Anti-fingerprint agent and preparation method and application thereof

Abstract

The present invention provides an anti-fingerprint agent and a preparation method and application thereof, belonging to the field of material technology. The anti-fingerprint agent is constructed by substitution reaction, addition reaction, polymerization reaction and the like of compounds such as trichlorotriazine, fluorinated aromatic diamine, methyl acrylate, chloroalkylsiloxane, etc. It has a hyperbranched three-dimensional structure, and has C-F bonds and silane end-capping groups. It has excellent hydrophobic antifouling, anti-fingerprint, friction resistance and other properties, and does not contain perfluorinated or polyfluorinated hydrocarbon-based substances (PFASs) restricted for use by the European Union, and is green and environmentally friendly. After coating it, the initial water drop angle on the substrate surface is above 111°, and after rubbing with rubber and steel wool 5000 times, it still maintains a water drop angle of about 105°, with excellent anti-fingerprint and friction resistance.

Description

Technical Field

[0001] The invention relates to an anti-fingerprint agent, in particular to an anti-fingerprint agent with a hyperbranched three-dimensional structure, containing CF bonds and siloxane end-capping, and also to a preparation method of the anti-fingerprint agent and an application of the anti-fingerprint agent, belonging to the technical field of new materials. Background Art

[0002] In recent years, high-tech products such as mobile phones, laptops, digital bracelets, and wearable electronic products have been very popular among consumers. However, during frequent use, the shells and screen surfaces of these electronic products are easily contaminated by fingerprints, skin oils, sweat, and cosmetics, which blur the windows and reduce the image quality and aesthetic appearance. Therefore, higher requirements are placed on the anti-fingerprint performance of coatings used in the shells and screen surfaces of electronic products.

[0003] Fluorocarbon compounds have excellent heat resistance and chemical stability, water and oil repellency and low surface energy, and are often used for hydrophobic and oleophobic modification of various materials. Therefore, fluorocarbon compounds / polymers have generally become the main components of anti-fingerprint coatings. For example, the Chinese patent (publication number CN104559761A) discloses that a silane coupling agent, water, a cosolvent and heptadecafluorodecyl triethoxysilane are reacted at 60~80℃ for 2~4h to prepare an anti-fingerprint coating, which is applied to a substrate and baked at 180~220℃ for 3~7min to obtain a fluorine-containing anti-fingerprint coating. The coating has good anti-fingerprint performance and good adhesion to the substrate. The Chinese patent (publication number CN113265199 A) uses perfluorononane, perfluorooctyl triethoxysilane, dodecafluoroheptyl methacrylate, polyvinylidene fluoride, methyl methacrylate, cosolvent, etc. to prepare a hydrophobic and light-release fluorine material coating, which has the characteristics of aging resistance, good hydrophobicity, oil resistance, and light release, and the coating hardness reaches 2H. However, the use of perfluorinated long-chain alkane compounds will inevitably cause adverse effects on the human body and the environment. In addition, with the EU's proposal to restrict perfluorinated or polyfluorinated hydrocarbon substances (PFASs), the use of long-chain perfluorinated and polyfluorinated alkane compounds is limited. Therefore, it is urgent to develop environmentally friendly anti-fingerprint agents with relatively low fluorine content. Summary of the invention

[0004] In view of the above-mentioned technical problems existing in the prior art, the first object of the present invention is to provide an anti-fingerprint agent, which has a hyperbranched three-dimensional structure, contains CF bonds and is end-capped with siloxane, giving the anti-fingerprint agent excellent hydrophobic anti-fouling, anti-fingerprint, friction resistance and other properties, and does not contain perfluorinated or polyfluorinated hydrocarbon substances (PFASs) restricted for use by the European Union, and is green and environmentally friendly.

[0005] The second object of the present invention is to provide a method for preparing an anti-fingerprint agent, which mainly constructs the anti-fingerprint agent through a very mature substitution reaction and addition reaction, has simple operation, high reaction rate, mild conditions, and is conducive to industrial production.

[0006] The third object of the present invention is to provide an application of an anti-fingerprint agent, which is used to prepare an anti-fingerprint coating on the surface of a substrate material, showing excellent hydrophobic antifouling, anti-fingerprint, friction resistance and other properties.

