Intermediates, modified hydrophobic tb polymers, and methods of making and using the same

Abstract

The application belongs to the technical field of materials, and relates to an intermediate, a modified hydrophobic TB polymer and a preparation method and application thereof. In an ice bath and under an inert atmosphere, 2,2-bis(3-amino-4-methylphenyl) hexafluoropropane, dimethoxymethane and trifluoroacetic acid are mixed and reacted by increasing temperature, and after the reaction is completed, an ammonia water solution is added to obtain the intermediate; the modified hydrophobic TB polymer is obtained by using the intermediate, a halogenated compound RX and a catalyst as reaction solvents. The coating prepared from the modified hydrophobic TB polymer is not only environmentally friendly, but also has good flexibility and excellent metal adhesion, and can meet the durability requirements of anticorrosive coatings.

Description

Technical Field

[0001] This invention belongs to the field of materials technology, specifically relating to intermediates, modified hydrophobic TB polymers, their preparation methods and applications. Background Technology

[0002] Aluminum alloys, with their lightweight, corrosion resistance, ease of forming, and convenient processing, play a crucial role in modern aerospace, shipbuilding, automotive, and many other industries, becoming an indispensable material. Their excellent chemical stability is often the primary factor in choosing aluminum alloys in many fields. However, it is worth noting that the naturally formed corrosion-resistant oxide layer of aluminum alloys is relatively thin (only a few nanometers thick). In natural environments, especially highly corrosive marine environments, this protective layer is easily eroded by corrosive media such as seawater, leading to corrosion of the base material. Furthermore, the attachment of marine microorganisms can significantly shorten the lifespan of metallic materials, affecting not only the normal operation and use of equipment but also potentially causing serious safety accidents and substantial property damage.

[0003] Coating aluminum alloy surfaces with epoxy resin anti-corrosion coatings is a common and effective way to improve their protective performance and broaden their application range. However, the bonding strength between epoxy resin and aluminum alloy surfaces is relatively weak, and uneven volume shrinkage during the curing process can easily generate internal stress, often leading to coating cracks and affecting the durability of anti-corrosion performance. Therefore, strengthening the bonding strength between epoxy resin and the aluminum alloy substrate is key to ensuring the effectiveness of the anti-corrosion coating. Furthermore, to address the adhesion of marine microorganisms, improving the hydrophobic properties of the coating can reduce the adhesion of pollutants and external impurities to the surface, reduce scaling, and enhance the substrate's antifouling ability. This is also an important measure to ensure the long-term stable use of the material.

[0004] Incorporating Tröger's Base (TB) polymers, which possess excellent mechanical, thermal, and chemical properties, into epoxy resin anticorrosive coatings can significantly improve the overall performance of the coating. However, due to the numerous fused rings in the TB structure, its adhesion to the substrate material is not ideal. By finely adjusting the hydrophilic and hydrophobic properties of the TB side chains, it is possible to enhance the adhesion strength to the substrate while optimizing the surface hydrophobic properties, thereby comprehensively improving the overall performance of epoxy resin anticorrosive coatings. Summary of the Invention

[0005] To address the shortcomings of the existing technology, this invention provides an intermediate, a modified hydrophobic TB polymer, its preparation method, and its application. By introducing the modified hydrophobic TB polymer into a composite coating on an aluminum alloy surface, the resulting coating is not only environmentally friendly but also possesses good flexibility and strong metal adhesion, thus meeting the durability requirements of anti-corrosion coatings.

[0006] To achieve the above objectives, the specific technical solution is as follows:

[0007] The first aspect of the present invention provides an intermediate having the following structure:

[0008] n = 20~200.

[0009] A second aspect of the present invention provides a method for preparing the intermediate, comprising the following steps: mixing 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, dimethoxymethane (DMM), and trifluoroacetic acid (TFA) in an ice bath and under an inert atmosphere, reacting the mixture at a rising temperature, and after the reaction is completed, adding an aqueous ammonia solution to obtain the intermediate. Specifically, in an ice bath and under an inert atmosphere, 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane and dimethoxymethane are mixed, followed by the addition of trifluoroacetic acid, and the reaction is carried out at a rising temperature.

