阅读说明：本技术 一种石墨烯基无溶剂型环氧导静电防腐涂料及其制备方法和使用方法 (Graphene-based solvent-free epoxy static conductive anticorrosive paint and preparation method and use method thereof ) 是由 孟祖超 颜黎栋 白莹 于 2021-08-20 设计创作，主要内容包括：本发明公开了一种石墨烯基无溶剂型环氧导静电防腐涂料及其制备方法和使用方法,属于导静电涂料技术领域。所述石墨烯基无溶剂型环氧导静电防腐涂料包括：A组分：环氧树脂35～45份、环氧活性稀释剂5～10份、钛白粉5～10份、绢云母粉3～6份、高岭土5～8份、沉淀硫酸钡8～15份、磷酸锌5～10份、滑石粉2～4份、云母氧化铁灰10～15份和RGO-2,6二氨基吡啶-Co复合物0.1～0.6份；B组分：改性脂环胺固化剂。本发明采用工艺简单、成本低的制备方法,制得了性能优异的防腐涂料,且其使用方法简单,同时克服了现有材料中导电填料密度大、易迁移等不足。(The invention discloses a graphene-based solvent-free epoxy static conductive anticorrosive paint, and a preparation method and a use method thereof, and belongs to the technical field of static conductive paints. The graphene-based solvent-free epoxy static conductive anticorrosive paint comprises: the component A comprises: 35-45 parts of epoxy resin, 5-10 parts of epoxy active diluent, 5-10 parts of titanium dioxide, 3-6 parts of sericite powder, 5-8 parts of kaolin, 8-15 parts of precipitated barium sulfate, 5-10 parts of zinc phosphate, 2-4 parts of talcum powder, 10-15 parts of mica iron oxide ash and 0.1-0.6 part of RGO-2,6 diaminopyridine-Co compound; and B component: a modified alicyclic amine curing agent. The invention adopts a preparation method with simple process and low cost to prepare the anticorrosive paint with excellent performance, and the application method is simple, and simultaneously overcomes the defects of high density, easy migration and the like of the conductive filler in the existing material.)

1. The graphene-based solvent-free epoxy static conductive anticorrosive paint is characterized by comprising the following components in parts by weight:

the component A comprises: 35-45 parts of epoxy resin, 5-10 parts of epoxy active diluent, 5-10 parts of titanium dioxide, 3-6 parts of sericite powder, 5-8 parts of kaolin, 8-15 parts of precipitated barium sulfate, 5-10 parts of zinc phosphate, 2-4 parts of talcum powder, 10-15 parts of mica iron oxide ash and 0.1-0.6 part of RGO-2,6 diaminopyridine-Co compound;

and B component: a modified alicyclic amine curing agent.

2. The graphene-based solvent-free epoxy static conductive anticorrosive coating as claimed in claim 1, wherein the epoxy reactive diluent is polypropylene glycol diglycidyl ether epoxy diluent; the epoxy resin is E51 epoxy resin.

3. The graphene-based solvent-free epoxy static conductive anticorrosive paint as claimed in claim 1, wherein the component A further comprises 2-3 parts by weight of an auxiliary agent;

The auxiliary agent comprises: 0.3-0.5 part of thixotropic agent, 0.4-0.6 part of flatting agent, 0.9-1.2 parts of dispersing agent and 0.4-0.7 part of defoaming agent.

4. The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint as claimed in any one of claims 1 to 3, wherein the preparation method of the component A comprises the following steps:

uniformly mixing epoxy resin and a polypropylene glycol diglycidyl ether epoxy diluent to obtain a mixed system A, and continuously adding a dispersing agent, a thixotropic agent, a flatting agent and an antifoaming agent into the mixed system A while stirring to obtain a mixed system B; adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into the obtained mixed system B, and uniformly mixing to obtain a mixed system C; continuously adding titanium dioxide and precipitated barium sulfate into the obtained mixed system C to obtain a mixed system D;

and grinding the obtained mixed system D, adding glass beads, continuously grinding to uniform fineness, and filtering to remove the glass beads to obtain the component A.

5. The method of claim 4, wherein the RGO-2,6 diaminopyridine-Co complex is prepared by a method comprising the steps of:

In N methyl pyrrolidone, carrying out mixed reaction on acylated graphene and 2, 6-diaminopyridine to obtain a first-stage product, and drying; and carrying out reflux reaction on the obtained dried product at the first stage and cobalt acetate, and standing to obtain the RGO-2, 6-diaminopyridine-Co compound.

