Coating prefabricated material as well as preparation method and application thereof

Abstract

The invention discloses a coating prefabricated material as well as a preparation method and application thereof, and relates to the technical field of anticorrosive coatings. The preparation method of the coating prefabricated material comprises the following steps: providing a carboxyl end-capping reagent solution and an amine curing agent solution, and mixing the carboxyl end-capping reagent solution and the amine curing agent solution to obtain ammonium carboxylate; ammonium carboxylate, graphene oxide, a reducing agent, epoxy resin and a first solvent are mixed, and a coating prefabricated material is obtained; according to the preparation method, the amine curing agent is sealed firstly and then mixed with other components for storage, in the long-time storage process, due to the fact that the curing agent is sealed, the curing agent cannot be subjected to a curing reaction with epoxy resin, due to the fact that graphene exists in the form of oxide, graphene cannot be agglomerated, and therefore the graphene can be stored for a long time and cannot deteriorate. When the anticorrosive coating needs to be used, only the coating prefabricated material needs to be heated, the high-activity curing agent is released, and the reduced graphene oxide is reduced, so that the anticorrosive coating is very convenient, and the anticorrosive effect of the anticorrosive coating is excellent.

Description

Technical Field

[0001] The present application relates to the technical field of anti-corrosion coatings, and in particular to a coating prefabricated material and a preparation method and application thereof. Background Art

[0002] Graphene is currently widely used in the field of coatings because it can improve the anti-corrosion performance of coatings. Graphene, epoxy resin and solvents are usually mixed to form anti-corrosion coatings. However, due to the poor wettability of graphene itself, it is difficult to disperse in oily slurries. Graphene and epoxy resin are difficult to be compatible, which affects the anti-corrosion effect of anti-corrosion coatings.

[0003] Usually, a curing agent is added to the anti-corrosion coating. The curing agent can not only react chemically with the epoxy component to form a three-dimensional network polymer, making the epoxy component exhibit excellent thermal stability, chemical resistance, and insulation, but also improve the dispersion of graphene. However, the anti-corrosion coating needs to be stored at room temperature for more than one year, or at 70°C for more than one month. Long-term static storage will still cause graphene to agglomerate, and the activity of the curing agent will decrease during long-term storage, and the epoxy resin cannot be fully and effectively cured, thereby affecting the anti-corrosion performance of the anti-corrosion coating, and then affecting the effect of the anti-corrosion coating.

[0004] Therefore, the anti-corrosion performance of anti-corrosion coatings needs to be further improved. Summary of the invention

[0005] In view of this, the present application provides a coating prefabricated material and a preparation method and application thereof, aiming to improve the corrosion resistance of anti-corrosion coatings.

[0006] The embodiment of the present application is implemented as follows: a method for preparing a coating prefabricated material, comprising: providing a carboxyl end-capping agent solution and an amine curing agent solution, mixing the carboxyl end-capping agent solution and the amine curing agent solution to obtain a carboxylic acid ammonium salt;

[0007] The ammonium carboxylate salt, graphene oxide, a reducing agent, an epoxy resin and a first solvent are mixed to obtain a coating prefabricated material.

[0008] Optionally, in some embodiments of the present application, the amine curing agent in the amine curing agent solution includes one or more of ethylenediamine, ethylenediamine, diethyltoluenediamine, m-phenylenediamine, dimethylthiotoluenediamine, and 4,4'-diaminodiphenylmethane; and / or

[0009] The reducing agent includes one or more of vitamin C, sodium citrate, hydrazine hydrate, HI, NaHB4, NaHSO3, and Zn; and / or

[0010] The epoxy resin includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy resin, and alicyclic epoxy resin; and / or

[0011] The solvent in the carboxyl end-capping agent solution, the solvent in the amine curing agent solution, and the first solvent independently include one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane.

[0012] Optionally, in some embodiments of the present application, the molar concentration of the carboxyl capping agent in the carboxyl capping agent solution is 0.1 mol / L to 0.5 mol / L; and / or

[0013] The molar concentration of the amine curing agent in the amine curing agent solution is 0.4 mol / L to 0.6 mol / L; and / or

[0014] The molar ratio of the carboxyl group of the carboxyl end-capping agent to the amino group of the amine curing agent is (1.1-1.3):1; and / or

[0015] The mass ratio of the reducing agent to the graphene oxide is (7-10):10; and / or

[0016] The molar ratio of the ammonium carboxylate salt to the epoxy resin is (0.9-1.2):1; and / or

[0017] The molar ratio of the epoxy resin to the graphene oxide is 1:(0.6-0.8).