[0007] In order to achieve the above technical objectives, the present invention provides an anti-fingerprint agent having the following structural formula:

[0008]

[0009] in,

[0010] Rf is a fluorine-containing aromatic unit;

[0011] The following structural units:

[0012] ;

[0013] n is an integer between 1 and 3000;

[0014] It is a fluorine-containing siloxane group.

[0015] The anti-fingerprint agent provided by the present invention has a special molecular structure. On the one hand, it has a hyperbranched three-dimensional structure, which significantly improves the tensile strength, friction resistance and other properties of a polyurethane matrix polymer. On the other hand, an appropriate amount of CF bonds are introduced into the hyperbranched main chain through an aromatic unit, and siloxane is introduced as an end-capping group. The introduction of fluorine and silicon improves the polarity, stability and heat resistance of the polyurethane matrix, and gives the anti-fingerprint agent excellent hydrophobic antifouling, anti-fingerprint, friction resistance and other properties.

[0016] As a preferred embodiment, the fluorine-containing aromatic unit has the following structural formula: , , , , or ; Using fluorine-containing aromatic units to replace existing perfluorinated or polyfluorinated hydrocarbon substances can achieve low toxicity and degradability of anti-fingerprint agents, which is environmentally friendly.

[0017] As a preferred embodiment, the fluorinated silicone has the following structural formula: , , , , , , or The preferred siloxane is used for the end-capping of the hyperbranched fluorinated polyurethane, thereby endowing the hyperbranched polymer with strong polarity, high stability and high heat resistance.

[0018] The present invention also provides an anti-fingerprint agent, which comprises the following preparation steps:

[0019] 1) 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine undergo substitution reaction I to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine;

[0020] or,

[0021] 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine undergo substitution reaction II to obtain 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine;

[0022] The 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine has the following structural formula:

[0023] ;

[0024] The 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine has the following structural formula:

[0025]

[0026] 2) 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and methyl acrylate undergo addition reaction Ⅰ to obtain intermediate Ⅰ;

[0027] The intermediate I has the following structural formula:

[0028] ;

[0029] 3) 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine and methyl acrylate undergo addition reaction II to obtain intermediate II;

[0030] The intermediate II has the following structural formula:

[0031] ;

[0032] 4) The intermediate II and the fluorinated aromatic diamine undergo substitution reaction III to obtain monomer I;

[0033] The monomer I has the following structural formula:

[0034]

[0035] 5) Intermediate Ⅰ and monomer Ⅰ undergo polymerization reaction to form hyperbranched fluorinated polyurethane;

[0036] The hyperbranched fluorinated polyurethane has the following structural formula:

[0037] ;

[0038] 6) Chloroalkylsiloxane and fluorine-containing aromatic diamine undergo substitution reaction IV to obtain siloxane-based fluorine-containing aromatic diamine;

[0039] The fluorine-containing aromatic diamine has the following structural formula:

[0040] , , , ,

[0041] , , or ;

[0042] 7) The hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine undergo a substitution reaction V to obtain the target product.

[0043] As a preferred embodiment, the fluorine-containing aromatic diamine includes: , , , , or At least one of them.

[0044] As a preferred embodiment, the chloroalkylsiloxane comprises: , , , , , , , At least one of them.

[0045] As a preferred embodiment, the substitution reaction I or the substitution reaction II or the substitution reaction The reaction conditions are: in the presence of a base, in an ice-water bath, for 2 to 6 hours. Among them, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine in substitution reaction I is 1: (3 to 3.8); the molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine in substitution reaction II is 1: (1.8 to 2.4); the molar ratio of intermediate II to fluorinated aromatic diamine in substitution reaction III is 1: (0.7 to 1.2).

[0046] As a preferred scheme, the reaction conditions of the substitution reaction IV are: reacting at room temperature for 2 to 4 hours, wherein the molar ratio of the chloroalkylsiloxane to the fluorinated aromatic diamine in the substitution reaction IV is 1:(1 to 1.6).

[0047] As a preferred scheme, the reaction conditions of the substitution reaction V are: under the catalysis of ferric chloride, at room temperature, the reaction is carried out for 4 to 8 hours; wherein the molar ratio of the hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine in the substitution reaction V is 1: (4 to 5) × (6 + 24n), and n is an integer between 0 and 3000.

[0048] As a preferred scheme, the conditions of the addition reaction I or the addition reaction II are: reflux at 80~120°C for 4~10 h under the catalysis of cupric chloride; wherein the molar ratio of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate in the addition reaction I is 1:(6~8); and the molar ratio of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate in the addition reaction II is 1:(4~5).

