Anti-corrosion material for seawater equipment and preparation method thereof

Abstract

The invention belongs to the technical field of anti-corrosion materials, and particularly relates to an anti-corrosion material for seawater equipment and a preparation method thereof. The raw materials of the anti-corrosion material include, by weight, 43 to 75 parts of fluorosilicone rubber, 30 to 55 parts of polynonylene urea, 12 to 35 parts of epoxy resin, 4 to 10 parts of a compatibilizer, 9 to 27 parts of an antioxidant, 10 to 30 parts of an antioxidant, 5 to 15 parts of a decomposer, 2 to 6 parts of nano silver, 2 to 6 parts of nano zinc oxide, 3 to 9 parts of a silane coupling agent, and 3 to 9 parts of an ultraviolet absorber. The new anti-corrosion material is evenly arranged on the surface of metal equipment and can be well cured on the metal surface. It has excellent anti-corrosion effect, ultraviolet resistance, and sterilization ability, thereby extending the service life of the metal equipment in seawater.

Description

Technical Field

[0001] The present invention belongs to the technical field of anti-corrosion materials, and in particular relates to an anti-corrosion material for seawater equipment and a preparation method thereof. Background Art

[0002] Metal equipment or metal parts serving in the marine environment are prone to corrosion due to being in a high-salt water body, which reduces the service life of the metal equipment or metal parts. Secondly, some plankton or bacteria often adhere to the surface of these metal equipment or metal parts, and they need to be cleaned regularly.

[0003] Patent CN107099119A discloses a new anti-corrosion material, comprising the following components in parts by mass: 100-200 parts of epoxy resin, 100-260 parts of alkyd resin, 20-40 parts of phenolic resin, 20-40 parts of silicone oil, 10-20 parts of compatibilizer, 5-15 parts of graphene, 15-25 parts of leveling agent, 3-7 parts of antioxidant, 5-7 parts of glycerol ether, 1-5 parts of flame retardant, 5-10 parts of curing agent, and 40-80 parts of filler. The invention provides a new anti-corrosion material and a preparation method thereof. Electrode induction enables the material molecules to have very good selective permeability, thereby enhancing the good functional effects of the new anti-corrosion material, and having very good anti-corrosion and insect-resistant properties. The material formula is simple, the price is low, and the preparation process is simple, which achieves cost savings and reduces labor intensity and meets actual use requirements. However, the new anti-corrosion material is prone to scaling and electrochemical corrosion in high-salinity and alkaline water bodies, and its anti-corrosion effect is poor.

[0004] Patent CN115991899A discloses a new anti-corrosion and rust-proof material for high-alkalinity and high-salinity water equipment, comprising the following raw materials in parts by weight: 26-43 parts by weight of carboxyl nitrile rubber, 17-38 parts by weight of epoxy resin, 3-6 parts by weight of antioxidant, 2-5 parts by weight of curing agent, 1-5 parts by weight of reinforcing agent, 3-8 parts by weight of compatibilizer, 2-6 parts by weight of decomposer, and 5-12 parts by weight of dimethyl silicone oil. However, the new anti-corrosion and rust-proof material has poor corrosion resistance, weak UV resistance, and poor mechanical properties. The resulting material has a certain shape, which narrows its application range and can only be used to protect metal equipment of a specific shape. It cannot protect metal equipment with larger size or more special shape. If the shape of the new anti-corrosion and rust-proof material is changed to protect such metal equipment, the cost is high. Moreover, the new anti-corrosion and rust-proof material cannot be sterilized, which easily leads to the growth of plankton and bacteria on the surface of the material, requiring regular cleaning. Summary of the Invention

[0005] In order to solve the problems existing in the prior art and the shortcomings of the solutions, the present invention provides an anti-corrosion material for seawater equipment and a preparation method thereof. The anti-corrosion material has excellent anti-corrosion performance in marine water bodies and the ability to resist ultraviolet rays from light, thereby extending the service life of marine equipment. It also has a bactericidal effect, avoiding the growth of plankton and bacteria. At the same time, the preparation method of the material is simple, and it can be used to protect metal equipment of various sizes and shapes, and has a wide range of applications.

[0006] In order to prevent corrosion of metal equipment or metal parts in seawater environments to ensure the service life of metal equipment or metal parts, prevent the attachment of plankton or the growth of bacteria on the surface of metal equipment or metal parts to ensure a reduction in the number of regular cleanings, and to be applicable to the protection of metal equipment and parts of various sizes and shapes, the present invention proposes an anti-corrosion material for seawater equipment. The specific solution is as follows:

[0007] The invention discloses an anti-corrosion material for seawater equipment. The raw materials include, by weight, 43 to 75 parts of fluorosilicone rubber, 30 to 55 parts of polynonylene urea, 12 to 35 parts of epoxy resin, 4 to 10 parts of compatibilizer, 9 to 27 parts of antioxidant, 10 to 30 parts of antioxidant, 5 to 15 parts of decomposer, 2 to 6 parts of nano silver, 2 to 6 parts of nano zinc oxide, 3 to 9 parts of silane coupling agent and 3 to 9 parts of ultraviolet absorber.