6. The preparation method according to claim 5, wherein the addition ratio of the acylated graphene, the 2,6 diaminopyridine and the cobalt acetate is 0.3-0.7 g: 3-5 g: 25-75 mg.

7. The preparation method according to claim 5, wherein the reaction temperature of the acylated graphene and the 2, 6-diaminopyridine is 100 to 140 ℃ and the reaction time is 20 to 40 min.

8. The preparation method according to claim 5, wherein the reflux reaction time is 1 to 3 hours.

9. The production method according to claim 5, wherein the acylated graphene is produced by reaction of graphene oxide and thionyl chloride;

wherein the reaction charge ratio of the graphene oxide to the thionyl chloride is 0.1-0.3 g: 70-100 mL;

the reaction temperature is 60-80 ℃, and the reaction time is 12-36 h.

10. The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint or the graphene-based solvent-free epoxy static conductive anticorrosive paint prepared by the preparation method of any one of claims 1 to 3 is characterized in that the component A and the component B are uniformly stirred according to the weight ratio of 2: 1-2.5: 1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a substrate when in use.

Technical Field

The invention belongs to the technical field of static conductive coatings, and relates to a graphene-based solvent-free epoxy static conductive anticorrosive coating, and a preparation method and a use method thereof.

Background

In recent years, with the increasing demand of China for petroleum, during the transportation, storage and filling processes of oil products, static electricity is often generated by friction between oil product molecules or between the oil products and a storage tank, and if the static electricity cannot be removed in time, when the voltage is increased to a certain degree, the static electricity discharge phenomenon occurs, so that disastrous accidents are caused. The conductive coating applied to the tank serves two main functions: firstly, prevent that static from gathering, guarantee the safety in the transportation, secondly prevent the corrosion of storage tank steel construction in long-time use. The epoxy resin has excellent corrosion resistance, mechanical property and chemical resistance, has small deformation shrinkage rate, shows good stability to most solvents, and has excellent bonding strength to the surfaces of various substrates, but the epoxy resin is an insulating material, has very high surface resistance and volume resistance, and cannot transfer charges, so that the research on the application of the epoxy anticorrosive paint with conductivity to the expansion of the epoxy paint is very important. Under the background, the epoxy static-conducting anticorrosive paint is produced at the same time, and the epoxy static-conducting anticorrosive paint has the greatest characteristic of reducing the corrosion rate and improving the anti-static effect of the storage tank.

The conductive filler is an important component of the conductive coating and has a large influence on the conductive coating, but the conventional metal fillers, carbon fillers, conductive fiber materials and other conductive fillers have the advantages and disadvantages, and graphene is suitable to be used as the excellent conductive filler due to the good conductivity of the graphene. At present, various graphene conductive anticorrosive coatings are prepared by using graphene and other conductive materials as conductive fillers, so that although the conductivity of the coatings is improved, the graphene is easy to agglomerate in the coatings, and the anticorrosive performance of the coatings is reduced.

Disclosure of Invention

In order to overcome the defects of the prior art, the invention aims to provide the graphene-based solvent-free epoxy static conductive anticorrosive paint, and the preparation method and the use method thereof, so that the problems of high density and easy migration of conductive fillers are solved while the conductive fillers are reduced to be put into preparation.

In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:

the invention discloses a graphene-based solvent-free epoxy static conductive anticorrosive paint which comprises the following components in parts by weight: the component A comprises: 35-45 parts of epoxy resin, 5-10 parts of epoxy active diluent, 5-10 parts of titanium dioxide, 3-6 parts of sericite powder, 5-8 parts of kaolin, 8-15 parts of precipitated barium sulfate, 5-10 parts of zinc phosphate, 2-4 parts of talcum powder, 10-15 parts of mica iron oxide ash and 0.1-0.6 part of RGO-2,6 diaminopyridine-Co compound; and B component: a modified alicyclic amine curing agent.

Preferably, the epoxy reactive diluent is a polypropylene glycol diglycidyl ether epoxy diluent.

Preferably, the epoxy resin is E51 epoxy resin.

Preferably, the component A also comprises 2-3 parts by weight of an auxiliary agent;

the auxiliary agent comprises: 0.3-0.5 part of thixotropic agent, 0.4-0.6 part of flatting agent, 0.9-1.2 parts of dispersing agent and 0.4-0.7 part of defoaming agent.

