Preparation method of high-temperature-resistant anticorrosive paint

Abstract

The invention relates to a preparation method of a high-temperature-resistant anticorrosive coating, and belongs to the technical field of anticorrosive coatings. The preparation method comprises the following steps: heating 1, 1 '-bis (dimethylsilyl) ferrocene, methylbenzene, chloroplatinic acid, 2, 2, 3, 3, 4, 4, 4-heptafluorobutyl acrylate and bis-(2-methylallyl) cyclooctyl-1, 5-diene ruthenium, and reacting to obtain an intermediate product 1; weighing methyltrimethoxysilane, phenyltrimethoxysilane and the intermediate product 1, uniformly stirring and mixing, slowly dropwise adding diluted hydrochloric acid, hydrolyzing, and heating to react, so as to obtain modified silicon resin; adding the modified silicon resin into petroleum ether, and adding silicone oil, an organic tin catalyst, a bis-ammonia coupling agent, a filler and a curing agent to obtain an anticorrosive coating; the surface of the metal equipment is polished and wiped clean, then is coated with an anticorrosive coating, and is cured at room temperature; the hydrolysis modified organic silicon high-temperature-resistant anticorrosive paint prepared by the invention has excellent corrosion resistance, good wear resistance and strong adhesive force.

Description

Technical Field

[0001] The present invention relates to the technical field of anti-corrosion coatings, and in particular to a preparation method of a high-temperature resistant anti-corrosion coating. Background Art

[0002] The corrosion of metals refers to the phenomenon that metals are damaged due to chemical or electrochemical actions when in contact with environmental media. This phenomenon widely exists in all corners of the national economy, causing huge losses to the national economy.

[0003] In order to address the problem of metal corrosion, people have been continuously exploring and adopting various protection technologies for a long time. Among these technologies, one of the most effective and commonly used methods is to coat a layer of anti-corrosion coating on the metal surface. This layer of coating can act as a barrier to effectively separate the corrosive medium from the metal substrate, thereby achieving the purpose of preventing corrosion.

[0004] Chinese Patent CN109929285A: discloses a composite material and its preparation method. Specifically, the composite material includes a metal substrate, a bottom coating, and a top coating. The bottom coating is a low surface energy coating; the top coating is a coating containing hydrophobic nanoparticles. The bottom coating is prepared from a low surface energy material, which can improve the wear resistance and adhesion of the coating without affecting the anti-frost performance of the coating; the top coating is a superhydrophobic nanostructure containing hydrophobic nanoparticles and has excellent anti-frost performance.

[0005] Chinese Patent CN105331284A: discloses a waterproof, high-temperature resistant, wear-resistant and anti-corrosion coating. Its raw materials by weight include: 45-48 parts of organosilicon epoxy resin polymer, 43-46 parts of acrylic emulsion, 9-12 parts of casein glue, 23-26 parts of modified graphene, 12-15 parts of nano-zinc oxide, 6-9 parts of aluminum tripolyphosphate, 4-6 parts of talc powder, 1.5-1.8 parts of silane coupling agent KH-570, 1.1-1.5 parts of anti-salt spray additive, 1.1-1.4 parts of leveling agent, 1.2-1.6 parts of defoaming agent, 1.2-1.5 parts of dispersant, and 45-48 parts of mixed solvent.

[0006] Chinese Patent CN105349000B: discloses a metal anti-corrosion coating, which is prepared from the following raw materials according to the weight ratio: 60-80 parts of epoxy acrylate resin, 10-15 parts of butylated amino resin, 5-8 parts of fluorocarbon resin, 2-5 parts of methyl isobutyl ketone, 2-4 parts of cobalt oxide, 1-2 parts of zinc phosphate, 1-2 parts of aluminum tripolyphosphate, 5-10 parts of polymer nanoparticles coated with benzotriazole, 2-4 parts of polyacrylate, 1-2 parts of xylene, 2-5 parts of triethylenetetramine, and 40-60 parts of industrial water.

