CN110343455B - Water-based heavy-duty anticorrosive coating containing silane coupling agent modified graphene, preparation method and application - Google Patents

Water-based heavy-duty anticorrosive coating containing silane coupling agent modified graphene, preparation method and application Download PDF

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CN110343455B
CN110343455B CN201810290270.9A CN201810290270A CN110343455B CN 110343455 B CN110343455 B CN 110343455B CN 201810290270 A CN201810290270 A CN 201810290270A CN 110343455 B CN110343455 B CN 110343455B
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silane coupling
coupling agent
water
graphene
heavy
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CN110343455A (en
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梁文涛
吴绍臣
韩琳
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Dalian Lichuang New Material Science & Technology Development Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • 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

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Abstract

The invention relates to a water-based heavy-duty coating, which comprises A) water-based industrial resin; and B) a silane coupling agent-modified graphene, wherein the amount of component B) is from 0.1 to 1.0% by weight, based on the amount of component A), and the amounts of components A) and B) add up to 100% by weight, wherein the weight ratio of silane coupling agent to graphene is from 2.0 to 7.0: 1. The invention also relates to a method for preparing the water-based heavy-duty anticorrosive coating and application of the water-based heavy-duty anticorrosive coating in the infrastructure, oil gas and power industries, industrial tanks, ships and chemical industries.

Description

Water-based heavy-duty anticorrosive coating containing silane coupling agent modified graphene, preparation method and application
Technical Field
The invention belongs to the field of coatings, and particularly relates to an industrial anticorrosive coating, especially a water-based heavy-duty anticorrosive coating, and a preparation method and application thereof.
Background
The industrial anticorrosive paint is widely applied to the fields of modern industry, traffic, energy, ocean engineering and the like. In recent decades, China has successfully developed a plurality of industrial anticorrosive paint products. At present, the market scale of industrial anticorrosive paint in China is second to that of building paint. According to statistics, the total yield of industrial anticorrosive paint in China in 2017 reaches about 600 ten thousand tons, and the data is continuously increased in the future. At present, although the market application range of the industrial anticorrosive paint in China is wide, the industrial anticorrosive paint has the limitations of high product homogeneity degree, low technical content and the like, and the use of the solvent-based industrial paint is increasingly limited with the increasing attention of human beings on environmental and health problems, so that the future industrial anticorrosive paint is bound to develop towards the directions of product refinement, clean production, paint coating integration, water-based, high curing and solvent-free.
As an important variety of environment-friendly industrial coatings, the water-based industrial anticorrosive coatings have been developed for decades abroad, and at present, the water-based industrial anticorrosive coatings permeate into the application fields of traditional solvent-based industrial coatings such as automobiles, steel structures, bridges, household appliances and the like at an unprecedented speed, and have a completely-substituted trend. With the implementation of environmental regulations in the european union and north american free trade agreements countries, the technological growth rate of waterborne industrial coatings significantly exceeds that of solvent-based coatings.
Although research and development and scale production of the water-based industrial coating in China have been carried out for over a decade, the improvement space is still large. In recent years, advanced water-based resin products and coating technologies abroad enter the coating market in China, and attention is paid to new product development of water-based coatings in China, so that the development and application of water-based coatings in China, particularly water-based industrial coatings, are driven.
Heavy-duty anticorrosive coatings refer to anticorrosive coatings that can be applied in relatively harsh corrosive environments compared to conventional anticorrosive coatings and have a longer protection period than conventional anticorrosive coatings. The water-based heavy-duty coating is an important branch of the development of water-based industrial coatings, the former heavy-duty coating fields like petrochemical industry, ship manufacturing and bridges and the like are monopolized by solvent-based heavy-duty coatings, and the water-based heavy-duty coating products are hardly applied, mainly because the performance of the current water-based industrial coatings has a certain difference with the solvent-based heavy-duty coatings.
There is a literature in the prior art that studies the use of graphene to prepare aqueous industrial coatings to improve some of the properties of the coatings. CN 105670474A relates to a graphene water-based industrial coating, which comprises the following substances: emulsion, graphene dispersion liquid, ammonia neutralizer, defoaming agent, wetting agent, leveling agent, color paste, thickening agent and water, wherein the prepared water-based industrial coating has excellent performance by utilizing various performances of graphene, such as huge specific surface area, special two-dimensional structure, high stability, high strength capability and excellent conductivity; but there is no teaching of modifying graphene, let alone modifying it with a silane coupling agent.
