CN114854262A - Preparation method of coating containing few-layer graphene and coating - Google Patents

Preparation method of coating containing few-layer graphene and coating Download PDF

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CN114854262A
CN114854262A CN202210646476.7A CN202210646476A CN114854262A CN 114854262 A CN114854262 A CN 114854262A CN 202210646476 A CN202210646476 A CN 202210646476A CN 114854262 A CN114854262 A CN 114854262A
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resin
aqueous
graphite
grinding
graphene
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丁古巧
周久顺
周建
姜忱
刘雷庭
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Shanghai Enwang New Material Technology Co ltd
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Shanghai Enwang New Material Technology Co ltd
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    • 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
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    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
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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
    • C09D5/24—Electrically-conducting paints
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
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    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
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Abstract

The invention discloses a preparation method of a coating containing few-layer graphene and the coating, and the method comprises the following steps: s1, adding aqueous grinding resin into water, and dispersing to obtain an aqueous dispersion of the aqueous grinding resin; s2, adding graphite into the aqueous dispersion of the aqueous grinding resin, and dispersing to obtain an aqueous dispersion of graphite; s3, mechanically stripping the aqueous dispersion of the graphite to obtain an aqueous dispersion of few-layer graphene; and S4, adding a surfactant into the graphene aqueous dispersion, and uniformly mixing to obtain the coating containing few-layer graphene. According to the invention, the water-based grinding resin is used as a dispersing agent in the graphene preparation process, and the obtained graphene-containing coating has the advantages of good stability and good adhesion with a base material, and can be used in the fields of electromagnetic shielding coatings, conductive coatings, heating coatings or textile finishing coatings and the like.

Description

Preparation method of coating containing few-layer graphene and coating
Technical Field
The invention belongs to the field of composite materials, and relates to a preparation method of a coating containing few-layer graphene and the coating containing few-layer graphene.
Background
The graphene has the characteristics of high theoretical specific surface area, excellent electric conductivity, heat conductivity, mechanical properties and high electron mobility. Based on the advantages, the graphene is widely developed and applied in the fields of composite material reinforcement, semiconductor wafers, biomedicine, textile clothes, special coatings and the like. However, since graphene has no affinity with a substrate due to its own functional group structure, the current graphene special coating is often attached to the surface of the substrate simply by coating graphene with a coating, and it is difficult to improve the adhesion and various fastnesses of the coating to the substrate after modifying graphene. Or the graphene oxide is polymerized and enters the resin chain segment for reduction application, but the method has the disadvantages of complex operation, long production flow, limitation of the addition amount and the reduction degree of the graphene oxide and influence on the expression of special coating performance.
Regarding the conductive coating containing graphene, chinese patent publication No. CN114181576A [ zhou wei jian et al, title of the invention: an anti-static industrial coating of wear-resistant graphene and a preparation method thereof disclose a method for preparing the anti-static industrial coating of wear-resistant graphene by polymerizing graphene oxide into a resin chain segment, wherein the method has long reaction time consumption and large energy consumption, and the performance expression of the coating is limited by the addition amount and the reduction degree of the graphene oxide. Chinese patent publication No. CN 109666350a [ zhao yong bin, etc., the invention name: a water-based conductive coating containing high-conductivity graphene and a preparation method thereof disclose a conductive coating prepared by screening graphene, water-based resin and an auxiliary agent. In the prior art, the methods are difficult to fully modify graphene, and the preparation process is complicated.
