A fluorophenylsilane, a preparation method thereof, a coating and a preparation method thereof

Abstract

The present invention provides a fluorophenylsilane and a preparation method thereof, a coating and a preparation method thereof, and belongs to the field of coatings. Due to the introduction of amino and siloxane groups, the adhesion of the waterproof coating formed by the hydrolysis of the fluorophenylsilane is significantly increased; at the same time, the introduction of phenyl groups improves the heat resistance of the coating, and the position and content of fluorine are controlled to achieve a balance between heat resistance and water resistance, thereby having broader application prospects in the field of heat-resistant and water-resistant coatings. Through testing, the waterproof coating formed by the hydrolysis of the fluorophenylsilane monomer synthesized by the present invention can reach a contact angle of 152° to water, belonging to a super-hydrophobic material, and its water resistance is superior to similar products.

Description

Technical Field

[0001] The present invention relates to the field of coatings, and in particular to a fluorine-containing phenylsilane and a preparation method thereof, a coating and a preparation method thereof. Background Art

[0002] Fluorinated silicone compounds utilize the hydrolysis and condensation reaction of the siloxane group to form chemical crosslinks with the surface of the substrate, providing adhesion, while the fluorinated organic group has a low critical surface tension and can provide anti-fouling properties. In recent years, the excellent hydrophobic properties of fluorosilicone hydrophobic coatings have been widely used in the fields of building materials, bridge steel structures, marine engineering equipment, etc. Fluorosilicone materials usually have low surface energy, and such coatings often exhibit excellent super-hydrophobicity and self-cleaning capabilities, which can effectively prevent dust, water mist and other pollutants from depositing on the surface of the protected substrate in a long-term manner, thereby avoiding the electrostatic effects of dust, water mist, and droplets, and avoiding electrical equipment from being damaged by short circuits caused by static electricity, and in serious cases, fire accidents. However, existing fluorosilicone products have problems with heat resistance, hydrophobicity, and adhesion to the substrate that do not meet the requirements. Summary of the Invention

[0003] The present invention provides a fluorinated phenylsilane and a preparation method thereof, a coating and a preparation method thereof. The coating prepared by the fluorinated phenylsilane of the present invention has excellent water resistance, strong adhesion to the substrate, is not easy to fall off, and has good high temperature resistance.

[0004] The present invention provides a fluorine-containing phenylsilane having the structural formula shown in Formula I:

[0005] Formula I;

[0006] R1 to R5 are one or more of -CF3, -F and -H, and they are not all -H at the same time;

[0007] The M includes a carbonyl group or a sulfonyl group.

[0008] Preferably, at least one of R1 to R5 is -H.

[0009] The present invention also provides a method for preparing the fluorinated phenylsilane described in the above technical solution, comprising the following steps:

[0010] A solution containing 3-aminopropyltriethoxysilane, an acid-binding agent, and a solution of a compound having the structure represented by Formula II are mixed and subjected to a condensation reaction to obtain the fluorine-containing phenylsilane;

[0011] Formula II; said X comprises -Cl, -Br or -I.

[0012] Preferably, the acid binding agent includes one or more of triethylamine, pyridine, potassium carbonate and sodium hydroxide.

[0013] Preferably, the molar ratio of 3-aminopropyltriethoxysilane to triethylamine is 1:2~5.

[0014] Preferably, the molar ratio of the 3-aminopropyltriethoxysilane to the compound having the structure represented by Formula II is 1:1.05-2.

[0015] Preferably, the condensation reaction temperature is -5 to 5°C, and the time is 1 to 6 hours.

[0016] The present invention also provides a method for preparing a coating, comprising the following steps:

[0017] coating the solution obtained by mixing the fluorophenylsilane described in the above technical solution or the fluorophenylsilane prepared by the preparation method described in the above technical solution with an organic solvent and adjusting the mixture with a pH regulator to obtain an initial coating;

[0018] The initial coating is dried and cured to obtain the coating.

[0019] Preferably, the pH value of the solution is 6.5-7 or 7.5-8.

[0020] The present invention also provides a coating prepared by the preparation method described in the above technical solution.

[0021] The introduction of amino and siloxane groups significantly increases the adhesion of the waterproof coating formed by hydrolysis of the fluorophenylsilane. The introduction of phenyl groups also improves the coating's heat resistance, and controlling the position and content of fluorine achieves a balance between heat resistance and water resistance, potentially opening up new applications in the field of heat-resistant and waterproof coatings. Testing has shown that the waterproof coating formed by hydrolysis of the fluorophenylsilane monomer synthesized in this invention exhibits a water contact angle of 152°, making it a superhydrophobic material with superior water resistance compared to similar products. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The static water hydrophobic angle test diagram of the cured coating and the untreated substrate in Examples 1 to 3;

[0023] Figure 2 The static water hydrophobic angle test diagram of the coating after heat-resistant treatment and the untreated substrate in Examples 1 to 3;

[0024] Figure 3 NMR of the product of Example 1 1 H-graph;

[0025] Figure 4 NMR of the product of Example 2 1H-graph;

[0026] Figure 5 NMR of the product of Example 3 1 Figure H. DETAILED DESCRIPTION

[0027] The present invention provides a fluorine-containing phenylsilane having the structural formula shown in Formula I:

[0028] Formula I;

[0029] R1 to R5 are one or more of -CF3, -F and -H, and they are not all -H at the same time;

[0030] The M includes a carbonyl group or a sulfonyl group.

