Modified quaternary ammonium salt and preparation method thereof, modified zinc molybdate, coating and workpiece

Abstract

The invention discloses a modified quaternary ammonium salt and a preparation method thereof, modified zinc molybdate, a coating and a workpiece. The preparation method of the modified quaternary ammonium salt comprises the following steps: in a nitrogen environment, carrying out a first reaction on octanoic acid and hydroxyethyl ethylenediamine in xylene, and then adding ethanol and phosphorus oxychloride to carry out a second reaction so as to prepare the modified quaternary ammonium salt. The prepared modified quaternary ammonium salt has excellent corrosion resistance, the corrosion resistance of a base material in a high-corrosion environment can be remarkably improved, and the service life of the base material is prolonged for a long time. Meanwhile, the modified quaternary ammonium salt is further loaded in the zinc molybdate tube nano material, so that the slow release function of the modified quaternary ammonium salt can be realized, and the long-term protection effect on the base material is further improved. The modified quaternary ammonium salt prepared by the method can be widely applied to a high-corrosion environment.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coatings technology, and in particular to a modified quaternary ammonium salt and its preparation method, modified zinc molybdate, coatings, and components. Background Technology

[0002] Organic coatings are widely used in power facilities to extend equipment lifespan and ensure operational safety due to their strong adaptability to substrates, ease of application, relatively low cost, and good decorative properties. However, organic coatings have limited corrosion resistance in highly corrosive or extreme environments. During use, they often develop surface defects such as microcracks, blistering, and micropores. Corrosive media can diffuse inward along these local defects, causing localized corrosion of the metal substrate, significantly reducing the coating's protective performance, leading to functional degradation and eventual failure, resulting in substantial maintenance costs and a relatively short protective lifespan. Therefore, in addition to widely used organic coating materials such as organic resins, developing corrosion inhibitors with excellent anti-corrosion properties remains a key solution for improving the corrosion resistance of coatings. Summary of the Invention

[0003] Therefore, it is necessary to provide a modified quaternary ammonium salt with excellent anti-corrosion properties, which can significantly improve the corrosion resistance of organic coatings in highly corrosive environments, provide long-term protection for the substrate, and extend its service life.

[0004] In a first aspect, this application provides a method for preparing a modified quaternary ammonium salt, comprising the following steps:

[0005] In a nitrogen atmosphere, octanoic acid and hydroxyethyl ethylenediamine are reacted in an organic benzene solvent for a first reaction, followed by the addition of an alcohol solvent and phosphorus oxychloride for a second reaction to prepare a modified quaternary ammonium salt.

[0006] In some embodiments, the preparation method further satisfies at least one of the following (1) to (11):

[0007] (1) The molar ratio of the octanoic acid and the hydroxyethyl ethylenediamine is 1:(0.5-2);

[0008] (2) The temperature of the first reaction is 130℃-260℃;

[0009] Optionally, the first reaction is carried out at two different temperatures, the first temperature being 130℃-200℃ and the second temperature being 200℃-260℃;

[0010] (3) The time for the first reaction is 2h-10h;

[0011] (4) The first reaction includes a first-stage reaction and a second-stage reaction;

[0012] Optionally, the temperature of the first-stage reaction is 130℃-200℃;

[0013] Optionally, the reaction time for the first stage is 2-4 hours;

[0014] Optionally, the temperature of the second-stage reaction is 200℃-260℃;

[0015] Optionally, the second-stage reaction time is 2-6 hours;

[0016] (5) During the first reaction, water produced during the reaction is continuously removed;

[0017] (6) The molar ratio of the octanoic acid and the phosphorus oxychloride is 1:(0.1-0.5);

[0018] (7) The temperature of the second reaction is 40℃-90℃;

[0019] (8) The second reaction takes 2-6 hours;

[0020] (9) After the first reaction is completed, the temperature is lowered to 40°C to 85°C, and then an alcohol solvent and phosphorus oxychloride are added to carry out the second reaction;

[0021] (10) The organic benzene solvent includes one or more of benzene, toluene, and xylene;

[0022] (11) The alcohol solvents include one or more of methanol and ethanol.

[0023] Secondly, this application also provides a modified quaternary ammonium salt, which is prepared by the method for preparing the modified quaternary ammonium salt provided in the first aspect.

[0024] Thirdly, this application also provides a method for preparing modified zinc molybdate, comprising the following steps:

[0025] Zinc molybdate was added to an aqueous solution of a modified quaternary ammonium salt, and the mixture was treated under vacuum to remove water and dry, thus preparing modified zinc molybdate.

[0026] The modified quaternary ammonium salt includes the modified quaternary ammonium salt prepared by the method provided in the first aspect.

[0027] In some embodiments, the preparation method further satisfies at least one of the following (1) to (5):

[0028] (1) The mass ratio of the modified quaternary ammonium salt to the zinc molybdate is 1:(10-1000).

[0029] (2) The zinc molybdate includes zinc molybdate nanotubes;

[0030] Optionally, the diameter of the zinc molybdate nanotubes is 50 nm-100 nm;

[0031] Optionally, the length of the zinc molybdate nanotubes is 0.5 μm-10 μm;

[0032] (3) Treat under vacuum conditions for 0.5h-24h;

[0033] (4) The drying temperature is 45℃-55℃;

[0034] (5) The drying time is 10h-15h.

[0035] Fourthly, this application also provides a modified zinc molybdate, which is prepared by the method for preparing modified zinc molybdate provided in the third aspect.

