Siloxane modified terpyridyl anti-corrosion additive and application thereof in preparation of intrinsic metal anti-corrosion epoxy resin coating

Abstract

The invention discloses a siloxane modified terpyridyl corrosion-resistant auxiliary agent and application thereof in preparation of an intrinsic metal corrosion-resistant epoxy resin coating, the structural formula of the siloxane modified terpyridyl corrosion-resistant auxiliary agent is # imgabs0, a terpyridyl structure is introduced, and the siloxane modified terpyridyl corrosion-resistant auxiliary agent has an efficient metal corrosion-resistant effect; the physical state of metal in the corrosion process can be changed by taking the strong coordination effect of terpyridyl as driving force, so that long-term corrosion prevention is realized; a terpyridyl structure is introduced into the epoxy resin, a rigid structure of a benzene ring and heterocyclic nitrogen atoms can form hydrogen bonds with side hydroxyl groups of the epoxy resin, the durability and corrosion resistance of the epoxy resin are greatly improved, and a siloxane structure on a main chain improves the flexibility of a molecular chain and improves the hydrophobicity of the epoxy resin.

Description

Technical Field

[0001] The invention relates to the technical field of metal anticorrosion functional coatings, and in particular to a siloxane-modified terpyridine anticorrosion aid and application thereof in preparing an intrinsic metal anticorrosion epoxy resin coating. Background Art

[0002] Metal corrosion is very common, such as rusting of iron products (Fe2O3·xH2O), white spots on the surface of aluminum products (Al2O3), verdigris on the surface of copper products [Cu2(OH)2CO3], and blackening of the surface of silver products (Ag2S, Ag2O). These are all metal corrosion, among which the corrosion of iron products, the metal with the largest usage, is the most common. Metal corrosion is everywhere. With the rapid development of my country's economy, it has received more and more attention in recent years. Metal corrosion will bring huge equipment maintenance costs, and severe corrosion has caused significant economic losses. Therefore, anti-corrosion is imminent, and the application of anti-corrosion coatings is an important measure to reduce the corrosion of metal surfaces. Therefore, it is extremely necessary to improve the service life of metal devices by studying anti-corrosion coatings. As a common metal ion ligand, terpyridine can chelate with metal ions to form complexes. The strong coordination effect between terpyridine and metal ions also has great potential in the field of corrosion protection. The existing technology forms a new type of intrinsic epoxy resin anti-corrosion coating through the reaction of terpyridine derivatives with epichlorohydrin. The strong coordination effect of terpyridine is used as the driving force to change the physical state of the metal during the corrosion process, thereby achieving long-term corrosion protection.

[0003] Epoxy resin (EP) is widely used in anti-corrosion coatings because of its high chemical resistance, excellent toughness, good barrier properties and high adhesion to metal surfaces. However, after the epoxy resin is cured, microscopic defects will appear due to solvent volatilization, which will reduce the anti-corrosion performance of the epoxy coating and make it difficult to achieve long-term anti-corrosion effects. Therefore, it is necessary to add corrosion inhibitors to improve the anti-corrosion performance of the epoxy resin.

[0004] In recent years, the applicant has been committed to the research of improving the anti-corrosion ability of epoxy coatings and has achieved certain results. The application of WO2022205522A1 discloses a serialized terpyridine epoxy resin, in which the nitrogen atom of the pyridine group can form a strong coordination bond with the metal atom of the substrate, which can be used for high-efficiency anti-corrosion coatings, and the introduction of epoxy groups and alkanes effectively improves the adhesion of the anti-corrosion coating. However, this technical solution introduces terpyridine monomers with excessive polarity and steric hindrance, which will cause the toughness and hydrophobicity of the coating to decrease to a certain extent compared with pure epoxy resin. Summary of the invention

[0005] The purpose of the present invention is to overcome the defects of the prior art and provide a siloxane-modified terpyridine antiseptic additive.

[0006] Another object of the present invention is to provide a method for preparing the above-mentioned siloxane-modified terpyridine antiseptic additive.

[0007] Another object of the present invention is to provide an application of the above-mentioned siloxane-modified terpyridine antiseptic additive.