[0008] Preferably, the antioxidant is 2,6-di-tert-butyl-4-methoxyphenol and the decomposition agent is terephthalate

[0009] Preferably, the epoxy resin may be one or more of bisphenol A epoxy resin, polyphenol glycidyl ether epoxy resin, and aliphatic glycidyl ether epoxy resin; the compatibilizer is a non-reactive compatibilizer; the antioxidant is one of amines, phenols, heterocycles, and phosphites; the silane coupling agent is one of methyltrichlorosilane, aminosilane, vinylsilane, epoxysilane, and allyltrimethylsilane; the ultraviolet absorber is one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines.

[0010] Preferably, the particle size of nano-silver is 5 to 40 nm, and the particle size of nano-zinc oxide is 10 to 50 nm.

[0011] The present invention adopts fluorosilicone rubber and polynonyl urea to work together to achieve the effect of synchronous enhancement, which can effectively improve the tensile and compressive strength of the material. Fluorosilicone rubber has good oil resistance, solvent resistance and chemical resistance, and polynonyl urea has good corrosion resistance and can slow down the erosion of seawater on the material. Fluorosilicone rubber and polynonyl urea work together to achieve the effect of synchronous enhancement, and the two can complement each other's advantages. At the same time, fluorosilicone rubber and polynonyl urea can be better cured on the surface of the equipment in combination with epoxy resin. The hardness and modulus of epoxy resin are high and it is not easy to deform. Epoxy resin can effectively improve the hardness and modulus of the material; fluorosilicone rubber, polynonyl urea and epoxy resin can complement each other's performance advantages and effectively improve the mechanical properties and corrosion resistance of the material; the antioxidant 2,6-di-tert-butyl-4-methoxyphenol is combined with terephthalate, nano-silver and nano-zinc oxide. When used, nanosilver can provide free radicals to the antioxidant 2,6-di-tert-butyl-4-methoxyphenol during oxidation, allowing it to regenerate. Nanosilver and the antioxidant 2,6-di-tert-butyl-4-methoxyphenol can play a synergistic role and can more effectively inhibit the oxidation of new materials. Nanosilver oxide generated after nanosilver is oxidized acts as a UV shielding agent. At the same time, nanosilver oxide has a strong inactivation ability for proteins and can play a bactericidal role. The antioxidant 2,6-di-tert-butyl-4-methoxyphenol can act as a hydrogen donor to provide hydrogen atoms to generate antioxidant free radicals, reduce oxidized fluorosilicone rubber, polynonyl urea, and epoxy resin, and prevent these components from being oxidized by oxygen and other substances in seawater. The purpose is to prevent oxidation and aging of these materials and extend the service life of the materials. After terephthalate is decomposed, it combines with nano-zinc oxide to form zinc terephthalate, which improves the material's ability to shield light and ultraviolet rays.

[0012] The above-mentioned method for preparing an anti-corrosion material for seawater equipment comprises the following steps:

[0013] S1: mixing antioxidant, antioxidant, nano silver and water to obtain a mixed solution;

[0014] S2: adding a compatibilizer and a silane coupling agent to the mixed solution, and after fully dissolving, sequentially adding fluorosilicone rubber and polynonylene urea to the mixed solution, heating and stirring, to obtain a first blank;

[0015] S3: placing the first blank on the surface of the metal material to be protected as a first protective layer with a thickness of 1 to 2 mm, heating and dehydrating the blank so that the blank is solidified on the surface of the metal material, and the solidified protective layer is allowed to stand for 6 to 12 hours;

[0016] S4: mixing the antioxidant, antioxidant, nano silver, nano zinc oxide, ultraviolet absorber and water to obtain a mixed solution;

[0017] S5: adding a compatibilizer, a silane coupling agent, and a decomposing agent to the mixed solution, and after fully dissolving, adding fluorosilicone rubber, polynonylene urea, and epoxy resin to the mixed solution in sequence, heating and stirring, to obtain a second blank;

[0018] S6: placing the second blank on the first protective layer on the surface of the protected metal material as the second protective layer, maintaining a thickness of 1 to 2 mm, heating and dehydrating it to solidify it on the first protective layer on the surface of the metal material, and letting it stand for 4 to 10 hours after forming the solidified protective layer.

[0019] Preferably, the blank is arranged on the surface of the metal material by spraying, immersing, brushing and other methods already known in the prior art.

[0020] Preferably, in S1, the weight ratio of the antioxidant, antioxidant, and nanosilver is 3-6:3-5:1-2. Under this ratio, the weight ratio of the antioxidant and antioxidant is close, which can achieve good synergistic effect and prevent material aging and oxidation. Secondly, a small amount of nanosilver can assist the antioxidant in preventing material oxidation. Secondly, a larger amount of antioxidant and antioxidant can protect nanosilver from oxidation and prolong the sterilization time of nanosilver. In S4, the weight ratio of the antioxidant, antioxidant, decomposition agent, nanosilver, nano zinc oxide, and ultraviolet absorber is 3-5:4-8:1-2:1-3:2-5.

[0021] Preferably, the mass ratio of the antioxidant in S1: the antioxidant in S4 is 5-15:4-12; the mass ratio of the antioxidant in S1: the antioxidant in S4 is 2-6:3-9; the mass ratio of the nanosilver in S1: the nanosilver in S4 is 1-3:1-3; the mass ratio of the compatibilizer in S2: the compatibilizer in S5 is 1-3:3-7; the mass ratio of the silane coupling agent in S2: the silane coupling agent in S5 is 1-4:2-5; the mass ratio of the fluorosilicone rubber in S2: the fluorosilicone rubber in S5 is 18-35:25-40; the mass ratio of the polynonylene urea in S2: the polynonylene urea in S5 is 3-5:3-6.