[0010] The synthesis reaction formula is as follows:

[0011]

[0012] Furthermore, the ice bath temperature is 0~10℃.

[0013] Further, the mass ratio of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane to dimethoxymethane is 1:(5~15), and the mass ratio of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane to trifluoroacetic acid is 1:(10~30); preferably, the purity of the dimethoxymethane is 99%, and the purity of the trifluoroacetic acid is 99%.

[0014] Furthermore, the reaction temperature is 20~40℃, and the reaction time is 12~72h.

[0015] Furthermore, the mass fraction of the ammonia solution is 1% to 10%, and the mass ratio of the ammonia solution to 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane is (0.5 to 2):1.

[0016] A third aspect of the present invention provides a modified hydrophobic TB polymer, the modified hydrophobic TB polymer having the following structure:

[0017] ;

[0018] Wherein, R is selected from long-chain aliphatic alkyl or fluorinated benzyl, wherein the long-chain aliphatic alkyl is preferably a long-chain aliphatic alkyl with more than twelve carbon atoms; more preferably, R is selected from , , , n is 20~200.

[0019] A fourth aspect of the present invention provides a method for preparing the modified hydrophobic TB polymer, comprising the following steps: using an organic solvent as a reaction solvent, and reacting the intermediate, the halogenated compound RX, and a catalyst to obtain the modified hydrophobic TB polymer;

[0020] In the halogenated compound RX, R is selected from at least one of long-chain aliphatic alkyl groups or fluorinated benzyl groups, wherein the long-chain aliphatic alkyl group is preferably a long-chain aliphatic alkyl group with more than twelve carbon atoms; more preferably, R is selected from... , , , At least one of the following, X is selected from at least one of chlorine, bromine, and iodine;

[0021] The synthesis reaction formula is as follows:

[0022]

[0023] Furthermore, the reaction temperature is -80~0℃, and the reaction time is 1~48h.

[0024] Preferably, the preparation method specifically involves: dispersing the intermediate in an organic solvent, adding a catalyst under low temperature conditions, mixing evenly, and then adding a halogenated compound RX to react and obtain the modified hydrophobic TB polymer; the low temperature conditions are preferably -80~0℃.

[0025] Furthermore, the organic solvent is preferably at least one of tetrahydrofuran, dimethyl sulfoxide, diethyl ether, and 1,4-dioxane.

[0026] Furthermore, the catalyst is at least one of lithium diisopropylamino, lithium n-butyl, and lithium hexamethyldisilamino.

[0027] Furthermore, the mass ratio of the intermediate, the halogenated compound RX, the catalyst, and the organic solvent is 1:(0.2~5):(0.02~0.1):(2~10).

[0028] A fifth aspect of the present invention provides an application of the modified hydrophobic TB polymer, wherein the application is a superhydrophobic antifouling and anticorrosion composite coating; more preferably, a superhydrophobic antifouling and anticorrosion composite coating for marine environments. The modified hydrophobic TB polymer serves as a toughening agent in the superhydrophobic antifouling and anticorrosion composite coating.

[0029] Furthermore, the superhydrophobic, antifouling, and anticorrosive composite coating also includes epoxy resin, nano-Al2O3, graphene, antisettling agent, curing agent, leveling agent, antibacterial agent, organic solvent M, and organic solvent N.

[0030] Preferably, the superhydrophobic, antifouling, and anticorrosive composite coating comprises, by weight, 15-45 parts epoxy resin, 1-20 parts modified hydrophobic TB polymer, 5-20 parts nano Al2O3, 15-40 parts organic solvent M, 0.5-5 parts graphene, 0.5-5 parts anti-settling agent, 35-80 parts curing agent, 2-10 parts leveling agent, 1-5 parts antibacterial agent, and 15-55 parts organic solvent N.

