WO2023035485A1 - Hyperbranched epoxy zinc-rich coating and preparation method therefor - Google Patents

Hyperbranched epoxy zinc-rich coating and preparation method therefor Download PDF

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Publication number
WO2023035485A1
WO2023035485A1 PCT/CN2021/139894 CN2021139894W WO2023035485A1 WO 2023035485 A1 WO2023035485 A1 WO 2023035485A1 CN 2021139894 W CN2021139894 W CN 2021139894W WO 2023035485 A1 WO2023035485 A1 WO 2023035485A1
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parts
component
zinc
graphene oxide
hyperbranched epoxy
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PCT/CN2021/139894
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French (fr)
Chinese (zh)
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谢海
唐帆
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江苏冠军科技集团股份有限公司
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Publication of WO2023035485A1 publication Critical patent/WO2023035485A1/en

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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
    • 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
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium

Definitions

  • the invention relates to the technical field of coatings, in particular to a hyperbranched epoxy zinc-rich coating and a preparation method thereof.
  • Epoxy zinc-rich coating is a heavy-duty anti-corrosion coating with excellent corrosion resistance, which has been applied to various fields of industrial anti-corrosion.
  • the anti-corrosion mechanism of zinc-rich coatings is mainly that zinc plays the role of cathodic protection, that is, to protect steel by sacrificing zinc powder in a corrosive environment.
  • cathodic protection that is, to protect steel by sacrificing zinc powder in a corrosive environment.
  • a large amount of zinc powder is often added to the coating.
  • the content of zinc is too high, the pores of the coating will increase and the flatness will be poor, resulting in a decrease in the adhesion, impact resistance and mechanical properties of the coating, which will cause the coating to fall off due to collision during coating and use.
  • the protective effect of the substrate is reduced.
  • Graphene has a sheet structure with a large specific surface area. Due to the existence of conjugated chemical bonds between the sheets, a dense protective film can be formed, which has a good physical shielding effect on the diffusion of water, oxygen, and ions, and can enhance the protection of metal materials. corrosion performance. Graphene also has good flexibility, which can improve the impact resistance and mechanical properties of the coating. However, as an inert material, graphene has limited compatibility with organic resins, which limits the application of graphene in epoxy zinc-rich coatings; the density difference between zinc powder and graphene oxide is large, which may easily cause graphene The gradient distribution in the layer structure reduces the adhesion of the coating and affects the water penetration resistance and anti-corrosion ability of the coating.
  • the object of the present invention is to provide a kind of hyperbranched epoxy zinc-rich coating and preparation method thereof for the deficiencies in the prior art.
  • the hyperbranched epoxy zinc-rich paint of the present invention has no foaming, no wrinkling, no shedding, no rust in water for 1450 hours, salt spray resistance time ⁇ 2500 hours, flexibility ⁇ 1mm, and impact resistance ⁇ 70cm.
  • the invention provides a hyperbranched epoxy zinc-rich coating, which comprises component A and component B with a mass ratio of 1 to 2:1;
  • the component A contains the following components by mass: 45-60 parts of zinc powder, 8-15 parts of curing agent, 0.1-0.3 parts of defoamer, 0.1-0.4 parts of dispersant, 0.5-2 parts of filler, 12 parts of solvent ⁇ 20 copies;
  • the B component includes the following components in parts by mass: 50-65 parts of silicone-modified epoxy resin emulsion, and 3-6 parts of polyaniline-grafted graphene oxide.
  • the zinc powder is flake zinc powder and spherical zinc powder; the mass ratio of the flake zinc powder to spherical zinc powder is 2 to 3:7 to 9; the mass ratio of the flake zinc powder to spherical zinc powder
  • the particle size is independently 10 to 20 ⁇ m.
  • the curing agent contains one or more of diethylenetriamine, p-phenylenediamine and triethylenetetramine; the defoamer is methyl silicone oil and/or polyether modified methyl silicone alkyl.
  • the dispersant includes one or more of sodium carboxylate, sodium polyacrylate, and ethylene bisstearamide;
  • the filler includes one of white corundum powder, aluminum titanate, and diatomaceous earth powder or several types, the particle size of the filler is 0.5-3 ⁇ m.
  • the solvent comprises N-methylpyrrolidone and dipropylene glycol methyl ether in a volume ratio of 40-50:10-15.
  • the preparation method of described polyaniline grafted graphene oxide comprises the following steps:
  • the mass volume ratio of m-phenylenediamine, graphene oxide and ethanol solution in step 1) is 2-4g:0.1-0.5g:5-8mL; the temperature of the grafting reaction is 75-90°C, The time is 1-3 hours; the mass fraction of the ethanol solution is 50-75%.
  • the mass volume ratio of the aniline, ammonium persulfate solution, ethanol solution in step 2) and m-phenylenediamine in step 1) is 2-4g: 2-4mL: 5-8mL: 2-4g, the The reaction temperature is 1-10° C., and the reaction time is 6-9 hours; the mass fraction of the ethanol solution is 50-75%, and the mass fraction of ammonium persulfate in the ammonium persulfate solution is 5-10%.
  • the present invention also provides a kind of preparation method of described hyperbranched epoxy zinc-rich coating, comprises the steps:
  • component A (1) Mix zinc powder, curing agent, defoamer, dispersant, filler and solvent to obtain component A;
  • the mixing time of step (1) is 15 to 20 min, and the mixing is carried out at a rotating speed of 1500 to 2000 r/min;
  • the mixing time of step (2) is 10 to 18 min, and the mixing is carried out at 1500 It is carried out at a rotational speed of ⁇ 2500r/min;
  • the mixing time in step (3) is 5-10min, and the mixing is carried out at a rotational speed of 1800-2500r/min.
  • the hyperbranched epoxy zinc-rich coating of the present invention reduces the consumption of zinc powder, has low VOC content, is environmentally friendly, has no pollution, and reduces production costs.
  • the hyperbranched epoxy zinc-rich coating of the present invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance, significantly improved storage stability and corrosion resistance, excellent mechanical properties, and extended service life .
  • the invention provides a hyperbranched epoxy zinc-rich coating, which comprises component A and component B with a mass ratio of 1 to 2:1;
  • the component A contains the following components by mass: 45-60 parts of zinc powder, 8-15 parts of curing agent, 0.1-0.3 parts of defoamer, 0.1-0.4 parts of dispersant, 0.5-2 parts of filler, 12 parts of solvent ⁇ 20 copies;
  • the B component includes the following components in parts by mass: 50-65 parts of silicone-modified epoxy resin emulsion, and 3-6 parts of polyaniline-grafted graphene oxide.
  • the mass ratio of component A to component B is preferably 1.2-1.7:1, more preferably 1.5:1.
  • the component A of the present invention contains 45-60 parts of zinc powder, preferably 50-56 parts, more preferably 52-54 parts.
  • the zinc powder of the present invention is preferably flaky zinc powder and spherical zinc powder; the mass ratio of the flaky zinc powder and spherical zinc powder is preferably 2 to 3:7 to 9, more preferably 2.5:8;
  • the particle size of the spherical zinc powder and the spherical zinc powder is independently preferably 10-20 ⁇ m, more preferably 12-18 ⁇ m, even more preferably 14-16 ⁇ m.
  • Component A of the present invention includes 8 to 15 parts of curing agent, preferably 10 to 13 parts, more preferably 11 to 12 parts; the curing agent preferably includes diethylenetriamine, p-phenylenediamine and triethylenetetramine One or more of them; when the curing agent contains several components at the same time, each component is preferably mixed in an equal mass ratio.
  • the curing agent of the invention has good heat resistance, and the mass loss rate and hardness change are small under high temperature.
  • Component A of the present invention contains 0.1 to 0.3 parts of defoamer, preferably 0.2 part; said defoamer is preferably methyl silicone oil and/or polyether-modified methyl siloxane, when the defoamer also contains methyl When base silicone oil and polyether modified methyl siloxane are used, the two are preferably mixed in an equal mass ratio.
  • Component A of the present invention contains 0.1 to 0.4 parts of dispersant, preferably 0.2 to 0.3 parts; said dispersant preferably contains one or more of sodium carboxylate, sodium polyacrylate and ethylene bis stearamide; When the powder contains several components at the same time, each component is preferably mixed in an equal mass ratio.
