CN108707355B - Anticorrosive paint - Google Patents
Anticorrosive paint Download PDFInfo
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- CN108707355B CN108707355B CN201810654298.6A CN201810654298A CN108707355B CN 108707355 B CN108707355 B CN 108707355B CN 201810654298 A CN201810654298 A CN 201810654298A CN 108707355 B CN108707355 B CN 108707355B
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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
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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
- 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
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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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0853—Vinylacetate
- C09D123/0861—Saponified vinylacetate
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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
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- 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
Abstract
The invention relates to the technical field of preparation of anticorrosive coatings, and provides an anticorrosive coating which comprises the steps of firstly preparing an ethylene-vinyl alcohol copolymer precursor, further heating the ethylene-vinyl alcohol copolymer precursor and graphene oxide modified by a coupling agent under the conditions of high pressure and uniform stirring to complete the combination reaction of silane and the ethylene-vinyl alcohol copolymer precursor, and combining the ethylene-vinyl alcohol copolymer precursor and the coupling agent on the surface layer of the graphene oxide to form a compact film, so that the dispersity of the graphene oxide is greatly improved, and the graphene oxide can be uniformly and stably dispersed in resin to form an efficient graphene hot-melt anticorrosive coating.
Description
Technical Field
The invention relates to the technical field of preparation of anticorrosive coatings, and particularly relates to an anticorrosive coating.
Background
For anticorrosive coatings, the traditional protective coating is limited by the material properties and the process, the corrosion protection effect on a metal matrix is not ideal, the cost of the specific performance is high, the cost performance of the coating is reduced, a certain environmental pollution risk exists for a part of coatings containing heavy metals or toxic substances such as lead, zinc or chromate, a large amount of non-renewable resources are consumed, and the sustainable development of social economy is not facilitated. Therefore, the development of various novel long-acting environment-friendly anticorrosive coatings becomes a new hotspot.
The wide and unique properties of graphene represent a great potential in the field of metal material corrosion prevention. Firstly, a physical barrier layer can be formed between metal and an active medium due to a stable sp2 hybrid structure of graphene, so that diffusion and permeation are prevented; secondly, graphene has good thermal and chemical stability, and can be stable under high temperature conditions (up to 1500 ℃), and in corrosive or oxidative gas and liquid environments. In addition, the good electric conduction and heat conduction performance of the graphene provides favorable conditions for the metal service environment. Graphene is also by far the thinnest material, with negligible effect on the base metal. Meanwhile, the coating has high strength and good tribological performance, can improve the conductivity or salt spray resistance, further reduce the thickness of the coating, increase the adhesive force to a base material, and improve the wear resistance of the coating.
The novel coating prepared by adding the graphene on the basis of the common epoxy anticorrosive coating not only has the cathode protection effect of the epoxy zinc-rich coating and the shielding effect of the glass flake coating, but also has the characteristics of good toughness, strong adhesive force, good water resistance, high hardness and the like. The potential of the coating prepared by graphene in the aspect of improving the corrosion resistance of metal is improved, and a test of coating graphene on the surfaces of copper and nickel proves that the corrosion speed of copper is reduced by 7 times and the corrosion speed of nickel is reduced by 4 times when the coating is cultivated by chemical vapor deposition. These findings indicate that graphene is the thinnest corrosion protection coating known. Therefore, graphene will be the most ideal corrosion resistant coating.
Due to the conjugated structure of graphene, the compatibility of graphene with water, organic solvents and polymers is poor, and the application difficulty of graphene in the field of coatings is increased. Since graphene can generate self-aggregation to destroy the uniformity and compactness of dispersion of graphene, the graphene is aggregated when the graphene is applied to a coating, stress concentration is generated inside a coating film, the mechanical property is reduced, and the prepared coating is poor in anticorrosion effect and unsatisfactory in barrier property.
Disclosure of Invention
Aiming at the defects that graphene used for an anticorrosive coating has poor compatibility with a polymer, self-agglomeration and damages the dispersion uniformity and compactness of the anticorrosive coating, the invention provides a high-efficiency preparation method of a graphene hot-melt anticorrosive coating. Can solve the defects of poor anticorrosive effect and poor barrier property of the coating caused by self-aggregation of graphene at present.