[0031] Preferably, the epoxy resin is selected from one or more of epoxy resin E44, epoxy resin E42, and epoxy resin E20; the organic solvent M is selected from one or more of xylene, butyl acetate, ethyl acetate, n-butanol, and isopropanol; the anti-settling agent is selected from one or more of silane coupling agents KH550, KH560, and KH570; and the curing agent is selected from one or more of aliphatic polyamine curing agents, aliphatic amine adduct curing agents, and polyamide curing agents, preferably diethylenetriamine, dimethylaminopropylamine, EPIKURE™ 3295, and EPIKURE™ The leveling agent is selected from one or more of polydimethylsiloxane and polyacrylate leveling agents, preferably BYK-381, Sago-3880, BYK-358N, and EFKA-3777; the antibacterial agent is selected from nano ZnO or CuO particles, wherein the particle size of the nano ZnO or nano CuO particles is 300-400 mesh; the organic solvent N is selected from one or more of ethylbenzene, ethyl acetate, n-butanol, and propylene glycol methyl ether acetate.

[0032] Preferably, the particle size of the nano-Al2O3 and graphene is 200-600 mesh, more preferably 300-400 mesh.

[0033] The method for preparing the superhydrophobic, antifouling, and anticorrosion composite coating includes the following steps:

[0034] S1 involves stirring epoxy resin, organic solvent M, modified hydrophobic TB polymer, nano-Al2O3, and graphene to obtain component A;

[0035] S2 involves stirring and reacting the curing agent, leveling agent, organic solvent N, anti-settling agent, and antibacterial agent to obtain component B;

[0036] S3 Mix component A and component B to obtain the superhydrophobic, antifouling and anticorrosion composite coating.

[0037] Preferably, in step S1, the stirring reaction temperature is 15~40℃, the time is 0.5~6h, and the speed is 500~2000r / min.

[0038] Preferably, in step S2, the stirring reaction temperature is 15~40℃, the time is 0.5~6h, and the speed is 500~2000r / min.

[0039] Preferably, in step S3, the weight ratio of component A to component B is 100:(30~80).

[0040] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0041] (1) The present invention further modifies the fluorine-containing intermediate to obtain a modified hydrophobic TB polymer, which is then added to the anti-corrosion coating as a toughening agent. The modified TB polymer contains a large number of hydrophobic groups such as fluorine or long-chain alkanes, which can greatly reduce the surface free energy of the coating and make it superhydrophobic. This significantly improves the antifouling and anti-corrosion protection performance of the epoxy resin coating, extends the service life of aluminum alloys and other metal materials in complex and harsh marine environments, and reduces the maintenance cost of equipment.

[0042] (2) The long-chain alkyl groups in the modified hydrophobic TB polymer prepared by the present invention have excellent flexibility, which can increase the distance between molecules, enhance the flexibility and impact resistance of the coating, and prevent the metal base from being exposed due to breakage. In addition, the non-polar long-chain alkanes have low surface energy, which can effectively weaken the strong van der Waals forces, hydrogen bonds and other interactions between polymer chains, thereby increasing their flexibility.

[0043] (3) The fluorinated groups in the modified hydrophobic TB polymer prepared by the present invention have extremely high chemical bond energy and have extremely high tolerance to various environments such as acids, alkalis, and free radicals, which can stabilize the coating material; at the same time, the fluorinated coating has excellent electrical insulation properties, which can isolate the metal from the electrolyte in the environment and prevent the occurrence of the electrochemical process of metal corrosion; in addition, for the high chlorine environment in seawater, the inert fluorinated coating will not be corroded by chloride ions, which can effectively prevent the spread and expansion of pitting corrosion.

[0044] (4) The superhydrophobic antifouling and anticorrosive composite coating designed in this invention is green and environmentally friendly, with good stability and long service life. It can adapt to complex and ever-changing marine environments, and the preparation method is simple and low-cost, which is conducive to large-scale production. Attached Figure Description

[0045] Figure 1 Fourier transform infrared spectrum of the modified hydrophobic TB polymer prepared in Example 1 of this invention;

[0046] Figure 2 The Fourier transform infrared spectrum of the intermediate prepared in Example 1 of this invention;

[0047] Figure 3The H NMR spectrum of the modified hydrophobic TB polymer prepared in Example 1 of this invention;

[0048] Figure 4 The H NMR spectrum of the intermediate prepared in Example 1 of this invention;

[0049] Figure 5 The contact angle of the coating prepared in Application Example 1 of this invention;

[0050] Figure 6 The contact angle of the coating prepared in Application Example 5 of this invention;

[0051] Figure 7 This is a scanning electron microscope image of the modified hydrophobic TB polymer prepared in Example 1 of the present invention. Detailed Implementation

[0052] The embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and should not be construed as limiting the scope of the invention. Unless otherwise specified, the experimental methods used in the following examples are conventional methods. Unless otherwise specified, the materials and reagents used in the following examples are commercially available.