[0031] In the present invention, at least one of the R1 to R5 is preferably -H.

[0032] The present invention also provides a method for preparing the fluorinated phenylsilane described in the above technical solution, comprising the following steps:

[0033] A solution containing 3-aminopropyltriethoxysilane, an acid-binding agent, and a solution of a compound having the structure represented by Formula II are mixed and subjected to a condensation reaction to obtain the fluorine-containing phenylsilane;

[0034] Formula II; said X comprises -Cl, -Br or -I.

[0035] In the present invention, the mixing preferably includes:

[0036] The solution containing 3-aminopropyltriethoxysilane is mixed with an acid binding agent and then mixed with a solution of a compound having the structure shown in Formula II.

[0037] In the present invention, the molar ratio of the 3-aminopropyltriethoxysilane to the acid binding agent is preferably 1:2 to 5. In a specific embodiment of the present invention, the molar ratio of the 3-aminopropyltriethoxysilane to the acid binding agent can be 1:2, 1:3, 1:4 or 1:5; the acid binding agent preferably includes one or more of triethylamine, pyridine, potassium carbonate and sodium hydroxide.

[0038] In the present invention, the concentration of 3-aminopropyltriethoxysilane in the solution containing 3-aminopropyltriethoxysilane is preferably 0.3-0.4 mmol / mL, and the solvent in the solution containing 3-aminopropyltriethoxysilane preferably includes dichloromethane.

[0039] In the present invention, the temperature for mixing the solution containing 3-aminopropyltriethoxysilane with the acid binding agent is preferably -10 to 5°C, and the time is preferably 3 to 10 min. In a specific embodiment of the present invention, the temperature for mixing the solution containing 3-aminopropyltriethoxysilane with the acid binding agent may be -10°C, -8°C, -6°C, -4°C, -2°C, 0°C, 2°C, 4°C or 5°C, and the time may be 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min or 10 min.

[0040] In the present invention, the mixing of the solution containing 3-aminopropyltriethoxysilane and the acid binding agent is preferably carried out under stirring.

[0041] In the present invention, the mixing of the solution of the compound having the structure represented by Formula II preferably comprises dropwise adding the solution of the compound having the structure represented by Formula II into a mixture of the solution containing 3-aminopropyltriethoxysilane and the acid binding agent.

[0042] In the present invention, the molar ratio of the 3-aminopropyltriethoxysilane to the compound having the structure represented by Formula II is preferably 1:1.05~2. In a specific embodiment of the present invention, the molar ratio can be 1:1.05, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2.

[0043] In the present invention, the concentration of the compound having the structure represented by Formula II in the solution of the compound having the structure represented by Formula II is preferably 1.05 to 2 mmol / 10 mL, and the solvent in the solution of the compound having the structure represented by Formula II preferably includes dichloromethane.

[0044] In the present invention, the temperature of the condensation reaction is preferably -5~5°C, and the time is preferably 1~6h. In a specific embodiment of the present invention, the temperature of the condensation reaction can be -5°C, -4°C, -3°C, -2°C, -1°C, 0°C, 1°C, 2°C, 3°C, 4°C or 5°C, and the time can be 1h, 2h, 3h, 4h, 5h or 6h.

[0045] The condensation reaction equation is shown in Formula 1:

[0046] Formula 1.

[0047] After the condensation reaction, the present invention preferably mixes the product obtained from the condensation reaction with a saturated NaHCO3 solution for quenching, and then mixes the obtained product with an extractant for extraction to obtain an extract; the extract is mixed with a desiccant for drying, and then solid-liquid separation is performed, and then the extractant in the obtained liquid is removed.

[0048] In the present invention, the extractant preferably includes dichloromethane, and the desiccant is preferably anhydrous magnesium sulfate.

[0049] The present invention also provides a method for preparing a coating, comprising the following steps:

[0050] Applying a solution obtained by mixing the fluorophenylsilane described in the above technical solution or the fluorophenylsilane prepared by the preparation method described in the above technical solution with an organic solvent and adjusting the mixture with a pH adjuster to obtain an initial coating;

[0051] The initial coating is dried and cured to obtain the coating.

