CN114836098A - Preparation method of anticorrosive paint for offshore petroleum pipeline - Google Patents
Preparation method of anticorrosive paint for offshore petroleum pipeline 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
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- 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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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
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Abstract
The invention relates to the technical field of paint preparation, and discloses a preparation method of an anticorrosive paint for an offshore petroleum pipeline, wherein the paint comprises a component A and a component B in a mass ratio of 6: 1, mixing to obtain the product; the component A comprises the following raw materials in parts by weight: 50-80 parts of modified epoxy resin emulsion, 15-30 parts of modified graphene, 2-5 parts of dispersing agent, 1-3 parts of flatting agent, 1-3 parts of defoaming agent, 10-20 parts of film forming assistant and 20-30 parts of deionized water; the modified epoxy resin emulsion molecular chain main chain contains sulfur atoms, the sulfur atoms are easily combined with sulfydryl through hydrogen bonds, and the amino acid structure necessary for bacteria growth and reproduction contains sulfydryl, so that the amino acid required by bacteria can be combined with the epoxy resin emulsion molecular chain to influence the bacteria metabolism, meanwhile, the side chain contains a capsaicin structure, marine organisms can be prevented from being adsorbed on the surface of the coating, and further, the influence of the marine organisms and microorganisms on corrosion resistance is avoided.
Description
Technical Field
The invention relates to the technical field of paint preparation, in particular to a preparation method of an anticorrosive paint for an offshore petroleum pipeline.
Background
The anticorrosive coating is generally divided into a conventional anticorrosive coating and a heavy anticorrosive coating, and is an indispensable coating in paint coatings, the conventional anticorrosive coating plays a role in corrosion resistance on metals and the like under general conditions and protects the service life of nonferrous metals, and the heavy anticorrosive coating is a type of anticorrosive coating which can be applied in a relatively harsh corrosion environment compared with the conventional anticorrosive coating and has a longer protection period than the conventional anticorrosive coating;
the heavy anti-corrosion coating is mainly different from the conventional anti-corrosion coating in that the technical content is high, the technical difficulty is high, technical progress and product development in many aspects are involved, the heavy anti-corrosion coating does not depend on knowledge and experience of the coating excessively, but depends on knowledge and intersection of multiple subjects such as electronics, physics, ecology, machinery, instruments and management, the synthesis of high-corrosion-resistant resin, the application of efficient dispersing agent and rheological aid, the development of novel anti-corrosion anti-permeability pigment and filler, the application of advanced construction tools, construction maintenance technology, field detection technology and the like, and the heavy anti-corrosion coating and the coating are required to be comprehensively applied, so how the development level and performance of the heavy anti-corrosion coating are, the sign for marking the national scientific and technical level, and the sign for measuring the advanced technology of the anti-corrosion coating;
the existing anticorrosive coating for offshore petroleum pipelines has the advantages that the anticorrosive performance is gradually reduced or even disappears along with the long-time use of the petroleum pipelines, and a large amount of marine organisms and microorganisms are attached to the petroleum pipelines, so that the corrosion speed of the surfaces of the pipelines is increased;
a solution is now proposed to address the technical drawback in this respect.
Disclosure of Invention
The invention aims to provide a preparation method of an anticorrosive coating for an offshore petroleum pipeline.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an anticorrosive coating for offshore petroleum pipelines comprises the following steps of: 1, mixing to obtain the product;
the component A comprises the following raw materials in parts by weight: 50-80 parts of modified epoxy resin emulsion, 15-30 parts of modified graphene, 2-5 parts of dispersing agent, 1-3 parts of flatting agent, 1-3 parts of defoaming agent, 10-20 parts of film forming assistant and 20-30 parts of deionized water;
the component A is prepared by the following steps:
stirring the raw materials for 1-2h at the rotation speed of 1500-;
the component B is ethylenediamine, benzoyl peroxide and ethylene glycol in a mass ratio of 1: 1: 10, and mixing.