[0053] Example 1

[0054] A method for preparing a modified hydrophobic TB polymer includes the following steps:

[0055] Preparation of S1 intermediate: Under a nitrogen atmosphere at 5°C, 20g of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane and 100g of dimethoxymethane (purity 99%) were mixed, and then 200g of trifluoroacetic acid (purity 99%) was added dropwise to the above mixture. The mixture was heated to 25°C and stirred for 12h. After the reaction was completed, 20g of 5% ammonia water was added, stirred and filtered. The filtered product was washed three times with deionized water, and then purified twice by recrystallization with a chloroform / methanol (mass ratio 1:2). Finally, the product was dried in a vacuum oven at 120°C for 24h to obtain the intermediate.

[0056] Preparation of S2 modified hydrophobic TB polymer: 10 g of the intermediate prepared in step S1 was added to 50 g of anhydrous tetrahydrofuran and stirred to dissolve. The mixture was placed in a low temperature environment of -78℃ and stirred for 30 min. 0.5 g of n-butyllithium was slowly added to the solution and stirred for 2 h. Then, 20 g of hexadecane bromo was slowly added and reacted for 12 h. After the reaction was completed, 20 mL of saturated ammonium chloride solution was added to quench the reaction. After the temperature was raised to room temperature, the mixture was extracted three times with 50 mL of ethyl acetate. The organic phase was washed with 30 mL of saturated brine, separated, and anhydrous sodium sulfate was added. The mixture was stirred for 30 min to absorb trace amounts of water. After filtration, the solvent was evaporated to obtain the modified hydrophobic TB polymer.

[0057] Figure 1 The Fourier transform infrared spectrum of the modified hydrophobic TB polymer prepared in Example 1 confirms that the Tröger's Base (TB) polymer structure obtained in this invention is:

[0058] , where n is 144.

[0059] like Figure 2 As shown, at 1460cm -1 A characteristic C=C absorption peak representing the benzene ring appeared at 1659 cm⁻¹. -1 A characteristic absorption peak representing the CN bond appeared at 1092 cm⁻¹. -1 and 798cm -1 The presence of these three peaks, representing the characteristic absorption peaks of the CNC bond, indicates the presence of a tertiary amine structure in the intermediate, at 2928 cm⁻¹. -1 and 2860cm -1 A characteristic absorption peak representing -CH2- appeared at 1325 cm⁻¹. -1 The appearance of a characteristic absorption peak representing the CF bond indicates that the intermediate has been successfully synthesized. Figure 1 Fourier transform infrared spectra show that the infrared spectra of the modified hydrophobic TB polymer are basically similar to those of the intermediate. Figure 2 ), but at 735cm -1 The presence of a characteristic absorption peak for a long-chain alkyl-CH2- group indicates that hexadecane bromide has been successfully grafted into the TB polymer.

[0060] like Figure 4 As shown, the chemical shifts at δ=7.5~8.2 (1, 2) and 4.0~4.6 (3~5) are attributed to hydrogen atoms on the benzene ring and -CH2 group of the intermediate, respectively, while the chemical shift at δ=2.4 (6) is attributed to hydrogen atoms on the -CH3 group of the benzene ring of the intermediate. The appearance of these characteristic peaks indicates that the intermediate has been successfully synthesized. Figure 3The H NMR spectrum shows that the modified hydrophobic TB polymer has a similar H NMR spectrum to that of the intermediate. Figure 4 However, a characteristic peak of hydrogen atoms on the long-chain alkyl-CH2- group appeared at a chemical shift of 3.3~3.4, indicating that hexadecane bromide had been successfully grafted into the TB polymer.