[0036] Fifthly, this application also provides a coating, wherein the raw materials for preparing the coating include component A and component B, wherein component A comprises resin, corrosion inhibitor, first additive and first solvent, and component B comprises curing agent, second additive and second solvent;

[0037] The corrosion inhibitor includes a modified quaternary ammonium salt and / or a modified zinc molybdate, wherein the modified quaternary ammonium salt is prepared by the method for preparing modified quaternary ammonium salt provided in the first aspect, and the modified zinc molybdate is prepared by the method for preparing modified zinc molybdate provided in the third aspect.

[0038] In some embodiments, the coating also satisfies at least one of the features shown in (1) to (6) below:

[0039] (1) By mass, the composition of component A includes: 80-100 parts of resin, 5-20 parts of corrosion inhibitor, 0.2-9 parts of first auxiliary agent and 20-50 parts of first solvent;

[0040] (2) By mass, the composition of component B includes: 10-20 parts of curing agent, 0.5-3 parts of second auxiliary agent and 5-10 parts of second solvent;

[0041] (3) The resin includes epoxy resin;

[0042] Optionally, the epoxy resin includes an aqueous epoxy resin;

[0043] Optionally, the epoxy resin has a solid content of 50%-60%;

[0044] Optionally, the epoxy equivalent of the epoxy resin is 800 g / eq-1050 g / eq;

[0045] (4) The first auxiliary agent includes one or more of dispersants, wetting agents and defoamers;

[0046] Optionally, the dispersant includes one or more of TEGO Dispers 652, BYK-190, and ADDITOL® VXW 6208;

[0047] Optionally, the wetting agent includes one or more of TEGO Twin 4100, BYK-346, and Afcona-3590;

[0048] Optionally, the defoamer includes one or more of TEGO Airex 902 W, BYK-024, and Afcona-2508;

[0049] (5) The curing agent includes an epoxy resin curing agent;

[0050] Optionally, the epoxy resin curing agent includes a water-based epoxy resin curing agent;

[0051] Optionally, the solid content of the epoxy resin curing agent is 79%-90%;

[0052] Optionally, the active hydrogen equivalent of the epoxy resin curing agent is 100 g / eq-200 g / eq;

[0053] (6) The second auxiliary agent includes a flash rust inhibitor;

[0054] Optionally, the flash rust inhibitor includes one or more of Raybo 60, CK-34, and Qichuang R-706F;

[0055] (7) The first solvent and the second solvent are each independently an aqueous solvent;

[0056] Optionally, the aqueous solvent includes water;

[0057] (8) The mass ratio of component A to component B is (5-10):1.

[0058] Sixthly, this application also provides a method for preparing the coating provided in the fifth aspect, comprising the following steps:

[0059] The first solvent was added to the water-based epoxy resin for dispersion, followed by the addition of the first additive and corrosion inhibitor for further dispersion, to prepare component A:

[0060] The curing agent, the second additive, and the second solvent are mixed to prepare component B:

[0061] The coating is prepared by mixing component A and component B.

[0062] In a seventh aspect, this application also provides an article comprising a body and a coating disposed on the surface of the body, the coating being prepared using a coating material provided in the fifth aspect.

[0063] Compared with traditional technologies, the beneficial effects of the technical solution in this application include:

[0064] This application prepares a modified quaternary ammonium salt with excellent anti-corrosion properties by reacting octanoic acid, hydroxyethyl ethylenediamine and phosphorus oxychloride. It can significantly improve the anti-corrosion protection of the substrate and slow down the corresponding electrochemical corrosion reaction, thus achieving a long-term anti-corrosion effect. The modified quaternary ammonium salt prepared in this application still has a long-term anti-corrosion effect in highly corrosive environments. Attached Figure Description

[0065] Figure 1 This is a molecular structure diagram of the modified quaternary ammonium salt prepared in this application. Detailed Implementation

[0066] To facilitate understanding of this application, a more complete description will be provided below with reference to the accompanying drawings. Preferred embodiments of this application are shown in the drawings. However, this application can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of this application.

[0067] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0068] As used herein, "optional," "optional," and "optional" refer to either "with" or "without" parallel options. If multiple "optional" entries appear in a technical solution, each "optional" entry is independent unless otherwise specified and there are no contradictions or mutual constraints. The term "and / or" as used herein includes any and all combinations of one or more related listed items. Unless otherwise specified, "multiple," "multiple," etc., as used herein refer to a quantity greater than 2 or equal to 2; for example, "one or more" indicates one, two, or more than two. In open-ended technical features or solutions described herein using words such as "containing," "including," and "comprising," unless otherwise specified, additional members beyond the listed members are not excluded. This can be considered as providing both a closed-ended feature or solution consisting of the listed members and an open-ended feature or solution that includes additional members beyond the listed members.

[0069] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0070] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0071] In order to improve the long-term anti-corrosion performance of anti-corrosion coatings, this application aims to provide a compound with excellent anti-corrosion effect and long-term anti-corrosion protection function.

[0072] In a first aspect, this application provides a method for preparing a modified quaternary ammonium salt, comprising the following steps:

[0073] In a nitrogen atmosphere, octanoic acid and hydroxyethyl ethylenediamine are reacted in an organic benzene solvent for a first reaction, followed by the addition of an alcohol solvent and phosphorus oxychloride for a second reaction to prepare a modified quaternary ammonium salt.

[0074] The molecular structure of the modified quaternary ammonium salt synthesized in this application is as follows:

[0075]

[0076] In this application, octanoic acid and hydroxyethyl ethylenediamine are reacted to generate an intermediate product with an imidazoline structure, which is then further reacted with phosphorus oxychloride to synthesize a modified quaternary ammonium salt with the above-mentioned molecular structure.