[0018] Optionally, in some embodiments of the present application, the temperature at which the carboxyl end-capping agent solution and the amine curing agent solution are mixed is 20° C. to 30° C.; and / or

[0019] The carboxyl end-capping agent solution and the amine curing agent solution are mixed for 20 minutes to 40 minutes.

[0020] Optionally, in some embodiments of the present application, the method for preparing the carboxyl capping agent in the carboxyl capping agent solution includes: providing an acid anhydride, a terminal hydroxyl compound and a second solvent, mixing them, and obtaining the carboxyl capping agent.

[0021] Optionally, in some embodiments of the present application, the acid anhydride includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride; and / or

[0022] The terminal hydroxyl compound includes one or more of bisphenol A and terminal hydroxyl polybutadiene; and / or

[0023] The molar ratio of the acid anhydride to the hydroxyl group of the terminal hydroxyl compound is (1.2-1.8):1; and / or

[0024] The second solvent includes one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane; and / or

[0025] The temperature at which the acid anhydride, the terminal hydroxyl compound and the second solvent are mixed is 130° C. to 170° C.; and / or

[0026] The acid anhydride, the terminal hydroxyl compound and the second solvent are mixed for 7 hours to 9 hours.

[0027] Correspondingly, an embodiment of the present application further provides a coating prefabricated material, which is prepared by the above-mentioned coating prefabricated material preparation method.

[0028] Correspondingly, an embodiment of the present application also provides a method for preparing an anti-corrosion coating, comprising: heating the coating prefabricated material prepared by the preparation method of the above-mentioned coating prefabricated material to obtain an anti-corrosion coating.

[0029] Optionally, in some embodiments of the present application, the temperature of heating the coating prefabricated material is 90° C. to 120° C.; and / or

[0030] The time for heating the coating prefabricated material is 20 minutes to 30 minutes.

[0031] Optionally, in some embodiments of the present application, after heating the coating prefabricated material, a stabilizer is further added; and / or

[0032] After heating the coating prefabricated material, graphene is added; and / or

[0033] After heating the coating prefabricated material, the method further includes adding alkaline oxide.

[0034] Optionally, in some embodiments of the present application, the stabilizer includes one or more of L-tryptophan and 3,4,5-trihydroxybenzoic acid; and / or

[0035] The molar ratio of the stabilizer to the graphene oxide is (0.6-0.8):1; and / or

[0036] The mass ratio of the graphene to the graphene oxide is (2-3):1; and / or

[0037] The basic oxide includes one or more of zinc oxide and aluminum oxide; and / or

[0038] The mass ratio of the basic oxide to the ammonium carboxylate salt is 1:(1.2-1.5).

[0039] Correspondingly, an embodiment of the present application also provides an anti-corrosion coating, which is prepared by the above-mentioned preparation method of the anti-corrosion coating.

[0040] The preparation method of the coating prefabricated material described in the present application first uses a carboxyl end-capping agent to suppress and seal the amine curing agent in the carboxylic acid ammonium salt system, and then mixes the carboxylic acid ammonium salt, graphene oxide, a reducing agent, an epoxy resin and a first solvent to obtain the coating prefabricated material. During the long-term storage of the coating prefabricated material, since the curing agent is sealed, the curing agent will not undergo a curing reaction with the epoxy resin, and since graphene exists in the form of an oxide, the graphene will not agglomerate, so the coating prefabricated material can be stored for a long time without deterioration. When it is needed, the coating prefabricated material is heated to make the carboxylic acid ammonium salt release a highly active curing agent to achieve a curing reaction on the epoxy resin, and the reducing agent reduces the graphene oxide to generate graphene. The graphene has good dispersibility in the curing agent and is not easy to agglomerate, which effectively improves the anti-corrosion performance of the anti-corrosion coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For those skilled in the art, other drawings can be obtained based on these drawings without creative work.

[0042] Figure 1 It is a flow chart of a method for preparing a coating prefabricated material provided in an embodiment of the present application. DETAILED DESCRIPTION

[0043] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without making creative work belong to the scope of protection of the present application. In addition, it should be understood that the specific implementation methods described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0044] In this application, unless otherwise stated, directional words such as "upper" and "lower" generally refer to the upper and lower parts of the device in actual use or working state, specifically the drawing direction in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. In addition, in the description of this application, the term "including" means "including but not limited to". The terms first, second, third, etc. are used only as labels and do not impose numerical requirements or establish an order.

