WO2019076203A1 - 一种防腐涂料用石墨烯环氧树脂分散液的制备方法、环氧富锌防腐涂料及其制备方法 - Google Patents

一种防腐涂料用石墨烯环氧树脂分散液的制备方法、环氧富锌防腐涂料及其制备方法 Download PDF

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WO2019076203A1
WO2019076203A1 PCT/CN2018/109285 CN2018109285W WO2019076203A1 WO 2019076203 A1 WO2019076203 A1 WO 2019076203A1 CN 2018109285 W CN2018109285 W CN 2018109285W WO 2019076203 A1 WO2019076203 A1 WO 2019076203A1
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graphene
mixing
epoxy resin
dispersion
stirring
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PCT/CN2018/109285
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English (en)
French (fr)
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张栋
张在忠
赵永彬
李伟铭
程金杰
刘海波
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山东欧铂新材料有限公司
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Publication of WO2019076203A1 publication Critical patent/WO2019076203A1/zh

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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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • C09D7/80—Processes for incorporating ingredients
    • 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

Definitions

  • the invention belongs to the technical field of anticorrosive coatings, relates to a method for preparing a graphene epoxy resin dispersion, a resin anticorrosive coating and a preparation method thereof, in particular to a method for preparing a graphene epoxy resin dispersion for an anticorrosive coating, and an epoxy Zinc-rich anticorrosive coating and preparation method thereof.
  • Graphene is a new material of a single-layered sheet-like structure composed of carbon atoms. It is a two-dimensional crystal composed of carbon atoms and only one layer of atomic thickness. It is the thinnest in the field of application. The material and the toughest material have a breaking strength 200 times higher than that of steel, and have good elasticity. The stretching range can reach 20% of its own size. At the same time, graphene also has excellent conductivity and can be reduced inside. Resistance, improve the cycle stability of supercapacitors; in addition, graphene is almost completely transparent, only absorbs 2.3% of light, and is very dense, even the smallest gas atoms (deuterium atoms) can not penetrate.
  • the anti-corrosion road has a long way to go.
  • the most important anti-corrosion coatings are mainly epoxy, polyurethane and zinc-rich primer coatings.
  • epoxy anticorrosive coating has excellent adhesion, excellent mechanical properties, good resistance to alkali and chemical medium corrosion, high solid content, etc., but the initial hardness of the paint film is high, the flexibility is poor, asphalt and chromium
  • the acid-based anticorrosive paint of the acid salt is very destructive to the environment and endangers human health.
  • Zinc-rich primer coatings have shielding effect, electrochemical protection, white coating repair and passivation, but the anti-corrosion performance is at the expense of zinc powder, and a large amount of zinc oxide mist will be generated during welding, which will harm the operators. Life is healthy. Domestically, marine engineering, shipbuilding and green marine wind energy industries are developing rapidly. Under the new international situation and national policies, the economic benefits of marine corrosion protection are huge. In this context, it is imperative to vigorously develop new anti-corrosion coatings.
  • the technical problem to be solved by the present invention is to provide a method for preparing a graphene epoxy resin dispersion and a resin anticorrosive coating, particularly a method for preparing a graphene epoxy resin dispersion for an anticorrosive coating, and an epoxy zinc-rich solution.
  • Anticorrosive coating the invention prepares the graphene epoxy resin dispersion by a simple method, and obtains the resin anticorrosive coating by using the graphene epoxy resin dispersion liquid, and solves the problem that the graphene is not easily dispersed in the coating and the sheet structure is difficult to maintain. .
  • the invention provides a preparation method of a graphene epoxy resin dispersion, which comprises the following steps:
  • the graphene comprises one or more of graphene oxide, single layer graphene, multilayer graphene and reduced oxy graphene;
  • the epoxy resin includes a bisphenol A type epoxy resin
  • the organic solvent includes one of acetone, methyl isobutyl ketone, ethanol, isopropanol, methyl ethyl ketone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate, and butyl acetate. Or a variety;
  • the sulfonate surfactant includes an alkylbenzenesulfonate, an ⁇ -olefinsulfonate, an alkylsulfonate, an ⁇ -sulfomonocarboxylate, a fatty acid sulfoalkyl ester, and a succinic acid sulfonic acid.
  • a salt an alkylnaphthalene sulfonate, a petroleum sulfonate, a lignosulfonate, and an alkyl glyceryl ether sulfonic acid;
  • the Tween-based surfactant includes one or more of Tween-80, Tween-20, Tween-60, and Tween-40.
  • the mass ratio of the graphene to the organic solvent is 1: (5 to 30);
  • the mass ratio of the graphene to the sulfonate surfactant is 1: (0.3 to 1.8);
  • the mass ratio of the graphene to the Tween surfactant is 1: (0.8 ⁇ 2.5);
  • the mass ratio of the epoxy resin to the graphene is 100: (0.5 to 3);
  • the mass ratio of the epoxy resin to the organic solvent is 100: (25 to 66).
  • the stirring and mixing comprises magnetic stirring and/or mechanical stirring
  • the mixing and mixing time is 15 to 30 minutes;
  • the stirring and mixing speed is 300 to 600 r/min.
  • the re-mixing mixing comprises magnetic stirring and/or mechanical stirring;
  • the time of stirring and mixing again is 15 to 40 minutes;
  • the speed of the stirring and mixing again is 300 to 600 r/min.
  • the third agitation mixing comprises magnetic stirring and/or mechanical agitation
  • the mixing time of the third stirring is 20 to 60 minutes;
  • the speed of the third agitation mixing is 400 to 1000 r/min.
  • the adding is a slow addition
  • the grinding time is 5 to 20 minutes.
  • the invention provides a resin anticorrosive coating, which comprises, by mass fraction, comprising:
  • the auxiliary agent includes one or more of an anti-settling agent, an antifoaming agent, a curing agent, and an accelerator.
  • the antifoaming agent is added in an amount of 0.2 to 1 part by weight;
  • the anti-settling agent is added in an amount of 0.5 to 2 parts by weight;
  • the curing agent is added in an amount of 15 to 35 parts by weight;
  • the accelerator is added in an amount of 0.5 to 2 parts by weight;
  • the anti-settling agent includes one or more of an anti-settling agent 3300, an organic clay, an organic clay, a fumed silica, a polyethylene wax, and a cellulose ether;
  • the antifoaming agent comprises one or more of an organosiloxane antifoaming agent, a polyether antifoaming agent and a dimethicone defoaming agent;
  • the filler includes one or more of phosphorus iron oxide powder, aluminum powder slurry, mica powder, iron oxide red, calcium carbonate and talc;
  • the accelerator includes DMP-30;
  • the curing agent includes one or more of polyamide, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethenepolyamine, and polyether diamine.
  • the invention also provides a preparation method of a resin anticorrosive coating, comprising the following steps:
  • the invention provides a method for preparing a graphene epoxy resin dispersion, which comprises the following steps: firstly, a graphene and an organic solvent are stirred and mixed to obtain a graphene mixture; then the graphene mixture obtained in the above step is sulfonated. The acid salt surfactant and the Tween surfactant are stirred and mixed again to obtain a graphene dispersion; finally, the epoxy resin is added to the graphene dispersion obtained in the above step, and the mixture is stirred for the third time, and then After grinding, a graphene epoxy resin dispersion is obtained.
  • the invention adds the graphene to the existing anticorrosive paint, usually after the filler is added or dispersed in the solvent, the graphene is seriously dispersed unevenly in the coating, and the specific surface area of the graphene is large, The surface energy is high, and its lateral dimension far exceeds the thickness. Under the shear dispersion of conventional mechanical agitation, graphene is easy to curl into a mass, which cannot maintain the structure of the lamellar structure to form a layer superimposed structure, and finally leads to the prepared coating. Corrosion resistance is not ideal.
  • the invention creatively changes the manner of adding the graphene-based material, firstly dispersing the epoxy resin in the graphene and the coating to obtain a graphene epoxy resin dispersion liquid, and then performing subsequent treatment to obtain a resin anticorrosive coating, which can be very It solves the problem of graphene dispersion well, guarantees the perfect performance of its excellent performance, and adopts the additives for later coatings, so that no unnecessary additives need to be added, the introduction of impurities is reduced, and the preparation process of the invention is carried out at normal temperature. It also abandons the traditional method of using ultrasonic dispersion to effectively reduce energy consumption and cost, and is more conducive to industrialized production.
  • the invention fundamentally solves the disadvantages of uneven mixing of the flexible graphene materials in the coating system, can ensure the uniform dispersion of the graphene, and thus has better performance.
  • the experimental results show that the preparation method provided by the invention has the advantages of simple process and low cost, and the prepared graphene-coated paint can be uniformly dispersed, forming a protective film on the surface layer, greatly improving the performance of the coating, and maintaining the sheet-like structure of graphene to form a layer.
  • the superimposed structure has a long-lasting salt spray resistance and is 51% higher than the blank epoxy resin.
  • FIG. 1 is a schematic flow chart of a process for preparing a graphene epoxy resin dispersion according to the present invention
  • Example 2 is a metallographic diagram of a graphene epoxy resin dispersion prepared in Example 1 of the present invention
  • Example 3 is a metallographic diagram of an epoxy zinc-rich coating prepared in Example 1 of the present invention.
  • Example 4 is a Raman microscopic image of a graphene oxide zinc-rich zinc coating film prepared in Example 1 of the present invention
  • Example 5 is a mixing graph of Raman microscopic imaging of a graphene epoxy zinc-rich coating film prepared in Example 1 of the present invention.
  • All the raw materials of the present invention are not particularly limited in their source, and are commercially available or prepared according to a conventional method well known to those skilled in the art.
  • the purity of all the raw materials of the present invention is not particularly limited, and the present invention preferably employs a conventional purity used in the field of analytically pure or graphene composite materials.
  • the invention provides a preparation method of a graphene epoxy resin dispersion, which comprises the following steps:
  • a graphene and an organic solvent are stirred and mixed to obtain a graphene mixture.
