Anti-fouling and anti-abrasion polyurea coating, preparation method and use method thereof

Abstract

This invention provides an anti-fouling and anti-wear polyurea coating, its preparation method, and its application method, belonging to the field of petroleum drilling and production technology. The coating includes a primer and a topcoat; the topcoat includes component A and component B. Component A includes: isophorone diisocyanate, polyethylene glycol, a dispersion of partially reduced graphene oxide modified with α-Al₂O₃ and YSZ nanopowders, and a mixture of α-Al₂O₃ micro / nano powders and YSZ micro / nano powders; component B includes: a chain extender, terminal amino polyethers, a diluent, a foaming agent, modified nano-molybdenum disulfide, and additives; the primer includes component C and component D. Component C includes: isophorone diisocyanate, polyethylene glycol, a dispersion of partially reduced graphene oxide modified with cerium dioxide nanopowders, a mixture of cerium dioxide micro / nano powders and yttrium oxide-stabilized zirconium oxide micro / nano powders; component D includes: a chain extender, terminal amino polyethers, a diluent, a foaming agent, modified nano-cerium dioxide, and additives.

Description

Technical Field

[0001] This invention belongs to the field of petroleum drilling and production technology, specifically relating to an anti-scaling and anti-wear polyurea coating, its preparation method, and its application method. Background Technology

[0002] Currently, with the deepening of oil and gas exploration and development, the damage and failure of oil pipelines are intensifying due to factors such as oil deterioration, placing higher demands on the corrosion resistance and high-temperature resistance of anti-corrosion coatings for oil pipelines. Besides insufficient high-temperature resistance and corrosion resistance, the poor scale resistance and wear resistance of existing anti-corrosion coatings in oilfields have become major factors affecting their long-term service life under harsh conditions. Regarding scale resistance, high-salinity formation water contains not only corrosive media such as chloride ions and carbon dioxide, but also microorganisms such as sulfate-reducing bacteria, planktonic bacteria, and iron bacteria, as well as scale-forming ions such as calcium and magnesium ions. The deposition and interaction of microorganisms with localized scale and corrosion products on the surface of oil pipeline coatings leads to scale formation and under-deposit corrosion. Furthermore, the use of chemical flooding and ternary composite flooding processes in oilfields further exacerbates scale formation on the surface of oil pipelines, increasing the difficulty of subsequent production operations. In terms of wear resistance, coatings face multiphase media environments such as oil, water, gas, and solids. High-speed and complex fluids can cause erosion and wear on the coating. In addition, mechanical extraction methods such as sucker rods and submersible pumps, as well as operations such as pipe diameter checks and periodic pipe inspections, inevitably cause wear damage to the coating. Therefore, there is an urgent need to obtain anti-scaling and wear-resistant coating protection technologies that can improve the service life and performance stability of oil pipelines.

[0003] In recent years, polyurea coatings have been widely used in the field of corrosion protection due to their excellent impact resistance, flexibility, waterproofing, corrosion resistance, and application performance. However, polyurea coatings have a high coefficient of friction and lack anti-scaling properties. Meanwhile, graphene-modified coatings have attracted widespread attention due to their superior corrosion resistance. However, the application of graphene in anti-corrosion coatings currently faces technical challenges, such as graphene dispersion. Due to its large specific surface area, graphene is prone to aggregation, often requiring functionalization to improve its dispersibility in organic solvents. Therefore, there is a need for a polyurea coating modified with functionalized graphene that can significantly improve both corrosion resistance and high-temperature resistance, while also enhancing its anti-scaling and wear resistance. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, the present invention aims to provide an anti-scaling and anti-wear polyurea coating, its preparation method, and its application method, so as to solve the problem that the existing polyurea coating has a large coefficient of friction on its surface and does not have the function of preventing scaling; and to solve the technical problem of graphene dispersion in the current application of graphene in anti-corrosion coatings, which is that graphene is prone to agglomeration due to its large specific surface area, thus obtaining a coating with anti-scaling and wear-resistant properties.

[0005] To achieve the above objectives, the present invention employs the following technical solution:

[0006] This invention provides an anti-scaling and anti-wear polyurea coating, comprising a primer and a topcoat; the topcoat comprises component A and component B, wherein the weight ratio of component A to component B is 1:(1.9-2.1); by parts, the raw materials for preparing component A of the topcoat include: 46-61 parts of isophorone diisocyanate, 15-30 parts of polyethylene glycol, 5-15 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 5-9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder, totaling 100 parts;

[0007] The raw materials for preparing component B of the topcoat, by parts, include: 29-32 parts of chain extender, 30-39 parts of amino-terminated polyether, 11-15 parts of diluent, 6-8 parts of foaming agent, 11-15 parts of modified nano molybdenum disulfide, and 1-3 parts of additives, totaling 100 parts.

[0008] The primer comprises component C and component D, wherein the weight ratio of component C to component D is 1:(1.9-2.1); by parts, the raw materials for preparing component C of the primer include: 46-61 parts of isophorone diisocyanate, 15-30 parts of polyethylene glycol, 5-15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 5-9 parts of a mixture of cerium dioxide micro / nano powder and yttrium oxide stabilized zirconium oxide micro / nano powder, for a total of 100 parts;

[0009] The raw materials for preparing component D of the primer, by parts, include: 29-32 parts of chain extender, 30-39 parts of amino-terminated polyether, 11-15 parts of diluent, 6-8 parts of foaming agent, 11-15 parts of modified nano-cerium dioxide, and 1-3 parts of additives, totaling 100 parts.

[0010] In a further embodiment of the present invention, the mass ratio of α-Al2O3 micro / nano powder to yttrium-stabilized zirconia micro / nano powder in the mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder is 1:3; the mass ratio of nano powder to micron powder in the α-Al2O3 micro / nano powder is 1:1; and the mass ratio of nano powder to micron powder in the yttrium oxide-stabilized zirconia micro / nano powder is 2:1.

[0011] In a further embodiment of the present invention, the mass ratio of cerium dioxide micro / nano powder to yttrium oxide-stabilized zirconia micro / nano powder in the mixture of cerium dioxide micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder is 2:1; the mass ratio of nano powder to micron powder in the cerium dioxide micro / nano powder is 2:1; and the mass ratio of nano powder to micron powder in the yttrium oxide-stabilized zirconia micro / nano powder is 2:1.