In order to realize the purpose, the following technical scheme is adopted:
a preparation method of a high-efficiency graphene hot-melt anticorrosive coating is characterized by preparing an ethylene-vinyl alcohol copolymer precursor, mixing the ethylene-vinyl alcohol copolymer precursor with coupling agent modified graphene oxide, reacting, extruding and granulating, and finally grinding particles into dry powder and adding the dry powder into resin to prepare the high-efficiency graphene hot-melt anticorrosive coating; the preparation method comprises the following specific steps:
(1) mixing vinyl acetate monomer and solvent, adding initiator, mixing uniformly, adding into a reaction kettle, introducing inert gas while stirring at a certain speed to remove oxygen from the raw materials, introducing ethylene monomer after the oxygen removal is finished, and heating and polymerizing to obtain an ethylene-vinyl alcohol copolymer precursor; the solvent is composed of methanol, ethanol and tert-butyl alcohol in any proportion; the mass ratio of the vinyl acetate monomer to the solvent is 1: 1.5-3; the initiator is any one of azodiisobutyronitrile or tert-amyl peroxyneodecanoate, and the addition amount of the initiator is 0.2-1% of the total mass of the vinyl acetate monomer and the solvent;
(2) uniformly mixing graphene oxide and a silane coupling agent according to the mass ratio of 10: 1-3, performing ultrasonic dispersion treatment, heating in a water bath, stirring for reacting for a certain time, washing, and drying to obtain coupling agent modified graphene oxide for later use;
(3) heating the silane coupling agent modified graphene oxide obtained in the step (2) and the ethylene-vinyl alcohol copolymer precursor obtained in the step (1) according to the feeding weight ratio of 1: 5-8, under the conditions of high pressure and uniform stirring, completing the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, cutting and granulating after extrusion, and obtaining composite particles of graphene oxide and the ethylene-vinyl alcohol copolymer;
(4) and (4) refining the particles obtained in the step (3) into dry powder in an ultrafine pulverizer, sieving and sorting out particles with proper particle size, and mixing the particles with resin according to a proportion to obtain the graphene hot-melt anticorrosive coating.
Preferably, the silane coupling agent in step (2) is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane and N- (2-aminoethyl) -3-aminopropyl-triethoxysilane.
Preferably, the stirring speed for removing oxygen in the step (1) is 100-120 rpm, and lasts for 10-15 min.
Preferably, the ethylene monomer in the step (1) is introduced in an amount to make the pressure of the reaction kettle be 30-50 bar.
Preferably, the heating polymerization temperature after the ethylene monomer is introduced in the step (1) is 65-75 ℃.
Preferably, the heating polymerization time in the step (1) is 4-6 hours.
Preferably, the high pressure in the step (3) is 2-3MPa, the heating temperature is 75-85 ℃, and the combination reaction time is 4-5 hours.
Preferably, the diameter of the particles separated after the crushing in the step (4) is 10-30 microns.
Preferably, the resin in step (4) is at least one of epoxy resin, polyurethane resin and alkyd resin.
Preferably, the mass ratio of the particles to the resin in the step (4) is 1: 2-5.
Generally, modification technologies such as surface decarboxylation and dehydroxylation are adopted to improve the oleophylic property of graphene oxide and enhance the dispersibility of the graphene oxide in an oil paint system, but the effect is limited, the graphene oxide subjected to surface treatment can be well dispersed in a short time, and after the standing time is prolonged, the phenomena of paint layering and uneven color often occur, so that the bonding force between the paint and a substrate is reduced, and the weather resistance and the service life of the paint are reduced. According to the invention, the aminosilane coupling agent is used for modifying graphene oxide, and then the ethylene-vinyl alcohol copolymer precursor and the coupling agent are combined on the surface layer of the graphene oxide to form a compact film, so that the dispersibility of the graphene oxide is greatly improved, and the graphene oxide can be uniformly and stably dispersed in resin. By controlling the ratio of the aminosilane coupling agent to the graphene oxide, the optimal film forming efficiency of the ethylene-polyvinyl alcohol copolymer can be obtained, the dispersibility of the graphene oxide is maximized, and the outstanding adhesion of the coating to the substrate can be obtained. Due to the crosslinking effect of the graphene oxide, the graphene oxide is tightly connected with the ethylene-vinyl alcohol copolymer, the crosslinking effect solves the technical problem of poor dispersion of the graphene, and when the graphene oxide is dispersed in the coating, the graphene oxide is dispersed more stably by a network structure formed by crosslinking, so that the coating is endowed with a good anticorrosion effect.
