WO2022267396A1 - 一种石墨烯型水性环氧富锌涂料及其制备方法 - Google Patents

一种石墨烯型水性环氧富锌涂料及其制备方法 Download PDF

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WO2022267396A1
WO2022267396A1 PCT/CN2021/139903 CN2021139903W WO2022267396A1 WO 2022267396 A1 WO2022267396 A1 WO 2022267396A1 CN 2021139903 W CN2021139903 W CN 2021139903W WO 2022267396 A1 WO2022267396 A1 WO 2022267396A1
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water
parts
component
graphene
zinc
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PCT/CN2021/139903
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English (en)
French (fr)
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胡明
钱金均
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 WO2022267396A1 publication Critical patent/WO2022267396A1/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
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • 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 relates to the technical field of coatings, in particular to a graphene-type water-based epoxy zinc-rich coating and a preparation method thereof.
  • Epoxy zinc-rich coating is a special coating composed of epoxy resin and zinc powder as the main raw materials, fillers, additives, solvents, etc. It has excellent anti-corrosion performance, strong adhesion, and cathodic protection. It is suitable for storage tanks, containers, Coatings for steel structures, steel pipes, offshore platforms, ships, seaport facilities, and harsh anti-corrosion environments.
  • epoxy zinc-rich coatings are mostly used in oil-based coatings.
  • oil-based anti-corrosion coatings contain high VOC content, which will make the coating contain a porous structure, resulting in poor performance.
  • Waterborne epoxy zinc-rich coatings have broad prospects in the field of heavy anti-corrosion due to their environmental protection and high corrosion resistance.
  • the connection between the atoms of graphene is very flexible. When the surface of the carbon atoms is subjected to external force, it deforms and bends, but the positions of the carbon atoms do not rearrange.
  • the layer-by-layer superposition of graphene can form a dense insulating layer, which can inhibit the infiltration and penetration of external water to the paint film, and then play a role in anti-corrosion.
  • graphene when graphene is applied to water-based epoxy zinc-rich coatings, there is a large difference in the density of zinc powder and graphene, resulting in a gradient distribution of graphene in the coating structure, which will not only affect the adhesion of the coating, but also affect the The anti-water penetration ability of the coating leads to insufficient anti-corrosion performance of the waterborne epoxy zinc-rich coating.
  • the purpose of the present invention is to provide a kind of graphene type waterborne epoxy zinc-rich coating and preparation method thereof for the deficiency of prior art.
  • the water-based epoxy zinc-rich paint of the invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance; storage stability and corrosion resistance are remarkably improved, excellent mechanical properties and prolong service life.
  • the water-based epoxy zinc-rich paint of the present invention has no foaming, no wrinkling, no shedding, no rust in water for 1300 hours, salt spray resistance time ⁇ 2300 hours, flexibility ⁇ 1mm, impact resistance ⁇ 50cm.
  • the invention provides a graphene-type water-based epoxy zinc-rich coating, which comprises component A and component B with a mass ratio of 1.5 to 3:1;
  • the component A includes the following components by mass: 45-60 parts of zinc powder, 5-10 parts of polyamide curing agent, 0.05-0.1 part of defoamer, 0.1-0.5 part of dispersant, and 8-12 parts of water ;
  • the B component includes the following components in parts by mass: 70-80 parts of water-based epoxy resin emulsion, 3-7 parts of water-based graphene slurry, and 0.8-1.5 parts of functional additives.
  • the zinc powder is flaky zinc powder and spherical zinc powder; the mass ratio of the flaky zinc powder to spherical zinc powder is 2-3:10; the particle size of the zinc powder is 8-20 ⁇ m.
  • the solid content of the polyamide curing agent is 85-95%, and the active hydrogen equivalent is 220-280; the solid content of the water-based epoxy resin emulsion is 55-60%, and the epoxy equivalent is 1200-1500 .
  • the defoamer is mineral oil, methyl silicone oil, tributyl phosphate or polyoxypropylene pentaerythritol ether.
  • the dispersant is one or more of polyethylene glycol, polyglycerol and sodium tripolyphosphate.
  • the mass fraction of graphene is 15-20%, and the particle size of graphene is 0.05-0.3 ⁇ m.
  • the functional auxiliary agent is one or more of 2-amino-2-methyl-1-pentanol, ethylene glycol ether, propylene glycol butyl ether and cellulose ether.