[0045] In this application, "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural.

[0046] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one", "at least one of the following" or similar expressions refer to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, c can be single or multiple, respectively.

[0047] Various embodiments of the present application may be presented in the form of a range; it should be understood that the description in the form of a range is only for convenience and brevity, and should not be understood as a rigid limitation on the scope of the present application; therefore, the range description should be considered to have specifically disclosed all possible sub-ranges and single numerical values ​​within the range. For example, the range description from 1 to 6 should be considered to have specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5 and 6, which apply regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integer) within the indicated range.

[0048] The technical solution of this application is as follows:

[0049] First, as Figure 1 As shown, the embodiment of the present application provides a method for preparing a coating prefabricated material, comprising:

[0050] S11, providing a carboxyl end-capping agent solution and an amine curing agent solution, and mixing the carboxyl end-capping agent solution and the amine curing agent solution to obtain a carboxylate ammonium salt;

[0051] S12, mixing the ammonium carboxylate salt, graphene oxide, a reducing agent, an epoxy resin and a first solvent to obtain a coating prefabricated material.

[0052] It should be noted that the end-capping agent has a terminal functional group, which can react and combine with the functional group to be protected, inhibit and seal the functional group to be protected, make the functional group to be protected very stable, and release it when needed, thereby retaining the activity of the functional group to be protected.

[0053] The preparation method of the coating prefabricated material provided in the present application is to first use a carboxyl end-capping agent to suppress and seal the amine curing agent in the carboxylic acid ammonium salt system, and then mix the carboxylic acid ammonium salt, graphene oxide, a reducing agent, an epoxy resin and a first solvent to obtain the coating prefabricated material. During the long-term storage of the coating prefabricated material, since the curing agent is sealed, the curing agent will not react with the epoxy resin to cure, and since the graphene exists in the form of an oxide, the graphene will not agglomerate, so the coating prefabricated material can be stored for a long time without deterioration. When it is needed, the coating prefabricated material is heated to make the carboxylic acid ammonium salt release a highly active curing agent to achieve a curing reaction on the epoxy resin, and the reducing agent reduces the graphene oxide to generate graphene. The graphene has good dispersibility in the curing agent and is not easy to agglomerate, which effectively improves the anti-corrosion performance of the anti-corrosion coating.

[0054] In the S11:

[0055] In some embodiments, the solvent in the carboxyl capping agent solution includes one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane.

[0056] In some embodiments, the molar concentration of the carboxyl capping agent in the carboxyl capping agent solution is 0.1 mol / L to 0.5 mol / L, for example, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, etc. Within the molar concentration range, the carboxyl capping agent is dispersed and dissolved.

[0057] In some embodiments, the preparation method of the carboxyl capping agent in the carboxyl capping agent solution includes: providing an acid anhydride, a terminal hydroxyl compound, and a second solvent, and mixing them to obtain the carboxyl capping agent.

[0058] It can be understood that the terminal hydroxyl compound is a compound having a hydroxyl group at the end.

[0059] In some embodiments, the acid anhydride includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0060] In some embodiments, the terminal hydroxyl compound includes one or more of bisphenol A and terminal hydroxyl polybutadiene.

[0061] In some embodiments, the molar ratio of the acid anhydride to the hydroxyl group of the terminal hydroxyl compound is (1.2-1.8):1, for example, (1.3-1.7):1, (1.4-1.6):1, 1.5:1, etc. Within the molar ratio range, it is beneficial for the acid anhydride to fully react with the hydroxyl group.

[0062] In some embodiments, the second solvent includes one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane.

[0063] In some embodiments, the temperature at which the anhydride, the terminal hydroxyl compound and the second solvent are mixed is 130°C to 170°C, for example, 132°C to 168°C, 135°C to 165°C, 138°C to 162°C, 140°C to 160°C, 145°C to 150°C, etc.

[0064] In some embodiments, the acid anhydride, the terminal hydroxyl compound and the second solvent are mixed for 7 hours to 9 hours, for example, 8 hours.

[0065] Thus, within the mixing temperature and time range, it is conducive to the acid anhydride and the hydroxyl group to fully react and modify the terminal hydroxyl compound.

