CN113527679B - Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof - Google Patents
Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1092—Polysuccinimides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
- C09K8/528—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning inorganic depositions, e.g. sulfates or carbonates
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Abstract
The invention provides a polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer and application thereof. Wherein the relative molecular weight of the polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft is 3800-8600.
Description
Technical Field
The invention relates to a polyaspartic acid/2-amino-4, 6-dimethoxy pyrimidine graft copolymer, in particular to application of the copolymer as a corrosion inhibitor in oxidation resistance, corrosion prevention and scale inhibition.
Background
The corrosion inhibition efficiency of the existing antioxidant corrosion inhibitor is about 90 percent, but the existing antioxidant corrosion inhibitor does not have the function of scale prevention. The prior antioxidant corrosion inhibitor which is milder to the environment cannot bear higher temperature and mineralization degree; under the conditions of high temperature, high oxygen and high salinity, the corrosion inhibitor with the effects of resisting oxidation, corrosion inhibition and scale inhibition simultaneously needs to be added with various corrosion inhibitors and scale inhibitors to achieve the effects of corrosion inhibition and scale inhibition, and the filling process is complex, high in cost and harmful to the environment.
Therefore, in order to solve the problems of Tahe oil field, the development of a novel antioxidant scale-inhibiting multifunctional corrosion inhibitor is urgently needed, and the filling process is simplified.
Disclosure of Invention
One of the present invention provides a polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer having a relative molecular weight of 3800 to 8600.
In one embodiment, the mass ratio of polyaspartic acid units to 2-amino-4, 6-dimethoxypyrimidine units is 1.5.
The second aspect of the present invention provides a process for preparing a graft copolymer according to the first aspect of the present invention, which comprises the steps of:
1) Mixing polyaspartic acid with water to obtain a first solution;
2) Dissolving 2-amino-4, 6-dimethoxypyrimidine by using a first inorganic alkali solution to obtain a 2-amino-4, 6-dimethoxypyrimidine solution;
3) Dropwise adding the 2-amino-4, 6-dimethoxypyrimidine solution into the first solution, and adjusting the pH value after reaction to obtain a second solution;
4) And adding the second solution into alcohol, discarding the supernatant, and drying the precipitated solid to obtain the graft copolymer. In one embodiment, in step 2), the temperature of the reaction is 20 to 30 ℃ and the time of the reaction is 24 to 48 hours.
In a particular embodiment, in step 3), the pH is 7 to 9.
In one embodiment, the polyaspartic acid is hydrolyzed from polysuccinimide.
In one embodiment, the polyaspartic acid is obtained by mixing polysuccinimide and water, adjusting the pH to 8 to 10 with a second inorganic base, and hydrolyzing at 60 to 80 ℃ for 40 to 60 minutes.
In one embodiment, the polysuccinimide is formed by the polycondensation of ammonium maleate salts.
In one embodiment, the ammonium maleate salt is dissolved in water, reacted at 170 to 180 ℃ for 3 to 4 hours using palladium on carbon as a catalyst, cooled, and dried to obtain the polysuccinimide, wherein the mass ratio of the ammonium maleate salt to the palladium on carbon is (1 to 1.5): (0.5 to 1).
In one embodiment, the ammonium maleate salt is obtained from the reaction of maleic anhydride and urea.
In one embodiment, maleic anhydride and water are mixed, dissolved with stirring at 180 to 220 ℃, and then added with urea to react at 180 to 220 ℃ for 2 to 3 hours to obtain the ammonium maleate salt, wherein the molar ratio of the maleic anhydride to the urea is (1 to 1.5): (1 to 2).
In one embodiment, the first inorganic base is sodium hydroxide and/or potassium hydroxide.
In one embodiment, the second inorganic base is sodium hydroxide and/or potassium hydroxide.
In one embodiment, the alcohol is at least one of ethanol, propanol, and ethylene glycol.
The third invention provides the application of the graft copolymer of the second invention or the graft copolymer prepared by the method of any one of the second invention in resisting oxygen, corrosion and scale.
The polyaspartic acid, polysuccinimide, ammonium maleate salt and the like used in the present invention may be prepared by themselves or may be commercially available.