[0012] In a further embodiment of the present invention, the chain extender is diethyltoluenediamine; the diluent is a mixture of propylene carbonate, n-butyl acetate, and n-butanol, wherein the mass ratio of propylene carbonate, n-butyl acetate, and n-butanol is 3:3:1; the foaming agent is azobisisobutyronitrile; and the additives include leveling agents, defoamers, and dispersants.

[0013] The present invention also provides a method for preparing an anti-scaling and anti-wear polyurea coating according to any one of the claims, comprising the following steps:

[0014] S1: After mixing isophorone diisocyanate and polyethylene glycol and heating, polymer A is obtained. A dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder is prepared. A mixture of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder are added sequentially to polymer A and stirred to obtain component A of the topcoat.

[0015] S2: To prepare modified nano molybdenum disulfide, chain extender, amino-terminated polyether, diluent, foaming agent, and modified nano molybdenum disulfide are mixed, stirred, and heated. Then, additives are added and mixed evenly to obtain component B of the topcoat.

[0016] S3: Prepare a dispersion of partially reduced graphene oxide modified with cerium dioxide nanopowder; add the dispersion of partially reduced graphene oxide modified with cerium dioxide nanopowder, a mixture of cerium dioxide micro-nano powder and yttrium oxide-stabilized zirconium oxide micro-nano powder to polymer A in sequence, and stir to obtain component C of the primer.

[0017] S4: To prepare modified nano-cerium dioxide, the chain extender, amino-terminated polyether, diluent, foaming agent and modified nano-cerium dioxide are mixed, stirred and heated, and then the additives are added and mixed evenly to obtain component D of the primer.

[0018] S5: Mix component A and component B of the prepared topcoat evenly to obtain the topcoat; mix component C and component D of the prepared primer evenly to obtain the primer. The topcoat and primer are anti-scaling and anti-wear polyurea coatings for oil and gas well pipes.

[0019] Furthermore, in step S1, the process of preparing the α-Al₂O₃ nanoparticles and yttrium oxide-stabilized zirconia nanoparticles modified partially reduced graphene oxide dispersion is as follows:

[0020] Trimethylsiloxane was mixed with partially reduced graphene oxide X to undergo a first modification reaction, resulting in mixture a. α-Al₂O₃ nanoparticles and yttrium-stabilized zirconia nanoparticles were added to mixture a, and the reaction yielded mixture b. Mixture b was dried to obtain partially reduced graphene oxide modified with α-Al₂O₃ nanoparticles and yttrium-stabilized zirconia nanoparticles. Then, n-butanol, polydimethylsiloxane, and a silane coupling agent were sequentially added to the partially reduced graphene oxide modified with α-Al₂O₃ nanoparticles and yttrium-stabilized zirconia nanoparticles for a second modification reaction, followed by ultrasonic treatment, resulting in a dispersion of partially reduced graphene oxide modified with α-Al₂O₃ nanoparticles and yttrium-stabilized zirconia nanoparticles.

[0021] The mass ratio of the α-Al2O3 nanopowder to the yttrium oxide-stabilized zirconium oxide nanopowder is 1:2;

[0022] The oxygen content of the partially reduced graphene oxide X is 10%.

[0023] Furthermore, in step S2, the process for preparing modified nano-molybdenum disulfide is as follows:

[0024] Nano-molybdenum disulfide, n-butanol, and anhydrous ethanol were mixed, and the pH was adjusted to neutral to obtain a nano-molybdenum disulfide suspension. Vinyltriethoxysilane and the nano-molybdenum disulfide suspension were mixed, and then some reduced graphene oxide Y was added to react and obtain a modified nano-molybdenum disulfide dispersion. The mixture was filtered and vacuum dried to obtain modified nano-molybdenum disulfide.

[0025] The volume ratio of the vinyltriethoxysilane and the nano-molybdenum disulfide suspension is 1:10;

[0026] The oxygen content of the partially reduced graphene oxide Y is 15%.

[0027] Furthermore, in step S3, the process of preparing the cerium dioxide nanopowder modified partially reduced graphene oxide dispersion is as follows:

[0028] Trimethylsiloxane was mixed with partially reduced graphene oxide X to carry out the first modification reaction, resulting in mixture a. Cerium dioxide nanopowder was added to mixture a to carry out the reaction, resulting in mixture c. Mixture b was dried to obtain cerium dioxide nanopowder modified partially reduced graphene oxide. Then, n-butanol, polydimethylsiloxane and silane coupling agent were added to the cerium dioxide nanopowder modified partially reduced graphene oxide in sequence to carry out the second modification reaction and ultrasonic treatment, resulting in a dispersion of cerium dioxide nanopowder modified partially reduced graphene oxide.

[0029] The oxygen content of the partially reduced graphene oxide X is 10%.

[0030] Furthermore, in step S4, the process for preparing modified nano-cerium dioxide is as follows:

[0031] Nano-cerium disulfide, n-butanol and anhydrous ethanol were mixed and the pH was adjusted to neutral to obtain a nano-cerium disulfide suspension. Vinyltriethoxysilane and nano-cerium disulfide suspension were mixed, and partially reduced graphene oxide Y was added to react and obtain a modified nano-cerium disulfide dispersion. Then, the mixture was filtered and vacuum dried to obtain modified nano-cerium dioxide.

[0032] The volume ratio of the vinyltriethoxysilane and the nano-cerium disulfide suspension is 1:10;

[0033] The oxygen content of the partially reduced graphene oxide Y is 15%.

[0034] This invention provides a method for using the aforementioned anti-scaling and anti-wear polyurea coating, wherein the polyurea coating is used for anti-scaling and anti-wear purposes on oil and gas well pipes, and the method of use is as follows:

[0035] The primer in the polyurea coating is applied to the pretreated substrate and then cured to obtain a substrate with primer; a topcoat is applied to the substrate with primer and then cured to form an anti-scaling and anti-wear polyurea coating.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] This invention provides a method for preparing an anti-fouling and anti-wear polyurea coating. In the topcoat, trimethylsiloxane is first used to graft and modify partially reduced graphene oxide (X). Then, nanoparticles α-Al₂O₃ and YSZ (yttrium-stabilized zirconium oxide) are used. Their unique surface and small size effects allow them to undergo grafting reactions with trimethylsiloxane, polydimethylsiloxane, silane coupling agents, etc., in a highly active state. By sharing "O" atoms, the modified partially reduced graphene oxide coats α-Al₂O₃ and YSZ nanoparticles, achieving the beneficial effect of efficient dispersion and organic integration of organic and inorganic materials (partially reduced graphene oxide, α-Al₂O₃, and YSZ).

