Solvent-free epoxy composite ceramic coating

Abstract

The invention relates to the technical field of anticorrosive coatings, in particular to a solvent-free epoxy composite ceramic coating. Comprising a component A and a component B. The component A comprises, by weight, 160-270 parts of epoxy resin, 10-30 parts of an epoxy reactive diluent, 30-80 parts of organic bentonite, 1-25 parts of a leveling agent and 3-30 parts of a wetting dispersant. And the component B comprises the following components in parts by weight: 100-280 parts of an amine curing agent and 5-100 parts of organic bentonite. On the basis of improving corrosion resistance, heat resistance and the like, the coating material prepared by the invention is higher in hardness, excellent in wear resistance, capable of being cured at normal temperature, convenient to construct and operate and suitable for a high-temperature environment.

Description

Technical Field

[0001] The present invention relates to the technical field of anticorrosive coatings, and specifically, to a solvent-free epoxy-based composite ceramic coating. Background Art

[0002] In industrial fields such as chemical engineering, electric power, and minerals, metal equipment is exposed to medium erosion and chemical corrosion environments for a long time, resulting in rapid deterioration of material properties, which severely restricts the service life of equipment. To solve this problem, various surface treatment technologies have been gradually developed in the industry, but there are still many limitations in practical applications: for lining protection technology, when using rubber or ceramic materials as linings, interlayer peeling often occurs due to insufficient interfacial bonding strength under the action of thermal stress or mechanical vibration, and it is difficult to repair after damage. For example, although rubber lining is suitable for hydrochloric acid storage tanks, it may harden and crack under high-temperature working conditions. Solvent-based anticorrosive products, traditional anticorrosive materials represented by vinyl resins, release a large amount of volatile organic compounds such as benzene and ketones during the construction process, which not only pollutes the environment but also poses a fire and explosion hazard, and it is difficult to meet the environmental protection requirements of modern industry. The weather resistance of such products in high-temperature strong acid environments is also insufficient, and coating powdering and peeling are likely to occur.

[0003] Chinese Patent Application CN109971305A discloses a solvent-free high-temperature anticorrosive coating, an anticorrosive coating, and a container, but there are problems such as uneven particle size distribution and low content of fillers, poor wear resistance, and weak acid and alkali corrosion resistance; Chinese Patent Application CN106947368A discloses a resin ceramic material and its preparation method, and the aliphatic curing agent used has weak anticorrosive performance, low load deformation temperature, and limited temperature resistance for use; Chinese Patent CN108753107B discloses a strong acid and alkali resistant composite ceramic anticorrosive coating and its preparation method, and its coating has weak wear resistance, and the aliphatic polyamine used is limited in high-temperature acid resistance. The coatings in the above patents cannot have high wear resistance, high temperature resistance, high corrosion resistance, and high impermeability at the same time. Summary of the Invention

[0004] The present invention provides a solvent-free epoxy-based composite ceramic coating, which includes component A and component B. By weight, component A includes: 160 - 270 parts of epoxy resin, 10 - 30 parts of epoxy active diluent, 30 - 80 parts of organic bentonite, 1 - 25 parts of leveling agent, 3 - 30 parts of wetting and dispersing agent; component B includes: 100 - 280 parts of amine curing agent, 5 - 100 parts of organic bentonite.

[0005] Both component A and component B further include wollastonite.

[0006] Both component A and component B further include silicon carbide.

[0007] The silicon carbide includes silicon carbide with a mesh number of 50 - 80 and silicon carbide with a mesh number of 100 - 300.

[0008] The research of this invention discovers that both component A and component B also include wollastonite and silicon carbide, which can improve wear resistance and Brinell hardness. Coarse silicon carbide particles form the main framework and bear the main wear. Fine acicular wollastonite crystals fill the voids, reducing the exposure of the resin area. The grading of the two reduces the porosity of the coating and increases the Brinell hardness. At the same time, the rigid silicon carbide particles disperse the external impact stress, while the fibrous structure of wollastonite absorbs energy through plastic deformation, forming a "rigid-flexible combination" synergistic effect.

[0009] Component B also includes talcum powder.

[0010] Both component A and component B also include coupling agents.

[0011] Component B also includes accelerators.

[0012] In component A, the weight ratio of silicon carbide to wollastonite is (4 - 8):1.

[0013] Optionally, in component A, the weight ratio of silicon carbide to wollastonite is (5 - 8):1.

[0014] In component B, the weight ratio of silicon carbide to wollastonite is (4 - 7):1.