[0049] As a preferred scheme, the conditions of the polymerization reaction are: in the presence of a base, at a temperature of 80-120° C., and reflux for 8-12 hours; wherein the molar ratio of intermediate I to monomer I in the polymerization reaction is 1: (1-1.2)×(6+24n), where n is an integer between 0 and 3000.

[0050] The invention also provides an application of an anti-fingerprint agent, which is used for preparing an anti-fingerprint coating.

[0051] The anti-fingerprint agent provided by the present invention is coated on a substrate by vacuum evaporation, and the initial water drop angle on the substrate surface is above 111°. After being rubbed 5000 times with rubber and steel wool, the water drop angle is still maintained at about 105°. The adhesion test result shows 5B, and the agent has excellent anti-fingerprint and friction resistance.

[0052] The preparation method of the anti-fingerprint agent provided by the present invention comprises the following specific preparation steps:

[0053] 1) Weigh 2,4,6-trichloro-1,3,5-triazine, fluorinated aromatic diamine, acetone and sodium carbonate and add them to a reactor. React in an ice-water bath for 2-6 hours. By controlling the ratio of 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine, substitution reaction I and substitution reaction II occur respectively. Separate and purify by chromatographic column (hexane: ethyl acetate) to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine. Their structural formulas are shown below:

[0054] ;

[0055] The fluorine-containing aromatic diamine is an aromatic diamine containing a fluorine-containing substituent or an aromatic diamine containing a short-chain fluoroalkyl group. For example, the fluorine-containing aromatic diamine can be at least one of the following compounds:

[0056] ; It is further preferred that the fluorinated aromatic diamine is 4,4'-diaminooctafluorobiphenyl. By selecting a suitable ratio of 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine, 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine or 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine can be obtained. For example, the molar ratio of 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine in the substitution reaction I is 1:(3~3.8); It is further preferred that the molar ratio of 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine is 1:3.4, and 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine is obtained. For example, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine in the substitution reaction II is 1:(1.8-2.4); more preferably, the molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine is 1:2.1. In this case, 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine is obtained.

[0057] 2) Weigh 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid and cupric chloride into a reactor, reflux at 80-120°C for 4-10 h in a nitrogen atmosphere, and allow addition reaction I to occur. After washing and vacuum distillation, purification is performed on a silica chromatography column to obtain an intermediate I, the structural formula of which is shown below:

[0058] ;

[0059] In the addition reaction I, the molar ratio of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(6-8); more preferably, the molar ratio of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:7.2.

[0060] 3) Weigh 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, methyl acrylate, acetic acid, and cupric chloride into a reactor, reflux at 80-120°C for 4-10 h in a nitrogen atmosphere, and allow addition reaction II to occur. After washing and vacuum distillation, purify with a silica chromatography column to obtain intermediate II, the structural formula of which is shown below:

[0061] ;

[0062] In the addition reaction II, the molar ratio of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(4-5); more preferably, the molar ratio of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:4.1.

[0063] 4) Weigh the intermediate II, fluorinated aromatic diamine, acetone and sodium carbonate and add them to the reactor. React in an ice-water bath for 2-6 hours to cause substitution reaction III. After washing and vacuum distillation, monomer I is obtained. Its structural formula is shown below:

[0064]

[0065] The molar ratio of the intermediate II to the fluorinated aromatic diamine in the substitution reaction III is 1:(0.7-1.2); more preferably, the molar ratio of the intermediate II to the fluorinated aromatic diamine is 1:1.1.

[0066] 5) Weigh intermediate I, monomer I, acetone, and sodium hydroxide (0.5wt%) and add them to the reactor. Under the condition of heating and reflux at 80-120°C, the excess monomer I and intermediate I undergo polymerization reaction to generate monomer III having a three-dimensional hyperbranched fluorinated polyurethane structure, the structural formula of which is shown below:

[0067] ;

[0068] The molar ratio of intermediate I to monomer I in the polymerization reaction is 1: (1-1.2) × (6 + 24n), wherein n is an integer between 0 and 3000; more preferably, the molar ratio of intermediate I to monomer I is 1: 1.1 × (6 + 24n), wherein n is an integer between 0 and 3000.