CN 107523201 a discloses a method for preparing a light-resistant aqueous coating by using graphene, wherein it is disclosed that graphene is used to improve light resistance and wear resistance of an aqueous industrial coating and increase elongation at break of a film formed by the aqueous coating, and is a grafted graphene solution prepared by using graphene oxide and a silane coupling agent; however, the advantages of the aqueous industrial resin, not to mention the advantages of the aqueous coating prepared by grafting the graphene and the aqueous industrial resin, are not mentioned. The conditions for preparing the grafted graphene using graphene oxide and a silane coupling agent are broadly described therein, however, the conditions may be further improved to obtain the grafted graphene for preparing a more excellent aqueous coating material.
Thus, there is still a further improvement with respect to the use of graphene for the preparation of aqueous industrial coatings, resulting in aqueous coatings which are improved at least in some properties.
Disclosure of Invention
The invention aims to provide a water-based heavy-duty anticorrosive coating with excellent performance, in particular to a water-based heavy-duty anticorrosive coating with excellent mechanical strength, salt mist resistance and chemical resistance.
The object of the present invention is achieved by providing a novel aqueous heavy duty coating comprising:
A) an aqueous industrial resin;
B) a silane coupling agent-modified graphene, which is a graphene,
wherein the amount of component B) is from 0.1 to 1.0% by weight, based on the amount of component A),
and the amounts of components A) and B) add up to 100% by weight,
wherein the weight ratio of the silane coupling agent to the graphene is 2.0-7.0: 1.
Another object of the present invention is to provide a method for preparing the above aqueous heavy duty anticorrosive coating, comprising:
1) preparing component B) silane coupling agent modified graphene by the following procedure:
a) adding a silane coupling agent into a dispersion system of graphene oxide in a solvent at the temperature of 45-70 ℃, heating to the temperature of 90-110 ℃, and preserving the heat for 20-40 hours at the temperature to obtain a mixture a;
b) cooling the mixture a obtained in the step a) to 50-70 ℃, adding a reducing agent into the mixture a, and preserving the heat for 1.5-3.5 hours to obtain a product b;
c) removing the solvent of the product b obtained in the step b) to obtain the needed silane coupling agent modified graphene;
2) 0.1 to 1.0 wt.%, based on the amount of the component A), of the component B) silane coupling agent modified graphene obtained in step 1) is added to the aqueous industrial resin of the component A), thereby obtaining an aqueous heavy-duty anticorrosive coating.
The water-based heavy-duty anticorrosive coating has excellent adhesive force, acid and alkali resistance, salt fog resistance and chemical resistance, particularly has excellent performance on the salt fog resistance, can achieve no change of a paint film for more than 1000 hours, is 2-3 times of that of a common water-based industrial coating, and has excellent and durable anticorrosive performance.
Therefore, the invention also provides the application of the water-based heavy-duty anticorrosive paint in the infrastructure, oil-gas and electric power industries, industrial tanks, ships and chemical industries.
Detailed Description
Hereinafter, the present invention will be described in more detail.
In this context, all percentages are by weight unless stated to the contrary; unless otherwise stated, the operation was carried out at normal temperature and normal pressure.
All amounts are by weight unless otherwise indicated herein.
In this context, all proportions are by weight unless stated to the contrary.
The invention provides a water-based heavy-duty anticorrosive paint, which comprises the following components:
A) an aqueous industrial resin; and
B) a silane coupling agent-modified graphene, which is a graphene,
wherein the amount of component B) is from 0.1 to 1.0% by weight, based on the amount of component A),
and the amounts of components A) and B) add up to 100% by weight,
wherein the weight ratio of the silane coupling agent to the graphene is 2.0-7.0: 1.
In a preferred embodiment, the amount of component B) is preferably from 0.12 to 0.8% by weight, more preferably from 0.15 to 0.6% by weight, based on the amount of component A).
In a preferred embodiment, in the silane coupling agent-modified graphene, the weight ratio of the silane coupling agent to the graphene is 3.0 to 5.5: 1.
In a preferred embodiment, the resulting silane coupling agent modified graphene is dissolved in isopropanol and the particle size D of the graphene is then determined by static laser diffraction using a Mastersizer 2000 (available from Malvern Instruments Ltd)90Repeating the operation three times to obtain D90Is less than 3.0 μm, more preferably less than 1.1 μm, most preferably less than 0.6 μm.