[0015] Optionally, in component B, the weight ratio of silicon carbide to wollastonite is (5 - 7):1.

[0016] In component A, the weight of silicon carbide and wollastonite is not less than 70%.

[0017] In component B, the weight content of silicon carbide, wollastonite and talcum powder is not less than 70%.

[0018] Optionally, by weight, component A includes: 160 - 270 parts of epoxy resin, 10 - 30 parts of epoxy active diluent, 490 - 635 parts of silicon carbide, 50 - 110 parts of wollastonite, 30 - 80 parts of organic bentonite, 1 - 25 parts of leveling agent, 3 - 30 parts of wetting and dispersing agent, 1 - 10 parts of coupling agent A; Component B includes: 100 - 280 parts of amine curing agent, 450 - 590 parts of silicon carbide, 30 - 100 parts of wollastonite, 40 - 120 parts of talcum powder, 5 - 100 parts of organic bentonite, 1 - 10 parts of accelerator, 1 - 5 parts of coupling agent B.

[0019] Optionally, by weight parts, the component A includes: 200-270 parts of epoxy resin, 10-15 parts of epoxy active diluent, 490-635 parts of silicon carbide, 50-110 parts of wollastonite, 30-60 parts of organic bentonite, 1-8 parts of leveling agent, 3-10 parts of wetting and dispersing agent, 1-5 parts of coupling agent A; the component B includes: 100-180 parts of amine curing agent, 450-590 parts of silicon carbide, 30-100 parts of wollastonite, 40-100 parts of talc powder, 50-100 parts of organic bentonite, 1-10 parts of accelerator, 1-5 parts of coupling agent B.

[0020] The epoxy resin includes at least one of bisphenol A epoxy resin, linear phenolic epoxy resin, and brominated phenolic epoxy resin.

[0021] Optionally, the epoxy resin includes at least one of the following grades: Nanya 128, Nanya 127, Nanya 170, Nanya 631, Nanya 400, Huntsman 8220, Huntsman 8240, Zhilun ZLA-175H, Zhilun 175S, Zhilun 160H, Zhilun 160S, Zhilun 170H, Zhilun 170S.

[0022] The epoxy active diluent includes at least one of diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, butanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, and propylene glycol triglycidyl ether.

[0023] Optionally, the epoxy active diluent includes at least one of the following grades: Huntsman GE-21LC, Huntsman GE-22, Huntsman GE-25, Green Home LS-622, Green Home LS-678, Green Home LS-669, Anhui Xinyuan XY205, Anhui Xinyuan XY207, Anhui Xinyuan XY622, Zhenzhengfeng MF-2133, Zhenzhengfeng MF-3101L, Zhenzhengfeng MF-3102L.

[0024] Optionally, the organic bentonite is selected from at least one of the following: FHGEL-140, FHGEL-180, FHGEL-217 of Zhejiang Fenghong New Materials Co., Ltd., YH-908, YH-978, YH938H of Zhejiang Yuhong New Materials Co., Ltd.

[0025] Optionally, the leveling agent includes at least one of the following grades: BYK-331, BYK-333, BYK-378, Tiger Tech-2306, Tiger Tech-222, Tiger Tech-231.

[0026] Optionally, the wetting dispersant includes at least one of the following grades: BYK-9076, BYK-9077, BYK-W903, BYK-W9011, Tegor Tech-2778, Huntsman DY65010.

[0027] The coupling agent A includes at least one of 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0028] The amine curing agent includes at least one of alicyclic amines and aromatic amines.

[0029] Optionally, the amine curing agent includes at least one of modified alicyclic amines and modified aromatic amines;

[0030] Optionally, the amine curing agent is self-made, and the preparation raw materials include: phenolic substances, aldehyde substances, amine substances, and chain extender aids.

[0031] The phenolic substances include phenol or cardanol.

[0032] The aldehyde substances include at least one of decanoic aldehyde, trioxane, paraformaldehyde, 4-(diethylamino)salicylaldehyde, salicylaldehyde, propionaldehyde, valeraldehyde, and acetaldehyde.

[0033] The amine substances include alicyclic amines or aromatic amines.

[0034] Optionally, the amine substances include at least one of methylcyclohexanediamine, isophorone diamine, 4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, m-phenylenediamine, m-xylylenediamine, and diaminodiphenylmethane.

[0035] The chain extender aids include polyfunctional epoxy resins.