[0069] 6) Weigh chloroalkylsiloxane, fluorine-containing aromatic diamine, and dichloromethane and add them to the reactor. React at room temperature for 2-4 hours to cause substitution reaction IV. After washing and distillation, siloxane-based fluorine-containing aromatic diamine is obtained, and its structural formula is as follows:

[0070] ;

[0071] The chloroalkylsiloxane is specifically for example:

[0072] At least one of them. More preferably, chloromethyltriethoxysilane. The molar ratio of the chloroalkylsiloxane to the fluorine-containing aromatic diamine in the substitution reaction IV is 1:(1-1.6); more preferably, the molar ratio of the chloroalkylsiloxane to the fluorine-containing aromatic diamine is 1:1.1.

[0073] 7) Weighing a three-dimensional hyperbranched fluorinated polyurethane, a siloxane-based fluorinated aromatic diamine, ferric chloride, and dichloromethane, adding them to a reactor, reacting at room temperature for 4 to 8 hours, causing a substitution reaction V, and obtaining a final product after washing and distillation; in the substitution reaction V, the molar ratio of the three-dimensional hyperbranched fluorinated polyurethane to the siloxane-based fluorinated aromatic diamine is 1: (4 to 5) × (6 + 24 n), where n is an integer between 0 and 3000; more preferably, the molar ratio of the three-dimensional hyperbranched fluorinated polyurethane to the siloxane-based fluorinated aromatic diamine is 1: 4.6 × (6 + 24 n), where n is an integer between 0 and 3000.

[0074] Compared with the prior art solutions, the technical solutions of the present invention have the following beneficial effects:

[0075] 1) The anti-fingerprint agent provided by the present invention has a hyperbranched three-dimensional structure, which gives polyurethane good tensile resistance, friction resistance and other properties. At the same time, the CF bond and the siloxane used for end-capping give polyurethane excellent properties such as strong polarity, high stability, and high heat resistance. In summary, the fingerprint agent has excellent hydrophobic antifouling, anti-fingerprint, and friction resistance properties.

[0076] 2) The anti-fingerprint agent provided by the present invention avoids the use of perfluorinated or polyfluorinated hydrocarbon substances (PFASs) in the EU restriction proposal, and can achieve low toxicity and degradability of the anti-fingerprint agent, meeting the requirements of being friendly to the human body and the environment.

[0077] 3) The preparation method of the anti-fingerprint agent provided by the present invention is synthesized by existing very mature substitution reaction and addition reaction, which is simple to operate, has a high reaction rate, mild conditions, and is conducive to industrial production;

[0078] 3) After the anti-fingerprint agent provided by the present invention is coated by vacuum evaporation, the initial water drop angle on the substrate surface is above 111°, and after being rubbed 5000 times with rubber and steel wool, the water drop angle is still maintained at about 105°. The adhesion test result shows 5B, which has excellent anti-fingerprint and friction resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0079] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the anti-fingerprint agent with a three-dimensional structure prepared in Example 1. DETAILED DESCRIPTION

[0080] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0081] Example 1

[0082] The anti-fingerprint agent provided in this embodiment has the following structural formula:

[0083] ,

[0084] Among them, Rf is the main structure of 4,4'-diaminooctafluorobiphenyl, and its structural formula is as follows:

[0085] ;

[0086] It is a polymer main structure of 4,4'-diaminooctafluorobiphenyl, methyl acrylate, and trichlorotriazine, and its structural formula is as follows:

[0087] ,

[0088] Where n=10;

[0089] It is the product of substitution reaction between chloromethyltriethoxysilane and 4,4'-diaminooctafluorobiphenyl, and its structural formula is as follows:

[0090] .

[0091] The specific preparation steps are as follows:

[0092] 1) Weigh 2,4,6-trichloro-1,3,5-triazine (184.4 g, 1 mol) and 4,4'-diaminooctafluorobiphenyl in a molar ratio of 1:3.4 and 1:2.1, as well as acetone (5 mol) and sodium carbonate (2.5 wt%), respectively, and add them into two reactors, and carry out substitution reaction I and substitution reaction II in an ice-water bath, respectively, for a reaction time of 2 h, and separate and purify by a chromatographic column (hexane: ethyl acetate) to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, respectively;

[0093] 2) Weigh 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine (1 mol) and methyl acrylate, acetic acid (5 mol) and cupric chloride (2 wt%) in a molar ratio of 1:7.2 and add them into a reactor. Reflux at 120°C for 5 h in a nitrogen atmosphere to cause addition reaction I. After washing and vacuum distillation, purify on a silica chromatography column to obtain intermediate I.