[0022] Preferably, the water content of the mixed liquid in S1 is 20-35%, and the water content of the mixed liquid in S4 is 15-30%.

[0023] Preferably, the heating temperature in S2 is 150-240°C, and the heating temperature in S5 is 160-230°C.

[0024] Preferably, the heating temperature in S3 is 180-200°C, and the heating temperature in S5 is 170-195°C.

[0025] The nanosilver added in step S1 of the preparation method of the present invention can partially directly contact the metal equipment or metal parts during curing, and can destroy the protein structure of bacteria and fungi before they reach the metal equipment or metal, thereby preventing bacteria from growing inside the material and causing corrosion of the metal material; the compatibilizer and silane coupling agent in S2 can improve the compatibility of fluorosilicone rubber and polynonyl urea; the addition of the ultraviolet absorber in S4 can effectively absorb the free radicals generated by ultraviolet light on the material components, thereby extending the service life of the material; S3 and S6 are divided into two steps to cure the material, and the components in S3 are evenly arranged on the surface of the metal equipment or metal parts to form a first protective layer, thereby achieving the purpose of the first layer of corrosion protection; the components in S6 are evenly arranged on the first protective layer of the metal equipment or metal parts to form a second protective layer, which can protect the first protective layer and at the same time improve the mechanical properties of the protective layer, and improve the hardness and modulus of the protective material. The double-layer protection can more effectively ensure that the metal equipment or metal parts are not corroded by seawater. The second protective layer material is attached to the first protective layer, playing a synergistic role. The second protective layer material has better tensile strength and hardness, which can better protect the first protective layer material. Secondly, the UV absorber in the second protective layer material can effectively block ultraviolet rays, preventing the material's service life from being significantly shortened due to light exposure. The first and second protective layers have different material compositions and proportions. The first protective layer is mainly used to protect the internal metal equipment or metal parts and prevent bacteria and mold from penetrating into the bottom of the material. The antioxidants, anti-aging agents, and UV absorbers contained in the second protective layer can better block ultraviolet rays. The second protective layer material has better UV shielding ability, anti-oxidation and anti-aging capabilities than the first layer, which can better protect the first layer material from oxidation, aging, and decomposition, and improve the overall stability of the material.

[0026] The present invention provides an anti-corrosion material for seawater equipment and a preparation method thereof. The anti-corrosion material has excellent anti-corrosion performance, UV resistance and sterilization performance, as well as excellent mechanical energy. The anti-corrosion material effectively extends the service life of equipment in seawater. The preparation method is simple and can be applied to metal equipment of various shapes and sizes, with a wide range of applications. DETAILED DESCRIPTION

[0027] The following is a further description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. The described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Various changes or modifications made within the technical solutions of the present invention also fall within the scope of protection of the present invention.

[0028] The purpose of the embodiment of the present invention is to provide an anti-corrosion material for seawater equipment. The raw materials include, by weight: 43 to 75 parts of fluorosilicone rubber, 30 to 55 parts of polynonyl urea, 12 to 35 parts of epoxy resin, 4 to 10 parts of compatibilizer, 9 to 27 parts of antioxidant, 10 to 30 parts of antioxidant, 5 to 15 parts of decomposer, 2 to 6 parts of nano silver, 2 to 6 parts of nano zinc oxide, 3 to 9 parts of silane coupling agent, and 3 to 9 parts of ultraviolet absorber.

[0029] In another embodiment, the antioxidant is 2,6-di-tert-butyl-4-methoxyphenol, the decomposition agent is terephthalate; the epoxy resin can be one or more of bisphenol A epoxy resin, polyphenol glycidyl ether epoxy resin, and aliphatic glycidyl ether epoxy resin; the compatibilizer is a non-reactive compatibilizer; the antioxidant is one of amines, phenols, heterocycles, and phosphites; the silane coupling agent is one of methyltrichlorosilane, aminosilane, vinylsilane, epoxysilane, and allyltrimethylsilane; the ultraviolet absorber is one of salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine; the particle size of nanosilver is 5 to 40 nm; and the particle size of nanozinc oxide is 10 to 50 nm.

[0030] A method for preparing an anti-corrosion material for seawater equipment, comprising the following steps:

[0031] S1: Adding antioxidant, antioxidant, nanosilver and water into a reactor and stirring them thoroughly to obtain a mixed solution with a water content of 20-35%. This mixed solution is conducive to better dispersion of the antioxidant, antioxidant and nanosilver. Too high a water content will lead to uneven curing and solidification dents during subsequent curing. Too low a water content will cause the nanosilver to agglomerate and cannot be evenly dispersed into the fluorosilicone rubber and polynonylene urea.

