A stainless steel surface anti-corrosion treatment agent and preparation method thereof

Abstract

The present invention relates to the technical field of stainless steel surface treatment, specifically to an anti-corrosion treatment agent for stainless steel surfaces and a preparation method thereof. The preparation comprises the following components by weight: 3-5 parts modified microspheres and 2-3 parts modified polymer. The resulting anti-corrosion treatment agent effectively resists corrosion through the synergistic effect of the modified microspheres and the modified polymer.

Description

Technical Field

[0001] The invention relates to the technical field of stainless steel surface treatment, and in particular to a stainless steel surface anti-corrosion treatment agent and a preparation method thereof. Background Art

[0002] Stainless steel, a widely used industrial material, is employed in various fields of society due to its numerous advantages, including superior wear resistance and corrosion resistance. However, corrosion of stainless steel remains a common occurrence in many corrosive environments. Chemical treatment methods can form a corrosion-resistant conversion film on the surface of stainless steel, essentially leaving the surface appearance unchanged. To improve the corrosion resistance of stainless steel, a protective layer is required. For example, patent application CN102899653A discloses a method for chemically passivating stainless steel using a mixture of ammonium molybdate, aminosulfonic acid, organophosphoric acid, and sodium citrate. Although the resulting oxide film is a chromium-free conversion film, its corrosion resistance is poor and cannot meet the salt resistance requirements of stainless steel. The surface is easily corroded and oxidized again in air. Traditional surface treatment techniques, such as electroless nickel plating and thermal spraying, have certain limitations. For example, while electroless nickel plating can improve surface corrosion resistance, its protective effect may be insufficient under extreme conditions such as high temperature and high pressure. Therefore, it is of great significance to develop a treatment agent with stable performance that significantly improves the corrosion resistance of stainless steel. Summary of the Invention

[0003] In view of the shortcomings of the prior art, the present invention provides a stainless steel surface anti-corrosion treatment agent and a preparation method thereof.

[0004] The present invention is achieved through the following technical solutions:

[0005] A stainless steel surface anti-corrosion treatment agent is prepared from raw materials comprising the following components in parts by weight: 3-5 parts of modified microspheres and 2-3 parts of modified polymers.

[0006] Furthermore, the raw materials for preparing the modified microspheres include the following components in parts by weight: 2-3 parts of 1,3-propanedithiol, 1.4-2.1 parts of propargyl glycidyl ether, 0.32-0.48 parts of 1,7-octanediyne, 0.15-0.2 parts of dimethyl benzoate (DMPA), and 0.15-0.2 parts of polyethylene glycol (PEG, M n =10000 g / mol) 1.2-1.8 parts, mercaptoethanol 1-1.5 parts, hexamethylene diisocyanate (HDI) 4-6 parts.

[0007] Furthermore, the preparation method of the modified microspheres comprises the following steps:

[0008] L1. Mix 1,3-propanedithiol, propargyl glycidyl ether, 1,7-octanediyne, DMPA, PEG, and chloroform, seal the container, stir to dissolve, and then add the mixture dropwise to a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate (SDBS). Bubble the mixture with high-purity nitrogen for 40-60 minutes. Irradiate the mixture with continuous UV light (λ=365 nm) at 0°C for 2 hours. Wash the mixture with water, tetrahydrofuran (THF), and methanol, sequentially, and dry it in a vacuum at 30-40°C.

[0009] L2 The product obtained in step L1 was mixed with water and mercaptoethanol, and the pH was adjusted to 11 with 1 M NaOH solution. The reaction was stirred magnetically for 24 h, centrifuged at 14000 r / min for 5 min, and the precipitate was washed with deionized water and dried in vacuo;

[0010] L3. In an 80°C water bath, add HDI to toluene with stirring to obtain an HDI solution. Add the product from step L2 and stannous octoate (SO) to toluene, mix thoroughly, and then add dropwise to the HDI solution. After the addition is complete, continue incubating for 2-3 hours. Centrifuge, wash the precipitate with toluene, and vacuum dry to obtain modified microspheres.