The invention discloses a preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint, wherein the preparation method of the component A comprises the following steps: uniformly mixing E51 epoxy resin and polypropylene glycol diglycidyl ether epoxy diluent to obtain a mixed system A, and continuously adding a dispersing agent, a thixotropic agent, a flatting agent and an antifoaming agent into the mixed system A while stirring to obtain a mixed system B; adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into the obtained mixed system B, and uniformly mixing to obtain a mixed system C; continuously adding titanium dioxide and precipitated barium sulfate into the obtained mixed system C to obtain a mixed system D; and grinding the obtained mixed system D, adding glass beads, continuously grinding to uniform fineness, and filtering to remove the glass beads to obtain the component A.

Preferably, the operating parameters to obtain the mixed system a are: stirring for 15min at the rotating speed of 500 r/min; the operating parameters of the resulting mixed system B were: the rotating speed is 600 r/min; the operating parameters of the resulting mixed system C were: stirring for 30min at the rotating speed of 1000 r/min; the operating parameters of the resulting mixed system D were: stirring at 1000r/min for 60 min.

Preferably, a sand grinding disc is adopted for stirring for 3 hours at 1500 r/min; the operation parameters of continuously grinding the glass beads to uniform fineness are as follows: stirring for 3h at 1500r/min by using a sand grinding disc.

Preferably, the method for preparing RGO-2,6 diaminopyridine-Co complexes comprises the steps of: in N methyl pyrrolidone, carrying out mixed reaction on acylated graphene and 2, 6-diaminopyridine to obtain a first-stage product, and drying; and carrying out reflux reaction on the obtained dried product at the first stage and cobalt acetate, and standing to obtain the RGO-2, 6-diaminopyridine-Co compound.

Further preferably, the addition ratio of the acylated graphene, the 2, 6-diaminopyridine and the cobalt acetate is 0.3-0.7 g: 3-5 g: 25-75 mg.

Further preferably, the reaction temperature of the acylated graphene and the 2, 6-diaminopyridine is 100-140 ℃, and the reaction time is 20-40 min.

Further preferably, the reflux reaction time is 1-3 h.

Further preferably, the acylated graphene is prepared by the reaction of graphene oxide and thionyl chloride;

wherein the reaction charge ratio of the graphene oxide to the thionyl chloride is 0.1-0.3 g: 70-100 mL;

the reaction temperature is 60-80 ℃, and the reaction time is 12-36 h.

Preferably, the particle size of the component A is 20-40 μm.

The invention discloses a using method of a graphene-based solvent-free epoxy static conductive anticorrosive paint, wherein a component A and a component B are uniformly stirred according to the weight part of 2: 1-2.5: 1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a substrate when in use.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a graphene-based solvent-free epoxy static conductive anticorrosive paint which has strong adhesive force to a tinplate substrate, and in addition, the combination of physical corrosion resistance and chemical corrosion resistance is realized by selecting mica iron oxide ash with low oil absorption as one of antirust pigments and selecting a chemical anticorrosive pigment zinc phosphate, so that the performance of the solvent-free epoxy anticorrosive paint is greatly improved. Meanwhile, on the basis of the solvent-free epoxy anticorrosive coating, the RGO-2,6 diaminopyridine-Co compound with good conductivity and dispersibility is added, so that the coating has static conductivity and corrosion resistance. Therefore, the graphene-based solvent-free epoxy static conductive anticorrosive coating has good adhesive force and hardness and better corrosion resistance.

The invention discloses a preparation method of the graphene-based solvent-free epoxy static-conducting anticorrosive coating, and the added conductive filler RGO-2, 6-diaminopyridine-Co ensures that the prepared material has good conductivity and good dispersibility in epoxy resin, so that the coating has good static-conducting capacity and corrosion resistance; and the addition of other conductive fillers is reduced, the cost investment of the preparation method is reduced, and the defects of high density, easy migration and the like of the conductive fillers in the existing material are overcome.

The invention also discloses a use method of the graphene self-repairing solvent-free epoxy anticorrosive coating, and a simple and efficient use mode can be realized through a reasonable mixing ratio, so that the use convenience of the material is improved.