[0036] Optionally, the chain extender aids include at least one of the following grades: Shin-Etsu S-720, Shin-Etsu S-510, Shin-Etsu S-186, Huntsman MY0500, Huntsman MY0510, Huntsman MY720, Huntsman MY721.

[0037] The preparation method of the amine curing agent: Add phenolic substances and amine substances to the reaction kettle, stir and heat up to 50-65°C, wait for the temperature to be constant, then stir and heat up to 100-120°C, and dropwise add aldehyde substances and react for 2-6 hours. Finally, add chain extender aids and use a rotary evaporator to remove the water in the product.

[0038] The accelerator includes at least one of tertiary amines and phenols.

[0039] Optionally, the accelerator includes at least one of DMP-30 and triethanolamine.

[0040] The coupling agent B includes at least one of 3-aminopropyl(diethoxy)methylsilane, (3-aminopropyl)triethoxysilane, (3-aminopropyl)trimethoxysilane, phenylaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane, and N-(2-aminoethyl)-3-aminopropyltrimethoxysilane.

[0041] The mesh number of the talc powder is 200-1000 meshes.

[0042] Optionally, the mesh number of the talc powder is 325 meshes.

[0043] Optionally, the mesh number of the wollastonite is 800-1000 meshes.

[0044] Beneficial effects

[0045] 1. Both component A and component B further include wollastonite and silicon carbide, which can improve wear resistance and Brinell hardness.

[0046] 2. Component B further includes talc powder, and the mesh number of the talc powder is 200-1000 meshes, which can effectively improve heat resistance while improving dispersibility.

[0047] 3. The silicon carbide includes silicon carbide with a mesh number of 50-80 meshes and silicon carbide with a mesh number of 100-300 meshes, which can improve wear resistance (<20 mg) and Brinell hardness (>60 HBa).

[0048] 4. The weight ratio of silicon carbide to wollastonite in component A is (4-8):1, and the weight ratio of silicon carbide to wollastonite in component B is (4-7):1. It can further improve wear resistance (<15 mg) and Brinell hardness (>

[0049] 62 HBa).

[0050] 5. The solvent-free epoxy-based composite ceramic coating prepared by the present invention has excellent adhesion, heat resistance, and corrosion resistance (penetration resistance), and can meet the application requirements in high-temperature environments.

[0051] 6. The ceramic coating can be cured at room temperature by the self-made amine curing agent of the present invention, improving the convenience of construction operation. Specific embodiments

[0052] Examples 1-10

[0053] A solvent-free epoxy composite ceramic coating, composed of component A and component B, the formula of which is shown in Table 1 in parts by weight:

[0054] Table 1

[0055]

[0056] Among them, the brands or parameters corresponding to the components in Table 1 are as follows: brand of epoxy resin: Nan Ya 128; brand of epoxy reactive diluent: Huntsman GE-21LC; organic bentonite adopts FHGEL-140 of Zhejiang Fenghong New Materials Co., Ltd.; brand of wetting and dispersing agent: BYK-9076; brand of leveling agent: BYK-331; coupling agent A is 3-glycidyloxypropyltrimethoxysilane; the particle size of the talc is 325 mesh; the accelerator is triethanolamine; coupling agent B is 3-aminopropyl (diethoxy) methyl silane.

[0057] The particle size of the talc is 325 mesh; the mesh number of the wollastonite is 800-1000 mesh; wherein the silicon carbide described in Examples 1-9 is a compound of silicon carbide with a mesh number of 50-80 mesh and silicon carbide with a mesh number of 100-300 mesh (the ratio of the two is 70:30), and the silicon carbide in Example 10 is silicon carbide with a mesh number of 100-300 mesh. The silicon carbide, wollastonite, and talc are not limited to manufacturer brands.

[0058] The amine curing agent is homemade, and the raw materials for preparation include phenolic substances, amine substances, aldehyde substances, and chain extension aids. The preparation method is: add phenolic substances (phenol, 10.0 mol) and amine substances (methylcyclohexanediamine, 10.8 mol) into a reactor, stir and heat to 60°C, wait until the temperature is constant, stir and heat to 110°C, and slowly add aldehyde substances (decanoic acid aldehyde, 11.8 mol) to react for 4 hours, finally, add chain extension aids (brand: Synnax S-720, 0.03 mol), and use a rotary evaporator to remove water from the product.

[0059] The preparation method of the solvent-free epoxy-based composite ceramic coating comprises the following steps: uniformly mixing all raw materials of component A to obtain component A; and uniformly mixing all raw materials of component B to obtain component B.