[0061] Example 2

[0062] A method for preparing a modified hydrophobic TB polymer includes the following steps:

[0063] Preparation of S1 intermediate: Under a nitrogen atmosphere at 5°C, 20g of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane and 300g of dimethoxymethane (purity 99%) were mixed, and then 200g of trifluoroacetic acid (purity 99%) was added dropwise to the above mixture. The mixture was heated to 30°C and stirred for 12h. After the reaction was completed, 20g of 5% ammonia water was added, stirred and filtered. The filtered product was washed three times with deionized water, and then purified twice by recrystallization with a chloroform / methanol (mass ratio 1:2) mixture. Finally, the product was dried in a vacuum oven at 120°C for 24h to obtain the intermediate.

[0064] Preparation of S2 modified hydrophobic polymer: 10g of the intermediate prepared in step S1 was added to 20g of anhydrous tetrahydrofuran and stirred until dissolved. The mixture was placed in a low-temperature environment of -30℃ and stirred for 30min. 0.2g of n-butyllithium was slowly added dropwise to the solution and stirred for 2h. Then, 5g of 4-fluorobenzyl chloride was slowly added dropwise and the reaction was allowed to proceed for 8h. After the reaction was completed, 20mL of saturated ammonium chloride solution was added to quench the reaction. After warming to room temperature, the mixture was extracted three times with 50mL of ethyl acetate. The organic phase was washed with 30mL of saturated brine, separated, and anhydrous sodium sulfate was added. The mixture was stirred for 30min to absorb trace amounts of water. After filtration, the solvent was evaporated to obtain the modified hydrophobic TB polymer.

[0065] The modified hydrophobic polymer structure prepared in this embodiment is as follows:

[0066] Where n is 136.

[0067] Example 3

[0068] A method for preparing a modified hydrophobic TB polymer includes the following steps:

[0069] Preparation of S1 intermediate: Under a nitrogen atmosphere at 5°C, 20g of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane and 200g of dimethoxymethane (purity 99%) were mixed, and then 600g of trifluoroacetic acid (purity 99%) was added dropwise to the above mixture. The mixture was heated to 20°C and stirred for 48h. After the reaction was completed, 40g of 10% ammonia water was added, stirred and filtered. The filtered product was washed three times with deionized water, and then purified twice by recrystallization with a chloroform / methanol (mass ratio 1:1). Finally, the product was dried in a vacuum oven at 120°C for 48h to obtain the intermediate.

[0070] Preparation of S2 modified hydrophobic polymer: 10g of the intermediate prepared in step S1 was added to 80g of anhydrous tetrahydrofuran and stirred until dissolved. The mixture was placed in a low-temperature environment of -78℃ and stirred for 30min. 0.5g of n-butyllithium was slowly added to the solution and stirred for 2h. Then, 20g of bromododecane was slowly added and the reaction was allowed to proceed for 12h. After the reaction was completed, 20mL of saturated ammonium chloride solution was added to quench the reaction. After the temperature was raised to room temperature, the mixture was extracted three times with 80mL of ethyl acetate. The organic phase was washed with 30mL of saturated brine, separated, and anhydrous sodium sulfate was added. The mixture was stirred for 30min to absorb trace amounts of water. After filtration, the solvent was evaporated to obtain the modified hydrophobic TB polymer.

[0071] The modified hydrophobic polymer structure prepared in this embodiment is as follows:

[0072] Where n is 183.

[0073] Example 4

[0074] A method for preparing a modified hydrophobic TB polymer includes the following steps:

[0075] Preparation of S1 intermediate: Under a nitrogen atmosphere at 5°C, 20g of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane and 150g of dimethoxymethane (purity 99%) were mixed, and then 300g of trifluoroacetic acid (purity 99%) was added dropwise to the above mixture. The mixture was heated to 40°C and stirred for 72h. After the reaction was completed, 30g of 2% ammonia water was added, stirred and filtered. The filtered product was washed three times with deionized water, and then purified twice by recrystallization with a chloroform / methanol (mass ratio 1:2). Finally, the product was dried in a vacuum oven at 120°C for 24h to obtain the intermediate.