Detailed Description

In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It is noted that the terms first, second and the like in the description and in the claims of the present invention are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

The invention discloses a graphene-based solvent-free epoxy static conductive anticorrosive paint which is mainly prepared from the following raw materials in parts by weight: the component A comprises: 35-45 parts of epoxy resin, 5-10 parts of epoxy active diluent, 5-10 parts of titanium dioxide, 3-6 parts of sericite powder, 5-8 parts of kaolin, 8-15 parts of precipitated barium sulfate, 5-10 parts of zinc phosphate, 2-4 parts of talcum powder, 10-15 parts of mica iron oxide ash and 0.1-0.6 part of RGO-2,6 diaminopyridine-Co compound; the component A also comprises 2-3 parts by weight of an auxiliary agent, wherein the auxiliary agent comprises 0.3-0.5 part of a thixotropic agent, 0.4-0.6 part of a flatting agent, 0.9-1.2 parts of a dispersing agent and 0.4-0.7 part of a defoaming agent. And B component: 100% of modified alicyclic amine curing agent. Wherein the epoxy reactive diluent is polypropylene glycol diglycidyl ether epoxy diluent, and the epoxy resin is E51 epoxy resin.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether epoxy diluent for 15min at the rotating speed of 500r/min in a reaction kettle;

2)adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3)adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4)continuously adding titanium dioxide and precipitated barium sulfate into the reaction kettle, continuously stirring for 60min, and then changing the sand and grinding disc to stir at 1500r/minAnd 3h, then changing a sand mill, adding the glass beads into the coating to obtain a proper particle size (the particle size is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The preparation method of the RGO-2,6 diaminopyridine-Co compound comprises the following steps:

firstly, 0.3-0.7 g of acylated graphene (acylated GO) and 3-5 g of 2, 6-diaminopyridine are mixed in N-methylpyrrolidone at 100-140 ℃ for 20-40 min to obtain a first-stage product, and then the first-stage product is dried. And then, carrying out reflux reaction on the obtained dried first-stage product and 25-75 mg of cobalt acetate with methanol for 1-3 h. The reaction flask was allowed to stand at room temperature (25 ℃) for 2 days to obtain the final product, i.e., RGO-2,6 diaminopyridine-Co complex.

When the acylated graphene is prepared, the addition amount of GO (graphene oxide) is 0.1-0.3 g, the addition amount of thionyl chloride is 70-100 mL, the reaction temperature is 60-80 ℃, the reaction time is 12-36 h, and the acylated graphene is obtained through reaction under the stirring condition.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive coating comprises the following steps: uniformly stirring the component A and the component B according to the weight ratio of 2: 1-2.5: 1, filtering and curing to obtain the graphene-based solvent-free epoxy static conductive anticorrosive paint, and uniformly coating the graphene-based solvent-free epoxy static conductive anticorrosive paint on the surface of a substrate.

The base metal is a tinplate with the length of 15cm and the width of 5 cm.

The invention is further illustrated by the following embodiments, wherein all the raw materials used in the following embodiments are raw materials commonly used in the market of the industry if no special indication is given; all the processing methods used in the following examples are general processing methods in the industry unless otherwise specified.

Example 1

In this embodiment, the filler functionalized graphene RGO-2,6 diaminopyridine-Co composite in the graphene-based solvent-free epoxy static conductive anticorrosive coating is prepared by the following method:

(1) Preparing acylated graphene: in a nitrogen atmosphere, 70mL of thionyl chloride is added to 0.1g of GO, and the mixture is refluxed at 60 ℃ for 12 hours to synthesize acylated GO. Five times anhydrous toluene and tetrahydrofuran were used during the washing of the acylated GO prepared. After washing and purification, the product is dried.

(2) Preparation of RGO-2,6 diaminopyridine-Co complexes: first, 0.3g of acylated GO was mixed with 3g of 2, 6-diaminopyridine in N-methylpyrrolidone at 100 ℃ for 20 min. Thereafter, 0.3g of the obtained dried product was reacted with 25mg of cobalt acetate with methanol under reflux for 1 hour. The reaction flask was kept at room temperature for 2 days to obtain the final product RGO-2,6 diaminopyridine-Co complex.