  • Component A of the present invention includes 0.5 to 2 parts of filler, preferably 0.8 to 1.6 parts, more preferably 1 to 1.3 parts; the filler preferably includes one or more of white corundum powder, aluminum titanate and diatomaceous earth powder Several kinds, when the filler contains several components at the same time, each component is preferably mixed in an equal mass ratio; the particle size of the filler is preferably 0.5-3 ⁇ m, more preferably 1-2.5 ⁇ m, more preferably 1.5-2 ⁇ m .
  • the filler of the invention can improve the compactness of the epoxy zinc-rich paint, make the paint have higher hardness and mechanical properties, and enhance the filling and fluidity of the paint.
  • Component A of the present invention includes 12 to 20 parts of solvent, preferably 14 to 18 parts, more preferably 15 to 16 parts; said solvent preferably includes N-methylpyrrolidone and dipropylene glycol methyl ether, said N-methyl
  • the volume ratio of pyrrolidone and dipropylene glycol methyl ether is preferably 40-50:10-15, more preferably 42-48:11-14, more preferably 44-46:12-13.
  • the solvent of the present invention can fully dissolve zinc powder, curing agent, filler and polyaniline grafted graphene oxide, effectively improve the dispersion uniformity of the epoxy zinc-rich coating, and is beneficial to the improvement of coating anticorrosion performance and mechanical performance.
  • the component B of the present invention contains 50-65 parts of silicone-modified epoxy resin emulsion, preferably 54-62 parts, more preferably 58-60 parts.
  • the organosilicon-modified epoxy resin emulsion of the present invention and polyaniline grafted graphene oxide form a strong force, have good dispersibility in the coating, and significantly improve the water penetration resistance, salt spray resistance and adhesion of the coating .
  • the component B of the present invention contains 3-6 parts of polyaniline-grafted graphene oxide, preferably 4-5 parts, more preferably 4.5 parts.
  • the polyaniline grafted graphene oxide of the present invention has high specific surface area, good gas barrier performance and adsorption performance, high mechanical strength, polyaniline can improve the dispersibility of graphene in coating, reduce agglomeration phenomenon, polyaniline graft oxidation Graphene, silicone-modified epoxy resin emulsion and zinc powder work together to improve the anti-corrosion performance, flexibility and impact strength of the coating at the same time; it can also reduce the amount of zinc powder used and save costs.
  • the preparation method of polyaniline grafted graphene oxide of the present invention preferably comprises the following steps:
  • the mass volume ratio of m-phenylenediamine, graphene oxide and ethanol solution in step 1) of the present invention is preferably 2-4g: 0.1-0.5g: 5-8mL, more preferably 3g: 0.2-0.4g: 6-7mL , more preferably 3g:0.3g:6.5mL.
  • the m-phenylenediamine of the present invention has large steric hindrance and can effectively improve the agglomeration problem of graphene oxide; the two amine groups on the m-phenylenediamine molecule are compatible with the epoxy groups of graphene oxide and silicone modified epoxy resin Bonding separately improves the compatibility between graphene oxide and epoxy resin.
  • step 1) of the present invention before the grafting reaction, m-phenylenediamine and ethanol solution are preferably mixed evenly and then mixed with graphene oxide; the temperature of the grafting reaction is preferably 75-90° C., more preferably 78-86° C. °C, more preferably 80-82 °C; the time of the grafting reaction is preferably 1-3 h, more preferably 2 h; the mass fraction of the ethanol solution is preferably 50-75%, more preferably 55-70%, More preferably, it is 60 to 65%.
  • the particle size after refinement is preferably 0.3 to 0.5 ⁇ m;
  • the reagent for washing is preferably absolute ethanol, and the number of times of washing is preferably 2 to 3 times;
  • the temperature of the drying treatment is preferably 70 to 80 °C, more preferably 75 °C; time is preferably 4-6 hours, more preferably 5 hours.
  • the mass volume ratio of the aniline, ammonium persulfate solution, ethanol solution in step 2) of the present invention and m-phenylenediamine in step 1) is preferably 2-4g: 2-4mL: 5-8mL: 2-4g, more preferably 2.5-3.5g: 2.5-3.5mL: 6-7mL: 2.5-3.5g, more preferably 3g: 3mL: 6.5mL: 3g;
  • step 2) of the present invention the mixing preferably mixes m-phenylenediamine grafted graphene oxide and ethanol solution evenly, then mixes with aniline, and finally mixes with ammonium persulfate solution;
  • the temperature of the reaction is preferably 1-10°C, More preferably 3-8°C, more preferably 5-6°C;
  • the reaction time is preferably 6-9h, more preferably 7-8h;
  • the mass fraction of the ethanol solution is preferably 50-75%, more preferably 55-70%, more preferably 60-65%; in the ammonium persulfate solution, the mass fraction of ammonium persulfate is preferably 5-10%, more preferably 6-8%.
  • the particle size after refinement is preferably 0.3 to 0.5 ⁇ m;
  • the reagent for washing is preferably absolute ethanol, and the number of times of washing is preferably 2 to 3 times;
  • the temperature of the drying treatment is preferably 70 to 80 °C, more preferably 75 °C; time is preferably 4-6 hours, more preferably 5 hours.
  • the present invention also provides a kind of preparation method of described hyperbranched epoxy zinc-rich coating, comprises the steps:
  • component A (1) Mix zinc powder, curing agent, defoamer, dispersant, filler and solvent to obtain component A;
  • the mixing time of step (1) of the present invention is preferably 15 to 20 minutes, more preferably 16 to 19 minutes, more preferably 17 to 18 minutes; the mixing is preferably carried out at a speed of 1500 to 2000 r/min, more preferably 1600 ⁇ 1800r/min; the mixing time of step (2) is preferably 10 ⁇ 18min, more preferably 12 ⁇ 16min, more preferably 14 ⁇ 15min; the mixing is preferably carried out at a rotating speed of 1500 ⁇ 2500r/min, further It is preferably 1700 ⁇ 2200r/min, more preferably 2000r/min; the mixing time in step (3) is preferably 5 ⁇ 10min, more preferably 6 ⁇ 8min; the mixing is preferably at a speed of 1800 ⁇ 2500r/min Carrying out, more preferably 2000 ⁇ 2200r/min.
  • Example 3 The m-phenylenediamine-grafted graphene oxide in Example 3 was replaced with polyethyleneimine-grafted modified graphene oxide of equal mass, and other conditions were the same as in Example 3.
  • Example 3 The white corundum powder and triethylenetetramine in Example 3 were respectively replaced with kaolin and polyamide curing agent of equal quality, and other conditions were the same as in Example 3.
  • the hyperbranched epoxy zinc-rich paint of the present invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance, and has low VOC content.
  • the storage stability and corrosion resistance of the hyperbranched epoxy zinc-rich coating of the present invention are significantly improved, the mechanical properties are excellent, and the service life is prolonged; the hyperbranched epoxy zinc-rich coating has no foaming, no wrinkling, no shedding, no cracking in water for 1450 hours Rust, salt spray resistance time ⁇ 2500h, flexibility ⁇ 1mm, impact resistance ⁇ 70cm.

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Abstract

The present invention belongs to the technical field of coatings. Provided in the present invention is a hyperbranched epoxy zinc-rich coating, containing a component A and a component B at a mass ratio of 1-2 : 1. The component A contains the following components in parts by mass: 45-60 parts of a zinc powder, 8-15 parts of a curing agent, 0.1-0.3 parts of a defoaming agent, 0.1-0.4 parts of a dispersing agent, 0.5-2 parts of a filler and 12-20 parts of a solvent; and the component B contains the following components in parts by mass: 50-65 parts of a silicone-modified epoxy resin emulsion, and 3-6 parts of polyaniline-grafted graphene oxide. Further provided in the present invention is a method for preparing the hyperbranched epoxy zinc-rich coating. The hyperbranched epoxy zinc-rich coating of the present invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance, significantly improved storage stability and corrosion resistance, good mechanical properties and prolonged service life.