[0076] Preparation of S2 modified hydrophobic polymer: 10g of the intermediate prepared in step S1 was added to 30g of anhydrous tetrahydrofuran and stirred until dissolved. The mixture was placed in a low-temperature environment of -50℃ and stirred for 30min. 0.6g of n-butyllithium was slowly added dropwise to the solution and stirred for 2h. Then, 20g of 2,6-difluorobenzyl bromide was slowly added dropwise, and the reaction was allowed to proceed for 12h. The reaction was quenched by adding 20mL of saturated ammonium chloride solution, and after warming to room temperature, the mixture was extracted three times with 50mL of ethyl acetate. The organic phase was washed with 30mL of saturated brine, separated, and anhydrous sodium sulfate was added. The mixture was stirred for 30min to absorb trace amounts of water. After filtration, the solvent was evaporated to obtain the modified hydrophobic TB polymer toughening agent.

[0077] The modified hydrophobic polymer structure prepared in this embodiment is as follows:

[0078] Where n is 167.

[0079] Example 5

[0080] The preparation method is the same as in Example 1, except that in step S2, the reaction temperature is -80℃, the reaction time is 48h, and the amount of hexadecane added is 2g.

[0081] Example 6

[0082] The preparation method is the same as in Example 1, except that in step S2, the reaction temperature is 0°C, the reaction time is 1 h, the amount of hexadecane added is 50 g, the amount of n-butyllithium added is 1 g, and the amount of anhydrous tetrahydrofuran is 100 g.

[0083] Comparative Example 1

[0084] A method for preparing a modified hydrophobic TB polymer includes the following steps:

[0085] Preparation of intermediate S1: Under a nitrogen atmosphere at 5°C, 20g of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane and 100g of dimethoxymethane (purity 99%) were mixed, and then 200g of trifluoroacetic acid (purity 99%) was added dropwise to the mixture. The mixture was heated to 25°C and stirred for 12h. After the reaction was completed, 20g of 5% ammonia water was added, and the mixture was stirred and filtered. The filtered product was washed three times with deionized water, and then purified twice by recrystallization with a chloroform / methanol (mass ratio 1:2) mixture. Finally, the product was dried in a vacuum oven at 120°C for 24h to obtain the intermediate.

[0086] Preparation of S2 modified hydrophobic polymer: 10g of the intermediate prepared in step (1) was added to 30g of acetonitrile, and 30g of hexadecane bromide was added. The mixture was reacted at 80℃ for 72h. The acetonitrile was removed by evaporation, washed with ethyl acetate, filtered and dried to obtain the modified hydrophobic TB polymer.

[0087] The modified hydrophobic polymer structure obtained in this comparative example is as follows:

[0088] Where n is 141.

[0089] Application Example 1

[0090] Application Example 1 provides an application of a modified hydrophobic TB polymer in a superhydrophobic, antifouling, and anticorrosion composite coating.

[0091] The superhydrophobic, antifouling, and anticorrosive composite coating comprises, by weight fraction, 30 parts epoxy resin E44, 20 parts nano Al2O3 (particle size 300-400 mesh), 2 parts graphene (particle size 300-400 mesh), 30 parts ethyl acetate (organic solvent M), 5 parts KH550, 60 parts polyamide 650, 3 parts nano ZnO (particle size 300-400 mesh), 5 parts polydimethylsiloxane, 50 parts n-butanol (organic solvent N), and 10 parts of the modified hydrophobic TB polymer prepared in Example 1.

[0092] The preparation method includes the following steps:

[0093] S1. Modified hydrophobic TB polymer, ethyl acetate, nano-Al2O3 and graphene were added to epoxy resin E44. The mixture was stirred at 20℃ for 2 hours at a stirring speed of 800 r / min to obtain component A.

[0094] S2 Add n-butanol, polydimethylsiloxane, KH550 and nano ZnO to polyamide 650, and stir for 1 hour at a reaction temperature of 20℃ and a stirring speed of 500r / min to obtain component B;

[0095] S3 mixes 100g of component A and 80g of component B to obtain a composite coating, applies it to the surface of an aluminum alloy after sandblasting, and cures it for 24 hours to obtain a superhydrophobic, antifouling and anticorrosive composite coating for the surface of aluminum alloy.