  • the present invention also provides a kind of preparation method of described waterborne epoxy zinc-rich paint, comprises the steps:
  • component A 1) Mix zinc powder, polyamide curing agent, defoamer, dispersant and water to obtain component A;
  • component B 1) mixing water-based epoxy resin emulsion, water-based graphene slurry and functional additives to obtain component B;
  • the mixing time of step 1) is 10-20min, and the mixing is carried out at a rotating speed of 1200-1800r/min; It is carried out at a rotating speed of 2000 to 3000 r/min; step 3) the mixing time is 5 to 10 minutes, and the mixing is carried out at a rotating speed of 2000 to 3000 r/min.
  • the water-based epoxy zinc-rich paint of the present invention reduces the consumption of zinc powder, uses water as a solvent, reduces the discharge of VOC, is environmentally friendly, has no pollution, and reduces production costs.
  • the water-based epoxy zinc-rich paint of the present invention has good flexibility, storage stability and adhesion, excellent water resistance, corrosion resistance and mechanical properties, and prolongs the service life.
  • the invention provides a graphene-type water-based epoxy zinc-rich coating, which comprises component A and component B with a mass ratio of 1.5 to 3:1;
  • the component A includes the following components by mass: 45-60 parts of zinc powder, 5-10 parts of polyamide curing agent, 0.05-0.1 part of defoamer, 0.1-0.5 part of dispersant, and 8-12 parts of water ;
  • the B component includes the following components in parts by mass: 70-80 parts of water-based epoxy resin emulsion, 3-7 parts of water-based graphene slurry, and 0.8-1.5 parts of functional additives.
  • the graphene-based waterborne epoxy zinc-rich coating of the present invention comprises component A and component B in a mass ratio of 1.5-3:1, preferably 1.75-2.75:1, more preferably 2-2.5:1.
  • the component A of the present invention contains 45-60 parts of zinc powder, preferably 48-57 parts, more preferably 50-55 parts, more preferably 52-54 parts.
  • the zinc powder of the present invention is preferably a mixture of flake zinc powder and spherical zinc powder; the mass ratio of the flake zinc powder to spherical zinc powder is preferably 2 to 3:10, more preferably 2.5:10; the zinc
  • the particle size of the powder is preferably 8-20 ⁇ m, more preferably 10-18 ⁇ m, more preferably 12-15 ⁇ m; the mixed use of flake zinc powder and spherical zinc powder in the present invention improves the contact area and shielding performance of the zinc powder.
  • the component A of the present invention contains 5-10 parts of polyamide curing agent, preferably 6-9 parts, more preferably 7-8 parts.
  • the solid content of the polyamide curing agent of the present invention is preferably 85-95%, more preferably 88-92%, more preferably 90%; the active hydrogen equivalent of the polyamide curing agent is preferably 220-280, More preferably, it is 240-260, More preferably, it is 245-255.
  • the polyamide curing agent of the present invention is an amide compound obtained by polycondensation reaction of azelaic acid and diphenylmethanediamine; the molar ratio of the azelaic acid and diphenylmethanediamine is preferably 1 to 2:1 ⁇ 2, more preferably 1:1; the temperature of the polycondensation reaction is preferably 90 ⁇ 110°C, and more preferably 1 ⁇ 3h; the polyamide curing agent of the present invention can shorten the curing time, and at room temperature Can be cured and the coating has good flexibility.
  • Component A of the present invention contains 0.05-0.1 part of defoamer, preferably 0.06-0.09 part, more preferably 0.07-0.08 part.
  • the defoamer of the present invention is preferably mineral oil, methyl silicone oil, tributyl phosphate or polyoxypropylene pentaerythritol ether.
  • Component A of the present invention contains 0.1-0.5 parts of dispersants, preferably 0.2-0.4 parts, more preferably 0.3 parts.
  • the dispersant of the present invention is preferably one or more of polyethylene glycol, polyglycerol and sodium tripolyphosphate; when the dispersant contains several components at the same time, each component is preferably mixed in an equal mass ratio.
  • the component A of the present invention contains 8-12 parts of water, preferably 9-11 parts, more preferably 10 parts.
  • the component B of the present invention contains 70-80 parts of water-based epoxy resin emulsion, preferably 72-78 parts, more preferably 74-76 parts.