  • the definition of the graphene in the present invention is not particularly limited, and may be defined by a graphene-based material well known to those skilled in the art, and those skilled in the art may select and adjust according to actual application conditions, product requirements, and quality requirements.
  • the graphene of the invention is preferably a generalized graphene, which may also be called graphene and its derivatives or graphene-based materials, preferably including one of narrow graphene, graphene oxide, reduced graphene oxide and modified graphene.
  • the specific parameters of the graphene of the present invention are not particularly limited, and the parameters of the conventional graphene-based materials well known to those skilled in the art may be selected, and those skilled in the art may select and according to actual application conditions, product requirements, and quality requirements.
  • the proportion of graphene having a lamellar layer of 5 or less is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
  • the sheet diameter of the graphene of the present invention is preferably from 1 to 100 ⁇ m, more preferably from 10 to 90 ⁇ m, still more preferably from 30 to 70 ⁇ m, still more preferably from 40 to 60 ⁇ m, and most preferably from 10 to 50 ⁇ m.
  • the selection of the organic solvent in the present invention is not particularly limited, and a conventional organic solvent well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements, and quality requirements.
  • the organic solvent preferably includes one of acetone, methyl isobutyl ketone, ethanol, isopropanol, methyl ethyl ketone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate, and butyl acetate.
  • acetone, methyl isobutyl ketone, ethanol, isopropanol, methyl ethyl ketone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate or butyl acetate more preferably Is two or more of acetone, methyl isobutyl ketone, ethanol, isopropanol, methyl ethyl ketone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate and butyl acetate, Specifically, it may be xylene and n-butanol.
  • the amount of the organic solvent to be added in the present invention is not particularly limited, and the amount of the conventional organic solvent known to those skilled in the art may be added, and those skilled in the art may select and adjust according to actual application conditions, product requirements, and quality requirements.
  • the mass ratio of the graphene to the organic solvent in the present invention is preferably 1: (5 to 30), more preferably 1: (10 to 25), and still more preferably 1: (15 to 20).
  • the specific manner of the agitation mixing in the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality control by a person skilled in the art, and the present invention is
  • the homogeneity and performance of the dispersion and subsequent coating products are further enhanced to optimize the process route, preferably including magnetic stirring and/or mechanical agitation, more preferably magnetic or mechanical agitation, more preferably magnetic agitation.
  • the mixing and mixing time of the present invention is not particularly limited, and the mixing and mixing time well known to those skilled in the art can be used. Those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control. The uniformity and performance of the dispersion and subsequent coating products are further improved, and the process route is optimized, and the mixing and mixing time is preferably 15 to 30 minutes, more preferably 17 to 28 minutes, still more preferably 20 to 25 minutes.
  • the speed of the agitation mixing is not particularly limited in the present invention, and the speed of agitation mixing well known to those skilled in the art can be selected, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control.
  • the uniformity and performance of the dispersion and the subsequent coating product are further improved, and the process route is optimized.
  • the speed of the stirring and mixing is preferably from 300 to 600 r/min, more preferably from 350 to 550 r/min, still more preferably from 400 to 500 r/min.
  • the graphene mixture liquid, the sulfonate surfactant, and the Tween-type surfactant obtained in the above step are stirred and mixed again to obtain a graphene dispersion.
  • the selection of the sulfonate surfactant in the present invention is not particularly limited, and a conventional sulfonate surfactant known to those skilled in the art may be used, and those skilled in the art may, according to the actual application, product requirements and quality. The selection and adjustment are required.
  • the sulfonate surfactant of the present invention preferably comprises an alkylbenzenesulfonate, an ⁇ -olefinsulfonate, an alkylsulfonate, an ⁇ -sulfomonocarboxylate, a fatty acid sulfonate.
  • an alkyl ester a succinate sulfonate, an alkylnaphthalene sulfonate, a petroleum sulfonate, a lignosulfonate, and an alkyl glyceryl ether sulfonic acid, more preferably an alkylbenzenesulfonate Acid salt, ⁇ -olefin sulfonate, alkyl sulfonate, ⁇ -sulfomonocarboxylate, fatty acid sulfoalkyl ester, succinate sulfonate, alkylnaphthalene sulfonate, petroleum sulfonate,
  • the lignosulfonate or alkyl glyceryl ether sulfonic acid may specifically be sodium dodecylbenzenesulfonate or sodium dodecylsulfonate.
  • the amount of the sulfonate surfactant added in the present invention is not particularly limited, and may be conventionally added in a manner well known to those skilled in the art, and those skilled in the art can select and according to actual application conditions, product requirements, and quality requirements.
  • the mass ratio of the graphene to the sulfonate surfactant of the present invention is preferably 1: (0.3 to 1.8), more preferably 1: (0.5 to 1.6), still more preferably 1: (0.7 to 1.4). More preferably, it is 1: (0.9 to 1.2).
  • the selection of the Tween-type surfactant in the present invention is not particularly limited, and a conventional Tween-based surfactant well known to those skilled in the art may be used, and those skilled in the art may perform according to actual application conditions, product requirements, and quality requirements.
  • the Tween-based surfactant of the present invention comprises one or more of Tween-80, Tween-20, Tween-60 and Tween-40, more preferably Tween-80. Tween-20, Tween-60 or Tween-40, specifically Tween-80 or Tween-20.
  • the amount of the Tween-based surfactant to be added in the present invention is not particularly limited, and can be selected and adjusted according to actual application conditions, product requirements, and quality requirements by a conventional addition amount well known to those skilled in the art.
  • the mass ratio of the graphene to the Tween-based surfactant of the present invention is preferably 1: (0.8 to 2.5), more preferably 1: (1.0 to 2.2), still more preferably 1: (1.2 to 2.0), more Preferably it is 1: (1.4 to 1.8).
  • the process route is optimized, preferably including magnetic stirring and/or mechanical agitation, more preferably magnetic or mechanical agitation, more preferably magnetic agitation.
  • the time for the re-mixing and mixing of the present invention is not particularly limited, and the mixing and mixing time well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control.
  • the process route is optimized, and the time of the re-mixing and mixing is preferably 15 to 40 minutes, more preferably 20 to 35 minutes, still more preferably 25 to 30 minutes.
  • the speed of the re-mixing and mixing of the present invention is not particularly limited, and the speed of agitation mixing well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control, and the present invention
  • the process route is optimized, and the speed of the re-mixing and mixing is preferably 300 to 600 r/min, more preferably 350 to 550 r/min, still more preferably 400 to 500 r/ Min.
  • an epoxy resin is added to the graphene dispersion obtained in the above step, and after the third stirring and mixing, it is further ground to obtain a graphene epoxy resin dispersion.
  • the epoxy resin is not particularly limited in the present invention, and can be selected and adjusted according to actual production conditions, product requirements, and quality control, and the ring of the present invention can be selected by those skilled in the art.
  • the oxyresin preferably comprises a bisphenol A type epoxy resin, more specifically preferably an E-51 bisphenol A type epoxy resin and/or a 601 bisphenol A type epoxy resin, most preferably an E-51 bisphenol A type epoxy resin. Resin or 601 bisphenol A type epoxy resin.
  • the other parameters of the epoxy resin in the present invention are not particularly limited, and the parameters of the conventional epoxy resin well known to those skilled in the art may be selected, and those skilled in the art may select and adjust according to actual application conditions, product requirements, and quality requirements. .
  • the amount of the epoxy resin to be added in the present invention is not particularly limited, and can be selected and adjusted according to actual application conditions, product requirements, and quality requirements by the conventional addition amount well known to those skilled in the art.
  • the present invention The mass ratio of the epoxy resin to graphene is preferably 100: (0.5 to 3), more preferably 100: (1.0 to 2.5), still more preferably 100: (1.5 to 2.0).
  • the manner of adding the epoxy resin in the present invention is not particularly limited, and can be selected and adjusted according to actual production conditions, product requirements, and quality control by a conventional joining method well known to those skilled in the art.
  • the present invention To further improve the uniformity and performance of the dispersion and subsequent coating products, the process route is optimized, preferably with slow addition.
  • the specific manner of the third agitation mixing is not particularly limited, and the mixing and mixing method well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control.
  • the present invention optimizes the process route to further improve the uniformity and performance of the dispersion and subsequent coating products.
  • the third agitation mixing preferably includes magnetic stirring and/or mechanical agitation, more preferably magnetic stirring or mechanical agitation, more preferably Mechanical agitation.
  • the time for the third agitation mixing in the present invention is not particularly limited, and the mixing and mixing time well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control.
  • the present invention optimizes the process route, and the mixing and mixing time is preferably 20 to 60 minutes, more preferably 25 to 55 minutes, still more preferably 30 to 50 minutes, more preferably It is 35 to 45 minutes.
  • the speed of the third agitation mixing is not particularly limited in the present invention, and the speed of the agitation mixing well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control.
  • the present invention optimizes the process route, and the speed of the re-mixing and mixing is preferably 400 to 1000 r/min, more preferably 500 to 900 r/min, and still more preferably 600 to 800r/min.
  • the grinding method is not particularly limited in the present invention, and can be selected and adjusted according to actual production conditions, product requirements, and quality control by those skilled in the art.
  • the present invention further improves dispersion.
  • the uniformity and performance of the liquid and subsequent coating products are optimized, and the grinding is preferably wet milling.
  • the polishing time of the present invention is not particularly limited, and the grinding time is well known to those skilled in the art, and those skilled in the art can select and adjust according to actual production conditions, product requirements, and quality control, and the present invention further improves dispersion.
  • the uniformity and performance of the liquid and subsequent coating products are optimized, and the grinding time is preferably from 5 to 20 min, more preferably from 7 to 18 min, still more preferably from 10 to 15 min.
  • the invention provides a resin anticorrosive coating, which comprises, by mass fraction, comprising:
  • the auxiliary agent includes one or more of an anti-settling agent, an antifoaming agent, a curing agent, and an accelerator.