[0008] The technical solution of the present invention is as follows:

[0009] A siloxane-modified terpyridine antiseptic additive, the structural formula of which is

[0010]

[0011] The preparation method of the above-mentioned siloxane-modified terpyridine antiseptic auxiliary agent comprises the following steps:

[0012] (1) dissolving a nitro compound and 2-acetylpyridine in methanol at a molar ratio of 1:1-5, wherein the concentration of the nitro compound in methanol is 0.5-15 mg / mL; then adding concentrated aqueous ammonia and potassium hydroxide solution, wherein the volume ratio of concentrated aqueous ammonia to methanol is 0.5-1.5:1, and the volume ratio of potassium hydroxide solution to methanol is 0.01-0.2:1; stirring at room temperature for 2-4 days, filtering and drying to obtain a nitro-containing terpyridine derivative monomer; mixing the nitro-containing terpyridine derivative monomer and stannous chloride hydrate at a molar ratio of 1:2-7; Dissolved in concentrated hydrochloric acid, reacted at 40-100°C for 6-10h to obtain an amino-containing terpyridine derivative monomer; the nitro compound is at least one of p-nitrobenzaldehyde, 4-methoxy-3-nitrobenzaldehyde, 3-chloromethyl-5-nitrosalicylicaldehyde, 3-bromo-2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, crotonaldehyde 2,4-dinitrophenylhydrazone, 2,3-dihydro-2,2,6-trimethylbenzaldehyde and 2,3-dimethoxybenzaldehyde;

[0013] (2) adding the above-mentioned amino-containing terpyridine derivative and epichlorohydrin into a reaction vessel, and performing a ring-opening reaction at 50-100° C. for 2-8 hours;

[0014] (3) adding sodium hydroxide solution dropwise to the material obtained in step (2), carrying out a ring-closing reaction at 60-90° C. for 2-8 hours, washing with deionized water, separating the liquid to remove the brine, then removing water with anhydrous magnesium sulfate, and then removing the solvent by vacuum rotary evaporation;

[0015] (4) adding the material obtained in step (3), hydroxyl-terminated polydimethylsiloxane and phosphoric acid in a mass ratio of 1:2-10:0.02 into a reaction container, stirring at room temperature for 1-3 days, and filtering to obtain the siloxane-modified terpyridine antiseptic additive.

[0016] In a preferred embodiment of the present invention, the molar ratio of the nitro compound to the 2-acetylpyridine is 1:1-3, and the molar ratio of the nitro compound to the stannous chloride hydrate is 1:3-5.

[0017] Further preferably, in the step (1), the concentration of the nitro compound in methanol is 1-10 mg / mL.

[0018] Further preferably, the volume ratio of the concentrated ammonia water to methanol is 0.8-1.2:1, and the volume ratio of the potassium hydroxide solution to methanol is 0.05-0.15:1; the concentration of the concentrated ammonia water is 25-28wt%, and the concentration of the potassium hydroxide solution is 12-18wt%.

[0019] In a preferred embodiment of the present invention, in the step (2), the molar ratio of the amino-containing terpyridine derivative to the epichlorohydrin is 1:2-5.

[0020] In a preferred embodiment of the present invention, in the step (3), the molar ratio of the sodium hydroxide in the sodium hydroxide solution to the amino-containing terpyridine derivative is 5-10:1.

[0021] Further preferably, the concentration of the sodium hydroxide solution is 10-15wt%.

[0022] The use of the above-mentioned siloxane-modified terpyridine anticorrosion additive in the preparation of intrinsic metal anticorrosion epoxy resin coating.

[0023] A method for preparing an intrinsic metal anticorrosive epoxy resin coating comprises adding the above-mentioned siloxane-modified terpyridine anticorrosive additive to epoxy resin at 0.5wt%-2wt% of the total mass, and then adding crosslinking agent polyamide 8200 and curing at room temperature for 2-3 days to obtain the coating.

[0024] The beneficial effects of the present invention are:

[0025] 1. The present invention introduces the structure of terpyridine and its derivatives, which have heteroatoms and higher electron density and work through an adsorption mechanism, in which the corrosion inhibitor molecules are adsorbed on the surface of the metal solution to form an inhibitor molecular film, which protects the metal from the influence of the corrosive environment by physically blocking or delaying the electrochemical process.

[0026] 2. The present invention introduces siloxane and a hydroxyl structure at the end group into the terpyridine molecule. The siloxane structure introduced on the main chain can improve the flexibility of the molecular chain and the toughness of the epoxy resin; and the siloxane structure has a lower surface energy, and can have better liquid repellency and better anti-corrosion performance. The hydroxyl group on the end group can participate in the curing process of the epoxy resin and introduce siloxane into the epoxy resin. Due to the presence of the siloxane structure in this intrinsic epoxy resin coating, the modified epoxy resin coating has higher toughness and liquid repellency.