[0094] 3) Weigh 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine (1 mol) and methyl acrylate, acetic acid (5 mol) and cupric chloride (2 wt%) in a molar ratio of 1:4.1 and add them into a reactor. Reflux at 120°C for 5 h in a nitrogen atmosphere to cause addition reaction II. After washing and vacuum distillation, purify on a silica chromatography column to obtain intermediate II.

[0095] 4) Weighing intermediate II (1 mol) and 4,4'-diaminooctafluorobiphenyl, acetone (5 mol) and sodium carbonate (2 wt%) in a molar ratio of 1:1.1, adding them into a reactor, reacting in an ice-water bath for 3 h, causing substitution reaction III, and obtaining monomer I after washing and vacuum distillation;

[0096] 5) Weighing intermediate I (1 mol) and monomer I in a molar ratio of 1:1.1×(6+24n)(n=10) as well as acetone (5 mol) and sodium hydroxide (0.5 wt%), and adding them into a reactor, heating under reflux at 110°C, the excess monomer I and intermediate I undergo polymerization reaction for 9 hours to generate monomer III of a three-dimensional hyperbranched fluorinated polyurethane;

[0097] 6) Weighing 1 mol of chloromethyltriethoxysilane, 4,4'-diaminooctafluorobiphenyl and dichloromethane (2 mol) in a molar ratio of 1:1.1, adding them into a reactor, reacting at room temperature for 2 hours, causing substitution reaction IV, and obtaining siloxane-based fluorinated aromatic diamine after washing and distillation;

[0098] 7) Weigh the monomer III (1 mol) and siloxane-based fluorinated aromatic diamine in a molar ratio of 1:4.6×(6+24n)(n=10), as well as ferric chloride (3wt%) and dichloromethane (10 mol) and add them to the reactor. React at room temperature for 6 hours to cause substitution reaction V. After washing and distillation, the final product is obtained. Its structural diagram is shown in the figure below. Figure 1 shown.

[0099] The new environmentally friendly anti-fingerprint agent prepared in Example 1 was used for substrate coating (plasma treatment for 3 minutes, voltage 65-68V, current 2.5-3A; electron gun preheating power 10%-15%, silicon plating 12nm, turntable rotation 99.9%, evaporation A:B:C three-stage voltage ratio of 20.5%:22.1%:22.1%). After completion, the adhesion of the substrate surface, initial water drop angle, rubber friction resistance, steel wool friction resistance, oil pen resistance and other properties were tested, and the results are shown in Table 1.

[0100] Example 2

[0101] This embodiment provides an anti-fingerprint agent, the structural formula of which is as follows:

[0102] ,

[0103] Wherein, Rf is the main structure of tetrafluoro-p-phenylenediamine, and its structural formula is as follows:

[0104] ;

[0105] It is a polymer main structure of tetrafluoro-p-phenylenediamine, methyl acrylate, and trichlorotriazine, and its structural formula is as follows:

[0106] ,

[0107] Where n=10;

[0108] It is the product of substitution reaction between chloroethyltrimethoxysilane and tetrafluoro-p-phenylenediamine, and its structural formula is as follows:

[0109] .

[0110] The specific preparation steps are as follows:

[0111] 1) 2,4,6-trichloro-1,3,5-triazine (184.4 g, 1 mol) and tetrafluoro-p-phenylenediamine, acetone (5 mol) and sodium carbonate (2.5 wt%) were weighed in molar ratios of 1:3.5 and 1:2.2 respectively and added into two reactors, and substitution reaction I and substitution reaction II were respectively carried out in an ice-water bath for 3 h. The products were separated and purified by a chromatographic column (hexane: ethyl acetate) to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine respectively;

[0112] 2) Weigh 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine (1 mol) and methyl acrylate, acetic acid (5 mol) and copper chloride (2 wt%) in a molar ratio of 1:7 and add them into a reactor. Reflux at 120°C for 6 h in a nitrogen atmosphere to cause addition reaction I. After washing and vacuum distillation, purification by silica chromatography column is performed to obtain intermediate I.

[0113] 3) Weigh 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine (1 mol) and methyl acrylate, acetic acid (5 mol) and copper chloride (2 wt%) in a molar ratio of 1:4.3 and add them into a reactor. Reflux at 120°C for 6 h in a nitrogen atmosphere to cause addition reaction II. After washing and vacuum distillation, purify on a silica chromatography column to obtain intermediate II.