[0038] Furthermore, by addressing the requirements of coating nanofillers for impermeability, wear resistance, corrosion resistance, pore filling, density mismatch design (anti-settling), and organic integration with organic coatings, and through material structure design and experimental verification, partially reduced graphene oxide X with an oxygen content of 10% was used as the raw material. Utilizing the hydroxyl and carboxyl groups retained in partially reduced graphene oxide, a coupling reaction was carried out with trimethylsiloxane, polydimethylsiloxane, and silane coupling agents to prepare modified partially reduced graphene oxide. This achieved efficient dispersion and fusion of organic and inorganic materials while retaining the beneficial effects of partially reduced graphene oxide, such as high impermeability, corrosion resistance, high toughness, superhydrophobicity, self-lubrication, and antibacterial and anti-scaling properties.

[0039] This invention provides an anti-scaling and anti-wear polyurea coating for use in oil and gas well pipes. The topcoat contains α-Al2O3 and YSZ micro / nano powders, modified nano-molybdenum disulfide, and reduced graphene oxide. These micro / nano particles / nanoflakes of different sizes effectively seal the voids of different scales in the coating through size mismatch, improving the coating's impermeability and corrosion resistance. In addition, α-Al2O3 and YSZ micro / nano powders effectively improve the coating's hardness and strength, thereby improving the coating's wear resistance and impact resistance. Furthermore, the topcoat also takes into account the self-lubricating properties of modified nano-molybdenum disulfide, further improving the coating's wear resistance. The primer contains modified partially reduced graphene oxide, cerium dioxide (CeO2), YSZ micro / nano powder, and modified nano-cerium dioxide. In addition to the corrosion resistance, hydrophobicity, wear resistance, and other performance advantages of the topcoat, cerium dioxide has a unique oxygen storage capacity. It can absorb free oxygen that diffuses into the coating through the topcoat, preventing free oxygen from further entering the interface between the oil pipe and the coating, thus significantly improving the corrosion resistance of the coating.

[0040] Furthermore, by organically combining CeO2, α-Al2O3, and YSZ ceramic or rare earth oxide micro-nano particles with partially reduced graphene oxide, the average density is close to that of the resin matrix, effectively solving the problems of single b-RGO floating in coatings and single CeO2, α-Al2O3, and YSZ ceramic or rare earth oxide micro-nano particles sinking in coatings.

[0041] Furthermore, based on the characteristics of different nanopowders, two types of partially reduced graphene oxide, X and Y, with different oxygen contents, were used to ensure that the graphene surface has sufficient and appropriate functional groups to participate in the grafting reaction.

[0042] This invention provides a method for using an anti-scaling and anti-wear polyurea coating for oil and gas well pipes. Based on the service conditions required for oil and gas well pipes and considering the functional differences of each component, this invention precisely designs and controls the composition of each coating and the coating preparation process. Under high pressure (up to 100 MPa), high mineralization (not exceeding 200,000 ppm), and high bacterial content (not exceeding 50,000 CFU / ml), and at 160°C, the coating exhibits an unexpectedly long service life (over 6 years) on the surface of the oil and gas well pipe. The wear resistance index, measured using the drop sand method according to SY / T 6717-2016 (Technical Conditions for Inner Coatings of Tubing and Casing) standard, is higher than 3.5 L / μm, far exceeding the 2 L / μm wear resistance requirement in that standard. According to the T / CSTM 00242-2021 (Quality Requirements and Inspection of Graphene Modified Coatings for Oil Pipelines) standard, the scale prevention performance index of this coating was determined by the weight gain method to be Grade 1 (<0.5 mg / cm³). 2 This is far higher than the Class 2 (0.5 mg / cm²) anti-corrosion coating for conventional oil pipes. 2 ～ 1.0 mg / cm 2 ) or grade 3 (1.0 mg / cm³) 2 ～ 1.5mg / cm 2 ) performance.

[0043] The coating of this invention has a temperature resistance of up to 180°C and excellent anti-scaling and wear-resistant properties in drilling and extraction conditions at or below 160°C. Detailed Implementation

[0044] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.

[0045] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.

[0046] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values ​​(including integers and fractions) within those ranges.

[0047] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”

[0048] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0049] This invention provides an anti-scaling and anti-wear polyurea coating, its preparation method, and its application method.

[0050] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.

[0051] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.

[0052] This invention provides an anti-scaling and anti-wear polyurea coating, the coating comprising a primer and a topcoat, the topcoat being disposed above the primer. The topcoat is composed of component A and component B, and the primer is composed of component C and component D. The weight ratio of component A and component B of the topcoat and component C and component D of the primer is 1:(1.9-2.1), that is, the weight ratio of component A and component B of the topcoat is 1:(1.9-2.1), and the weight ratio of component C and component D of the primer is 1:(1.9-2.1).

[0053] The raw materials for preparing component A of the topcoat, by part number, include: 46-61 parts of isophorone diisocyanate, 15-30 parts of polyethylene glycol, 5-15 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium-stabilized zirconia nanopowder, and 5-9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium-stabilized zirconia (YSZ) micro / nano powder, totaling 100 parts; the raw materials for preparing component B include: 29-32 parts of chain extender, 30-39 parts of amino-terminated polyether, 11-15 parts of diluent, 6-8 parts of foaming agent, 11-15 parts of modified nano molybdenum disulfide, and 1-3 parts of additives, totaling 100 parts.

[0054] The mass ratio of α-Al₂O₃ micro / nano powder to yttrium-stabilized zirconia micro / nano powder in the mixture of α-Al₂O₃ micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder is 1:3; the mass ratio of nanoparticles to micron-sized particles in the α-Al₂O₃ micro / nano powder is 1:1; the mass ratio of nanoparticles to micron-sized particles in the yttrium oxide-stabilized zirconia micro / nano powder is 2:1; the particle size of the nanoparticles in the α-Al₂O₃ micro / nano powder is 10-80 nm, and the particle size of the micron-sized particles in the α-Al₂O₃ micro / nano powder is 0.5-3 μm; the particle size of the nanoparticles in the yttrium oxide-stabilized zirconia micro / nano powder is 20-50 nm, and the particle size of the micron-sized particles in the yttrium oxide-stabilized zirconia micro / nano powder is 0.5-2 μm; the particle size of the nano-molybdenum disulfide is 30-60 nm.