Further, the dispersing agent is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate which are mixed in any proportion, the flatting agent is one or two of isophorone and diacetone alcohol which are mixed in any proportion, the defoaming agent is one or more of polydimethylsiloxane, dimethylpolysiloxane and simethicone which are mixed in any proportion, and the film-forming auxiliary agent is one or two of propylene glycol butyl ether and propylene glycol methyl ether acetate which are mixed in any proportion.
Further, the modified epoxy resin emulsion is prepared by the following steps:
step A1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding toluene under the conditions of conversion to 150-plus-one at 200r/min and temperature of 10-15 ℃, reacting for 1-1.5h under the condition of temperature of 40-45 ℃ to obtain an intermediate 1, mixing the intermediate 1 with deionized water, refluxing for 10-15min under the condition of temperature of 110-plus-one at 120 ℃ to obtain an intermediate 2, adding the intermediate 2, hydroxylamine hydrochloride, ethanol and deionized water into the reaction kettle, stirring and adding sodium hydroxide under the conditions of rotation speed of 120-plus-one at 150r/min and temperature of 30-40 ℃, reacting for 3-4h, heating to 70-80 ℃, adding a hydrochloric acid solution, and preserving heat for 10-15min to obtain an intermediate 3;
the reaction process is as follows:
step A2: adding the intermediate 3, ethanol and concentrated hydrochloric acid into a reaction kettle, stirring and adding zinc powder under the conditions of the rotation speed of 150-, adding cuprous oxide, and reacting for 20-30min to obtain intermediate 6;
the reaction process is as follows:
step A3: adding the intermediate 6, potassium carbonate, tetrahydrofuran and tetraethylammonium bromide into a reaction kettle, carrying out reflux reaction for 2-3h to obtain an intermediate 7, reacting the epoxy resin E-44 and the intermediate 7 for 2-4h under the conditions that the rotating speed is 120-160 ℃ and the temperature is 150-160 ℃ to obtain an intermediate 8, dissolving hydroxylamine hydrochloride into deionized water, stirring and adding a potassium hydroxide solution under the condition of ice-water bath, adding vanillin, carrying out reaction for 2-3h to obtain an intermediate 9, dissolving the intermediate 9 into ethanol, adding raney nickel, and introducing hydrogen to react for 5-8h under the condition that the temperature is 35-40 ℃ to obtain an intermediate 10;
the reaction process is as follows:
step A4: reacting the intermediate 10, acryloyl chloride, potassium carbonate and tetrahydrofuran at 50-60 ℃ for 5-6h to obtain an intermediate 11, dissolving the intermediate 8 in ethylene glycol monobutyl ether, stirring and adding methacrylic acid, styrene, the intermediate 11 and dibenzoyl peroxide at the rotation speed of 150-200r/min and the temperature of 90-95 ℃, heating to the temperature of 110-120 ℃, reacting for 6-8h, adding deionized water and adjusting the reaction liquid to 7 to obtain the modified epoxy resin emulsion.
The reaction process is as follows:
further, the dosage ratio of aluminum trichloride, carbon tetrachloride and toluene in the step A1 is 8.5 g: 0.1 mol: 0.2mol, wherein the dosage ratio of the intermediate 2, hydroxylamine hydrochloride, ethanol, deionized water, sodium hydroxide and hydrochloric acid solution is 0.05 mol: 0.085 mol: 20mL of: 5mL of: 11 g: 200mL, the mass fraction of the hydrochloric acid solution is 25%.
Further, the dosage ratio of the intermediate 3, ethanol, concentrated hydrochloric acid, zinc powder, ammonia water and sodium hydroxide solution in the step A2 is 0.02 mol: 12mL of: 30mL of: 0.2 mol: 28mL of: 60mL, 30 percent of ammonia water, 20 percent of sodium hydroxide solution, 0.1mol of intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride: 0.1 mol: 0.2 g: 200mL, wherein the dosage ratio of the intermediate 5, concentrated hydrochloric acid, acetone, copper sulfate, sodium nitrite solution, ethyl acrylate and cuprous oxide is 0.1 mol: 24mL of: 100 g: 0.01 mol: 15mL of: 0.5 mol: 0.6g, the mass fraction of the sodium nitrite solution is 70 percent, and the mass fraction of the concentrated hydrochloric acid is 36 percent.