[0027] 3. The present invention introduces the terpyridine structure into the epoxy resin. The rigid structure of terpyridine and the heterocyclic nitrogen atom can form hydrogen bonds with the side hydroxyl groups of the epoxy resin, which greatly improves the rigidity of the intrinsic epoxy resin and increases the durability of the coating.

[0028] 4. The present invention has simple operation, mild reaction conditions, short cycle, easy post-processing and easy control. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the H-NMR spectrum of the siloxane-modified terpyridine antiseptic additive obtained in Example 1 of the present invention.

[0030] Figure 2 This is the H NMR spectrum of the terpyridine epoxy intermediate obtained in Comparative Example 1 of the present invention.

[0031] Figure 3 The infrared spectrum of the siloxane-modified terpyridine antiseptic additive prepared in Example 1 of the present invention is

[0032] Figure 4 This is the infrared spectrum of the terpyridine epoxy intermediate obtained in Comparative Example 1 of the present invention.

[0033] Figure 5 This is the Bode plot of pure epoxy resin.

[0034] Figure 6 This is the Bode plot of the epoxy resin coating with 1% siloxane-modified terpyridine antiseptic added prepared in Example 1 of the present invention.

[0035] Figure 7 The salt spray test results of the embodiments of the present invention are shown in Figure 2, wherein: (a) is the salt spray test result of the pure epoxy resin coating, and (b) is the salt spray test result of the intrinsic anti-corrosion epoxy resin coating prepared in Example 1 of the present invention.

[0036] Figure 8The contact angle test results of the embodiments of the present invention are shown in Figure 1, where: (a) is the contact angle test result of the pure epoxy resin coating, (b) is the contact angle test result of the epoxy resin coating prepared in Example 1 of the present invention with 1% of the metal anticorrosion functional epoxy resin coating modifier added. (c) is the contact angle test result of the epoxy resin coating prepared in Comparative Example 1 of the present invention with 1% of the epoxy resin added. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is further illustrated and described below through specific implementation modes in combination with the accompanying drawings.

[0038] Example 1

[0039] (1) 21 mmol of p-nitrobenzaldehyde and 41.5 mmol of 2-acetylpyridine were dissolved in 170 mL of methanol, 160 mL of 26 wt % ammonia water was added, and 15 mL of 15 wt % potassium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 days. After filtering and drying, a nitro-containing terpyridine derivative monomer was obtained;

[0040] (2) 1.3 mmol of the above nitro-containing terpyridine derivative monomer and 6.8 mmol of stannous chloride hydrate were added to 12 mL of 36 wt% concentrated hydrochloric acid, heated with stirring at 60° C. for 8 h, cooled to room temperature, filtered and dried to obtain Figure 1 and Figure 3 The amine-containing terpyridine derivative monomer is shown.

[0041] (3) adding the above-mentioned amino-containing terpyridine derivative monomer and epichlorohydrin in a molar ratio of 1:5 into a reaction vessel, and performing a ring-opening reaction at 80° C. for 6 hours;

[0042] (4) A 10 wt % sodium hydroxide solution in a molar ratio of 5:1 to the above-mentioned amino-containing terpyridine derivative monomer is added dropwise to the material obtained in step (3), and a ring-closing reaction is carried out at 80° C. for 6 h. The brine is removed by separation, and the mixture is washed thoroughly with deionized water. Then, water is removed with anhydrous magnesium sulfate, and then the solvent is removed by rotary evaporation under reduced pressure to obtain a terpyridine epoxy resin intermediate shown in the following structural formula.

[0043]

[0044] (5) Add the material obtained in step (4) and hydroxyl-terminated polydimethylsiloxane in a mass ratio of 1:10 into a reaction vessel, stir at room temperature for 24 hours, then filter under reduced pressure and wash with deionized water several times to obtain Figure 1 and Figure 3 The siloxane-modified terpyridine antiseptic additive shown.

