Anti-aging super-hydrophobic steel structure anticorrosive coating material and preparation method thereof

Abstract

The invention discloses an anti-aging super-hydrophobic steel structure anticorrosive coating material, and relates to the technical field of anticorrosive paint. Comprising the following substances: (1) a component A comprises the following raw materials in parts by weight: 30-35 parts of fluorine-modified hydrogenated bisphenol A epoxy resin, 15-20 parts of an epoxy-terminated fluorosilicone polymer, 5-8 parts of graphene oxide, 3-5 parts of ferrophosphorus powder, 6-8 parts of titanium dioxide, 10-12 parts of silica powder and 2.5-3 parts of an auxiliary agent; and (2) the component B comprises the following raw materials in parts by weight: 28-38 parts of a fatty amine curing agent and 6-9 parts of a curing accelerator. According to the invention, the epoxy resin is modified, and the epoxy-terminated fluorosilicone polymer is added, so that the prepared coating has excellent super-hydrophobicity and ageing resistance.

Description

Technical Field

[0001] This invention relates to the field of anti-corrosion coating technology, specifically to an anti-aging superhydrophobic steel structure anti-corrosion coating material and its preparation method. Background Technology

[0002] Superhydrophobic coatings possess excellent hydrophobicity, non-wetting properties, and self-cleaning characteristics. When a superhydrophobic coating is applied to a metal substrate, a gas film is formed at the interface with water, which can inhibit direct contact between the aqueous medium and the substrate surface, effectively prevent the penetration of corrosive media into the coating, isolate the metal from the corrosive medium, and greatly reduce the corrosion rate. Superhydrophobic modification of the coating can improve its anti-corrosion performance while adding other application functions.

[0003] Among various anti-corrosion coatings, epoxy resin is one of the most widely used coating materials. It possesses good adhesion, chemical resistance, and good mechanical properties, making it widely used in coatings. However, it also suffers from insufficient anti-aging properties, high surface energy, and insufficient hydrophobicity, limiting its application in the anti-corrosion field. To improve anti-aging and hydrophobic properties, epoxy coatings need to be modified. Current methods involve modifying epoxy with low surface energy substances such as fluorine. For example, Chinese invention patent CN 115403991 B discloses a superhydrophobic epoxy anti-corrosion coating and its preparation method. This coating is obtained by reacting medium- and short-chain perfluoroalkyl acids with aliphatic amine curing agents to produce a low-surface-energy fluoroamine curing agent. By adding the fluoroamine curing agent to the epoxy resin, a low-surface-energy fluorinated material is introduced, giving the coating excellent superhydrophobicity. However, the epoxy resin is bisphenol A epoxy resin, which contains benzene rings. The double bonds in the benzene rings are prone to aging, resulting in insufficient overall anti-aging properties of the coating. Summary of the Invention

[0004] To address the above problems, the technical problem to be solved by the present invention is to provide an anti-aging superhydrophobic steel structure anti-corrosion coating material with good anti-aging and superhydrophobic properties.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] An anti-aging superhydrophobic steel structure anti-corrosion coating material, comprising the following substances:

[0007] (1) The raw material weight parts of component A are as follows:

[0008] 30-35 parts of fluorine-modified hydrogenated bisphenol A epoxy resin, 15-20 parts of epoxy-terminated fluorosilicone polymer, 5-8 parts of graphene oxide, 3-5 parts of ferrophosphorus powder, 6-8 parts of titanium dioxide, 10-12 parts of silica powder, and 2.5-3 parts of additives.

[0009] (2) The raw material weight parts of component B are as follows:

[0010] 28-38 parts of fatty amine curing agent and 6-9 parts of curing accelerator.

[0011] As a further improvement of the present invention, the fluorinated hydrogenated bisphenol A epoxy resin is a hydrogenated bisphenol A epoxy resin with fluorinated side chains synthesized by esterification reaction of hydrogenated bisphenol A epoxy resin and perfluoroalkyl acid under the action of toluenesulfonic acid catalyst at a temperature of 50-55°C.

[0012] As a further improvement of the present invention, the perfluoroalkyl acid is one of perfluorobutyric acid, perfluorooctanoic acid, and perfluorodecanoic acid.

[0013] As a further improvement to the present invention, the molar ratio of the hydrogenated bisphenol A epoxy resin to perfluoroalkyl acid is 1:3-4.

[0014] As a further improvement to the present invention, the preparation process of the epoxy-terminated fluorosilicone polymer is as follows:

[0015] Trifluoropropylmethylcyclotrisiloxane was dissolved in 10-15 times its volume of anhydrous ethanol solvent and subjected to ring-opening bulk polymerization at 35-40°C for 1-2 hours under the action of an alkali metal initiator. Then (3-epoxypropoxypropyl)dimethylethoxysilane was added and the reaction was continued for 2 hours. The solvent was removed under vacuum at low temperature to obtain an epoxy-terminated fluorosilicone polymer.