[0032] S2: After the compatibilizer and the silane coupling agent are added into the reactor and stirred to fully dissolve, the fluorosilicone rubber and the polynonylene urea are added into the reactor in sequence and heated and stirred to obtain the first blank, wherein the heating temperature is 150-240° C. This temperature is conducive to the mutual dissolution of the compatibilizer and the coupling agent with the fluorosilicone rubber and the polynonylene urea, and cross-linking into relatively uniform components. Too low a temperature will lead to poor compatibilization and coupling effects, and too high a temperature will lead to overheating and decomposition of the raw materials;

[0033] S3: After taking out the first blank, evenly place it on the surface of the protected metal material to form a first protective layer, maintain the spraying thickness of 1 to 2 mm, and solidify it on the surface of the metal material after heating and dehydration, wherein the heating temperature is 180 to 200 ° C. After the solidified protective layer is formed, let it stand for 6 to 12 hours, and evenly place the first blank on the surface of the metal equipment or metal parts. The formed protective layer can effectively prevent the metal from contacting seawater and oxygen to cause corrosion. The long-term standing allows the ingredients to be better solidified on the surface of the metal equipment or metal parts, which is also conducive to the second protective layer adhering to the first protective layer. The heating and dehydration temperature is moderate. If it is too low, the dehydration is not thorough and the residual water will slowly corrode the metal equipment or metal parts. If the temperature is too high, it will cause uneven dehydration and unevenness in some areas.

[0034] S4: adding antioxidant, antioxidant, nano silver, nano zinc oxide, ultraviolet absorber and water into the reactor and stirring and mixing them thoroughly to obtain a mixed solution with a water content of 15-30%, which is conducive to better dispersion of the antioxidant, antioxidant, decomposition agent, nano silver, nano zinc oxide and ultraviolet absorber. Too high a water content will lead to uneven curing and curing dents during subsequent curing, and holes will be left inside the material. The presence of these holes will easily lead to a decrease in the corrosion resistance of the material. Too low a water content will cause the nano silver and nano zinc oxide to agglomerate and cannot be evenly dispersed into the fluorosilicone rubber, polynonyl urea and epoxy resin.

[0035] S5: After the compatibilizer, silane coupling agent, and decomposer are added to the reactor and stirred to fully dissolve, the fluorosilicone rubber, polynonylene urea, and epoxy resin are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 160-230° C. This temperature is conducive to the mutual dissolution of the compatibilizer, coupling agent, and decomposer with the fluorosilicone rubber and polynonylene urea, and cross-linking into relatively uniform components. If the temperature is too low, the compatibilization and coupling effects will be deteriorated. If the temperature is too high, some raw materials will be overheated and decomposed. Overheating and decomposition will lead to poor material properties and reduced corrosion resistance of the material.

[0036] S6: After taking out the second blank, evenly place it on the first protective layer on the surface of the protected metal material to form a second protective layer, maintain the spraying thickness of 1 to 2 mm, heat and dehydrate it to solidify it on the surface of the metal material, and let it stand for 4 to 10 hours after forming the solidified protective layer. The second blank is evenly placed on the first protective layer on the surface of the metal equipment or metal parts. The formed second protective layer can effectively prevent the metal from contacting seawater and oxygen to cause corrosion, and secondly, it can better protect the first protective layer. By standing for a long time, the second blank is better solidified on the first protective layer on the surface of the metal equipment or metal parts. The second protective layer is attached to the first protective layer, and the heating and dehydration temperature is moderate. If it is too low, the dehydration will not be thorough and the residual water will slowly penetrate into the first protective layer material, thereby corroding metal equipment or metal parts. If the heating and dehydration temperature is too high, it will cause uneven dehydration and unevenness in some areas. The second protective layer is attached to the first protective layer, which plays a synergistic enhancement role. The second protective layer has better tensile strength and hardness, and can better protect the first protective layer. Secondly, the ultraviolet absorber in the second protective layer can effectively shield ultraviolet rays, avoiding the significant shortening of the service life of the material due to light.

[0037] In the above, the mass ratio of the antioxidant in S1: the antioxidant in S4 is 5-15:4-12; the mass ratio of the antioxidant in S1: the antioxidant in S4 is 2-6:3-9; the mass ratio of the nanosilver in S1: the nanosilver in S4 is 1-3:1-3; the mass ratio of the compatibilizer in S2: the compatibilizer in S5 is 1-3:3-7; the mass ratio of the silane coupling agent in S2: the silane coupling agent in S5 is 1-4:2-5; the mass ratio of the fluorosilicone rubber in S2: the fluorosilicone rubber in S5 is 18-35:25-40; the mass ratio of the polynonylene urea in S2: the polynonylene urea in S5 is 3-5:3-6.

[0038] In another embodiment, the blank is arranged on the surface of the metal material by spraying, immersing, brushing and other methods already known in the prior art.

[0039] According to the differences in the amount of raw materials used and the process parameters during the preparation process, the anti-corrosion material for seawater equipment and the preparation method thereof provided by the present invention are further described through the following specific examples:

[0040] The following medium fluorine silicone rubber uses γ-trifluoropropyl methyl polysiloxane with a molecular weight of 200,000 to 700,000, and the epoxy resin uses bisphenol A epoxy resin E51 with an epoxy equivalent of 148-195g / mol -1The molecular weight of the polynonylene urea is between 100,000 and 600,000, wherein the molar ratio of nonanediamine to urea during polymerization is 1:1, the particle size of the nanosilver is 5 to 40 nm, the particle size of the nanozinc oxide is 10 to 50 nm, cyclohexanol is used as a compatibilizer, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine is used as an antioxidant, 2,6-di-tert-butyl-4-methoxyphenol is used as an antioxidant, sodium terephthalate is used as a decomposition agent, γ-aminopropyltriethoxysilane is used as a silane coupling agent, and 2-(2-hydroxy-3',5'-di-tert-phenyl)-5-chlorobenzotriazole is used as the ultraviolet absorber.