A graphene-based solvent-free epoxy static conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight: 36 parts of E51 epoxy resin, 7 parts of epoxy active diluent, 5 parts of sericite powder, 6 parts of kaolin, 3 parts of talcum powder, 10 parts of titanium dioxide, 10 parts of precipitated barium sulfate, 8 parts of zinc phosphate, 12 parts of mica iron oxide ash, 0.4 part of RGO-2,6 diaminopyridine-Co compound, 0.3 part of thixotropic agent, 0.4 part of flatting agent, 1 part of dispersing agent and 0.5 part of defoaming agent. The component B comprises the following raw materials: 100% alicyclic amine curing agent.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether in a reaction kettle at the rotating speed of 500r/min for 15 min;

2) adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3) adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4) adding titanium dioxide and precipitated barium sulfate into the reaction kettle continuously, stirring for 60min, then stirring for 3h at 1500r/min by using a sand changing millstone, then changing the sand changing millstone, adding glass beads into the coating so as to obtain proper granularity (the granularity is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps: the component A and the component B are uniformly stirred according to the weight ratio of 2:1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly smeared on the surface of a tinplate substrate when in use.

In the embodiment, the model of the leveling agent is BYK-361N; the type of the dispersant is BYK-ATU; the model of the defoaming agent is TEGO Airex 900; the thixotropic agent type is: polyamide wax powder, wherein the amine curing agent is modified alicyclic amine 1618; talcum powder, Lingshou county Peng Xian talcum powder factory; zinc phosphate, gallery silver horse pigment limited; precipitated barium sulfate, hebei barium abundance chemical products ltd; sericite powder, a pearl dragon Guangdong sericite powder factory in Chuzhou; kaolin, Shijiazhuang, Xinsheng chemical Co., Ltd; the added dosage of the titanium dioxide and Hebei pigment Only color Limited company is adjusted according to the industry general standard, of course, the protection scope of the invention is not limited to the specific types of the additives, and any prior art mixture ratio which can achieve the same or similar technical effect can be used.

Example 2

In this embodiment, the filler functionalized graphene in the graphene-based solvent-free epoxy static conductive anticorrosive coating is prepared by the following method:

(1) preparing acylated graphene: in a nitrogen atmosphere, 85mL of thionyl chloride is added to 0.2g of GO, and the mixture is refluxed at 70 ℃ for 24 hours to synthesize acylated GO. Five times anhydrous toluene and tetrahydrofuran were used during the washing of the acylated GO prepared. After washing and purification, the product is dried.

(2) Preparation of RGO-2,6 diaminopyridine-Co complexes: first, 0.5g of acylated GO was mixed with 4g of 2, 6-diaminopyridine in N-methylpyrrolidone at 120 ℃ for 30 min. Thereafter, 0.5g of the obtained dried product was reacted with 52mg of cobalt acetate with methanol under reflux for 2 hours. The reaction flask was kept at room temperature for 2 days to obtain the final product.

A graphene-based solvent-free epoxy static conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight: 36 parts of E51 epoxy resin, 7 parts of epoxy active diluent, 5 parts of sericite powder, 6 parts of kaolin, 3 parts of talcum powder, 10 parts of titanium dioxide, 10 parts of precipitated barium sulfate, 8 parts of zinc phosphate, 12 parts of mica iron oxide ash, 0.4 part of RGO-2,6 diaminopyridine-Co compound, 0.4 part of thixotropic agent, 0.5 part of flatting agent, 1 part of dispersing agent and 0.5 part of defoaming agent. The component B comprises the following raw materials: 100% alicyclic amine curing agent.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether in a reaction kettle at the rotating speed of 500r/min for 15 min;

2) adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3) Adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4) adding titanium dioxide and precipitated barium sulfate into the reaction kettle continuously, stirring for 60min, then stirring for 3h at 1500r/min by using a sand changing millstone, then changing the sand changing millstone, adding glass beads into the coating so as to obtain proper particle size (the particle size is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps: the component A and the component B are uniformly stirred according to the weight ratio of 2.2:1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a tinplate substrate when in use.

In the embodiment, the model of the leveling agent is BYK-361N; the type of the dispersant is BYK-ATU; the model of the defoaming agent is TEGO Airex 900; the thixotropic agent type is: polyamide wax powder, wherein the amine curing agent is modified alicyclic amine 1618; talcum powder, Lingshou county Peng Xian talcum powder factory; zinc phosphate, gallery silver horse pigment limited; precipitated barium sulfate, hebei barium abundance chemical products ltd; sericite powder, a pearl dragon Guangdong sericite powder factory in Chuzhou; kaolin, Shijiazhuang, Xinsheng chemical Co., Ltd; the added dosage of the titanium dioxide and Hebei pigment Only color Limited company is adjusted according to the industry general standard, of course, the protection scope of the invention is not limited to the specific types of the additives, and any prior art mixture ratio which can achieve the same or similar technical effect can be used.

