CN112080187A - Graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention and preparation method thereof - Google Patents
Graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention and preparation method thereof Download PDFInfo
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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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
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- 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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- 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
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- 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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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention provides a graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention and a preparation method thereof, wherein the graphene modified solvent-free epoxy anticorrosive paint comprises a first component and a second component; the first component comprises the following raw materials in parts by weight: 1 part of polyether modified epoxy resin and 0.8 part of novolac epoxy resin1 part of modified graphene, 0.005-0.01 part of pigment and filler, 1.55-1.96 parts of defoamer, 0.02-0.03 part of dispersant, 0.01-0.02 part of flatting agent; the second component comprises 1 part of modified aromatic amine curing agent and 0.8-1 part of phenol curing agent. The coating disclosed by the invention has good physical and chemical properties, a 1.5-degree bending resistant coating has no crack, the impact resistance is 8J, the wear resistance is less than 50mg, the cathodic disbonding resistance is less than 12mm, a high-temperature and high-pressure resistant paint film is intact, and the chemical medium resistance is excellent. The paint can be used for corrosion prevention of the inside and the outside of a steel oil sleeve, and can adapt to high temperature, high pressure and H2S and CO2And (4) environment.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a graphene modified solvent-free epoxy anticorrosive coating for oil casing corrosion prevention and a preparation method thereof.
Background
The corrosion damage of the casing of the oil-water well is a great technical problem for development and production of oil fields in Changqing. The Changqing oil field belongs to a low-yield low-permeability oil field, and the developed old oil field accumulated casing damage well is nearly thousand. Except for the preserved areas and newly-built oil fields, the corrosion and damage of the casing pipes occur in all areas, and the old oil fields in Longdong, Ningxia and Shanxi are particularly prominent. The casing damage well seriously influences the stable production and development benefits of the oil field, and is a production technical problem which is urgently needed to be solved. Therefore, the research on the oil well casing anticorrosion technology which is low in cost, suitable for being implemented in the production field of the Changqing oil field, economic and effective has great significance.
In oil and gas production, the pipe is in an extremely harsh and complex environment (high temperature, high pressure, H)2S、CO2) Lower serviceThe surface of the material is provided with the corrosion-resistant coating, so that a corrosion medium can be effectively isolated to achieve the corrosion-resistant effect. However, the corrosion prevention of the coating layer also has some problems in practical application, such as high crosslinking density of the coating layer, large internal stress, brittleness, poor impact resistance, poor cathodic disbonding resistance and the like. The sleeve pipe can collide with each other in the transportation, loading and unloading and oil field operation, the damage to the outer coating of the sleeve pipe is difficult to avoid, the damage of an anticorrosive coating is caused, and under the action of an underground electrolyte solution, cathode stripping occurs, so that the coating fails. Meanwhile, the currently applied solvent-based epoxy coating mainly discharges a large amount of VOC in the coating drying process and pollutes the environment. Therefore, the development of solventless epoxy coatings and the resolution of the performance deficiencies of novolac epoxy coatings have been the focus of research on such coatings.
Disclosure of Invention
Aiming at the problems in the prior art, the main object of the invention is to provide a graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention and a preparation method thereof, wherein the prepared solvent-free epoxy paint has good cathodic disbonding resistance, flexibility, impact resistance, chemical stability, heat resistance, acid resistance, alkali resistance, wear resistance and low VOC.
In order to achieve the purpose, the invention adopts the following technical scheme:
a graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention comprises a first component and a second component;
the first component comprises the following raw materials in parts by weight:
1 part of polyether modified epoxy resin;
0.8-1 part of phenolic epoxy resin;
0.005-0.01 part of ethylenediamine graft modified graphene;
1.55-1.96 parts of pigment and filler;
0.02-0.03 part of defoaming agent;
0.01-0.02 part of a dispersant;
0.01-0.02 part of a leveling agent;
the second component includes an epoxy curing agent.
As a further improvement of the invention, the epoxy equivalent of the polyether modified epoxy resin is 300-320 g/eq, and the epoxy equivalent of the novolac epoxy resin is 195-235 g/eq.
As a further improvement of the invention, the second component comprises 1 part of modified aromatic amine curing agent and 0.8-1 part of phenolic curing agent.