[0114] 4) Weighing intermediate II (1 mol), tetrafluoro-p-phenylenediamine, acetone (5 mol), and sodium carbonate (2.5 wt%) in a molar ratio of 1:1.1, adding them into a reactor, reacting in an ice-water bath for 4 h, causing substitution reaction III, and obtaining monomer I after washing and vacuum distillation;

[0115] 5) Weighing intermediate Ⅰ (1 mol) and monomer Ⅰ in a molar ratio of 1:1.1×(6+24n)(n=10) as well as acetone (5 mol) and sodium hydroxide (0.5 wt%), and adding them into a reactor, heating under reflux at 120°C, the excess monomer Ⅰ and intermediate Ⅰ undergo polymerization reaction (10 h) to generate monomer Ⅲ of a three-dimensional hyperbranched fluorinated polyurethane;

[0116] 6) Weigh 1 mol of chloroethyltrimethoxysilane, tetrafluoro-p-phenylenediamine and dichloromethane (2 mol) in a molar ratio of 1:1.3 and add them to a reactor. React at room temperature for 2 hours to cause substitution reaction IV. After washing and distillation, siloxane-based fluorinated aromatic diamine is obtained;

[0117] 7) Monomer III (1 mol) and siloxane-based fluorinated aromatic diamine in a molar ratio of 1:4.6×(6+24n)(n=10), as well as ferric chloride (3 wt%) and dichloromethane (10 mol) were weighed and added into a reactor. The mixture was reacted at room temperature for 7 h to cause substitution reaction V. The final product was obtained after washing and distillation.

[0118] The same method as in Example 1 was adopted. After completion, the adhesion, initial water drop angle, rubber friction resistance, steel wool friction resistance, oil pen resistance and other properties of the substrate surface were tested. The results are shown in Table 1.

[0119] Example 3

[0120] The anti-fingerprint agent provided in this embodiment has the following structural formula:

[0121] ,

[0122] Wherein, Rf is the main structure of tetrafluoro-1,3-phenylenediamine, and its structural formula is as follows:

[0123] ;

[0124] It is a polymer main structure of tetrafluoro-1,3-phenylenediamine, methyl acrylate, and trichlorotriazine, and its structural formula is as follows:

[0125] ,

[0126] Where n=10;

[0127] It is the product of substitution reaction between chloromethyltrimethoxysilane and tetrafluoro-1,3-phenylenediamine, and its structural formula is as follows:

[0128] .

[0129] The specific preparation steps are as follows:

[0130] 1) 2,4,6-trichloro-1,3,5-triazine (184.4 g, 1 mol) and tetrafluoro-1,3-phenylenediamine in a molar ratio of 1:3.6 and 1:2.1, as well as acetone (5 mol) and sodium carbonate (3 wt%) were weighed and added into two reactors, and substitution reaction I and substitution reaction II were respectively carried out in an ice-water bath for 2 h. The reaction was separated and purified by a chromatographic column (hexane: ethyl acetate) to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine, respectively;

[0131] 2) Weigh 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine (1 mol) and methyl acrylate, acetic acid (5 mol) and cupric chloride (2.5 wt%) in a molar ratio of 1:6.8 and add them into a reactor. Reflux at 120°C for 8 h in a nitrogen atmosphere to cause addition reaction I. After washing and vacuum distillation, purification by silica chromatography column is performed to obtain intermediate I.

[0132] 3) Weigh 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine (1 mol) and methyl acrylate, acetic acid (5 mol) and cupric chloride (2.5 wt%) in a molar ratio of 1:4.2 and add them into a reactor. Reflux at 120°C for 8 h in a nitrogen atmosphere to cause addition reaction II. After washing and vacuum distillation, purification by silica chromatography column is performed to obtain intermediate II.