Description

一种超支化环氧富锌涂料及其制备方法A kind of hyperbranched epoxy zinc-rich coating and preparation method thereof 技术领域technical field
本发明涉及涂料技术领域，尤其涉及一种超支化环氧富锌涂料及其制备方法。The invention relates to the technical field of coatings, in particular to a hyperbranched epoxy zinc-rich coating and a preparation method thereof.
背景技术Background technique
环氧富锌涂料是一种耐腐蚀性能优异的重防腐涂料，已应用到工业防腐的各个领域。富锌涂料的防腐蚀机理主要是锌起到阴极保护的作用，即在腐蚀环境中牺牲锌粉而保护钢铁。为了使富锌涂层充分发挥阴极保护作用，涂料中往往添加大量的锌粉。然而，锌的含量过高，会造成涂层的孔隙增多、平整性差，导致涂层的附着力、抗冲击性能和力学性能下降，使得涂层在涂装和使用过程中受到碰撞而脱落，对基材的防护效果下降。Epoxy zinc-rich coating is a heavy-duty anti-corrosion coating with excellent corrosion resistance, which has been applied to various fields of industrial anti-corrosion. The anti-corrosion mechanism of zinc-rich coatings is mainly that zinc plays the role of cathodic protection, that is, to protect steel by sacrificing zinc powder in a corrosive environment. In order to fully exert the cathodic protection effect of the zinc-rich coating, a large amount of zinc powder is often added to the coating. However, if the content of zinc is too high, the pores of the coating will increase and the flatness will be poor, resulting in a decrease in the adhesion, impact resistance and mechanical properties of the coating, which will cause the coating to fall off due to collision during coating and use. The protective effect of the substrate is reduced.
石墨烯具有片层结构，比表面积大，片层之间由于共轭化学键的存在能够形成致密的保护膜，对水、氧气和离子等的扩散具有良好的物理屏蔽作用，能够增强金属材料的防腐蚀性能。石墨烯还具有良好的柔韧性，能够提高涂层的抗冲击性能和力学性能。但是，石墨烯作为惰性材料，与有机树脂的相容性有限，限制了石墨烯在环氧富锌涂料中的应用；锌粉和氧化石墨烯的密度差异较大，容易造成氧化石墨烯在涂层结构中呈梯度分布，使得涂层的附着力下降，影响涂层的抗水渗透性能和防腐能力。Graphene has a sheet structure with a large specific surface area. Due to the existence of conjugated chemical bonds between the sheets, a dense protective film can be formed, which has a good physical shielding effect on the diffusion of water, oxygen, and ions, and can enhance the protection of metal materials. corrosion performance. Graphene also has good flexibility, which can improve the impact resistance and mechanical properties of the coating. However, as an inert material, graphene has limited compatibility with organic resins, which limits the application of graphene in epoxy zinc-rich coatings; the density difference between zinc powder and graphene oxide is large, which may easily cause graphene The gradient distribution in the layer structure reduces the adhesion of the coating and affects the water penetration resistance and anti-corrosion ability of the coating.
因此，研究开发一种分散均匀性好，能够同时提高防腐性能、抗水渗透性能、力学性能和附着力的环氧富锌涂料，具有重要的价值和意义。Therefore, it is of great value and significance to research and develop an epoxy zinc-rich coating with good dispersion uniformity, which can simultaneously improve anti-corrosion performance, water penetration resistance, mechanical properties and adhesion.
发明内容Contents of the invention
本发明的目的是针对现有技术的不足提供一种超支化环氧富锌涂料及其制备方法。本发明的超支化环氧富锌涂料在水中1450h无起泡、无起皱、不脱落、不生锈，耐盐雾时间≥2500h，柔韧性≤1mm，耐冲击性≥70cm。The object of the present invention is to provide a kind of hyperbranched epoxy zinc-rich coating and preparation method thereof for the deficiencies in the prior art. The hyperbranched epoxy zinc-rich paint of the present invention has no foaming, no wrinkling, no shedding, no rust in water for 1450 hours, salt spray resistance time ≥ 2500 hours, flexibility ≤ 1mm, and impact resistance ≥ 70cm.
为了实现上述发明目的，本发明提供以下技术方案：In order to achieve the above-mentioned purpose of the invention, the present invention provides the following technical solutions:
本发明提供了一种超支化环氧富锌涂料，包含质量比为1～2:1的A组分和B组分；The invention provides a hyperbranched epoxy zinc-rich coating, which comprises component A and component B with a mass ratio of 1 to 2:1;
所述A组分包含如下质量份的组分：锌粉45～60份，固化剂8～15份，消泡剂0.1～0.3份，分散剂0.1～0.4份，填料0.5～2份，溶剂12～20份；The component A contains the following components by mass: 45-60 parts of zinc powder, 8-15 parts of curing agent, 0.1-0.3 parts of defoamer, 0.1-0.4 parts of dispersant, 0.5-2 parts of filler, 12 parts of solvent ~20 copies;
所述B组分包含如下质量份的组分：有机硅改性环氧树脂乳液50～65份，聚苯胺接枝氧化石墨烯3～6份。The B component includes the following components in parts by mass: 50-65 parts of silicone-modified epoxy resin emulsion, and 3-6 parts of polyaniline-grafted graphene oxide.
作为优选，所述锌粉为片状锌粉和球状锌粉；所述片状锌粉和球状锌粉的质量比为2～3:7～9；所述片状锌粉和球状锌粉的粒径独立的为10～20μm。Preferably, the zinc powder is flake zinc powder and spherical zinc powder; the mass ratio of the flake zinc powder to spherical zinc powder is 2 to 3:7 to 9; the mass ratio of the flake zinc powder to spherical zinc powder The particle size is independently 10 to 20 μm.
作为优选，所述固化剂包含二乙烯三胺、对苯二胺和三乙烯四胺中的一种或几种；所述消泡剂为甲基硅油和/或聚醚改性甲基硅氧烷。Preferably, the curing agent contains one or more of diethylenetriamine, p-phenylenediamine and triethylenetetramine; the defoamer is methyl silicone oil and/or polyether modified methyl silicone alkyl.
作为优选，所述分散剂包含羧酸钠、聚丙烯酸钠和乙撑双硬脂酰胺中的一种或几种；所述填料包含白刚玉粉、钛酸铝和硅藻土粉中的一种或几种，所述填料的粒径为0.5～3μm。Preferably, the dispersant includes one or more of sodium carboxylate, sodium polyacrylate, and ethylene bisstearamide; the filler includes one of white corundum powder, aluminum titanate, and diatomaceous earth powder or several types, the particle size of the filler is 0.5-3 μm.
作为优选，所述溶剂包含体积比为40～50:10～15的N-甲基吡咯烷酮和二丙二醇甲醚。Preferably, the solvent comprises N-methylpyrrolidone and dipropylene glycol methyl ether in a volume ratio of 40-50:10-15.
作为优选，所述聚苯胺接枝氧化石墨烯的制备方法包含如下步骤：As preferably, the preparation method of described polyaniline grafted graphene oxide comprises the following steps:
1)将间苯二胺、氧化石墨烯在乙醇溶液中进行接枝反应，对接枝产物顺次进行细化、洗涤、干燥处理，得到间苯二胺接枝氧化石墨烯；1) Carrying out grafting reaction of m-phenylenediamine and graphene oxide in an ethanol solution, sequentially refining, washing and drying the grafted product to obtain m-phenylenediamine grafted graphene oxide;
2)将间苯二胺接枝氧化石墨烯、苯胺、过硫酸铵溶液和乙醇溶液混合进行反应，对反应产物顺次进行细化、洗涤、干燥处理，得到聚苯胺接枝氧化石墨烯。2) Mix m-phenylenediamine-grafted graphene oxide, aniline, ammonium persulfate solution and ethanol solution for reaction, and sequentially refine, wash and dry the reaction product to obtain polyaniline-grafted graphene oxide.