[0041] Example 1

[0042] A method for preparing an anti-corrosion material for seawater equipment:

[0043] S1: 5 parts by weight of an antioxidant, 4 parts by weight of an antioxidant, 1 part by weight of nanosilver, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 20%;

[0044] S2: 1 part by weight of a compatibilizer and 1 part by weight of a silane coupling agent were added to a reactor and stirred to fully dissolve. Then, 18 parts by weight of fluorosilicone rubber and 15 parts by weight of polynonylene urea were added to the reactor in sequence and heated and stirred to obtain a first blank, wherein the heating temperature was 150° C.

[0045] S3: taking out the first blank and spraying it on the surface of the metal material to be protected to form a first protective layer, maintaining the spraying thickness at 1.5 mm, and then heating and dehydrating it to solidify it on the surface of the metal material, wherein the heating temperature is 180°C, and after forming the solidified protective layer, it is left to stand for 6 hours;

[0046] S4: 4 parts by weight of an antioxidant, 6 parts by weight of an antioxidant, 1 part by weight of nano silver, 2 parts by weight of nano zinc oxide, 3 parts by weight of an ultraviolet absorber, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 15%;

[0047] S5: 3 parts by weight of a compatibilizer, 2 parts by weight of a silane coupling agent, and 5 parts by weight of a decomposition agent are added to a reactor and stirred to fully dissolve. Then, 25 parts by weight of a fluorosilicone rubber, 15 parts by weight of a polynonylene urea, and 12 parts by weight of an epoxy resin are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 170° C.

[0048] S6: Take out the second blank and spray it on the first protective layer on the surface of the protected metal material to form a second protective layer. Maintain the spraying thickness at 1.5 mm. Heat and dehydrate it to solidify it on the first protective layer on the surface of the metal material. The heating temperature is 170°C. After the solidified protective layer is formed, let it stand for 4 hours.

[0049] Example 2

[0050] A method for preparing an anti-corrosion material for seawater equipment:

[0051] S1: 12.5 parts by weight of an antioxidant, 10 parts by weight of an antioxidant, 2.5 parts by weight of nanosilver, and water were added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 35%;

[0052] S2: 2.5 parts by weight of a compatibilizer and 3 parts by weight of a silane coupling agent were added to a reactor and stirred to fully dissolve. 32 parts by weight of fluorosilicone rubber and 23 parts by weight of polynonylene urea were then added to the reactor in sequence and heated and stirred to obtain a first blank, wherein the heating temperature was 170° C.

[0053] S3: taking out the first blank and spraying it on the surface of the metal material to be protected to form a first protective layer, maintaining the spraying thickness at 1.5 mm, and then heating and dehydrating it to solidify it on the surface of the metal material, wherein the heating temperature is 185°C, and after forming the solidified protective layer, it is left to stand for 10 hours;

[0054] S4: 10 parts by weight of an antioxidant, 15 parts by weight of an antioxidant, 2.5 parts by weight of nano silver, 5 parts by weight of nano zinc oxide, 7.5 parts by weight of an ultraviolet absorber, and water are added to a reactor and stirred thoroughly to obtain a mixed solution with a water content of 30%;

[0055] S5: 6 parts by weight of a compatibilizer, 4 parts by weight of a silane coupling agent, and 13 parts by weight of a decomposition agent are added to a reactor and stirred to fully dissolve. Then, 38 parts by weight of fluorosilicone rubber, 27 parts by weight of polynonylene urea, and 32 parts by weight of an epoxy resin are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 185° C.

[0056] S6: Take out the second blank and spray it on the first protective layer on the surface of the protected metal material to form a second protective layer. Maintain the spraying thickness at 1.5 mm. Heat and dehydrate it to solidify it on the first protective layer on the surface of the metal material. The heating temperature is 175°C. After the solidified protective layer is formed, let it stand for 9 hours.

[0057] Example 3

[0058] A method for preparing an anti-corrosion material for seawater equipment:

[0059] S1: 10 parts by weight of an antioxidant, 8 parts by weight of an antioxidant, 2 parts by weight of nanosilver, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 27%;

[0060] S2: 2 parts by weight of a compatibilizer and 2 parts by weight of a silane coupling agent were added to a reactor and stirred to fully dissolve. Then, 25 parts by weight of fluorosilicone rubber and 20 parts by weight of polynonylene urea were added to the reactor in sequence and heated and stirred to obtain a first blank, wherein the heating temperature was 190° C.

[0061] S3: taking out the first blank and spraying it on the surface of the metal material to be protected to form a first protective layer, maintaining the spraying thickness at 1.5 mm, and then heating and dehydrating it to solidify it on the surface of the metal material, wherein the heating temperature is 190° C. After the solidified protective layer is formed, it is left to stand for 9 hours;

[0062] S4: 8 parts by weight of antioxidant, 10 parts by weight of antioxidant, 2 parts by weight of nano silver, 4 parts by weight of nano zinc oxide, 6 parts by weight of ultraviolet absorber, and water are added into a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 23%;

[0063] S5: 5 parts by weight of a compatibilizer, 3.5 parts by weight of a silane coupling agent, and 10 parts by weight of a decomposition agent are added to a reactor and stirred to fully dissolve. Then, 32.5 parts by weight of fluorosilicone rubber, 22.5 parts by weight of polynonylene urea, and 23.5 parts by weight of an epoxy resin are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 200° C.