[0055] The raw materials for preparing component C of the primer, by part number, include: 46-61 parts of isophorone diisocyanate, 15-30 parts of polyethylene glycol, 5-15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 5-9 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder, totaling 100 parts; the raw materials for preparing component D of the primer include: 29-32 parts of chain extender, 30-39 parts of amino-terminated polyether, 11-15 parts of diluent, 6-8 parts of foaming agent, 11-15 parts of modified nano cerium dioxide, and 1-3 parts of additives, totaling 100 parts.

[0056] The mass ratio of cerium dioxide micro / nano powder to yttrium-stabilized zirconia micro / nano powder in the mixture of cerium dioxide micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder is 2:1; the mass ratio of nanoparticles to microparticles in the cerium dioxide micro / nano powder is 2:1; the mass ratio of nanoparticles to microparticles in the yttrium oxide-stabilized zirconia micro / nano powder is 2:1; the particle size of the nanoparticles in the cerium dioxide micro / nano powder is 10–50 nm, and the particle size of the microparticles in the cerium dioxide micro / nano powder is 0.5–2 μm; the particle size of the nanoparticles in the yttrium oxide-stabilized zirconia micro / nano powder is 30–80 nm, and the particle size of the microparticles in the yttrium oxide-stabilized zirconia micro / nano powder is 0.5–3 μm; the particle size of the modified nano-cerium dioxide is 30–80 nm.

[0057] The chain extender is preferably diethyltoluenediamine; the diluent is preferably a mixture of propylene carbonate, n-butyl acetate, and n-butanol in a mass ratio of 3:3:1; the foaming agent is preferably azobisisobutyronitrile; and the additives include leveling agents, defoamers, and dispersants.

[0058] This invention also provides a method for preparing an anti-scaling and anti-wear polyurea coating, comprising the following steps:

[0059] Raw material preparation: Isophorone diisocyanate, modified partially reduced graphene oxide slurry (i.e., α-Al2O3 nanoparticles and yttrium oxide-stabilized zirconia nanoparticles modified partially reduced graphene oxide dispersion, cerium dioxide nanoparticles modified partially reduced graphene oxide dispersion, amino-terminated polyether and modified nano-molybdenum disulfide, and modified nano-cerium dioxide.

[0060] S1: Mix 46-61 parts of isophorone diisocyanate and 15-30 parts of polyethylene glycol, heat to 50-70℃ and react for 4-6 hours to obtain polymer A. Prepare a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder. Add 5-15 parts of the dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 5-9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder to polymer A. Stir at 2100-2500 r / min for 2-3 hours to obtain topcoat component A, wherein the viscosity of topcoat component A is 900-1000 mPa·s.

[0061] S2: Mix 29-32 parts of chain extender, 30-39 parts of amino-terminated polyether, 11-15 parts of diluent, 6-8 parts of foaming agent, and 11-15 parts of modified nano molybdenum disulfide, stir at 2100-2500 r / min for 20-30 min, then heat at 90-102℃ for 3-4 h, add additives, and stir at 2100-2500 r / min for 20-30 min to obtain topcoat component B;

[0062] Mixing of components A and B: Mix component A and component B thoroughly at 50-70°C.

[0063] S3: Add 5-15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion and 5-9 parts of a mixture of cerium dioxide micro-nano powder and yttrium oxide stabilized zirconium oxide micro-nano powder to polymer A in sequence, stir at 2100-2500 r / min for 2-3 h to obtain primer component C, wherein the viscosity of primer component C is 900-1000 mPa·s;

[0064] S4: Mix 29-32 parts of chain extender, 30-39 parts of amino-terminated polyether, 11-15 parts of diluent, 6-8 parts of foaming agent, and 11-15 parts of modified nano-cerium dioxide, and stir at 2100-2500 r / min for 20-30 min. Then heat at 90-102℃ for 3-4 h, add the additives, and stir at 2100-2500 r / min for 20-30 min to obtain primer component D; CD component mixing: Mix component C and component D evenly at 50-70℃. The topcoat and primer are anti-scaling and anti-wear polyurea coatings for oil and gas well pipes.

[0065] The process for preparing a dispersion of partially reduced graphene oxide modified with α-Al₂O₃ nanoparticles and yttrium oxide-stabilized zirconia nanoparticles is as follows:

[0066] Trimethylsiloxane and partially reduced graphene oxide X were mixed at a volume-to-weight ratio of 100 mL: 1 g at 25–30 °C for a first modification reaction of 25–30 min to obtain mixture a. 3 g of α-Al₂O₃ nanoparticles and yttrium oxide-stabilized zirconium oxide nanoparticles were added to mixture a, and the mixture was reacted at 80–100 °C for 5–8 h to obtain mixture b. In mixture b, α-Al₂O₃ and YSZ nanoparticles were mixed at a mass ratio of 1:2, wherein the particle size of the α-Al₂O₃ nanoparticles was 10–80 nm, and the particle size of the YSZ nanoparticles was 20–50 nm. Mixture b was then reacted at 90–100 °C. The graphene oxide was partially reduced by drying for 9–12 h to obtain α-Al₂O₃ nanoparticles and yttrium oxide-stabilized zirconia nanoparticles. Then, 50 mL of n-butanol, 100 mL of polydimethylsiloxane, and 50 mL of silane coupling agent were added sequentially to the partially reduced graphene oxide modified by α-Al₂O₃ nanoparticles and yttrium oxide-stabilized zirconia nanoparticles at 50–80 °C for a second modification reaction of 60–80 min. After ultrasonic treatment at 55–60 kHz for 60–80 min, a dispersion of partially reduced graphene oxide modified by α-Al₂O₃ nanoparticles and yttrium oxide-stabilized zirconia nanoparticles was obtained.

[0067] The mass ratio of α-Al₂O₃ nanoparticles to yttrium oxide-stabilized zirconium oxide nanoparticles is 1:2; the partially reduced graphene oxide X has an oxygen content of 10% and a specific surface area of ​​150–250 g / m². 2 The particle size is 3-5 μm.

[0068] The process for preparing modified nano-molybdenum disulfide is as follows:

[0069] Nano-molybdenum disulfide, n-butanol, and anhydrous ethanol were mixed at a mass-volume ratio of 30g:50mL and 100mL, respectively. The mixture was then stirred at 1600–1800 rpm for 30 min. The pH was then adjusted to neutral using ammonia to obtain a nano-molybdenum disulfide suspension. Vinyltriethoxysilane and the nano-molybdenum disulfide suspension were then mixed at a volume ratio of 10:100. 2g of partially reduced graphene oxide Y was added, and the mixture was reacted at 50–60°C and 1000–1500 rpm for 18–22 h to obtain a modified nano-molybdenum disulfide dispersion. The dispersion was filtered and then dried under vacuum at 80–100°C for 3 h to obtain modified nano-molybdenum disulfide.