[0011] Furthermore, in step L1, the mass ratio of chloroform to PEG is 5-6:1.

[0012] Furthermore, in step L1, the ratio of the SDBS aqueous solution to 1,3-propanedithiol is 25 mL:1 g.

[0013] Furthermore, in step L2, the ratio of mercaptoethanol to water is 2 mg:1 mL.

[0014] Furthermore, in step L3, the mass concentration of HDI in toluene is 0.2-0.3 g / mL.

[0015] Furthermore, in step L3, the amount of SO used is 0.8-1 wt % of HDI.

[0016] Furthermore, in step L3, the mass concentration of SO in toluene is 1 mg / mL.

[0017] Furthermore, the raw materials for preparing the modified polymer include the following components in parts by weight: 6-9 parts of N,N'-methylenebisacrylamide (MBA), 4-6 parts of butanediamine (BDA), 1.2-1.8 parts of 4,4'-diaminodicyclohexylmethane (HMDA), and 0.8-1.2 parts of 3,4-dihydroxyphenylpropionic acid (DHCA).

[0018] Furthermore, the preparation method of the modified polymer comprises the following steps:

[0019] V1. Add MBA to a mixture of methanol and deionized water (v:v = 2:1) and stir at 30°C to dissolve. Add BDA and HMDA and stir at 30°C for 24 h. Pour into acetone and centrifuge. Wash the precipitate with acetone and dry in a vacuum at 30-40°C.

[0020] V2. The product from step V1 was added to a chloroform / DMF mixture (v:v = 2:1) and mixed thoroughly. DHCA, N-hydroxybenzotriazole (HOBt), HBTU, and triethylamine were added and reacted for 1 h. The solvent was removed under reduced pressure, the mixture was washed with acetone, and vacuum dried to obtain a modified polymer.

[0021] Furthermore, in step V1, the mass concentration of the MBA in the methanol / deionized water mixture is 80-100 mg / mL.

[0022] Furthermore, in step V1, the volume ratio of the acetone to the methanol / deionized water mixture is 8-10:1.

[0023] Furthermore, in step V2, the mass ratio of DHCA, HOBt and HBTU is 2-3:1.5-2.2:4.2-6.2.

[0024] Furthermore, in step V2, the usage ratio of DHCA to triethylamine is 1 g:1.1 mL.

[0025] Furthermore, in step V2, the mass concentration of DHCA in the chloroform / DMF mixture is 5 mg / mL.

[0026] Furthermore, the present invention also provides a method for preparing the stainless steel surface anti-corrosion treatment agent, comprising the following steps:

[0027] S1. The stainless steel surface was repeatedly polished with 400-grit sandpaper, rinsed with water and ethanol, air-dried, and then cleaned with oxygen plasma for 20 min.

[0028] S2. The modified polymer was added to deionized water and stirred to mix, and the stainless steel was added after step S1 treatment, and the reaction was continued for 12 h. After removal, the mixture was washed with water and ethanol and dried under a stream of nitrogen;

[0029] S3: After step S2 is completed, stainless steel is added to toluene, modified microspheres are added, stirred for reaction for 1 h, washed with water and ethanol, and dried with nitrogen to obtain a stainless steel surface anti-corrosion treatment agent.

[0030] Furthermore, in step S2, the mass concentration of the modified polymer in deionized water is 5 mg / mL.