[0066] In some embodiments, after the acid anhydride, the terminal hydroxyl compound and the second solvent are mixed, the mixed product is subjected to a first drying treatment to obtain a carboxyl end-capping agent.

[0067] In some embodiments, the first drying includes vacuum drying, natural drying or heat drying.

[0068] In some embodiments, the first drying temperature is 40°C to 60°C, for example, 42°C to 58°C, 45°C to 56°C, 48°C to 55°C, 50°C to 52°C, etc.

[0069] In some embodiments, the first drying time is 11 hours to 13 hours, for example, 12 hours.

[0070] Thus, within the temperature and time range of the first drying, it is beneficial to effectively remove the solution of the carboxyl end-capping agent.

[0071] In some embodiments, the preparation formula of the carboxyl end-capping agent is as shown in formula (I):

[0072]

[0073] In some embodiments, the amine curing agent in the amine curing agent solution includes one or more of ethylenediamine, ethylenediamine, diethyltoluenediamine, m-phenylenediamine, dimethylthiotoluenediamine, and 4,4'-diaminodiphenylmethane.

[0074] In some embodiments, the molar concentration of the amine curing agent in the amine curing agent solution is 0.4 mol / L to 0.6 mol / L, for example, 0.42 mol / L to 0.58 mol / L, 0.45 mol / L to 0.55 mol / L, 0.48 mol / L to 0.52 mol / L, 0.5 mol / L to 0.51 mol / L, etc. Within the molar concentration range, the dissolution and dispersion of the amine curing agent is facilitated.

[0075] In some embodiments, the solvent in the amine curing agent solution includes one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane.

[0076] It should be noted that the amine curing agent contains an amino group, and the carboxyl end-capping agent contains a carboxyl group. The amino group and the carboxyl group undergo a neutralization reaction to generate an ammonium carboxylate salt.

[0077] In some embodiments, the molar ratio of the carboxyl group of the carboxyl capping agent to the amino group of the amine curing agent is (1.1-1.3):1, for example, 1.2:1, etc. Within the molar ratio range, it is beneficial for the carboxyl group to be fully capped to suppress the amino group.

[0078] In some embodiments, the mixing temperature of the carboxyl end-capping agent solution and the amine curing agent solution is 20°C to 30°C, for example, 21°C to 29°C, 22°C to 28°C, 23°C to 27°C, 24°C to 26°C, etc.

[0079] In some embodiments, the mixing time of the carboxyl capping agent solution and the amine curing agent solution is 20 min to 40 min, for example, 22 min to 38 min, 25 min to 36 min, 26 min to 35 min, 28 min to 32 min, 29 min to 30 min, etc.

[0080] Thus, under the temperature and time conditions of mixing the carboxyl end-capping agent solution and the amine curing agent solution, the carboxyl group and the amino group are fully combined, and the amino group is suppressed and sealed in the carboxylate ammonium salt system.

[0081] In at least one embodiment, the method of mixing the carboxyl end-capping agent solution and the amine curing agent solution comprises: dropping the amine curing agent solution into the carboxyl end-capping agent solution. It can be understood that mixing the carboxyl end-capping agent solution and the amine curing agent solution in the form of dropwise addition can promote the neutralization reaction of the amine curing agent and the carboxyl end-capping agent.

[0082] In some embodiments, after the carboxyl end-capping agent solution and the amine curing agent solution are mixed, the mixed product is further subjected to a second drying treatment to obtain an ammonium carboxylate salt.

[0083] In some embodiments, the second drying comprises vacuum drying, natural drying or heat drying.

[0084] In some embodiments, the preparation formula of the carboxylic acid ammonium salt is as shown in formula (II):

[0085]

[0086] In S12:

[0087] In some embodiments, the reducing agent includes one or more of vitamin C, sodium citrate, hydrazine hydrate, HI, NaHB4, NaHSO3, and Zn.

[0088] In some embodiments, the epoxy resin includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy resin, and alicyclic epoxy resin.

[0089] In some embodiments, the first solvent includes one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane.

[0090] In some embodiments, the mass ratio of the reducing agent to the graphene oxide is (7-10):10, for example, 8:10, 9:10, etc. Within the mass ratio range, the reducing agent is conducive to reducing the graphene oxide.