The invention has the beneficial effects that:
the invention provides a multifunctional corrosion inhibitor with functions of oxidation resistance, corrosion resistance and scale inhibition, which can quickly form a compact and firm hydrophobic protective film on the surface of a steel test piece, thereby effectively preventing the occurrence of oxygen corrosion and scaling, solving the problem of serious corrosion and scaling of pipelines and injection wells of a Tahe oilfield and meeting the requirements of corrosion resistance and scale inhibition of the Tahe oilfield.
The polyaspartic acid is an amino acid polymer, has good biodegradability and is environment-friendly, and the final degradation products are ammonia, carbon dioxide and water which are harmless to the environment, so the multifunctional corrosion inhibitor has the characteristic of environmental protection.
In addition, the synthesis method is simple, easy for industrial mass production, low in cost and the like.
Detailed Description
The above-described aspects of the invention are explained in more detail below by means of preferred embodiments, but they are not intended to limit the invention.
The reagents in the examples of the present invention were all commercially available unless otherwise specified.
Example 1
Synthesis of polyaspartic acid
40mL of distilled water and 0.1mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 200 ℃, and after the maleic anhydride was completely dissolved, 0.1mol of urea was added to the three-necked flask. Reacting for 2h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 10g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 170 ℃ for 3h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
Weighing 6g of polysuccinimide, putting the polysuccinimide into a three-neck flask, adding 50mL of water into the three-neck flask, adjusting the pH value to 9 by using NaOH, stirring the mixture to dissolve the polysuccinimide into the mixture, heating the mixture to 60 ℃ to hydrolyze the polysuccinimide, and reacting the mixture for 45min to obtain the polyaspartic acid.
The relative molecular weight of polyaspartic acid was 4615 as determined by mass spectrometry.
Example 2
Synthesis of polyaspartic acid
40mL of distilled water and 0.1mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved by stirring at 180 ℃ and 0.2mol of urea was added to the three-necked flask after the maleic anhydride was completely dissolved. Reacting for 3h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 10g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 170 ℃ for 3h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
Weighing 6g of polysuccinimide, putting the polysuccinimide into a three-neck flask, adding 50mL of water into the three-neck flask, adjusting the pH value to 9 by using NaOH, stirring the mixture to dissolve the polysuccinimide into the mixture, heating the mixture to 60 ℃ to hydrolyze the polysuccinimide, and reacting the mixture for 45min to obtain the polyaspartic acid.
The relative molecular weight of polyaspartic acid was 2385 as determined by mass spectrometry.
Example 3
Synthesis of polyaspartic acid
40mL of distilled water and 0.15mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 220 ℃, and after the maleic anhydride was completely dissolved, 0.1mol of urea was added to the three-necked flask. Reacting for 2h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 10g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 170 ℃ for 3h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
Weighing 6g of polysuccinimide, putting the polysuccinimide into a three-neck flask, adding 50mL of water into the three-neck flask, adjusting the pH value to 9 by using NaOH, stirring the mixture to dissolve the polysuccinimide into the mixture, heating the mixture to 60 ℃ to hydrolyze the polysuccinimide, and reacting the mixture for 45min to obtain the polyaspartic acid.
The relative molecular weight of polyaspartic acid was 3064 as determined by mass spectrometry.
Example 4
Synthesis of polyaspartic acid
40mL of distilled water and 0.15mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 200 ℃, and after the maleic anhydride was completely dissolved, 0.2mol of urea was added to the three-necked flask. Reacting for 3h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 10g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 170 ℃ for 4h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
6g of polysuccinimide is weighed and placed in a three-neck flask, 50mL of water is added into the polysuccinimide, the pH value is adjusted to 9 by NaOH, the polysuccinimide is stirred to be dissolved in the polysuccinimide, the polysuccinimide is heated to 60 ℃ to be hydrolyzed, and the polyaspartic acid can be obtained after the reaction for 45 min.
The relative molecular weight of polyaspartic acid is 5340 as determined by a mass spectrometer.
Example 5
Synthesis of polyaspartic acid
40mL of distilled water and 0.1mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 200 ℃ and 0.1mol of urea was added to the three-necked flask after the maleic anhydride was completely dissolved. Reacting for 2h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 15g of ammonium maleate and 50mL of water into a three-neck flask, adding 5g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 180 ℃ for 3h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
6g of polysuccinimide is weighed and placed in a three-neck flask, 50mL of water is added into the polysuccinimide, the pH value is adjusted to 9 by NaOH, the polysuccinimide is stirred to be dissolved in the polysuccinimide, the polysuccinimide is heated to 70 ℃ to be hydrolyzed, and the polyaspartic acid can be obtained after the reaction for 45 min.