Wherein D is90The particle size representing 90% of the graphene particles is smaller than this particle size.
In a preferred embodiment, the prepared water-based heavy-duty coating has the following relationship:
0.03g/μm3≤M/D90 3≤9.30g/μm3，
preferably 0.75 g/. mu.m3≤M/D90 3≤4.85g/μm3，
Wherein M represents the amount of graphene contained in the aqueous heavy duty coating.
According to the invention, the aqueous industrial resins of component A) are any resins known to the person skilled in the art to be suitable for the preparation of coatings. Preferably, the number average molecular weight (Mn) of the aqueous industrial resin is in the range of 5000 to 20000, preferably in the range of 8000 to 15000, more preferably in the range of 9000 to 12000, as determined by Gel Permeation Chromatography (GPC) using tetrahydrofuran as eluent in GB/T21863-2008.
Specifically, examples of the aqueous industrial resin include, but are not limited to, any one of aqueous alkyd resins, aqueous epoxy resins, aqueous amino resins, aqueous acrylic resins, aqueous hydroxyacrylic resins, aqueous epoxy asphalt resins, aqueous urethane resins, and aqueous inorganic resins, or a mixture of two or more thereof. Preferably, waterborne alkyds are used in the present invention.
In particular, in the present invention, the component B) silane coupling agent modified graphene is prepared by the following process:
a) adding a silane coupling agent into a dispersion system of graphene oxide in a solvent at the temperature of 45-70 ℃, heating to the temperature of 90-110 ℃, and preserving the heat for 20-40 hours at the temperature to obtain a mixture a;
b) cooling the mixture a obtained in the step a) to 50-70 ℃, adding a reducing agent into the mixture a, and preserving the heat for 1.5-3.5 hours to obtain a product b;
c) removing the solvent in the product b obtained in the step b) to obtain the required silane coupling agent modified graphene.
In one embodiment of the present invention, in step a), the ratio of silane coupling agent to graphene oxide added is 30-65:1, more preferably 40-60: 1.
In one embodiment of the invention, after the addition of the silane coupling agent in step a), the temperature is preferably raised to 95 to 100 ℃ and is preferably maintained at this temperature for 24 to 36 hours.
Preferably, in step a), the reaction conditions should satisfy the following formula, such that the weight ratio of the silane coupling agent to the graphene in the prepared modified graphene is 2.0-7.0:1 in the range of:
5.5≤0.01×R×ln(T+273.15)×ln(t)≤14；
preferably 7.5. ltoreq.0.01 XRXln (T + 273.15). times.ln (T). ltoreq.12,
wherein R represents the weight ratio of the added silane coupling agent to the graphene oxide,
t represents the holding temperature after addition of the silane coupling agent, in degrees Celsius, and
t represents the holding time in hours after the silane coupling agent is added.
Preferably, the solvent used in step a) may be methanol, ethanol, butanol, carbon tetrachloride, acetone, dichloroethane or a mixture thereof, but is not limited thereto. In the present invention, methanol or a mixture of methanol and butanol of 0.3 to 2:1, preferably 0.5 to 1.5:1, is preferred. The solvent may be used in an amount of 50 to 80% by weight, more preferably 60 to 70% by weight, based on the total amount of the solvent, graphene oxide and silane coupling agent added in step a).
In one embodiment of the present invention, in step a), the added graphene oxide is prepared by a method known to those skilled in the art, for example, by hummers method, more specifically, after subjecting potassium permanganate in concentrated sulfuric acid to oxidation reaction with graphite, a brown graphite flake having derivatized carboxyl groups at the edges and mainly phenolic hydroxyl groups and epoxy groups in the plane is obtained, and this graphite flake layer can be exfoliated into graphene oxide by vigorous stirring with ultrasound or high shear.
The silane coupling agent added in step a) has the general formula (I)
YSiX3 (I)
Wherein the content of the first and second substances,
y is a non-hydrolyzable group including C1-6Alkenyl, substituted or unsubstituted C1-6Alkyl or C1-6An alkoxy group; and
x is a hydrolyzable group including halogen, C1-6Alkoxy and acetoxy.