[0077] In some embodiments, the molar ratio of the octanoic acid and the hydroxyethyl ethylenediamine is 1:(0.5-2), including but not limited to 1:0.5, 1:0.8, 1:1, 1:1.5, 1:2 or any of the foregoing ranges and values ​​within those ranges.

[0078] In some embodiments, the temperature of the first reaction is 130°C-260°C, including but not limited to 130°C, 150°C, 180°C, 200°C, 220°C, 240°C, 260°C or any combination thereof and values ​​within that range.

[0079] In some embodiments, the time for the first reaction is 2h-10h, including but not limited to 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or any of the foregoing ranges and values ​​within that range.

[0080] In some embodiments, the first reaction includes a first-stage reaction and a second-stage reaction, wherein the first-stage reaction involves an amidation reaction of octanoic acid and hydroxyethyl ethylenediamine in xylene, and the second-stage reaction causes a further cyclization reaction, ultimately synthesizing an intermediate product with an imidazoline structure in stages.

[0081] In some embodiments, the temperature of the first-stage reaction is 130°C-200°C, including but not limited to 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or any of the foregoing ranges and values ​​within those ranges.

[0082] In some embodiments, the time for a first-stage reaction is 2h-4h, including but not limited to 2h, 2.5h, 3h, 3.5h, 4h or any of the foregoing ranges and values ​​within that range.

[0083] In some embodiments, the temperature of the two-stage reaction is 200°C-260°C, including but not limited to 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C or any of the foregoing ranges and values ​​within those ranges.

[0084] In some embodiments, the two-stage reaction time is 2h-6h, including but not limited to 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h or any of the foregoing ranges and values ​​within that range.

[0085] In some embodiments, water generated during the first reaction is continuously removed. Water is generated during the amidation and cyclization reactions of octanoic acid and hydroxyethyl ethylenediamine in xylene. Continuous water separation is necessary to promote the forward reaction, maintain the activity of the reaction system, reduce reversible reactions, improve reaction efficiency and yield, suppress side reactions, reduce impurity formation, and ensure product purity.

[0086] The intermediate product synthesized in this application, having an imidazoline structure, is further subjected to a quaternization reaction with phosphorus oxychloride. In some embodiments, the molar ratio of the octanoic acid to the phosphorus oxychloride is 1:(0.1-0.5), including but not limited to 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, or any of the foregoing ranges and values ​​within those ranges.

[0087] In some embodiments, the temperature of the second reaction is 40°C-90°C, including but not limited to 40°C, 50°C, 60°C, 70°C, 80°C, 90°C or any combination thereof and values ​​within that range.

[0088] In some embodiments, the time for the second reaction is 2h-6h, including but not limited to 2h, 3h, 4h, 5h, 6h or any of the foregoing ranges and values ​​within that range.

[0089] In some embodiments, after the first reaction is completed, the temperature is lowered to 40°C to 85°C, and then an alcohol solvent and phosphorus oxychloride are added to carry out a second reaction, including but not limited to 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C or any of the foregoing ranges and values ​​within the range.

[0090] In some embodiments, the organic benzene solvent includes one or more of benzene, toluene, and xylene. In this application, the use of xylene is more conducive to the synthesis of modified quaternary ammonium salts.

[0091] In some embodiments, the alcohol solvent includes one or more of methanol and ethanol. In this application, the use of ethanol is more conducive to the synthesis of modified quaternary ammonium salts.

[0092] In some specific embodiments, the preparation method of the modified quaternary ammonium salt of this application includes the following steps:

[0093] Nitrogen gas was introduced into the apparatus to purge air. Octanoic acid, hydroxyethyl ethylenediamine, and xylene were then added to initiate the first reaction. Nitrogen gas was continuously introduced, and the temperature was adjusted to the temperature of the first-stage reaction using a gradient heating method, while continuously separating the produced water. The temperature was then further increased to the temperature of the second-stage reaction, and the produced water was continuously separated. After the apparatus cooled, anhydrous ethanol was added, followed by the slow dropwise addition of phosphorus oxychloride. The reaction was carried out at the temperature of the second reaction, and the mixture was distilled under reduced pressure to obtain the modified quaternary ammonium salt.

[0094] This application describes the preparation of a modified quaternary ammonium salt compound with corrosion inhibition effects. Compared to traditional quaternary ammonium corrosion inhibitors, the modified quaternary ammonium salt prepared in this application exhibits stronger adsorption capacity on the surface of metal and other substrates, forming a more tightly packed hydrophobic layer. This creates a dual effect of "chemical adsorption + physical barrier," making the coating less susceptible to erosion by water flow or corrosive media, thus providing long-lasting corrosion protection. Furthermore, the modified quaternary ammonium salt prepared in this application preferentially adheres to active metal sites, preferentially covering corrosion-sensitive areas, improving corrosion inhibition efficiency, and demonstrating high corrosion inhibition effect even at low concentrations. In addition, the modified quaternary ammonium salt with an imidazoline structure prepared in this application exhibits better environmental friendliness and biocompatibility compared to traditional quaternary ammonium salts.

[0095] Secondly, this application also provides a modified quaternary ammonium salt, which is prepared by the method for preparing the modified quaternary ammonium salt provided in the first aspect.

[0096] Thirdly, this application also provides a method for preparing modified zinc molybdate, comprising the following steps:

[0097] Zinc molybdate was added to an aqueous solution of a modified quaternary ammonium salt, and the mixture was treated under vacuum to remove water and dry, thus preparing modified zinc molybdate.

[0098] The modified quaternary ammonium salt includes the modified quaternary ammonium salt prepared by the method provided in the first aspect.

[0099] In some embodiments, the mass ratio of the modified quaternary ammonium salt to the zinc molybdate is 1:(10-1000), including but not limited to 1:10, 1:15, 1:20, 1:50, 1:100, 1:200, 1:500, 1:800, 1:1000 or any of the foregoing ranges and values ​​within those ranges.