[0045] (6) Adding the siloxane-modified terpyridine anticorrosion agent obtained in step (5) to the epoxy resin at 1 wt% of the total mass, and then adding the crosslinking agent polyamide 8200 to cure at room temperature for 3 days to obtain the following Figure 6 Intrinsic metal anti-corrosion epoxy coating shown (can be used with Figure 5 Compared with the Bode diagram of pure epoxy resin shown in the figure, the contact angle is Figure 8 The Bode plot represents the degree of change in the impedance value of the coating at different frequencies, with the impedance value at low frequencies being the main one. When the frequency is 0.01Hz, the greater the impedance value of the coating, the weaker the surface corrosion tendency, that is, the better the anti-corrosion performance of the coating. Figure 5 As shown, the low frequency impedance (Z 0.01Hz ) can reach about 1×10 11 Ωcm 2 , but on the third day it dropped rapidly to about 8×10 9 Ωcm 2 , and in the subsequent tests, it dropped by half almost every 7 days, indicating that the anti-corrosion effect of the EP coating was almost invalid, and the corrosive medium penetrated into the defect gaps of the coating and may have reacted with the steel plate. Figure 6 ), the first day has a higher impedance, close to 5×10 10 Ωcm 2 However, in the subsequent corrosion process, the slow release of the corrosion inhibitor caused the impedance to rise, and the low-frequency impedance value on the 28th day was slightly higher than that of the pure EP on the first day. The above results show that the epoxy resin coating with the addition of siloxane-modified terpyridine anticorrosion additive has a long-term anticorrosion effect.

[0046] The salt spray test results of the intrinsic metal anticorrosion epoxy resin coating prepared in this embodiment are as follows: Figure 7 The prepared coating and pure epoxy EP were crossed and placed in a salt spray chamber to effectively test the anti-corrosion performance of the coating under simulated harsh conditions. Figure 7 This is the corrosion condition after being placed in the smoke box for seven days. Since the coating has been damaged, corrosion products such as rust can be observed in the early stage of the experiment. The corrosion area of ​​the pure EP coating sample has a large area of ​​corrosion, compared with the epoxy resin coating sample with 1% siloxane-modified terpyridine anti-corrosion agent, which only has pitting in some areas and has not expanded, indicating that the sustained release effect of the terpyridine derivative can effectively inhibit the expansion of the corrosion area and effectively improve the corrosion durability of the coating.

[0047] Example 2

[0048] (1) 21 mmol of 4-methoxy-3-nitrobenzaldehyde and 41.5 mmol of 2-acetylpyridine were dissolved in 170 mL of methanol, 160 mL of 26 wt % ammonia water was added, and 15 mL of 15 wt % potassium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 d. After filtering and drying, a nitro-containing terpyridine derivative monomer was obtained.

[0049] (2) 1.3 mmol of the above-mentioned nitro-containing terpyridine derivative monomer and 6.8 mmol of stannous chloride hydrate were added to 12 mL of 36 wt% concentrated hydrochloric acid, stirred and heated at 60° C. for 8 h, cooled to room temperature, filtered and dried to obtain an amino-containing terpyridine derivative monomer.

[0050] (3) adding the above-mentioned amino-containing terpyridine derivative monomer and epichlorohydrin in a molar ratio of 1:5 to a mixed solvent consisting of ethanol and water in a volume ratio of 3:2 (the ratio of the mixed solvent to the solute therein is 10 mL: 1 g), performing a ring-opening reaction at 80° C. for 6 h, and then adding excess acetone to terminate the ring-opening reaction;

[0051] (4) Add a 10 wt % sodium hydroxide solution in a molar ratio of 5:1 to the above-mentioned amino-containing terpyridine derivative monomer dropwise into the material obtained in step (3), carry out a ring-closing reaction at 80° C. for 6 h, separate the liquid to remove the brine, wash thoroughly with deionized water, then remove water with anhydrous magnesium sulfate, and then remove the solvent by vacuum rotary evaporation to obtain Figure 2 and Figure 4 The terpyridine epoxy resin intermediate shown.

[0052] (5) The material obtained in step (4) and hydroxyl-terminated polydimethylsiloxane are added to a reaction vessel in a mass ratio of 1:10, stirred at room temperature for 24 hours, then filtered under reduced pressure and washed with deionized water several times to obtain a siloxane-modified terpyridine antiseptic additive.

[0053] (6) Add the siloxane-modified terpyridine anticorrosion agent obtained in step (5) to the epoxy resin at 1 wt% of the total mass, then add the cross-linking agent polyamide 8200 and cure at room temperature for 3 days to obtain an intrinsic metal anticorrosion epoxy resin coating.