[0064] S6: Take out the second blank and spray it on the first protective layer on the surface of the protected metal material to form a second protective layer. Maintain the spraying thickness at 1.5 mm. Heat and dehydrate it to solidify it on the first protective layer on the surface of the metal material. The heating temperature is 180°C. After the solidified protective layer is formed, let it stand for 7 hours.

[0065] Example 4

[0066] A method for preparing an anti-corrosion material for seawater equipment:

[0067] S1: 5 parts by weight of an antioxidant, 4 parts by weight of an antioxidant, 1 part by weight of nanosilver, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 20%;

[0068] S2: 2 parts by weight of a compatibilizer and 2 parts by weight of a silane coupling agent were added to a reactor and stirred to fully dissolve. Then, 28 parts by weight of fluorosilicone rubber and 22 parts by weight of polynonylene urea were added to the reactor in sequence and heated and stirred to obtain a first blank, wherein the heating temperature was 210° C.

[0069] S3: taking out the first blank and spraying it on the surface of the metal material to be protected to form a first protective layer, maintaining the spraying thickness at 1.5 mm, and then heating and dehydrating it to solidify it on the surface of the metal material, wherein the heating temperature is 195°C, and after forming the solidified protective layer, it is left to stand for 6 hours;

[0070] S4: 6 parts by weight of an antioxidant, 9 parts by weight of an antioxidant, 1.5 parts by weight of nano silver, 3 parts by weight of nano zinc oxide, 4.5 parts by weight of an ultraviolet absorber, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 15%;

[0071] S5: 4 parts by weight of a compatibilizer, 3 parts by weight of a silane coupling agent, and 8 parts by weight of a decomposition agent are added to a reactor and stirred to fully dissolve. Then, 30 parts by weight of a fluorosilicone rubber, 24 parts by weight of a polynonylene urea, and 28 parts by weight of an epoxy resin are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 215° C.

[0072] S6: Take out the second blank and spray it on the first protective layer on the surface of the protected metal material to form a second protective layer. Maintain the spraying thickness at 1.5 mm. Heat and dehydrate it to solidify it on the first protective layer on the surface of the metal material. The heating temperature is 185°C. After the solidified protective layer is formed, let it stand for 4 hours.

[0073] Example 5

[0074] A method for preparing an anti-corrosion material for seawater equipment:

[0075] S1: 15 parts by weight of an antioxidant, 12 parts by weight of an antioxidant, 3 parts by weight of nanosilver, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 35%;

[0076] S2: 3 parts by weight of a compatibilizer and 3 parts by weight of a silane coupling agent were added to a reactor and stirred to fully dissolve. 33 parts by weight of fluorosilicone rubber and 23 parts by weight of polynonylene urea were then added to the reactor in sequence and heated and stirred to obtain a first blank, wherein the heating temperature was 230° C.

[0077] S3: After taking out the first blank, spray it on the surface of the protected metal material to form a first protective layer, maintaining the spraying thickness at 1.5 mm, and then heat and dehydrate it to solidify it on the surface of the metal material, wherein the heating temperature is 200°C, and after forming the solidified protective layer, it is left to stand for 12 hours;

[0078] S4: 12 parts by weight of an antioxidant, 18 parts by weight of an antioxidant, 3 parts by weight of nano silver, 6 parts by weight of nano zinc oxide, 9 parts by weight of an ultraviolet absorber, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution with a water content of 30%;

[0079] S5: 5 parts by weight of a compatibilizer, 4 parts by weight of a silane coupling agent, and 13 parts by weight of a decomposition agent are added to a reactor and stirred to fully dissolve. Then, 38 parts by weight of fluorosilicone rubber, 28 parts of polynonylene urea, and 34 parts by weight of an epoxy resin are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 230° C.

[0080] S6: Take out the second blank and spray it on the first protective layer on the surface of the protected metal material to form a second protective layer. Maintain the spraying thickness at 1.5 mm. Heat and dehydrate it to solidify it on the first protective layer on the surface of the metal material. The heating temperature is 190°C. After the solidified protective layer is formed, let it stand for 10 hours.

[0081] Comparative Example 1

[0082] This comparative example adopts the preparation method of Example 3, except that the antioxidant is missing and the rest remains unchanged.

[0083] Comparative Example 2

[0084] This comparative example adopts the preparation method of Example 3, except that the antioxidant is missing, and the rest remains unchanged.

[0085] Comparative Example 3

[0086] This comparative example adopts the preparation method of Example 3, except that nanosilver is missing, and the rest remains unchanged.

[0087] Comparative Example 4

[0088] This comparative example adopts the preparation method of Example 3, except that nano zinc oxide is missing, and the rest remains unchanged.

[0089] Comparative Example 5

[0090] This comparative example adopts the preparation method of Example 3, except that the ultraviolet absorber is missing, and the rest remains unchanged.

[0091] Comparative Example 6

[0092] This comparative example adopts the preparation method of Example 3, except that the silane coupling agent is missing, and the rest remains unchanged.

[0093] Comparative Example 7

[0094] This comparative example adopts the preparation method of Example 3, except that the decomposing agent is missing, and the rest remains unchanged.