  • the specific amount of the graphene epoxy resin dispersion liquid to be added in the present invention is not particularly limited, and can be selected according to the actual application, product requirements, and quality requirements by a person skilled in the art.
  • the amount of the graphene epoxy resin dispersion of the present invention is preferably 8 to 25 parts by weight, more preferably 10 to 22 parts by weight, still more preferably 12 to 20 parts by weight, still more preferably 15 to 18 parts by weight. .
  • the zinc powder of the present invention is not particularly limited, and the zinc powder for anticorrosive coatings well known to those skilled in the art can be selected, and those skilled in the art can select and adjust according to actual application conditions, product requirements and quality requirements, and the present invention
  • the zinc powder is preferably a spherical zinc powder.
  • the other parameters of the zinc powder of the present invention are not particularly limited, and the parameters of the conventional zinc powder well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements, and quality requirements.
  • the zinc powder of the invention preferably has a particle diameter of 0.1 to 200 ⁇ m, more preferably 0.5 to 100 ⁇ m, still more preferably 1 to 80 ⁇ m, and most preferably 5 to 50 ⁇ m.
  • the zinc powder of the present invention is preferably added in an amount of 30 to 90 parts by weight, more preferably 40 to 80 parts by weight, most preferably 50 to 70 parts by weight.
  • the specific selection of the filler in the present invention is not particularly limited, and the filler for anticorrosive coatings well known to those skilled in the art may be selected, and those skilled in the art may select and adjust according to actual application conditions, product requirements, and quality requirements.
  • the filler preferably comprises one or more of phosphorus iron oxide powder, aluminum powder slurry, mica powder, iron oxide red, calcium carbonate and talc powder, more preferably phosphorus iron oxide powder, aluminum powder slurry, mica powder, iron oxide powder. Two or more of red, calcium carbonate and talc.
  • the filler of the present invention is preferably added in an amount of 5 to 50 parts by weight, more preferably 10 to 45 parts by weight, still more preferably 15 to 40 parts by weight, still more preferably 20 to 35 parts by weight.
  • the solvent is not particularly limited in the present invention, and the solvent for the anticorrosive coating which is well known to those skilled in the art may be selected, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements, and the present invention
  • the solvent preferably includes one or more of acetone, methyl isobutyl ketone, ethanol, isopropanol, methyl ethyl ketone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate, and butyl acetate.
  • it is acetone, methyl isobutyl ketone, ethanol, isopropanol, methyl ethyl ketone, 2-pyrrolidone, toluene, xylene, n-butanol, propylene glycol methyl ether, propylene carbonate and butyl acetate. Or more, more preferably a plurality of xylene, n-butanol and propylene glycol methyl ether.
  • the solvent to be added in the present invention is preferably added in an amount of 10 to 50 parts by weight, more preferably 15 to 45 parts by weight, still more preferably 20 to 40 parts by weight, still more preferably 25 to 35 parts by weight.
  • the auxiliaries of the present invention are not particularly limited, and the auxiliaries for anticorrosive coatings well known to those skilled in the art may be selected, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements, and the present invention
  • the auxiliary agent preferably includes one or more of an anti-settling agent, an antifoaming agent, a curing agent, and an accelerator, and more preferably a plurality of anti-settling agents, antifoaming agents, curing agents, and accelerators.
  • the type of the auxiliary agent is not particularly limited in the present invention, and the auxiliary agent for coatings well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements, and the present invention
  • the auxiliaries preferably include an auxiliary agent for the coating itself (component A) and an auxiliary agent for the use of the coating (component B), and the auxiliary for the component of the component preferably includes one of an anti-settling agent, an antifoaming agent and a filler.
  • the auxiliary agent for the component B preferably comprises one or more of a curing agent, a promoter and a solvent, more preferably A plurality of curing agents, accelerators, and solvents.
  • the amount of the auxiliary agent to be added in the present invention is not particularly limited, and the ratio of the conventional auxiliary agent of the resin anticorrosive coating which is well known to those skilled in the art can be used, and those skilled in the art can carry out according to the actual application, product requirements and quality requirements. Select and adjust.
  • the amount of the antifoaming agent to be added in the present invention is not particularly limited, and the ratio of the conventional antifoaming agent of the anticorrosive coating which is well known to those skilled in the art can be used, and those skilled in the art can according to the actual application, product requirements and quality requirements.
  • the amount of the antifoaming agent to be added according to the present invention is preferably 0.2 to 1 part by weight, more preferably 0.3 to 0.9 part by weight, still more preferably 0.4 to 0.8 part by weight, and most preferably 0.5 to 0.7 part by weight.
  • the specific selection of the antifoaming agent in the present invention is not particularly limited, and the defoaming agent for anticorrosive coatings well known to those skilled in the art can be used, and those skilled in the art can select and adjust according to actual application conditions, product requirements and quality requirements.
  • the antifoaming agent of the present invention preferably comprises one or more of an organosiloxane antifoaming agent, a polyether antifoaming agent and a dimethyl silicone oil antifoaming agent, more preferably an organosilicone defoaming agent, Polyether defoamer or dimethicone defoamer.
  • the amount of the anti-settling agent added in the present invention is not particularly limited, and the ratio of the conventional anti-settling agent of the anti-corrosion coating which is well known to those skilled in the art may be used, and those skilled in the art may according to the actual application, product requirements and quality requirements.
  • the amount of the anti-settling agent to be added according to the present invention is preferably 0.5 to 2 parts by weight, more preferably 0.7 to 1.8 parts by weight, still more preferably 0.9 to 1.6 parts by weight, most preferably 1.1 to 1.4 parts by weight.
  • the specific selection of the anti-settling agent in the present invention is not particularly limited, and the anti-settling agent for anti-corrosion coatings well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements.
  • the anti-settling agent of the present invention preferably comprises one or more of anti-settling agent 3300, organic clay, organic clay, fumed silica, polyethylene wax and cellulose ether, more preferably anti-settling agent 3300, organic Clay, organic clay, fumed silica, polyethylene wax or cellulose ether, specifically preferably (monolone) MONORAL 3300.
  • the amount of the curing agent to be added in the present invention is not particularly limited, and the ratio of the conventional curing agent of the anticorrosive coating which is well known to those skilled in the art can be selected, and those skilled in the art can select according to the actual application, product requirements and quality requirements.
  • the amount of the curing agent to be added in the present invention is preferably from 15 to 35 parts by weight, more preferably from 18 to 32 parts by weight, most preferably from 20 to 30 parts by weight.
  • the specific selection of the curing agent in the present invention is not particularly limited, and the curing agent for anticorrosive coatings well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements.
  • the curing agent of the invention preferably comprises one or more of polyamide, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethenepolyamine and polyether diamine, more preferably polyamide, ethylenediamine Diethylenetriamine, triethylenetetramine, polyethenepolyamine or polyether diamine, specifically preferably polyamide 200.
  • the amount of the accelerator added in the present invention is not particularly limited, and the ratio of the conventional accelerator of the anticorrosive coating which is well known to those skilled in the art can be selected, and those skilled in the art can select according to the actual application, product requirements and quality requirements.
  • the amount of the accelerator to be added in the present invention is preferably 0.5 to 2 parts by weight, more preferably 0.7 to 1.8 parts by weight, still more preferably 0.9 to 1.6 parts by weight, most preferably 1.1 to 1.4 parts by weight.
  • the specific selection of the accelerator in the present invention is not particularly limited, and the accelerator for anticorrosive coatings well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements.
  • the accelerator of the invention preferably comprises DMP-30.
  • the resin anticorrosive coating of the present invention is not particularly limited, and the resin anticorrosive coating for anticorrosion well known to those skilled in the art may be used, and those skilled in the art may select and adjust according to actual application conditions, product requirements and quality requirements.
  • the resin anticorrosive coating of the invention is preferably an epoxy coating or a zinc-rich primer coating, more preferably a zinc-rich primer coating or a zinc-rich epoxy (spherical zinc powder) anticorrosive coating.
  • the above steps of the present invention provide a resin anticorrosive coating using a graphene epoxy resin dispersion, which firstly disperses graphene and an epoxy resin to obtain a dispersion, which is then combined with other components to form an anticorrosive coating.
  • the invention obtains a wider range of resin anticorrosive coatings by selecting components and optimizing the ratios, and combining various additives.
  • the invention adds an auxiliary agent to the dispersion liquid, can continue to be applied in the subsequent anti-corrosion coating, does not need to add a dispersing agent, does not add other excess reagents at all, and reduces the introduction of impurities.
  • the resin anticorrosive coating provided by the invention effectively solves the inherent defects that the conventional graphene-based material is easy to curl into a mass and cannot maintain the shape of the sheet structure.
  • the invention also provides a preparation method of a resin anticorrosive coating, comprising the following steps:
  • the selection and composition of the raw materials required in the above preparation process, and the corresponding preferred principles, can be corresponding to the selection and composition of the corresponding raw materials in the foregoing resin anticorrosive coating, and the corresponding preferred principles, and no longer A narrative.
  • the auxiliary agent includes one or more of an anti-settling agent, an antifoaming agent, a filler, a curing agent, and an accelerator.
  • the invention further preferably adopts a specific order of addition, so that the graphene is more uniformly dispersed in the resin anticorrosive coating, which can effectively solve the problem of uneven dispersion of graphene and better exert its excellent performance. Moreover, a resin anticorrosive coating which uniformly disperses the graphene material can be obtained, and the performance of the resin anticorrosive coating is further improved. Moreover, the present invention performs the above operations particularly in the absence of a protective gas, thereby simplifying the production process, production equipment, and reducing production consumption.
  • the above composite method provided by the invention has the advantages of simple process, mild condition, safety and environmental protection, and is more suitable for large-scale production of the process.