作为优选，步骤1)所述间苯二胺、氧化石墨烯和乙醇溶液的质量体积比为2～4g:0.1～0.5g：5～8mL；所述接枝反应的温度为75～90℃，时间为1～3h；所述乙醇溶液的质量分数为50～75％。As a preference, the mass volume ratio of m-phenylenediamine, graphene oxide and ethanol solution in step 1) is 2-4g:0.1-0.5g:5-8mL; the temperature of the grafting reaction is 75-90°C, The time is 1-3 hours; the mass fraction of the ethanol solution is 50-75%.
作为优选，步骤2)所述苯胺、过硫酸铵溶液、乙醇溶液和步骤1)所述间苯二胺的质量体积比为2～4g：2～4mL：5～8mL：2～4g，所述反应的温度为1～10℃，时间为6～9h；所述乙醇溶液的质量分数为50～75％，所述过硫酸铵溶液中，过硫酸铵的质量分数为5～10％。As a preference, the mass volume ratio of the aniline, ammonium persulfate solution, ethanol solution in step 2) and m-phenylenediamine in step 1) is 2-4g: 2-4mL: 5-8mL: 2-4g, the The reaction temperature is 1-10° C., and the reaction time is 6-9 hours; the mass fraction of the ethanol solution is 50-75%, and the mass fraction of ammonium persulfate in the ammonium persulfate solution is 5-10%.
本发明还提供了一种所述的超支化环氧富锌涂料的制备方法，包含如下步骤：The present invention also provides a kind of preparation method of described hyperbranched epoxy zinc-rich coating, comprises the steps:
(1)将锌粉、固化剂、消泡剂、分散剂、填料和溶剂混合，得到A组分；(1) Mix zinc powder, curing agent, defoamer, dispersant, filler and solvent to obtain component A;
(2)将有机硅改性环氧树脂乳液和聚苯胺接枝氧化石墨烯混合，得到B 组分；(2) Mixing silicone-modified epoxy resin emulsion and polyaniline-grafted graphene oxide to obtain component B;
(3)将A组分和B组分混合，得到超支化环氧富锌涂料。(3) Mix component A and component B to obtain a hyperbranched epoxy zinc-rich coating.
作为优选，步骤(1)所述混合的时间为15～20min，所述混合在1500～2000r/min的转速下进行；步骤(2)所述混合的时间为10～18min，所述混合在1500～2500r/min的转速下进行；步骤(3)所述混合的时间为5～10min，所述混合在1800～2500r/min的转速下进行。As preferably, the mixing time of step (1) is 15 to 20 min, and the mixing is carried out at a rotating speed of 1500 to 2000 r/min; the mixing time of step (2) is 10 to 18 min, and the mixing is carried out at 1500 It is carried out at a rotational speed of ~2500r/min; the mixing time in step (3) is 5-10min, and the mixing is carried out at a rotational speed of 1800-2500r/min.
本发明的有益效果包括以下几点：The beneficial effects of the present invention include the following points:
1)本发明的超支化环氧富锌涂料减少了锌粉的用量，VOC含量低，绿色环保，无污染，降低了生产成本。1) The hyperbranched epoxy zinc-rich coating of the present invention reduces the consumption of zinc powder, has low VOC content, is environmentally friendly, has no pollution, and reduces production costs.
2)本发明的超支化环氧富锌涂料具有良好的柔韧性、附着力、耐盐雾性能、耐水性和耐冲击性，贮存稳定性和耐腐蚀性能显著提高，力学性能优异，使用寿命延长。2) The hyperbranched epoxy zinc-rich coating of the present invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance, significantly improved storage stability and corrosion resistance, excellent mechanical properties, and extended service life .
具体实施方式Detailed ways
本发明提供了一种超支化环氧富锌涂料，包含质量比为1～2:1的A组分和B组分；The invention provides a hyperbranched epoxy zinc-rich coating, which comprises component A and component B with a mass ratio of 1 to 2:1;
所述A组分包含如下质量份的组分：锌粉45～60份，固化剂8～15份，消泡剂0.1～0.3份，分散剂0.1～0.4份，填料0.5～2份，溶剂12～20份；The component A contains the following components by mass: 45-60 parts of zinc powder, 8-15 parts of curing agent, 0.1-0.3 parts of defoamer, 0.1-0.4 parts of dispersant, 0.5-2 parts of filler, 12 parts of solvent ~20 copies;
所述B组分包含如下质量份的组分：有机硅改性环氧树脂乳液50～65份，聚苯胺接枝氧化石墨烯3～6份。The B component includes the following components in parts by mass: 50-65 parts of silicone-modified epoxy resin emulsion, and 3-6 parts of polyaniline-grafted graphene oxide.
本发明所述超支化环氧富锌涂料中，A组分和B组分的质量比优选为1.2～1.7:1，进一步优选为1.5:1。In the hyperbranched epoxy zinc-rich coating of the present invention, the mass ratio of component A to component B is preferably 1.2-1.7:1, more preferably 1.5:1.
本发明的A组分包含45～60份锌粉，优选为50～56份，进一步优选为52～54份。The component A of the present invention contains 45-60 parts of zinc powder, preferably 50-56 parts, more preferably 52-54 parts.
本发明所述锌粉优选为片状锌粉和球状锌粉；所述片状锌粉和球状锌粉的质量比优选为2～3:7～9，进一步优选为2.5:8；所述片状锌粉和球状锌粉的粒径独立的优选为10～20μm，进一步优选为12～18μm，更优选为14～16μm。The zinc powder of the present invention is preferably flaky zinc powder and spherical zinc powder; the mass ratio of the flaky zinc powder and spherical zinc powder is preferably 2 to 3:7 to 9, more preferably 2.5:8; The particle size of the spherical zinc powder and the spherical zinc powder is independently preferably 10-20 μm, more preferably 12-18 μm, even more preferably 14-16 μm.
本发明的A组分包含8～15份固化剂，优选为10～13份，进一步优选为11～12份；所述固化剂优选包含二乙烯三胺、对苯二胺和三乙烯四胺中的一 种或几种；当固化剂同时包含几种组分时，各组分优选以等质量比进行混合。Component A of the present invention includes 8 to 15 parts of curing agent, preferably 10 to 13 parts, more preferably 11 to 12 parts; the curing agent preferably includes diethylenetriamine, p-phenylenediamine and triethylenetetramine One or more of them; when the curing agent contains several components at the same time, each component is preferably mixed in an equal mass ratio.
本发明的固化剂耐热性能良好，在高温下质量损失率及硬度变化较小。The curing agent of the invention has good heat resistance, and the mass loss rate and hardness change are small under high temperature.
本发明的A组分包含0.1～0.3份消泡剂，优选为0.2份；所述消泡剂优选为甲基硅油和/或聚醚改性甲基硅氧烷，当消泡剂同时包含甲基硅油和聚醚改性甲基硅氧烷时，二者优选以等质量比进行混合。Component A of the present invention contains 0.1 to 0.3 parts of defoamer, preferably 0.2 part; said defoamer is preferably methyl silicone oil and/or polyether-modified methyl siloxane, when the defoamer also contains methyl When base silicone oil and polyether modified methyl siloxane are used, the two are preferably mixed in an equal mass ratio.
本发明的A组分包含0.1～0.4份分散剂，优选为0.2～0.3份；所述分散剂优选包含羧酸钠、聚丙烯酸钠和乙撑双硬脂酰胺中的一种或几种；当分散剂同时包含几种组分时，各组分优选以等质量比进行混合。Component A of the present invention contains 0.1 to 0.4 parts of dispersant, preferably 0.2 to 0.3 parts; said dispersant preferably contains one or more of sodium carboxylate, sodium polyacrylate and ethylene bis stearamide; When the powder contains several components at the same time, each component is preferably mixed in an equal mass ratio.
本发明的A组分包含0.5～2份填料，优选为0.8～1.6份，进一步优选为1～1.3份；所述填料优选包含白刚玉粉、钛酸铝和硅藻土粉中的一种或几种，当填料同时包含几种组分时，各组分优选以等质量比进行混合；所述填料的粒径优选为0.5～3μm，进一步优选为1～2.5μm，更优选为1.5～2μm。Component A of the present invention includes 0.5 to 2 parts of filler, preferably 0.8 to 1.6 parts, more preferably 1 to 1.3 parts; the filler preferably includes one or more of white corundum powder, aluminum titanate and diatomaceous earth powder Several kinds, when the filler contains several components at the same time, each component is preferably mixed in an equal mass ratio; the particle size of the filler is preferably 0.5-3 μm, more preferably 1-2.5 μm, more preferably 1.5-2 μm .