The relative molecular weight of polyaspartic acid was 3922 as determined by mass spectrometry.
Example 6
Synthesis of polyaspartic acid
40mL of distilled water and 0.1mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 200 ℃ and 0.1mol of urea was added to the three-necked flask after the maleic anhydride was completely dissolved. Reacting for 2h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 5g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 180 ℃ for 4h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
Weighing 6g of polysuccinimide, putting the polysuccinimide into a three-neck flask, adding 50mL of water into the three-neck flask, adjusting the pH value to 9 by using NaOH, stirring the mixture to dissolve the polysuccinimide into the mixture, heating the mixture to 60 ℃ to hydrolyze the polysuccinimide, and reacting the mixture for 60min to obtain the polyaspartic acid.
The relative molecular weight of polyaspartic acid was 4230 as determined by mass spectrometry.
Example 7
Synthesis of polyaspartic acid
40mL of distilled water and 0.1mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 200 ℃, and after the maleic anhydride was completely dissolved, 0.1mol of urea was added to the three-necked flask. Reacting for 2h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 10g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 170 ℃ for 4h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
Weighing 6g of polysuccinimide, putting the polysuccinimide into a three-neck flask, adding 50mL of water into the three-neck flask, adjusting the pH value to 10 by using NaOH, stirring the mixture to dissolve the polysuccinimide into the mixture, heating the mixture to 60 ℃ to hydrolyze the polysuccinimide, and reacting the mixture for 60min to obtain the polyaspartic acid.
The relative molecular weight of polyaspartic acid was 4871 as determined by mass spectrometry.
Example 8
Synthesis of polyaspartic acid
40mL of distilled water and 0.1mol of maleic anhydride were added to a three-necked flask equipped with a thermometer and a stirrer, and dissolved with stirring at 200 ℃, and after the maleic anhydride was completely dissolved, 0.1mol of urea was added to the three-necked flask. Reacting for 2h, and cooling to obtain ammonium maleate. No purification is required before proceeding to the next step.
Adding 10g of ammonium maleate and 50mL of water into a three-neck flask, adding 10g of palladium-carbon (the palladium content is 10 wt%) catalyst under stirring, carrying out polycondensation reaction at 170 ℃ for 4h, and cooling and drying the product to obtain powdery and light yellow polysuccinimide.
6g of polysuccinimide is weighed and placed in a three-neck flask, 50mL of water is added into the polysuccinimide, the pH value is adjusted to 8 by NaOH, the polysuccinimide is stirred to be dissolved in the polysuccinimide, the polysuccinimide is heated to 80 ℃ to be hydrolyzed, and the polyaspartic acid can be obtained after 40min of reaction.
The relative molecular weight of polyaspartic acid was 3284 as determined by mass spectrometry.
Example 9
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 1 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using NaOH aqueous solution with the concentration of 1mol/L, slowly and dropwisely adding the solution into the polyaspartic acid suspension, wherein the reaction system gradually changes into brown solution, the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 7365 as determined by mass spectrometry.
Example 10
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 2 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using a NaOH aqueous solution with the concentration of 1mol/L, slowly dripping the solution into the polyaspartic acid suspension, gradually changing a reaction system into a brown solution, wherein the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 3806 as determined by mass spectrometry.
Example 11
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 3 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using a KOH aqueous solution with the concentration of 1mol/L, slowly dripping the solution into the polyaspartic acid suspension, gradually changing a reaction system into a brown solution, wherein the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 4889 as determined by mass spectrometry.
Example 12
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 4 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using a NaOH aqueous solution with the concentration of 1mol/L, slowly dripping the solution into the polyaspartic acid suspension, gradually changing a reaction system into a brown solution, wherein the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 8524 as determined by mass spectrometry.
Example 13
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 5 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using a NaOH aqueous solution with the concentration of 1mol/L, slowly dripping the solution into the polyaspartic acid suspension, gradually changing a reaction system into a brown solution, wherein the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 6259 as determined by mass spectrometry.
Example 14
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 6 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using a NaOH aqueous solution with the concentration of 1mol/L, slowly dripping the solution into the polyaspartic acid suspension, gradually changing a reaction system into a brown solution, wherein the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 6756 as determined by mass spectrometry.