  • the solid content of the water-based epoxy resin emulsion of the present invention is preferably 55-60%, more preferably 57-59%, more preferably 58%; the epoxy equivalent of the water-based epoxy resin emulsion is preferably 1200-1500, More preferably, it is 1300-1400, More preferably, it is 1330-1350.
  • the water-based epoxy resin emulsion of the present invention is used as a film-forming substance, which can reduce the phenomenon of demulsification caused by the migration of emulsion microspheres during the use of the emulsion, and improve the storage stability of the system; the water-based epoxy resin emulsion has a larger specific surface area, The number of hydroxyl groups on the surface is significantly increased, and the water resistance of the coating is improved.
  • Component B of the present invention comprises 3-7 parts of aqueous graphene slurry, preferably 4-6 parts, more preferably 5 parts.
  • the mass fraction of graphene is preferably 15-20%, more preferably 16-18%, more preferably 17%; the particle diameter of graphene is preferably 0.05-0.3 ⁇ m, further Preferably it is 0.1-0.25 micrometers, More preferably, it is 0.15-0.2 micrometers.
  • the invention utilizes water-based graphene slurry for modification, and in the case of reducing the amount of zinc powder, the coating has excellent electrical conductivity, thermal conductivity and corrosion resistance, and can also reduce the content of organic volatiles, and has environmental protection performance; water-based graphene The slurry can improve the flexibility, corrosion resistance and adhesion of the coating; the water-based graphene slurry, flaky zinc powder, and spherical zinc powder can be evenly dispersed in the coating, effectively avoiding the easy aggregation when directly adding graphene powder And the disadvantage of being difficult to disperse; the coating formed by water-based graphene slurry, spherical zinc powder and flake zinc powder is dense and has less pores, which together form a good conductive network and a continuous barrier layer, which prolongs the coating's resistance to water and oxygen in the environment.
  • the shielding path improves the cathodic protection effect of zinc powder, effectively blocks the corrosion of water, oxygen and carbon dioxide in the air, enhances the corrosion resistance of steel,
  • Component B of the present invention contains 0.8-1.5 parts of functional additives, preferably 1-1.4 parts, more preferably 1.2-1.3 parts.
  • the functional auxiliary agent described in the present invention is preferably one or more of 2-amino-2-methyl-1-pentanol, ethylene glycol ether, propylene glycol butyl ether and cellulose ether; when the functional auxiliary agent contains several When using different components, each component is preferably mixed in an equal mass ratio; the functional additives described in the present invention can not only improve the dispersion of pigments and fillers in the system, but also play a role in defoaming and thickening, and improve the water resistance of the coating. It can reduce the emission of organic solvents in the coating system.
  • the present invention also provides a kind of preparation method of described waterborne epoxy zinc-rich paint, comprises the steps:
  • component A 1) Mix zinc powder, polyamide curing agent, defoamer, dispersant and water to obtain component A;
  • component B 1) mixing water-based epoxy resin emulsion, water-based graphene slurry and functional additives to obtain component B;
  • the mixing time of step 1) of the present invention is preferably 10 to 20 minutes, more preferably 12 to 18 minutes, more preferably 14 to 16 minutes; the mixing is preferably carried out at a speed of 1200 to 1800 r/min, more preferably 1300 to 1700 r/min /min, more preferably 1400-1500r/min.
  • the mixing time of step 2) of the present invention is preferably 15-25 minutes, more preferably 18-22 minutes, more preferably 20 minutes; the mixing is preferably carried out at a speed of 1500-2500 r/min, more preferably 1700-2200 r/min , more preferably 1900-2100r/min.
  • the water-based epoxy zinc-rich paint of the present invention has good flexibility, adhesion, salt spray resistance, water resistance and impact resistance.