[0091] In some embodiments, the molar ratio of the ammonium carboxylate salt to the epoxy resin is (0.9-1.2):1, for example, 1:1, 1.1:1, etc.

[0092] In some embodiments, the molar ratio of the epoxy resin to the graphene oxide is 1:(0.6-0.8), for example, 1:0.7.

[0093] It is understandable that stabilizers and other substances may be added to the coating prefabricated material as required.

[0094] In a second aspect, an embodiment of the present application provides a coating prefabricated material, which is prepared by the above-mentioned coating prefabricated material preparation method.

[0095] In a third aspect, an embodiment of the present application also provides a method for preparing an anti-corrosion coating, comprising: heating the above-mentioned coating prefabricated material to obtain the anti-corrosion coating.

[0096] The preparation method of the anti-corrosion coating provided in the present application can be used by heating the prefabricated coating material, which is very simple and convenient. After heating, the reducing agent reduces the graphene oxide to generate graphene, which can improve the anti-corrosion performance of the coating. Heating can also cause the carboxylic acid ammonium salt to release highly active amine curing agent monomers to cure the epoxy resin, so that the epoxy resin forms a network of three-dimensional polymers to exert an anti-corrosion effect. The released amine curing agent monomers can also improve the compatibility of the reduced graphene and the epoxy resin, further improving the performance of the anti-corrosion coating. When the anti-corrosion coating prepared by the present application is used to prepare a coating, the adhesion of the anti-corrosion coating, the wear resistance and hardness of the coating and other properties can be improved.

[0097] In some embodiments, the temperature for heating the coating preform material is 90°C to 120°C, for example, 92°C to 118°C, 95°C to 115°C, 100°C to 112°C, 102°C to 110°C, 105°C to 108°C, etc.

[0098] In some embodiments, the time for heating the coating prefabricated material is 20 min to 30 min, for example, 21 min to 29 min, 22 min to 28 min, 23 min to 27 min, 24 min to 26 min, 25 min, etc.

[0099] In this way, within the heating temperature and time range, the reduction of graphene oxide and the release of the amine curing agent in the ammonium carboxylate salt can be achieved simultaneously, and the epoxy resin can be cured very simply and conveniently. It should be noted that when the reducing agent performs a reduction reaction on the graphene oxide, heat is released, and the released heat energy can further promote the decomposition of the ammonium carboxylate salt to release the amine curing agent.

[0100] In some embodiments, after heating the coating preform material, a stabilizer is further added.

[0101] In some embodiments, the stabilizer includes one or more of L-tryptophan and 3,4,5-trihydroxybenzoic acid.

[0102] It can be understood that stabilizers can improve the dispersion and stability of graphene and prevent graphene from agglomerating and affecting the performance of anti-corrosion coatings. Based on the π-π interaction theory, L-tryptophan contains an electron-rich indole aromatic group that can serve as an electron functional donor, and the carboxylic acid at the end of its molecule can provide sufficient negative charge and electrostatic repulsion, thereby stabilizing the dispersion of graphene.

[0103] In some embodiments, the molar ratio of the stabilizer to the graphene oxide is (0.6-0.8):1, for example, 0.7:1.

[0104] In some embodiments, after heating the coating preform material, graphene is further added.

[0105] In some embodiments, the mass ratio of the graphene to the graphene oxide is (2-3):1, for example, (2.1-2.9):1, (2.2-2.8):1, (2.3-2.7):1, (2.4-2.6):1, etc. It can be understood that the addition of the graphene can further exert the beneficial effect of graphene on the anti-corrosion coating and improve the anti-corrosion performance of the anti-corrosion coating.

[0106] It can be understood that the stabilizer and the graphene can be added to the coating prefabricated material before heating, or can be added to the coating prefabricated material after heating.

[0107] In some embodiments, after heating the coating preform material, an alkaline oxide is further added.

[0108] In some embodiments, the basic oxide comprises a metal oxide.

[0109] In some embodiments, the alkaline oxide includes one or more of zinc oxide and aluminum oxide. It should be noted that the zinc oxide can react with the carboxyl functional group in the epoxy resin to form zinc soap, thereby improving the flexibility and strength of the coating. In addition, zinc oxide is a white light stabilizer with good ultraviolet light shielding ability, which can increase the service life of the coating. At the same time, zinc oxide also has strong sterilization ability; the aluminum oxide can significantly increase the hardness of the anti-corrosion coating, making the anti-corrosion coating more wear-resistant and scratch-resistant. At the same time, the addition of aluminum oxide can also improve the thermal conductivity of the anti-corrosion coating.