Example 15
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 7 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using a NaOH aqueous solution with the concentration of 1mol/L, slowly dripping the solution into the polyaspartic acid suspension, gradually changing a reaction system into a brown solution, wherein the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 7775 as determined by mass spectrometry.
Example 16
Synthesis of antioxidant scale and corrosion inhibitor
Adding the polyaspartic acid obtained in example 8 into a proper amount of distilled water to form a suspension, dissolving 2-amino-4, 6-dimethoxypyrimidine by using NaOH aqueous solution with the concentration of 1mol/L, slowly and dropwisely adding the solution into the polyaspartic acid suspension, wherein the reaction system gradually changes into brown solution, the mass ratio of the polyaspartic acid to the 2-amino-4, 6-dimethoxypyrimidine is 1.5.
The polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft has a relative molecular weight of 5245 as determined by mass spectrometry.
Slow release efficiency of polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft:
the corrosion inhibition performance of the antioxidant, anticorrosion and antisludging multifunctional corrosion inhibitor prepared in each embodiment is respectively inspected by taking GB/T35509-2017 as a test standard.
Specifically, the test material is P110 steel sheet with specification of 50mm × 13mm × 1.5mm, which is wiped clean with filter paper, then placed in a vessel containing acetone, degreased cotton is used to remove grease on the surface of the steel sheet, and then the steel sheet is soaked in absolute ethyl alcohol for about 5min, and further degreased and dehydrated. Taking out the steel sheet, placing the steel sheet on filter paper, drying the steel sheet by cold air, wrapping the steel sheet by the filter paper, storing the steel sheet in a dryer, standing the steel sheet for 1 hour, and then measuring and weighing the steel sheet.
According to the table 1, the solution A and the solution B are mixed according to the volume ratio of 1.
The results of corrosion inhibition are shown in Table 3.
TABLE 1 simulated mineralized Water composition
TABLE 2 Experimental conditions
| Temperature of experiment | Pressure of experiment | Experimental Environment | Experimental period | Stirring speed |
| 130℃ | Total pressure 10MPa | 2.5％O 2 | 72h | 60r/min |
TABLE 3 evaluation of the corrosion inhibition rate of the antioxidant, anticorrosive and antiscale multifunctional corrosion inhibitor in each example
The test results in table 3 show that the antioxidant, anticorrosive and scale inhibiting multifunctional corrosion inhibitor of the invention has good corrosion inhibition effect under the conditions of high temperature, high oxygen and high salinity in the Tahe oil field, wherein the corrosion inhibition efficiency of the antioxidant, anticorrosive and scale inhibiting multifunctional corrosion inhibitor prepared from the antioxidant, anticorrosive and scale inhibiting multifunctional corrosion inhibitors D and G can even reach more than 80%.
Scale inhibition ratio of polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft
SY-T5673-1993 is used as a test standard, according to the table 1, the solution A and the solution B are mixed according to the volume ratio of 1 to prepare simulated mineralized water (the mineralization is 104175 mg/L), and the antioxidant, anticorrosive and scale-inhibiting multifunctional corrosion inhibitor prepared in each example is added into the mineralized water under the experimental condition that the temperature is 55 ℃ until the concentration is 50ppm and static scale is formed for 25 hours, so as to investigate the scale inhibition performance and obtain the scale inhibition rate. The results are shown in Table 4.
TABLE 4 evaluation data table of antioxidant scale-inhibiting multifunctional corrosion inhibitor in each example
As shown in Table 4, the antioxidant, anticorrosive and scale-inhibiting multifunctional corrosion inhibitor has a good scale inhibition rate under the conditions of high temperature, high oxygen and high salinity in Tahe oil field, the scale inhibition rates of the antioxidant, anticorrosive and scale-inhibiting multifunctional corrosion inhibitor B, C and F are all over 70 percent, and the scale inhibitor does not contain nitrogen and phosphorus elements and is environment-friendly. The antioxidant, anticorrosive and scale inhibiting multifunctional corrosion inhibitor has good scale inhibiting performance and corrosion inhibiting performance under high salinity.
While the invention has been described with reference to specific embodiments, it will be appreciated by those skilled in the art that various changes can be made without departing from the true spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, and method to the essential scope and spirit of the present invention. All such modifications are intended to be included within the scope of the present invention as defined in the appended claims.
Claims (14)
1. Polyaspartic acid/2-amino-4, 6-dimethoxypyrimidine graft copolymer, the relative molecular weight of which is 3800 to 8600.