In addition, it is also common in the prior art to prepare corresponding coatings by mixing commercially available graphene with other materials, but the use of commercially available graphene has the problem that the thickness of the graphene sheet layer cannot be controlled and is relatively expensive.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of the coating containing few-layer graphene, the graphene in the coating prepared by the method is small in transverse size, the number of layers is uniformly distributed in 10 layers, and the coating has the advantages of stable slurry and good adhesion with a base material, and can be used in the fields of electromagnetic shielding coatings, conductive coatings, heating coatings or textile finishing coatings and the like.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of a coating containing few-layer graphene comprises the following steps:
s1, adding aqueous grinding resin into water, and dispersing to obtain an aqueous dispersion of the aqueous grinding resin;
s2, adding graphite into the aqueous dispersion of the aqueous grinding resin, and dispersing to obtain an aqueous dispersion of graphite;
s3, mechanically stripping the aqueous dispersion of the graphite to obtain an aqueous dispersion of few-layer graphene;
and S4, adding a surfactant into the graphene aqueous dispersion, and uniformly mixing to obtain the coating containing few layers of graphene.
Preferably, the water is deionized water or distilled water.
Preferably, S4 is added with resin, and the resin accounts for 0-900% of the weight of the graphite.
Preferably, the resin added in S4 is selected from one or more of acrylic resin, polyurethane resin and polycarbonate resin.
Preferably, the aqueous grinding resin is one or more selected from the group consisting of aqueous grinding acrylic resin, aqueous grinding polyurethane resin and aqueous grinding polycarbonate resin.
Preferably, the aqueous grinding acrylic resin is selected from chinese patent publication No. CN113980163A [ wannational wei et al, title of the invention: aqueous acrylic acid grinding resin in the aqueous acrylic acid grinding resin and preparation method thereof ] and products of PyM-16449, SL16827 and ZZYM-16455 of Synbanum nanotechnology Co.
Preferably, the aqueous grinding polyurethane resin is selected from the group consisting of a product of DB16103 of synfei nano technology GmbH, a product of F0409 of Shenzhen Jitian chemical engineering GmbH, and a product of GSB-03-56 of Wenzhou Shibang high polymer material GmbH.
Preferably, the aqueous abrasive polycarbonate resin is selected from the group consisting of the Eternacoll-PH series and the Eternacoll-BH series of the Utsu Hippon company Limited.
Preferably, when the aqueous grinding resin is selected from aqueous grinding acrylic resins, the resin added in S4 is selected from acrylic resins.
Preferably, when the aqueous grinding resin is selected from aqueous grinding polyurethane resins, the resin added in S4 is selected from polyurethane resins.
Preferably, when the aqueous grinding resin is selected from aqueous grinding polycarbonate resins, the resin added in S4 is selected from polycarbonate resins.
Preferably, the graphite is selected from one or more of natural crystalline flake graphite, expandable graphite, expanded graphite, intercalated graphite and graphite nanosheets.
Preferably, the surfactant is selected from one or more of a wetting agent, a penetrating agent, a defoaming agent and a leveling agent.
Preferably, the amount of the aqueous polishing resin is 20 to 200% by weight of the graphite.
Preferably, the addition amount of the surfactant is 0.1 to 5% of the total mass of the coating.
Preferably, the concentration of the aqueous polishing resin in the aqueous dispersion of the aqueous polishing resin in S1 is 10 mg/mL-300 mg/mL.
Preferably, the concentration of graphite in the aqueous dispersion of graphite in S2 is 10mg/L to 200 mg/mL.
Preferably, the mechanical peeling in S3 is performed by one or more of a colloid mill apparatus, a ball mill apparatus, a sand mill apparatus, a high pressure homogenizing apparatus and an ultrasonic apparatus.
More preferably, the mechanical peeling in S3 is performed by a high-pressure homogenizing apparatus.
Preferably, the treatment pressure of the high-pressure homogenizing equipment is 60-300 MPa, and the solution treatment times are 1-5 times;
preferably, the temperature of the graphene obtained by mechanically stripping graphite in the step S3 is 10-80 ℃.
In another aspect, the present invention provides a coating containing few-layer graphene, the coating comprising:
the graphene-containing aqueous grinding resin comprises, by weight, 0.1-10% of few-layer graphene, 0.01-2% of a surfactant, 1-60% of an aqueous grinding resin, 0-50% of a resin and the balance water.