[0095] Comparative Example 8

[0096] This comparative example adopts the preparation method of Example 3, except that the fluorosilicone rubber is missing, and the rest remains unchanged.

[0097] Comparative Example 9

[0098] This comparative example adopts the preparation method of Example 3, except that polynonylene urea is missing, and the rest remains unchanged.

[0099] Comparative Example 10

[0100] This comparative example adopts the preparation method of Example 3, except that the epoxy resin is missing and the rest remains unchanged.

[0101] Comparative Example 11

[0102] In this comparative example, based on Example 3, the heating temperature in S3 is set to 160° C., and the rest remain unchanged.

[0103] Comparative Example 12

[0104] In this comparative example, based on Example 3, the moisture content in S4 is set to 35%, and the rest remain unchanged.

[0105] Comparative Example 13

[0106] In this comparative example, based on Example 3, the heating temperature in S5 is set to 250° C., and the rest remain unchanged.

[0107] Comparative Example 14

[0108] In this comparative example, based on Example 3, the nozzle thicknesses in S3 and S6 are both set to 0.8 mm.

[0109] Comparative Example 15

[0110] This comparative example is based on comparative example 3, except that the standing time in S6 is set to 2 h, and the rest remains unchanged.

[0111] Comparative Example 16

[0112] This comparative example is based on Example 3, except that the first protective layer and the second protective layer in Example 3 are swapped, and the rest remain unchanged. The specific steps are as follows:

[0113] S1: 8 parts by weight of an antioxidant, 10 parts by weight of an antioxidant, 2 parts by weight of nano silver, 4 parts by weight of nano zinc oxide, 6 parts by weight of an ultraviolet absorber, and water are added to a reactor and stirred thoroughly to obtain a mixed solution with a water content of 23%;

[0114] S2: 5 parts by weight of a compatibilizer, 3.5 parts by weight of a silane coupling agent, and 10 parts by weight of a decomposition agent were added to a reactor and stirred to fully dissolve. Then, 32.5 parts by weight of fluorosilicone rubber, 22.5 parts by weight of polynonylene urea, and 23.5 parts by weight of an epoxy resin were added to the reactor in sequence and heated and stirred to obtain a first blank, wherein the heating temperature was 200° C.

[0115] S3: After taking out the first blank, spray it on the surface of the metal material to be protected to form a first protective layer, maintaining the spraying thickness at 1.5 mm, and then heat and dehydrate it to solidify it on the surface of the metal material, wherein the heating temperature is 180°C, and after forming the solidified protective layer, it is left to stand for 7 hours;

[0116] S4: 10 parts by weight of an antioxidant, 8 parts by weight of an antioxidant, 2 parts by weight of nanosilver, and water are added to a reaction kettle and stirred thoroughly to obtain a mixed solution having a water content of 27%;

[0117] S5: 2 parts by weight of a compatibilizer and 2 parts by weight of a silane coupling agent are added to a reactor and stirred to fully dissolve, and then 25 parts by weight of fluorosilicone rubber and 20 parts by weight of polynonylene urea are added to the reactor in sequence and heated and stirred to obtain a second blank, wherein the heating temperature is 190° C.

[0118] S6: Take out the second blank and spray it on the first protective layer on the surface of the protected metal material to form a second protective layer. Maintain the spraying thickness at 1.5 mm. Heat and dehydrate it to solidify it on the first protective layer on the surface of the metal material. The heating temperature is 190°C. After the solidified protective layer is formed, let it stand for 9 hours.

[0119] Test example

[0120] First, the metal block to be sprayed (protected) is weighed m1. Then, according to the preparation method of the anti-corrosion material for seawater equipment provided in Examples 1 to 5 and Comparative Examples 1 to 16, a metal block sprayed with the new anti-corrosion material is obtained, and the weight is weighed m2. The metal block sprayed with the new anti-corrosion material is placed in a seawater environment (the seawater environment of Qingdao coast) (10-30°C) and served for 60 days. After that, it is taken out, cleaned, and dried, and then weighed again m3. The weight reduction ratio formula is:

[0121]

[0122] The calculated weight reduction ratio is recorded in Table 1, wherein the smaller the weight reduction, the better the corrosion resistance of the new material.

[0123] Table 1 Comparison of corrosion resistance of new materials prepared in Examples 1 to 5 and Comparative Examples 1 to 16

[0124] Weight reduction / % Example 1 0.29 Example 2 0.25 Example 3 0.21 Example 4 0.27 Example 5 0.24 Comparative Example 1 0.40 Comparative Example 2 0.37 Comparative Example 3 0.32 Comparative Example 4 0.33 Comparative Example 5 0.36 Comparative Example 6 0.41 Comparative Example 7 0.36 Comparative Example 8 0.37 Comparative Example 9 0.39 Comparative Example 10 0.41 Comparative Example 11 0.43 Comparative Example 12 0.35 Comparative Example 13 0.39 Comparative Example 14 0.37 Comparative Example 15 0.39 Comparative Example 16 0.43

[0125] According to Table 1, compared with the new materials prepared in Examples 1 to 5 and the new materials prepared in Comparative Examples 1 to 16, the weight reduction of the new anti-corrosion materials in the embodiments is less than the weight reduction of the new anti-corrosion materials in the comparative examples, and the weight reduction of the new anti-corrosion materials in the embodiments is less than 0.30%. Therefore, the new anti-corrosion material provided by the present invention has excellent corrosion resistance.