[0031] Furthermore, in step S2, the mass ratio of the surface area of ​​the stainless steel to the modified polymer is 1 cm 2 :25-30mg.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] The present invention provides a stainless steel surface anti-corrosion treatment agent. Through the synergistic effect of modified microspheres and modified polymers, a protective layer with high corrosion resistance, strong bonding force and excellent mechanical properties is constructed on the stainless steel surface. The present invention prepares modified microspheres. 1,3-propanedithiol, propargyl glycidyl ether and 1,7-octanediyne are used as reaction monomers to synthesize polysulfide polymer microspheres by mercapto-alkyne click reaction. The active groups such as thiol and alkyne are polymerized by ultraviolet light, cross-linked to form a microsphere structure, and form a physical barrier on the stainless steel surface to block corrosive media (such as Cl - , O2) penetration. The surface of the obtained microspheres contains epoxy groups, which can react with mercaptoethanol to introduce hydroxyl functional groups on the microspheres. The HDI isocyanate group can react with the hydroxyl group. The isocyanate group introduced on the microspheres can be cross-linked with the amino group in the modified polymer to construct a "microsphere-polymer-metal" three-dimensional network structure and enhance the interface bonding strength. The present invention uses N,N'-methylenebisacrylamide, dibutyleneamine and 4,4'-diaminodicyclohexylmethane as monomers for polymerization reaction to form an amino-terminated polymer. On the one hand, it can react with the isocyanate group in the modified microspheres so that the modified polymer and the modified microspheres are covalently bonded to construct a three-dimensional cross-linked network. The two work together to form a composite protective layer of "polymer + microspheres" to effectively block the penetration of corrosive media; on the other hand, it can undergo an amidation reaction with the carboxyl group of 3,4-dihydroxyphenylpropionic acid, introduce a catechol group into the modified polymer, and firmly bond with the hydroxylated layer on the surface of stainless steel to enhance the interface bonding strength. At the same time, the polymer main chain is hydrogen bonded with the stainless steel oxide layer to achieve molecular-level anchoring. Oxygen plasma treatment of the stainless steel surface creates a large number of hydroxyl (-OH) groups and unsaturated bonds, providing more reaction sites for the treatment agent and significantly improving the coating's adhesion. The modified microspheres and modified polymer form an interpenetrating network structure. The microspheres act as physical crosslinks to enhance the coating's hardness, while the polymer segments impart deformation resistance. When subjected to friction or wear, the network dissipates energy through segment slippage, minimizing coating damage. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only for the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0035] Figure 1 The anti-corrosion effect of the treatment agents described in Examples 1-3 and Comparative Examples 1-4 of the present invention;

[0036] Figure 2 The results of tape peeling tests of the treatment agents described in Example 1 and Comparative Example 4 of the present invention are shown;

[0037] Figure 3 These are the sandpaper abrasion test results of the treatment agents described in Example 1 of the present invention and Comparative Examples 1-3. DETAILED DESCRIPTION

[0038] In order to make the purpose, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below in conjunction with specific examples, but the present invention is not limited to the following examples. It should be noted that, unless otherwise specified, the chemical reagents involved in the present invention were purchased through commercial channels.

[0039] Example 1: A stainless steel surface anti-corrosion treatment agent, prepared by raw materials including the following components in parts by weight: 5 parts of modified microspheres and 3 parts of modified polymer.

[0040] The raw materials for preparing the modified microspheres include the following components in parts by weight: 3 parts of 1,3-propanedithiol, 2.1 parts of propargyl glycidyl ether, 0.48 parts of 1,7-octanediyne, 0.2 parts of dimethyl benzoate (DMPA), 0.2 parts of polyethylene glycol (PEG, M n =10000 g / mol) 1.8 parts, mercaptoethanol 1.5 parts, hexamethylene diisocyanate (HDI) 6 parts.

[0041] The preparation method of the modified microspheres comprises the following steps:

[0042] L1. Combine 3 g of 1,3-propanedithiol, 2.1 g of propargyl glycidyl ether, 0.48 g of 1,7-octanediyne, 0.2 g of DMPA, 1.8 g of PEG, and 10.8 g of chloroform. Seal the container and stir to dissolve. Add the mixture dropwise to 75 mL of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate (SDBS). Bubble high-purity nitrogen gas for 60 min. Irradiate the mixture with continuous ultraviolet light (λ = 365 nm) at 0°C for 2 h. Wash the mixture with water, tetrahydrofuran (THF), and methanol, sequentially, and dry in a vacuum at 40°C.