[0070] The volume ratio of the vinyltriethoxysilane and the nano-molybdenum disulfide suspension is 1:10; the partially reduced graphene oxide Y has an oxygen content of 15% and a specific surface area of ​​100-200 g / m². 2 The particle size is 0.5–3 μm.

[0071] The process for preparing a dispersion of partially reduced graphene oxide modified with cerium dioxide nanopowder is as follows:

[0072] At 25–30 °C, trimethylsiloxane and partially reduced graphene oxide X were mixed at a volume-to-weight ratio of 100 mL: 1 g, and the first modification reaction was carried out for 25–30 min to obtain mixture a. 3 g of cerium dioxide nanopowder was added to mixture a, and the mixture was reacted at 80–100 °C for 5–8 h to obtain mixture c. Mixture c was dried at 90–100 °C for 9–12 h to obtain cerium dioxide nanopowder modified partially reduced graphene oxide. Then, at 50–80 °C, 50 mL of n-butanol, 100 mL of polydimethylsiloxane, and 50 mL of silane coupling agent were added sequentially to the cerium dioxide nanopowder modified partially reduced graphene oxide, and the second modification reaction was carried out for 60–80 min. After ultrasonic treatment at 55–60 kHz for 60–80 min, a dispersion of cerium dioxide nanopowder modified partially reduced graphene oxide was obtained.

[0073] The oxygen content of the partially reduced graphene oxide X is 10%.

[0074] The process for preparing modified nano-cerium dioxide is as follows:

[0075] Nano-cerium disulfide, n-butanol, and anhydrous ethanol were mixed at a mass-to-volume ratio of 30 g: 50 mL and 100 mL, respectively. The mixture was then stirred at 1600–1800 rpm for 30 min. The pH was then adjusted to neutral using ammonia to obtain a nano-cerium disulfide suspension. Vinyltriethoxysilane and the nano-cerium disulfide suspension were then mixed at a volume ratio of 10:100. 2 g of partially reduced graphene oxide Y was added, and the mixture was reacted at 50–60 °C and 1000–1500 rpm for 18–22 h to obtain a modified nano-cerium disulfide dispersion. The dispersion was filtered and then dried under vacuum at 80–100 °C for 3 h to obtain the modified nano-cerium disulfide.

[0076] The volume ratio of the vinyltriethoxysilane to the nano-cerium disulfide suspension is 1:10; the partially reduced graphene oxide Y has an oxygen content of 15% and a specific surface area of ​​100-200 g / m². 2 The particle size is 0.5–3 μm.

[0077] This invention also provides a method for using an anti-scaling and anti-wear polyurea coating for oil and gas well pipes in the context of corrosion and scale prevention. The method is as follows: A primer for the anti-scaling and anti-wear polyurea coating for oil and gas well pipes is sprayed onto a pre-treated substrate and cured at 100–140°C for 40–60 minutes; then a topcoat is sprayed onto the primer-coated substrate and cured at 100–140°C for 1.5–2 hours to form a coating layer. This coating is used in the surface coating of oil and gas well pipes.

[0078] The purpose of this invention is to provide an anti-scaling and anti-wear polyurea coating, its preparation method, and its application method, in order to solve the problem that existing polyurea coatings are far from achieving a superhydrophobic surface and have a large coefficient of friction, which makes it impossible to promote droplet rolling, delay the crystallization process, and reduce the adhesion of scale to the substrate after crystallization, thus lacking the function of preventing scale formation.

[0079] Example 1

[0080] The weight ratio of component A to component B in the topcoat is 1:1.9; the weight ratio of component C to component D in the primer is 1:2.1.

[0081] The raw materials for preparing component A of the topcoat include: 60 parts of isophorone diisocyanate, 20 parts of polyethylene glycol, 15 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 5 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, 14 parts of modified nano molybdenum disulfide, and 1 part of additive.

[0082] The raw materials for preparing component C of the primer include: 60 parts of isophorone diisocyanate, 20 parts of polyethylene glycol, 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 5 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, 14 parts of modified nano cerium dioxide, and 1 part of additive.

[0083] The preparation process is as follows:

[0084] S1: 60 parts of isophorone diisocyanate and 20 parts of polyethylene glycol were mixed and heated to 50°C for 4 hours to obtain polymer A. A dispersion of partially reduced graphene oxide modified with α-Al2O3 nanoparticles and yttrium-stabilized zirconia nanoparticles was prepared. 15 parts of the dispersion of partially reduced graphene oxide modified with α-Al2O3 nanoparticles and yttrium-stabilized zirconia nanoparticles, and 5 parts of a mixture of α-Al2O3 micro / nano powders and yttrium-stabilized zirconia micro / nano powders were added sequentially to polymer A. The mixture was stirred at 2100 r / min for 2 hours to obtain topcoat component A, with a viscosity of 900 mPa·s.

[0085] S2: Mix 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, and 14 parts of modified nano molybdenum disulfide, stir at 2100 r / min for 20 min, then heat at 90℃ for 3 h, add 1 part of additive, and stir at 2100 r / min for 20 min to obtain topcoat component B.

[0086] Mixing of components A and B: Mix component A and component B thoroughly at 50°C.

[0087] S3: Add 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion and 5 parts of a mixture of cerium dioxide micro-nano powder and yttrium oxide stabilized zirconium oxide micro-nano powder to polymer A in sequence, stir at 2100 r / min for 2 h to obtain primer component C, wherein the viscosity of primer component C is 900 mPa·s.

[0088] S4: Mix 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, and 14 parts of modified nano-cerium dioxide, stir at 2100 r / min for 20 min, then heat at 90℃ for 3 h, add 1 part of additive, and stir at 2100 r / min for 20 min to obtain primer component D; CD component mixing: mix component C and component D evenly at 50℃. The topcoat and primer are anti-scaling and anti-wear polyurea coatings for oil and gas well pipes.

[0089] Example 2

[0090] The weight ratio of component A to component B in the topcoat is 1:2.0; the weight ratio of component C to component D in the primer is 1:2.0.

[0091] The raw materials for preparing component A of the topcoat include: 46 parts of isophorone diisocyanate, 30 parts of polyethylene glycol, 15 parts of a partially reduced graphene oxide dispersion modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 8 parts of foaming agent, 14 parts of modified nano molybdenum disulfide, and 1 part of additive.