2. The graft copolymer according to claim 1, wherein the mass ratio of the polyaspartic acid unit to the 2-amino-4, 6-dimethoxypyrimidine unit is 1.5.
3. A process for preparing the graft copolymer of claim 1 or 2, comprising the steps of:
1) Mixing polyaspartic acid with water to obtain a first solution;
2) Dissolving 2-amino-4, 6-dimethoxypyrimidine by using a first inorganic base solution to obtain a 2-amino-4, 6-dimethoxypyrimidine solution;
3) Dropwise adding the 2-amino-4, 6-dimethoxypyrimidine solution into the first solution, and adjusting the pH value after reaction to obtain a second solution;
4) And adding the second solution into alcohol, discarding the supernatant, and drying the precipitated solid to obtain the graft copolymer.
4. The method according to claim 3, wherein the reaction temperature in step 3) is 20 to 30 ℃ and the reaction time is 24 to 48 hours.
5. The method according to claim 3 or 4, characterized in that in step 3) the pH value is 7 to 9.
6. The method of claim 3 or 4, wherein the polyaspartic acid is hydrolyzed from polysuccinimide.
7. The method according to claim 6, wherein the polyaspartic acid is obtained by mixing polysuccinimide and water, adjusting the pH to 8 to 10 with a second inorganic base, and hydrolyzing at 60 to 80 ℃ for 40 to 60 minutes.
8. The method of claim 6, wherein the polysuccinimide is formed by the polycondensation of ammonium maleate salts.
9. The method according to claim 8, wherein the ammonium maleate salt is dissolved in water, reacted at 170 to 180 ℃ for 3 to 4 hours using palladium on carbon as a catalyst, cooled, and dried to obtain the polysuccinimide, wherein the mass ratio of the ammonium maleate salt to the palladium on carbon is (1 to 1.5): (0.5 to 1).
10. A process according to claim 8, characterized in that said ammonium maleate salt is obtained by reacting maleic anhydride and urea.
11. The method as claimed in claim 10, wherein maleic anhydride and water are mixed, dissolved with stirring at 180 to 220 ℃, and then added with urea to react at 180 to 220 ℃ for 2 to 3 hours to obtain the ammonium maleate, wherein the molar ratio of the maleic anhydride and the urea is (1 to 1.5): 1 to 2.
12. The process according to claim 3 or 4, characterized in that the first inorganic base is sodium hydroxide and/or potassium hydroxide; and/or
The alcohol is at least one of ethanol, propanol and glycol.
13. The process according to claim 7, characterized in that the second inorganic base is sodium hydroxide and/or potassium hydroxide.
14. Use of the graft copolymer according to claim 1 or 2 or the graft copolymer prepared by the process according to any one of claims 3 to 13 for oxidation, corrosion protection and scale inhibition.
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Citations (5)
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| WO1997028230A1 (en) * | 1996-01-29 | 1997-08-07 | Baker Hughes Limited | Scale inhibition in petroleum and natural gas production |
| JP2000044680A (en) * | 1998-07-30 | 2000-02-15 | Mitsui Chemicals Inc | Polymer and its production |
| CN1876696A (en) * | 2006-07-05 | 2006-12-13 | 太原理工大学 | Aspartate copolymer and method for preparing same |
| CN101181273A (en) * | 2007-11-22 | 2008-05-21 | 复旦大学 | Method for preparing chitosan-polyasparagic acid-5efudix nano particle |
| CN105482117A (en) * | 2016-01-19 | 2016-04-13 | 北京理工大学 | Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028230A1 (en) * | 1996-01-29 | 1997-08-07 | Baker Hughes Limited | Scale inhibition in petroleum and natural gas production |
| JP2000044680A (en) * | 1998-07-30 | 2000-02-15 | Mitsui Chemicals Inc | Polymer and its production |
| CN1876696A (en) * | 2006-07-05 | 2006-12-13 | 太原理工大学 | Aspartate copolymer and method for preparing same |
| CN101181273A (en) * | 2007-11-22 | 2008-05-21 | 复旦大学 | Method for preparing chitosan-polyasparagic acid-5efudix nano particle |
| CN105482117A (en) * | 2016-01-19 | 2016-04-13 | 北京理工大学 | Polyaspartic acid/urea graft copolymer as well as preparation method and application thereof |
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