Preferably, the aqueous grinding resin is selected from one or more of the following: an aqueous grinding acrylic resin, an aqueous grinding polyurethane resin and an aqueous grinding polycarbonate resin.
Preferably, the resin is selected from one or more of the following: one or more of an acrylic resin, a polyurethane resin, and a polycarbonate resin.
Preferably, the surfactant is selected from one or more of a wetting agent, a penetrating agent, a defoaming agent, and a leveling agent.
According to the preparation method of the coating containing few-layer graphene, the aqueous grinding resin is used as a dispersing agent in the process of preparing graphene from graphite, the transverse size of the graphene in the prepared coating is small, the number of layers is uniformly distributed in 10 layers, and the aqueous grinding resin can modify the surface of the graphene, so that the adhesion between the graphene and a base material is large.
Drawings
Fig. 1 is a TEM image of a few-layer graphene coating prepared in example 1 of the present invention, where the left and right images are a low-magnification image representing the graphene sheet layer size and a lattice image representing the graphene sheet layer thickness, respectively.
Fig. 2 is a TEM image of a few-layer graphene coating prepared in example 2 of the present invention, wherein the left and right images are a low-magnification image representing the graphene sheet layer size and a lattice image representing the graphene sheet layer thickness, respectively. Fig. 3 is a TEM image of a few-layer graphene coating prepared in example 3 of the present invention, wherein the left and right images are a low-magnification image representing the graphene sheet layer size and a lattice image representing the graphene sheet layer thickness, respectively. Fig. 4 is a TEM image of the few-layer graphene coating prepared in comparative example 1 of the present invention, wherein the left and right images are a low magnification image representing the size of the graphene sheet layer and a lattice image representing the thickness of the graphene sheet layer, respectively.
Fig. 5 is a TEM image of the few-layer graphene coating prepared in comparative example 2 of the present invention, wherein the left and right images are a low magnification image representing the size of the graphene sheet layer and a lattice image representing the thickness of the graphene sheet layer, respectively.
Detailed Description
Aiming at the defects of the coating containing graphene in the prior art, the inventor of the application finds that the water-based grinding resin can be used as a dispersing agent in the process of preparing graphene by mechanically stripping graphite and can be used as a surfactant to modify the surface of finally prepared graphene, so that the adhesion between the graphene and a base material is strong, and the invention is completed on the basis.
The preparation method of the coating containing few-layer graphene comprises the following steps: s1, adding aqueous grinding resin into water, and dispersing to obtain an aqueous dispersion of the aqueous grinding resin; s2, adding graphite into the aqueous grinding resin dispersion liquid, and dispersing to obtain an aqueous graphite dispersion liquid; s3, mechanically stripping the aqueous dispersion of the graphite to obtain an aqueous dispersion of few-layer graphene; and S4, adding a surfactant into the graphene aqueous dispersion, and uniformly mixing to obtain the coating containing few-layer graphene.
In the preparation method of the invention, the steps S1-S4 can be carried out at normal temperature or ambient temperature.
In the preparation method, the aqueous grinding resin is a modified aqueous resin which can be used for grinding and has the functions of serving as a dispersant to better disperse the raw material graphite in water on one hand and serving as a modifier of graphene to be attached to the surface of the graphene so that the graphene has stronger adhesion on a substrate when the coating is coated on the substrate on the other hand. The aqueous grinding resin that can be used in the present invention includes, but is not limited to, aqueous grinding acrylic resin, aqueous grinding polyurethane, and aqueous grinding polycarbonate resin.