Preferably, Y is terminated with halogen, amino, mercapto, C containing at least one heteroatom selected from N, O or S1-6Heterocyclyl, (meth) acryloyloxy, isocyanato-substituted C1-6Alkyl or C1-6An alkoxy group.
More preferably, Y is C having one O atom and being terminated by an amino group1-4Heterocyclyl-substituted C1-4Alkyl or C1-4An alkoxy group.
Particularly preferably, Y is a propyl group and a butoxy group, the terminal of which is substituted with an amino group, a heterocyclic propyl group containing an O atom.
Preferably, X is C1-6An alkoxy group.
More preferably, X is methoxy and ethoxy.
In one embodiment of the present invention, the silane coupling agents used are gamma-aminopropyltriethoxysilane and gamma-glycidoxypropyltrimethoxysilane.
In step b), the temperature is preferably reduced to 55 to 65 ℃.
In one embodiment of the present invention, in step b), the reducing agent added may be a metal simple substance (such as sodium, magnesium, aluminum); elemental non-metals (e.g., hydrogen, carbon); non-metallic anions (e.g., ferrous ions) and compounds thereof (e.g., ferrous sulfate). In the present invention, ferrous sulfate is preferably used as a reducing agent in an amount of 10 to 30% by weight, preferably 15 to 25% by weight, based on the total amount of the solvent, graphene oxide, silane coupling agent and reducing agent added in steps a) and b).
In step b), the incubation is preferably carried out for 2 to 3 hours after the addition of the reducing agent.
In step c), the solvent is removed in any suitable manner known to the person skilled in the art, for example by raising the temperature to 90-120 ℃ and then carrying out vacuum distillation. After the solvent is removed, the residue is washed, centrifuged, and dried, and then the desired silane coupling agent-modified graphene is obtained.
Optionally, the aqueous heavy duty coating further comprises component C) additives. Examples of the additives include dispersants, antifoaming agents, thickeners, co-solvents, fillers, and other auxiliaries, but are not limited thereto.
The dispersant used in the present invention may be, but is not limited to, fatty acids; an aliphatic amide; esters, such as vinyl bis stearamide, glycerol monostearate, glycerol tristearate; paraffin wax such as liquid paraffin, microcrystalline paraffin; metal soaps such as barium stearate, zinc stearate, calcium stearate; low molecular wax, such as polyethylene wax, polyethylene glycol 200. The dispersants may be used in amounts of from 0.3 to 1.0% by weight, preferably from 0.5 to 0.8% by weight, based on the amount of the aqueous technical resin of component A).
The antifoaming agent used in the present invention may be, but is not limited to, silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether and polyoxypropylene polyoxyethylene glycerol ether, polydimethylsiloxane. The defoamers can be used in amounts of from 0.3 to 1.0% by weight, preferably from 0.5 to 0.8% by weight, based on the amount of the aqueous industrial resin of component A).
The thickener used in the present invention may be, but is not limited to, inorganic thickeners such as bentonite, attapulgite, aluminum silicate; celluloses such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose; polyacrylates such as polyacrylates, homopolymers of acrylic and methacrylic acids, and the like; a polyurethane thickener. The thickeners can be used in amounts of from 0.0 to 1.0% by weight, preferably from 0.3 to 0.7% by weight, based on the amount of the aqueous industrial resin of component A). Preferably, no thickener is used in the present invention.
The co-solvent used in the present invention may be a compound containing both an ether bond and a hydroxyl group. Examples thereof are, but not limited to, lower alcohol ether compounds of ethylene glycol and propylene glycol, such as ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, diethylene glycol methyl ether and mixtures thereof. In the present invention, one or a mixture of two of ethylene glycol butyl ether and diethylene glycol butyl ether is preferably used, and ethylene glycol butyl ether is most preferably used. The amount of co-solvent used in the present invention is from 5 to 18% by weight, preferably from 8 to 15% by weight, based on the amount of aqueous industrial resin of component A).