[0100] In some embodiments, the zinc molybdate comprises zinc molybdate nanotubes. Zinc molybdate nanotubes are one-dimensional molybdate nanotubes with a large specific surface area. Their tubular cavity structure can be used to load various guest molecules, while also possessing good mechanical strength. Organic corrosion inhibitors are corrosion inhibitors with organic compounds as the main component. They mainly inhibit metal corrosion through adsorption, film formation, or complexation, and are widely used in oil and gas fields, industrial water treatment, and seawater pipelines. Organic corrosion inhibitors typically also contain nucleophilic groups such as carboxylic acids, amino groups, and thiol groups to coordinate and complex with metals. This application, by loading organic corrosion inhibitors (i.e., the modified quaternary ammonium salt prepared in the first aspect) into nanotubes, can effectively improve the utilization efficiency of the corrosion inhibitor and increase the protective performance of the coating.

[0101] In some embodiments, the diameter of the zinc molybdate nanotubes is 50 nm to 100 nm, including but not limited to 50 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm or any combination thereof and values ​​within that range.

[0102] In some embodiments, the length of the zinc molybdate nanotubes is 0.5 μm-10 μm, including but not limited to 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm or any combination thereof and values ​​within that range.

[0103] In some embodiments, the treatment is carried out under vacuum conditions for 0.5h-24h, including but not limited to 0.5h, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 18h, 20h, 24h or any of the foregoing ranges and values ​​within those ranges.

[0104] In some embodiments, the drying temperature is 45°C-55°C, including but not limited to 45°C, 46°C, 48°C, 50°C, 52°C, 55°C or any combination thereof and values ​​within that range.

[0105] In some embodiments, the drying time is 10h-15h, including but not limited to 10h, 11h, 12h, 13h, 14h, 15h or any of the foregoing ranges and values ​​within that range.

[0106] This application utilizes a preparation process to load organic corrosion inhibitors onto zinc molybdate and / or zinc molybdate nanotubes, which possess excellent adsorption and loading capabilities. Specifically, it loads the modified quaternary ammonium salt prepared in the first aspect of this application. This process enables the organic corrosion inhibitor to bind with zinc molybdate and / or zinc molybdate nanotubes, thereby achieving the gradual release of the organic corrosion inhibitor and its continuous replenishment to the corrosion sites. Simultaneously, the modified zinc molybdate prepared in this application achieves a synergistic effect between the organic and inorganic corrosion inhibitors, enabling the formation of a dense passivation film on the surface of metal and other substrates. This film effectively blocks corrosive media, reduces their penetration, and achieves better anodic inhibition. The combined effect of both organic and inorganic phases covers the anodic active sites (organic phase) and cathodic reaction zone (inorganic phase) on the surface of metal and other substrates, comprehensively blocking electron transfer in the corrosion microcell. The corrosion inhibition efficiency far exceeds that of traditional organic or inorganic corrosion inhibitor systems, especially in complex corrosive environments.

[0107] Fourthly, this application also provides a modified zinc molybdate, prepared using the method for preparing modified zinc molybdate provided in the third aspect. The modified zinc molybdate of this application is loaded with an organic corrosion inhibitor (i.e., the modified quaternary ammonium salt prepared in this application), achieving a slow release function of the modified quaternary ammonium salt and improving the long-term protection of the substrate. Furthermore, zinc molybdate itself is also a rust-preventive pigment, providing corrosion protection for metal and other substrates. Therefore, this application, through the synergistic effect of the organic corrosion inhibitor and the inorganic rust-preventive pigment, significantly reduces the corrosion current density, meeting the requirements for long-term corrosion resistance, and exhibiting excellent long-term anti-corrosion protection, especially in highly corrosive environments.

[0108] Fifthly, this application also provides a coating, wherein the raw materials for preparing the coating include component A and component B, wherein component A comprises resin, corrosion inhibitor, first additive and first solvent, and component B comprises curing agent, second additive and second solvent;

[0109] The corrosion inhibitor includes a modified quaternary ammonium salt and / or a modified zinc molybdate, wherein the modified quaternary ammonium salt is prepared by the method for preparing modified quaternary ammonium salt provided in the first aspect, and the modified zinc molybdate is prepared by the method for preparing modified zinc molybdate provided in the third aspect.

[0110] In some embodiments, the composition of component A, by mass parts, includes: 80-100 parts of resin, 5-20 parts of corrosion inhibitor, 0.2-9 parts of first auxiliary agent, and 20-50 parts of first solvent.

[0111] In some embodiments, the composition of component A, by mass parts, includes: 80-90 parts of resin, 5-10 parts of corrosion inhibitor, 0.2-2 parts of first additive, and 20-50 parts of first solvent.

[0112] In some embodiments, the composition of component B, by weight, includes: 10-20 parts of curing agent, 0.5-3 parts of second auxiliary agent, and 5-10 parts of second solvent.

[0113] In some embodiments, the composition of component B, by weight, includes: 15-20 parts of epoxy resin curing agent, 2-3 parts of second additive, and 5-10 parts of second solvent.

[0114] In some embodiments, the resin comprises an epoxy resin. The epoxy resin includes an aqueous epoxy resin.

[0115] In some embodiments, the epoxy resin has a solid content of 50%-60%, including but not limited to 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, or any combination thereof and values ​​within that range.

[0116] In some embodiments, the epoxy equivalent of the epoxy resin is 800 g / eq-1050 g / eq, including but not limited to 800 g / eq, 850 g / eq, 900 g / eq, 950 g / eq, 1000 g / eq, 1050 g / eq, or any of the foregoing ranges and values ​​within that range.