Further, the amount ratio of the intermediate 6, potassium carbonate, tetrahydrofuran and tetraethylammonium bromide in the step A3 is 3 g: 8.5 g: 100mL of: 3mL, and the molar ratio of the epoxy resin E-44 to the intermediate 7 is 2: 1, the dosage ratio of hydroxylamine hydrochloride, potassium hydroxide solution and vanillin is 2.5 mol: 200mL of: 0.5mol, the mass fraction of the potassium hydroxide solution is 50%, and the dosage ratio of the intermediate 9 to the Raney nickel is 0.05 mol: 8 g.
Further, the dosage ratio of the intermediate 10, acryloyl chloride, potassium carbonate and tetrahydrofuran in the step A4 is 2 mol: 2 mol: 25 mol: 8mL, wherein the mass ratio of the intermediate 8, the methacrylic acid, the styrene, the intermediate 11, the dibenzoyl peroxide and the deionized water is 30: 10: 4: 4: 0.8: 80.
further, the modified graphene is prepared by the following steps:
step B1: mixing graphene, aniline and N, N-dimethylformamide, carrying out ultrasonic treatment for 50-60min under the condition of 40-45kHz frequency, adding deionized water, and uniformly mixing to obtain a mixed solution;
step B2: and adding the mixed solution and ammonium persulfate into a reaction kettle, reacting for 8-10h at the temperature of 5-10 ℃, filtering and drying to obtain the modified graphene.
Further, the using amount ratio of the graphene, the aniline, the N, N-dimethylformamide and the deionized water in the step B1 is 5 g: 1 g: 30mL of: 90 mL.
Further, the dosage ratio of the mixed solution in the step B2 to the ammonium persulfate is 4 mL: 1g of the total weight of the composition.
The invention has the following beneficial effects:
the invention prepares a modified epoxy resin emulsion in the process of preparing an anticorrosive coating for offshore oil pipelines, the modified epoxy resin emulsion takes carbon tetrachloride and toluene as raw materials to react to prepare an intermediate 1, the intermediate 1 is treated by deionized water reflux to prepare an intermediate 2, the intermediate 2 is reacted with hydroxylamine hydrochloride to prepare an intermediate 3, the intermediate 3 is treated by zinc powder to prepare an intermediate 4, the intermediate 4 is reacted with nitrogen-bromosuccinimide to prepare an intermediate 5, the intermediate 5 is reacted with ethyl acrylate to prepare an intermediate 6, the intermediate 6 is further treated to prepare an intermediate 7, the intermediate 7 is used as a chain extender to react with epoxy resin E-44 to prepare an intermediate 8, the hydroxylamine hydrochloride and vanillin are reacted to prepare an intermediate 9, the intermediate 9 is treated by Raney nickel, preparing an intermediate 10, reacting the intermediate 10 with acryloyl chloride to prepare an intermediate 11, polymerizing the intermediate 8, methacrylic acid, styrene and the intermediate 11, reacting unsaturated double bonds of the methacrylic acid with methylene beside ether bonds of the intermediate 8 to prepare a modified epoxy resin emulsion, wherein the main chain of a molecular chain of the modified epoxy resin emulsion contains sulfur atoms which are easily combined with sulfydryl through hydrogen bonds, and an amino acid structure necessary for bacterial growth and reproduction contains sulfydryl, so that the amino acid required by bacteria can be combined with the molecular chain of the epoxy resin emulsion to influence bacterial metabolism, meanwhile, the side chain contains a capsaicin structure, marine organisms can be prevented from being adsorbed on the surface of a coating, further, the influence of the marine organisms and the microorganisms on corrosion resistance is avoided, and meanwhile, a layer of polyaniline layer can be formed inside a paint film by adding the modified graphene, so that the corrosion resistance of the coating is further improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of an anticorrosive coating for offshore petroleum pipelines comprises the following steps of: 1, mixing to obtain the product;
the component A comprises the following raw materials in parts by weight: 50 parts of modified epoxy resin emulsion, 15 parts of modified graphene, 2 parts of dispersing agent, 1 part of flatting agent, 1 part of defoaming agent, 10 parts of film-forming assistant and 20 parts of deionized water;
the component A is prepared by the following steps:
stirring the raw materials for 1h at the rotating speed of 1500r/min to prepare a component A;
the component B is ethylenediamine, benzoyl peroxide and ethylene glycol in a mass ratio of 1: 1: 10, and mixing.