本发明的填料能提高环氧富锌涂料的致密性，使涂料具有较高的硬度和力学性能，增强涂料的填充性和流动性。The filler of the invention can improve the compactness of the epoxy zinc-rich paint, make the paint have higher hardness and mechanical properties, and enhance the filling and fluidity of the paint.
本发明的A组分包含12～20份溶剂，优选为14～18份，进一步优选为15～16份；所述溶剂优选包含N-甲基吡咯烷酮和二丙二醇甲醚，所述N-甲基吡咯烷酮和二丙二醇甲醚的体积比优选为40～50:10～15，进一步优选为42～48:11～14，更优选为44～46:12～13。Component A of the present invention includes 12 to 20 parts of solvent, preferably 14 to 18 parts, more preferably 15 to 16 parts; said solvent preferably includes N-methylpyrrolidone and dipropylene glycol methyl ether, said N-methyl The volume ratio of pyrrolidone and dipropylene glycol methyl ether is preferably 40-50:10-15, more preferably 42-48:11-14, more preferably 44-46:12-13.
本发明的溶剂能够充分溶解锌粉、固化剂、填料、聚苯胺接枝氧化石墨烯，有效提高环氧富锌涂料的分散均匀性，有利于涂层防腐性能和力学性能的提高。The solvent of the present invention can fully dissolve zinc powder, curing agent, filler and polyaniline grafted graphene oxide, effectively improve the dispersion uniformity of the epoxy zinc-rich coating, and is beneficial to the improvement of coating anticorrosion performance and mechanical performance.
本发明的B组分包含50～65份有机硅改性环氧树脂乳液，优选为54～62份，进一步优选为58～60份。The component B of the present invention contains 50-65 parts of silicone-modified epoxy resin emulsion, preferably 54-62 parts, more preferably 58-60 parts.
本发明的有机硅改性环氧树脂乳液和聚苯胺接枝氧化石墨烯形成较强的作用力，在涂料中分散性好，显著提高了涂料的抗水渗透性、耐盐雾性能和附着力。The organosilicon-modified epoxy resin emulsion of the present invention and polyaniline grafted graphene oxide form a strong force, have good dispersibility in the coating, and significantly improve the water penetration resistance, salt spray resistance and adhesion of the coating .
本发明的B组分包含3～6份聚苯胺接枝氧化石墨烯，优选为4～5份，进一步优选为4.5份。The component B of the present invention contains 3-6 parts of polyaniline-grafted graphene oxide, preferably 4-5 parts, more preferably 4.5 parts.
本发明的聚苯胺接枝氧化石墨烯具有高比表面积，良好的气体隔绝性能 和吸附性能，机械强度高，聚苯胺能够改善石墨烯在涂料中的分散性，减少团聚现象，聚苯胺接枝氧化石墨烯、有机硅改性环氧树脂乳液和锌粉共同作用，能够同时提高涂料的防腐性能、柔韧性和抗冲击强度；还能够减少锌粉的使用量，节约成本。The polyaniline grafted graphene oxide of the present invention has high specific surface area, good gas barrier performance and adsorption performance, high mechanical strength, polyaniline can improve the dispersibility of graphene in coating, reduce agglomeration phenomenon, polyaniline graft oxidation Graphene, silicone-modified epoxy resin emulsion and zinc powder work together to improve the anti-corrosion performance, flexibility and impact strength of the coating at the same time; it can also reduce the amount of zinc powder used and save costs.
本发明所述聚苯胺接枝氧化石墨烯的制备方法优选包含如下步骤：The preparation method of polyaniline grafted graphene oxide of the present invention preferably comprises the following steps:
1)将间苯二胺、氧化石墨烯在乙醇溶液中进行接枝反应，对接枝产物顺次进行细化、洗涤、干燥处理，得到间苯二胺接枝氧化石墨烯；1) Carrying out grafting reaction of m-phenylenediamine and graphene oxide in an ethanol solution, sequentially refining, washing and drying the grafted product to obtain m-phenylenediamine grafted graphene oxide;
2)将间苯二胺接枝氧化石墨烯、苯胺、过硫酸铵溶液和乙醇溶液混合进行反应，对反应产物顺次进行细化、洗涤、干燥处理，得到聚苯胺接枝氧化石墨烯。2) Mix m-phenylenediamine-grafted graphene oxide, aniline, ammonium persulfate solution and ethanol solution for reaction, and sequentially refine, wash and dry the reaction product to obtain polyaniline-grafted graphene oxide.
本发明步骤1)所述间苯二胺、氧化石墨烯和乙醇溶液的质量体积比优选为2～4g：0.1～0.5g：5～8mL，进一步优选为3g：0.2～0.4g：6～7mL，更优选为3g：0.3g：6.5mL。The mass volume ratio of m-phenylenediamine, graphene oxide and ethanol solution in step 1) of the present invention is preferably 2-4g: 0.1-0.5g: 5-8mL, more preferably 3g: 0.2-0.4g: 6-7mL , more preferably 3g:0.3g:6.5mL.
本发明的间苯二胺空间位阻大，能够有效改善氧化石墨烯的团聚问题；间苯二胺分子上的两个胺基与氧化石墨烯和有机硅改性环氧树脂的环氧基团分别键合，改善氧化石墨烯和环氧树脂间的相容性。The m-phenylenediamine of the present invention has large steric hindrance and can effectively improve the agglomeration problem of graphene oxide; the two amine groups on the m-phenylenediamine molecule are compatible with the epoxy groups of graphene oxide and silicone modified epoxy resin Bonding separately improves the compatibility between graphene oxide and epoxy resin.
本发明步骤1)所述接枝反应前优选将间苯二胺和乙醇溶液混合均匀后再与氧化石墨烯混合；所述接枝反应的温度优选为75～90℃，进一步优选为78～86℃，更优选为80～82℃；所述接枝反应的时间优选为1～3h，进一步优选为2h；所述乙醇溶液的质量分数优选为50～75％，进一步优选为55～70％，更优选为60～65％。In step 1) of the present invention, before the grafting reaction, m-phenylenediamine and ethanol solution are preferably mixed evenly and then mixed with graphene oxide; the temperature of the grafting reaction is preferably 75-90° C., more preferably 78-86° C. °C, more preferably 80-82 °C; the time of the grafting reaction is preferably 1-3 h, more preferably 2 h; the mass fraction of the ethanol solution is preferably 50-75%, more preferably 55-70%, More preferably, it is 60 to 65%.
本发明步骤1)所述细化后的粒径优选为0.3～0.5μm；洗涤的试剂优选为无水乙醇，洗涤的次数优选为2～3次；所述干燥处理的温度优选为70～80℃，进一步优选为75℃；时间优选为4～6h，进一步优选为5h。In step 1) of the present invention, the particle size after refinement is preferably 0.3 to 0.5 μm; the reagent for washing is preferably absolute ethanol, and the number of times of washing is preferably 2 to 3 times; the temperature of the drying treatment is preferably 70 to 80 °C, more preferably 75 °C; time is preferably 4-6 hours, more preferably 5 hours.