  • the above steps of the present invention provide a method for preparing a graphene epoxy resin dispersion, a resin anticorrosive coating and a preparation method thereof, and the invention abandons the preparation process of adding conventional graphene to an anticorrosive coating, and uniformly disperses the graphene in the ring.
  • a graphene epoxy resin dispersion is prepared by grinding, stirring, and adding a surfactant.
  • the whole process of preparation is carried out at room temperature, which changes the traditional method of using ultrasonic dispersion, reduces noise pollution and energy consumption, and avoids the harm of noise to the human body; the solvent used is no need to use additional solvent for anti-corrosion coating preparation. Reduce environmental pollution caused by the preparation process.
  • the invention disperses the graphene in the epoxy resin and prepares the anticorrosive coating with the dispersion solution, solves the problem that the graphene is dispersed unevenly in the anticorrosive coating, and effectively ensures that the graphene is added in the form of a sheet layer to form a layer.
  • the superimposed structure effectively solves the problem that the graphene in the prior art is not in the form of a sheet structure in the resin, and the corrosion resistance of the graphene anticorrosive coating is not improved, thereby avoiding the conventional method of adding graphene to the coating.
  • the problem of poor dispersion of graphene in the coating greatly reduces the performance of the coating, and at the same time improves the corrosion resistance of the anticorrosive coating, and has a good application prospect in the anticorrosion field of the coating.
  • the present invention prepares a graphene epoxy resin dispersion liquid by a simple method, and the epoxy zinc-rich (spherical zinc powder) primer prepared by using the graphene epoxy resin dispersion liquid solves the problem that graphene is difficult to disperse in the coating, and is difficult. Keep the problem of the sheet structure.
  • the prepared graphene anticorrosive coating also avoids environmental pollution.
  • the experimental results show that the preparation method provided by the invention has the advantages of simple process and low cost, and the prepared graphene-coated paint can be uniformly dispersed, forming a protective film on the surface layer, greatly improving the performance of the coating, and maintaining the sheet-like structure of graphene to form a layer.
  • the superimposed structure has a long-lasting salt spray resistance and is 51% higher than the blank epoxy resin.
  • This embodiment is an anticorrosive coating made of a blank epoxy resin.
  • a graphene epoxy resin dispersion is prepared by the following steps:
  • the graphene powder was mixed with a mixed solvent of xylene and n-butanol (the mass ratio of xylene to n-butanol was 7:3), and then magnetically stirred for 15 minutes to obtain a graphene mixture.
  • the graphene epoxy resin mixture obtained in the step 3 is ground or ball-milled for 10 minutes to obtain a graphene epoxy resin dispersion.
  • FIG. 1 is a schematic diagram of a process flow for preparing a graphene epoxy resin dispersion according to the present invention.
  • Example 1 of the present invention The graphene epoxy resin dispersion prepared in Example 1 of the present invention was subjected to metallographic image observation using a metallographic microscope.
  • FIG. 2 is a metallographic diagram of a graphene epoxy resin dispersion prepared in Example 1 of the present invention. As can be seen from Fig. 2, graphene exists in a sheet-like structure in the resin and is uniformly dispersed.
  • the graphene epoxy resin dispersion is used instead of the ordinary epoxy resin to prepare the coating according to the normal preparation process of the epoxy zinc-rich coating:
  • Example 1 of the present invention The graphene epoxy zinc-rich paint prepared in Example 1 of the present invention was observed for metallographic images by a metallographic microscope.
  • Figure 3 is a metallographic view of an epoxy zinc-rich coating prepared in Example 1 of the present invention. 2 and 3, graphene exists in a sheet-like structure in both the resin and the coating, and is uniformly dispersed.
  • Example 1 of the present invention The graphene epoxy zinc-rich coating prepared in Example 1 of the present invention was coated, and the film layer was subjected to Raman spectroscopy.
  • FIG. 4 is a Raman microscopic image of a graphene oxide zinc-rich zinc coating film prepared in Example 1 of the present invention. Among them, the red peak of graphene (red) and the gray peak of epoxy resin (blue).
  • FIG. 5 is a mixing graph of Raman microscopic imaging of a graphene epoxy zinc-rich coating film prepared in Example 1 of the present invention. Among them, the red peak of graphene (red) and the gray peak of epoxy resin (blue).
  • the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example were subjected to a neutral salt spray resistance test.
  • Table 1 is the experimental data of neutral salt spray resistance of the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example.
  • a graphene epoxy resin dispersion is prepared by the following steps:
  • the graphene powder was mixed with a mixed solvent of xylene and n-butanol (the mass ratio of xylene to n-butanol was 7:3), and then magnetically stirred for 15 minutes to obtain a graphene mixture.
  • the graphene epoxy resin mixture obtained in the step 3 is ground or ball-milled for 10 minutes to obtain a graphene epoxy resin dispersion.
  • the graphene epoxy resin dispersion is used instead of the ordinary epoxy resin to prepare the coating according to the normal preparation process of the epoxy zinc-rich coating:
  • the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example were subjected to a neutral salt spray resistance test.
  • Table 1 is the experimental data of neutral salt spray resistance of the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example.
  • a graphene epoxy resin dispersion is prepared by the following steps:
  • the graphene powder was mixed with a mixed solvent of xylene and n-butanol (the mass ratio of xylene to n-butanol was 7:3), and then magnetically stirred for 15 minutes to obtain a graphene mixture.
  • the graphene epoxy resin mixture obtained in the step 3 is ground or ball-milled for 10 minutes to obtain a graphene epoxy resin dispersion.
  • the graphene epoxy resin dispersion is used instead of the ordinary epoxy resin to prepare the coating according to the normal preparation process of the epoxy zinc-rich coating:
  • the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example were subjected to a neutral salt spray resistance test.
  • Table 1 is the experimental data of neutral salt spray resistance of the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example.
  • a graphene epoxy resin dispersion is prepared by the following steps:
  • the graphene powder was mixed with a mixed solvent of xylene and n-butanol (the mass ratio of xylene to n-butanol was 7:3), and then magnetically stirred for 15 minutes to obtain a graphene mixture.
  • the graphene epoxy resin mixture obtained in the step 3 is ground or ball-milled for 10 minutes to obtain a graphene epoxy resin dispersion.
  • the graphene epoxy resin dispersion is used instead of the ordinary epoxy resin to prepare the coating according to the normal preparation process of the epoxy zinc-rich coating:
  • Table 1 is the experimental data of neutral salt spray resistance of the graphene epoxy zinc-rich coating prepared in the examples of the present invention and the blank epoxy zinc-rich coating prepared in the comparative example.

Abstract

本发明提供了一种石墨烯环氧树脂分散液的制备方法，包括以下步骤，首先将石墨烯和有机溶剂搅拌混合后，得到石墨烯混合液；然后将上述步骤得到的石墨烯混合液、磺酸盐类表面活性剂和吐温类表面活性剂再次搅拌混合后，得到石墨烯分散液；最后向上述步骤得到的石墨烯分散液中加入环氧树脂，并进行第三次搅拌混合后，再经过研磨，得到石墨烯环氧树脂分散液。本发明改变了石墨烯类材料的添加方式，首先得到石墨烯环氧树脂分散液，很好地解决石墨烯分散问题，保证其优良性能的完美发挥，同时采用了后期涂料用助剂，从而不需要加入多余助剂，减少了杂质的引入，而且全程在常温下进行，摒弃了传统的超声分散，有效降低能源损耗，更有利于工业化大生产。

Description

一种防腐涂料用石墨烯环氧树脂分散液的制备方法、环氧富锌防腐涂料及其制备方法
本申请要求于2017年10月16日提交中国专利局、申请号为201710958059.5、发明名称为“一种防腐涂料用石墨烯环氧树脂分散液的制备方法、环氧富锌防腐涂料及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于防腐涂料技术领域，涉及一种石墨烯环氧树脂分散液的制备方法、树脂防腐涂料及其制备方法，尤其涉及一种防腐涂料用石墨烯环氧树脂分散液的制备方法、环氧富锌防腐涂料及其制备方法。
背景技术
石墨烯(Graphene)是一种由碳原子构成的单层片状结构的新材料，作为一种由碳原子组成的只有一层原子厚度的二维晶体，它是目前进入应用领域中最薄的材料和最强韧的材料，断裂强度比钢材还要高200倍，还有很好的弹性，拉伸幅度能达到自身尺寸的20％；同时，石墨烯还具有优异的导电性，可以降低内阻，提高超级电容器的循环稳定性；另外，石墨烯几乎是完全透明的，只吸收2.3％的光，并且非常致密，即使是最小的气体原子(氦原子)也无法穿透。这些特征使得它非常适合用于多种学科和领域，也正是由于石墨烯具有上述诸多的优异物理化学性质，其在储能材料，环境工程，灵敏传感方面被广泛应用，被称为“黑金”或是“新材料之王”，而且潜在的应用前景广大，目前已成为全世界的关注焦点与研究热点，同时关于石墨烯等衍生物也从研究阶段走向了产业化，引起了各行各业的广泛参与。
目前全球，所有材料每年因腐蚀损失约1％的重量，腐蚀带来的经济损失约占国家经济总量的4％，防腐道路任重道远。在防腐涂料行业，最主要的几种防腐涂料主要为环氧类、聚氨脂类和富锌底漆类涂料。其中环氧类防腐涂料具有优异的附着力、优良的力学性能、良好的抗碱性和耐化学介质腐蚀性、固体组分含量高等优点，但是漆膜初期硬度高，柔韧性差，沥青类和铬酸盐类的环氧防腐漆，对环境具有很大的破坏性，同时危害人类健康。富锌底漆类涂料 具有屏蔽作用、电化学防护作用、涂膜白修复和钝化作用，但防腐性能是以牺性锌粉为代价，且在焊接时会产生大量氧化锌雾气，危害作业人员生命健康。而国内，海洋工程、船舶制造及绿色海洋风能等产业迅猛发展，在新的国际形势和国家政策下，海洋腐蚀防护经济效益巨大，再此背景下大力发展新型防腐涂料势在必行。
近几年，含有石墨烯类材料的涂料产品已逐渐有相关报道，然而在实际应用中，石墨烯还存在着诸多的问题和制约因素，如石墨烯极易团聚。由于石墨烯及其衍生物比表面积较大，相互间存在较强的范德华作用力，团聚和缠绕现象明显，使其不能稳定分散，分散后也容易再次团聚在一起难以打开。虽然有大量研究通过添加不同类型的分散剂或者改性的方式来提高石墨烯的分散效果，但实际应用中效果较差，并且还会额外引入其他杂质，对后续研究造成负面影响，而且石墨烯作为一种柔性材料，在与涂料中其他材料，如锌粉混合时，更容易发生团聚情况，直接影响了石墨烯类材料在涂料中起到的效果。
因此，如何制备一种树脂防腐涂料，使得石墨烯能够在涂料体系中更好的分布，进一步提高涂料的性能，已成为诸多应用厂商和一线研发人员亟待解决的问题。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种石墨烯环氧树脂分散液的制备方法及树脂防腐涂料，特别是防腐涂料用石墨烯环氧树脂分散液的制备方法及环氧富锌防腐涂料，本发明通过简易的方法制备石墨烯环氧树脂分散液，利用此石墨烯环氧树脂分散液制得树脂防腐涂料，解决了石墨烯在涂料中不易分散，难保持片状结构的问题。
本发明提供了一种石墨烯环氧树脂分散液的制备方法，包括以下步骤：
A)将石墨烯和有机溶剂搅拌混合后，得到石墨烯混合液；
B)将上述步骤得到的石墨烯混合液、磺酸盐类表面活性剂和吐温类表面活性剂再次搅拌混合后，得到石墨烯分散液；
C)向上述步骤得到的石墨烯分散液中加入环氧树脂，并进行第三次搅拌混合后，再经过研磨，得到石墨烯环氧树脂分散液。
优选的，所述石墨烯包括氧化石墨烯、单层石墨烯、多层石墨烯和还原氧 化石墨烯中的一种或多种；
所述环氧树脂包括双酚A型环氧树脂；
所述有机溶剂包括丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2-吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯和醋酸丁酯中的一种或多种；
所述磺酸盐类表面活性剂包括烷基苯磺酸盐、α-烯烃磺酸盐、烷基磺酸盐、α-磺基单羧酸酯、脂肪酸磺烷基酯、琥珀酸酯磺酸盐、烷基萘磺酸盐、石油磺酸盐、木质素磺酸盐和烷基甘油醚磺酸中的一种或多种；
所述吐温类表面活性剂包括吐温-80、吐温-20、吐温-60和吐温-40中的一种或多种。
优选的，所述石墨烯与有机溶剂的质量比为1：(5～30)；
所述石墨烯与磺酸盐类表面活性剂的质量比为1：(0.3～1.8)；
所述石墨烯与吐温类表面活性剂的质量比为1：(0.8～2.5)；
所述环氧树脂与石墨烯的质量比为100：(0.5～3)；
所述环氧树脂与有机溶剂的质量比为100：(25～66)。
优选的，所述搅拌混合包括磁力搅拌和/或机械搅拌；
所述搅拌混合的时间为15～30min；
所述搅拌混合的速度为300～600r/min。
优选的，所述再次搅拌混合包括磁力搅拌和/或机械搅拌；
所述再次搅拌混合的时间为15～40min；
所述再次搅拌混合的速度为300～600r/min。
优选的，所述第三次搅拌混合包括磁力搅拌和/或机械搅拌；
所述第三次搅拌混合的时间为20～60min；
所述第三次搅拌混合的速度为400～1000r/min。
优选的，所述加入为缓慢加入；
所述研磨的时间为5～20min。
本发明提供了一种树脂防腐涂料，以质量分数计，包括：
Figure PCTCN2018109285-appb-000001
Figure PCTCN2018109285-appb-000002
所述助剂包括防沉剂、消泡剂、固化剂和促进剂中的一种或多种。