The modified epoxy resin emulsion is prepared by the following steps:
step A1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding toluene under the conditions of 150r/min and 10 ℃, reacting for 1h under the condition of 40 ℃ to obtain an intermediate 1, mixing the intermediate 1 with deionized water, refluxing for 10min under the condition of 110 ℃ to obtain an intermediate 2, adding the intermediate 2, hydroxylamine hydrochloride, ethanol and deionized water into the reaction kettle, stirring and adding sodium hydroxide under the conditions of 120r/min of rotation speed and 30 ℃, reacting for 3h, heating to 70 ℃, adding a hydrochloric acid solution, and preserving heat for 10min to obtain an intermediate 3;
step A2: adding the intermediate 3, ethanol and concentrated hydrochloric acid into a reaction kettle, stirring and adding zinc powder under the conditions of the rotation speed of 150r/min and the temperature of 40 ℃, reacting for 4 hours, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, continuously stirring for 1 hour to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours under the temperature of 80 ℃ to obtain an intermediate 5, mixing and dropwise adding a sodium nitrite solution into the intermediate 5, concentrated hydrochloric acid, acetone and copper sulfate under the condition of an ice water bath, stirring for 10 minutes under the condition of the rotation speed of 120r/min, adding ethyl acrylate, heating to the temperature of 30 ℃, adding cuprous oxide, and reacting for 20 minutes to obtain an intermediate 6;
step A3: adding the intermediate 6, potassium carbonate, tetrahydrofuran and tetraethylammonium bromide into a reaction kettle, carrying out reflux reaction for 2 hours to obtain an intermediate 7, reacting the epoxy resin E-44 and the intermediate 7 for 2 hours at the rotation speed of 120r/min and the temperature of 150 ℃ to obtain an intermediate 8, dissolving hydroxylamine hydrochloride into deionized water, stirring and adding a potassium hydroxide solution under the condition of ice-water bath, adding vanillin, carrying out reaction for 2 hours to obtain an intermediate 9, dissolving the intermediate 9 into ethanol, adding raney nickel, and introducing hydrogen to react for 5 hours at the temperature of 35 ℃ to obtain an intermediate 10;
step A4: reacting the intermediate 10, acryloyl chloride, potassium carbonate and tetrahydrofuran for 5 hours at the temperature of 50 ℃ to obtain an intermediate 11, dissolving the intermediate 8 in ethylene glycol butyl ether, stirring and adding methacrylic acid, styrene, the intermediate 11 and dibenzoyl peroxide at the rotation speed of 150r/min and the temperature of 90 ℃, heating to the temperature of 110 ℃, reacting for 6 hours, adding deionized water and adjusting the reaction solution to be 7 to obtain the modified epoxy resin emulsion.
The modified graphene is prepared by the following steps:
step B1: mixing graphene, aniline and N, N-dimethylformamide, carrying out ultrasonic treatment for 50min under the condition that the frequency is 40kHz, adding deionized water, and uniformly mixing to obtain a mixed solution;
step B2: and adding the mixed solution and ammonium persulfate into a reaction kettle, reacting for 8 hours at the temperature of 5 ℃, filtering and drying to obtain the modified graphene.
Example 2:
a preparation method of an anticorrosive coating for offshore petroleum pipelines comprises the following steps of: 1, mixing to obtain the product;
the component A comprises the following raw materials in parts by weight: 65 parts of modified epoxy resin emulsion, 18 parts of modified graphene, 3 parts of dispersing agent, 2 parts of flatting agent, 2 parts of defoaming agent, 15 parts of film-forming assistant and 25 parts of deionized water;
the component A is prepared by the following steps:
stirring the raw materials for 2 hours at the rotating speed of 1500r/min to prepare a component A;
the component B is ethylenediamine, benzoyl peroxide and ethylene glycol in a mass ratio of 1: 1: 10, and mixing.