[0054] Example 3

[0055] (1) 21 mmol of 3-chloromethyl-5-nitrosalicylicylaldehyde and 41.5 mmol of 2-acetylpyridine were dissolved in 170 mL of methanol, 160 mL of 26 wt % ammonia water was added, and 15 mL of 15 wt % potassium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 d. After filtering and drying, a nitro-containing terpyridine derivative monomer was obtained.

[0056] (2) 1.3 mmol of a nitro-containing terpyridine derivative monomer and 6.8 mmol of stannous chloride hydrate were added to 12 mL of 36 wt % concentrated hydrochloric acid, stirred and heated at 60° C. for 8 h, cooled to room temperature, filtered and dried to obtain an amino-containing terpyridine derivative monomer.

[0057] (3) adding the above-mentioned amino-containing terpyridine derivative monomer and epichlorohydrin in a molar ratio of 1:5 to a mixed solvent consisting of ethanol and water in a volume ratio of 3:2 (the ratio of the mixed solvent to the solute therein is 10 mL: 1 g), performing a ring-opening reaction at 80° C. for 6 h, and then adding excess acetone to terminate the ring-opening reaction;

[0058] (4) Add a 10 wt % sodium hydroxide solution at a molar ratio of 5:1 to the above-mentioned amino-containing terpyridine derivative monomer dropwise into the material obtained in step (3), carry out a ring-closing reaction at 80° C. for 6 h, separate the liquid to remove the brine, wash thoroughly with deionized water, then remove water with anhydrous magnesium sulfate, and then remove the solvent by reduced pressure rotary evaporation to obtain a terpyridine epoxy resin intermediate.

[0059] (5) The material obtained in step (4) and hydroxyl-terminated polydimethylsiloxane are added to a reaction vessel in a mass ratio of 1:10, stirred at room temperature for 24 hours, then filtered under reduced pressure and washed with deionized water several times to obtain a siloxane-modified terpyridine antiseptic additive.

[0060] (6) Add the siloxane-modified terpyridine anticorrosion agent obtained in step (5) to the epoxy resin at 1 wt% of the total mass, then add the cross-linking agent polyamide 8200 and cure at room temperature for 3 days to obtain an intrinsic metal anticorrosion epoxy resin coating.

[0061] Example 4

[0062] (1) 21 mmol of 3-bromo-2-hydroxy-5-nitrobenzaldehyde and 41.5 mmol of 2-acetylpyridine were dissolved in 170 mL of methanol, 160 mL of 26 wt % ammonia water was added, and 15 mL of 15 wt % potassium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 d. After filtering and drying, a nitro-containing terpyridine derivative monomer was obtained.

[0063] (2) 1.3 mmol of a nitro-containing terpyridine derivative monomer and 6.8 mmol of stannous chloride hydrate were added to 12 mL of 36 wt % concentrated hydrochloric acid, stirred and heated at 60° C. for 8 h, cooled to room temperature, filtered and dried to obtain an amino-containing terpyridine derivative monomer.

[0064] (3) adding the above-mentioned amino-containing terpyridine derivative monomer and epichlorohydrin in a molar ratio of 1:5 to a mixed solvent consisting of ethanol and water in a volume ratio of 3:2 (the ratio of the mixed solvent to the solute therein is 10 mL: 1 g), performing a ring-opening reaction at 80° C. for 6 h, and then adding excess acetone to terminate the ring-opening reaction;

[0065] (4) Add a 10 wt % sodium hydroxide solution at a molar ratio of 5:1 to the above-mentioned terpyridine derivative monomer dropwise into the material obtained in step (3), carry out a ring-closing reaction at 80° C. for 6 h, separate the liquid to remove the brine, wash thoroughly with deionized water, then remove water with anhydrous magnesium sulfate, and then remove the solvent by reduced pressure rotary evaporation to obtain a terpyridine epoxy resin intermediate.

[0066] (5) The material obtained in step (4) and hydroxyl-terminated polydimethylsiloxane are added to a reaction vessel in a mass ratio of 1:10, stirred at room temperature for 24 hours, then filtered under reduced pressure and washed several times with deionized water to obtain a siloxane-modified terpyridine preservative.

[0067] (6) Add the siloxane-modified terpyridine anticorrosion agent obtained in step (5) to the epoxy resin at 1 wt% of the total mass, then add the cross-linking agent polyamide 8200 and cure at room temperature for 3 days to obtain an intrinsic metal anticorrosion epoxy resin coating.