本发明步骤2)所述苯胺、过硫酸铵溶液、乙醇溶液和步骤1)所述间苯二胺的质量体积比优选为2～4g：2～4mL：5～8mL：2～4g，进一步优选为2.5～3.5g：2.5～3.5mL：6～7mL：2.5～3.5g，更优选为3g：3mL：6.5mL：3g；The mass volume ratio of the aniline, ammonium persulfate solution, ethanol solution in step 2) of the present invention and m-phenylenediamine in step 1) is preferably 2-4g: 2-4mL: 5-8mL: 2-4g, more preferably 2.5-3.5g: 2.5-3.5mL: 6-7mL: 2.5-3.5g, more preferably 3g: 3mL: 6.5mL: 3g;
本发明步骤2)所述混合优选将间苯二胺接枝氧化石墨烯和乙醇溶液混合均匀后再和苯胺混合，最后与过硫酸铵溶液混合；所述反应的温度优选为 1～10℃，进一步优选为3～8℃，更优选为5～6℃；所述反应的时间优选为6～9h，进一步优选为7～8h；所述乙醇溶液的质量分数优选为50～75％，进一步优选为55～70％，更优选为60～65％；所述过硫酸铵溶液中，过硫酸铵的质量分数优选为5～10％，进一步优选为6～8％。In step 2) of the present invention, the mixing preferably mixes m-phenylenediamine grafted graphene oxide and ethanol solution evenly, then mixes with aniline, and finally mixes with ammonium persulfate solution; the temperature of the reaction is preferably 1-10°C, More preferably 3-8°C, more preferably 5-6°C; the reaction time is preferably 6-9h, more preferably 7-8h; the mass fraction of the ethanol solution is preferably 50-75%, more preferably 55-70%, more preferably 60-65%; in the ammonium persulfate solution, the mass fraction of ammonium persulfate is preferably 5-10%, more preferably 6-8%.
本发明步骤2)所述细化后的粒径优选为0.3～0.5μm；洗涤的试剂优选为无水乙醇，洗涤的次数优选为2～3次；所述干燥处理的温度优选为70～80℃，进一步优选为75℃；时间优选为4～6h，进一步优选为5h。In step 2) of the present invention, the particle size after refinement is preferably 0.3 to 0.5 μm; the reagent for washing is preferably absolute ethanol, and the number of times of washing is preferably 2 to 3 times; the temperature of the drying treatment is preferably 70 to 80 °C, more preferably 75 °C; time is preferably 4-6 hours, more preferably 5 hours.
本发明还提供了一种所述的超支化环氧富锌涂料的制备方法，包含如下步骤：The present invention also provides a kind of preparation method of described hyperbranched epoxy zinc-rich coating, comprises the steps:
(1)将锌粉、固化剂、消泡剂、分散剂、填料和溶剂混合，得到A组分；(1) Mix zinc powder, curing agent, defoamer, dispersant, filler and solvent to obtain component A;
(2)将有机硅改性环氧树脂乳液和聚苯胺接枝氧化石墨烯混合，得到B组分；(2) Mixing the silicone-modified epoxy resin emulsion and the polyaniline-grafted graphene oxide to obtain the B component;
(3)将A组分和B组分混合，得到超支化环氧富锌涂料。(3) Mix component A and component B to obtain a hyperbranched epoxy zinc-rich coating.
本发明步骤(1)所述混合的时间优选为15～20min，进一步优选为16～19min，更优选为17～18min；所述混合优选在1500～2000r/min的转速下进行，进一步优选为1600～1800r/min；步骤(2)所述混合的时间优选为10～18min，进一步优选为12～16min，更优选为14～15min；所述混合优选在1500～2500r/min的转速下进行，进一步优选为1700～2200r/min，更优选为2000r/min；步骤(3)所述混合的时间优选为5～10min，进一步优选为6～8min；所述混合优选在1800～2500r/min的转速下进行，进一步优选为2000～2200r/min。The mixing time of step (1) of the present invention is preferably 15 to 20 minutes, more preferably 16 to 19 minutes, more preferably 17 to 18 minutes; the mixing is preferably carried out at a speed of 1500 to 2000 r/min, more preferably 1600 ～1800r/min; the mixing time of step (2) is preferably 10～18min, more preferably 12～16min, more preferably 14～15min; the mixing is preferably carried out at a rotating speed of 1500～2500r/min, further It is preferably 1700～2200r/min, more preferably 2000r/min; the mixing time in step (3) is preferably 5～10min, more preferably 6～8min; the mixing is preferably at a speed of 1800～2500r/min Carrying out, more preferably 2000～2200r/min.
下面结合实施例对本发明提供的技术方案进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。The technical solutions provided by the present invention will be described in detail below in conjunction with the examples, but they should not be interpreted as limiting the protection scope of the present invention.
实施例1Example 1
将2kg间苯二胺在5L乙醇溶液(质量分数为55％)中混合均匀后，加入0.1kg氧化石墨烯，充分混合后在78℃下接枝反应3h。得到的接枝产物筛分处理，得到粒径为0.48μm的粉末，用无水乙醇洗涤2次后在72℃下干燥处理6h，得到间苯二胺接枝氧化石墨烯。将间苯二胺接枝氧化石墨烯在6L 乙醇溶液(质量分数为55％)中混合均匀后，再加入2kg苯胺，最后加入2L过硫酸铵溶液(过硫酸铵的质量分数为6％)，在6℃下反应8h，反应完成后的产物筛分处理，得到粒径为0.46μm的粉末，用无水乙醇洗涤2次后在72℃下干燥处理6h，得到聚苯胺接枝氧化石墨烯。2 kg of m-phenylenediamine was uniformly mixed in 5 L of ethanol solution (55% by mass), then 0.1 kg of graphene oxide was added, mixed well, and grafted at 78° C. for 3 h. The obtained grafted product was sieved to obtain a powder with a particle size of 0.48 μm, which was washed twice with absolute ethanol and then dried at 72° C. for 6 h to obtain m-phenylenediamine grafted graphene oxide. After mixing m-phenylenediamine grafted graphene oxide in 6L ethanol solution (mass fraction is 55%), then add 2kg aniline, and finally add 2L ammonium persulfate solution (mass fraction of ammonium persulfate is 6%), Reacted at 6°C for 8 hours, and sieved the product after the reaction to obtain a powder with a particle size of 0.46 μm, washed twice with absolute ethanol and dried at 72°C for 6 hours to obtain polyaniline-grafted graphene oxide.
将1kg片状锌粉(粒径为10μm)、3kg球状锌粉(粒径为10μm)、0.9kg二乙烯三胺、0.01kg甲基硅油、0.01kg羧酸钠、0.06kg硅藻土粉(粒径为0.8μm)和1.2kg溶剂(溶剂为体积比42:12的N-甲基吡咯烷酮和二丙二醇甲醚的混合液)在1600r/min的转速下混合20min，得到A组分。将5.2kg有机硅改性环氧树脂乳液和0.35kg聚苯胺接枝氧化石墨烯在1600r/min的转速下混合18min，得到B组分。将A组分和B组分在1800r/min的转速下混合10min，得到超支化环氧富锌涂料。1kg flake zinc powder (particle size is 10 μm), 3kg spherical zinc powder (particle size is 10 μm), 0.9kg diethylenetriamine, 0.01kg methyl silicone oil, 0.01kg sodium carboxylate, 0.06kg diatomite powder ( The particle size is 0.8 μm) and 1.2 kg of solvent (the solvent is a mixture of N-methylpyrrolidone and dipropylene glycol methyl ether with a volume ratio of 42:12) at a speed of 1600 r/min for 20 minutes to obtain component A. 5.2 kg of silicone-modified epoxy resin emulsion and 0.35 kg of polyaniline-grafted graphene oxide were mixed for 18 min at a rotational speed of 1600 r/min to obtain component B. Mix component A and component B for 10 minutes at a speed of 1800r/min to obtain a hyperbranched epoxy zinc-rich coating.
实施例2Example 2
将3.8kg间苯二胺在7.8L乙醇溶液(质量分数为70％)中混合均匀后，加入0.45kg氧化石墨烯，充分混合后在88℃下接枝反应1h。得到的接枝产物筛分处理，得到粒径为0.32μm的粉末，用无水乙醇洗涤3次后在78℃下干燥处理4h，得到间苯二胺接枝氧化石墨烯。将间苯二胺接枝氧化石墨烯在8L乙醇溶液(质量分数为70％)中混合均匀后，再加入4kg苯胺，最后加入4L过硫酸铵溶液(过硫酸铵的质量分数为9％)，在1℃下反应6h，反应完成后的产物筛分处理，得到粒径为0.32μm的粉末，用无水乙醇洗涤3次后在78℃下干燥处理4h，得到聚苯胺接枝氧化石墨烯。After mixing 3.8kg of m-phenylenediamine in 7.8L of ethanol solution (70% by mass), 0.45kg of graphene oxide was added, mixed well, and grafted at 88°C for 1 hour. The obtained grafted product was sieved to obtain a powder with a particle size of 0.32 μm, which was washed with absolute ethanol three times and then dried at 78° C. for 4 h to obtain m-phenylenediamine grafted graphene oxide. After m-phenylenediamine grafted graphene oxide was mixed uniformly in 8L ethanol solution (mass fraction is 70%), then add 4kg aniline, finally add 4L ammonium persulfate solution (mass fraction of ammonium persulfate is 9%), React at 1°C for 6 hours, and sieve the product after the reaction to obtain a powder with a particle size of 0.32 μm, wash with absolute ethanol three times and dry at 78°C for 4 hours to obtain polyaniline-grafted graphene oxide.