The modified epoxy resin emulsion is prepared by the following steps:
step A1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding toluene under the conditions of 150r/min and 15 ℃, reacting for 1.5h under the condition of 40 ℃ to obtain an intermediate 1, mixing the intermediate 1 with deionized water, refluxing for 15min under the condition of 110 ℃ to obtain an intermediate 2, adding the intermediate 2, hydroxylamine hydrochloride, ethanol and deionized water into the reaction kettle, stirring and adding sodium hydroxide under the conditions of 120r/min of rotation speed and 40 ℃, reacting for 3h, heating to 80 ℃, adding a hydrochloric acid solution, and preserving heat for 10min to obtain an intermediate 3;
step A2: adding the intermediate 3, ethanol and concentrated hydrochloric acid into a reaction kettle, stirring and adding zinc powder under the conditions of the rotation speed of 200r/min and the temperature of 40 ℃, reacting for 5 hours, cooling to the temperature of 0 ℃, adding ammonia water and a sodium hydroxide solution, continuously stirring for 1.5 hours to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours under the temperature of 80 ℃ to obtain an intermediate 5, mixing and dropwise adding a sodium nitrite solution into the intermediate 5, concentrated hydrochloric acid, acetone and copper sulfate under the condition of an ice water bath, stirring for 15 minutes under the condition of the rotation speed of 120r/min, adding ethyl acrylate, heating to the temperature of 30 ℃, adding cuprous oxide, and reacting for 30 minutes to obtain an intermediate 6;
step A3: adding the intermediate 6, potassium carbonate, tetrahydrofuran and tetraethylammonium bromide into a reaction kettle, carrying out reflux reaction for 2 hours to obtain an intermediate 7, reacting epoxy resin E-44 and the intermediate 7 for 4 hours at the rotation speed of 150r/min and the temperature of 150 ℃ to obtain an intermediate 8, dissolving hydroxylamine hydrochloride into deionized water, stirring and adding a potassium hydroxide solution under the condition of ice-water bath, adding vanillin, carrying out reaction for 2 hours to obtain an intermediate 9, dissolving the intermediate 9 into ethanol, adding raney nickel, and introducing hydrogen to react for 5 hours at the temperature of 40 ℃ to obtain an intermediate 10;
step A4: reacting the intermediate 10, acryloyl chloride, potassium carbonate and tetrahydrofuran for 5 hours at the temperature of 60 ℃ to obtain an intermediate 11, dissolving the intermediate 8 in ethylene glycol monobutyl ether, stirring and adding methacrylic acid, styrene, the intermediate 11 and dibenzoyl peroxide at the rotation speed of 200r/min and the temperature of 90 ℃, heating to 120 ℃, reacting for 6 hours, adding deionized water and adjusting the reaction liquid to 7 to obtain the modified epoxy resin emulsion.
The modified graphene is prepared by the following steps:
step B1: mixing graphene, aniline and N, N-dimethylformamide, carrying out ultrasonic treatment for 50min under the condition that the frequency is 45kHz, adding deionized water, and uniformly mixing to obtain a mixed solution;
step B2: and adding the mixed solution and ammonium persulfate into a reaction kettle, reacting for 8 hours at the temperature of 10 ℃, filtering and drying to obtain the modified graphene.
Example 3:
a preparation method of an anticorrosive coating for offshore petroleum pipelines comprises the following steps of: 1, mixing to obtain the product;
the component A comprises the following raw materials in parts by weight: 80 parts of modified epoxy resin emulsion, 30 parts of modified graphene, 5 parts of dispersing agent, 3 parts of flatting agent, 3 parts of defoaming agent, 20 parts of film-forming assistant and 30 parts of deionized water;
the component A is prepared by the following steps:
stirring the raw materials for 2 hours at the rotating speed of 2000r/min to prepare a component A;
the component B is ethylenediamine, benzoyl peroxide and ethylene glycol in a mass ratio of 1: 1: 10, and mixing.