[0007] The anti-corrosion coatings prepared by the above patents and the prior art have poor adhesion to the metal substrate, poor wear resistance, and the anti-corrosion performance needs to be further improved. Summary of the Invention

[0008] In order to solve the above problems, the present invention provides a preparation method of a high-temperature resistant anti-corrosion coating, and its operation steps are as follows: S1: By weight, weigh 30-60 parts of 1,1′-bis(dimethylsilyl)ferrocene CAS: 1295-15-4, 60-80 parts of toluene, 0.8-1.6 parts of chloroplatinic acid catalyst, stir and heat up to 50-60 °C, slowly dropwise add 25-50 parts of 2,2,3,3,4,4,4-heptafluorobutyl acrylate CAS: 424-64-6, 0.002-0.02 parts of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium CAS number: 12289-94-0, react for 90-120 min; heat up to 85-95 °C, continue to react for 5-8 h; cool to room temperature, and remove toluene by vacuum distillation to obtain intermediate product 1; S2: Weigh 20-30 parts of methyltrimethoxysilane, 30-50 parts of phenyltrimethoxysilane, 5-9 parts of intermediate product 1, stir and mix evenly, then slowly dropwise add dilute hydrochloric acid catalyst, and hydrolyze at 25-30 °C for 40-60 min; heat up to 50-60 °C, react for 90-120 min; after the reaction is completed, distill at 75-85 °C for 150-180 min; obtain modified silicone resin; S3: Add 70-90 parts of modified silicone resin to 10-20 parts of petroleum ether, stir and mix evenly, then add 20-30 parts of silicone oil, 1-5 parts of organotin catalyst, 1-3 parts of diamine coupling agent, mix evenly, and then add 5-10 parts of filler, 1-3 parts of curing agent to obtain anti-corrosion coating; S4: Sand the surface of the metal equipment, and then wipe it clean with anhydrous ethanol; S5: Apply the anti-corrosion coating on the surface of the cleaned metal equipment, the film thickness is 70-80 μm, and cure at room temperature for 5-7 d.

[0009] The mass concentration of the dilute hydrochloric acid is 10-20%.

[0010] The organotin catalyst is one of dibutyltin dichloride, dibutyltin dilaurate, stannous octoate, bis(dodecylthio)dibutyltin, dibutyltin diacetate.

[0011] The diamine coupling agent is one of Dow Corning 6020 silane coupling agent, Shin-Etsu amino coupling agent KBM-603, silane coupling agent KH-792, Momentive coupling agent Y-9627.

[0012] The filler described above is one of silica, mica, titanium dioxide, ferric oxide, and aluminum powder.

[0013] The curing agent described above is one of glycidyl ester curing agents, hydroxyalkylamide curing agents, basic epoxy resin curing agents, acidic epoxy resin curing agents, addition-type epoxy resin curing agents, and amine curing agents.

[0014] The preparation method of the silicone oil described above is as follows: Slowly drop dilute hydrochloric acid catalyst into 33 - 45 parts of methylphenyl dimethoxysilane, and hydrolyze at 25 - 30 °C for 40 - 60 min; raise the temperature to 50 - 60 °C and react for 90 - 120 min; after the reaction is completed, distill off methanol to obtain silicone oil.

[0015] Reaction mechanism The two Si-H bonds of 1,1′-bis(dimethylsilyl)ferrocene respectively carry out hydrosilylation reactions with the olefins of 2,2,3,3,4,4,4-heptafluorobutyl acrylate and bis-(2-methylallyl)cyclooct-1,5-diene ruthenium, thereby grafting the functional groups of ferrocene, heptafluorobutyl, and cyclooct-1,5-diene ruthenium together. This grafting reaction not only improves the high-temperature resistance of the material but also enhances its anti-corrosion performance.

[0016] The two Si-H bonds of ferrocene respectively carry out hydrosilylation reactions with the olefins of heptafluorobutyl acrylate and the olefins of cyclooct-1,5-diene ruthenium. In this process, ferrocene acts as a nucleophile to attack the double bond of the olefin, resulting in the cleavage of the double bond and the formation of a new Si-C bond. At the same time, the original Si-H bond breaks, releasing hydrogen. Through the above hydrosilylation reaction, the functional groups of ferrocene, heptafluorobutyl, and cyclooct-1,5-diene ruthenium are grafted together to form a new macromolecule. This macromolecule combines the thermal stability and chemical stability of ferrocene, the chemical corrosion resistance of heptafluorobutyl, and the specific properties of cyclooct-1,5-diene ruthenium.