As a further improvement of the invention, the preparation method of the ethylenediamine graft modified graphene comprises the following steps:
1) adding crystalline flake graphite into sulfuric acid, slowly adding potassium permanganate while stirring, controlling the reaction temperature to be less than 5 ℃ all the time, and standing to obtain dark green liquid;
2) adding the obtained dark green liquid into deionized water, uniformly stirring, and heating to 95 ℃;
3) adding hydrogen peroxide while the solution is hot, standing for reaction, filtering, washing and drying to obtain a graphene sample;
4) adding the obtained sample into DMF, and carrying out ultrasonic treatment to obtain a suspension;
5) then adding ethylenediamine and dicyclohexylcarbodiimide, reacting at 120 ℃ after ultrasonic mixing, adding absolute ethyl alcohol, and standing;
6) and removing the supernatant, filtering the lower precipitate, washing with ethanol and deionized water, and drying the obtained sample to obtain the modified graphene.
As a further improvement of the invention, the weight ratio of the first component to the second component is 1 (0.2-0.3).
As a further preference, the weight ratio of the first component to the second component is 1: 0.25.
Preferably, the pigment and filler comprises barium sulfate, talcum powder, titanium dioxide, mica powder and fumed silica.
As a further improvement of the invention, the pigment and filler comprises, by weight, 0.6-0.75 part of barium sulfate, 0.2-0.35 part of talcum powder, 0.25-0.3 part of titanium dioxide, 0.3-0.45 part of mica powder and 0.003-0.005 part of fumed silica.
As a further improvement of the invention, the first component comprises the following raw materials in parts by weight:
1 part of polyether modified epoxy resin,
0.9 part of phenolic epoxy resin,
0.0075 part of ethylenediamine graft modified graphene,
0.7 part of barium sulfate, 0.3 part of talcum powder,
0.27 part of titanium dioxide, 0.41 part of mica powder, 0.004 part of fumed silica,
0.0254 part of a defoaming agent,
0.0178 parts of a dispersing agent,
0.018 parts of a leveling agent;
the second component comprises 1 part of modified aromatic amine curing agent and 0.85 part of phenolic curing agent.
As a further improvement of the invention, the coating has the advantages of no crack in a 1.5-degree bending resistant coating, 8J impact resistance, less than 50mg wear resistance, less than 12mm cathodic disbonding resistance and good high-temperature and high-pressure resistant paint film.
The preparation method of the graphene modified solvent-free epoxy anticorrosive paint comprises the following steps:
1) placing the novolac epoxy resin into an oven for preheating;
2) heating the pigment and filler to remove water;
3) mixing phenolic epoxy resin, polyether modified epoxy resin, a defoaming agent, a dispersing agent and a flatting agent, stirring, adding the modified graphene and pigment filler under the condition of stirring, continuing stirring to uniformly disperse the components, and grinding to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint;
4) mixing the modified aromatic amine curing agent and the phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
5) and uniformly mixing the first component and the second component to obtain the graphene modified solvent-free epoxy anticorrosive paint.
In the step 1), the preheating temperature is 50-60 ℃, and the preheating time is 4-5 h; in the step 2), the heating temperature is 120-180 ℃, and the water removal time is 10-15 h.
Further preferably, in the step 3), the temperature during the stirring is 20 to 40 ℃.
As a further preference, in the step 3), the grinding time is 0.5 to 1 hour.
As a further preferred option, in the step 5), the second component is mixed with the first component after being uniformly stirred and dispersed.