[0126] The present invention provides an anti-corrosion material for seawater equipment and a preparation method thereof. The anti-corrosion material has excellent anti-corrosion performance, UV resistance and sterilization performance, as well as excellent mechanical energy. The anti-corrosion material effectively extends the service life of equipment in seawater. The preparation method is simple and can be applied to metal equipment of various shapes and sizes, with a wide range of applications.

[0127] The basic principle, main features, formulation ratio, preparation process, main features and advantages of the present invention are shown and described above. The embodiments described should be understood to be merely illustrative of the present invention and not intended to limit the scope of the present invention. They are merely examples of formulation inventions, and the formulation ratios are merely reference ranges. The above embodiments and comparative examples are merely distances of the present invention and are not intended to limit the present invention. In addition, it should be understood that various changes or modifications made within the spirit and scope of the technical solutions of the present invention also fall within the scope protected by the present invention. The scheme described in the present invention is merely for illustrative purposes and should be understood to be the protection of the present invention for various ingredient ratios that appear in the formulation.

Claims

1. An anti-corrosion material for seawater equipment, characterized in that: The raw materials include, by weight: 43-75 parts of fluorosilicone rubber, 30-55 parts of polynonylene urea, 12-35 parts of epoxy resin, 4-10 parts of compatibilizer, 9-27 parts of antioxidant, 10-30 parts of antioxidant, 5-15 parts of decomposer, 2-6 parts of nano silver, 2-6 parts of nano zinc oxide, 3-9 parts of silane coupling agent, and 3-9 parts of ultraviolet absorber; The antioxidant is 2,6-di-tert-butyl-4-methoxyphenol, and the decomposition agent is terephthalate; The compatibilizer is cyclohexanol; The silane coupling agent is one of methyltrichlorosilane, aminosilane, vinylsilane, epoxysilane and allyltrimethylsilane; The particle size of the nano silver is 5 to 40 nm, and the particle size of the nano zinc oxide is 10 to 50 nm; The method for preparing the anti-corrosion material for seawater equipment comprises the following steps: S1: mixing antioxidant, antioxidant, nano silver and water to obtain a mixed solution; S2: adding a compatibilizer and a silane coupling agent to the mixed solution, and after fully dissolving, sequentially adding fluorosilicone rubber and polynonylene urea to the mixed solution, heating and stirring, to obtain a first blank; S3: placing the first blank on the surface of the metal material to be protected as a first protective layer with a thickness of 1 to 2 mm, heating and dehydrating the blank so that the blank is solidified on the surface of the metal material, and the solidified protective layer is allowed to stand for 6 to 12 hours; S4: mixing the antioxidant, antioxidant, nano silver, nano zinc oxide, ultraviolet absorber and water to obtain a mixed solution; S5: adding a compatibilizer, a silane coupling agent, and a decomposing agent to the mixed solution, and after fully dissolving, adding fluorosilicone rubber, polynonylene urea, and epoxy resin to the mixed solution in sequence, heating and stirring, to obtain a second blank; S6: placing the second blank on the first protective layer on the surface of the protected metal material as the second protective layer, maintaining a thickness of 1 to 2 mm, heating and dehydrating it to solidify it on the first protective layer on the surface of the metal material, and letting it stand for 4 to 10 hours after forming the solidified protective layer.

2. The anti-corrosion material for seawater equipment according to claim 1, characterized in that: The epoxy resin is bisphenol A epoxy resin; the antioxidant is one of amines, phenols, heterocycles, and phosphites; and the ultraviolet absorber is one of salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, and triazines.

3. The anti-corrosion material for seawater equipment according to claim 1, characterized in that: The mass ratio of the antioxidant in S1: the antioxidant in S4 is 5-15:4-12; the mass ratio of the antioxidant in S1: the antioxidant in S4 is 2-6:3-9; the mass ratio of the nanosilver in S1: the nanosilver in S4 is 1-3:1-3; the mass ratio of the compatibilizer in S2: the compatibilizer in S5 is 1-3:3-7; the mass ratio of the silane coupling agent in S2: the silane coupling agent in S5 is 1-4:2-5; the mass ratio of the fluorosilicone rubber in S2: the fluorosilicone rubber in S5 is 18-35:25-40; the mass ratio of the polynonylene urea in S2: the polynonylene urea in S5 is 3-5:3-6.

4. The anti-corrosion material for seawater equipment according to claim 1, characterized in that: The water content of the mixed liquid in S1 is 20-35%, and the water content of the mixed liquid in S4 is 15-30%.

5. The anti-corrosion material for seawater equipment according to claim 1, characterized in that: The heating temperature in S2 is 150-240°C, and the heating temperature in S5 is 160-230°C.

6. The anti-corrosion material for seawater equipment according to claim 1, characterized in that: The heating temperature in S3 is 180-200°C, and the heating temperature in S5 is 170-195°C.

7. The anti-corrosion material for seawater equipment according to claim 1, characterized in that: In S1, the weight ratio of the antioxidant, antioxidant and nano silver is 3-6:3-5:1-2; in S4, the weight ratio of the antioxidant, antioxidant, nano silver, nano zinc oxide and ultraviolet absorber is 3-5:4-8:1-2:1-3:2-5.