将1.2kg片状锌粉(粒径为18μm)、4.8kg球状锌粉(粒径为18μm)、0.7kg对苯二胺、0.7kg三乙烯四胺、0.03kg聚醚改性甲基硅氧烷、0.04kg乙撑双硬脂酰胺、0.2kg钛酸铝(粒径为2.8μm)和2kg溶剂(溶剂为体积比48:14的N-甲基吡咯烷酮和二丙二醇甲醚的混合液)在2000r/min的转速下混合15min，得到A组分。将6.3kg有机硅改性环氧树脂乳液和0.55kg聚苯胺接枝氧化石墨烯在2300r/min的转速下混合10min，得到B组分。将A组分和B组分在2500r/min的转速下混合5min，得到超支化环氧富锌涂料。1.2kg flake zinc powder (particle size 18μm), 4.8kg spherical zinc powder (particle size 18μm), 0.7kg p-phenylenediamine, 0.7kg triethylenetetramine, 0.03kg polyether modified methyl silicone Alkanes, 0.04kg ethylene bis stearamide, 0.2kg aluminum titanate (particle size is 2.8μm) and 2kg solvent (the solvent is the mixed solution of N-methylpyrrolidone and dipropylene glycol methyl ether with a volume ratio of 48:14) in Mix for 15 minutes at a rotational speed of 2000r/min to obtain component A. 6.3kg of silicone-modified epoxy resin emulsion and 0.55kg of polyaniline-grafted graphene oxide were mixed for 10 minutes at a speed of 2300r/min to obtain component B. Mix component A and component B for 5 minutes at a speed of 2500r/min to obtain a hyperbranched epoxy zinc-rich coating.
实施例3Example 3
将3kg间苯二胺在6L乙醇溶液(质量分数为60％)中混合均匀后，加 入0.35kg氧化石墨烯，充分混合后在82℃下接枝反应2h。得到的接枝产物筛分处理，得到粒径为0.4μm的粉末，用无水乙醇洗涤3次后在75℃下干燥处理5h，得到间苯二胺接枝氧化石墨烯。将间苯二胺接枝氧化石墨烯在6L乙醇溶液(质量分数为60％)中混合均匀后，再加入3kg苯胺，最后加入6L过硫酸铵溶液(过硫酸铵的质量分数为8％)，在3℃下反应8h，反应完成后的产物筛分处理，得到粒径为0.4μm的粉末，用无水乙醇洗涤3次后在75℃下干燥处理5h，得到聚苯胺接枝氧化石墨烯。After 3kg m-phenylenediamine was mixed uniformly in 6L ethanol solution (mass fraction is 60%), 0.35kg graphene oxide was added, fully mixed and grafted at 82°C for 2h. The obtained grafted product was sieved to obtain a powder with a particle size of 0.4 μm, which was washed with absolute ethanol three times and then dried at 75° C. for 5 h to obtain m-phenylenediamine grafted graphene oxide. After m-phenylenediamine grafted graphene oxide is mixed uniformly in 6L ethanol solution (mass fraction is 60%), then add 3kg aniline, finally add 6L ammonium persulfate solution (mass fraction of ammonium persulfate is 8%), React at 3°C for 8 hours, and sieve the product after the reaction to obtain a powder with a particle size of 0.4 μm, wash with absolute ethanol three times and dry at 75°C for 5 hours to obtain polyaniline-grafted graphene oxide.
将1.3kg片状锌粉(粒径为15μm)、3.9kg球状锌粉(粒径为15μm)、1.2kg三乙烯四胺、0.02kg聚醚改性甲基硅氧烷、0.03kg聚丙烯酸钠、0.12kg白刚玉粉(粒径为1.5μm)和1.5kg溶剂(溶剂为体积比45:12的N-甲基吡咯烷酮和二丙二醇甲醚的混合液)在1800r/min的转速下混合16min，得到A组分。1.3kg flake zinc powder (particle size is 15μm), 3.9kg spherical zinc powder (particle size is 15μm), 1.2kg triethylenetetramine, 0.02kg polyether modified methyl siloxane, 0.03kg sodium polyacrylate , 0.12kg white corundum powder (particle size is 1.5μm) and 1.5kg solvent (the solvent is the mixed solution of N-methylpyrrolidone and dipropylene glycol methyl ether with a volume ratio of 45:12) mixed at a speed of 1800r/min for 16min, Obtain the A component.
将5.8kg有机硅改性环氧树脂乳液和0.45kg聚苯胺接枝氧化石墨烯在2000r/min的转速下混合15min，得到B组分。将A组分和B组分在2200r/min的转速下混合7min，得到超支化环氧富锌涂料。5.8 kg of silicone-modified epoxy resin emulsion and 0.45 kg of polyaniline-grafted graphene oxide were mixed for 15 min at a rotational speed of 2000 r/min to obtain component B. Mix component A and component B for 7 minutes at a speed of 2200r/min to obtain a hyperbranched epoxy zinc-rich coating.
对比例1Comparative example 1
将实施例3的间苯二胺接枝氧化石墨烯替换成等质量的聚乙烯亚胺接枝改性氧化石墨烯，其他条件和实施例3相同。The m-phenylenediamine-grafted graphene oxide in Example 3 was replaced with polyethyleneimine-grafted modified graphene oxide of equal mass, and other conditions were the same as in Example 3.
对比例2Comparative example 2
将实施例3的白刚玉粉和三乙烯四胺分别替换成等质量的高岭土和聚酰胺固化剂，其他条件和实施例3相同。The white corundum powder and triethylenetetramine in Example 3 were respectively replaced with kaolin and polyamide curing agent of equal quality, and other conditions were the same as in Example 3.
对比例3Comparative example 3
不添加聚醚改性甲基硅氧烷，溶剂采用体积比为4:1的二甲苯和丁醇的混合液，其他条件和实施例3相同。No polyether-modified methylsiloxane was added, the solvent was a mixture of xylene and butanol with a volume ratio of 4:1, and other conditions were the same as in Example 3.
对实施例1～3和对比例1～3的环氧富锌涂料的附着力、耐盐雾性能、耐水性、柔韧性、耐冲击性、可挥发性有机物(VOC)含量进行测试，结果如表1所示。The adhesion, salt spray resistance, water resistance, flexibility, impact resistance, volatile organic compound (VOC) content of the epoxy zinc-rich paint of embodiments 1～3 and comparative examples 1～3 are tested, and the results are as follows Table 1 shows.
表1不同实施例和对比例的环氧富锌涂料的测试结果The test result of the epoxy zinc-rich paint of table 1 different embodiment and comparative example
Figure PCTCN2021139894-appb-000001
Figure PCTCN2021139894-appb-000001
Figure PCTCN2021139894-appb-000002
Figure PCTCN2021139894-appb-000002
由表1可知，本发明的超支化环氧富锌涂料具有良好的柔韧性、附着力、耐盐雾性能、耐水性和耐冲击性，并且，VOC含量低。本发明超支化环氧富锌涂料的贮存稳定性和耐腐蚀性能显著提高，力学性能优异，使用寿命延长；超支化环氧富锌涂料在水中1450h无起泡、无起皱、不脱落、不生锈，耐盐雾时间≥2500h，柔韧性≤1mm，耐冲击性≥70cm。It can be seen from Table 1 that the hyperbranched epoxy zinc-rich paint of the present invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance, and has low VOC content. The storage stability and corrosion resistance of the hyperbranched epoxy zinc-rich coating of the present invention are significantly improved, the mechanical properties are excellent, and the service life is prolonged; the hyperbranched epoxy zinc-rich coating has no foaming, no wrinkling, no shedding, no cracking in water for 1450 hours Rust, salt spray resistance time ≥ 2500h, flexibility ≤ 1mm, impact resistance ≥ 70cm.