The filler used in the present invention may be, but is not limited to, titanium white, calcium carbonate, zinc phosphate, mica, mill base, talc, and mixtures thereof. Preferably, the titanium white used according to the invention is rutile titanium white, which is used in an amount of from 10 to 60% by weight, preferably from 15 to 55% by weight, based on the amount of the aqueous industrial resin of component A). Preferably, the calcium carbonate, zinc phosphate, mica, mill base, talc used in the present invention are any suitable products known to those skilled in the art. Wherein, the calcium carbonate is used in an amount of 5-60 wt%, preferably 10-55 wt%; the amount of zinc phosphate is 10 to 35% by weight, preferably 15 to 30% by weight; the mica is used in an amount of 5 to 30% by weight, preferably 10 to 25% by weight; the color pastes are used in amounts of from 13 to 35% by weight, preferably from 15 to 30% by weight, based in each case on the amount of the aqueous industrial resins of component A).
Other adjuvants useful in the present invention can be, but are not limited to, industrial driers, for example, metal oxides such as cobalt oxide, metal salts such as lead naphthenate, metal soaps such as lead soaps, and mixtures thereof. Preferably, cobalt driers are used in the present invention in amounts of 0.2 to 1.0% by weight, preferably 0.4 to 0.8% by weight, based on the amount of the aqueous industrial resin of component A).
Where it is to be noted that the amounts of components A), B) and, if present, optional component C) add up to 100% by weight.
In another aspect of the present invention, there is provided a method for preparing the aqueous heavy duty anticorrosive coating of the present invention, comprising:
1) preparing component B) silane coupling agent modified graphene by the following procedure:
a) adding a silane coupling agent into a dispersion system of graphene oxide in a solvent, heating to 90-110 ℃, and preserving heat for 20-40 hours at the temperature to obtain a mixture a;
b) cooling the mixture a obtained in the step a) to 45-70 ℃, adding a reducing agent into the mixture a, and preserving the heat for 1.5-3.5 hours to obtain a product b;
c) removing the solvent in the product b obtained in the step b) to obtain the required silane coupling agent modified graphene,
2) 0.1 to 1.0 wt.%, based on the amount of the component A), of the component B) silane coupling agent modified graphene obtained in step 1) is added to the aqueous industrial resin of the component A), thereby obtaining an aqueous heavy-duty anticorrosive coating.
Optionally, before adding the silane coupling agent modified graphene obtained in the step 1) into the aqueous industrial resin, the following process is further included: adding the dispersant, the defoaming agent, the cosolvent and other additives into the aqueous industrial resin in the above-mentioned amounts, uniformly stirring, then adding the titanium white, the zinc phosphate, the calcium carbonate, the mica and the color paste into the system, pre-dispersing and grinding the materials to a specified fineness, namely, the granularity is less than or equal to 80 microns, preferably less than or equal to 50 microns, then adding the silane coupling agent modified graphene in the above-mentioned amount into the system, and stirring until the system is transparent and has no granules; then, the viscosity is adjusted to be more than or equal to 100s, preferably more than or equal to 50s, and the required target product, namely the water-based heavy anti-corrosion coating is obtained. The viscosity was measured by QND-4 paint-4 viscometer (at 23 ℃) of Shanghai Mei apparatus Equipment Co.
In yet another aspect of the invention, there is also provided the use of the aqueous heavy duty coating of the invention in the infrastructure, oil and gas and power industries, as well as in industrial tanks, ships and chemical industries. For example, the aqueous heavy duty coating of the present invention is applied to a base material, which is a substrate commonly used in the infrastructure, oil and gas and electric power industries, and industrial tanks, ships and chemical industries, such as concrete, in a coating manner commonly used in the art (such as spraying, rolling, and brushing); wood; metals, such as tinplate and steel; and a resin layer. In a preferred embodiment, the resin layer comprises a cement-based resin layer, an epoxy-based resin layer, a polyurethane-based resin layer, an acrylate-based resin layer, a polyethylene layer, a polypropylene layer, a polyvinyl chloride layer, a rubber layer, an asphalt layer, and a polymer-modified asphalt layer. The application temperature of the aqueous heavy duty material can be 5 ℃ to 40 ℃, preferably 10 ℃ to 30 ℃. Furthermore, the application relative humidity of the aqueous heavy duty material is from 15% to 85%, preferably from 20% to 80%.
It is to be noted that the individual features, parameters, conditions and combinations thereof described above in connection with the aqueous heavy duty coating products apply in connection with the preparation and use thereof.
The invention is further described by the following examples, but is not limited thereto.