[0117] In some embodiments, the first adjuvant includes one or more of a dispersant, a wetting agent, and a defoamer. As a non-limiting example, the dispersant includes one or more of TEGO Dispers 652, BYK-190, and ADDITOL® VXW 6208. As a non-limiting example, the wetting agent includes one or more of TEGO Twin 4100, BYK-346, and Afcona-3590. As a non-limiting example, the defoamer includes one or more of TEGO Airex 902 W, BYK-024, and Afcona-2508.

[0118] In some embodiments, the curing agent includes an epoxy resin curing agent, and the epoxy resin curing agent includes an aqueous epoxy resin curing agent.

[0119] In some embodiments, the epoxy resin curing agent has a solid content of 79%-90%, including but not limited to 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, or any of the foregoing ranges and values ​​within those ranges.

[0120] In some embodiments, the active hydrogen equivalent of the epoxy resin curing agent is 100 g / eq-200 g / eq, including but not limited to 100 g / eq, 120 g / eq, 140 g / eq, 150 g / eq, 160 g / eq, 180 g / eq, 200 g / eq, or any of the foregoing ranges and values ​​within those ranges.

[0121] In some embodiments, the second additive includes a flash rust inhibitor. As a non-limiting example, the flash rust inhibitor includes one or more of Raybo 60, CK-34 (Qingdao Enze Chemical), and Qichuang R-706F.

[0122] In some embodiments, the first solvent and the second solvent are each independently an aqueous solvent. As a non-limiting example, the aqueous solvent includes water.

[0123] In some embodiments, the mass ratio of component A to component B is (5-10):1, including but not limited to 5:1, 6:1, 6.25:1, 7:1, 8:1, 8.5:1, 9:1, 10:1, or any range formed by both of the foregoing and values ​​within that range. Furthermore, a mass ratio of component A to component B of (5-7):1 can better achieve the technical effects of this application.

[0124] This application achieves not only the slow release of modified quaternary ammonium salts by loading them into zinc lignomolybdate nanotubes, thus improving long-term protection of the substrate, but also enhances the compatibility of the modified quaternary ammonium salts with other components of the coating.

[0125] Sixthly, this application also provides a method for preparing the coating provided in the fifth aspect, comprising the following steps:

[0126] S10. The first solvent is added to the waterborne epoxy resin for dispersion, and then the first additive and corrosion inhibitor are added for dispersion to prepare component A.

[0127] S20. Mix the curing agent, the second additive, and the second solvent to prepare component B.

[0128] S30. Mix component A and component B to prepare a coating.

[0129] In a seventh aspect, this application also provides an article comprising a body and a coating disposed on the surface of the body, the coating being prepared using a coating material provided in the fifth aspect.

[0130] The coating provided in this application can be used on substrates including but not limited to metals and can be widely applied in various environments, including seawater, freshwater and humid air environments.

[0131] It should be noted that experimental methods in the following embodiments of this application, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All commonly used chemical reagents used in the embodiments are commercially available products, or can be prepared by those skilled in the art using known methods.

[0132] The types and sources of some of the raw materials and reagents involved in the specific embodiments of this application are as follows:

[0133] The water-based epoxy resin, model ER2153, was purchased from Guangzhou Jinghao New Materials Co., Ltd.

[0134] The water-based epoxy resin curing agent, model AMH1180, was purchased from Guangzhou Jinghao New Materials Co., Ltd.

[0135] Modified quaternary ammonium salts and their synthesis methods:

[0136] A synthesis apparatus was constructed, and N2 was introduced into the apparatus for 15 min to purge air. 0.1 mol of octanoic acid, 0.1 mol of hydroxyethyl ethylenediamine, and 20 mL of xylene were added. N2 was continued to be introduced, and the temperature was adjusted to 150 °C using a gradient heating method for 4 h of amidation reaction. Water produced was separated using a water separator. The temperature was then increased to 230 °C for 3 h of cyclization reaction, with water continuously separated using a water separator. When the apparatus cooled to 70 °C, 20 mL of anhydrous ethanol was added. 0.05 mol of phosphorus oxychloride was slowly added dropwise to the apparatus using a constant pressure funnel. Quaternization reaction was carried out at 60 °C for 3 h, followed by rotary evaporation at 70 °C for 2 h to obtain the modified quaternary ammonium salt. The molecular structure of the modified quaternary ammonium salt is shown in the appendix. Figure 1 As shown.

[0137] Modified zinc molybdate and its synthesis method:

[0138] First, 50 g of modified quaternary ammonium salt was dissolved in 500 mL of water, and 500 g of zinc molybdate nanotubes were added under continuous stirring. The mixture was stirred and dispersed for 2 h to obtain a mixture. Then, the mixture was vacuum-dried in a vacuum dryer for 12 h, and the zinc molybdate nanotubes loaded with modified quaternary ammonium salt were separated from the water by vacuum filtration. Finally, the mixture was dried in an oven at 50 °C for 12 h to obtain modified zinc molybdate, i.e., zinc molybdate nanotubes loaded with modified quaternary ammonium salt.

[0139] Example 1

[0140] Coatings and their preparation methods

[0141] The raw materials for preparing the coating in this embodiment include component A and component B.

[0142] By mass parts, component A comprises:

[0143] 30 parts deionized water

[0144] Dispersant ADDITOL® VXW 6208 0.6 parts

[0145] TEGO Dispers 4100 wetting agent 0.3 parts

[0146] 0.3 parts of TEGO Airex 902 W defoamer

[0147] 85 parts of waterborne epoxy resin ER2153, and

[0148] Six parts of modified quaternary ammonium salt.