[0110] In some embodiments, the mass ratio of the alkaline oxide to the ammonium carboxylate salt is 1:(1.2-1.5), for example, 1:1.3, 1:1.4, etc. It is understood that the ammonium carboxylate salt decomposes under heating conditions to produce carboxylic acid, and the addition of the alkaline oxide within the range can neutralize the carboxylic acid and improve the anti-corrosion effect of the anti-corrosion coating.

[0111] In a fourth aspect, an embodiment of the present application also provides an anti-corrosion coating, which is prepared by the above-mentioned method for preparing the anti-corrosion coating.

[0112] The present application is described in detail below through specific embodiments. The following embodiments are only partial embodiments of the present application and are not limitations of the present application.

[0113] Example 1

[0114] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0115] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0116] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0117] The above-mentioned ammonium carboxylate salt, graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0118] Example 2

[0119] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0120] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0121] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0122] The above-mentioned ammonium carboxylate salt, graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0123] Example 3

[0124] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0125] Methyltetrahydrophthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0126] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0127] The above-mentioned ammonium carboxylate salt, graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0128] Example 4

[0129] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0130] Phthalic anhydride and terminal hydroxyl polybutadiene are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl amount in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0131] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0132] The above-mentioned ammonium carboxylate salt, graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0133] Example 5

[0134] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0135] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0136] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0137] The above-mentioned ammonium carboxylate salt, graphene oxide, sodium citrate, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0138] Example 6

[0139] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0140] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0141] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.1:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0142] The above-mentioned ammonium carboxylate salt, graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0143] Example 7

[0144] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0145] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0146] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.3:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0147] The above-mentioned ammonium carboxylate salt, graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.7, to obtain a coating prefabricated material.

[0148] Example 8

[0149] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0150] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0151] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0152] The ammonium carboxylate salt and graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.6, to obtain a coating prefabricated material.

[0153] Example 9

[0154] This embodiment provides a coating prefabricated material, and the preparation method thereof is as follows:

[0155] Phthalic anhydride and bisphenol A are added to a flask containing o-xylene and mixed, and the molar ratio of the anhydride to the hydroxyl group in the terminal hydroxyl compound is controlled to be 1.5:1. The mixture is stirred and reacted at 150° C. for 8 hours. After the reaction is completed, the product is taken out while hot, and after the product is cooled to room temperature, it is crushed and washed. Then, the product is transferred to a vacuum drying oven and vacuum dried at 50° C. for 12 hours to obtain a carboxyl end-capping agent.

[0156] A 0.5 mol / L ethanol solution of ethylenediamine curing agent is added dropwise to the N,N-dimethylformamide of the carboxyl end-capping agent, and the molar ratio of the carboxyl group in the carboxyl end-capping agent to the amino group in the ethylenediamine is controlled to be 1.2:1. After the addition is completed, the mixture is stirred for 30 minutes. After the reaction is completed, the solvent is recovered and the product is extracted into a vacuum drying oven to obtain a carboxylic acid amine salt;

[0157] The ammonium carboxylate salt and graphene oxide, vitamin C, epoxy resin and tetrahydrofuran solvent are mixed, the mass ratio of vitamin C to graphene oxide is 8:10, and the molar ratio of epoxy resin to graphene oxide is 1:0.8, to obtain a coating prefabricated material.

[0158] Comparative Example

[0159] This comparative example provides an anti-corrosion coating, and the preparation method includes: mixing graphene, epoxy resin, amine curing agent and tetrahydrofuran solvent to obtain the anti-corrosion coating.

[0160] Application Example 1

[0161] Application Example 1 provides an anti-corrosion paint and an anti-corrosion coating, and the preparation method includes:

[0162] The coating prefabricated material of Example 1 was placed at room temperature for one month, and the coating prefabricated material was heated to 100° C. to obtain an anticorrosive coating;

[0163] A zinc substrate is provided, and the anti-corrosion paint is sprayed on the surface of the substrate to form an anti-corrosion coating.

[0164] Application Examples 2 to 9

[0165] Application Examples 2 to 9 are substantially the same as Application Example 1, except that the coating prefabricated material of Example 1 is replaced by the coating prefabricated material of Examples 2 to 9, respectively.