Compared with the prior art, the invention has the following beneficial effects:
the graphene modified solvent-free epoxy anticorrosive paint provided by the invention is prepared by blending phenolic epoxy resin and polyether modified epoxy resin with good flexibility, so that the flexibility of a paint system is improved. The modified aromatic curing agent capable of improving the heat resistance of the coating and the phenolic curing agent capable of improving the curing speed and the flexibility of the coating are selected, so that the curing time is shortened and the working efficiency is improved while the performance of the coating is ensured to meet the requirements. The selection of the resin system and the curing agent enables the coating to have the advantages of good chemical stability, heat resistance, acid resistance, alkali resistance, wear resistance and the like of the traditional solvent type novolac epoxy coating, and also has good flexibility, impact resistance and low VOC (volatile organic compounds) emission. The graphene which is prepared and modified by self is used, so that the problem that the graphene is difficult to disperse in the coating is well solved. The graphene has the advantages of good thermal stability, chemical medium resistance, good thermal conductivity, high hardness and the like, and the heat resistance, the shock resistance and the wear resistance of the coating can be improved by adding the graphene into the coating. Meanwhile, the flaky graphene can be arranged in an oriented manner in the coating drying process and overlapped with each other, so that H is effectively shielded2O、CO2、Cl-1And the like, so that the unicorn platelets cannot directly permeate the unicorn platelets and only can permeate by roundabout, the permeation path is prolonged, the labyrinth effect is achieved, capillary microscopic channels in the coating are cut off, the permeability is reduced, and the corrosion resistance and the cathodic disbonding resistance of the coating are improved. The graphene modified solvent-free epoxy anticorrosive paint coating prepared by the invention has good physical and chemical properties, no crack in 1.5-degree bending resistance, 8J impact resistance, less than 50mg of wear resistance (1000g, 1000r and CS17 turns), less than 12mm of cathodic disbonding resistance, high temperature and high pressure resistance (90 ℃,total pressure 20MPa, H2S partial pressure 0.5MPa, CO2Partial pressure of 0.5MPa, 168h) is good, and the chemical medium resistance is excellent.
The graphene modified solvent-free epoxy anticorrosive paint can be used for corrosion prevention of the inside and the outside of an oil casing, and can adapt to high temperature, high pressure and H2S and CO2And (4) environment.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, shall fall within the scope of protection of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The first purpose of the invention is to provide a graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention, which comprises a first component and a second component; the first component comprises the following raw materials in parts by weight: 1 part of polyether modified epoxy resin, 0.8-1 part of novolac epoxy resin, 0.005-0.01 part of modified graphene, 1.55-1.96 parts of pigment and filler, 0.02-0.03 part of defoaming agent, 0.01-0.02 part of dispersing agent and 0.01-0.02 part of flatting agent; the second component comprises 1 part of modified aromatic amine curing agent and 0.8-1 part of phenolic curing agent.
The invention also provides a preparation method of the graphene modified solvent-free epoxy anticorrosive paint, which comprises the following steps:
1) placing the novolac epoxy resin into an oven for preheating; the preheating temperature is 50-60 ℃, and the preheating time is 4-5 h;
2) heating the pigment and filler to remove water; the heating temperature is 120-180 ℃, and the water removal time is 10-15 h.
3) Mixing phenolic epoxy resin, polyether modified epoxy resin, a defoaming agent, a dispersing agent and a flatting agent, stirring, adding the modified graphene and pigment filler under the condition of stirring, continuing stirring to uniformly disperse the components, and grinding to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint; the temperature during stirring is 20-40 ℃. The grinding time is 0.5-1 h.
4) Mixing the modified aromatic amine curing agent and the phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
5) and uniformly stirring and dispersing the second component, and then mixing the second component with the first component. And uniformly mixing the first component and the second component to obtain the graphene modified solvent-free epoxy anticorrosive paint.
The preparation method of the invention is explained in detail below with reference to specific examples (the proportions of the components are in parts by weight):
example 1
The preparation method of the graphene modified solvent-free epoxy anticorrosive paint in the embodiment 1 includes the following steps:
step (1), placing novolac epoxy resin into a 40 ℃ oven for 5 hours for preheating;
step (2), 0.6 part of barium sulfate, 0.2 part of talcum powder, 0.25 part of titanium dioxide, 0.3 part of mica powder and 0.003 part of fumed silica are placed in a high-temperature box at 150 ℃ to be heated and dewatered for 12 hours to obtain the coating pigment and filler;
step (3), mixing 1 part of polyether modified epoxy resin, 0.8 part of novolac epoxy resin, 0.02 part of defoaming agent, 0.015 part of dispersing agent and 0.015 part of flatting agent, stirring at normal temperature, adding coating pigment and filler and 0.005 part of modified graphene under the stirring condition, continuing stirring at high speed for 30-40min to uniformly disperse the components, and then grinding for 0.5-1h by using a grinding machine to obtain a first component of the graphene modified solvent-free epoxy anticorrosive coating;
step (4), mixing 1 part of modified aromatic amine curing agent and 0.8 part of phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
and (5) uniformly mixing the first component and the second component in a weight ratio of 1:0.3 to obtain the graphene modified solvent-free epoxy anticorrosive paint.