[0043] L2 The product obtained in step L1 was mixed with 750 mL of water and 1.5 g of mercaptoethanol, and the pH was adjusted to 11 with 1 M NaOH solution. The reaction was stirred magnetically for 24 h, centrifuged at 14000 r / min for 5 min, and the precipitate was washed with deionized water and dried in vacuo.

[0044] L3. In an 80°C water bath, add 6 parts of HDI to 20 mL of toluene with stirring to obtain an HDI solution. Add the product from step L2 and 60 mg of stannous octoate (SO) to 60 mL of toluene, mix thoroughly, and add the mixture dropwise to the HDI solution. After the addition is complete, continue incubating for 3 hours. Centrifuge, wash the precipitate with toluene, and vacuum dry to obtain modified microspheres.

[0045] The raw materials for preparing the modified polymer include the following components in parts by weight: 9 parts of N,N'-methylenebisacrylamide (MBA), 6 parts of butanediamine (BDA), 1.8 parts of 4,4'-diaminodicyclohexylmethane (HMDA), and 1.2 parts of 3,4-dihydroxyphenylpropionic acid (DHCA).

[0046] The preparation method of the modified polymer comprises the following steps:

[0047] V1. Add 9 g of MBA to 90 mL of a methanol / deionized water (v:v = 2:1) mixture and stir at 30°C to dissolve. Add 6 g of BDA and 1.8 g of HMDA and stir at 30°C for 24 h. Pour into 900 mL of acetone and centrifuge. Wash the precipitate with acetone and dry in a vacuum at 40°C.

[0048] V2. The product from step V1 was added to 240 mL of a chloroform / DMF (v:v = 2:1) mixture and mixed thoroughly. 1.2 g of DHCA, 0.88 g of N-hydroxybenzotriazole (HOBt), 2.48 g of HBTU, and 1.32 mL of triethylamine were added. The mixture was reacted for 1 h. The solvent was removed under reduced pressure, the mixture was washed with acetone, and vacuum dried to obtain a modified polymer.

[0049] This embodiment also provides a method for preparing the stainless steel surface anti-corrosion treatment agent, comprising the following steps:

[0050] S1. Place stainless steel (surface area 100 cm 2 ) The surface was repeatedly polished with 400-grit sandpaper, rinsed with water and ethanol, dried in air, and cleaned with oxygen plasma for 20 min;

[0051] S2. The modified polymer was added to 600 mL of deionized water and stirred, and then placed on the stainless steel treated in step S1. The reaction was continued for 12 h, and the mixture was washed with water and ethanol and dried under a stream of nitrogen.

[0052] S3: After step S2 is completed, stainless steel is added to toluene, 5 g of modified microspheres are added, the mixture is stirred for reaction for 1 h, washed with water and ethanol, and dried with nitrogen to obtain a stainless steel surface anti-corrosion treatment agent.

[0053] Example 2: A stainless steel surface anti-corrosion treatment agent, prepared by preparing raw materials including the following components in parts by weight: 3 parts of modified microspheres and 2 parts of modified polymer.

[0054] The raw materials for preparing the modified microspheres include the following components in parts by weight: 2 parts of 1,3-propanedithiol, 1.4 parts of propargyl glycidyl ether, 0.32 parts of 1,7-octanediyne, 0.15 parts of dimethyl benzoate (DMPA), 0.15 parts of polyethylene glycol (PEG, M n =10000g / mol) 1.2 parts, mercaptoethanol 1 part, hexamethylene diisocyanate (HDI) 4 parts.

[0055] The preparation method of the modified microspheres comprises the following steps:

[0056] L1. Combine 2 g of 1,3-propanedithiol, 1.4 g of propargyl glycidyl ether, 0.32 g of 1,7-octanediyne, 0.15 g of DMPA, 1.2 g of PEG, and 6 g of chloroform. Seal the mixture, stir to dissolve, and add dropwise to 50 mL of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate (SDBS). Bubble high-purity nitrogen gas for 40 min. Irradiate the mixture with continuous ultraviolet light (λ = 365 nm) at 0°C for 2 h. Wash the mixture with water, tetrahydrofuran (THF), and methanol, sequentially, and dry in a vacuum at 30°C.