The invention provides an efficient graphene hot-melt anticorrosive paint and a preparation method thereof, and compared with the prior art, the efficient graphene hot-melt anticorrosive paint has the outstanding characteristics and excellent effects that:
1. the graphene oxide surface layer in the anticorrosive coating is an ethylene-polyvinyl alcohol copolymer film, so that the dispersibility of the coating is greatly improved, and the phenomena of layering and uneven color of the coating are avoided.
2. According to the invention, the ethylene-polyvinyl alcohol copolymer precursor is innovatively combined with the graphene oxide, so that the dispersibility of the graphene oxide is greatly improved, and the graphene oxide is tightly connected with the ethylene-vinyl alcohol copolymer to form a network structure under the crosslinking action of the graphene oxide, so that the dispersibility of the coating is more stable.
3. The raw materials adopted by the invention are rich in source and low in price, the preparation process is simple to operate, continuous and efficient production can be carried out, and the provided product is low in cost, so that the technical scheme has a wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
A preparation method of an efficient graphene hot-melt anticorrosive coating comprises the following steps:
uniformly mixing 1kg of vinyl acetate monomer and 2kg of methanol, adding 5g of azobisisobutyronitrile as an initiator, uniformly mixing, adding into a reaction kettle, introducing nitrogen gas while stirring at a speed of 100rpm to remove oxygen from the raw material, continuing for 12min, finishing the oxygen removal, introducing ethylene monomer to stabilize the pressure of the reaction kettle at 35bar, heating for polymerization reaction, raising the temperature to 70 ℃, keeping the temperature for 4h, continuously introducing ethylene monomer to maintain the pressure, and cooling after the reaction is finished to obtain the ethylene-vinyl alcohol copolymer precursor. Weighing 100g of graphene oxide and 20g of 3-aminopropyltrimethoxysilane, uniformly mixing, performing ultrasonic dispersion treatment, heating in a water bath to 80 ℃, simultaneously stirring and reacting for 5 hours, filtering, washing and drying to obtain the coupling agent modified graphene oxide. Heating silane coupling agent modified graphene oxide and an ethylene-vinyl alcohol copolymer precursor to 80 ℃ under the conditions of 2MPa and uniform stirring, preserving heat for 2h to complete the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, performing thermal extrusion before cooling a product, and then cutting and granulating to obtain the composite particles of the graphene oxide and the ethylene-vinyl alcohol copolymer. Micronizing the granules into dry powder, sieving, and separating out particles with particle diameter of 10-30 μm; and mixing 1kg of sieved dry powder with 4kg of epoxy resin to obtain the graphene hot-melt anticorrosive coating.
The graphene hot-melt type anticorrosive paint obtained in example 1 is tested according to the paint standard JISK5664-2002, and the obtained results are shown in table 1, and it can be seen that the graphene anticorrosive paint obtained by dispersing graphene with an ethylene-vinyl alcohol copolymer has impact resistance, acid resistance, alkali resistance and salt water resistance meeting the standard requirements, and has more excellent corrosion resistance than the conventional graphene resin paint.
Example 2
A preparation method of an efficient graphene hot-melt anticorrosive coating comprises the following steps:
uniformly mixing 1kg of vinyl acetate monomer, 1.5kg of methanol and 0.8g of ethanol, adding 8g of azobisisobutyronitrile as an initiator, uniformly mixing, adding into a reaction kettle, introducing nitrogen gas while stirring at a speed of 120rpm to remove oxygen from the raw materials, after continuing for 10min, finishing the oxygen removal, introducing ethylene monomer to stabilize the pressure of the reaction kettle at 50bar, heating to carry out polymerization reaction, raising the temperature to 65 ℃, keeping the temperature for 6h, continuously introducing ethylene monomer to maintain the pressure during the period, cooling after the reaction is finished to obtain a crude product, and removing residual monomers to obtain an ethylene-vinyl alcohol copolymer precursor. Weighing 150g of graphene oxide and 30g of 3-aminopropyltriethoxysilane, uniformly mixing, performing ultrasonic dispersion treatment, heating in a water bath to 85 ℃, simultaneously stirring for reaction for 4 hours, filtering, washing, and blow-drying to obtain the coupling agent modified graphene oxide. Heating silane coupling agent modified graphene oxide and an ethylene-vinyl alcohol copolymer precursor to 85 ℃ under the conditions of 2.5MPa and uniform stirring, preserving heat for 2h to complete the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, performing thermal extrusion before cooling a product, and then cutting and granulating to obtain the composite particles of the graphene oxide and the ethylene-vinyl alcohol copolymer. Micronizing the granules into dry powder, sieving, and separating out particles with particle diameter of 10-20 μm; and mixing 1kg of sieved dry powder with 2kg of epoxy resin to obtain the graphene hot-melt anticorrosive coating.