[0092] The raw materials for preparing component C of the primer include: 46 parts of isophorone diisocyanate, 30 parts of polyethylene glycol, 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 9 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 8 parts of foaming agent, 14 parts of modified nano cerium dioxide, and 1 part of additive.

[0093] The preparation process is as follows:

[0094] S1: 46 parts of isophorone diisocyanate and 30 parts of polyethylene glycol were mixed and heated to 70℃ and reacted for 6 hours to obtain polymer A. A dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder was prepared. 15 parts of the dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder were added sequentially to polymer A. The mixture was stirred at 2500 r / min for 3 hours to obtain topcoat component A, with a viscosity of 1000 mPa·s.

[0095] S2: Mix 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 8 parts of foaming agent, and 14 parts of modified nano molybdenum disulfide, stir at 2500 r / min for 30 min, then heat at 102℃ for 4 h, add 1 part of additive, and stir at 2500 r / min for 30 min to obtain topcoat component B;

[0096] Mixing of components A and B: Mix component A and component B thoroughly at 70°C.

[0097] S3: Add 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion and 9 parts of a mixture of cerium dioxide micro-nano powder and yttrium oxide stabilized zirconium oxide micro-nano powder to polymer A in sequence, stir at 2500 r / min for 3 h to obtain primer component C, wherein the viscosity of primer component C is 1000 mPa·s.

[0098] S4: Mix 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 8 parts of foaming agent, and 14 parts of modified nano-cerium dioxide, stir at 2500 r / min for 30 min, then heat at 102℃ for 4 h, add the additives, and stir at 2500 r / min for 30 min to obtain primer component D; CD component mixing: mix component C and component D evenly at 70℃. The topcoat and primer are anti-scaling and anti-wear polyurea coatings for oil and gas well pipes.

[0099] Example 3

[0100] The weight ratio of component A to component B in the topcoat is 1:2.1; the weight ratio of component C to component D in the primer is 1:1.9.

[0101] The raw materials for preparing component A of the topcoat include: 55 parts of isophorone diisocyanate, 30 parts of polyethylene glycol, 10 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 5 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 29 parts of chain extender, 37 parts of amino-terminated polyether, 14 parts of diluent, 6 parts of foaming agent, 11 parts of modified nano molybdenum disulfide, and 3 parts of additives.

[0102] The raw materials for preparing component C of the primer include: 55 parts of isophorone diisocyanate, 30 parts of polyethylene glycol, 10 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 5 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 29 parts of chain extender, 37 parts of amino-terminated polyether, 14 parts of diluent, 6 parts of foaming agent, 11 parts of modified nano cerium dioxide, and 3 parts of additives.

[0103] The preparation process is as follows:

[0104] S1: 55 parts of isophorone diisocyanate and 30 parts of polyethylene glycol were mixed and heated to 70℃ and reacted for 6 h to obtain polymer A. A dispersion of partially reduced graphene oxide modified with α-Al2O3 nanoparticles and yttrium oxide-stabilized zirconia nanoparticles was prepared. 10 parts of the dispersion of partially reduced graphene oxide modified with α-Al2O3 nanoparticles and yttrium oxide-stabilized zirconia nanoparticles, and 5 parts of a mixture of α-Al2O3 micro / nano powders and yttrium oxide-stabilized zirconia micro / nano powders were added sequentially to polymer A. The mixture was stirred at 2100 r / min for 2.5 h to obtain topcoat component A, with a viscosity of 1000 mPa·s.

[0105] S2: Mix 29 parts of chain extender, 37 parts of amino-terminated polyether, 14 parts of diluent, 6 parts of foaming agent, and 11 parts of modified nano molybdenum disulfide, stir at 2100 r / min for 30 min, then heat at 90-102℃ for 3-4 h, add 3 parts of additives, and stir at 2500 r / min for 30 min to obtain topcoat component B;

[0106] Mixing of components A and B: Mix component A and component B thoroughly at 70°C.

[0107] S3: Add 10 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion and 5 parts of a mixture of cerium dioxide micro-nano powder and yttrium oxide stabilized zirconium oxide micro-nano powder to polymer A in sequence, stir at 2500 r / min for 3 h to obtain primer component C, wherein the viscosity of primer component C is 1000 mPa·s.

[0108] S4: Mix 29 parts of chain extender, 37 parts of amino-terminated polyether, 14 parts of diluent, 6 parts of foaming agent, and 11 parts of modified nano-cerium dioxide, stir at 2100 r / min for 30 min, then heat at 102℃ for 3-4 h, add additives, and stir at 2500 r / min for 30 min to obtain primer component D; CD component mixing: mix component C and component D evenly at 70℃. The topcoat and primer are anti-scaling and anti-wear polyurea coatings for oil and gas well pipes.

[0109] Example 4

[0110] The weight ratio of component A to component B in the topcoat is 1:2.1; the weight ratio of component C to component D in the primer is 1:1.9.

[0111] The raw materials for preparing component A of the topcoat include: 60 parts of isophorone diisocyanate, 16 parts of polyethylene glycol, 15 parts of a partially reduced graphene oxide dispersion modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 7 parts of foaming agent, 15 parts of modified nano-molybdenum disulfide, and 1 part of additive.

[0112] The raw materials for preparing component C of the primer include: 60 parts of isophorone diisocyanate, 16 parts of polyethylene glycol, 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 9 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 7 parts of foaming agent, 15 parts of modified nano cerium dioxide, and 1 part of additive.

[0113] The preparation process is as follows:

[0114] S1: 60 parts of isophorone diisocyanate and 16 parts of polyethylene glycol were mixed and heated to 60℃ and reacted for 5 h to obtain polymer A. A dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder was prepared. 15 parts of the dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia micro / nano powder were added sequentially to polymer A. The mixture was stirred at 2500 r / min for 3 h to obtain topcoat component A, with a viscosity of 950 mPa·s.

[0115] S2: Mix 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 7 parts of foaming agent, and 15 parts of modified nano molybdenum disulfide, stir at 2500 r / min for 25 min, then heat at 100℃ for 3.5 h, add additives, and stir at 2500 r / min for 25 min to obtain topcoat component B;

[0116] Mixing of components A and B: Mix component A and component B thoroughly at 60°C.

[0117] S3: Add 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion and 9 parts of a mixture of cerium dioxide micro-nano powder and yttrium oxide stabilized zirconium oxide micro-nano powder to polymer A in sequence, stir at 2500 r / min for 3 h to obtain primer component C, wherein the viscosity of primer component C is 1000 mPa·s.