以上所述仅是本发明的优选实施方式，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，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种超支化环氧富锌涂料，其特征在于，包含质量比为1～2:1的A组分和B组分；A hyperbranched epoxy zinc-rich coating, characterized in that it comprises component A and component B with a mass ratio of 1 to 2:1;
    所述A组分包含如下质量份的组分：锌粉45～60份，固化剂8～15份，消泡剂0.1～0.3份，分散剂0.1～0.4份，填料0.5～2份，溶剂12～20份；The component A contains the following components by mass: 45-60 parts of zinc powder, 8-15 parts of curing agent, 0.1-0.3 parts of defoamer, 0.1-0.4 parts of dispersant, 0.5-2 parts of filler, 12 parts of solvent ~20 copies;
    所述B组分包含如下质量份的组分：有机硅改性环氧树脂乳液50～65份，聚苯胺接枝氧化石墨烯3～6份。The B component includes the following components in parts by mass: 50-65 parts of silicone-modified epoxy resin emulsion, and 3-6 parts of polyaniline-grafted graphene oxide.
  2. 根据权利要求1所述的超支化环氧富锌涂料，其特征在于，所述锌粉为片状锌粉和球状锌粉；所述片状锌粉和球状锌粉的质量比为2～3:7～9；所述片状锌粉和球状锌粉的粒径独立的为10～20μm。The hyperbranched epoxy zinc-rich coating according to claim 1, wherein the zinc powder is flake zinc powder and spherical zinc powder; the mass ratio of the flake zinc powder to spherical zinc powder is 2 to 3 : 7～9; The particle diameters of the flaky zinc powder and the spherical zinc powder are independently 10～20 μm.
  3. 根据权利要求1或2所述的超支化环氧富锌涂料，其特征在于，所述固化剂包含二乙烯三胺、对苯二胺和三乙烯四胺中的一种或几种；所述消泡剂为甲基硅油和/或聚醚改性甲基硅氧烷。The hyperbranched epoxy zinc-rich paint according to claim 1 and 2, wherein said curing agent comprises one or more of diethylenetriamine, p-phenylenediamine and triethylenetetramine; said The defoaming agent is methyl silicone oil and/or polyether modified methyl silicone.
  4. 根据权利要求3所述的超支化环氧富锌涂料，其特征在于，所述分散剂包含羧酸钠、聚丙烯酸钠和乙撑双硬脂酰胺中的一种或几种；所述填料包含白刚玉粉、钛酸铝和硅藻土粉中的一种或几种，所述填料的粒径为0.5～3μm。The hyperbranched epoxy zinc-rich coating according to claim 3, wherein the dispersant comprises one or more of sodium carboxylate, sodium polyacrylate and ethylene bis stearamide; the filler comprises One or more of white corundum powder, aluminum titanate and diatomaceous earth powder, the particle size of the filler is 0.5-3 μm.
  5. 根据权利要求4所述的超支化环氧富锌涂料，其特征在于，所述溶剂包含体积比为40～50:10～15的N-甲基吡咯烷酮和二丙二醇甲醚。The hyperbranched epoxy zinc-rich coating according to claim 4, wherein the solvent comprises N-methylpyrrolidone and dipropylene glycol methyl ether in a volume ratio of 40-50:10-15.
  6. 根据权利要求4或5所述的超支化环氧富锌涂料，其特征在于，所述聚苯胺接枝氧化石墨烯的制备方法包含如下步骤：According to claim 4 or 5 described hyperbranched epoxy zinc-rich coatings, it is characterized in that, the preparation method of described polyaniline grafted graphene oxide comprises the steps:
    1)将间苯二胺、氧化石墨烯在乙醇溶液中进行接枝反应，对接枝产物顺次进行细化、洗涤、干燥处理，得到间苯二胺接枝氧化石墨烯；1) Carrying out grafting reaction of m-phenylenediamine and graphene oxide in an ethanol solution, sequentially refining, washing and drying the grafted product to obtain m-phenylenediamine grafted graphene oxide;
    2)将间苯二胺接枝氧化石墨烯、苯胺、过硫酸铵溶液和乙醇溶液混合进行反应，对反应产物顺次进行细化、洗涤、干燥处理，得到聚苯胺接枝氧化石墨烯。2) Mix m-phenylenediamine-grafted graphene oxide, aniline, ammonium persulfate solution and ethanol solution for reaction, and sequentially refine, wash and dry the reaction product to obtain polyaniline-grafted graphene oxide.
  7. 根据权利要求6所述的超支化环氧富锌涂料，其特征在于，步骤1)所述间苯二胺、氧化石墨烯和乙醇溶液的质量体积比为2～4g:0.1～0.5g：5～8mL；所述接枝反应的温度为75～90℃，时间为1～3h；所述乙醇溶液的质量分数为50～75％。The hyperbranched epoxy zinc-rich coating according to claim 6, wherein the mass volume ratio of m-phenylenediamine, graphene oxide and ethanol solution in step 1) is 2～4g:0.1～0.5g:5 ~8mL; the temperature of the grafting reaction is 75-90°C, and the time is 1-3h; the mass fraction of the ethanol solution is 50-75%.
  8. 根据权利要求7所述的超支化环氧富锌涂料，其特征在于，步骤2)所述苯胺、过硫酸铵溶液、乙醇溶液和步骤1)所述间苯二胺的质量体积比为2～4g：2～4mL：5～8mL：2～4g，所述反应的温度为1～10℃，时间为6～9h；所述乙醇溶液的质量分数为50～75％，所述过硫酸铵溶液中，过硫酸铵的质量分数为5～10％。The hyperbranched epoxy zinc-rich coating according to claim 7, wherein the mass volume ratio of aniline, ammonium persulfate solution, ethanol solution and step 1) m-phenylenediamine described in step 2) is 2～ 4g: 2 ~ 4mL: 5 ~ 8mL: 2 ~ 4g, the temperature of the reaction is 1 ~ 10 ° C, the time is 6 ~ 9h; the mass fraction of the ethanol solution is 50 ~ 75%, the ammonium persulfate solution Among them, the mass fraction of ammonium persulfate is 5-10%.
  9. 权利要求1～8任意一项所述的超支化环氧富锌涂料的制备方法，包含如下步骤：The preparation method of the hyperbranched epoxy zinc-rich coating described in any one of claims 1 to 8, comprising the steps of:
    (1)将锌粉、固化剂、消泡剂、分散剂、填料和溶剂混合，得到A组分；(1) Mix zinc powder, curing agent, defoamer, dispersant, filler and solvent to obtain component A;
    (2)将有机硅改性环氧树脂乳液和聚苯胺接枝氧化石墨烯混合，得到B组分；(2) Mixing the silicone-modified epoxy resin emulsion and the polyaniline-grafted graphene oxide to obtain the B component;
    (3)将A组分和B组分混合，得到超支化环氧富锌涂料。(3) Mix component A and component B to obtain a hyperbranched epoxy zinc-rich coating.
  10. 根据权利要求9所述的制备方法，其特征在于，步骤(1)所述混合的时间为15～20min，所述混合在1500～2000r/min的转速下进行；步骤(2)所述混合的时间为10～18min，所述混合在1500～2500r/min的转速下进行；步骤(3)所述混合的时间为5～10min，所述混合在1800～2500r/min的转速下进行。The preparation method according to claim 9, characterized in that, the mixing time of the step (1) is 15 to 20 minutes, and the mixing is carried out at a rotating speed of 1500 to 2000 r/min; the mixing of the step (2) The mixing time is 10-18 min, and the mixing is performed at a rotational speed of 1500-2500 r/min; the mixing time of step (3) is 5-10 min, and the mixing is performed at a rotational speed of 1800-2500 r/min.
PCT/CN2021/139894 2021-09-07 2021-12-21 Hyperbranched epoxy zinc-rich coating and preparation method therefor WO2023035485A1 (en)

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