The graphene hot-melt anticorrosive paint obtained in example 2 is tested according to paint standard JISK5664-2002, and the obtained results are shown in table 1, and it can be seen that the graphene anticorrosive paint obtained by dispersing graphene with an ethylene-vinyl alcohol copolymer has impact resistance, acid resistance, alkali resistance and salt water resistance meeting the standard requirements, and has more excellent corrosion resistance than the conventional graphene resin paint.
Example 3
A preparation method of an efficient graphene hot-melt anticorrosive coating comprises the following steps:
uniformly mixing 1kg of vinyl acetate monomer and 2.5kg of tert-butyl alcohol, adding 7g of tert-amyl peroxyneodecanoate as an initiator, uniformly mixing, adding into a reaction kettle, introducing nitrogen gas while stirring at a speed of 110rpm to perform raw material deoxygenation, after continuing for 10min, finishing deoxygenation, introducing ethylene monomer to stabilize the pressure of the reaction kettle at 30bar, heating for polymerization reaction, raising the temperature to 75 ℃, keeping the temperature for 4h, continuously introducing ethylene monomer to maintain the pressure during the period, cooling after the reaction is finished to obtain a crude product, and removing residual monomers to obtain an ethylene-vinyl alcohol copolymer precursor. Weighing 180g of graphene oxide, 20g of 3-aminopropyltrimethoxysilane and 30g of N- (2-aminoethyl) -3-aminopropyl-trimethoxysilane, uniformly mixing, performing ultrasonic dispersion treatment, heating in a water bath to 85 ℃, simultaneously stirring and reacting for 4.5 hours, filtering, washing and drying to obtain the coupling agent modified graphene oxide. Feeding the obtained silane coupling agent modified graphene oxide and an ethylene-vinyl alcohol copolymer precursor according to the mass ratio of 1:5, heating to 90 ℃ under the conditions of 3MPa and uniform stirring, preserving heat for 2h to complete the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, carrying out thermal extrusion before cooling a product, and then cutting and granulating to obtain the graphene oxide and ethylene-vinyl alcohol composite particles. Micronizing the granules into dry powder, sieving, and separating out particles with particle diameter of 20-30 μm; and mixing 1kg of sieved dry powder with 4kg of polyurethane resin to obtain the graphene hot-melt anticorrosive coating.
The graphene hot-melt type anticorrosive paint obtained in example 3 is tested according to the paint standard JISK5664-2002, and the obtained results are shown in table 1, and it can be seen that the graphene anticorrosive paint obtained by dispersing graphene with an ethylene-vinyl alcohol copolymer has impact resistance, acid resistance, alkali resistance and salt water resistance meeting the standard requirements, and has more excellent corrosion resistance than the conventional graphene resin paint.
Example 4
A preparation method of an efficient graphene hot-melt anticorrosive coating comprises the following steps:
uniformly mixing 1kg of vinyl acetate monomer with 1kg of methanol, 1kg of ethanol and 1kg of tert-butyl alcohol, adding 10g of azobisisobutyronitrile as an initiator, uniformly mixing, adding into a reaction kettle, introducing nitrogen gas while stirring at a speed of 100rpm to perform raw material deoxygenation, after 12min, finishing deoxygenation, introducing ethylene monomer to stabilize the pressure of the reaction kettle at 45bar, heating for polymerization reaction, raising the temperature to 72 ℃, keeping the temperature for 4h, continuously introducing ethylene monomer during the period to maintain the pressure, cooling after the reaction is finished to obtain a crude product, and removing residual monomers to obtain an ethylene-vinyl alcohol copolymer precursor. Weighing 150g of graphene oxide and 10g of 3-aminopropyltrimethoxysilane, uniformly mixing, performing ultrasonic dispersion treatment, heating in a water bath to 75 ℃, simultaneously stirring and reacting for 5 hours, filtering, washing and drying to obtain the coupling agent modified graphene oxide. Feeding the obtained silane coupling agent modified graphene oxide and an ethylene-vinyl alcohol copolymer precursor according to the mass ratio of 1:7, heating to 80 ℃ under the conditions of 2MPa and uniform stirring, preserving heat for 2h to complete the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, carrying out thermal extrusion before cooling a product, and then cutting and granulating to obtain the composite particles of the graphene oxide and the ethylene-vinyl alcohol copolymer. Micronizing the granules into dry powder, sieving, and separating out particles with particle diameter of 10-30 μm; and mixing 1kg of sieved dry powder with 3.2kg of alkyd resin to obtain the graphene hot-melt anticorrosive paint.