  • the storage stability and corrosion resistance of the water-based epoxy zinc-rich coating of the present invention are significantly improved, the mechanical properties are excellent, and the service life is prolonged; the water-based epoxy zinc-rich coating has no foaming, no wrinkling, no shedding, and no growth in water for 1300 hours Rust, salt spray resistance time ⁇ 2300h, flexibility ⁇ 1mm, impact resistance ⁇ 50cm.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Paints Or Removers (AREA)

Abstract

本发明属于涂料技术领域。本发明提供了一种石墨烯型水性环氧富锌涂料，包含质量比为1.5～3:1的A组分和B组分；A组分包含锌粉45～60份，聚酰胺类固化剂5～10份，消泡剂0.05～0.1份，分散剂0.1～0.5份，水8～12份；B组分包含水性环氧树脂乳液70～80份，水性石墨烯浆料3～7份，功能助剂0.8～1.5份。本发明还提供了一种石墨烯型水性环氧富锌涂料的制备方法。本发明的水性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；在水中1300h无起泡、无起皱、不脱落、不生锈，耐盐雾时间≥2300h，柔韧性≤1mm，耐冲击性≥50cm。

Description

一种石墨烯型水性环氧富锌涂料及其制备方法 技术领域
本发明涉及涂料技术领域，尤其涉及一种石墨烯型水性环氧富锌涂料及其制备方法。
背景技术
环氧富锌涂料是以环氧树脂、锌粉为主要原料，填料、助剂、溶剂等组成的特种涂料，其防腐性能优异，附着力强，具有阴极保护作用，适用于储罐、集装箱、钢结构、钢管、海洋平台、船舶、海港设施以及恶劣防腐蚀环境的涂层等。
目前，环氧富锌涂料多用于油性涂料，然而，油性的防腐涂料含有VOC的含量较高，会使涂层含有多孔结构，导致其性能变差。水性环氧富锌涂料因其环保型和高耐腐蚀性的优点，在重防腐蚀领域具有广阔的前景。石墨烯的原子之间连接柔韧性好，当碳原子面受到外力时变形弯曲，但碳原子的位置不发生重新排列。同时石墨烯的层层叠加可以形成致密的隔绝层，抑制外界水对漆膜的浸润和渗透，进而起到防腐的作用。但是，将石墨烯应用到水性环氧富锌涂料中，锌粉和石墨烯的密度存在较大差异，造成石墨烯在涂层结构中呈现梯度分布，不仅会影响涂料的附着力，更会影响涂料的抗水渗透能力，导致水性环氧富锌涂料的防腐性能不足。
因此，研究开发一种同时提升防腐性能、附着力、分散均匀性和柔韧性，并且降低锌含量和VOC含量的水性环氧富锌涂料，具有重要的经济价值和环保意义。
发明内容
本发明的目的是针对现有技术的不足提供一种石墨烯型水性环氧富锌涂料及其制备方法。本发明的水性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。本发明的水性环氧富锌涂料在水中1300h无起泡、无起皱、不脱落、不生锈，耐盐雾时间≥2300h，柔韧性≤1mm，耐冲击性≥50cm。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种石墨烯型水性环氧富锌涂料，包含质量比为1.5～3:1的A组分和B组分；
所述A组分包含如下质量份的组分：锌粉45～60份，聚酰胺类固化剂5～10份，消泡剂0.05～0.1份，分散剂0.1～0.5份，水8～12份；
所述B组分包含如下质量份的组分：水性环氧树脂乳液70～80份，水性石墨烯浆料3～7份，功能助剂0.8～1.5份。
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2～3:10；所述锌粉的粒径为8～20μm。
作为优选，所述聚酰胺类固化剂的固含量为85～95％，活泼氢当量为220～280；所述水性环氧树脂乳液的固含量为55～60％，环氧当量为1200～1500。