The modified epoxy resin emulsion is prepared by the following steps:
step A1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding toluene under the conditions of 200r/min and 15 ℃, reacting for 1.5h under the condition of 45 ℃ to obtain an intermediate 1, mixing the intermediate 1 with deionized water, refluxing for 15min under the condition of 120 ℃ to obtain an intermediate 2, adding the intermediate 2, hydroxylamine hydrochloride, ethanol and deionized water into the reaction kettle, stirring and adding sodium hydroxide under the conditions of 150r/min of rotation speed and 40 ℃, reacting for 4h, heating to 80 ℃, adding a hydrochloric acid solution, and preserving heat for 15min to obtain an intermediate 3;
step A2: adding the intermediate 3, ethanol and concentrated hydrochloric acid into a reaction kettle, stirring and adding zinc powder under the conditions of the rotation speed of 200r/min and the temperature of 50 ℃, reacting for 5 hours, cooling to the temperature of 3 ℃, adding ammonia water and a sodium hydroxide solution, continuously stirring for 1.5 hours to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours under the temperature of 90 ℃ to obtain an intermediate 5, mixing and dropwise adding a sodium nitrite solution into the intermediate 5, concentrated hydrochloric acid, acetone and copper sulfate under the ice-water bath condition, stirring for 10-15 minutes under the rotation speed of 150r/min, adding ethyl acrylate, heating to the temperature of 35 ℃, adding cuprous oxide, and reacting for 30 minutes to obtain an intermediate 6;
step A3: adding the intermediate 6, potassium carbonate, tetrahydrofuran and tetraethylammonium bromide into a reaction kettle, carrying out reflux reaction for 3 hours to obtain an intermediate 7, reacting epoxy resin E-44 and the intermediate 7 for 4 hours at the rotation speed of 150r/min and the temperature of 160 ℃ to obtain an intermediate 8, dissolving hydroxylamine hydrochloride into deionized water, stirring and adding a potassium hydroxide solution under the condition of ice-water bath, adding vanillin, carrying out reaction for 3 hours to obtain an intermediate 9, dissolving the intermediate 9 into ethanol, adding raney nickel, and introducing hydrogen to react for 8 hours at the temperature of 40 ℃ to obtain an intermediate 10;
step A4: reacting the intermediate 10, acryloyl chloride, potassium carbonate and tetrahydrofuran for 6 hours at the temperature of 60 ℃ to obtain an intermediate 11, dissolving the intermediate 8 in ethylene glycol monobutyl ether, stirring and adding methacrylic acid, styrene, the intermediate 11 and dibenzoyl peroxide at the rotation speed of 200r/min and the temperature of 95 ℃, heating to 120 ℃, reacting for 8 hours, adding deionized water and adjusting the reaction liquid to 7 to obtain the modified epoxy resin emulsion.
The modified graphene is prepared by the following steps:
step B1: mixing graphene, aniline and N, N-dimethylformamide, carrying out ultrasonic treatment for 60min under the condition that the frequency is 45kHz, adding deionized water, and uniformly mixing to obtain a mixed solution;
step B2: and adding the mixed solution and ammonium persulfate into a reaction kettle, reacting for 10 hours at the temperature of 10 ℃, filtering and drying to obtain the modified graphene.
Comparative example 1:
this comparative example compared with example 1, the same procedure was followed except that epoxy resin E-44 was used in place of the modified epoxy resin emulsion.
Comparative example 2:
the comparative example and example 1 were carried out in the same manner except that no modified graphene was added.
Comparative example 3:
the comparative example is an anticorrosive paint disclosed in Chinese patent CN 110564279A.
The anticorrosive coatings prepared in examples 1 to 3 and comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in the following table;
salt spray resistance: and (5) detecting the standard GB/T1771-91, putting the test steel plate into a detection environment for 3000 hours, 5000 hours and 10000 hours, and observing the change condition of the coating.
The microorganism attachment rate: the hanging plate test is carried out on the test steel plate in certain sea area of Shandong, the state of the petroleum pipe in seawater is simulated, and the microbial attachment rate on the test steel plate is counted on 30 th, 60 th, 90 th and 120 th days.