[0017] Technical effects The preparation method of a high-temperature resistant and anti-corrosion coating of the present invention has the following remarkable effects compared with the prior art: The modified silicone resin prepared through the above hydrosilylation reaction performs excellently in the field of anti-corrosion coatings. First of all, as an organometallic compound, ferrocene's unique structure and properties endow the grafted coating with excellent thermal stability and chemical stability, enabling it to maintain stable performance in high-temperature environments. Secondly, the introduction of heptafluorobutyl significantly improves the chemical corrosion resistance of the coating, especially the resistance to fluorine-containing compounds, which is particularly important for anti-corrosion in fields such as chemical equipment and ocean engineering. Finally, the addition of cyclooct-1,5-diene ruthenium may further enhance the mechanical strength and wear resistance of the coating, enabling the coating to still maintain good protective performance in harsh environments.

[0018] Through a hydrolysis reaction, a modified silicone resin is prepared. This modified silicone resin not only inherits the advantages of ferrocene, heptafluorobutyl, and ruthenium cyclooct-1,5-diene, but also further improves its high-temperature resistance and anti-corrosion performance through hydrosilylation reaction and hydrolysis reaction.

[0019] In summary, by grafting the functional groups of ferrocene, heptafluorobutyl, and ruthenium cyclooct-1,5-diene together through hydrosilylation reaction, the prepared modified silicone resin has broad application prospects in the field of anti-corrosion coatings and can significantly improve the high-temperature resistance and anti-corrosion performance of the coatings. Specific Embodiments

[0020] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with examples and comparative examples: Wear resistance test: The wear amount at 1000 revolutions was measured using a JM-V abrasion tester; Self-corrosion potential test: The test was carried out using a CHI-660 electrochemical workstation; Adhesion test: The test was carried out in accordance with GB / T5210-2006; Salt spray resistance performance: The test was carried out in accordance with GB / T1771-2007, and the test results are shown in Table 1.

[0021] Example 1 A preparation method of a high-temperature resistant and anti-corrosion coating, the operation steps of which are as follows: S1: Weigh 30 g of 1,1′-bis(dimethylsilyl)ferrocene CAS: 1295-15-4, 60 g of toluene, and 0.8 g of chloroplatinic acid catalyst, stir and heat to 50 °C, slowly dropwise add 25 g of 2,2,3,3,4,4,4-heptafluorobutyl acrylate CAS: 424-64-6, 0.002 g of bis-(2-methylallyl)cyclooct-1,5-diene ruthenium CAS No.: 12289-94-0, and react for 90 min; heat to 85 °C and continue to react for 5 h; cool to room temperature, and remove toluene by vacuum distillation to obtain Intermediate Product 1; S2: Weigh 20 g of methyltrimethoxysilane, 30 g of phenyltrimethoxysilane, and 5 g of Intermediate Product 1, stir and mix evenly, then slowly dropwise add dilute hydrochloric acid catalyst, and hydrolyze at 25 °C for 40 min; heat to 50 °C and react for 90 min; after the reaction is completed, distill at 75 °C for 150 min; obtain a modified silicone resin; S3: Add 70 g of the modified silicone resin to 10 g of petroleum ether, stir and mix evenly, then add 20 g of silicone oil, 1 g of organotin catalyst, 1 g of diamine coupling agent, mix evenly, and then add 5 g of filler and 1 g of curing agent to obtain an anti-corrosion coating; S4: Polish the surface of the metal hook with sandpaper and then wipe it clean with anhydrous ethanol; S5: Apply the anti-corrosion coating on the surface of the cleaned metal hook, with a coating thickness of 70 μm, and cure at room temperature for 5 days.

[0022] The mass concentration of the dilute hydrochloric acid is 10%.

[0023] The organotin catalyst is dibutyltin dilaurate.

[0024] The diamine coupling agent is Dow Corning 6020 silane coupling agent.

[0025] The filler is silica.