[0057] L2. The product obtained in step L1 was mixed with 500 mL of water and 1 g of mercaptoethanol, and the pH was adjusted to 11 with 1 M NaOH solution. The reaction was stirred magnetically for 24 h, centrifuged at 14,000 r / min for 5 min, and the precipitate was washed with deionized water and dried in vacuo.

[0058] L3. In an 80°C water bath, add 4 g of HDI to 20 mL of toluene with stirring to obtain an HDI solution. Add the product from step L2 and 32 mg of stannous octoate (SO) to 32 mL of toluene, mix thoroughly, and add the mixture dropwise to the HDI solution. After the addition is complete, continue incubating for 2 h. Centrifuge, wash the precipitate with toluene, and dry in vacuo to obtain modified microspheres.

[0059] The raw materials for preparing the modified polymer include the following components in parts by weight: 6 parts of N,N'-methylenebisacrylamide (MBA), 4 parts of butanediamine (BDA), 1.2 parts of 4,4'-diaminodicyclohexylmethane (HMDA), and 0.8 parts of 3,4-dihydroxyphenylpropionic acid (DHCA).

[0060] The preparation method of the modified polymer comprises the following steps:

[0061] V1. Add 6 g of MBA to 75 mL of a methanol / deionized water (v:v = 2:1) mixture and stir at 30°C to dissolve. Add 4 g of BDA and 1.2 g of HMDA and stir at 30°C for 24 h. Pour into 600 mL of acetone and centrifuge. Wash the precipitate with acetone and dry in a vacuum at 30°C.

[0062] V2. The product from step V1 was added to 160 mL of a chloroform / DMF (v:v = 2:1) mixture and mixed thoroughly. 0.8 g of DHCA, 0.6 g of N-hydroxybenzotriazole (HOBt), 1.68 g of HBTU, and 0.88 mL of triethylamine were added. The mixture was reacted for 1 h. The solvent was removed under reduced pressure, the mixture was washed with acetone, and vacuum dried to obtain a modified polymer.

[0063] This embodiment also provides a method for preparing the stainless steel surface anti-corrosion treatment agent, comprising the following steps:

[0064] S1. Stainless steel (surface area 80 cm 2 ) The surface was repeatedly polished with 400-grit sandpaper, rinsed with water and ethanol, dried in air, and cleaned with oxygen plasma for 20 min;

[0065] S2. The modified polymer was added to 400 mL of deionized water and stirred, and then placed on the stainless steel treated in step S1. The reaction was continued for 12 h, and the mixture was washed with water and ethanol and dried under a stream of nitrogen.

[0066] S3: After step S2 is completed, stainless steel is added to toluene, 3 g of modified microspheres are added, the mixture is stirred for reaction for 1 h, washed with water and ethanol, and dried with nitrogen to obtain a stainless steel surface anti-corrosion treatment agent.

[0067] Example 3: A stainless steel surface anti-corrosion treatment agent, prepared by preparing raw materials including the following components in parts by weight: 4 parts of modified microspheres and 2.5 parts of modified polymer.

[0068] The raw materials for preparing the modified microspheres include the following components in parts by weight: 2.5 parts of 1,3-propanedithiol, 1.6 parts of propargyl glycidyl ether, 0.4 parts of 1,7-octanediyne, 0.18 parts of dimethyl benzoate (DMPA), and 0.18 parts of polyethylene glycol (PEG, M n =10000g / mol) 1.5 parts, mercaptoethanol 1.2 parts, hexamethylene diisocyanate (HDI) 5 parts.