[0149] The specific formulation of component B, by mass parts, is as follows:

[0150] 6 parts deionized water

[0151] RAYBO 60 anti-flash rust agent 3 parts, and

[0152] 20 parts of water-based epoxy resin curing agent AMH1180.

[0153] In this embodiment, the mass ratio of component A to component B is 25:4.

[0154] According to the above-described raw material composition formula, the preparation method of the coating in this embodiment includes:

[0155] Preparation of Component A: Deionized water was added to waterborne epoxy resin ER2153 and dispersed for 10 min. Then, dispersant ADDITOL® VXW 6208, wetting agent TEGO Dispers 4100 defoamer, defoamer TEGO Airex 902 W, and modified quaternary ammonium salt were added and dispersed for 60 min to obtain Component A.

[0156] Preparation of Component B: Component B is prepared by uniformly mixing waterborne epoxy resin curing agent AMH1180, flash rust inhibitor RAYBO 60, and deionized water.

[0157] Mix component A and component B in a specific ratio until homogeneous to obtain the coating.

[0158] Example 2: Coating and its preparation method

[0159] The raw materials for preparing the coating in this embodiment include component A and component B.

[0160] By mass parts, component A comprises:

[0161] 30 parts deionized water

[0162] Dispersant ADDITOL® VXW 6208 0.6 parts

[0163] TEGO Dispers 4100 wetting agent 0.3 parts

[0164] 0.3 parts of TEGO Airex 902 W defoamer

[0165] 85 parts of waterborne epoxy resin ER2153, and

[0166] Six parts of modified zinc molybdate.

[0167] The specific formulation of component B, by mass parts, is as follows:

[0168] 6 parts deionized water

[0169] RAYBO 60 anti-flash rust agent 3 parts, and

[0170] 20 parts of water-based epoxy resin curing agent AMH1180.

[0171] In this embodiment, the mass ratio of component A to component B is 25:4.

[0172] According to the above-described raw material composition formula, the preparation method of the coating in this embodiment includes:

[0173] Preparation of Component A: Deionized water was added to waterborne epoxy resin ER2153 and dispersed for 10 min. Then, dispersant ADDITOL® VXW 6208, wetting agent TEGO Dispers 4100 defoamer, defoamer TEGO Airex 902 W, and modified zinc molybdate were added and dispersed for 60 min to obtain Component A.

[0174] Preparation of Component B: Component B is prepared by uniformly mixing waterborne epoxy resin curing agent AMH1180, flash rust inhibitor RAYBO 60, and deionized water.

[0175] Mix component A and component B in a specific ratio until homogeneous to obtain the coating.

[0176] Example 3: Coating and its preparation method

[0177] The raw materials for preparing the coating in this embodiment include component A and component B.

[0178] By mass parts, component A comprises:

[0179] 30 parts deionized water

[0180] Dispersant BYK-190 0.6 parts

[0181] Wetting agent BYK-346 0.3 parts

[0182] Defoamer BYK-024 0.3 parts

[0183] 85 parts of waterborne epoxy resin ER2153, and

[0184] Six parts of modified zinc molybdate.

[0185] The specific formulation of component B, by mass parts, is as follows:

[0186] 6 parts deionized water

[0187] 3 parts of anti-flash rust agent CK-34, and

[0188] 20 parts of water-based epoxy resin curing agent AMH1180.

[0189] In this embodiment, the mass ratio of component A to component B is 25:4.

[0190] According to the above-described raw material composition formula, the preparation method of the coating in this embodiment includes:

[0191] Preparation of Component A: Deionized water was added to waterborne epoxy resin ER2153 and dispersed for 10 min. Then, dispersant BYK-190, wetting agent BYK-346, defoamer BYK024, and modified zinc molybdate were added and dispersed for 60 min to obtain Component A.

[0192] Preparation of Component B: Component B is prepared by uniformly mixing waterborne epoxy resin curing agent AMH1180, flash rust inhibitor CK-34, and deionized water.

[0193] Mix component A and component B in a specific ratio until homogeneous to obtain the coating.

[0194] Example 4: Coating and its preparation method

[0195] The raw materials for preparing the coating in this embodiment include component A and component B.

[0196] By mass parts, component A comprises:

[0197] 30 parts deionized water

[0198] TEGO Dispers 652 dispersant 0.6 parts

[0199] 0.3 parts of TEGO Twin 4100 wetting agent

[0200] 0.3 parts of TEGO Airex 902 W defoamer

[0201] 85 parts of waterborne epoxy resin ER2153, and

[0202] Six parts of modified zinc molybdate.

[0203] The specific formulation of component B, by mass parts, is as follows:

[0204] 6 parts deionized water

[0205] 3 parts of anti-flash rust agent Qichuang R-706F, and

[0206] 20 parts of water-based epoxy resin curing agent AMH1180.

[0207] In this embodiment, the mass ratio of component A to component B is 25:4.

[0208] According to the above-described raw material composition formula, the preparation method of the coating in this embodiment includes:

[0209] Preparation of Component A: Deionized water was added to waterborne epoxy resin ER2153 and dispersed for 10 min. Then, dispersant TEGO Dispers 652, wetting agent TEGO Twin 4100, defoamer TEGO Airex 902 W, and modified zinc molybdate were added and dispersed for 60 min to obtain Component A.

[0210] Preparation of Component B: Component B is prepared by uniformly mixing waterborne epoxy resin curing agent AMH1180, flash rust inhibitor Qichuang R-706F, and deionized water.

[0211] Mix component A and component B in a specific ratio until homogeneous to obtain the coating.

[0212] Example 5

[0213] The raw materials for preparing the coating in this embodiment include component A and component B.