Examples
The raw materials used are as follows:
silane coupling agent: KH550 (i.e., gamma-aminopropyltriethoxysilane) and KH560 (i.e., gamma-glycidoxypropyltrimethoxysilane) available from nahao new materials limited;
water-based alkyd resin: alkyd resins 3530 available from DSM corporation;
dispersing agent: 755, available from digao corporation;
defoaming agent: 830 from digao corporation;
a drier: cobalt drier available from Guangshu chemical company;
titanium dioxide: titanium white 996 from the titanium bouon of the Sichuan dragon;
calcium carbonate: calcium carbonate 1250 mesh product available from Guangxi Kelong powder company;
zinc phosphate: zinc phosphate product industrial grade zinc phosphate purchased from Shijiazhuang Queen chemical;
mica: a 600 mesh wet mica product from Hebei lingshou baofeng mica processing Co., Ltd;
color paste: the Guangdong Kedi universal color paste products are bright red, iron oxide red, phthalocyanine blue and carbon black color pastes.
The test method used was:
appearance of the coating film: coating the prepared product on a tin base in a spraying mode to obtain a coating, and observing the appearance of the coating after 7 days of drying time;
impact strength: according to GB/T18178-2000.
Flexibility: determined according to GB/T1731-1993.
Adhesion force: according to GB/T18178-2000.
Surface drying time: it means the time for the surface of the paint film to dry, determined according to GB/T1728-1979.
The actual drying time is as follows: it refers to the time for which the paint film actually dries, determined according to GB/T1728-1979.
Salt spray resistance: according to GB/T18178-2000.
Chemical resistance (e.g. acid, base): determined according to JSCE-E549-2000.
Gasoline, kerosene and diesel oil resistant: determined according to GB/T9274-.
I. Preparation examples
Preparation of silane coupling agent modified graphene
Example 1
565g of methanol solvent was placed in a 2L four-necked flask equipped with a stirrer, thermometer, distiller, condenser under nitrogen protection, and 5g of graphene oxide was slowly added with stirring and stirred slowly for 30 minutes, raising the temperature to 55 ℃ (referred to as first temperature in Table 1). Then, 250g of a silane coupling agent KH560 was slowly dropped thereinto, and after completion of the dropping, the temperature was raised to 90 ℃ (referred to as a second temperature in Table 1), and the temperature was maintained for 24 hours (referred to as a first keeping time in Table 1), to obtain a mixture a. Then, the temperature is reduced to 65 ℃ (referred to as a third temperature in table 1), 180g of ferrous sulfate reducing agent is slowly added while stirring, and the temperature is maintained for 2.5 hours (referred to as a second temperature maintaining time in table 1), so that a product b is obtained. Then, the vacuum pump was turned on, the temperature of the system was raised to 100 ℃ (referred to as a fourth temperature in table 1), and the solvent in the product b was distilled off to finally obtain a product c. Then, c was washed with deionized water, and then centrifuged and dried to obtain silane coupling agent-modified graphene in a solid form, and the results are shown in table 1 below.
Examples 2 to 5
The procedure of example 1 was repeated except that the amounts of the raw materials and the experimental conditions listed in Table 1 were used.
Examples 6 to 7 (used as comparative examples)
The procedure of example 4 was repeated except that the amounts of the raw materials and the experimental conditions listed in Table 1 were used.
Table 1: experimental data and results for examples 1-7
Figure GDA0003164347330000101
Note: in the formula 0.01 × R × ln (T +273.15) × ln (T), R represents the ratio of the silane coupling agent added to the graphene oxide; t represents a second temperature in units of; and, t represents a first soaking time in hours.
The content of the residual silane coupling agent in the prepared graphene modified by the silane coupling agent is tested by using a capillary chromatograph, so that the optimal ratio of the silane coupling agent to the graphene in the prepared modified graphene is calculated, and the experimental ratio is shown in the following table 2:
TABLE 2
Figure GDA0003164347330000111
According to the detection result, the weight ratio of the silane coupling agent to the graphene in the modified graphene prepared under the specific conditions is in the range of 2.0-7.0:1, and the adhesion between the water-based resin and the base material can be further improved by using the modified graphene.
0.1g of the prepared silane coupling agent modified graphene is dissolved in 20g of isopropanol, and then static laser derivatization is carried outParticle size D of graphene was determined using a Mastersizer 2000 (available from Malvern Instruments Ltd)90Repeating the operation three times to obtain D90The average values of (A) are shown in Table 3 below.