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Salt spray resistance 3000h | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film had bubbles or bubbles Rust on the base | The coating film had bubbles or bubbles Rust on the base | The coating film has no bubbles and falling off Bottom is not rusted |
| Salt spray resistance 5000h | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film has no bubble and can not fall off, no rusting of the substrate | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film had bubbles or bubbles Rust on the base | The coating film had bubbles or bubbles Rust on the base | The coating film has air bubbles and does not fall off, no rusting of the substrate |
| Salt spray resistance 10000h | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film has no bubble and can fall off, no rusting of the substrate | The coating film had bubbles or bubbles Rust on the base | The coating film had bubbles or bubbles Rust on the base | The coating film has bubbles and drops off Bottom rust |
| Attachment of microorganisms The rate is 30 days | 8.5% | 8.3% | 8.8% | 25% | 9.2% | 13% |
| Attachment of microorganisms The rate is 60 days | 8.7% | 8.5% | 9.1% | 28.6% | 9.3% | 18.2% |
| Attachment of microorganisms The rate is 90 days | 9.8% | 9.5% | 9.6% | 33.4% | 10.2% | 22.5% |
| Attachment of microorganisms The rate is 120 days | 10.3% | 10.2% | 10.5% | 48.6% | 13.7% | 28.7% |
As can be seen from the above table, the anticorrosive coatings prepared in examples 1 to 3 have excellent salt spray resistance and low adhesion to microorganisms and marine organisms.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (7)
1. A preparation method of an anticorrosive paint for offshore petroleum pipelines is characterized by comprising the following steps: the coating comprises a component A and a component B in a mass ratio of 6: 1, mixing to obtain the product;
the component A comprises the following raw materials in parts by weight: 50-80 parts of modified epoxy resin emulsion, 15-30 parts of modified graphene, 2-5 parts of dispersing agent, 1-3 parts of flatting agent, 1-3 parts of defoaming agent, 10-20 parts of film forming assistant and 20-30 parts of deionized water;
the component A is prepared by the following steps:
stirring the raw materials for 1-2h at the rotation speed of 1500-;
the component B is ethylenediamine, benzoyl peroxide and ethylene glycol in a mass ratio of 1: 1: 10, and mixing.
2. The method for preparing the anticorrosive paint for the offshore petroleum pipeline according to claim 1, wherein the method comprises the following steps: the dispersing agent is one or more of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate which are mixed in any proportion, the flatting agent is one or two of isophorone and diacetone alcohol which are mixed in any proportion, the defoaming agent is one or more of polydimethylsiloxane, dimethylpolysiloxane and simethicone which are mixed in any proportion, and the film-forming auxiliary agent is one or two of propylene glycol butyl ether and propylene glycol methyl ether acetate which are mixed in any proportion.
3. The method for preparing the anticorrosive paint for the offshore petroleum pipeline according to claim 1, wherein the method comprises the following steps: the modified epoxy resin emulsion is prepared by the following steps:
step A1: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring, adding toluene, reacting to obtain an intermediate 1, mixing and refluxing the intermediate 1 and deionized water to obtain an intermediate 2, adding the intermediate 2, hydroxylamine hydrochloride, ethanol and deionized water into the reaction kettle, stirring, adding sodium hydroxide, reacting, heating, adding a hydrochloric acid solution, and preserving heat to obtain an intermediate 3;
step A2: adding the intermediate 3, ethanol and concentrated hydrochloric acid into a reaction kettle, stirring and adding zinc powder, after reaction, cooling, adding ammonia water and a sodium hydroxide solution, continuing stirring to obtain an intermediate 4, adding the intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting to obtain an intermediate 5, mixing and dropwise adding a sodium nitrite solution into the intermediate 5, the concentrated hydrochloric acid, acetone and copper sulfate under the ice-water bath condition, uniformly stirring, adding ethyl acrylate, heating, adding cuprous oxide, and reacting to obtain an intermediate 6;
step A3: adding the intermediate 6, potassium carbonate, tetrahydrofuran and tetraethylammonium bromide into a reaction kettle, performing reflux reaction to obtain an intermediate 7, reacting epoxy resin E-44 with the intermediate 7 to obtain an intermediate 8, dissolving hydroxylamine hydrochloride in deionized water, stirring and adding a potassium hydroxide solution under the condition of ice-water bath, adding vanillin, reacting to obtain an intermediate 9, dissolving the intermediate 9 in ethanol, adding raney nickel, and introducing hydrogen to react to obtain an intermediate 10;
step A4: and (2) reacting the intermediate 10, acryloyl chloride, potassium carbonate and tetrahydrofuran to obtain an intermediate 11, dissolving the intermediate 8 in ethylene glycol butyl ether, stirring, adding methacrylic acid, styrene, the intermediate 11 and dibenzoyl peroxide, heating for reaction, adding deionized water, and adjusting the reaction liquid to be 7 to obtain the modified epoxy resin emulsion.