The graphene hot-melt type anticorrosive paint obtained in example 4 is tested according to the paint standard JISK5664-2002, and the obtained results are shown in table 1, and it can be seen that the graphene anticorrosive paint obtained by dispersing graphene with an ethylene-vinyl alcohol copolymer has impact resistance, acid resistance, alkali resistance and salt water resistance meeting the standard requirements, and has more excellent corrosion resistance than the conventional graphene resin paint.
Example 5
A preparation method of an efficient graphene hot-melt anticorrosive coating comprises the following steps:
uniformly mixing 1kg of vinyl acetate monomer and 1.8kg of ethanol, adding 2g of azobisisobutyronitrile as an initiator, uniformly mixing, adding into a reaction kettle, introducing nitrogen gas while stirring at a speed of 120rpm to deoxidize the raw material, continuing for 15min, finishing deoxidization, introducing ethylene monomer to stabilize the pressure of the reaction kettle at 30bar, heating for polymerization reaction, raising the temperature to 75 ℃, keeping the temperature for 6h, continuously introducing ethylene monomer to maintain the pressure, cooling after the reaction is finished to obtain a crude product, and removing residual monomers to obtain an ethylene-vinyl alcohol copolymer precursor. Weighing 120g of graphene oxide and 28g of N- (2-aminoethyl) -3-aminopropyl-triethoxysilane, uniformly mixing, performing ultrasonic dispersion treatment, heating in a water bath to 80 ℃, simultaneously stirring for reaction for 4 hours, filtering, washing and drying to obtain the coupling agent modified graphene oxide. Feeding the obtained silane coupling agent modified graphene oxide and an ethylene-vinyl alcohol copolymer precursor according to the weight ratio of 1:8, heating to 90 ℃ under the conditions of 3MPa and uniform stirring, preserving heat for 2h to complete the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, carrying out thermal extrusion before cooling a product, and then cutting and granulating to obtain the composite particles of the graphene oxide and the ethylene-vinyl alcohol copolymer. Micronizing the granules into dry powder, sieving, and separating out particles with particle diameter of 15-25 μm; and mixing 1kg of sieved dry powder with 2.2kg of alkyd resin to obtain the graphene hot-melt anticorrosive paint.
The graphene hot-melt type anticorrosive paint obtained in example 5 is tested according to the paint standard JISK5664-2002, and the obtained results are shown in table 1, and it can be seen that the graphene anticorrosive paint obtained by dispersing graphene with an ethylene-vinyl alcohol copolymer has impact resistance, acid resistance, alkali resistance and salt water resistance meeting the standard requirements, and has more excellent corrosion resistance than the conventional graphene resin paint.
Comparative example 1
Weighing 120g of graphene oxide and 28g of N- (2-aminoethyl) -3-aminopropyl-triethoxysilane, uniformly mixing, performing ultrasonic dispersion treatment, heating in a water bath to 80 ℃, simultaneously stirring for reaction for 4 hours, filtering, washing and drying to obtain the coupling agent modified graphene oxide. Feeding the obtained silane coupling agent modified graphene oxide and a commercially available ethylene-vinyl alcohol copolymer according to the weight ratio of 1:8, heating to 90 ℃ under the conditions of 3MPa and uniform stirring, preserving heat for 2h to complete the bonding reaction of silane and the ethylene-vinyl alcohol copolymer, carrying out thermal extrusion before cooling a product, and then cutting and granulating to obtain the composite particles of the graphene oxide and the ethylene-vinyl alcohol copolymer. Micronizing the granules into dry powder, sieving, and separating out particles with particle diameter of 15-25 μm; and mixing 1kg of sieved dry powder with 2.2kg of alkyd resin to obtain the graphene hot-melt anticorrosive paint.
The graphene coating obtained in comparative example 1 was also tested according to coating standard JISK5664-2002, and the results are shown in table 1.