[0052] In the present invention, the concentration of fluorophenylsilane in the mixed solution is preferably 10-30 mg / mL, and the pH value after adjustment by the pH adjuster is preferably 6.5-7 or 7.5-8; the pH adjuster is preferably NaOH solution or HCl solution.

[0053] In the present invention, the drying temperature is preferably 80-100°C, and the drying time is preferably 1-3 hours. In a specific embodiment of the present invention, the drying temperature can be 80°C, 90°C or 100°C, and the drying time can be 1 hour, 2 hours or 3 hours.

[0054] In the present invention, the curing temperature is preferably 150° C., and the curing time is preferably 3 to 30 minutes. In a specific embodiment of the present invention, the curing time can be 3 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes or 30 minutes.

[0055] The present invention also provides a coating prepared by the preparation method described in the above technical solution.

[0056] The fluorinated phenylsilane and its preparation method, the coating and its preparation method provided by the present invention are described in detail below with reference to the examples, but they should not be construed as limiting the scope of protection of the present invention.

[0057] Example 1

[0058] In the pear-shaped bottle equipped with a magnetic device, 2.35mL (10mmol, 1 equivalent) 3-aminopropyltriethoxysilane was added, 30mL dichloromethane was added to fully dissolve, and then 4.17mL (3 equivalents) triethylamine was added. The reactor was placed in a low-temperature reaction tank set to zero degree and stirred for 5 minutes. After 2.565g (1.05 equivalents) p-trifluoromethylbenzenesulfonyl chloride was dissolved in 10mL dichloromethane, it was added dropwise to the resulting solution through a syringe, and the reaction was fully reacted for 1.5 hours under zero degree conditions. After the full reaction, saturated NaHCO solution was added to quench the solution, and the product was extracted with dichloromethane three times. The organic layer was combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. 3.37g of the target product N-(triethoxysilyl)-4-(trifluoromethyl) benzenesulfonamide was obtained in an oily state, with a productive rate of 79%.

[0059] Example 2

[0060] To a round-bottom flask equipped with a magnetic rod, 2.35 mL of 3-aminopropyltriethoxysilane (10 mmol, 1 equivalent) was added. 30 mL of dichloromethane was added to fully dissolve the mixture, followed by 4.17 mL (3 equivalents) of triethylamine. The reactor was placed in a low-temperature reaction tank set to zero degrees Celsius and stirred for 5 minutes. 2.904 g (1.05 equivalents) of 3,5-bis(trifluoromethyl)benzoyl chloride was dissolved in 10 mL of dichloromethane and added dropwise via syringe to the resulting solution. The mixture was allowed to react for 2 hours at zero degrees Celsius. After the reaction was complete, saturated NaHCO₃ solution was added to quench the reaction. The mixture was extracted three times with dichloromethane. The organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The desired product, N-(triethoxysilyl)-3,5-(bis(trifluoromethyl)benzamide), was obtained as an oily product (3.17 g, yield 68%).

[0061] Example 3

[0062] To a pear-shaped flask equipped with a magnetic rod, 2.35 mL (10 mmol, 1 equivalent) of 3-aminopropyltriethoxysilane was added. 30 mL of dichloromethane was added to fully dissolve the mixture, followed by 4.17 mL (3 equivalents) of triethylamine. The reactor was placed in a low-temperature reaction tank set to zero degrees Celsius and stirred for 5 minutes. 2.043 g (1.05 equivalents) of p-fluorobenzenesulfonyl chloride was dissolved in 10 mL of dichloromethane and added dropwise via syringe to the resulting solution. The mixture was allowed to react for 3 hours at zero degrees Celsius. After the reaction was complete, saturated NaHCO₃ solution was added to quench the reaction. The mixture was extracted three times with dichloromethane. The organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation to yield 2.63 g of the desired product, N-(triethoxysilyl)-4-fluorobenzenesulfonamide, as an oil in a 66% yield.

[0063] Example 4

[0064] To a pear-shaped flask equipped with a magnetic rod, add 2.35 mL (10 mmol, 1 equivalent) of 3-aminopropyltriethoxysilane, add 30 mL of dichloromethane to fully dissolve it, and then add 4.17 mL (3 equivalents) of triethylamine. The reactor is placed in a low-temperature reaction tank set to zero degrees Celsius and stirred for 5 minutes. Dissolve 1.396 mL (1.05 equivalents) of m-fluorobenzenesulfonyl chloride in 10 mL of dichloromethane and add it dropwise to the resulting solution via syringe. Let it react for 3 hours at zero degrees Celsius. After the reaction is complete, saturated NaHCO3 solution is added to quench the reaction. Extract with dichloromethane, combine the organic layers, dry over anhydrous magnesium sulfate, filter, and remove the solvent by rotary evaporation. The target product, N-(triethoxysilyl)-3-fluorobenzenesulfonamide, is obtained as an oily product with a yield of 67%.