The aqueous grinding acrylic resin (also referred to as an aqueous acrylic grinding resin) is an aqueous resin in which a functional monomer having or capable of obtaining a branched structure modifies an acrylic resin to improve the dispersion grinding effect and coating stability of particles. For example, the functional monomer of claim 3 in Chinese patent publication No. CN113980163A (title of the invention: an aqueous acrylic polishing resin and its preparation method) improves cohesion degree between the aqueous acrylic polishing resin and particles, enhances binding force between the resin and the particles, and improves stability of graphite sheet during mechanical peeling. Such aqueous grinding acrylic resins that can be used in the present invention include, but are not limited to, those available from Nippon Federation nanotechnology Co., Ltd, models PYM-16449, SL16827, and ZZYM-16455, and those disclosed in Chinese patent publication No. CN113980163A (title of the invention: an aqueous acrylic grinding resin and a method for preparing the same).
The aqueous grinding urethane resin (also referred to as an aqueous urethane grinding resin) is an aqueous urethane resin which is modified by a functional monomer having or capable of obtaining a branched structure and can improve the dispersion grinding effect and coating stability of particles. Such aqueous abrasive polyurethane resins useful in the present invention include, but are not limited to, product number DB16103 of Synfei Nippon nanotechnology, Inc., product number F0409 of Shenzhen Jitian chemical, Inc., product number GSB-03-56 of Wenzhou Shibang Polymer materials, Inc., and the like.
The aqueous grinding polycarbonate resin (also referred to as an aqueous polycarbonate grinding resin) is an aqueous polycarbonate resin which is modified by a functional monomer having or capable of obtaining a branched structure and can improve the dispersion grinding effect on particles and the coating stability. Such aqueous abrasive polycarbonate resins useful in the present invention include, but are not limited to, products of the Eternacoll-PH series, the Eternacoll-BH series, and the like, available from Kyowa (Shanghai) Co., Ltd.
In the preparation method of the present invention, the acrylic resin, the polyurethane resin and the polycarbonate resin are not particularly limited, and such resins commonly used in the coating materials in the market can be used in the present invention. In the preparation method of the present invention, "graphite" refers to graphite serving as a raw material for preparing graphene, and includes, but is not limited to, natural flake graphite, expandable graphite, expanded graphite, intercalated graphite, and graphite nanosheets.
In the preparation method of the present invention, the equipment used for mechanical stripping includes, but is not limited to, colloid mill equipment, ball mill equipment, sand mill equipment, high-pressure homogenizing equipment and ultrasonic equipment.
In the preparation method, the surfactant is added to adjust the surface tension of the coating so as to improve the spreadability of the coating and the base material. Surfactants useful in the present invention include, but are not limited to, wetting agents, penetrants, defoamers, and leveling agents. The wetting agent is preferably a branched alcohol ethoxy block compound, e.g., altader 5060. The penetrant is preferably a fatty alcohol polyoxyethylene ether, for example, JFC. The defoamer is preferably a fumed silica-containing polyether siloxane copolymer, e.g., digao 810. The leveling agent is preferably a polyether modified silicone, for example, BYK-333.
In the preparation method of the invention, the resin is added to further improve the adhesion between the coating and the base material, and the resin which can be used in the invention includes but is not limited to acrylic resin, polyurethane resin and polycarbonate resin. Preferably, the type of resin is the same as the type of aqueous grinding resin. In a preferred embodiment of the present invention, the coating material containing few-layer graphene is used for treatment of conductive coating, antistatic coating, and heat-generating coating of substrates such as textile chemical fibers and organic glass, and the aqueous polishing resin used is an aqueous polishing acrylic resin, and the resin used is an acrylic resin. In a preferred embodiment of the present invention, the coating material containing few-layer graphene is used for the treatment of conductive coating, antistatic coating, and heat-generating coating on the surface of leather, textile, packaging, and the like, and the aqueous polishing resin used is an aqueous polishing polyurethane resin and the resin used is polyurethane. In a preferred embodiment of the present invention, the coating material containing few-layer graphene is used for a polyimide film, a conductive coating layer for automobile surfaces and interiors, an antistatic coating layer, a heat-generating coating layer treatment, and the like, and the aqueous polishing resin used is an aqueous polishing polycarbonate resin, and the resin used is a polycarbonate resin.