Table 1:
Claims (1)
1. a graphene hot-melt anticorrosive coating is characterized in that an ethylene-vinyl alcohol copolymer precursor is prepared, and is mixed with graphene oxide modified by a coupling agent, and then the mixture is subjected to reaction, extrusion and granulation, and finally the particles are ground into dry powder and added into resin to prepare the efficient graphene hot-melt anticorrosive coating; the preparation method comprises the following specific steps:
(1) mixing vinyl acetate monomer and solvent, adding initiator, mixing uniformly, adding into a reaction kettle, introducing inert gas while stirring at a certain speed to remove oxygen from the raw materials, introducing ethylene monomer after the oxygen removal is finished, and heating and polymerizing to obtain an ethylene-vinyl alcohol copolymer precursor; the solvent is composed of methanol, ethanol and tert-butyl alcohol in any proportion; the mass ratio of the vinyl acetate monomer to the solvent is 1: 1.5-3; the initiator is any one of azodiisobutyronitrile or tert-amyl peroxyneodecanoate, and the addition amount of the initiator is 0.2-1% of the total mass of the vinyl acetate monomer and the solvent;
(2) uniformly mixing graphene oxide and a silane coupling agent according to the mass ratio of 10: 1-3, performing ultrasonic dispersion treatment, heating in a water bath, stirring for reacting for a certain time, washing, and drying to obtain coupling agent modified graphene oxide for later use;
(3) heating the silane coupling agent modified graphene oxide obtained in the step (2) and the ethylene-vinyl alcohol copolymer precursor obtained in the step (1) according to the feeding weight ratio of 1: 5-8, under the conditions of high pressure and uniform stirring, completing the combined reaction of silane and the ethylene-vinyl alcohol copolymer precursor, cutting and granulating after extrusion, and obtaining composite particles of graphene oxide and the ethylene-vinyl alcohol copolymer;
(4) the particles obtained in the step (3) are refined into dry powder in an ultrafine pulverizer, particles with proper particle size are screened out and separated, and the particles are mixed with resin according to a proportion to obtain the graphene hot-melt anticorrosive coating;
the deoxidizing stirring speed in the step (1) is 100-120 rpm, and lasts for 10-15 min;
the introduction amount of the ethylene monomer in the step (1) is such that the pressure of the reaction kettle is 30-50 bar;
the heating polymerization temperature of the ethylene monomer introduced in the step (1) is 65-75 ℃;
the heating polymerization time in the step (1) is 4-6 hours.
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| CN201810654298.6A CN108707355B (en) | 2017-10-17 | 2017-10-17 | Anticorrosive paint |
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| CN201810654298.6A CN108707355B (en) | 2017-10-17 | 2017-10-17 | Anticorrosive paint |
| CN201710963356.9A CN107641422B (en) | 2017-10-17 | 2017-10-17 | A kind of preparation method of efficient graphene hot melt anticorrosive paint |
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| CN105838183B (en) * | 2016-04-01 | 2019-01-29 | 常州华科聚合物股份有限公司 | Aqueous corrosion-resistant finishes material of modified graphene and its preparation method and application |
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- 2017-10-17 CN CN201810654296.7A patent/CN108929615A/en not_active Withdrawn
- 2017-10-17 CN CN201710963356.9A patent/CN107641422B/en not_active Expired - Fee Related
- 2017-10-17 CN CN201810654298.6A patent/CN108707355B/en active Active
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| CN1861715A (en) * | 2006-06-13 | 2006-11-15 | 马锡华 | Environment protection type colour thermosol |
| WO2009123771A2 (en) * | 2008-02-05 | 2009-10-08 | Crain John M | Coatings containing functionalized graphene sheets and articles coated therewith |
| CN101358097A (en) * | 2008-09-19 | 2009-02-04 | 河北科技大学 | Nano composite powder coatings and dispersion polymerization preparation method thereof |
| CN105085835A (en) * | 2014-05-14 | 2015-11-25 | 泰山玻璃纤维有限公司 | Graphene modified polyvinyl acetate film forming agent preparation method |
| CN105985711A (en) * | 2015-03-18 | 2016-10-05 | 关西涂料株式会社 | Powder coating composition and coated film forming method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108929615A (en) | 2018-12-04 |
| CN107641422B (en) | 2018-08-07 |
| CN108948954A (en) | 2018-12-07 |
| CN108707355A (en) | 2018-10-26 |
| CN107641422A (en) | 2018-01-30 |
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