[0133] 4) Weighing the intermediate II (1 mol) and tetrafluoro-1,3-phenylenediamine, acetone (5 mol) and sodium carbonate (2 wt%) in a molar ratio of 1:0.9, adding them into the reactor, reacting in an ice-water bath for 2 h, causing substitution reaction III, and obtaining monomer I after washing and vacuum distillation;

[0134] 5) Weighing intermediate I (1 mol) and monomer I in a molar ratio of 1:1.2×(6+24n)(n=10) as well as acetone (5 mol) and sodium hydroxide (0.5 wt%), adding them into a reactor, heating and refluxing at 110°C for 10 h, the excess monomer I and intermediate I undergo polymerization reaction to generate monomer III of a hyperbranched fluorinated polyurethane having a three-dimensional structure;

[0135] 6) Weigh 1 mol of chloromethyltrimethoxysilane, tetrafluoro-1,3-phenylenediamine and dichloromethane (2 mol) in a molar ratio of 1:1.2 and add them into a reactor, react at room temperature for 2 hours, and substitution reaction IV occurs. After washing and distillation, siloxane-based fluorinated aromatic diamine is obtained;

[0136] 7) Monomer III (1 mol) and siloxane-based fluorinated aromatic diamine in a molar ratio of 1:4.3×(6+24n)(n=10), as well as ferric chloride (3 wt%) and dichloromethane (10 mol) were weighed and added into a reactor. The mixture was reacted at room temperature for 7 h to cause substitution reaction V. The final product was obtained after washing and distillation.

[0137] The same method as in Example 1 was adopted. After completion, the adhesion, initial water drop angle, rubber friction resistance, steel wool friction resistance, oil pen resistance and other properties of the substrate surface were tested. The results are shown in Table 1.

[0138] Comparative Example 1

[0139] The difference between this comparative example and Example 1 is that 4,4'-diaminooctafluorobiphenyl is replaced by 4,4'-diaminobiphenyl, and the other preparation steps and conditions are the same.

[0140] The same method as in Example 1 was adopted. After completion, the adhesion, initial water drop angle, rubber friction resistance, steel wool friction resistance, oil pen resistance and other properties of the substrate surface were tested. The results are shown in Table 1.

[0141] Comparative Example 2

[0142] The difference between this comparative example and Example 1 is that chloromethyltriethoxysilane is no longer added for end-capping treatment, and the other preparation steps and conditions are the same.

[0143] The same method as Example 1 was adopted. After completion, the adhesion, initial water drop angle, rubber friction resistance, steel wool friction resistance, oil pen resistance and other properties of the substrate surface (tempered film for mobile phone) were tested. The results are shown in Table 1.

[0144]

[0145] Adhesion: Draw a hundred grids and test with 3M 600 tape 3 times.

[0146] Hydrophobic angle test method: The static contact angle of the coating is measured by a JGW-360a contact angle meter. The test liquid volume is 2 microliters, the test environment is 24 ± 1 ℃, and the relative humidity is 45 ± 1 %. The water droplet touch angle is measured at 5 points and the average value is taken.

[0147] Rubber abrasion resistance test method: The rubber abrasion resistance test is measured by ZJ-339-GSR wear tester. The coated substrate is fixed on the tester, the pressure is set to 1000g, the stroke is set to 40 mm, and the speed is 40 cycles / min. After the test, the water drop angle test results of the substrate are recorded.

[0148] Steel wool abrasion resistance test method: The steel wool abrasion resistance test is measured by ZJ-339-GSR wear tester. The coated substrate is fixed on the tester. The rubber model is MUNBANGSAWOO, the pressure is set to 1000g, the stroke is set to 40 mm, and the speed is 40 cycles / min. After the test, the water drop angle test results of the substrate are recorded.

[0149] Oil-resistant pen test: mark two points symmetrically in the middle of the sampling plate, with a distance of 5 cm between the two points; use an oil-resistant pen to draw a straight line between the two points and wipe it with a dust-free cloth, which is recorded as 1; then use an oil-resistant pen to draw a straight line at the same position and wipe it with a dust-free cloth. Repeat this process until the oil-resistant pen marks cannot be wiped clean with a dust-free cloth, which is recorded as N times. The number of times the oil-resistant pen is used is (N-1). The more times the oil-resistant pen is used, the better the oil resistance of the surface.

[0150] From the data of Examples 1 to 3, it can be seen that the anti-fingerprint agent has excellent adhesion fastness, hydrophobic antifouling, friction resistance and oil pen resistance after being attached to the substrate surface as a film material. Since no CF functional group and siloxane for end-capping were added in Comparative Examples 1 and 2, the resulting substrate surfaces showed no significant difference in adhesion, but showed obvious decreases in hydrophobicity, friction resistance and oil pen resistance. Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the anti-fingerprint agent prepared in Example 1, indicating that the anti-fingerprint agent was successfully prepared.