[0016] The molecular structural formula of the epoxy-terminated fluorosilicone polymer is as follows:

[0017]

[0018] As a further improvement of the present invention, the molar ratio of trifluoropropylmethylcyclotrisiloxane to (3-epoxypropoxypropyl)dimethylethoxysilane is 5-7:1.

[0019] As a further improvement of the present invention, the amount of the alkali metal initiator is 1% of the total weight of the solution.

[0020] As a further improvement to the present invention, the fatty amine curing agent is a mixture of polyetheramine D230 and isophorone diamine in a mass ratio of 1:1.

[0021] As a further improvement of the present invention, the additives include defoamer BYK-065, leveling agent PV88, and dispersant BYK-P104 in a mass ratio of 0.5:1:1.

[0022] A method for preparing an anti-aging superhydrophobic anti-corrosion coating material for steel structures includes the following preparation steps:

[0023] Fluorine-modified hydrogenated bisphenol A epoxy resin, epoxy-terminated fluorosilicone polymer, graphene oxide, and iron phosphate powder were mixed and stirred for 10 minutes. Then, titanium dioxide, silica powder, and additives were added, and the mixture was stirred and dispersed for another 20 minutes to obtain component A. Fatty amine curing agent and curing accelerator were mixed and stirred for 5 minutes to obtain component B. Component A and component B were uniformly mixed, coated, and cured to obtain an anti-corrosion coating material.

[0024] Compared with the prior art, the present invention has the following beneficial effects:

[0025] The epoxy resin used in this invention is fluorinated hydrogenated bisphenol A epoxy resin, with the addition of terminal epoxy group fluorosilicone polymer. It is cross-linked and cured by a curing agent, so that the siloxane segments are embedded in the epoxy resin segments and are firmly bonded to the epoxy resin. The fluorinated alkyl chain, as a side chain, is suspended on the main chain of epoxy resin and siloxane, which is conducive to the migration and enrichment of fluorine atoms to the surface. As a low surface energy group, fluorine can effectively reduce the surface energy of the coating and improve the hydrophobicity of the coating.

[0026] Epoxy-terminated fluorosilicone polymers are polymers that combine the properties of organosilicon and organofluorine. The excellent high and low temperature resistance, flexibility, and weather resistance of siloxane chains improve the flexibility and anti-aging properties of epoxy resins. The epoxy-terminated fluorosilicone polymers are reacted with epoxy resins through a curing agent, allowing them to be embedded in the epoxy resin chain segments. This solves the problem of poor compatibility between organosilicon and epoxy resins. At the same time, the introduction of fluorine atoms into the epoxy resin and siloxane side chains greatly enhances the resin's solvent resistance, oil resistance, and hydrophobicity. Detailed Implementation

[0027] The specific embodiments of the present invention will be further described below with reference to examples.

[0028] Example 1

[0029] (1) Preparation of fluorine-modified hydrogenated bisphenol A epoxy resin

[0030] Hydrogenated bisphenol A epoxy resin and perfluorobutyric acid were mixed and stirred at a molar ratio of 1:3. Toluenesulfonic acid of 0.2% of the total solution was added as a catalyst and reacted at 50-55℃ for 4-5 hours to allow the hydroxyl groups in the hydrogenated bisphenol A epoxy resin and the carboxyl groups in the perfluorobutyric acid to undergo an esterification reaction, thereby synthesizing hydrogenated bisphenol A epoxy resin with fluorinated side chains.

[0031] (2) Preparation of epoxy-terminated fluorosilicone polymers

[0032] Trifluoropropylmethylcyclotrisiloxane was dissolved in 10 times its volume of anhydrous ethanol and subjected to ring-opening bulk polymerization at 35-40°C for 1-2 hours under the action of an alkali metal initiator. Then, (3-epoxypropoxypropyl)dimethylethoxysilane was added, and the reaction was continued for 2 hours. The solvent was removed under vacuum at low temperature to obtain a terminal epoxy fluorosilicone polymer. The molar ratio of trifluoropropylmethylcyclotrisiloxane to (3-epoxypropoxypropyl)dimethylethoxysilane was 5:1, and the amount of alkali metal initiator was 1% of the total weight of the solution.

[0033] (3) Preparation of component A

[0034] 30 parts of fluorine-modified hydrogenated bisphenol A epoxy resin, 15 parts of epoxy-terminated fluorosilicone polymer, 5 parts of graphene oxide and 3 parts of iron phosphate powder were mixed and stirred and dispersed for 10 min. Then, 6 parts of titanium dioxide, 10 parts of silica powder, 0.5 parts of defoamer BYK-065, 1 part of leveling agent PV88 and 1 part of dispersant BYK-P104 were added and stirred and dispersed for another 20 min to obtain component A.