[0096] Application Example 2

[0097] Referring to Application Example 1, the difference is that the modified hydrophobic TB polymer was prepared in Example 2.

[0098] Application Example 3

[0099] Referring to Application Example 1, the difference is that the modified hydrophobic TB polymer was prepared in Example 3.

[0100] Application Example 4

[0101] Referring to Application Example 1, the difference is that the modified hydrophobic TB polymer was prepared in Example 4.

[0102] Application Example 5

[0103] Referring to Application Example 1, the difference is that the modified hydrophobic TB polymer in Application Example 1 is replaced with the intermediate prepared in Example 1.

[0104] Application Example 6

[0105] Referring to Application Example 1, the difference is that no modified hydrophobic TB polymer was added.

[0106] Application Example 7

[0107] Referring to Application Example 1, the difference is that the modified hydrophobic TB polymer was prepared in Comparative Example 1.

[0108] Application Example 8

[0109] Referring to Application Example 1, the difference is that epoxy resin E44 is 45 parts, modified hydrophobic TB polymer is 20 parts, nano Al2O3 is 5 parts, ethyl acetate is 15 parts, graphene is 0.5 parts, KH550 is 0.5 parts, polyamide 650 is 35 parts, polydimethylsiloxane is 2 parts, nano ZnO is 1 part, and n-butanol is 55 parts.

[0110] Application Example 9

[0111] Referring to Application Example 1, the difference is that epoxy resin E44 is 15 parts, modified hydrophobic TB polymer is 1 part, nano Al2O3 is 10 parts, ethyl acetate is 40 parts, graphene is 5 parts, KH550 is 2 parts, polyamide 650 is 80 parts, polydimethylsiloxane is 10 parts, nano ZnO is 5 parts, and n-butanol is 15 parts.

[0112] The superhydrophobic, antifouling, and anticorrosive composite coatings prepared in Examples 1-7 were subjected to salt spray resistance and mechanical property tests in a salt spray test chamber.

[0113] Among them, the salt spray resistance test was conducted according to GB / T 1771-2007 "Determination of resistance to neutral salt spray of paints and varnishes"; the adhesion test was conducted according to GB / T 5210-2006 "Adhesion test by pull-off method for paints and varnishes"; the pencil hardness test was conducted according to GB / T 6739-2006 "Determination of hardness of coating film by pencil method for paints and varnishes"; the contact angle test was conducted according to GB / T 30693-2014 "Measurement of contact angle between plastic film and water"; the impact resistance test was conducted according to GB / T 1732-2020 "Determination of impact resistance of paint film"; and the abrasion resistance test was conducted according to GB / T 1768-2006 "Determination of abrasion resistance of paints and varnishes by rotating rubber grinding wheel method".

[0114] The test results are shown in Tables 1 and 2.

[0115] Table 1 Salt spray resistance and contact angle test results of the superhydrophobic, antifouling and anticorrosion composite coating.

[0116]

[0117] Table 2 Mechanical property tests of superhydrophobic, antifouling and anticorrosion composite coatings

[0118]

[0119] As can be seen from the test results in Tables 1 and 2, compared to Application Example 5, Application Example 1 of this invention uses the modified hydrophobic TB polymer toughening agent prepared in Example 1, resulting in improved salt spray resistance and mechanical properties of the coating; simultaneously, due to Figure 5 It can be seen that adding the modified hydrophobic TB polymer prepared in Example 1 to the coating can achieve a contact angle of 157.3°, as shown in the figure. Figure 6 As shown, the coating prepared from the intermediate has a contact angle of 94.5°, indicating that although the selected intermediate itself has a certain degree of hydrophobicity, after modification according to this invention, the coating exhibits superior superhydrophobicity; Figure 7 Scanning electron microscopy images show that the modified hydrophobic TB polymer prepared in Example 1 is an aggregate of nanoparticles. Adding it to the coating further enhances the coating's tear resistance and stress-strain resistance, and improves its corrosion resistance. Compared to Application Example 6 without the added modified hydrophobic TB polymer toughening agent, the modified toughening agent added in Application Example 1 of this invention contains hydrophobic groups that can prevent Cl... - Plasma penetrates the coating along with the solution, corroding the aluminum alloy substrate, resulting in a coating with better salt spray resistance and mechanical properties. Compared to Application Example 7, the modified toughening agent added in Application Example 1 contains neutral hydrophobic tertiary groups, which can reduce the surface energy of the coating and effectively block water penetration. Furthermore, the alkylated tertiary amine is more stable and less prone to detachment, while the quaternized coating reacts with Na...+ Ions undergo ion exchange, which alters the properties of the coating, resulting in poor long-term stability.