[0068] Example 5

[0069] (1) 21 mmol of 2-hydroxy-3-nitrobenzaldehyde and 41.5 mmol of 2-acetylpyridine were dissolved in 170 mL of methanol, 160 mL of 26 wt % ammonia water was added, and 15 mL of 15 wt % potassium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 d. After filtering and drying, a nitro-containing terpyridine derivative monomer was obtained.

[0070] (2) 1.3 mmol of a nitro-containing terpyridine derivative monomer and 6.8 mmol of stannous chloride hydrate were added to 12 mL of 36 wt % concentrated hydrochloric acid, stirred and heated at 60° C. for 8 h, cooled to room temperature, filtered and dried to obtain an amino-containing terpyridine derivative monomer.

[0071] (3) adding the above-mentioned amino-containing terpyridine derivative monomer and epichlorohydrin in a molar ratio of 1:5 to a mixed solvent consisting of ethanol and water in a volume ratio of 3:2 (the ratio of the mixed solvent to the solute therein is 10 mL: 1 g), performing a ring-opening reaction at 80° C. for 6 h, and then adding excess acetone to terminate the ring-opening reaction;

[0072] (4) Add a 10 wt % sodium hydroxide solution at a molar ratio of 5:1 to the above-mentioned amino-containing terpyridine derivative monomer dropwise into the material obtained in step (3), carry out a ring-closing reaction at 80° C. for 6 h, separate the liquid to remove the brine, wash thoroughly with deionized water, then remove water with anhydrous magnesium sulfate, and then remove the solvent by reduced pressure rotary evaporation to obtain a terpyridine epoxy resin intermediate.

[0073] (5) The material obtained in step (4) and hydroxyl-terminated polydimethylsiloxane are added to a reaction vessel in a mass ratio of 1:10, stirred at room temperature for 24 hours, then filtered under reduced pressure and washed with deionized water several times to obtain a siloxane-modified terpyridine antiseptic additive.

[0074] (6) Add the siloxane-modified terpyridine anticorrosion agent obtained in step (5) to the epoxy resin at 1 wt% of the total mass, then add the cross-linking agent polyamide 8200 and cure at room temperature for 3 days to obtain an intrinsic metal anticorrosion epoxy resin coating.

[0075] Comparative Example 1

[0076] (1) 21 mmol of 2-hydroxy-3-nitrobenzaldehyde and 41.5 mmol of 2-acetylpyridine were dissolved in 170 mL of methanol, 160 mL of 26 wt % ammonia water was added, and 15 mL of 15 wt % potassium hydroxide solution was added dropwise, and the mixture was stirred at room temperature for 3 d. After filtering and drying, a nitro-containing terpyridine derivative monomer was obtained.

[0077] (2) 1.3 mmol of a nitro-containing terpyridine derivative monomer and 6.8 mmol of stannous chloride hydrate were added to 12 mL of 36 wt % concentrated hydrochloric acid, stirred and heated at 60° C. for 8 h, cooled to room temperature, filtered and dried to obtain an amino-containing terpyridine derivative monomer.

[0078] (3) adding the above-mentioned amino-containing terpyridine derivative monomer and epichlorohydrin in a molar ratio of 1:5 to a mixed solvent consisting of ethanol and water in a volume ratio of 3:2 (the ratio of the mixed solvent to the solute therein is 10 mL: 1 g), performing a ring-opening reaction at 80° C. for 6 h, and then adding excess acetone to terminate the ring-opening reaction;

[0079] (4) Add a 10 wt % sodium hydroxide solution in a molar ratio of 5:1 to the above-mentioned amino-containing terpyridine derivative monomer dropwise into the material obtained in step (3), carry out a ring-closing reaction at 80° C. for 6 h, separate the liquid to remove the brine, wash thoroughly with deionized water, then remove water with anhydrous magnesium sulfate, and then remove the solvent by rotary evaporation under reduced pressure to obtain Figure 2 and 4 The terpyridine epoxy resin intermediate shown.

[0080] (5) The terpyridine epoxy resin intermediate obtained in step (4) was added to the epoxy resin at 1 wt% of the total mass, and then a crosslinking agent polyamide 8200 was added and cured at room temperature for 3 days to obtain a terpyridine epoxy resin intermediate epoxy resin coating (contact angle such as Figure 8 shown).