作为优选，所述消泡剂为矿物油、甲基硅油、磷酸三丁酯或聚氧丙烯季戊四醇醚。
作为优选，所述分散剂为聚乙二醇、聚丙三醇和三聚磷酸钠中的一种或几种。
作为优选，所述水性石墨烯浆料中，石墨烯的质量分数为15～20％，石墨烯的粒径为0.05～0.3μm。
作为优选，所述功能助剂为2-氨基-2-甲基-1-戊醇、乙二醇乙醚、丙二醇丁醚和纤维素醚中的一种或几种。
本发明还提供了一种所述的水性环氧富锌涂料的制备方法，包含如下步骤：
1)将锌粉、聚酰胺类固化剂、消泡剂、分散剂和水混合，得到A组分；
2)将水性环氧树脂乳液、水性石墨烯浆料和功能助剂混合，得到B组分；
3)将A组分和B组分混合，得到石墨烯型水性环氧富锌涂料。
作为优选，步骤1)所述混合的时间为10～20min，所述混合在1200～1800r/min的转速下进行；步骤2)所述混合的时间为15～25min，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2000～3000r/min的转速下进行。
本发明的有益效果包括以下几点：
1)本发明的水性环氧富锌涂料减少了锌粉的用量，以水作为溶剂，减少了VOC的排放量，绿色环保，无污染，降低了生产成本。
2)本发明的水性环氧富锌涂料具有良好的柔韧性、贮存稳定性和附着力，耐水、耐腐蚀性能和力学性能优异，使用寿命延长。
具体实施方式
本发明提供了一种石墨烯型水性环氧富锌涂料，包含质量比为1.5～3：1的A组分和B组分；
所述A组分包含如下质量份的组分：锌粉45～60份，聚酰胺类固化剂5～10份，消泡剂0.05～0.1份，分散剂0.1～0.5份，水8～12份；
所述B组分包含如下质量份的组分：水性环氧树脂乳液70～80份，水性石墨烯浆料3～7份，功能助剂0.8～1.5份。
本发明的石墨烯型水性环氧富锌涂料包含质量比为1.5～3：1的A组分和B组分，优选为1.75～2.75：1，进一步优选为2～2.5：1。
本发明的A组分包含45～60份锌粉，优选为48～57份，进一步优选为50～55份，更优选为52～54份。
本发明所述锌粉优选为片状锌粉和球状锌粉的混合物；所述片状锌粉和球状锌粉的质量比优选为2～3:10，进一步优选为2.5:10；所述锌粉的粒径优选为8～20μm，进一步优选为10～18μm，更优选为12～15μm；本发明将片状锌粉、球状锌粉混合使用提高了锌粉接触面积和屏蔽性能。
本发明的A组分包含5～10份聚酰胺类固化剂，优选为6～9份，进一步优选为7～8份。
本发明所述聚酰胺类固化剂的固含量优选为85～95％，进一步优选为88～92％，更优选为90％；所述聚酰胺类固化剂的活泼氢当量优选为220～280，进一步优选为240～260，更优选为245～255。
本发明所述聚酰胺类固化剂是由壬二酸和二苯基甲烷二胺进行缩聚反应而得的酰胺类化合物；所述壬二酸和二苯基甲烷二胺的摩尔比优选为1～2:1～2，进一步优选为1:1；所述缩聚反应的温度优选为90～110℃，进一步优选为时间为1～3h；本发明的聚酰胺类固化剂能够缩小固化时间，室温下能 够固化，涂层柔韧性好。
本发明的A组分包含0.05～0.1份消泡剂，优选为0.06～0.09份，进一步优选为0.07～0.08份。
本发明所述消泡剂优选为矿物油、甲基硅油、磷酸三丁酯或聚氧丙烯季戊四醇醚。
本发明的A组分包含0.1～0.5份分散剂，优选为0.2～0.4份，进一步优选为0.3份。
本发明所述分散剂优选为聚乙二醇、聚丙三醇和三聚磷酸钠中的一种或几种；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。
本发明的A组分包含8～12份水，优选为9～11份，进一步优选为10份。
本发明的B组分包含70～80份水性环氧树脂乳液，优选为72～78份，进一步优选为74～76份。
本发明所述水性环氧树脂乳液的固含量优选为55～60％，进一步优选为57～59％，更优选为58％；所述水性环氧树脂乳液的环氧当量优选为1200～1500，进一步优选为1300～1400，更优选为1330～1350。
本发明的水性环氧树脂乳液作为成膜物质，可以降低乳液在使用过程中因乳液微球发生迁移而导致破乳的现象，提高体系的贮存稳定性；水性环氧树脂乳液比表面积较大，表面羟基数明显提高，涂料耐水性得到提高。
本发明的B组分包含3～7份水性石墨烯浆料，优选为4～6份，进一步优选为5份。