优选的，所述消泡剂的加入量为0.2～1重量份；
所述防沉剂的加入量为0.5～2重量份；
所述固化剂的加入量为15～35重量份；
所述促进剂的加入量为0.5～2重量份；
所述防沉剂包括防沉剂3300、有机黏土、有机陶土、气相二氧化硅、聚乙烯蜡和纤维素醚中的一种或多种；
所述消泡剂包括有机硅氧烷消泡剂、聚醚消泡剂和二甲基硅油消泡剂中的一种或多种；
所述填料包括氧化磷铁粉、铝粉浆、云母粉、氧化铁红、碳酸钙和滑石粉中的一种或多种；
所述促进剂包括DMP-30；
所述固化剂包括聚酰胺、乙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺和聚醚二胺中的一种或多种。
本发明还提供了一种树脂防腐涂料的制备方法，包括以下步骤：
1)将石墨烯树脂分散液和溶剂经过初次混合后，再加入填料进行第二次混合，得到中间品；
2)将上述步骤得到的中间品和助剂第三次混合后，再加入锌粉进行第四次混合后，得到树脂防腐涂料。
本发明提供了一种石墨烯环氧树脂分散液的制备方法，包括以下步骤，首先将石墨烯和有机溶剂搅拌混合后，得到石墨烯混合液；然后将上述步骤得到的石墨烯混合液、磺酸盐类表面活性剂和吐温类表面活性剂再次搅拌混合后，得到石墨烯分散液；最后向上述步骤得到的石墨烯分散液中加入环氧树脂，并进行第三次搅拌混合后，再经过研磨，得到石墨烯环氧树脂分散液。与现有技术相比，本发明针对现有的防腐涂料中添加石墨烯通常以填料加入或在溶剂中分散后加入，石墨烯在涂料中严重分散不均匀，且由于石墨烯的比表面积大、 表面能高，再加上其横向尺寸远远超过厚度，在常规机械搅拌的剪切分散作用下，石墨烯易于卷曲成团，无法保持片状结构形成层层叠加的结构，最终导致制备的涂料抗腐蚀性能并不理想的问题。
本发明创造性的改变了石墨烯类材料的添加方式，首先将石墨烯和涂料中的环氧树脂进行分散，得到石墨烯环氧树脂分散液，然后再进行后续处理，得到树脂防腐涂料，能够很好地解决石墨烯分散问题，保证其优良性能的完美发挥，同时采用了后期涂料用助剂，从而不需要加入多余助剂，减少了杂质的引入，而且本发明的制备过程全程在常温下进行，还摒弃了传统利用超声分散的方法，有效降低能源损耗和成本，更有利于工业化大生产。本发明从根本上解决了柔性石墨烯类材料在涂料体系中混合不均匀的弊病，能够保证石墨烯的均匀分散，从而具有更好的性能。
实验结果表明，本发明提供的制备方法工艺简单成本低，而且制备的加石墨烯的涂料能够均匀分散，在表层形成保护膜，大幅度提高涂料的性能，保持石墨烯的片状结构形成层层叠加的结构，具有长久耐盐雾时间，比空白环氧树脂提高到51％。
附图说明
图1为本发明制备石墨烯环氧树脂分散液的工艺流程简图；
图2为本发明实施例1制备的石墨烯环氧树脂分散液的金相图；
图3为本发明实施例1制备的环氧富锌涂料的金相图；
图4为本发明实施例1制备的石墨烯环氧富锌涂料涂膜的拉曼显微成像图谱；
图5为本发明实施例1制备的石墨烯环氧富锌涂料涂膜的拉曼显微成像的混合曲线图。
具体实施方式
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为了进一步说明本发明的特征和优点，而不是对发明权利要求的限制。
本发明所有原料，对其来源没有特别限制，在市场上购买的或按照本领域技术人员熟知的常规方法制备的即可。
本发明所有原料，对其纯度没有特别限制，本发明优选采用分析纯或石墨烯复合材料领域使用的常规纯度。
本发明提供了一种石墨烯环氧树脂分散液的制备方法，包括以下步骤：
A)将石墨烯和有机溶剂搅拌混合后，得到石墨烯混合液；
B)将上述步骤得到的石墨烯混合液、磺酸盐类表面活性剂和吐温类表面活性剂再次搅拌混合后，得到石墨烯分散液；
C)向上述步骤得到的石墨烯分散液中加入环氧树脂，并进行第三次搅拌混合后，再经过研磨，得到石墨烯环氧树脂分散液。
本发明首先将石墨烯和有机溶剂搅拌混合后，得到石墨烯混合液。
本发明对所述石墨烯的定义没有特别限制，以本领域技术人员熟知的石墨烯类材料的定义即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述石墨烯优选为广义的石墨烯，也可称为石墨烯及其衍生物或石墨烯类材料，优选包括狭义石墨烯、氧化石墨烯、还原氧化石墨烯和改性石墨烯中的一种或多种，更优选为单层石墨烯、多层石墨烯、氧化石墨烯、还原氧化石墨烯或改性石墨烯，最优选为单层石墨烯、多层石墨烯或氧化石墨烯。
本发明对所述石墨烯的具体参数没有特别限制，以本领域技术人员熟知的常规的石墨烯类材料的参数即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述石墨烯中，片层小于等于5层的石墨烯的占比优选大于等于80％，更优选为大于等于85％，更优选为大于等于90％。本发明所述石墨烯的片径优选为1～100μm，更优选为10～90μm，更优选为30～70μm，更优选为40～60μm，具体最优选为10～50μm。
本发明对所述有机溶剂的选择没有特别限制，以本领域技术人员熟知的常规有机溶剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述有机溶剂优选包括丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2-吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯和醋酸丁酯中的一种或多种，更优选为丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2-吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯或醋酸丁酯，更优选为丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2- 吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯和醋酸丁酯中的两种或多种，具体可以为二甲苯和正丁醇。
本发明对所述有机溶剂的加入量没有特别限制，以本领域技术人员熟知的常规有机溶剂的加入量即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述石墨烯与有机溶剂的质量比优选为1：(5～30)，更优选为1：(10～25)，更优选为1：(15～20)。
本发明对所述搅拌混合的具体方式没有特别限制，以本领域技术人员熟知的搅拌混合方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述搅拌混合优选包括磁力搅拌和/或机械搅拌，更优选为磁力搅拌或机械搅拌，更优选为磁力搅拌。
本发明对所述搅拌混合的时间没有特别限制，以本领域技术人员熟知的搅拌混合的时间即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述搅拌混合的时间优选为15～30min，更优选为17～28min，更优选为20～25min。
本发明对所述搅拌混合的速度没有特别限制，以本领域技术人员熟知的搅拌混合的速度即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述搅拌混合的速度优选为300～600r/min，更优选为350～550r/min，更优选为400～500r/min。
本发明然后将上述步骤得到的石墨烯混合液、磺酸盐类表面活性剂和吐温类表面活性剂再次搅拌混合后，得到石墨烯分散液。
本发明对所述磺酸盐类表面活性剂的选择没有特别限制，以本领域技术人员熟知的常规磺酸盐类表面活性剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述磺酸盐类表面活性剂优选包括烷基苯磺酸盐、α-烯烃磺酸盐、烷基磺酸盐、α-磺基单羧酸酯、脂肪酸磺烷基酯、琥珀酸酯磺酸盐、烷基萘磺酸盐、石油磺酸盐、木质素磺酸盐和烷基甘油醚磺酸中的一种或多种，更优选为烷基苯磺酸盐、α-烯烃磺酸盐、 烷基磺酸盐、α-磺基单羧酸酯、脂肪酸磺烷基酯、琥珀酸酯磺酸盐、烷基萘磺酸盐、石油磺酸盐、木质素磺酸盐或烷基甘油醚磺酸，具体可以为十二烷基苯磺酸钠或十二烷基磺酸钠。
本发明对所述磺酸盐类表面活性剂的加入量没有特别限制，以本领域技术人员熟知的常规加入量即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述石墨烯与磺酸盐类表面活性剂的质量比优选为1：(0.3～1.8)，更优选为1：(0.5～1.6)，更优选为1：(0.7～1.4)，更优选为1：(0.9～1.2)。
本发明对所述吐温类表面活性剂的选择没有特别限制，以本领域技术人员熟知的常规吐温类表面活性剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述吐温类表面活性剂优选包括吐温-80、吐温-20、吐温-60和吐温-40中的一种或多种，更优选为吐温-80、吐温-20、吐温-60或吐温-40，具体可以为吐温-80或吐温-20。
本发明对所述吐温类表面活性剂的加入量没有特别限制，以本领域技术人员熟知的常规加入量即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述石墨烯与吐温类表面活性剂的质量比优选为1：(0.8～2.5)，更优选为1：(1.0～2.2)，更优选为1：(1.2～2.0)，更优选为1：(1.4～1.8)。
本发明对所述再次搅拌混合的具体方式没有特别限制，以本领域技术人员熟知的搅拌混合方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述再次搅拌混合优选包括磁力搅拌和/或机械搅拌，更优选为磁力搅拌或机械搅拌，更优选为磁力搅拌。
本发明对所述再次搅拌混合的时间没有特别限制，以本领域技术人员熟知的搅拌混合的时间即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述再次搅拌混合的时间优选为15～40min，更优选为20～35min，更优选为25～30min。
本发明对所述再次搅拌混合的速度没有特别限制，以本领域技术人员熟知 的搅拌混合的速度即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述再次搅拌混合的速度优选为300～600r/min，更优选为350～550r/min，更优选为400～500r/min。
本发明最后向上述步骤得到的石墨烯分散液中加入环氧树脂，并进行第三次搅拌混合后，再经过研磨，得到石墨烯环氧树脂分散液。
本发明对所述环氧树脂没有特别限制，以本领域技术人员熟知的环氧树脂即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明所述环氧树脂优选包括双酚A型环氧树脂，更具体优选为E-51双酚A型环氧树脂和/或601双酚A型环氧树脂，最优选为E-51双酚A型环氧树脂或601双酚A型环氧树脂。
本发明对所述环氧树脂的其他参数没有特别限制，以本领域技术人员熟知的常规环氧树脂的参数即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整。
本发明对所述环氧树脂的加入量没有特别限制，以本领域技术人员熟知的常规加入量即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述环氧树脂与石墨烯的质量比优选为100：(0.5～3)，更优选为100：(1.0～2.5)，更优选为100：(1.5～2.0)。
本发明对所述环氧树脂的加入方式没有特别限制，以本领域技术人员熟知的常规加入方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述加入优选为缓慢加入。
本发明对所述第三次搅拌混合的具体方式没有特别限制，以本领域技术人员熟知的搅拌混合方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述第三次搅拌混合优选包括磁力搅拌和/或机械搅拌，更优选为磁力搅拌或机械搅拌，更优选为机械搅拌。