[0120] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A modified hydrophobic TB polymer, characterized in that, The modified hydrophobic TB polymer has the following structure: Wherein, R is selected from long-chain aliphatic alkyl or fluorinated benzyl; n is 20~200.

2. A method for preparing the modified hydrophobic TB polymer as described in claim 1, characterized in that, The process includes the following steps: using an organic solvent as the reaction solvent, and reacting an intermediate, a halogenated compound RX, and a catalyst to obtain the modified hydrophobic TB polymer; Wherein, R is selected from at least one of long-chain aliphatic alkyl or fluorinated benzyl, and X is selected from at least one of chlorine, bromine, and iodine; The intermediate structure is as follows: n is 20~200.

3. The preparation method according to claim 2, characterized in that, The intermediate preparation method includes the following steps: 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane, dimethoxymethane and trifluoroacetic acid are mixed in an ice bath and under an inert atmosphere, and the mixture is heated to carry out the reaction. After the reaction is completed, an ammonia solution is added to obtain the intermediate.

4. The preparation method according to claim 3, characterized in that, The mass ratio of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane to dimethoxymethane is 1:(5~15), and the mass ratio of 2,2-bis(3-amino-4-methylphenyl)hexafluoropropane to trifluoroacetic acid is 1:(10~30); the reaction temperature is 20~40℃, and the reaction time is 12~72h.

5. The preparation method according to claim 2, characterized in that, The catalyst is at least one of lithium diisopropylamino, lithium n-butyl, and lithium hexamethyldisilamino; the organic solvent is at least one of tetrahydrofuran, dimethyl sulfoxide, diethyl ether, and 1,4-dioxane.

6. The preparation method according to claim 2, characterized in that, The reaction temperature is -80~0℃, and the time is 1~48h; the mass ratio of the intermediate, halogenated compound RX, catalyst and organic solvent is 1:(0.2~5):(0.02~0.1):(2~10).

7. The application of the modified hydrophobic TB polymer according to claim 1 or the modified hydrophobic TB polymer prepared by the preparation method according to any one of claims 2 to 6 in the field of superhydrophobic, antifouling and anticorrosion composite coatings.

8. The application according to claim 7, characterized in that, The superhydrophobic, antifouling, and anticorrosive composite coating comprises, by weight, 15-45 parts epoxy resin, 1-20 parts modified hydrophobic TB polymer, 5-20 parts nano Al2O3, 15-40 parts organic solvent M, 0.5-5 parts graphene, 0.5-5 parts anti-settling agent, 35-80 parts curing agent, 2-10 parts leveling agent, 1-5 parts antibacterial agent, and 15-55 parts organic solvent N.

9. The application according to claim 8, characterized in that, The epoxy resin is selected from one or more of epoxy resin E44, epoxy resin E42, and epoxy resin E20; the organic solvent M is selected from one or more of xylene, butyl acetate, ethyl acetate, n-butanol, and isopropanol; the anti-settling agent is selected from one or more of silane coupling agents KH550, KH560, and KH570; the curing agent is selected from one or more of aliphatic polyamine curing agents, aliphatic amine adduct curing agents, and polyamide curing agents; the leveling agent is selected from one or more of polydimethylsiloxane and polyacrylate leveling agents; the antibacterial agent is selected from nano-ZnO or CuO particles; and the organic solvent N is selected from one or more of ethylbenzene, ethyl acetate, n-butanol, and propylene glycol methyl ether acetate.

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