[0166] Application Example 10

[0167] Application Example 10 is substantially the same as Application Example 1, except that the coating preform material is heated to 90°C.

[0168] Application Example 11

[0169] Application Example 11 is substantially the same as Application Example 1, except that the coating preform material is heated to 120°C.

[0170] Application Example 12

[0171] Application Example 12 is substantially the same as Application Example 1, except that after the coating preform is heated to 90° C., L-tryptophan and graphene are added, wherein the mass ratio of graphene to graphene oxide in Example 1 is 2:1.

[0172] Application Example 13

[0173] Application Example 13 is basically the same as Application Example 1, except that the anti-corrosion paint and anti-corrosion coating are prepared after the paint prefabricated material of Example 1 is placed at 70° C. for one month.

[0174] Application Example 14

[0175] Application Example 14 is basically the same as Application Example 1, except that the anti-corrosion paint and anti-corrosion coating are prepared after the paint prefabricated material of Example 1 is left at room temperature for three months.

[0176] Application Comparative Example 1

[0177] Application of Comparative Example 1 The anti-corrosion coating of Comparative Example 1 was placed at room temperature for one month to prepare an anti-corrosion coating.

[0178] Application Comparative Example 2

[0179] Application of Comparative Example 1 The anti-corrosion coating of Comparative Example 1 was placed at 70° C. for one month to prepare an anti-corrosion coating.

[0180] Application Comparative Example 3

[0181] Application of Comparative Example 1 The anti-corrosion coating of Comparative Example 1 was placed at room temperature for three months to prepare an anti-corrosion coating.

[0182] The impact strength tester was used to test the anti-corrosion coatings in application examples 1 to 14 and application comparison examples 1 to 4. The salt spray resistance of the anti-corrosion coatings was measured in an artificially simulated salt spray environment, wherein the conditions of the artificially simulated salt spray environment were: 5% sodium chloride saline solution, pH value 6 to 7, sprayed as a spray, the test temperature was 35°C, and the sedimentation rate of the salt spray was 1 to 3 ml / 80 cm2 The impact strength and salt spray resistance of the anti-corrosion coating are shown in Table 1.

[0183] Table 1

[0184]

[0185] As can be seen from Table 1, the anti-corrosion coatings in application examples 1 to 14 are prepared by applying the coating prefabricated materials prepared by the present scheme to the anti-corrosion coatings. Compared with the anti-corrosion layers in application examples 1 to 3, the impact resistance and salt spray resistance are significantly improved; the anti-corrosion coatings in application examples 1 to 14 have high impact resistance, indicating that they are not easy to fall off from the substrate and have good adhesion to the substrate; the salt spray resistance of the anti-corrosion coatings in application examples 1 to 14 is significantly extended, indicating that they can effectively prevent corrosion and improve the anti-corrosion effect. This is because when the coating prefabricated materials are stored, the graphene is stored in the form of graphene oxide, which is not easy to agglomerate, and the amine curing agent is suppressed and enclosed in the carboxyl capping agent and is released when it is needed, which can retain the high activity of the amine curing agent, thereby achieving the curing effect on the epoxy resin.

[0186] In addition, it can be seen from Application Example 1, Application Examples 13-14 and Application Comparative Examples 1-3 that in the accelerated test at 70°C and the three-month storage test, the impact strength and salt spray resistance of the anticorrosive coating provided by the embodiment of the present application decreased slightly, while the anticorrosive coating of Comparative Example 1 significantly decreased in impact strength and salt spray resistance after high temperature storage or long-term storage, indicating that the anticorrosive coating has been significantly deteriorated and it is difficult to play an effective anticorrosive role. The coating prefabricated material provided by the embodiment of the present application can be stored for a long time without serious deterioration. When used, it only needs to be heated to obtain a high-performance anticorrosive coating, which is very convenient. The prepared anticorrosive coating has high hardness, strong adhesion and excellent anticorrosive effect.

[0187] The coating prefabricated materials and their preparation methods and applications provided in the embodiments of the present application are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present application. The description of the above embodiments is only used to help understand the methods and core ideas of the present application. At the same time, for technical personnel in this field, according to the ideas of the present application, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as a limitation on the present application.

Claims

1. A method for preparing a coating prefabricated material, characterized in that: include: Providing a carboxyl end-capping agent solution and an amine curing agent solution, and mixing the carboxyl end-capping agent solution and the amine curing agent solution to obtain a carboxylic acid ammonium salt; The ammonium carboxylate salt, graphene oxide, a reducing agent, an epoxy resin and a first solvent are mixed to obtain a coating prefabricated material.