[0069] The preparation method of the modified microspheres comprises the following steps:

[0070] L1. Combine 2.5 g of 1,3-propanedithiol, 1.6 g of propargyl glycidyl ether, 0.4 g of 1,7-octanediyne, 0.18 g of DMPA, 1.5 g of PEG, and 8.5 ml of chloroform. Seal the container and stir to dissolve. Add the mixture dropwise to 62.5 mL of a 5 wt% aqueous solution of sodium dodecylbenzenesulfonate (SDBS). Bubble high-purity nitrogen gas for 50 min. Irradiate the mixture with continuous ultraviolet light (λ = 365 nm) at 0°C for 2 h. Wash the mixture with water, tetrahydrofuran (THF), and methanol, sequentially, and dry in a vacuum at 30-40°C.

[0071] L2 The product obtained in step L1 was mixed with 600 mL of water and 1.2 g of mercaptoethanol, and the pH was adjusted to 11 with 1 M NaOH solution. The reaction was stirred magnetically for 24 h, centrifuged at 14000 r / min for 5 min, and the precipitate was washed with deionized water and dried in vacuo;

[0072] L3. In an 80°C water bath, add 5 g of HDI to 20 mL of toluene with stirring to obtain an HDI solution. Add the product from step L2 and 45 mg of stannous octoate (SO) to 45 mL of toluene, mix thoroughly, and add the mixture dropwise to the HDI solution. After the addition is complete, continue incubating for 2.5 h. Centrifuge, wash the precipitate with toluene, and dry in vacuo to obtain modified microspheres.

[0073] The raw materials for preparing the modified polymer include the following components in parts by weight: 7.5 parts of N,N'-methylenebisacrylamide (MBA), 5 parts of butanediamine (BDA), 1.5 parts of 4,4'-diaminodicyclohexylmethane (HMDA), and 1 part of 3,4-dihydroxyphenylpropionic acid (DHCA).

[0074] The preparation method of the modified polymer comprises the following steps:

[0075] V1. Add 7.5 g of MBA to 80 mL of a mixture of methanol and deionized water (v:v = 2:1) and stir at 30°C to dissolve. Add 5 g of BDA and 1.5 g of HMDA and stir at 30°C for 24 h. Pour into 720 mL of acetone and centrifuge. Wash the precipitate with acetone and dry it in a vacuum at 35°C.

[0076] V2. The product from step V1 was added to 200 mL of a chloroform / DMF (v:v = 2:1) mixture and mixed thoroughly. 1 g of DHCA, 0.72 g of N-hydroxybenzotriazole (HOBt), 2.08 g of HBTU, and 1.1 mL of triethylamine were added. The reaction was allowed to proceed for 1 h. The solvent was removed under reduced pressure, the mixture was washed with acetone, and vacuum dried to obtain a modified polymer.

[0077] This embodiment also provides a method for preparing the stainless steel surface anti-corrosion treatment agent, comprising the following steps:

[0078] S1. Stainless steel (surface area 90 cm 2 ) The surface was repeatedly polished with 400-grit sandpaper, rinsed with water and ethanol, dried in air, and cleaned with oxygen plasma for 20 min;

[0079] S2. The modified polymer 2.5 g was added to 500 mL of deionized water and stirred to mix, and then placed in the stainless steel treated in step S1, and the reaction was continued for 12 h. After removal, the mixture was washed with water and ethanol and dried under a stream of nitrogen.

[0080] S3: After step S2 is completed, stainless steel is added to toluene, 4 g of modified microspheres are added, the mixture is stirred for reaction for 1 h, washed with water and ethanol, and dried with nitrogen to obtain a stainless steel surface anti-corrosion treatment agent.

[0081] The only difference between Comparative Example 1 and Example 1 is that no modified microspheres are added.

[0082] The only difference between Comparative Example 2 and Example 1 is that the modified microspheres are replaced by the product obtained in step L2.

[0083] The only difference between Comparative Example 3 and Example 1 is that no modified polymer is added, and steps S1-S2 are replaced by the following steps: the stainless steel surface is repeatedly polished with 400-grit sandpaper, rinsed with water and ethanol, dried in air, cleaned with oxygen plasma for 20 min, and placed in a Tris-HCl (pH = 8.5) solution with a dopamine hydrochloride concentration of 2 mg / mL. After 12 h, the surface is removed and rinsed with distilled water and dried.