[0035] (4) Preparation of component B

[0036] Mix 14 parts of polyetheramine D230, 14 parts of isophorone diamine, and 6 parts of curing accelerator DMP-30 and stir for 5 minutes to obtain component B;

[0037] (5) Mix component A and component B evenly, coat and cure to obtain anti-corrosion coating material.

[0038] Example 2

[0039] (1) Preparation of fluorine-modified hydrogenated bisphenol A epoxy resin

[0040] Hydrogenated bisphenol A epoxy resin and perfluorobutyric acid were mixed and stirred at a molar ratio of 1:3. Toluenesulfonic acid, accounting for 0.2% of the total solution volume, was added as a catalyst and reacted at 50-55℃ for 4-5 hours to induce esterification between the hydroxyl groups in the hydrogenated bisphenol A epoxy resin and the carboxyl groups in the perfluorobutyric acid, thereby synthesizing hydrogenated bisphenol A epoxy resin with fluorinated side chains.

[0041] (2) Preparation of epoxy-terminated fluorosilicone polymers

[0042] Trifluoropropylmethylcyclotrisiloxane was dissolved in 10 times its volume of anhydrous ethanol and subjected to ring-opening bulk polymerization at 35-40°C for 1-2 hours under the action of an alkali metal initiator. Then, (3-epoxypropoxypropyl)dimethylethoxysilane was added, and the reaction was continued for 2 hours. The solvent was removed under vacuum at low temperature to obtain a terminal epoxy fluorosilicone polymer. The molar ratio of trifluoropropylmethylcyclotrisiloxane to (3-epoxypropoxypropyl)dimethylethoxysilane was 5:1, and the amount of alkali metal initiator was 1% of the total weight of the solution.

[0043] (3) Preparation of component A

[0044] 30 parts of fluorine-modified hydrogenated bisphenol A epoxy resin, 20 parts of epoxy-terminated fluorosilicone polymer, 5 parts of graphene oxide and 3 parts of iron phosphate powder were mixed and stirred and dispersed for 10 min. Then, 6 parts of titanium dioxide, 10 parts of silica powder, 0.5 parts of defoamer BYK-065, 1 part of leveling agent PV88 and 1 part of dispersant BYK-P104 were added and stirred and dispersed for another 20 min to obtain component A.

[0045] (4) Preparation of component B

[0046] Mix 15 parts of polyetheramine D230, 15 parts of isophorone diamine and 7 parts of curing accelerator DMP-30 and stir for 5 minutes to obtain component B;

[0047] (5) Mix component A and component B evenly, coat and cure to obtain anti-corrosion coating material.

[0048] Example 3

[0049] (1) Preparation of fluorine-modified hydrogenated bisphenol A epoxy resin

[0050] Hydrogenated bisphenol A epoxy resin and perfluorobutyric acid were mixed and stirred at a molar ratio of 1:4. Toluenesulfonic acid, accounting for 0.2% of the total solution volume, was added as a catalyst and reacted at 50-55℃ for 4-5 hours to induce esterification between the hydroxyl groups in the hydrogenated bisphenol A epoxy resin and the carboxyl groups in the perfluorobutyric acid, thereby synthesizing hydrogenated bisphenol A epoxy resin with fluorinated side chains.

[0051] (2) Preparation of epoxy-terminated fluorosilicone polymers

[0052] The monomer trifluoropropylmethylcyclotrisiloxane was dissolved in 15 times its volume of anhydrous ethanol and subjected to ring-opening bulk polymerization at 35-40°C for 1-2 hours in the presence of an alkali metal initiator. Then, (3-epoxypropoxypropyl)dimethylethoxysilane was added, and the reaction was continued for 2 hours. The solvent was removed under vacuum at low temperature to obtain a terminal epoxy fluorosilicone polymer. The molar ratio of trifluoropropylmethylcyclotrisiloxane to (3-epoxypropoxypropyl)dimethylethoxysilane was 7:1, and the amount of alkali metal initiator was 1% of the total weight of the solution.

[0053] (3) Preparation of component A

[0054] 35 parts of fluorine-modified hydrogenated bisphenol A epoxy resin, 20 parts of epoxy-terminated fluorosilicone polymer, 8 parts of graphene oxide and 5 parts of iron phosphate powder were mixed and stirred and dispersed for 10 min. Then, 8 parts of titanium dioxide, 12 parts of silica powder, 0.6 parts of defoamer BYK-065, 1.2 parts of leveling agent PV88 and 1.2 parts of dispersant BYK-P104 were added and stirred and dispersed for another 20 min to obtain component A.