4. The method for preparing the anticorrosive paint for the offshore petroleum pipeline according to claim 3, wherein the method comprises the following steps: the dosage ratio of the aluminum trichloride, the carbon tetrachloride and the toluene in the step A1 is 8.5 g: 0.1 mol: 0.2mol, wherein the dosage ratio of the intermediate 2, hydroxylamine hydrochloride, ethanol, deionized water, sodium hydroxide and hydrochloric acid solution is 0.05 mol: 0.085 mol: 20mL of: 5mL of: 11 g: 200mL, the mass fraction of the hydrochloric acid solution is 25%.
5. The method for preparing the anticorrosive paint for the offshore petroleum pipeline according to claim 3, wherein the method comprises the following steps: the dosage ratio of the intermediate 3, ethanol, concentrated hydrochloric acid, zinc powder, ammonia water and sodium hydroxide solution in the step A2 is 0.02 mol: 12mL of: 30mL of: 0.2 mol: 28mL of: 60mL, 30 mass percent of ammonia water, 20 mass percent of sodium hydroxide solution, 0.1mol of intermediate 4, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride: 0.1 mol: 0.2 g: 200mL, wherein the dosage ratio of the intermediate 5, concentrated hydrochloric acid, acetone, copper sulfate, sodium nitrite solution, ethyl acrylate and cuprous oxide is 0.1 mol: 24mL of: 100 g: 0.01 mol: 15mL of: 0.5 mol: 0.6g, the mass fraction of the sodium nitrite solution is 70 percent, and the mass fraction of the concentrated hydrochloric acid is 36 percent.
6. The method for preparing the anticorrosive paint for the offshore petroleum pipeline according to claim 3, wherein the method comprises the following steps: the dosage ratio of the intermediate 6, the potassium carbonate, the tetrahydrofuran and the tetraethylammonium bromide in the step A3 is 3 g: 8.5 g: 100mL of: 3mL, and the molar ratio of the epoxy resin E-44 to the intermediate 7 is 2: 1, the dosage ratio of hydroxylamine hydrochloride, potassium hydroxide solution and vanillin is 2.5 mol: 200mL of: 0.5mol, the mass fraction of the potassium hydroxide solution is 50%, and the dosage ratio of the intermediate 9 to the Raney nickel is 0.05 mol: 8 g.
7. The method for preparing the anticorrosive paint for the offshore petroleum pipeline according to claim 3, wherein the method comprises the following steps: the dosage ratio of the intermediate 10, the acryloyl chloride, the potassium carbonate and the tetrahydrofuran in the step A4 is 2 mol: 2 mol: 25mol of: 8mL, wherein the mass ratio of the intermediate 8, the methacrylic acid, the styrene, the intermediate 11, the dibenzoyl peroxide and the deionized water is 30: 10: 4: 4: 0.8: 80.
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| CN115594609A (en) * | 2022-10-09 | 2023-01-13 | 华中药业股份有限公司（Cn） | Preparation method and application of 2-amino-5-chlorodiphenylmethanone oxime |
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| CN115594609A (en) * | 2022-10-09 | 2023-01-13 | 华中药业股份有限公司（Cn） | Preparation method and application of 2-amino-5-chlorodiphenylmethanone oxime |
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