[0081] The above description is only a preferred embodiment of the present invention, and therefore cannot be used to limit the scope of the present invention. That is, equivalent changes and modifications made according to the patent scope of the present invention and the contents of the specification should still fall within the scope of the present invention.

Claims

1. A siloxane-modified terpyridine antiseptic adjuvant, characterized in that: Its structural formula is 2. The method for preparing a siloxane-modified terpyridine antiseptic additive according to claim 1, characterized in that: The steps include: (1) dissolving a nitro compound and 2-acetylpyridine in methanol at a molar ratio of 1:1-5, wherein the concentration of the nitro compound in methanol is 0.5-15 mg / mL; then adding concentrated aqueous ammonia and potassium hydroxide solution, wherein the volume ratio of concentrated aqueous ammonia to methanol is 0.5-1.5:1, and the volume ratio of potassium hydroxide solution to methanol is 0.01-0.2:1; stirring at room temperature for 2-4 days, filtering and drying to obtain a nitro-containing terpyridine derivative monomer; mixing the nitro-containing terpyridine derivative monomer and stannous chloride hydrate at a molar ratio of 1:2-7; Dissolved in concentrated hydrochloric acid, reacted at 40-100°C for 6-10h to obtain an amino-containing terpyridine derivative monomer; the nitro compound is at least one of p-nitrobenzaldehyde, 4-methoxy-3-nitrobenzaldehyde, 3-chloromethyl-5-nitrosalicylicaldehyde, 3-bromo-2-hydroxy-5-nitrobenzaldehyde, 2-hydroxy-3-nitrobenzaldehyde, 2-hydroxy-3-methoxy-5-nitrobenzaldehyde, crotonaldehyde 2,4-dinitrophenylhydrazone, 2,3-dihydro-2,2,6-trimethylbenzaldehyde and 2,3-dimethoxybenzaldehyde; (2) adding the above-mentioned amino-containing terpyridine derivative and epichlorohydrin into a reaction vessel, and performing a ring-opening reaction at 50-100° C. for 2-8 hours; (3) adding sodium hydroxide solution dropwise to the material obtained in step (2), carrying out a ring-closing reaction at 60-90° C. for 2-8 hours, washing with deionized water, separating the liquid to remove the brine, then removing water with anhydrous magnesium sulfate, and then removing the solvent by vacuum rotary evaporation; (4) adding the material obtained in step (3), hydroxyl-terminated polydimethylsiloxane and phosphoric acid in a mass ratio of 1:2-10:0.02 into a reaction container, stirring at room temperature for 1-3 days, and filtering to obtain the siloxane-modified terpyridine antiseptic additive.

3. The preparation method according to claim 2, characterized in that: The molar ratio of the nitro compound to the 2-acetylpyridine is 1:1-3, and the molar ratio of the nitro compound to the stannous chloride hydrate is 1:3-5.

4. The preparation method according to claim 3, characterized in that: In the step (1), the concentration of the nitro compound in methanol is 1-10 mg / mL.

5. The preparation method according to claim 3, characterized in that: The volume ratio of the concentrated ammonia water to methanol is 0.8-1.2:1, and the volume ratio of the potassium hydroxide solution to methanol is 0.05-0.15:1; the concentration of the concentrated ammonia water is 25-28wt%, and the concentration of the potassium hydroxide solution is 12-18wt%.

6. The preparation method according to claim 2, characterized in that: In the step (2), the molar ratio of the amino-containing terpyridine derivative to the epichlorohydrin is 1:2-5.

7. The preparation method according to claim 2, characterized in that: In the step (3), the molar ratio of the sodium hydroxide in the sodium hydroxide solution to the amino-containing terpyridine derivative is 5-10:

1.

8. The preparation method according to claim 7, characterized in that: The concentration of the sodium hydroxide solution is 10-15 wt %.

9. Use of the siloxane-modified terpyridine anticorrosion aid according to claim 1 in the preparation of an intrinsic metal anticorrosion epoxy resin coating.

10. A method for preparing an intrinsic metal anticorrosive epoxy resin coating, comprising adding the siloxane-modified terpyridine anticorrosive additive according to claim 1 to an epoxy resin at 0.5wt%-2wt% of the total mass, and then adding a crosslinking agent polyamide 8200 and curing at room temperature for 2-3 days.

Images