[0065] Example 5

[0066] To a pear-shaped flask equipped with a magnetic rod, 2.35 mL (10 mmol, 1 equivalent) of 3-aminopropyltriethoxysilane was added. 30 mL of dichloromethane was added to fully dissolve the mixture, followed by 4.17 mL (3 equivalents) of triethylamine. The reactor was placed in a low-temperature reaction tank set to zero degrees Celsius and stirred for 5 minutes. 1.712 mL (1.05 equivalents) of m-trifluoromethylbenzenesulfonyl chloride was dissolved in 10 mL of dichloromethane and added dropwise via syringe to the resulting solution. The mixture was allowed to fully react at zero degrees Celsius for 2.5 hours. After the reaction was fully reacted, saturated NaHCO₃ solution was added to quench the reaction. The mixture was extracted three times with dichloromethane. The organic layers were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed by rotary evaporation. The target product, N-(triethoxysilyl)-3-(trifluoromethyl)benzenesulfonamide, was obtained as an oily product (3.21 g) in a 75% yield.

[0067] Performance Testing

[0068] A 20 mg / mL solution of fluorophenylsilane synthesized using the methods described in Examples 1-5 (solvent: distilled water) was adjusted to pH 6.5 with a NaOH / HCl solution. Cotton fabric was immersed in the solution, then dried at 80°C for 1 hour and cured at 150°C for 3-30 minutes. Water resistance was then tested. Heat resistance was also tested after heating at 160°C for 6 hours. The test results for water resistance and heat resistance of the fluorophenylsilanes in Examples 1-3 are shown in Table 1.

[0069] in, Figure 1 The static water hydrophobic angle test diagram of the cured coating and the untreated substrate in Examples 1 to 3;

[0070] The materials after curing in Examples 1 to 5 all have a hydrophobic effect, and water droplets will not penetrate into the sample surface. However, the effect in Examples 1 to 3 is the best: the materials after curing in Examples 4 to 5 have water droplets penetrate into the cotton fabric within 10 seconds, while the materials after curing in Examples 1 to 3 can maintain no penetration for more than 10 minutes.

[0071] The cured materials of Examples 1 to 5 still have a hydrophobic effect after being rubbed multiple times.

[0072] Figure 2 The static water hydrophobic angle test diagram of the coating after heat-resistant treatment and the untreated substrate in Examples 1 to 3; Figures 1 and 2 In the table, 1 represents Example 1, 2 represents Example 2, and 3 represents Example 3.

[0073] Figure 3 NMR of the product of Example 1 1 H-graph;

[0074] Figure 4 NMR of the product of Example 2 1 H-graph;

[0075] Figure 5 NMR of the product of Example 3 1 Figure H.

[0076] Table 1 Test results of water resistance and heat resistance of fluorophenylsilane in Examples 1 to 3

[0077]

[0078] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A fluorinated phenylsilane, characterized in that It has the structural formula shown in Formula I: Formula I; R1, R2, R4, and R5 are -H, and R3 is -CF3; The M is a sulfonyl group.

2. The method for preparing the fluorinated phenylsilane according to claim 1, wherein The following steps are involved: A solution containing 3-aminopropyltriethoxysilane, an acid-binding agent, and a solution of a compound having the structure represented by Formula II are mixed and subjected to a condensation reaction to obtain the fluorine-containing phenylsilane; Formula II; wherein X is selected from -Cl, -Br or -I; The R1, R2, R4, and R5 are -H, R3 is -CF3; and M is a sulfonyl group.

3. The preparation method according to claim 2, characterized in that The acid binding agent is selected from one or more of triethylamine, pyridine, potassium carbonate and sodium hydroxide.

4. The preparation method according to claim 2 or 3, characterized in that The acid binding agent is triethylamine; the molar ratio of the 3-aminopropyltriethoxysilane to triethylamine is 1:2-5.

5. The preparation method according to claim 2 or 3, characterized in that The molar ratio of the 3-aminopropyltriethoxysilane to the compound having the structure represented by Formula II is 1:1.05-2.

6. The preparation method according to claim 2, characterized in that The condensation reaction temperature is -5 to 5°C and the time is 1 to 6 hours.

7. A method for preparing a coating, characterized in that: The following steps are involved: coating the solution obtained by mixing the fluorophenylsilane according to claim 1 or the fluorophenylsilane prepared by the preparation method according to any one of claims 2 to 6 with an organic solvent and adjusting the mixture with a pH adjuster to obtain an initial coating; The initial coating is dried and cured to obtain the coating.

8. The preparation method according to claim 7, characterized in that The pH value of the solution is 6.5-7 or 7.5-8.

9. The coating prepared by the preparation method according to claim 7 or 8.

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