[0214] By mass parts, component A comprises:

[0215] 50 parts deionized water

[0216] Dispersant ADDITOL® VXW 6208 3 parts

[0217] TEGO Dispers 4100 wetting agent, 1.5 parts

[0218] 1.5 parts of TEGO Airex 902 W defoamer

[0219] 100 parts of waterborne epoxy resin ER2153, and

[0220] 20 parts of modified zinc molybdate.

[0221] The specific formulation of component B, by mass parts, is as follows:

[0222] 10 parts deionized water

[0223] RAYBO 60 anti-flash rust agent 0.5 parts, and

[0224] 10 parts of water-based epoxy resin curing agent AMH1180.

[0225] In this embodiment, the mass ratio of component A to component B is 25:4.

[0226] According to the above-described raw material composition formula, the preparation method of the coating in this embodiment includes:

[0227] Preparation of Component A: Deionized water was added to waterborne epoxy resin ER2153 and dispersed for 10 min. Then, dispersant ADDITOL® VXW 6208, wetting agent TEGO Dispers 4100 defoamer, defoamer TEGO Airex 902 W, and modified zinc molybdate were added and dispersed for 60 min to obtain Component A.

[0228] Preparation of Component B: Component B is prepared by uniformly mixing waterborne epoxy resin curing agent AMH1180, flash rust inhibitor RAYBO 60, and deionized water.

[0229] Mix component A and component B in a specific ratio until homogeneous to obtain the coating.

[0230] Example 6: Coating and its preparation method

[0231] The difference from Example 2 is that the amount of modified zinc molybdate added in this example is 10 parts by mass, while the other components, addition amounts, and preparation methods are the same as in Example 1.

[0232] Example 7: Coating and its preparation method

[0233] The difference from Example 2 is that the amount of modified zinc molybdate added in this example is 17 parts by mass, while the remaining composition, amount added, and preparation method are the same as in Example 1.

[0234] Example 8

[0235] The difference from Example 2 is that the mass ratio of component A to component B in this example is 25:3, while the remaining components, addition amounts, and preparation methods are the same as in Example 1.

[0236] Comparative Example 1

[0237] The difference from Example 2 is that the modified zinc molybdate prepared in this application is not added to the coating of this comparative example, while the other components, addition amounts, and preparation methods are the same as in Example 2.

[0238] Comparative Example 2

[0239] The difference from Example 2 is that the modified zinc molybdate prepared in this application is not added to the coating of this comparative example. Instead, an equal amount of zinc molybdate nanotubes without modified quaternary ammonium salt is used as the substitute. The remaining composition, amount added, and preparation method are the same as in Example 2.

[0240] Experimental Example 1

[0241] The coating products prepared in the above-mentioned specific examples 1-8 and comparative examples 1-2 were subjected to the following tests: Salt spray resistance was tested according to GB / T 10125-2021 standard, using a neutral salt spray test. Electrochemical impedance spectroscopy (EIS) was used to evaluate the corrosion resistance of the coatings. The EIS was performed using a Gmary Reference 3000 electrochemical workstation, with the coating sample as the working electrode and an area of ​​12.56 cm². 2 The reference electrode was a saturated calomel electrode, the auxiliary electrode was a platinum sheet, and the test solution was a 3.5 wt% NaCl solution. The experiment lasted for 30 days. The coating was prepared by air spraying onto a 150 mm × 75 mm × 3 mm Q235 steel plate. After drying and curing at room temperature, the coating thickness was 90 μm ± 10 μm.

[0242] The test results obtained using the above testing method are shown in Table 1:

[0243] Table 1: Performance Test Results of Coatings

[0244]

[0245] A comparison of the test results of Examples 1-8 and Comparative Examples 1-2 shows that the modified quaternary ammonium salt prepared in this application can improve the corrosion resistance of coatings / coatings, exhibiting a significant advantage in corrosion resistance compared to commercially available corrosion inhibitors. The results of Example 2 and Comparative Examples 1-2 demonstrate that both the modified quaternary ammonium salt and the modified zinc molybdate prepared in this application possess excellent corrosion inhibition properties.

[0246] The coating / coating test data of Example 1 and Comparative Example 1 show that, compared with Comparative Example 1 (coating without corrosion inhibitor), the salt spray resistance time of Example 1 (coating with modified quaternary ammonium salt) can be increased by more than 150 hours, and the electrochemical impedance modulus under low frequency conditions (0.01 Hz) can be increased by more than one order of magnitude.

[0247] The coating / coating test data from Examples 2-8 and Comparative Examples 1-2 show that, compared to Comparative Example 1 (zinc molybdate nanotubes without modified quaternary ammonium salt), the salt spray resistance time of the coatings in Examples 2-8 (coatings with modified quaternary ammonium salt) is increased by more than 342 hours, and the electrochemical impedance modulus under low-frequency conditions (0.01 Hz) is increased by more than two orders of magnitude. Compared to Comparative Example 2 (zinc molybdate nanotubes without modified quaternary ammonium salt), the salt spray resistance time of the coatings in Examples 2-8 (zinc molybdate nanotubes with modified quaternary ammonium salt) is increased by more than 262 hours, and the electrochemical impedance modulus under low-frequency conditions (0.01 Hz) is increased by more than one order of magnitude. This sufficiently demonstrates that the coatings of this application possess significantly superior anti-corrosion performance and long-term corrosion protection, meeting the practical application needs of industrial coatings.

[0248] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0249] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A method for preparing modified quaternary ammonium salts, characterized in that, Includes the following steps: In a nitrogen atmosphere, octanoic acid and hydroxyethyl ethylenediamine are reacted in an organic benzene solvent for a first reaction, followed by the addition of an alcohol solvent and phosphorus oxychloride for a second reaction to prepare a modified quaternary ammonium salt.