本发明所述水性石墨烯浆料中，石墨烯的质量分数优选为15～20％，进一步优选为16～18％，更优选为17％；石墨烯的粒径优选为0.05～0.3μm，进一步优选为0.1～0.25μm，更优选为0.15～0.2μm。
本发明利用水性石墨烯浆料进行改性，在降低锌粉用量的情况下，使涂料具有优异的导电性、导热性和防腐性，还可以降低有机挥发物含量，具有环保性能；水性石墨烯浆料能够提升涂层的柔韧性、耐腐蚀性和附着力；水性石墨烯浆料和片状锌粉、球状锌粉能够均匀分散在涂料中，有效避免了直接添加石墨烯粉体时容易凝聚和难以分散的缺点；水性石墨烯浆料与球状锌粉和片状锌粉形成的涂层致密且孔隙较少，共同形成良好的导电网络和连续 阻隔层，延长涂层对环境中水和氧气的屏蔽路径，提高了锌粉的阴极保护效果，同时有效阻挡空气中的水、氧气和二氧化碳的腐蚀作用，增强了钢材的耐腐蚀性，提高防腐涂层的使用寿命。
本发明的B组分包含0.8～1.5份功能助剂，优选为1～1.4份，进一步优选为1.2～1.3份。
本发明所述功能助剂优选为2-氨基-2-甲基-1-戊醇、乙二醇乙醚、丙二醇丁醚和纤维素醚中的一种或几种；当功能助剂同时包含几种组分时，各组分优选以等质量比进行混合；本发明所述功能助剂不仅能够提高颜填料在体系中的分散性，也能够起到消泡、增稠作用，提高涂料的耐水性，减少涂料体系中有机溶剂排放量。
本发明还提供了一种所述的水性环氧富锌涂料的制备方法，包含如下步骤：
1)将锌粉、聚酰胺类固化剂、消泡剂、分散剂和水混合，得到A组分；
2)将水性环氧树脂乳液、水性石墨烯浆料和功能助剂混合，得到B组分；
3)将A组分和B组分混合，得到石墨烯型水性环氧富锌涂料。
本发明步骤1)所述混合的时间优选为10～20min，进一步优选为12～18min，更优选为14～16min；所述混合优选在1200～1800r/min的转速下进行，进一步优选1300～1700r/min，更优选1400～1500r/min。
本发明步骤2)所述混合的时间优选为15～25min，进一步优选为18～22min，更优选为20min；所述混合优选在1500～2500r/min的转速下进行，进一步优选1700～2200r/min，更优选1900～2100r/min。
本发明步骤3)所述混合的时间优选为5～10min，进一步优选为6～8min，更优选为7min；所述混合优选在2000～3000r/min的转速下进行，进一步优选2200～2800r/min，更优选2400～2600r/min；本发明步骤3)优选为将A组分和B组分混合得到涂料后立即使用；所述A组分和B组分的质量比优选为1.5～3:1，进一步优选为2～2.5:1。
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。
实施例1
将0.8kg片状锌粉(粒径为10μm)、4kg球状锌粉(粒径为8μm)、0.5kg聚酰胺类固化剂(固含量为85％，活泼氢当量为230)、0.005kg矿物油、0.01kg聚乙二醇和0.8kg水在1200r/min的转速下混合18min，得到均匀的A组分。将7kg水性环氧树脂乳液(固含量为55％，环氧当量为1250)、0.3kg水性石墨烯浆料(石墨烯的质量分数为16％，石墨烯的粒径为0.07μm)和0.08kg 2-氨基-2-甲基-1-戊醇在1600r/min的转速下混合25min，得到均匀的B组分，将质量比为1.5：1的A组分和B组分在2100r/min的转速下混合5min，得到石墨烯型水性环氧富锌涂料。
实施例2
将1.3kg片状锌粉(粒径为19μm)、4.5kg球状锌粉(粒径为18μm)、1kg聚酰胺类固化剂(固含量为95％，活泼氢当量为280)、0.005kg磷酸三丁酯、0.005kg聚氧丙烯季戊四醇醚、0.025kg聚丙三醇、0.025kg三聚磷酸钠和1.2kg水在1800r/min的转速下混合12min，得到均匀的A组分。将8kg水性环氧树脂乳液(固含量为60％，环氧当量为1500)、0.7kg水性石墨烯浆料(石墨烯的质量分数为20％，石墨烯的粒径为0.28μm)、0.5kg乙二醇乙醚和1kg丙二醇丁醚在2400r/min的转速下混合16min后，得到均匀的B组分，将质量比为2.8：1的A组分和B组分在3000r/min的转速下混合10min，得到石墨烯型水性环氧富锌涂料。
实施例3