本发明对所述第三次搅拌混合的时间没有特别限制，以本领域技术人员熟知的搅拌混合的时间即可，本领域技术人员可以根据实际生产情况、产品要求 以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述再次搅拌混合的时间优选为20～60min，更优选为25～55min，更优选为30～50min，更优选为35～45min。
本发明对所述第三次搅拌混合的速度没有特别限制，以本领域技术人员熟知的搅拌混合的速度即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述再次搅拌混合的速度优选为400～1000r/min，更优选为500～900r/min，更优选为600～800r/min。
本发明对所述研磨方式没有特别限制，以本领域技术人员熟知的常规研磨方式即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述研磨优选为湿法研磨。
本发明对所述研磨的时间没有特别限制，以本领域技术人员熟知的研磨时间即可，本领域技术人员可以根据实际生产情况、产品要求以及质量控制进行选择和调整，本发明为进一步提高分散液和后续涂料产品的均匀性和性能，优化工艺路线，所述研磨的时间优选为5～20min，更优选为7～18min，更优选为10～15min。
本发明提供了一种树脂防腐涂料，以质量分数计，包括：
Figure PCTCN2018109285-appb-000003
所述助剂包括防沉剂、消泡剂、固化剂和促进剂中的一种或多种。
本发明对所述树脂防腐涂料中的原料的选择和组成，以及相应的优选原则，与前述石墨烯环氧树脂分散液的制备方法中所对应原料的选择和组成，以及相应的优选原则均可以进行对应，在此不再一一赘述。
本发明对所述石墨烯环氧树脂分散液的具体加入量没有特别限制，以本领域技术人员熟知的常规比例即可，本领域技术人员可以根据实际应用情况、产 品要求以及质量要求进行选择和调整，本发明所述石墨烯环氧树脂分散液的加入量优选为8～25重量份，更优选为10～22重量份，更优选为12～20重量份，更优选为15～18重量份。
本发明对所述锌粉没有特别限制，以本领域技术人员熟知的用于防腐涂料的锌粉即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述锌粉优选为球形锌粉。本发明对所述锌粉的其他参数没有特别限制，以本领域技术人员熟知的常规锌粉的参数即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述锌粉的粒径优选为0.1～200μm，更优选为0.5～100μm，更优选为1～80μm，最优选为5～50μm。
本发明所述锌粉的加入量优选为30～90重量份，更优选为40～80重量份，最优选为50～70重量份。
本发明对所述填料的具体选择没有特别限制，以本领域技术人员熟知的防腐涂料用填料即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述填料优选包括氧化磷铁粉、铝粉浆、云母粉、氧化铁红、碳酸钙和滑石粉中的一种或多种，更优选为氧化磷铁粉、铝粉浆、云母粉、氧化铁红、碳酸钙和滑石粉中的两种或多种。
本发明所述填料的加入量优选为5～50重量份，更优选为10～45重量份，更优选为15～40重量份，更优选为20～35重量份。
本发明对所述溶剂没有特别限制，以本领域技术人员熟知的用于防腐涂料的溶剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述溶剂优选包括丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2-吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯和醋酸丁酯中的一种或多种，更优选为丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2-吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯和醋酸丁酯中的两种或多种，更优选为二甲苯、正丁醇和丙二醇甲醚中的多种。
本发明所述溶剂的加入量优选为10～50重量份，更优选为15～45重量份，更优选为20～40重量份，更优选为25～35重量份。
本发明对所述助剂没有特别限制，以本领域技术人员熟知的用于防腐涂料 的助剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述助剂优选包括防沉剂、消泡剂、固化剂和促进剂中的一种或多种，更优选为防沉剂、消泡剂、固化剂和促进剂中的多种。
本发明对所述助剂的种类没有特别限制，以本领域技术人员熟知的涂料用助剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述助剂优选包括涂料自身(甲组分)用助剂和涂料使用时(乙组分)用助剂，所述甲组分用助剂优选包括防沉剂、消泡剂和填料中的一种或多种，更优选为防沉剂、消泡剂和填料中的多种；所述乙组分用助剂优选包括固化剂、促进剂和溶剂中的一种或多种，更优选为固化剂、促进剂和溶剂中的多种。
本发明对所述助剂的加入量没有特别限制，以本领域技术人员熟知的树脂防腐涂料的常规助剂的配比即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整。
本发明对所述消泡剂的加入量没有特别限制，以本领域技术人员熟知的防腐涂料的常规消泡剂的配比即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述消泡剂的加入量优选为0.2～1重量份，更优选为0.3～0.9重量份，更优选为0.4～0.8重量份，最优选为0.5～0.7重量份。
本发明对所述消泡剂的具体选择没有特别限制，以本领域技术人员熟知的防腐涂料用消泡剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述消泡剂优选包括有机硅氧烷消泡剂、聚醚消泡剂和二甲基硅油消泡剂中的一种或多种，更优选为有机硅氧烷消泡剂、聚醚消泡剂或二甲基硅油消泡剂。
本发明对所述防沉剂的加入量没有特别限制，以本领域技术人员熟知的防腐涂料的常规防沉剂的配比即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述防沉剂的加入量优选为0.5～2重量份，更优选为0.7～1.8重量份，更优选为0.9～1.6重量份，最优选为1.1～1.4重量份。
本发明对所述防沉剂的具体选择没有特别限制，以本领域技术人员熟知的 防腐涂料用防沉剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述防沉剂优选包括防沉剂3300、有机黏土、有机陶土、气相二氧化硅、聚乙烯蜡和纤维素醚中的一种或多种，更优选为防沉剂3300、有机黏土、有机陶土、气相二氧化硅、聚乙烯蜡或纤维素醚，具体优选为(摩诺隆)MONORAL 3300。
本发明对所述固化剂的加入量没有特别限制，以本领域技术人员熟知的防腐涂料的常规固化剂的配比即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述固化剂的加入量优选为15～35重量份，更优选为18～32重量份，最优选为20～30重量份。
本发明对所述固化剂的具体选择没有特别限制，以本领域技术人员熟知的防腐涂料用固化剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述固化剂优选包括聚酰胺、乙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺和聚醚二胺中的一种或多种，更优选为聚酰胺、乙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺或聚醚二胺，具体优选为聚酰胺200。
本发明对所述促进剂的加入量没有特别限制，以本领域技术人员熟知的防腐涂料的常规促进剂的配比即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述促进剂的加入量优选为0.5～2重量份，更优选为0.7～1.8重量份，更优选为0.9～1.6重量份，最优选为1.1～1.4重量份。
本发明对所述促进剂的具体选择没有特别限制，以本领域技术人员熟知的防腐涂料用促进剂即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述促进剂优选包括DMP-30。
本发明对所述树脂防腐涂料没有特别限制，以本领域技术人员熟知的用于防腐的树脂防腐涂料即可，本领域技术人员可以根据实际应用情况、产品要求以及质量要求进行选择和调整，本发明所述树脂防腐涂料优选为环氧类涂料或富锌底漆类涂料，更优选为富锌底漆类涂料或富锌环氧(球形锌粉)防腐涂料。
本发明上述步骤提供了一种树脂防腐涂料，采用石墨烯环氧树脂分散液，首先将石墨烯和环氧树脂进行分散，得到分散液，然后再与其他成分组合成防 腐涂料。本发明通过成分的选择和优化配比，再结合多种助剂，得到应用更为广泛的树脂防腐涂料。而且本发明在分散液中加入助剂，能够在后续防腐涂料中继续应用，无需再加入分散剂，完全不加入其他多余试剂，减少了杂质的引入。本发明提供的树脂防腐涂料有效的解决了常规石墨烯类材料易于卷曲成团，无法保持片状结构形的固有缺陷。
本发明还提供了一种树脂防腐涂料的制备方法，包括以下步骤：
1)将石墨烯树脂分散液和溶剂经过初次混合后，再加入填料进行第二次混合，得到中间品；
2)将上述步骤得到的中间品和助剂第三次混合后，再加入锌粉进行第四次混合后，得到树脂防腐涂料。
本发明对上述制备过程中所需原料的选择和组成，以及相应的优选原则，与前述树脂防腐涂料中所对应原料的选择和组成，以及相应的优选原则均可以进行对应，在此不再一一赘述。
所述助剂包括防沉剂、消泡剂、填料、固化剂和促进剂中的一种或多种。
本发明对上述制备方法中各次混合的具体步骤和参数没有特别限制，以本领域技术人员熟知的常规混合的具体步骤和参数即可，本领域技术人员可以根据实际生产情况、产品要求以及质量要求进行选择和调整。
本发明在制备树脂防腐涂料的过程中，进一步优选采用了特定加入顺序，使得石墨烯更好均匀分散在树脂防腐涂料中，能够有效的解决石墨烯分散不均匀问题，更好地发挥其优良性能，而且还能得到均匀分散石墨烯材料的树脂防腐涂料，进一步提高了树脂防腐涂料的性能。而且本发明特别的在无需保护气体存在的条件下，进行上述操作，从而简化的生产流程、生产设备以及减少了生产消耗。本发明提供的上述复合方法工艺简单、条件温和、安全环保，更加适合工艺化大生产。
本发明上述步骤提供了一种石墨烯环氧树脂分散液的制备方法，树脂防腐涂料及其制备方法，本发明摒弃了传统石墨烯添加到防腐涂料中的制备工艺，将石墨烯均匀分散在环氧树脂中，通过研磨、搅拌及添加表面活性剂的方法制备出石墨烯环氧树脂分散液。制备过程全程在常温下进行，改变了传统利用超声分散的方法，降低了噪音污染和能耗，避免了噪音对人体的危害；所使用的 溶剂都为防腐涂料制备所需不再使用额外溶剂，减少制备过程引起的环境污染等问题。本发明将石墨烯在环氧树脂中分散并用此分散液制备的防腐涂料，解决了石墨烯在防腐涂料中分散不均易团聚的问题，同时有效保证石墨烯以片层形式加入从而形成层层叠加的结构，有效简单解决了现有技术中石墨烯在树脂中不是以片状结构存在，导致石墨烯防腐涂料的抗腐蚀性能得不到提升的桎梏，既避免传统方式在涂料中加入石墨烯导致石墨烯在涂料中分散差的问题使涂料性能大幅度下降，同时尤其提高了防腐涂料的耐腐蚀性能，在涂料的防腐领域具有良好的应用前景。
本实现方案通过简易方法制备石墨烯环氧树脂分散液，利用此石墨烯环氧树脂分散液制得的环氧富锌(球形锌粉)底漆，解决了石墨烯在涂料中不易分散，难保持片状结构的问题。制备的石墨烯防腐涂料，还避免了环境污染。
实验结果表明，本发明提供的制备方法工艺简单成本低，而且制备的加石墨烯的涂料能够均匀分散，在表层形成保护膜，大幅度提高涂料的性能，保持石墨烯的片状结构形成层层叠加的结构，具有长久耐盐雾时间，比空白环氧树脂提高到51％。
为了进一步说明本发明，以下结合实施例对本发明提供的涉及一种石墨烯环氧树脂分散液的制备方法、树脂防腐涂料及其制备方法进行详细描述，但是应当理解，这些实施例是在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制，本发明的保护范围也不限于下述的实施例。
对比例1
本实施例为空白环氧树脂制得防腐涂料。