[0060] The method for using the solvent-free epoxy composite ceramic coating is as follows: component A and component B are mixed evenly.

[0061] The mass ratio of component A to component B in Example 1, Example 3, and Examples 5-10 is 2:1, the mass ratio of component A to component B in Example 2 is 3:2, and the mass ratio of component A to component B in Example 4 is 5:4.

[0062] Comparative Example 1

[0063] The coating prepared according to Example 1 of Chinese Patent Application for Invention CN109971305A.

[0064] Comparative Example 2

[0065] The coating prepared according to Example 1 of Chinese Patent Application for Invention CN106947368A.

[0066] Comparative Example 3

[0067] The coating prepared according to Example 1 of Chinese Patent CN108753107B.

[0068] Comparative Example 4

[0069] The specific implementation method is the same as that of Example 1; the difference is that, by weight, the B component in Comparative Example 4 only contains 146 parts of amine curing agent and 5 parts of accelerator.

[0070] Performance testing method

[0071] Samples were prepared from the coatings obtained in the examples and comparative examples:

[0072] A double-layer metal mold was used, and a 4-mm gasket was used to control the thickness between the upper and lower plates of the mold. After the coating was mixed evenly, it was coated on the lower plate of the mold, with each layer having a coating thickness of about 2 mm, and at least three layers were coated to be >5 mm. The upper plate of the mold was pressed and the upper and lower plates were fastened. After curing at room temperature, the samples were taken out and cut to prepare test specimens and test plates.

[0073] The following performance tests were carried out on the specimens, and the test data are listed in Table 2-3.

[0074] 1. Heat distortion temperature refers to ISO 75-2-2013.

[0075] 2. Abrasion resistance refers to ASTM D 4060-19, CS-17, 1000 g.

[0076] 3. Barcol hardness refers to GB / T 3854-2017.

[0077] 4. Acid and alkali resistance refers to GB / T 11547-2008.

[0078] 5. Adhesion refers to GB / T 5210-2006.

[0079] 6. Dimensional linear shrinkage rate refers to HG / T 2625-1994.

[0080] Performance test data

[0081] Table 2

[0082]

[0083] Table 3

[0084]

[0085] As shown in the results of Table 2-3, factors such as the composition of resin and curing agent, the composition and mesh number of silicon carbide and wollastonite, and the content of talcum powder in the solvent-free composite ceramic coating prepared in this application all have an impact on the coating performance. On the basis of improving the anti-corrosion and heat resistance performance, this coating material has higher hardness and excellent wear resistance, which is superior to other resin composite coatings of this type.

Claims

1. A solvent-free epoxy-based composite ceramic coating, characterized in that, It includes Component A and Component B. By weight, Component A includes: 160 - 270 parts of epoxy resin, 10 - 30 parts of epoxy active diluent, 30 - 80 parts of organic bentonite, 1 - 25 parts of leveling agent, and 3 - 30 parts of wetting and dispersing agent; Component B includes: 100 - 280 parts of amine curing agent and 5 - 100 parts of organic bentonite.

2. The solvent-free epoxy-based composite ceramic coating according to claim 1, characterized in that, Both Component A and Component B further include wollastonite.

3. The solvent-free epoxy-based composite ceramic coating according to claim 2, characterized in that, Both Component A and Component B further include silicon carbide.

4. The solvent-free epoxy-based composite ceramic coating according to claim 3, wherein The silicon carbide includes silicon carbide with a mesh size of 50 - 80 and silicon carbide with a mesh size of 100 - 300.

5. The solvent-free epoxy-based composite ceramic coating according to claim 4, characterized in that, Component B further includes talcum powder.

6. The solventless epoxy-based composite ceramic coating according to claim 5, wherein Both Component A and Component B further include coupling agent.

7. The solvent-free epoxy-based composite ceramic coating according to claim 6, characterized in that, Component B further includes accelerator.

8. The solvent-free epoxy-based composite ceramic coating according to claim 7, characterized in that, The weight ratio of silicon carbide to wollastonite in Component A is (4 - 8):

1.

9. The solvent-free epoxy-based composite ceramic coating according to claim 8, characterized in that, The weight ratio of silicon carbide to wollastonite in Component B is (4 - 7):

1.

10. The solvent-free epoxy-based composite ceramic coating according to claim 9, characterized in that, The sum of the weights of silicon carbide and wollastonite in Component A is not less than 70wt%.

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