将1kg片状锌粉(粒径为16μm)、4kg球状锌粉(粒径为15μm)、0.8kg聚酰胺类固化剂(固含量为90％，活泼氢当量为260)、0.008kg聚氧丙烯季戊四醇醚、0.04kg聚丙三醇和1kg水在1600r/min的转速下混合16min，得到均匀的A组分。将7.6kg水性环氧树脂乳液(固含量为58％，环氧当量为1400)、0.5kg水性石墨烯浆料(石墨烯的质量分数为18％，石墨烯的粒径为0.25μm)和1.2kg纤维素醚在2100r/min的转速下混合20min，得到均匀的B组分，将质量比为2.5：1的A组分和B组分在2700r/min的转速下混合8min，得到石墨烯型水性环氧富锌涂料。
实施例4
将0.9kg片状锌粉(粒径为12μm)、4.5kg球状锌粉(粒径为12μm)、0.7kg聚酰胺类固化剂(固含量为88％，活泼氢当量为250)、0.006kg甲基硅油、0.03kg三聚磷酸钠和1kg水在1400r/min的转速下混合14min，得到均匀的A组分。将7.4kg水性环氧树脂乳液(固含量为56％，环氧当量为1300)、0.6kg水性石墨烯浆料(石墨烯的质量分数为17％，石墨烯的粒径为0.25μm)和1.1kg丙二醇丁醚在2000r/min的转速下混合18min，得到均匀的B组分，将质量比为2：1的A组分和B组分在2500r/min的转速下混合7min，得到石墨烯型水性环氧富锌涂料。
对实施例1～4的石墨烯型水性环氧富锌涂料的附着力、耐盐雾性能、耐水性、柔韧性、耐冲击性进行测试，结果如表1所示。
表1不同实施例的水性环氧富锌涂料的测试结果
Figure PCTCN2021139903-appb-000001
由表1可知，本发明的水性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。本发明的水性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；水性环氧富锌涂料在水中1300h无起泡、无起皱、不脱落、不生锈，耐盐雾时间≥2300h，柔韧性≤1mm，耐冲击性≥50cm。
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。

Claims (9)

  1. 一种石墨烯型水性环氧富锌涂料，其特征在于，包含质量比为1.5～3:1的A组分和B组分；
    所述A组分包含如下质量份的组分：锌粉45～60份，聚酰胺类固化剂5～10份，消泡剂0.05～0.1份，分散剂0.1～0.5份，水8～12份；
    所述B组分包含如下质量份的组分：水性环氧树脂乳液70～80份，水性石墨烯浆料3～7份，功能助剂0.8～1.5份。
  2. 根据权利要求1所述的水性环氧富锌涂料，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2～3:10；所述锌粉的粒径为8～20μm。
  3. 根据权利要求1或2所述的水性环氧富锌涂料，其特征在于，所述聚酰胺类固化剂的固含量为85～95％，活泼氢当量为220～280；所述水性环氧树脂乳液的固含量为55～60％，环氧当量为1200～1500。
  4. 根据权利要求3所述的水性环氧富锌涂料，其特征在于，所述消泡剂为矿物油、甲基硅油、磷酸三丁酯或聚氧丙烯季戊四醇醚。
  5. 根据权利要求4所述的水性环氧富锌涂料，其特征在于，所述分散剂为聚乙二醇、聚丙三醇和三聚磷酸钠中的一种或几种。
  6. 根据权利要求4或5所述的水性环氧富锌涂料，其特征在于，所述水性石墨烯浆料中，石墨烯的质量分数为15～20％，石墨烯的粒径为0.05～0.3μm。
  7. 根据权利要求6所述的水性环氧富锌涂料，其特征在于，所述功能助剂为2-氨基-2-甲基-1-戊醇、乙二醇乙醚、丙二醇丁醚和纤维素醚中的一种或几种。
  8. 权利要求1～7任意一项所述的水性环氧富锌涂料的制备方法，其特征在于，包含如下步骤：
    1)将锌粉、聚酰胺类固化剂、消泡剂、分散剂和水混合，得到A组分；
    2)将水性环氧树脂乳液、水性石墨烯浆料和功能助剂混合，得到第B组分；
    3)将A组分和B组分混合，得到石墨烯型水性环氧富锌涂料。
  9. 根据权利要求8所述的制备方法，其特征在于，步骤1)所述混合的 时间为10～20min，所述混合在1200～1800r/min的转速下进行；步骤2)所述混合的时间为15～25min，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2000～3000r/min的转速下进行。
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