Various performances of the graphene modified solvent-free epoxy anticorrosive paint obtained in the embodiment are tested, and various performances of the paint and a coating thereof are shown in table 1.
Table 1 properties of graphene-modified solvent-free epoxy anticorrosive paint obtained in example 1
Example 2
The preparation method of the graphene modified solvent-free epoxy anticorrosive paint of the embodiment 2 comprises the following steps of:
step (1), placing novolac epoxy resin into a 40 ℃ oven for 5 hours for preheating;
step (2), 0.7 part of barium sulfate, 0.3 part of talcum powder, 0.25 part of titanium dioxide, 0.4 part of mica powder and 0.004 part of fumed silica are placed in a high-temperature box at 150 ℃ to be heated and dewatered for 12 hours to obtain the pigment and filler of the coating;
step (3), mixing 1 part of polyether modified epoxy resin, 0.9 part of novolac epoxy resin, 0.0254 part of defoaming agent, 0.0178 part of dispersing agent and 0.018 part of flatting agent, stirring at normal temperature, adding paint pigment and filler and 0.0075 parts of modified graphene under the stirring condition, continuing stirring at high speed for 30-40min to uniformly disperse the components, and then grinding for 0.5-1h by using a grinding machine to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint;
step (4), mixing 1 part of modified aromatic amine curing agent and 0.85 part of phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
and (5) uniformly mixing the first component and the second component in a weight ratio of 1:0.25 to obtain the graphene modified solvent-free epoxy anticorrosive paint.
Various performances of the graphene modified solvent-free epoxy anticorrosive paint obtained in the embodiment are tested, and various performances of the paint and a coating thereof are shown in table 2.
Table 2 properties of graphene-modified solvent-free epoxy anticorrosive paint obtained in example 2
Example 3
In example 1 and example 2, the preparation and modification of graphene comprises the following steps:
1) adding 10g of flake graphite into 230mL of concentrated sulfuric acid, slowly adding 30g of potassium permanganate while stirring by using an electric stirrer, controlling the reaction temperature to be less than 5 ℃ all the time, and standing for 96 hours;
2) adding the obtained dark green liquid into 460mL of deionized water; stirring the obtained solution at 35 ℃ to react for 1.5h, then heating to 95 ℃ to react for 1 h;
3) 30mL of 30% hydrogen peroxide is added while the solution is hot, the solution is kept stand for 12h, filtered, washed by 1000mL of 5% hydrochloric acid, washed by 3000mL of deionized water until sulfate ions do not exist, and dried at 70 ℃ to obtain a graphene sample.
4) Adding 200mg of the sample obtained in the step 3) into 200mL of DMF, and carrying out ultrasonic treatment for 2.5h to obtain a suspension;
5) then adding 30g of Ethylenediamine (EDA) and 5g of dicyclohexylcarbodiimide, carrying out ultrasonic treatment for 5min, reacting for 48h at 120 ℃, adding 60mL of absolute ethyl alcohol, and standing overnight;
6) and removing the supernatant, filtering the lower precipitate by using a polytetrafluoroethylene membrane, washing by using ethanol and deionized water, and drying the obtained sample at 70 ℃ to obtain the modified graphene.
Example 4
A preparation method of graphene modified solvent-free epoxy anticorrosive paint comprises the following steps:
1) placing the novolac epoxy resin into an oven for preheating; the preheating temperature is 50 ℃, and the preheating time is 4 hours;
2) heating 0.6 part of barium sulfate, 0.2 part of talcum powder, 0.25 part of titanium dioxide, 0.3 part of mica powder and 0.003 part of fumed silica to remove water; the heating temperature is 120 ℃, and the water removing time is 10 hours.
3) Mixing 1 part of polyether modified epoxy resin, 0.8 part of novolac epoxy resin, 0.02 part of defoaming agent, 0.01 part of dispersing agent and 0.01 part of flatting agent, stirring, adding 0.005 part of modified graphene and 1.55 parts of pigment and filler under the stirring condition, continuing stirring to uniformly disperse the components, and grinding to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint; the temperature during the stirring was 20 ℃. The grinding time is 0.5 h.