[0026] The curing agent is a glycidyl ester curing agent.

[0027] The preparation method of the silicone oil is as follows: Slowly drop the dilute hydrochloric acid catalyst into 33 g of methylphenyldimethoxysilane, and hydrolyze at 25 °C for 40 min; raise the temperature to 50 °C and react for 90 min; after the reaction, distill off methanol to obtain silicone oil.

[0028] Example 2 A preparation method of a high-temperature resistant anti-corrosion coating, and its operation steps are as follows: S1: Weigh 40 g of 1,1′-bis(dimethylsilyl)ferrocene CAS: 1295-15-4, 65 g of toluene, and 1 g of chloroplatinic acid catalyst, stir and heat up to 55 °C, slowly drop 35 g of 2,2,3,3,4,4,4-heptafluorobutyl acrylate CAS: 424-64-6, and 0.01 g of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium CAS number: 12289-94-0, and react for 100 min; raise the temperature to 88 °C and continue to react for 6 h; cool to room temperature and remove toluene by vacuum distillation to obtain intermediate product 1; S2: Weigh 23 g of methyltrimethoxysilane, 35 g of phenyltrimethoxysilane, and 6 g of intermediate product 1, stir and mix evenly, then slowly drop the dilute hydrochloric acid catalyst, and hydrolyze at 26 °C for 45 min; raise the temperature to 55 °C and react for 100 min; after the reaction, distill at 78 °C for 160 min; obtain the modified silicone resin; S3: Add 75 g of the modified silicone resin to 13 g of petroleum ether, stir and mix evenly, then add 23 g of silicone oil, 2 g of organotin catalyst, and 2 g of diamine coupling agent, mix evenly, and then add 6 g of filler and 2 g of curing agent to obtain the anti-corrosion coating; S4: Sand the surface of the metal hook with sandpaper, and then wipe it clean with anhydrous ethanol; S5: Apply the anti-corrosion coating on the surface of the cleaned metal hook, with a coating thickness of 75 μm, and cure at room temperature for 6 days.

[0029] The mass concentration of the dilute hydrochloric acid is 15%.

[0030] The organotin catalyst is dibutyltin dilaurate.

[0031] The diamine coupling agent is Shin-Etsu amino coupling agent KBM-603.

[0032] The filler is mica.

[0033] The curing agent is a hydroxyalkylamide curing agent.

[0034] The preparation method of the silicone oil is as follows: Slowly drop the dilute hydrochloric acid catalyst into 38 g of methylphenyldimethoxysilane, and hydrolyze at 26 °C for 45 min; raise the temperature to 55 °C and react for 100 min; after the reaction is completed, distill off methanol to obtain silicone oil.

[0035] Example 3 A preparation method of a high-temperature resistant and anti-corrosion coating, and its operation steps are as follows: S1: Weigh 50 g of 1,1′-bis(dimethylsilyl)ferrocene CAS: 1295-15-4, 75 g of toluene, and 1.4 g of chloroplatinic acid catalyst, stir and raise the temperature to 55 °C, slowly drop 45 g of 2,2,3,3,4,4,4-heptafluorobutyl acrylate CAS: 424-64-6, and 0.015 g of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium CAS number: 12289-94-0, and react for 110 min; raise the temperature to 93 °C and continue to react for 7 h; cool to room temperature and remove toluene by vacuum distillation to obtain intermediate product 1; S2: Weigh 28 g of methyltrimethoxysilane, 45 g of phenyltrimethoxysilane, and 8 g of intermediate product 1, stir and mix evenly, then slowly drop the dilute hydrochloric acid catalyst, and hydrolyze at 28 °C for 55 min; raise the temperature to 55 °C and react for 110 min; after the reaction is completed, distill at 83 °C for 170 min; obtain the modified silicone resin; S3: Add 85 g of the modified silicone resin to 18 g of petroleum ether, stir and mix evenly, then add 28 g of silicone oil, 4 g of organotin catalyst, and 2 g of diamine coupling agent, mix evenly, and then add 8 g of filler and 2 g of curing agent to obtain the anti-corrosion coating; S4: Polish the surface of the metal hook with sandpaper and then wipe it clean with anhydrous ethanol; S5: Coat the anti-corrosion coating on the surface of the cleaned metal hook, with a film thickness of 75 μm, and cure at room temperature for 6 d.