[0055] (4) Preparation of component B

[0056] Mix 19 parts of polyetheramine D230, 19 parts of isophorone diamine, and 9 parts of curing accelerator DMP-30 for 5 minutes to obtain component B;

[0057] (5) Mix component A and component B evenly, coat and cure to obtain anti-corrosion coating material.

[0058] Comparative Example 1

[0059] Unlike Example 1, hydrogenated bisphenol A epoxy resin was used instead of fluorine-modified hydrogenated bisphenol A epoxy resin.

[0060] Comparative Example 2

[0061] Unlike Example 1, no epoxy-terminated fluorosilicone polymer was added.

[0062] During the spraying process, two coats of paint are applied, with a 45-minute interval between the two coats. A dry film forms within 24 hours after the second coat, achieving a dry film thickness of 220 micrometers with both coats. The properties of the paint films from Examples 1-3 and Comparative Examples 1-2 are shown in Table 1.

[0063] Table 1. Test results of Examples 1-3 and Comparative Examples 1-2

[0064]

[0065] As can be seen from the data in the table, the water contact angle of the coating material provided by the present invention can reach 155.3°-166°. After 1000 hours of salt spray resistance test, the coating showed no blistering, peeling, or red rust. After 240 hours of UV aging resistance test, the coating showed no cracking. This indicates that the coating material provided by Examples 1-3 of the present invention has high hydrophobicity, aging performance and excellent environmental resistance.

[0066] The above description is a detailed description of the preferred embodiments of the present invention. However, the embodiments are not intended to limit the scope of the patent application of the present invention. All equivalent changes or modifications made under the technical spirit of the present invention should be covered by the patent of the present invention.

Claims

1. An anti-aging, superhydrophobic anti-corrosion coating material for steel structures, characterized in that, Includes the following substances: (1) The raw material weight parts of component A are as follows: 30-35 parts of fluorine-modified hydrogenated bisphenol A epoxy resin, 15-20 parts of epoxy-terminated fluorosilicone polymer, 5-8 parts of graphene oxide, 3-5 parts of ferrophosphorus powder, 6-8 parts of titanium dioxide, 10-12 parts of silica powder, and 2.5-3 parts of additives. (2) The raw material weight parts of component B are as follows: 28-38 parts of fatty amine curing agent and 6-9 parts of curing accelerator.

2. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 1, characterized in that, The fluorinated modified hydrogenated bisphenol A epoxy resin is a hydrogenated bisphenol A epoxy resin with fluorinated side chains synthesized by esterification reaction of hydrogenated bisphenol A epoxy resin and perfluoroalkyl acid under the action of toluenesulfonic acid catalyst at a temperature of 50-55℃.

3. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 2, characterized in that, The perfluoroalkyl acid is one of perfluorobutyric acid, perfluorooctanoic acid, and perfluorodecanoic acid.

4. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 2, characterized in that, The molar ratio of the hydrogenated bisphenol A epoxy resin to perfluoroalkyl acid is 1:3-4.

5. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 1, characterized in that, The preparation process of the terminal epoxy-based fluorosilicone polymer is as follows: Trifluoropropylmethylcyclotrisiloxane was dissolved in 10-15 times its volume of anhydrous ethanol solvent and subjected to ring-opening bulk polymerization at 35-40°C for 1-2 hours under the action of an alkali metal initiator. Then (3-epoxypropoxypropyl)dimethylethoxysilane was added and the reaction was continued for 2 hours. The solvent was removed under vacuum at low temperature to obtain an epoxy-terminated fluorosilicone polymer.

6. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 5, characterized in that, The molar ratio of the trifluoropropylmethylcyclotrisiloxane to (3-epoxypropoxypropyl)dimethylethoxysilane is 5-7:

1.

7. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 5, characterized in that, The amount of the alkali metal initiator is 1% of the total weight of the solution.

8. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 1, characterized in that, The fatty amine curing agent is a mixture of polyetheramine D230 and isophorone diamine in a mass ratio of 1:

1.

9. The anti-aging superhydrophobic steel structure anti-corrosion coating material according to claim 1, characterized in that, The additives include defoamer BYK-065, leveling agent PV88, and dispersant BYK-P104 in a mass ratio of 0.5:1:

1.

10. A method for preparing an anti-aging superhydrophobic steel structure anti-corrosion coating material according to any one of claims 1-9, characterized in that, The preparation steps include the following: Fluorine-modified hydrogenated bisphenol A epoxy resin, epoxy-terminated fluorosilicone polymer, graphene oxide and iron phosphate powder were mixed and stirred and dispersed for 10 min. Then titanium dioxide, silica powder and additives were added and stirred and dispersed for another 20 min to obtain component A. Mix the fatty amine curing agent and curing accelerator for 5 minutes to obtain component B; mix component A and component B evenly, coat and cure to obtain the anti-corrosion coating material.

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