[0151] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it: although the present invention has been described in detail with reference to the aforementioned embodiments, a person of ordinary skill in the art should understand that he or she may still modify the technical solutions described in the aforementioned embodiments, or replace some of the technical features therein by equivalents; and these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. An anti-fingerprint agent, characterized in that: Has the following structural formula: ； in, Rf is a fluorine-containing aromatic unit; The following structural units: ; n is an integer between 1 and 3000; is a fluorine-containing siloxane group; The fluorine-containing aromatic unit has the following structural formula: , , , , or ; The fluorinated siloxane has the following structural formula: , , , , , , or .

2. The method for preparing an anti-fingerprint agent according to claim 1, characterized in that: The method comprises the following preparation steps: 1) 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine undergo substitution reaction I to obtain 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine; or, 2,4,6-trichloro-1,3,5-triazine and fluorinated aromatic diamine undergo substitution reaction II to obtain 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine; The 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine has the following structural formula: ; The 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine has the following structural formula: ; 2) 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine and methyl acrylate undergo addition reaction I to obtain intermediate I; The intermediate I has the following structural formula: ; 3) 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine and methyl acrylate undergo addition reaction II to obtain intermediate II; The intermediate II has the following structural formula: ; 4) The intermediate II and the fluorinated aromatic diamine undergo substitution reaction III to obtain monomer I; The monomer I has the following structural formula: ; 5) Intermediate Ⅰ and monomer Ⅰ undergo polymerization reaction to form hyperbranched fluorinated polyurethane; The hyperbranched fluorinated polyurethane has the following structural formula: ； 6) Chloroalkylsiloxane and fluorine-containing aromatic diamine undergo substitution reaction IV to obtain siloxane-based fluorine-containing aromatic diamine; The fluorine-containing aromatic diamine has the following structural formula: , , , , , or ; 7) The hyperbranched fluorinated polyurethane and the siloxane-based fluorinated aromatic diamine undergo a substitution reaction V to obtain the target product.

3. The method for preparing an anti-fingerprint agent according to claim 2, characterized in that: The fluorine-containing aromatic diamines include: , , , , or At least one of them.

4. The method for preparing an anti-fingerprint agent according to claim 2, characterized in that: The chloroalkylsiloxanes include: , , , , , , , At least one of them.

5. The method for preparing an anti-fingerprint agent according to claim 2, characterized in that: The reaction conditions of the substitution reaction I, the substitution reaction II, or the substitution reaction III are: reacting for 2 to 6 hours in an ice water bath in the presence of a base; The reaction conditions of the substitution reaction IV are: reacting for 2 to 4 hours at room temperature; The reaction conditions of the substitution reaction V are: reacting for 4 to 8 hours at room temperature under the catalysis of ferric chloride; in, The molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine in substitution reaction I is 1:(3-3.8); The molar ratio of 2,4,6-trichloro-1,3,5-triazine to fluorinated aromatic diamine in substitution reaction II is 1:(1.8~2.4); The molar ratio of intermediate II and fluorine-containing aromatic diamine in substitution reaction III is 1:(0.7~1.2); The molar ratio of chloroalkylsiloxane to fluorine-containing aromatic diamine in substitution reaction IV is 1:(1-1.6); In the substitution reaction V, the molar ratio of the hyperbranched fluorinated polyurethane to the siloxane-based fluorinated aromatic diamine is 1:(4-5)×(6+24 n), where n is an integer between 0 and 3000.

6. The method for preparing an anti-fingerprint agent according to claim 2, characterized in that: The conditions of the addition reaction I or the addition reaction II are: reflux at 80-120° C. for 4-10 h under the catalysis of copper chloride; in, In addition reaction I, the molar ratio of 2,4,6-tris(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(6~8); In addition reaction II, the molar ratio of 2-chloro-4,6-bis(fluorinated aromatic diamine)-1,3,5-triazine to methyl acrylate is 1:(4~5).

7. The method for preparing an anti-fingerprint agent according to claim 2, characterized in that: The polymerization reaction conditions are: in the presence of a base, at a temperature of 80-120° C., and reflux for 8-12 hours; The molar ratio of intermediate I to monomer I in the polymerization reaction is 1: (1-1.2) × (6+24n), where n is an integer between 0 and 3000.

8. The use of an anti-fingerprint agent according to claim 1, characterized in that: Used to prepare anti-fingerprint coatings.

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