[0036] The mass concentration of the dilute hydrochloric acid is 15%.

[0037] The organotin catalyst is stannous octoate.

[0038] The diamine coupling agent mentioned above is silane coupling agent KH-792.

[0039] The filler mentioned above is titanium dioxide.

[0040] The curing agent mentioned above is an alkaline epoxy resin curing agent.

[0041] The preparation method of the silicone oil mentioned above is as follows: Slowly drop dilute hydrochloric acid catalyst into 43 g of methylphenyldimethoxysilane, hydrolyze at 28 °C for 55 min; raise the temperature to 55 °C and react for 110 min; after the reaction is completed, distill off methanol to obtain silicone oil.

[0042] Example 4 A preparation method of a high-temperature resistant and anti-corrosive coating, the operation steps are as follows: S1: Weigh 60 g of 1,1′-bis(dimethylsilyl)ferrocene CAS: 1295-15-4, 80 g of toluene, and 1.6 g of chloroplatinic acid catalyst, stir and heat up to 60 °C, slowly drop 50 g of 2,2,3,3,4,4,4-heptafluorobutyl acrylate CAS: 424-64-6, and 0.02 g of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium CAS number: 12289-94-0, react for 120 min; raise the temperature to 95 °C and continue to react for 8 h; cool to room temperature and remove toluene by vacuum distillation to obtain intermediate product 1; S2: Weigh 30 g of methyltrimethoxysilane, 50 g of phenyltrimethoxysilane, and 9 g of intermediate product 1, stir and mix evenly, then slowly drop dilute hydrochloric acid catalyst, hydrolyze at 30 °C for 60 min; raise the temperature to 60 °C and react for 120 min; after the reaction is completed, distill at 85 °C for 180 min; obtain modified silicone resin; S3: Add 90 g of modified silicone resin to 20 g of petroleum ether, stir and mix evenly, then add 30 g of silicone oil, 5 g of organotin catalyst, and 3 g of diamine coupling agent, mix evenly, and then add 10 g of filler and 3 g of curing agent to obtain anti-corrosive coating; S4: Polish the surface of the metal hook with sandpaper and then wipe it clean with anhydrous ethanol; S5: Coat the anti-corrosive coating on the surface of the cleaned metal hook, the film thickness is 80 μm, and cure at room temperature for 7 d.

[0043] The mass concentration of the dilute hydrochloric acid mentioned above is 20%.

[0044] The organotin catalyst mentioned above is dibutyltin diacetate.

[0045] The diamine coupling agent mentioned above is Momentive coupling agent Y-9627.

[0046] The filler mentioned above is aluminum powder.

[0047] The curing agent described above is an amine curing agent.

[0048] The preparation method of the silicone oil described above is as follows: Slowly drop dilute hydrochloric acid catalyst into 45 g of methylphenyldimethoxysilane, hydrolyze at 30 °C for 60 min; raise the temperature to 60 °C and react for 120 min; after the reaction, distill off methanol to obtain silicone oil.

[0049] Comparative Example 1 Do not add 2,2,3,3,4,4,4-heptafluorobutyl acrylate and bis-(2-methylallyl)cycloocta-1,5-diene ruthenium, and the others are the same as in Example 1.

[0050] Comparative Example 2 Do not add 2,2,3,3,4,4,4-heptafluorobutyl acrylate, and the others are the same as in Example 1.

[0051] Comparative Example 3 Do not add bis-(2-methylallyl)cycloocta-1,5-diene ruthenium, and the others are the same as in Example 1.

[0052] Table 1 Wear resistance / mg Self - corrosion potential / V Adhesion / Mpa Salt spray resistance / h Example 1 2.31 -0.33 14.2 No change after 4800 h Example 2 2.25 -0.31 14.5 No change after 4800 h Example 3 2.18 -0.29 14.9 No change after 4800 h Example 4 2.13 -0.28 15.2 No change after 4800 h Comparative example 1 2.88 -0.45 11.3 No change after 3600 h Comparative example 2 2.51 -0.37 12.8 No change after 4500 h Comparative example 3 2.45 -0.36 13.1 No change after 4600 h Through the data analysis of the above examples and comparative examples, the hydrolytically modified silicone high-temperature resistant and anti-corrosion coating prepared by the present invention has excellent corrosion resistance, good wear resistance and strong adhesion.