实施例1
本实施例通过以下步骤制备石墨烯环氧树脂分散液：
1、将石墨烯粉体与二甲苯和正丁醇混合溶剂(二甲苯/正丁醇质量比为7：3)混合后，磁力搅拌15min后得到石墨烯混合液。
2、将十二烷基苯磺酸钠(石墨烯粉体/十二烷基苯磺酸钠质量比为1:1)和吐温-80(吐温类活性剂/石墨烯粉体的质量比为1：1.2)，加入到石墨烯混合液中，并继续磁力搅拌20min后，得到石墨烯分散液。
3、完成后换机械搅拌，并在搅拌过程在缓慢加入环氧树脂并继续机械搅拌，搅拌时间30min，搅拌速度600r/min得到石墨烯环氧树脂混合液。其中，环氧树脂/石墨烯质量比为100：2，环氧树脂/混合溶剂质量比为100：40。
4、将步骤3得到的石墨烯环氧树脂混合液进行研磨或球磨10min得到石墨烯环氧树脂分散液。
参见图1，图1为本发明制备石墨烯环氧树脂分散液的工艺流程简图。
对本发明实施例1制备的石墨烯环氧树脂分散液利用金相显微镜进行金相图像观察。
参见图2，图2为本发明实施例1制备的石墨烯环氧树脂分散液的金相图。由图2可知，石墨烯在树脂中是以片状结构存在的，而且均匀分散。
将石墨烯环氧树脂分散液代替普通的环氧树脂按环氧富锌涂料的正常制备工艺制备涂料：
5、将12重量份的石墨烯环氧树脂分散液与10重量份的磷铁粉和10重量份的滑石粉混合，高速搅拌至分散均匀。
6.向将步骤5得到的混合液中加入0.8重量份的气相二氧化硅和0.5份的消泡剂(看实际情况适量加入溶剂调节粘度)高速搅拌直至分散均匀。
7.向将步骤6中得到的混合液中加入60重量份的锌粉高速搅拌直接分散均匀，得到石墨烯环氧富锌涂料。
对本发明实施例1制备的石墨烯环氧富锌涂料利用金相显微镜进行金相图像观察。
参见图3，图3为本发明实施例1制备的环氧富锌涂料的金相图。由图2和3可知，石墨烯在树脂和涂料中均是以片状结构存在的，而且均匀分散。
将本发明实施例1制备的石墨烯环氧富锌涂料进行涂膜，对膜层进行拉曼光谱成像。
参见图4，图4为本发明实施例1制备的石墨烯环氧富锌涂料涂膜的拉曼显微成像图谱。其中，石墨烯(红色)的红色谱峰和环氧树脂(蓝色)的灰色谱峰。参见图5，图5为本发明实施例1制备的石墨烯环氧富锌涂料涂膜的拉曼显微成像的混合曲线图。其中，石墨烯(红色)的红色谱峰和环氧树脂(蓝色)的灰色谱峰。
由图4和图5可知，红色区域占总面积的绝大部分，证明石墨烯分散效果很好。
对本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料进行中性耐盐雾实验。
参见表1，表1为本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料的中性耐盐雾实验数据。
表1
制备的防腐涂料 实施例1 实施例2 实施例3 实施例4 对比例1
耐盐雾时间 1508h 1490h 1450h 1320h 996h
实施例2
本实施例通过以下步骤制备石墨烯环氧树脂分散液：
1、将石墨烯粉体与二甲苯和正丁醇混合溶剂(二甲苯/正丁醇质量比为7：3)混合后，磁力搅拌15min后得到石墨烯混合液。
2、将十二烷基磺酸钠(石墨烯粉体/十二烷基磺酸钠质量比为1:1)和吐温-80(吐温类活性剂/石墨烯粉体的质量比为1：1.2)，加入到石墨烯混合液中，并继续磁力搅拌20min后，得到石墨烯分散液。
3、完成后换机械搅拌，并在搅拌过程在缓慢加入环氧树脂并继续机械搅拌，搅拌时间30min，搅拌速度600r/min得到石墨烯环氧树脂混合液。其中，环氧树脂/石墨烯质量比为100：2，环氧树脂/混合溶剂质量比为100：40。
4、将步骤3得到的石墨烯环氧树脂混合液进行研磨或球磨10min得到石墨烯环氧树脂分散液。
将石墨烯环氧树脂分散液代替普通的环氧树脂按环氧富锌涂料的正常制备工艺制备涂料：
5、将12重量份的石墨烯环氧树脂分散液与10重量份的磷铁粉和10重量份的滑石粉混合，高速搅拌至分散均匀。
6.向将步骤5得到的混合液中加入0.8重量份的气相二氧化硅和0.5份的消泡剂(看实际情况适量加入溶剂调节粘度)高速搅拌直至分散均匀。
7.向将步骤6中得到的混合液中加入60重量份的锌粉高速搅拌直接分散均匀，得到石墨烯环氧富锌涂料。
对本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料进行中性耐盐雾实验。
参见表1，表1为本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料的中性耐盐雾实验数据。
实施例3
本实施例通过以下步骤制备石墨烯环氧树脂分散液：
1、将石墨烯粉体与二甲苯和正丁醇混合溶剂(二甲苯/正丁醇质量比为7：3)混合后，磁力搅拌15min后得到石墨烯混合液。
2、将十二烷基磺酸钠(石墨烯粉体/十二烷基磺酸钠质量比为1:1)和吐温-20(吐温类活性剂/石墨烯粉体的质量比为1：1.2)，加入到石墨烯混合液中，并继续磁力搅拌20min后，得到石墨烯分散液。
3、完成后换机械搅拌，并在搅拌过程在缓慢加入环氧树脂并继续机械搅拌，搅拌时间30min，搅拌速度600r/min得到石墨烯环氧树脂混合液。其中，环氧树脂/石墨烯质量比为100：2，环氧树脂/混合溶剂质量比为100：40。
4、将步骤3得到的石墨烯环氧树脂混合液进行研磨或球磨10min得到石墨烯环氧树脂分散液。
将石墨烯环氧树脂分散液代替普通的环氧树脂按环氧富锌涂料的正常制备工艺制备涂料：
5、将12重量份的石墨烯环氧树脂分散液与10重量份的磷铁粉和10重量份的滑石粉混合，高速搅拌至分散均匀。
6.向将步骤5得到的混合液中加入0.8重量份的气相二氧化硅和0.5份的消泡剂(看实际情况适量加入溶剂调节粘度)高速搅拌直至分散均匀。
7.向将步骤6中得到的混合液中加入60重量份的锌粉高速搅拌直接分散均匀，得到石墨烯环氧富锌涂料。
对本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料进行中性耐盐雾实验。
参见表1，表1为本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料的中性耐盐雾实验数据。
实施例4
本实施例通过以下步骤制备石墨烯环氧树脂分散液：
1、将石墨烯粉体与二甲苯和正丁醇混合溶剂(二甲苯/正丁醇质量比为7：3)混合后，磁力搅拌15min后得到石墨烯混合液。
2、将十二烷基苯磺酸钠(石墨烯粉体/十二烷基苯磺酸钠质量比为1:1)和吐温-20(吐温类活性剂/石墨烯粉体的质量比为1：1.2)，加入到石墨烯混合液中，并继续磁力搅拌20min后，得到石墨烯分散液。
3、完成后换机械搅拌，并在搅拌过程在缓慢加入环氧树脂并继续机械搅拌，搅拌时间30min，搅拌速度600r/min得到石墨烯环氧树脂混合液。其中，环氧树脂/石墨烯质量比为100：2，环氧树脂/混合溶剂质量比为100：40。
4、将步骤3得到的石墨烯环氧树脂混合液进行研磨或球磨10min得到石墨烯环氧树脂分散液。
将石墨烯环氧树脂分散液代替普通的环氧树脂按环氧富锌涂料的正常制备工艺制备涂料：
5、将12重量份的石墨烯环氧树脂分散液与10重量份的磷铁粉和10重量份的滑石粉混合，高速搅拌至分散均匀。
6.向将步骤5得到的混合液中加入0.8重量份的气相二氧化硅和0.5份的消泡剂(看实际情况适量加入溶剂调节粘度)高速搅拌直至分散均匀。
7.向将步骤6中得到的混合液中加入60重量份的锌粉高速搅拌直接分散均匀，得到石墨烯环氧富锌涂料。
对本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料进行中性耐盐雾实验，
参见表1，表1为本发明实施例制备的石墨烯环氧富锌涂料和对比例制备的空白环氧富锌涂料的中性耐盐雾实验数据。
以上对本发明提供的一种防腐涂料用石墨烯环氧树脂分散液的制备方法、环氧富锌防腐涂料及其制备方法进行了详细的介绍，本文中应用了具体个例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想，包括最佳方式，并且也使得本领域的任何技术人员 都能够实践本发明，包括制造和使用任何装置或系统，和实施任何结合的方法。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。本发明专利保护的范围通过权利要求来限定，并可包括本领域技术人员能够想到的其他实施例。如果这些其他实施例具有不是不同于权利要求文字表述的结构要素，或者如果它们包括与权利要求的文字表述无实质差异的等同结构要素，那么这些其他实施例也应包含在权利要求的范围内。

Claims (10)

  1. 一种石墨烯环氧树脂分散液的制备方法，其特征在于，包括以下步骤：
    A)将石墨烯和有机溶剂搅拌混合后，得到石墨烯混合液；
    B)将上述步骤得到的石墨烯混合液、磺酸盐类表面活性剂和吐温类表面活性剂再次搅拌混合后，得到石墨烯分散液；
    C)向上述步骤得到的石墨烯分散液中加入环氧树脂，并进行第三次搅拌混合后，再经过研磨，得到石墨烯环氧树脂分散液。
  2. 根据权利要求1所述的制备方法，其特征在于，所述石墨烯包括氧化石墨烯、单层石墨烯、多层石墨烯和还原氧化石墨烯中的一种或多种；
    所述环氧树脂包括双酚A型环氧树脂；
    所述有机溶剂包括丙酮、甲基异丁基甲酮、乙醇、异丙醇、丁酮、2-吡咯烷酮、甲苯、二甲苯、正丁醇、丙二醇甲醚、碳酸丙烯酯和醋酸丁酯中的一种或多种；
    所述磺酸盐类表面活性剂包括烷基苯磺酸盐、α-烯烃磺酸盐、烷基磺酸盐、α-磺基单羧酸酯、脂肪酸磺烷基酯、琥珀酸酯磺酸盐、烷基萘磺酸盐、石油磺酸盐、木质素磺酸盐和烷基甘油醚磺酸中的一种或多种；
    所述吐温类表面活性剂包括吐温-80、吐温-20、吐温-60和吐温-40中的一种或多种。
  3. 根据权利要求1所述的制备方法，其特征在于，所述石墨烯与有机溶剂的质量比为1：(5～30)；
    所述石墨烯与磺酸盐类表面活性剂的质量比为1：(0.3～1.8)；
    所述石墨烯与吐温类表面活性剂的质量比为1：(0.8～2.5)；
    所述环氧树脂与石墨烯的质量比为100：(0.5～3)；
    所述环氧树脂与有机溶剂的质量比为100：(25～66)。
  4. 根据权利要求1所述的制备方法，其特征在于，所述搅拌混合包括磁力搅拌和/或机械搅拌；
    所述搅拌混合的时间为15～30min；
    所述搅拌混合的速度为300～600r/min。
  5. 根据权利要求1所述的制备方法，其特征在于，所述再次搅拌混合包括磁力搅拌和/或机械搅拌；
    所述再次搅拌混合的时间为15～40min；
    所述再次搅拌混合的速度为300～600r/min。
  6. 根据权利要求1所述的制备方法，其特征在于，所述第三次搅拌混合包括磁力搅拌和/或机械搅拌；
    所述第三次搅拌混合的时间为20～60min；
    所述第三次搅拌混合的速度为400～1000r/min。
  7. 根据权利要求1所述的制备方法，其特征在于，所述加入为缓慢加入；
    所述研磨的时间为5～20min。
  8. 一种树脂防腐涂料，其特征在于，以质量分数计，包括：
    Figure PCTCN2018109285-appb-100001
    所述助剂包括防沉剂、消泡剂、固化剂和促进剂中的一种或多种。
  9. 根据权利要求8所述的制备方法，其特征在于，所述消泡剂的加入量为0.2～1重量份；
    所述防沉剂的加入量为0.5～2重量份；
    所述固化剂的加入量为15～35重量份；
    所述促进剂的加入量为0.5～2重量份；
    所述防沉剂包括防沉剂3300、有机黏土、有机陶土、气相二氧化硅、聚乙烯蜡和纤维素醚中的一种或多种；
    所述消泡剂包括有机硅氧烷消泡剂、聚醚消泡剂和二甲基硅油消泡剂中的一种或多种；
    所述填料包括氧化磷铁粉、铝粉浆、云母粉、氧化铁红、碳酸钙和滑石粉中的一种或多种；
    所述促进剂包括DMP-30；
    所述固化剂包括聚酰胺、乙二胺、二乙烯三胺、三乙烯四胺、多乙烯多胺和聚醚二胺中的一种或多种。
  10. 一种树脂防腐涂料的制备方法，其特征在于，包括以下步骤：
    1)将石墨烯树脂分散液和溶剂经过初次混合后，再加入填料进行第二次混合，得到中间品；
    2)将上述步骤得到的中间品和助剂第三次混合后，再加入锌粉进行第四次混合后，得到树脂防腐涂料。
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