In the present invention, "plural" means two or more.
The invention is further described below in connection with specific embodiments, it being understood that the following examples are intended only to provide the best mode of practicing the invention, and should not be interpreted as limiting the scope of the invention. Experimental procedures in the following examples, where specific conditions are not specified, are generally in accordance with conventional procedures and conditions, or with conditions recommended by the manufacturer. Unless otherwise indicated, percentages and parts are by weight.
The transmission electron microscope used in the following examples was manufactured by Hitachi, model HT 7800. The manufacturer of the rubbing color fastness instrument is Shanghai precision instrument and meter company Limited, and the model is Y571A. The Zeta potentiometric instrument was manufactured by Shanghai morning digital technology Equipment Inc. with model number JS 94H.
The specific method of dry crockfastness test in the following examples is according to the standard: GB/T3920-2008.
Example 1
Adding aqueous grinding acrylic resin (prepared according to example 3 in Chinese patent publication No. CN113980163A (name of the invention: aqueous acrylic grinding resin and preparation method thereof)) into deionized water, stirring to fully disperse the aqueous grinding acrylic resin into water, adding natural crystalline flake graphite (80 meshes, Qingdao Nissangsheng graphite Co., Ltd.) in which the weight (mass) ratio of the natural crystalline flake graphite to the aqueous acrylic grinding resin to water is 10:30:60, dispersing and shearing the mixed solution in a colloid mill for 20 minutes at 25 ℃ to obtain an aqueous dispersion of graphite, treating the aqueous dispersion of graphite by a ball mill for 8 hours at a rotation speed of 400r/min, homogenizing for 30 minutes by a high-pressure homogenizer at a pressure of 280MPa to obtain an aqueous dispersion of few-layer graphene modified by the aqueous grinding acrylic resin, and finally adding a penetrant JFC accounting for 1% of the total mass of the aqueous dispersion of the few-layer graphene, and stirring uniformly to obtain the high-adhesion graphene-containing coating.
This example resulted in a coating containing few layers of graphene consisting of the following components by weight:
29.7% of waterborne grinding acrylic resin, 9.9% of few-layer graphene, 0.99% of penetrating agent JFC and 59.41% of water.
TEM analysis of the coating containing few-layer graphene gave an image as shown in fig. 1, where the graphene sheet size was small as seen from the left side of fig. 1 and the graphene was 9 layers as seen from the right side of fig. 1. The coating is attached to a polyester fabric and dried and cured at 120 ℃ for 5min, and then a dry rubbing fastness test is carried out, wherein the fastness is good and is 4.5 grade (see table 1).
The coating can be used as a coating of textiles and used for antistatic and antibacterial finishing of textiles. The aqueous grinding acrylic resin is used as a dispersing agent of natural crystalline flake graphite to prepare few-layer graphene, so that graphene sheets can be fully modified, and the adhesive force between the graphene sheets and a polyester base material is improved.
Example 2
Adding waterborne grinding polyurethane resin (Shenzhen Jitian chemical industry Co., Ltd., F0409) into deionized water, stirring to fully disperse the waterborne grinding polyurethane resin into water, adding expanded graphite (Qingdao Risheng graphite Co., Ltd., 325 meshes, 95-99 fixed carbon-200) with the expansion multiple of 200 times (wherein the weight (mass) ratio of the expanded graphite to the waterborne polyurethane grinding resin to the water is 10:10:80), and carrying out dispersive shearing on the mixed solution in a stirrer at 25 ℃ for 20 minutes to obtain graphite dispersion liquid; homogenizing for 2 hours by using a high-pressure homogenizer at the pressure of 150MPa to obtain an aqueous dispersion of the aqueous ground polyurethane resin modified few-layer graphene, and finally adding a polyurethane resin (Implanil-DLH) accounting for 30% of the total mass of the aqueous dispersion of the few-layer graphene, 1% of a wetting agent Yitaide 5060 and 1% of a leveling agent BYK-333, and uniformly stirring to obtain the high-adhesion graphene coating.