[0053] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the equivalent embodiments by using the above-disclosed technical content within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A preparation method of a high-temperature resistant and anti-corrosive coating, and its operation steps are as follows: S1: Weigh 30 - 60 parts of 1,1′-bis(dimethylsilyl)ferrocene, 60 - 80 parts of toluene, and 0.8 - 1.6 parts of chloroplatinic acid catalyst by weight. Stir and heat up to 50 - 60 °C, and slowly dropwise add 25 - 50 parts of 2,2,3,3,4,4,4-heptafluorobutyl acrylate and 0.002 - 0.02 parts of bis-(2-methylallyl)cycloocta-1,5-diene ruthenium, and react for 90 - 120 min; heat up to 85 - 95 °C, and continue to react for 5 - 8 h; then cool to room temperature, and remove toluene by vacuum distillation to obtain intermediate product 1; S2: Weigh 20 - 30 parts of methyltrimethoxysilane, 30 - 50 parts of phenyltrimethoxysilane, and 5 - 9 parts of intermediate product 1, stir and mix evenly, then slowly dropwise add dilute hydrochloric acid catalyst, and hydrolyze at 25 - 30 °C for 40 - 60 min; heat up to 50 - 60 °C, and react for 90 - 120 min; after the reaction is completed, distill at 75 - 85 °C for 150 - 180 min to obtain modified silicone resin; S3: Add 70 - 90 parts of modified silicone resin to 10 - 20 parts of petroleum ether, stir and mix evenly, then add 20 - 30 parts of silicone oil, 1 - 5 parts of organotin catalyst, 1 - 3 parts of diamine coupling agent, mix evenly, and then add 5 - 10 parts of filler and 1 - 3 parts of curing agent to obtain anti-corrosive coating; S4: Polish the surface of the metal equipment with sandpaper, and then wipe it clean with anhydrous ethanol; S5: Apply the anti-corrosive coating on the surface of the cleaned metal equipment, with the coating thickness of 70 - 80 μm, and cure at room temperature for 5 - 7 d.

2. The preparation method of a high-temperature resistant and anti-corrosion coating according to claim 1, characterized in that: The mass concentration of the dilute hydrochloric acid is 10 - 20%.

3. The preparation method of a high-temperature resistant and anti-corrosion coating according to claim 1, wherein: The organotin catalyst is one of dibutyltin dichloride, dibutyltin dilaurate, stannous octoate, bis(dodecylthio)dibutyltin, and dibutyltin diacetate.

4. The preparation method of a high-temperature resistant and anti-corrosion coating according to claim 1, characterized in that: The diamine coupling agent is one of Dow Corning 6020 silane coupling agent, Shin-Etsu amino coupling agent KBM-603, silane coupling agent KH-792, and Momentive coupling agent Y-9627.

5. The preparation method of a high-temperature resistant and anti-corrosion coating according to claim 1, characterized in that: The filler is one of silica, mica, titanium dioxide, iron(III) oxide, and aluminum powder.

6. The preparation method of a high-temperature resistant and anti-corrosion coating according to claim 1, characterized in that: The curing agent is one of glycidyl ester curing agents, hydroxyalkylamide curing agents, basic epoxy resin curing agents, acidic epoxy resin curing agents, addition-type epoxy resin curing agents, and amine curing agents.

7. The preparation method of a high-temperature resistant and anti-corrosion coating according to claim 1, characterized in that: The preparation method of the silicone oil is as follows: Slowly dropwise add dilute hydrochloric acid catalyst to 33 - 45 parts of methylphenyldimethoxysilane, and hydrolyze at 25 - 30 °C for 40 - 60 min; heat up to 50 - 60 °C, and react for 90 - 120 min; after the reaction is completed, distill to remove methanol to obtain silicone oil.