2. The preparation method according to claim 1, characterized in that The amine curing agent in the amine curing agent solution includes one or more of ethylenediamine, ethylenediamine, diethyltoluenediamine, m-phenylenediamine, dimethylthiotoluenediamine, and 4,4'-diaminodiphenylmethane; and / or The reducing agent includes one or more of vitamin C, sodium citrate, hydrazine hydrate, HI, NaHB4, NaHSO3, and Zn; and / or The epoxy resin includes one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, aliphatic epoxy resin, and alicyclic epoxy resin; and / or The solvent in the carboxyl end-capping agent solution, the solvent in the amine curing agent solution, and the first solvent independently include one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane.

3. The preparation method according to claim 1, characterized in that: The molar concentration of the carboxyl end-capping agent in the carboxyl end-capping agent solution is 0.1 mol / L to 0.5 mol / L; and / or The molar concentration of the amine curing agent in the amine curing agent solution is 0.4 mol / L to 0.6 mol / L; and / or The molar ratio of the carboxyl group of the carboxyl end-capping agent to the amino group of the amine curing agent is (1.1-1.3):1; and / or The mass ratio of the reducing agent to the graphene oxide is (7-10):10; and / or The molar ratio of the ammonium carboxylate salt to the epoxy resin is (0.9-1.2):1; and / or The molar ratio of the epoxy resin to the graphene oxide is 1:(0.6-0.8).

4. The preparation method according to claim 1, characterized in that: The temperature at which the carboxyl end-capping agent solution and the amine curing agent solution are mixed is 20° C. to 30° C.; and / or The carboxyl end-capping agent solution and the amine curing agent solution are mixed for 20 minutes to 40 minutes.

5. The preparation method according to claim 1, characterized in that: The preparation method of the carboxyl end-capping agent in the carboxyl end-capping agent solution comprises: providing an acid anhydride, a terminal hydroxyl compound and a second solvent, mixing them, and obtaining the carboxyl end-capping agent.

6. The preparation method according to claim 5, characterized in that: The acid anhydride includes one or more of phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride; and / or The terminal hydroxyl compound includes one or more of bisphenol A and terminal hydroxyl polybutadiene; and / or The molar ratio of the acid anhydride to the hydroxyl group of the terminal hydroxyl compound is (1.2-1.8):1; and / or The second solvent includes one or more of toluene, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, pyridine, tetrahydrofuran, ethylene glycol, acetone, methanol, ethanol, 1-propanol, dichloromethane, o-xylene, and n-hexane; and / or The temperature at which the acid anhydride, the terminal hydroxyl compound and the second solvent are mixed is 130° C. to 170° C.; and / or The acid anhydride, the terminal hydroxyl compound and the second solvent are mixed for 7 hours to 9 hours.

7. A coating prefabricated material, characterized in that: The coating prefabricated material is prepared by the preparation method of any one of claims 1 to 6.

8. A method for preparing an anticorrosive coating, characterized in that: include: The coating prefabricated material is prepared by heating the coating prefabricated material according to any one of claims 1 to 6 to obtain an anti-corrosion coating.

9. The preparation method according to claim 8, characterized in that: The temperature of heating the coating prefabricated material is 90° C. to 120° C.; and / or The time for heating the coating prefabricated material is 20 minutes to 30 minutes.

10. The preparation method according to claim 8, characterized in that: After heating the coating prefabricated material, a stabilizer is added; and / or After heating the coating prefabricated material, graphene is added; and / or After heating the coating prefabricated material, the method further includes adding alkaline oxide.

11. The preparation method according to claim 10, characterized in that: The stabilizer includes one or more of L-tryptophan and 3,4,5-trihydroxybenzoic acid; and / or The molar ratio of the stabilizer to the graphene oxide is (0.6-0.8):1; and / or The mass ratio of the graphene to the graphene oxide is (2-3):1; and / or The basic oxide includes one or more of zinc oxide and aluminum oxide; and / or The mass ratio of the basic oxide to the ammonium carboxylate salt is 1:(1.2-1.5).

12. An anti-corrosion coating, characterized in that: The anti-corrosion coating is prepared by the preparation method of any one of claims 8 to 11.

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