The coating containing few-layer graphene obtained in this example is composed of the following components by weight:
7.58% of waterborne grinding polyurethane resin, 7.58% of few-layer graphene, 50600.76% of wetting agent Yitaide, 22.73% of waterborne polyurethane and 60.61% of water.
TEM analysis of the few-layer graphene coating resulted in an image as shown in fig. 2, where the graphene was seen to have a smaller size of the graphene sheet layer from the left image of fig. 2 and 3 graphene layers from the right image of fig. 2. The paint is adhered to the surface of leather, dried and cured at 120 ℃ for 5min, and then subjected to dry rubbing fastness test, wherein the fastness is good and is grade 5 (see table 1).
The paint can be used as a coating of leather and used for antibacterial and antistatic treatment of leather and conveyor belts. The aqueous polyurethane grinding resin is used as a dispersing agent of the expanded graphite to prepare few-layer graphene, so that graphene sheet layers can be fully modified, and the adhesive force between the graphene sheet layers and a leather base material is improved.
Example 3
Adding water-based grinding polycarbonate resin (Eternacol-PH-50, Shanghai, Inc., of Utsu, Utsuga, Japan) into deionized water, stirring to fully disperse the mixture into water, adding expandable graphite (2000 mesh, Nilapidao Nippon graphite Co., Ltd.) (wherein the weight (mass) ratio of the expandable graphite to the water-based polycarbonate resin to the water is 10:5:85), and dispersing and shearing the mixed solution in a stirrer at 25 ℃ for 20 minutes to obtain a graphite water dispersion; homogenizing for 4 hours by using a high-pressure homogenizer at the pressure of 260MPa to obtain an aqueous dispersion of the aqueous polycarbonate grinding resin modified few-layer graphene, adding polycarbonate resin (Bayhydrol 2648/1, manufactured by Corcission Polymer (China)) accounting for 30% of the total mass of the aqueous dispersion of the few-layer graphene, an antifoaming agent (DIHOH 810 accounting for 1% of the total mass of the dispersion) and a wetting agent (YITADE 5060 accounting for 1% of the total mass of the dispersion), and uniformly stirring to obtain the high-adhesion graphene coating.
The coating containing few-layer graphene obtained in this example is composed of the following components by weight:
3.79% of water-based ground polycarbonate resin, 7.58% of few-layer graphene, 8100.76% of antifoaming agent digao, 50600.76% of leveling agent Yitaide, 22.73% of polycarbonate resin and 64.39% of water.
TEM analysis of the few-layer graphene coating resulted in an image as shown in fig. 3, where the left image of fig. 3 shows that the graphene sheets were thin and small in size, and the right image of fig. 3 shows that the graphene was 5 layers. The coating is adhered to a PI film and dried and cured at 120 ℃ for 5min, and then a dry rubbing fastness test is carried out, and the results are shown in Table 1.
The coating can be used as a coating of PI for conductive or heat-dissipating coating treatment. The aqueous grinding acrylic resin is used as a dispersing agent of expandable graphite to prepare few-layer graphene, so that graphene sheets can be fully modified, and the adhesion between the graphene sheets and a PI (polyimide) substrate is improved.
Comparative example 1
Referring to example 1, the aqueous polishing resin was changed to polyvinylpyrrolidone (PVP) (K-30, national chemical company, ltd), the weight (mass) ratio of natural crystalline flake graphite, PVP, and water was 10:1:89, the preparation process and conditions were kept constant, an aqueous dispersion of graphene was prepared, and TEM analysis of the aqueous dispersion of graphene was performed to obtain an image shown in fig. 4, in which the graphene was thick in sheet layer and large in size, and 15 layers in the right image of fig. 4.
