉与其形成方法、陶瓷涂料、与保护涂层
CN103950919A (zh) * 2014-04-01 2014-07-30 华南理工大学 一种石墨烯的制备方法
CN105368185A (zh) * 2015-11-20 2016-03-02 平顶山市圣康炊具有限公司 一种不粘锅涂料
CN106189562A (zh) * 2016-07-28 2016-12-07 杭州吉华高分子材料股份有限公司 一种红外辐射散热水性耐磨不粘涂料及其制备方法
CN106519779A (zh) * 2016-11-11 2017-03-22 安徽易能新材料科技有限公司 一种石墨烯负载纳米锌及含有该石墨烯负载纳米锌的环氧富锌底漆
CN107099217A (zh) * 2017-04-28 2017-08-29 山东欧铂新材料有限公司 一种含有石墨烯/锌粉复合材料的树脂防腐涂料及其制备方法
WO2019217402A1 (en) * 2018-05-07 2019-11-14 Nanotek Instruments, Inc. Graphene-enabled anti-corrosion coating
CN111100512A (zh) * 2019-12-27 2020-05-05 杭州吉华高分子材料股份有限公司 一种可用于铁质炊具的石墨烯改性水性不粘涂料的制备方法

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102002268A (zh) * 2009-09-01 2011-04-06 东莞宜安科技股份有限公司 采用溶胶-凝胶杂化技术制备的超硬不粘硅炊具涂料
US8877846B2 (en) * 2012-04-17 2014-11-04 Xerox Corporation Surface coating and fuser member
CN103214897B (zh) * 2013-03-19 2015-01-07 宁波墨西新材料有限公司 一种石墨烯不粘涂料
CN104479494A (zh) * 2014-12-01 2015-04-01 湖南东博墨烯科技有限公司 一种石墨烯基纳米零价锌系涂料及其制备方法
CN105185432B (zh) * 2015-10-09 2017-10-27 重庆文理学院 一种多重保护的银纳米线透明导电薄膜
CN105348950A (zh) * 2015-11-30 2016-02-24 无锡大塘复合材料有限公司 一种石墨烯不粘涂料及其应用
CN105585911B (zh) * 2016-01-19 2018-04-27 杭州吉华高分子材料股份有限公司 一种高导热高耐磨不粘涂料
CN106854399B (zh) * 2016-12-23 2019-01-11 余姚市赫玛涂料有限公司 一种高导热水基防粘涂料及其制备方法和应用
CN109665520A (zh) * 2017-10-16 2019-04-23 山东欧铂新材料有限公司 一种石墨烯表面修饰改性的方法及二氧化硅/石墨烯类复合材料
CN110393447A (zh) * 2019-09-05 2019-11-01 广东健玺表面工程技术有限公司 一种导热均衡远红外增效金属塑复合不粘锅厨具制备方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102807845A (zh) * 2012-08-17 2012-12-05 叶全惠 一种薄层石墨烯层间包含金属颗粒的高导热散热材料的制备方法
CN103849092A (zh) * 2013-07-24 2014-06-11 广科工业股份有限公司 复合材料微粉与其形成方法、陶瓷涂料、与保护涂层
CN103950919A (zh) * 2014-04-01 2014-07-30 华南理工大学 一种石墨烯的制备方法
CN105368185A (zh) * 2015-11-20 2016-03-02 平顶山市圣康炊具有限公司 一种不粘锅涂料
CN106189562A (zh) * 2016-07-28 2016-12-07 杭州吉华高分子材料股份有限公司 一种红外辐射散热水性耐磨不粘涂料及其制备方法
CN106519779A (zh) * 2016-11-11 2017-03-22 安徽易能新材料科技有限公司 一种石墨烯负载纳米锌及含有该石墨烯负载纳米锌的环氧富锌底漆
CN107099217A (zh) * 2017-04-28 2017-08-29 山东欧铂新材料有限公司 一种含有石墨烯/锌粉复合材料的树脂防腐涂料及其制备方法
WO2019217402A1 (en) * 2018-05-07 2019-11-14 Nanotek Instruments, Inc. Graphene-enabled anti-corrosion coating
CN111100512A (zh) * 2019-12-27 2020-05-05 杭州吉华高分子材料股份有限公司 一种可用于铁质炊具的石墨烯改性水性不粘涂料的制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TIAN ZHENYU, LI ZHIGANG, QU YAN: "Application of Zinc/Graphene Composite Heavy-Duty Anticorrosive Coatings", COATINGS TECHNOLOGY & ABSTRACTS, vol. 36, no. 9, 1 September 2015 (2015-09-01), pages 30 - 34, XP055827155, ISSN: 2096-8639 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113466300A (zh) * 2021-07-16 2021-10-01 福建师范大学 一种石墨烯改性硅溶胶负载沙丁胺醇抗体传感器制备方法
CN113466300B (zh) * 2021-07-16 2023-04-14 福建师范大学 一种石墨烯改性硅溶胶负载沙丁胺醇抗体传感器制备方法
CN114096020A (zh) * 2021-12-31 2022-02-25 烯泽韩力石墨烯应用科技(无锡)有限公司 抗菌型石墨烯ptc电热膜浆料及其制备方法和电热膜

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