4) Mixing 1 part of modified aromatic amine curing agent and 0.8 part of phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
5) and uniformly stirring and dispersing the second component, and mixing the second component and the first component according to the weight ratio of 1: 0.2. And uniformly mixing the first component and the second component to obtain the graphene modified solvent-free epoxy anticorrosive paint.
Example 5
A preparation method of graphene modified solvent-free epoxy anticorrosive paint comprises the following steps:
1) placing the novolac epoxy resin into an oven for preheating; the preheating temperature is 60 ℃, and the preheating time is 5 hours;
2) heating 0.75 parts of barium sulfate, 0.35 parts of talcum powder, 0.3 parts of titanium dioxide, 0.45 parts of mica powder and 0.005 parts of fumed silica to remove water; the heating temperature is 180 ℃, and the water removing time is 15 h.
3) Mixing 1 part of polyether modified epoxy resin, 0.9 part of novolac epoxy resin, 0.025 part of defoaming agent, 0.015 part of dispersing agent and 0.015 part of flatting agent, stirring, adding 0.008 part of modified graphene and 1.8 parts of pigment and filler under the stirring condition, continuously stirring to uniformly disperse the components, and grinding to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint; the temperature during the stirring was 30 ℃. The grinding time is 0.7 h.
4) Mixing 1 part of modified aromatic amine curing agent and 0.9 part of phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
5) and uniformly stirring and dispersing the second component, and mixing the second component and the first component according to the weight ratio of 1: 0.25. And uniformly mixing the first component and the second component to obtain the graphene modified solvent-free epoxy anticorrosive paint.
Example 6
A preparation method of graphene modified solvent-free epoxy anticorrosive paint comprises the following steps:
1) placing the novolac epoxy resin into an oven for preheating; the preheating temperature is 55 ℃, and the preheating time is 4.5 h;
2) heating to remove water, wherein the weight parts of barium sulfate, talcum powder, titanium dioxide, mica powder and gas-phase silicon dioxide are respectively 0.7 part, 0.3 part, 0.28 part, 0.4 part and 0.004 part, respectively; the heating temperature is 16 ℃, and the water removal time is 14 h.
3) Mixing 1 part of polyether modified epoxy resin, 1 part of novolac epoxy resin, 0.03 part of defoaming agent, 0.02 part of dispersing agent and 0.02 part of flatting agent, stirring, adding modified graphene, 0.01 part of modified graphene and 1.96 parts of pigment and filler under the stirring condition, continuously stirring to uniformly disperse the components, and grinding to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint; the temperature during the stirring was 40 ℃. The grinding time is 1 h.
4) Mixing 1 part of modified aromatic amine curing agent and 1 part of phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
5) and uniformly stirring and dispersing the second component, and mixing the second component and the first component according to the weight ratio of 1: 0.3. And uniformly mixing the first component and the second component to obtain the graphene modified solvent-free epoxy anticorrosive paint.
The graphene modified solvent-free epoxy anticorrosive paint can be used for corrosion prevention of the inside and the outside of an oil casing, and can adapt to high temperature, high pressure and H2S and CO2And (4) environment. Particularly, under the action of the underground electrolyte solution, cathode stripping is not easy to occur.
The paint prepared by the invention has good physical and chemical properties, and can be obtained by testing: the coating has no crack when bending at 1.5 degrees, the impact resistance is 8J, the wear resistance (1000g, 1000r, CS17 wheel) is less than 50mg, the cathodic disbonding resistance is less than 12mm, and the coating resists high temperature and high pressure (90 ℃, the total pressure is 20MPa, H and H)2S partial pressure 0.5MPa, CO2Partial pressure of 0.5MPa, 168h) is good, and the chemical medium resistance is excellent. The paint can be used for corrosion prevention of the inside and the outside of a steel oil sleeve, and can adapt to high temperature, high pressure and H2S and CO2And (4) environment.
At present, tens of thousands of kilometers of underground oil casings and ground gathering and transporting pipelines in service of Changqing oil fields pass field tests, and if the corrosion inhibitor can be successfully applied to the oil casings and the ground gathering and transporting pipelines for corrosion prevention, the operation risk caused by corrosion failure can be effectively reduced, and the material and construction cost for replacing the pipes can be saved.