Example 3

In this embodiment, the filler functionalized graphene RGO-2,6 diaminopyridine-Co composite in the graphene-based solvent-free epoxy static conductive anticorrosive coating is prepared by the following method:

(1) preparing acylated graphene: in a nitrogen atmosphere, 90mL of thionyl chloride is added to 0.15g of GO, and the mixture is refluxed at 65 ℃ for 18 hours to synthesize acylated GO. Five times anhydrous toluene and tetrahydrofuran were used during the washing of the acylated GO prepared. After washing and purification, the product is dried.

(2) Preparation of RGO-2,6 diaminopyridine-Co complexes: first, 0.4g of acylated GO was mixed with 3.5g of 2, 6-diaminopyridine in N-methylpyrrolidone at 110 ℃ for 40 min. Thereafter, 0.3g of the obtained dried product was reacted with 32mg of cobalt acetate with methanol under reflux for 1 hour. The reaction flask was kept at room temperature for 2 days to obtain the final product RGO-2,6 diaminopyridine-Co complex.

A graphene-based solvent-free epoxy static conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight: the component A comprises: 35 parts of E51 epoxy resin, 5 parts of epoxy active diluent, 3 parts of sericite powder, 5 parts of kaolin, 2 parts of talcum powder, 5 parts of titanium dioxide, 15 parts of precipitated barium sulfate, 5 parts of zinc phosphate, 15 parts of mica iron oxide ash, 0.1 part of RGO-2,6 diaminopyridine-Co compound, 0.35 part of thixotropic agent, 0.45 part of flatting agent, 0.9 part of dispersing agent and 0.4 part of defoaming agent. The component B comprises the following raw materials: 100% alicyclic amine curing agent.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether in a reaction kettle at the rotating speed of 500r/min for 15 min;

2) adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3) adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4) adding titanium dioxide and precipitated barium sulfate into the reaction kettle continuously, stirring for 60min, then stirring for 3h at 1500r/min by using a sand changing millstone, then changing the sand changing millstone, adding glass beads into the coating so as to obtain proper particle size (the particle size is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps: the component A and the component B are uniformly stirred according to the weight ratio of 2.3:1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a tinplate substrate when in use.

In the embodiment, the model of the leveling agent is BYK-361N; the type of the dispersant is BYK-ATU; the model of the defoaming agent is TEGO Airex 900; the thixotropic agent type is: polyamide wax powder, wherein the amine curing agent is modified alicyclic amine 1618; talcum powder, Lingshou county Peng Xian talcum powder factory; zinc phosphate, gallery silver horse pigment limited; precipitated barium sulfate, hebei barium abundance chemical products ltd; sericite powder, a pearl dragon Guangdong sericite powder factory in Chuzhou; kaolin, Shijiazhuang, Xinsheng chemical Co., Ltd; the added dosage of the titanium dioxide and Hebei pigment Only color Limited company is adjusted according to the industry general standard, of course, the protection scope of the invention is not limited to the specific types of the additives, and any prior art mixture ratio which can achieve the same or similar technical effect can be used.

Example 4

In this embodiment, the filler functionalized graphene in the graphene-based solvent-free epoxy static conductive anticorrosive coating is prepared by the following method:

(1) preparing acylated graphene: in a nitrogen atmosphere, 95mL of thionyl chloride is added into 0.25g of GO, and the mixture is refluxed for 20 hours at 75 ℃ to synthesize acylated GO. Five times anhydrous toluene and tetrahydrofuran were used during the washing of the acylated GO prepared. After washing and purification, the product is dried.

(2) Preparation of RGO-2,6 diaminopyridine-Co complexes: first, 0.6g of acylated GO was mixed with 4.5g of 2, 6-diaminopyridine in N-methylpyrrolidone at 130 ℃ for 35 min. Thereafter, 0.5g of the obtained dried product was reacted with 67mg of cobalt acetate with methanol under reflux for 2 hours. The reaction flask was kept at room temperature for 2 days to obtain the final product.