[0118] S4: Mix 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 7 parts of foaming agent, and 15 parts of modified nano-cerium dioxide, stir at 2500 r / min for 30 min, then heat at 100℃ for 4 h, add the additives, and stir at 2500 r / min for 30 min to obtain primer component D; CD component mixing: mix component C and component D evenly at 70℃. The topcoat and primer are anti-scaling and anti-wear polyurea coatings for oil and gas well pipes.

[0119] Example 5

[0120] The weight ratio of component A to component B in the topcoat is 1:1.9; the weight ratio of component C to component D in the primer is 1:2.1.

[0121] The raw materials for preparing component A of the topcoat include: 46 parts of isophorone diisocyanate, 30 parts of polyethylene glycol, 15 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 7 parts of foaming agent, 15 parts of modified nano molybdenum disulfide, and 1 part of additive.

[0122] The raw materials for preparing component C of the primer include: 46 parts of isophorone diisocyanate, 30 parts of polyethylene glycol, 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 9 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 32 parts of chain extender, 30 parts of amino-terminated polyether, 15 parts of diluent, 7 parts of foaming agent, 15 parts of modified nano cerium dioxide, and 1 part of additive.

[0123] Example 6

[0124] The weight ratio of component A to component B in the topcoat is 1:1.9; the weight ratio of component C to component D in the primer is 1:2.1.

[0125] The raw materials for preparing component A of the topcoat include: 60 parts of isophorone diisocyanate, 26 parts of polyethylene glycol, 5 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 29 parts of chain extender, 37 parts of amino-terminated polyether, 14 parts of diluent, 6 parts of foaming agent, 11 parts of modified nano molybdenum disulfide, and 3 parts of additives.

[0126] The raw materials for preparing component C of the primer include: 60 parts of isophorone diisocyanate, 26 parts of polyethylene glycol, 5 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 9 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 29 parts of chain extender, 37 parts of amino-terminated polyether, 14 parts of diluent, 6 parts of foaming agent, 11 parts of modified nano cerium dioxide, and 3 parts of additives.

[0127] Example 7

[0128] The weight ratio of component A to component B in the topcoat is 1:2.0; the weight ratio of component C to component D in the primer is 1:2.1.

[0129] The raw materials for preparing component A of the topcoat include: 61 parts of isophorone diisocyanate, 15 parts of polyethylene glycol, 15 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 9 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, 14 parts of modified nano molybdenum disulfide, and 1 part of additive.

[0130] The raw materials for preparing component C of the primer include: 61 parts of isophorone diisocyanate, 15 parts of polyethylene glycol, 15 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 9 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, 14 parts of modified nano cerium dioxide, and 1 part of additive.

[0131] Example 8

[0132] The weight ratio of component A to component B in the topcoat is 1:2.0; the weight ratio of component C to component D in the primer is 1:2.0.

[0133] The raw materials for preparing component A of the topcoat include: 61 parts of isophorone diisocyanate, 29 parts of polyethylene glycol, 5 parts of a dispersion of partially reduced graphene oxide modified with α-Al2O3 nanopowder and yttrium oxide-stabilized zirconia nanopowder, and 5 parts of a mixture of α-Al2O3 micro / nano powder and yttrium oxide-stabilized zirconia (YSZ) micro / nano powder; the raw materials for preparing component B include: 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, 14 parts of modified nano molybdenum disulfide, and 1 part of additive.

[0134] The raw materials for preparing component C of the primer include: 61 parts of isophorone diisocyanate, 29 parts of polyethylene glycol, 5 parts of cerium dioxide nanopowder modified partially reduced graphene oxide dispersion, and 5 parts of a mixture of cerium dioxide micro (CeO2) nanopowder and yttrium oxide stabilized zirconium oxide micro nanopowder; the raw materials for preparing component D of the primer include: 29 parts of chain extender, 39 parts of amino-terminated polyether, 11 parts of diluent, 6 parts of foaming agent, 14 parts of modified nano cerium dioxide, and 1 part of additive.

[0135] The preparation process and temperature, time, and stirring conditions of Examples 5-8 are the same as those of Example 1.

[0136] Performance testing:

[0137] The coating samples from Examples 1, 2, and 3 were placed for 7 days before performance testing was conducted. The test results are as follows:

[0138]

[0139] As shown in the table above, the anti-scaling and anti-wear coating prepared by this invention has a low surface energy and a contact angle exceeding 105 degrees, exhibiting excellent hydrophobicity. It can form a highly adhesive and anti-scaling super-slippery polyurea coating on the surface of oil pipes. The wear resistance of the coating prepared by this invention is improved by more than 70%. The coating developed by this invention exhibits good corrosion resistance in harsh environments such as ultra-high temperature and high pressure acidic oil and gas media, alkaline media, and simulated formation water with high mineralization and high bacterial content. Therefore, the coating developed by this invention has significantly improved corrosion resistance, anti-scaling, and anti-wear performance, and has broad application prospects in deep and ultra-deep oil and gas drilling.

[0140] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.

Claims

1. A scale and wear resistant polyurea coating, characterized in that, The primer and the topcoat; the topcoat comprises A component and B component, the weight ratio of the A component and the B component is 1: (1.9~2.1); The preparation raw materials of the A component of the topcoat include: isophorone diisocyanate 46~61 parts, polyethylene glycol 15~30 parts, α~Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene oxide dispersion liquid 5~15 parts, and the mixture of α~Al2O3 micro-nano powder and yttria stabilized zirconia micro-nano powder 5~9 parts, with a total of 100 parts; The preparation raw materials of the B component of the topcoat include: chain extender 29~32 parts, amino-terminated polyether 30~39 parts, diluent 11~15 parts, foaming agent 6~8 parts, modified nano molybdenum disulfide 11~15 parts, and auxiliary agent 1~3 parts, with a total of 100 parts; The primer comprises C component and D component, the weight ratio of the C component and the D component is 1: (1.9~2.1); the preparation raw materials of the C component of the primer include: isophorone diisocyanate 46~61 parts, polyethylene glycol 15~30 parts, ceria nano powder modified partially reduced graphene oxide dispersion liquid 5~15 parts, and the mixture of ceria micro-nano powder and yttria stabilized zirconia micro-nano powder 5~9 parts, with a total of 100 parts; The preparation raw materials of the D component of the primer include: chain extender 29~32 parts, amino-terminated polyether 30~39 parts, diluent 11~15 parts, foaming agent 6~8 parts, modified nano ceria 11~15 parts, and auxiliary agent 1~3 parts, with a total of 100 parts.