It is to be understood that the above description is intended to be illustrative, and not restrictive. Many embodiments and many applications other than the examples provided would be apparent to those of skill in the art upon reading the above description. The scope of the present teachings should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are hereby incorporated by reference for all purposes. The omission in the foregoing claims of any aspect of subject matter that is disclosed herein is not intended to forego such subject matter, nor should the applicant consider that such subject matter is not considered part of the disclosed subject matter.
Claims (10)
1. The graphene modified solvent-free epoxy anticorrosive paint for oil casing corrosion prevention is characterized by comprising the following components in parts by weight: comprises a first component and a second component;
the first component comprises the following raw materials in parts by weight:
1 part of polyether modified epoxy resin;
0.8-1 part of phenolic epoxy resin;
0.005-0.01 part of ethylenediamine graft modified graphene;
1.55-1.96 parts of pigment and filler;
0.02-0.03 part of defoaming agent;
0.01-0.02 part of a dispersant;
0.01-0.02 part of a leveling agent;
the second component includes an epoxy curing agent.
2. The graphene-modified solvent-free epoxy anticorrosive paint according to claim 1, characterized in that: the second component comprises 1 part of modified aromatic amine curing agent and 0.8-1 part of phenol curing agent.
3. The graphene-modified solvent-free epoxy anticorrosive paint according to claim 1, characterized in that: the weight ratio of the first component to the second component is 1 (0.2-0.3).
4. The graphene-modified solvent-free epoxy anticorrosive paint according to claim 1, characterized in that: the preparation method of the ethylenediamine grafted modified graphene comprises the following steps:
1) adding crystalline flake graphite into sulfuric acid, slowly adding potassium permanganate while stirring, controlling the reaction temperature to be less than 5 ℃ all the time, and standing to obtain dark green liquid;
2) adding the obtained dark green liquid into deionized water, uniformly stirring, and heating to 95 ℃;
3) adding hydrogen peroxide while the solution is hot, standing for reaction, filtering, washing and drying to obtain a graphene sample;
4) adding the obtained sample into DMF, and carrying out ultrasonic treatment to obtain a suspension;
5) then adding ethylenediamine and dicyclohexylcarbodiimide, reacting at 120 ℃ after ultrasonic mixing, adding absolute ethyl alcohol, and standing;
6) and removing the supernatant, filtering the lower precipitate, washing with ethanol and deionized water, and drying the obtained sample to obtain the modified graphene.
5. The graphene-modified solvent-free epoxy anticorrosive paint according to claim 1, characterized in that: the pigment and filler comprises barium sulfate, talcum powder, titanium dioxide, mica powder and fumed silica; 0.6 to 0.75 portion of barium sulfate, 0.2 to 0.35 portion of talcum powder, 0.25 to 0.3 portion of titanium dioxide, 0.3 to 0.45 portion of mica powder and 0.003 to 0.005 portion of fumed silica.
6. The graphene-modified solvent-free epoxy anticorrosive paint according to claim 1, characterized in that:
the first component comprises the following raw materials in parts by weight:
1 part of polyether modified epoxy resin,
0.9 part of phenolic epoxy resin,
0.0075 part of ethylenediamine graft modified graphene,
0.7 part of barium sulfate, 0.3 part of talcum powder,
0.27 part of titanium dioxide, 0.41 part of mica powder, 0.004 part of fumed silica,
0.0254 part of a defoaming agent,
0.0178 parts of a dispersing agent,
0.018 parts of a leveling agent;
the second component comprises 1 part of modified aromatic amine curing agent and 0.85 part of phenolic curing agent.
7. The graphene-modified solvent-free epoxy anticorrosive paint according to any one of claims 1 to 7, characterized in that: the coating has the advantages of no crack of a 1.5-degree bending resistant coating, impact resistance of 8J, abrasion resistance of less than 50mg, cathodic disbonding resistance of less than 12mm and good high-temperature and high-pressure resistant paint film.