A graphene-based solvent-free epoxy static conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight: the component A comprises: 39 parts of E51 epoxy resin, 10 parts of epoxy active diluent, 4 parts of sericite powder, 7 parts of kaolin, 4 parts of talcum powder, 6.5 parts of titanium dioxide, 8 parts of precipitated barium sulfate, 6.5 parts of zinc phosphate, 10 parts of mica iron oxide ash, 0.2 part of RGO-2,6 diaminopyridine-Co compound, 0.45 part of thixotropic agent, 0.55 part of flatting agent, 1.2 parts of dispersing agent and 0.7 part of defoaming agent. The component B comprises the following raw materials: 100% alicyclic amine curing agent.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether in a reaction kettle at the rotating speed of 500r/min for 15 min;

2) adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3) Adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4) adding titanium dioxide and precipitated barium sulfate into the reaction kettle continuously, stirring for 60min, then stirring for 3h at 1500r/min by using a sand changing millstone, then changing the sand changing millstone, adding glass beads into the coating so as to obtain proper particle size (the particle size is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps: the component A and the component B are uniformly stirred according to the weight ratio of 2.1:1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a tinplate substrate when in use.

In the embodiment, the model of the leveling agent is BYK-361N; the type of the dispersant is BYK-ATU; the model of the defoaming agent is TEGO Airex 900; the thixotropic agent type is: polyamide wax powder, wherein the amine curing agent is modified alicyclic amine 1618; talcum powder, Lingshou county Peng Xian talcum powder factory; zinc phosphate, gallery silver horse pigment limited; precipitated barium sulfate, hebei barium abundance chemical products ltd; sericite powder, a pearl dragon Guangdong sericite powder factory in Chuzhou; kaolin, Shijiazhuang, Xinsheng chemical Co., Ltd; the added dosage of the titanium dioxide and Hebei pigment Only color Limited company is adjusted according to the industry general standard, of course, the protection scope of the invention is not limited to the specific types of the additives, and any prior art mixture ratio which can achieve the same or similar technical effect can be used.

Example 5

In this embodiment, the filler functionalized graphene in the graphene-based solvent-free epoxy static conductive anticorrosive coating is prepared by the following method:

(1) preparing acylated graphene: in a nitrogen atmosphere, 80mL of thionyl chloride is added to 0.28g of GO, and the mixture is refluxed at 80 ℃ for 30 hours to synthesize acylated GO. Five times anhydrous toluene and tetrahydrofuran were used during the washing of the acylated GO prepared. After washing and purification, the product is dried.

(2) Preparation of RGO-2,6 diaminopyridine-Co complexes: first, 0.45g of acylated GO was mixed with 5g of 2, 6-diaminopyridine in N-methylpyrrolidone at 135 ℃ for 25 min. Thereafter, 0.5g of the obtained dried product was reacted with 40mg of cobalt acetate with methanol under reflux for 3 hours. The reaction flask was kept at room temperature for 2 days to obtain the final product.

A graphene-based solvent-free epoxy static conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight: the component A comprises: 45 parts of E51 epoxy resin, 8.5 parts of epoxy active diluent, 6 parts of sericite powder, 8 parts of kaolin, 2.5 parts of talcum powder, 8 parts of titanium dioxide, 12 parts of precipitated barium sulfate, 10 parts of zinc phosphate, 13.5 parts of mica iron oxide ash, 0.5 part of RGO-2,6 diaminopyridine-Co compound, 0.5 part of thixotropic agent, 0.6 part of flatting agent, 1.1 part of dispersing agent and 0.6 part of defoaming agent. The component B comprises the following raw materials: 100% alicyclic amine curing agent.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether in a reaction kettle at the rotating speed of 500r/min for 15 min;

2) adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3) adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4) adding titanium dioxide and precipitated barium sulfate into the reaction kettle continuously, stirring for 60min, then stirring for 3h at 1500r/min by using a sand changing millstone, then changing the sand changing millstone, adding glass beads into the coating so as to obtain proper particle size (the particle size is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps: the component A and the component B are uniformly stirred according to the weight ratio of 2.5:1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a tinplate substrate when in use.

Example 6

In this embodiment, the filler functionalized graphene in the graphene-based solvent-free epoxy static conductive anticorrosive coating is prepared by the following method:

(1) preparing acylated graphene: in a nitrogen atmosphere, 100mL of thionyl chloride is added into 0.3g of GO, and the mixture is refluxed for 36 hours at 80 ℃ to synthesize acylated GO. Five times anhydrous toluene and tetrahydrofuran were used during the washing of the acylated GO prepared. After washing and purification, the product is dried.