2. The method for preparing the modified quaternary ammonium salt according to claim 1, characterized in that, The preparation method also satisfies at least one of the following (1) to (11): (1) The molar ratio of the octanoic acid and the hydroxyethyl ethylenediamine is 1:(0.5-2); (2) The temperature of the first reaction is 130℃-260℃; (3) The time for the first reaction is 2h-10h; (4) The first reaction includes a first-stage reaction and a second-stage reaction; Optionally, the temperature of the first-stage reaction is 130℃-200℃; Optionally, the reaction time for the first stage is 2-4 hours; Optionally, the temperature of the second-stage reaction is 201℃-260℃; Optionally, the second-stage reaction time is 2-6 hours; (5) During the first reaction, water produced during the reaction is continuously removed; (6) The molar ratio of the octanoic acid and the phosphorus oxychloride is 1:(0.1-0.5); (7) The temperature of the second reaction is 40℃-90℃; (8) The second reaction takes 2-6 hours; (9) After the first reaction is completed, the temperature is lowered to 40°C to 85°C, and then an alcohol solvent and phosphorus oxychloride are added to carry out the second reaction; (10) The organic benzene solvent includes one or more of benzene, toluene, and xylene; (11) The alcohol solvents include one or more of methanol and ethanol.

3. A modified quaternary ammonium salt, characterized in that, It is prepared by the method for preparing the modified quaternary ammonium salt according to claim 1 or 2.

4. A method for preparing modified zinc molybdate, characterized in that, Includes the following steps: Zinc molybdate was added to an aqueous solution of a modified quaternary ammonium salt, and the mixture was treated under vacuum to remove water and dry, thus preparing modified zinc molybdate. The modified quaternary ammonium salt includes the modified quaternary ammonium salt prepared by the preparation method of the modified quaternary ammonium salt according to claim 1 or 2.

5. The method for preparing modified zinc molybdate according to claim 4, characterized in that, The preparation method also satisfies at least one of the following (1) to (5): (1) The mass ratio of the modified quaternary ammonium salt to the zinc molybdate is 1:(10-1000). (2) The zinc molybdate includes zinc molybdate nanotubes; Optionally, the diameter of the zinc molybdate nanotubes is 50 nm-100 nm; Optionally, the length of the zinc molybdate nanotubes is 0.5 μm-10 μm; (3) Treat under vacuum conditions for 0.5h-24h; (4) The drying temperature is 45℃-55℃; (5) The drying time is 10h-15h.

6. Modified zinc molybdate, characterized in that, It is prepared by the method for preparing modified zinc molybdate as described in claim 4 or 5.

7. A coating, characterized in that, The raw materials for preparing the coating include component A and component B. Component A consists of resin, corrosion inhibitor, first additive and first solvent, and component B consists of curing agent, second additive and second solvent. The corrosion inhibitor includes a modified quaternary ammonium salt and / or a modified zinc molybdate, wherein the modified quaternary ammonium salt is a modified quaternary ammonium salt prepared by the method of preparation of the modified quaternary ammonium salt according to claim 1 or 2, and the modified zinc molybdate is a modified zinc molybdate prepared by the method of preparation of the modified zinc molybdate according to claim 4 or 5.

8. The coating according to claim 7, characterized in that, The coating also satisfies at least one of the following features (1) to (8): (1) By mass, the composition of component A includes: 80-100 parts of resin, 5-20 parts of corrosion inhibitor, 0.2-9 parts of first auxiliary agent and 20-50 parts of first solvent; (2) By mass, the composition of component B includes: 10-20 parts of curing agent, 0.5-3 parts of second auxiliary agent and 5-10 parts of second solvent; (3) The resin includes epoxy resin; Optionally, the epoxy resin includes an aqueous epoxy resin; Optionally, the epoxy resin has a solid content of 50%-60%; Optionally, the epoxy equivalent of the epoxy resin is 800 g / eq-1050 g / eq; (4) The first auxiliary agent includes one or more of dispersants, wetting agents and defoamers; Optionally, the dispersant includes one or more of TEGO Dispers 652, BYK-190, and ADDITOL® VXW 6208; Optionally, the wetting agent includes one or more of TEGO Twin 4100, BYK-346, and Afcona-3590; Optionally, the defoamer includes one or more of TEGO Airex 902 W, BYK-024, and Afcona-2508; (5) The curing agent includes an epoxy resin curing agent; Optionally, the epoxy resin curing agent includes a water-based epoxy resin curing agent; Optionally, the solid content of the epoxy resin curing agent is 79%-90%; Optionally, the active hydrogen equivalent of the epoxy resin curing agent is 100 g / eq-200 g / eq; (6) The second auxiliary agent includes a flash rust inhibitor; Optionally, the flash rust inhibitor includes one or more of Raybo 60, CK-34, and Qichuang R-706F; (7) The first solvent and the second solvent are each independently an aqueous solvent; Optionally, the aqueous solvent includes water; (8) The mass ratio of component A to component B is (5-10):1; Optionally, the mass ratio of component A to component B is (5-7):

1.

9. The method for preparing the coating according to claim 7 or 8, characterized in that, Includes the following steps: The first solvent is added to the resin for dispersion, and then the first additive and the corrosion inhibitor are added for dispersion to prepare component A: The curing agent, the second additive, and the second solvent are mixed to prepare component B: The coating is prepared by mixing component A and component B.

10. A component, characterized in that, It includes a body and a coating disposed on the surface of the body, the coating being prepared using a coating material as described in claim 7 or 8.

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