To this aqueous dispersion of graphene, an aqueous polishing acrylic resin (prepared in example 3 of chinese patent publication No. CN113980163a (title: an aqueous polishing acrylic resin and a method for preparing the same)) and a penetrant JFC were added to prepare a coating material having the same concentration components as those of example 1 except for PVP. And the polyester fiber is adhered to a polyester fabric, dried and cured at 120 ℃ for 5min and then subjected to dry rubbing fastness test, wherein the fastness is low and is only grade 3 (see table 1). The result shows that when the water-based grinding resin is used as a dispersing agent, the thickness of a sheet layer can be effectively reduced, and meanwhile, the adhesive force between a coating and a base material can be greatly improved.
Comparative example 2
Referring to example 2, the aqueous polishing resin was changed to polyvinylpyrrolidone (PVP) (K-30, a national group chemical agent limited), and the expanded graphite was changed to double-layer graphene, wherein the weight (mass) ratio of the double-layer graphene, PVP, and water was 10:1:89, these raw materials were mixed uniformly, a polyurethane resin (Impranil-DLH, a kossian polymer (china) limited), a wetting agent fortader 5060, and a leveling agent BYK-333 were added and stirred uniformly to prepare a coating material having the same concentration components as in example 2 except for PVP, and TEM analysis was performed on the coating material having a small number of layers to obtain an image as shown in fig. 5, in which the thickness of the graphene sheet layer was thick and the size was large as seen from the left image of fig. 5, and the thickness of the graphene was 2 layers as seen from the right image of fig. 5. The paint is adhered to the surface of leather, dried and cured at 120 ℃ for 5min, and then subjected to dry rubbing fastness test, wherein the fastness is grade 4 (see table 1). The result shows that compared with the method of directly compounding a finished graphene product, the method of adopting the water-based grinding resin as the dispersing agent in the graphene preparation process can uniformly modify the graphene sheet layer and can be used as an effective means for improving the adhesion fastness of the special graphene coating and the substrate.
The coatings containing graphene prepared in examples 1 to 3 and comparative examples 1 to 2 were measured for transverse dimension, number of layers, Zeta potential, and rubbing fastness of the coating, and the specific results are shown in table 1 below.
TABLE 1 specific test parameters for graphene-containing coatings prepared in examples 1-3 and comparative examples 1 and 2
Figure BDA0003684292820000121
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it is not limited to the embodiments, and those skilled in the art should understand that the technical solutions of the present invention can be modified or substituted with equivalents without departing from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. A preparation method of a coating containing few-layer graphene is characterized by comprising the following steps:
s1, adding aqueous grinding resin into water, and dispersing to obtain an aqueous dispersion of the aqueous grinding resin;
s2, adding graphite into the aqueous dispersion of the aqueous grinding resin, and dispersing to obtain an aqueous dispersion of graphite;
s3, mechanically stripping the aqueous dispersion of the graphite to obtain an aqueous dispersion of few-layer graphene;
and S4, adding a surfactant into the graphene aqueous dispersion, and uniformly mixing to obtain the coating containing few layers of graphene.
2. The method for preparing the coating containing few-layer graphene according to claim 1, wherein a resin is further added into S4, and the resin accounts for 0-900% of the weight of the graphite.
3. The method of claim 2, wherein the resin is selected from one or more of an acrylic resin, a polyurethane resin, and a polycarbonate resin.
4. The method for preparing the coating containing few-layer graphene according to claim 1 or 2, wherein the aqueous grinding resin is selected from one or more of aqueous grinding acrylic resin, aqueous grinding polyurethane resin and aqueous grinding polycarbonate resin, and/or
The graphite is selected from one or more of natural crystalline flake graphite, expandable graphite, expanded graphite, intercalated graphite and graphite nano-sheet, and/or
The surfactant is selected from one or more of a wetting agent, a penetrating agent, a defoaming agent and a leveling agent.