(2) Preparation of RGO-2,6 diaminopyridine-Co complexes: first, 0.7g of acylated GO was mixed with 5g of 2, 6-diaminopyridine in N-methylpyrrolidone at 140 ℃ for 40 min. Thereafter, 0.5g of the obtained dried product was reacted with 75mg of cobalt acetate with methanol under reflux for 3 hours. The reaction flask was kept at room temperature for 2 days to obtain the final product.

A graphene-based solvent-free epoxy static conductive anticorrosive paint is mainly prepared from the following raw materials in parts by weight: the component A comprises: 36 parts of E51 epoxy resin, 7 parts of epoxy active diluent, 5 parts of sericite powder, 6 parts of kaolin, 3 parts of talcum powder, 10 parts of titanium dioxide, 10 parts of precipitated barium sulfate, 8 parts of zinc phosphate, 12 parts of mica iron oxide ash, 0.6 part of RGO-2,6 diaminopyridine-Co compound, 0.4 part of thixotropic agent, 0.5 part of flatting agent, 1 part of dispersing agent and 0.5 part of defoaming agent. The component B comprises the following raw materials: 100% alicyclic amine curing agent.

The preparation method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps:

1) stirring E51 epoxy resin and polypropylene glycol diglycidyl ether in a reaction kettle at the rotating speed of 500r/min for 15 min;

2) adding the dispersing agent, the thixotropic agent, the flatting agent and the defoaming agent while stirring at the rotating speed of 600 r/min;

3) adding sericite powder, kaolin, RGO-2,6 diaminopyridine-Co compound, mica iron oxide ash and zinc phosphate into a reaction kettle, and continuously stirring for 30min at the rotating speed of 1000 r/min;

4) adding titanium dioxide and precipitated barium sulfate into the reaction kettle continuously, stirring for 60min, then stirring for 3h at 1500r/min by using a sand changing millstone, then changing the sand changing millstone, adding glass beads into the coating so as to obtain proper particle size (the particle size is less than or equal to 40 mu m and more than or equal to 20 mu m) in the coating, stirring for 3h at 1500r/min to uniform fineness, and then filtering to remove the glass beads to obtain the component A.

The use method of the graphene-based solvent-free epoxy static conductive anticorrosive paint comprises the following steps: the component A and the component B are uniformly stirred according to the weight ratio of 2.5:1, then the graphene-based solvent-free epoxy static conductive anticorrosive paint is obtained after filtration and curing treatment, and the obtained graphene-based solvent-free epoxy static conductive anticorrosive paint is uniformly coated on the surface of a tinplate substrate when in use.

In the embodiment, the model of the leveling agent is BYK-361N; the type of the dispersant is BYK-ATU; the model of the defoaming agent is TEGO Airex 900; the thixotropic agent type is: polyamide wax powder, wherein the amine curing agent is modified alicyclic amine 1618; talcum powder, Lingshou county Peng Xian talcum powder factory; zinc phosphate, gallery silver horse pigment limited; precipitated barium sulfate, hebei barium abundance chemical products ltd; sericite powder, a pearl dragon Guangdong sericite powder factory in Chuzhou; kaolin, Shijiazhuang, Xinsheng chemical Co., Ltd; the added dosage of the titanium dioxide and Hebei pigment Only color Limited company is adjusted according to the industry general standard, of course, the protection scope of the invention is not limited to the specific types of the additives, and any prior art mixture ratio which can achieve the same or similar technical effect can be used.

TABLE 1-1 conductivity of graphene-based solvent-free epoxy static conductive anticorrosive coatings with various addition amounts of RGO-2,6 diaminopyridine-Co composite

TABLE 1-2 physicochemical Properties of the coatings and coatings

In conclusion, the invention discloses a graphene-based solvent-free epoxy static conductive anticorrosive paint, and a preparation method and a use method thereof. The graphene-based solvent-free epoxy static conductive anticorrosive paint consists of epoxy resin, an epoxy diluent, various auxiliaries and a filler. The graphene oxide is partially reduced, so that part of oxygen-containing functional groups are removed, most of the electric conductivity is recovered, meanwhile, the electric conductivity of the graphene oxide is further enhanced by using a functional group in a metal atom coordination form, and the graphene oxide is added into a solvent-free epoxy anticorrosive paint to prepare the graphene-based solvent-free epoxy static-conducting anticorrosive paint.

The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.