TABLE 3
Figure GDA0003164347330000112
As can be seen from table 3, the silane coupling agent-modified graphene prepared in examples 1 to 5 of the present invention has a smaller particle size than examples 6 and 7.
Preparation of aqueous heavy-duty anticorrosive coating
Examples 9 to 15
The silane coupling agent modified graphene obtained in examples 1 to 7 is added to the aqueous alkyd resin, and the aqueous heavy anti-corrosion coating of examples 9 to 15 is prepared by adding corresponding additives, and the mixture ratio of the raw materials is shown in table 4 below.
Examples 16 to 17
The procedure of example 12 was repeated except that the amount of the silane coupling agent-modified graphene added thereto was different from that of example 12, as shown in table 4 below.
TABLE 4
Figure GDA0003164347330000121
Note: calcium carbonate, zinc phosphate, mica and mill base are products detailed in the beginning of the examples (i.e., the raw materials used).
Use examples
200g of the aqueous heavy duty anticorrosive coatings of examples 9 to 17 according to the present invention were spray-coated on a tin substrate at room temperature to obtain coating films having a thickness of 23 ± 2 μm, and then the coating films were subjected to performance tests, the results of which are shown in table 5 below.
Table 5:
Figure GDA0003164347330000122
Figure GDA0003164347330000131
note: with respect to the adhesion in the table, grade 0 means the best adhesion, grade 1 means the better adhesion, and grade 2 means the adhesion is acceptable.
As can be seen from the results of table 5, example 12 demonstrates that the aqueous heavy duty anticorrosive coatings prepared using the silane coupling agent-modified graphene prepared under the specific conditions of the present invention have excellent salt spray resistance, adhesion, and mechanical strength, as compared with the results of examples 14 to 15.
The aqueous heavy duty anticorrosive coatings of examples 9 to 13 of the present invention have excellent mechanical strength, salt spray resistance, acid and alkali resistance, and gasoline, kerosene, and diesel oil resistance, compared to the aqueous heavy duty anticorrosive coatings prepared in example 16 (in which no silane coupling agent-modified graphene is contained) and example 17 (in which a larger amount of silane coupling agent-modified graphene is contained).
Finally, the above embodiments are only used to illustrate the technical solution of the present invention and are not limited. Modifications and equivalents of the present invention may be made by those skilled in the art without departing from the spirit and scope of the present invention, and are intended to be included within the scope of the appended claims.

Claims (4)

1. The preparation method of the water-based heavy-duty anticorrosive paint is characterized by comprising the following steps:
(1) under the protection of nitrogen, 250g of methanol solvent and 215g of butanol solvent are placed into a 2L four-mouth bottle equipped with a stirrer, a thermometer, a distiller and a condenser, 4g of graphene oxide is slowly added under stirring, the mixture is slowly stirred for 30 minutes, and the temperature is increased to 60 ℃;
(2) slowly dripping 235g of a silane coupling agent KH550 into the mixture, heating to 95 ℃ after dripping is finished, and preserving heat for 36 hours to obtain a mixture a;
(3) cooling to 60 ℃, slowly adding 195g of ferrous sulfate reducing agent under the stirring state, and keeping the temperature for 2 hours to obtain a product b;
(4) starting a vacuum pump, raising the temperature of the system to 100 ℃, and distilling to remove the solvent in the product b to finally obtain a product c;
(5) washing the c by using deionized water, and centrifugally drying to obtain solid silane coupling agent modified graphene;
(6) 600g of waterborne alkyd resin, 3g of dispersant dygan 755, 2g of defoamer dygan 830, 3g of cobalt drier, 50g of ethylene glycol butyl ether, 100g of titanium white 996, 50g of calcium carbonate, 100g of zinc phosphate, 80g of mica, 11.5g of color paste and 1g of graphene modified by a silane coupling agent are mixed to obtain the waterborne heavy-duty anticorrosive coating.
2. The preparation method of the water-based heavy-duty anticorrosive coating according to claim 1, wherein D of the silane coupling agent-modified graphene is90The average value is less than 1.1 μm.
3. The method for preparing the water-based heavy-duty anticorrosive coating according to claim 1, wherein D of the silane coupling agent-modified graphene is90The average value is less than 0.6 μm.
4. Use of the aqueous heavy duty coating prepared according to the method of claim 1 in the infrastructure, oil and gas and power industries, and industrial tanks, ships and chemical industries.
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