[0084] The only difference between Comparative Example 4 and Example 1 is that the product obtained in Step V1 is used instead of the modified polymer.

[0085] Experimental Example 1: 316L stainless steel with a thickness of 1 mm was cut into 10 mm × 10 mm squares and the surfaces were treated according to the methods of Examples 1-3 and Comparative Examples 1-4. Artificial seawater was prepared according to the chemical composition in Table 1. The samples of Examples 1-3 and Comparative Examples 1-4 were placed in a container of seawater and soaked for 14 days (336 hours). Before the experiment began, the surface-treated samples were weighed. The seawater solution was replaced once a week during the experiment. After the experiment, the sample surface was cleaned with a soft brush and pickled. The pickling solution was 100 mL of 1.42 g / mL HNO3 solution mixed with 20 mL of 1.155 g / mL HF, and distilled water was added to make 1000 mL of pickling solution. The pickling temperature was 25°C and the pickling time was 5 minutes until the surface was bright. After drying, the samples were weighed and the corrosion rate (V) was calculated. V=△w×87600 / STD, △w is the mass loss of the sample before and after the test (g); S is the total surface area of ​​the sample before corrosion (cm2 ), T is the test time (h), D is the density of the material (g / cm 3 ). The result is as follows Figure 1 shown.

[0086] Table 1:

[0087]

[0088] Figure 1 The results showed that the corrosion rates of Examples 1-3 were lower than those of Comparative Examples 1-4, demonstrating better corrosion resistance. Comparative Example 1 did not add modified microspheres, resulting in reduced corrosion resistance. Comparative Example 2 did not modify the microspheres, resulting in poor fixation of the microspheres to the stainless steel surface and reduced corrosion resistance. Comparative Example 3 replaced the modified polymer with a polydopamine coating, resulting in reduced protection for the stainless steel surface and decreased corrosion resistance. Comparative Example 4 did not modify the polymer, resulting in reduced adhesion between the coating and the stainless steel surface and reduced corrosion resistance.

[0089] Experimental Example 2: Referring to ASTM D3359-09 Standard Method B, a sharp blade was used to scratch the stainless steel surfaces treated in Example 1 and Comparative Example 4 in both the vertical and horizontal directions with a spacing of 2 mm. 3 μm tape was then applied to the coating surface. The tape was pressed tightly with a 500 g weight and peeled off from the coating surface at 180°. The change in water contact angle was recorded after every 5 times. The results are shown in Figure 2. Figure 2 shown.

[0090] Figure 2 The results show that the water contact angle of Example 1 group does not change much after the surface peeling test, while the water contact angle of Comparative Example 4 group changes more than that of Example 1. The anti-corrosion treatment agent of the present invention has good bonding strength and mechanical properties on the stainless steel surface, and can better resist corrosion.

[0091] Experimental Example 3: The treated stainless steel of Example 1 and Comparative Examples 1-3 was abraded using 1000 grit sandpaper with a load of 100 g. The water contact angle change was recorded every 25 times by alternating 90° horizontal movements of 10 cm (total length 20 cm). The results are shown in the figure. Figure 3 shown.

[0092] Figure 3 The results show that after being abraded by sandpaper, the change in the water contact angle of Example 1 is smaller than that of Comparative Examples 1-3, indicating that the anti-corrosion treatment agent of the present invention has strong mechanical properties and is wear-resistant.

[0093] Those skilled in the art should understand that the discussion of any of the above embodiments is merely illustrative and is not intended to imply that the scope of the present invention is limited to these examples. Within the scope of the present invention, the technical features in the above embodiments or different embodiments may be combined, the steps may be implemented in any order, and there are many other variations of the different aspects of the present invention as described above, which are not provided in detail for the sake of simplicity.