8. The method for manufacturing the graphene-modified solvent-free epoxy anticorrosive paint according to any one of claims 1 to 7, comprising the steps of:
1) placing the novolac epoxy resin into an oven for preheating;
2) heating the pigment and filler to remove water;
3) mixing phenolic epoxy resin, polyether modified epoxy resin, a defoaming agent, a dispersing agent and a flatting agent, stirring, adding the modified graphene and pigment filler under the condition of stirring, continuing stirring to uniformly disperse the components, and grinding to obtain a first component of the graphene modified solvent-free epoxy anticorrosive paint;
4) mixing the modified aromatic amine curing agent and the phenolic curing agent, and uniformly stirring to obtain a second component of the graphene modified solvent-free epoxy anticorrosive paint;
5) and uniformly mixing the first component and the second component to obtain the graphene modified solvent-free epoxy anticorrosive paint.
9. The method for manufacturing the graphene-modified solvent-free epoxy anticorrosive paint according to claim 8, characterized in that: in the step 1), the preheating temperature is 50-60 ℃, and the preheating time is 4-5 h; in the step 2), the heating temperature is 120-180 ℃, and the water removal time is 10-15 h.
10. The graphene-modified solvent-free epoxy anticorrosive paint according to claim 1, characterized in that: and uniformly stirring and dispersing the second component, and then mixing the second component with the first component.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382555A (en) * | 2011-10-12 | 2012-03-21 | 上海海隆赛能新材料有限公司 | Solvent-free low-temperature solidified phenolic epoxy anticorrosive paint and preparation method thereof |
| CN110128943A (en) * | 2019-04-11 | 2019-08-16 | 宜昌市三峡天润纳米材料工程技术研究中心有限公司 | A kind of graphene high-efficiency energy anticorrosive paint and preparation method thereof and product |
| CN110607112A (en) * | 2019-08-26 | 2019-12-24 | 中国石油天然气集团公司 | Water-based epoxy heavy-duty anticorrosive paint and preparation method thereof |
| CN111087894A (en) * | 2019-12-18 | 2020-05-01 | 中国石油天然气股份有限公司 | Nano solvent-free epoxy anticorrosive paint and preparation method thereof |
-
2020
- 2020-08-28 CN CN202010888534.8A patent/CN112080187A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382555A (en) * | 2011-10-12 | 2012-03-21 | 上海海隆赛能新材料有限公司 | Solvent-free low-temperature solidified phenolic epoxy anticorrosive paint and preparation method thereof |
| CN110128943A (en) * | 2019-04-11 | 2019-08-16 | 宜昌市三峡天润纳米材料工程技术研究中心有限公司 | A kind of graphene high-efficiency energy anticorrosive paint and preparation method thereof and product |
| CN110607112A (en) * | 2019-08-26 | 2019-12-24 | 中国石油天然气集团公司 | Water-based epoxy heavy-duty anticorrosive paint and preparation method thereof |
| CN111087894A (en) * | 2019-12-18 | 2020-05-01 | 中国石油天然气股份有限公司 | Nano solvent-free epoxy anticorrosive paint and preparation method thereof |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248959A (en) * | 2021-05-18 | 2021-08-13 | 深圳优易材料科技有限公司 | High-temperature-wear-resistant anticorrosive paint and preparation method and application thereof |
| CN113930131A (en) * | 2021-11-11 | 2022-01-14 | 铜陵有色金属集团铜冠建筑安装股份有限公司 | Graphene modified epoxy anticorrosive paint and preparation method thereof |
| CN116265544A (en) * | 2021-12-16 | 2023-06-20 | 中国石油天然气股份有限公司 | Underground high-temperature-resistant anti-corrosion coating, and preparation method and application method thereof |
| CN114381182A (en) * | 2022-01-20 | 2022-04-22 | 陕西燕园众欣石墨烯科技有限公司 | Graphene type low-viscosity thin-coating high-hardness super-wear-resistant solvent-free epoxy coating and preparation method thereof |
| CN115109494A (en) * | 2022-08-17 | 2022-09-27 | 山东玉皇新能源科技有限公司 | Flame-retardant graphene anticorrosive paint |
| CN115181478A (en) * | 2022-08-17 | 2022-10-14 | 山东玉皇新能源科技有限公司 | Graphene modified anticorrosive paint, and preparation method and application thereof |
| CN115181478B (en) * | 2022-08-17 | 2023-09-15 | 山东玉皇新能源科技有限公司 | Graphene modified anticorrosive paint, preparation method and application thereof |
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