2. The anti-fouling anti-wear polyurea coating of claim 1, wherein, The mass ratio of α~Al2O3 micro-nano powder and yttria stabilized zirconia micro-nano powder in the mixture of α~Al2O3 micro-nano powder and yttria stabilized zirconia micro-nano powder is 1:3; the mass ratio of nano powder and micro powder in the α~Al2O3 micro-nano powder is 1:1; the mass ratio of nano powder and micro powder in the yttria stabilized zirconia micro-nano powder is 2:

1.

3. The anti-fouling anti-wear polyurea coating of claim 1, wherein, The mass ratio of ceria micro-nano powder and yttria stabilized zirconia micro-nano powder in the mixture of ceria micro-nano powder and yttria stabilized zirconia micro-nano powder is 2:1; the mass ratio of nano powder and micro powder in the ceria micro-nano powder is 2:1; the mass ratio of nano powder and micro powder in the yttria stabilized zirconia micro-nano powder is 2:

1.

4. The anti-fouling anti-wear polyurea coating of claim 1, wherein, The chain extender is diethyl toluene diamine; the diluent is the mixture of propylene carbonate, n-butyl acetate and n-butanol, the mass ratio of propylene carbonate, n-butyl acetate and n-butanol is 3:3:1; the foaming agent is azobis isobutyronitrile; the auxiliary agent includes leveling agent, defoaming agent and dispersant.

5. A method for preparing the anti-fouling and anti-wear polyurea coating according to any one of claims 1 to 4, characterized in that, The method comprises the following steps: S1: isophorone diisocyanate, polyethylene glycol is mixed after heating to obtain polymer A, preparation of alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene dispersion; to polymer A in turn adding alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene dispersion, alpha-Al2O3 micro-nano powder and yttria stabilized zirconia micro-nano powder mixture, stirring to prepare the A component of the topcoat; S2: preparation of modified nanometer molybdenum disulfide, chain extender, amino-terminated polyether, diluent, foaming agent, modified nanometer molybdenum disulfide is mixed after stirring and heating, then adding additives and mixing uniformly to prepare the B component of the topcoat; S3: preparation of cerium dioxide nano powder modified partially reduced graphene dispersion; to polymer A in turn adding cerium dioxide nano powder modified partially reduced graphene dispersion, cerium dioxide micro-nano powder and yttria stabilized zirconia micro-nano powder mixture, stirring to prepare the C component of the primer; S4: preparation of modified nanometer cerium dioxide, chain extender, amino-terminated polyether, diluent, foaming agent, modified nanometer cerium dioxide is mixed after stirring and heating, then adding additives and mixing uniformly to prepare the D component of the primer; S5: the A component of the topcoat and the B component of the topcoat are mixed uniformly to prepare the topcoat; the C component of the primer and the D component of the primer are mixed uniformly to prepare the primer, the topcoat and the primer are oil and gas well pipe anti-fouling and anti-abrasion polyurea coatings.

6. The preparation method according to claim 5, characterized in that, In the S1, the process of preparing alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene dispersion is as follows: Trimethylsiloxane is mixed with partially reduced graphene X to carry out the first modification reaction to obtain a mixed solution a; alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder are added to the mixed solution a to obtain a mixed solution b; the mixed solution b is dried to obtain alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene; n-butanol, polydimethylsiloxane and silane coupling agent are sequentially added to the alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene to carry out the second modification reaction and ultrasonic treatment, and then alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder modified partially reduced graphene dispersion is obtained; The mass ratio of alpha-Al2O3 nano powder and yttria stabilized zirconia nano powder is 1:2; The oxygen content of the partially reduced graphene X is 10%.

7. The preparation method according to claim 5, characterized in that, In the S2, the process of preparing modified nanometer molybdenum disulfide is as follows: Nanometer molybdenum disulfide, n-butanol and anhydrous ethanol are mixed, the pH value is adjusted to neutral to obtain nanometer molybdenum disulfide suspension; vinyltriethoxysilane and nanometer molybdenum disulfide suspension are mixed, and then partially reduced graphene Y is added to carry out the reaction to obtain modified nanometer molybdenum disulfide dispersion, which is filtered and vacuum dried to obtain modified nanometer molybdenum disulfide; The volume ratio of the vinyltriethoxysilane and the nanometer molybdenum disulfide suspension is 1:

10. The oxygen content of the partially reduced graphene oxide Y is 15%.

8. The preparation method according to claim 5, characterized in that, In the S3, the process for preparing the cerium dioxide nanometer powder modified partially reduced graphene oxide dispersion liquid is as follows: Trimethylsiloxane is mixed with the partially reduced graphene oxide X to perform a first modification reaction to obtain a mixed liquid a; cerium dioxide nanometer powder is added to the mixed liquid a to perform a reaction to obtain a mixed liquid c; the mixed liquid c is dried to obtain cerium dioxide nanometer powder modified partially reduced graphene oxide; n-butanol, polydimethylsiloxane and silane coupling agent are sequentially added to the cerium dioxide nanometer powder modified partially reduced graphene oxide to perform a second modification reaction and ultrasonic treatment, and then a cerium dioxide nanometer powder modified partially reduced graphene oxide dispersion liquid is obtained; The oxygen content of the partially reduced graphene oxide X is 10%.

9. The preparation method according to claim 5, characterized in that, In the S4, the process for preparing the modified nanometer cerium dioxide is as follows: Nanometer cerium dioxide, n-butanol and anhydrous ethanol are mixed, the pH value is adjusted to neutral to obtain a nanometer cerium dioxide suspension, vinyltriethoxysilane and the nanometer cerium dioxide suspension are mixed, partially reduced graphene oxide Y is added to perform a reaction to obtain a modified nanometer cerium dioxide dispersion liquid, and then the modified nanometer cerium dioxide is obtained by filtration and vacuum drying; The volume ratio of the vinyltriethoxysilane and the nanometer cerium dioxide suspension is 1:

10. The oxygen content of the partially reduced graphene oxide Y is 15%.

10. A method of using the anti-fouling and anti-wear polyurea coating of claim 1, characterized in that, The polyurea coating is used for scale and wear resistance of oil and gas well pipes, and the use method is as follows: The primer in the polyurea coating is applied to the pretreated substrate and cured to obtain a substrate coated with the primer; the topcoat is applied to the substrate coated with the primer and cured to form a scale and wear resistant polyurea coating.

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