5. The method for preparing the coating containing few-layer graphene according to claim 4, wherein when the aqueous grinding resin is selected from aqueous grinding acrylic resins, the resin added in S4 is selected from acrylic resins; or
When the aqueous grinding resin is selected from aqueous grinding polyurethane resins, the resin added in S4 is selected from polyurethane resins, or
When the aqueous grinding resin is selected from aqueous grinding polycarbonate resins, the resin added in S4 is selected from polycarbonate resins.
6. The method for preparing the coating containing few-layer graphene according to claim 4, wherein the aqueous grinding acrylic resin is selected from PYM-16449, SL16827 and ZZYM-16455 products of Nippon synephrine nanotechnology Limited, and/or
The water-based grinding polyurethane resin is selected from a product with the model number of DB16103 of Synfei Nippon nanometer technology Co., Ltd, a product with the model number of F0409 of Shenzhen Jitian chemical industry Co., Ltd, a product with the model number of GSB-03-56 of Wenzhou Shibang high polymer material Co., Ltd, and/or
The aqueous grinding polycarbonate resin is selected from products of Eternacoll-PH series and Eternacoll-BH series, which are produced by Shikuwa Kaisha (Shanghai) Co., Ltd.
7. The method for preparing the coating containing few-layer graphene according to claim 1 or 2, wherein the amount of the aqueous grinding resin is 20-200% of the graphite weight, and/or the surfactant is added in an amount of 0.1-5% of the total weight of the coating.
8. The method for preparing the coating containing few-layer graphene according to claim 1 or 2, wherein the concentration of the aqueous grinding resin in the aqueous dispersion of the aqueous grinding resin in S1 is 10mg/mL to 300 mg/mL; and/or the presence of a gas in the gas,
the concentration of graphite in the aqueous dispersion of graphite in S2 is 10 mg/L-200 mg/mL.
9. The method of claim 1 or 2, wherein the mechanical peeling in S3 is performed by one or more of colloid milling equipment, ball milling equipment, sand milling equipment, high pressure homogenizing equipment, and ultrasonic equipment.
10. A coating containing few layers of graphene, characterized in that the coating comprises:
aqueous grinding resin, few-layer graphene, surfactant, resin and water,
wherein the content of the few-layer graphene is 0.1-10% by weight, the content of the surfactant is 0.01-2%, the content of the aqueous grinding resin is 1-60% by weight, the content of the resin is 0-50% by weight, and the balance is water.
CN202210646476.7A 2022-06-08 2022-06-08 Preparation method of coating containing few-layer graphene and coating Pending CN114854262A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115558395A (en) * 2022-10-13 2023-01-03 江苏先丰纳米材料科技有限公司 Heating slurry with antibacterial and heat dissipation functions

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Publication number Priority date Publication date Assignee Title
CN106744870A (en) * 2016-10-25 2017-05-31 成都新柯力化工科技有限公司 A kind of abrasive media that Graphene is peeled off for slurry grinding
CN114286845A (en) * 2019-07-09 2022-04-05 应用石墨烯材料英国有限公司 Water-based paint
CN114302860A (en) * 2019-07-09 2022-04-08 应用石墨烯材料英国有限公司 Dispersion product

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106744870A (en) * 2016-10-25 2017-05-31 成都新柯力化工科技有限公司 A kind of abrasive media that Graphene is peeled off for slurry grinding
CN114286845A (en) * 2019-07-09 2022-04-05 应用石墨烯材料英国有限公司 Water-based paint
CN114302860A (en) * 2019-07-09 2022-04-08 应用石墨烯材料英国有限公司 Dispersion product

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115558395A (en) * 2022-10-13 2023-01-03 江苏先丰纳米材料科技有限公司 Heating slurry with antibacterial and heat dissipation functions

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