Claims

1. A stainless steel surface anti-corrosion treatment agent, characterized in that: The raw materials for preparation include the following components in parts by weight: 3-5 parts of modified microspheres and 2-3 parts of modified polymer; The raw materials for preparing the modified microspheres include the following components in parts by weight: 2-3 parts of 1,3-propanedithiol, 1.4-2.1 parts of propargyl glycidyl ether, 0.32-0.48 parts of 1,7-octanediyne, 0.15-0.2 parts of benzoin dimethyl ether, 1.2-1.8 parts of PEG, 1-1.5 parts of mercaptoethanol, and 4-6 parts of hexamethylene diisocyanate; The preparation method of the modified microspheres comprises the following steps: L1. 1,3-propanedithiol, propargyl glycidyl ether, 1,7-octanediyne, benzoin dimethyl ether, PEG and chloroform were mixed, sealed, stirred, and added dropwise to a 5wt% aqueous solution of sodium dodecylbenzenesulfonate, bubbling with nitrogen, irradiating with UV light, washing, and drying; L2 The product obtained in step L1 was mixed with water and mercaptoethanol, the pH was adjusted, stirred, centrifuged, washed, and dried; L3. In an 80°C water bath, hexamethylene diisocyanate was added to toluene to obtain a hexamethylene diisocyanate solution. The product obtained in step L2 and stannous octoate were added to toluene and mixed, and then added dropwise to the hexamethylene diisocyanate solution. The mixture was incubated, centrifuged, washed, and dried to obtain modified microspheres. The raw materials for preparing the modified polymer include the following components in parts by weight: 6-9 parts of N,N'-methylenebisacrylamide, 4-6 parts of butanediamine, 1.2-1.8 parts of 4,4'-diaminodicyclohexylmethane, and 0.8-1.2 parts of 3,4-dihydroxyphenylpropionic acid; The preparation method of the modified polymer comprises the following steps: V1. Add N,N'-methylenebisacrylamide to a methanol / deionized water mixture and stir. Then add diaminodiamine and 4,4'-diaminodicyclohexylmethane. Stir and pour into acetone to precipitate. Dry. V2. The product obtained in step V1 was added to a chloroform / DMF mixture and mixed evenly. 3,4-dihydroxyphenylpropionic acid, HOBt, HBTU and triethylamine were added, reacted, washed and dried to obtain a modified polymer.

2. The stainless steel surface anti-corrosion treatment agent according to claim 1, characterized in that In step L1, the mass ratio of chloroform to PEG is 5-6:1; the amount ratio of sodium dodecylbenzenesulfonate aqueous solution to 1,3-propanedithiol is 25 mL:1 g.

3. The stainless steel surface anti-corrosion treatment agent according to claim 2, characterized in that: In step L3, the mass concentration of hexamethylene diisocyanate in toluene is 0.2-0.3 g / mL; the amount of stannous octoate used is 0.8-1wt% of hexamethylene diisocyanate; and the mass concentration of stannous octoate in toluene is 1 mg / mL.

4. The stainless steel surface anti-corrosion treatment agent according to claim 3, characterized in that In step V2, the mass ratio of the 3,4-dihydroxyphenylpropionic acid, HOBt, and HBTU is 2-3:1.5-2.2:4.2-6.2; the amount ratio of 3,4-dihydroxyphenylpropionic acid to triethylamine is 1 g:1.1 mL; and the mass concentration of 3,4-dihydroxyphenylpropionic acid in the chloroform / DMF mixture is 5 mg / mL.

5. A method for preparing the stainless steel surface anti-corrosion treatment agent according to any one of claims 1 to 4, characterized in that: The following steps are involved: S1. The stainless steel surface was sanded, rinsed with water and ethanol, air-dried, and then cleaned with oxygen plasma. S2. The modified polymer was added to deionized water and stirred to mix, and then placed in stainless steel after treatment in step S1, reacted, washed, and dried; S3: After step S2 is completed, stainless steel is added to toluene, modified microspheres are added, reacted, washed, and dried to obtain a stainless steel surface anti-corrosion treatment agent.

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