Method for fluorinating inside equipment to form film

Abstract

The invention relates to a method for fluorinating and film forming in equipment, and belongs to the technical field of metal corrosion prevention. The metal equipment is filled with alkali liquor, so that the interior of the equipment is completely soaked in the alkali liquor, and ultrasonic cleaning is conducted till no oil stain or grease exists in the equipment; then draining, cleaning residual alkali liquor with deionized water, and drying; the interior of the equipment is polished and derusted through 600-mesh water-resistant sand; the preparation method comprises the following steps: fluorinating to form a film: introducing 3N pure-passing 10-alkenyl undecyltrihydrosilane, a 5, 5-divinyl-2, 2-dipyridyl / molybdenum complex, vinyl-1H-tetrazole, ethanol and a Karst catalyst into equipment, so as to prepare the film. According to the present invention, the 5, 5-divinyl-2, 2-dipyridyl / molybdenum complex is prepared from 5, 5-divinyl-2, 2-dipyridyl, molybdenum nitrate and ethanol, the interior of the equipment treated by the method has excellent acid and alkali resistance.

Description

Technical Field

[0001] The invention relates to the technical field of metal anticorrosion, in particular to a method for forming a fluorination film inside equipment. Background Art

[0002] Metal corrosion protection is to protect easily corroded metal objects through various means, or to protect metal objects by slowing down corrosion, so as to extend the service life of metal objects. Commonly used corrosion protection methods include physical corrosion protection, chemical corrosion protection and electrochemical corrosion protection.

[0003] Chinese patent CN118931306A: provides a metal anticorrosive coating, the raw materials of which include the following components: solvent, emulsifier, carboxyl monomer, epoxy monomer, phosphate monomer, furfural methacrylate, soft monomer, hard monomer, versatate vinyl ester and tetraethyl orthosilicate.

[0004] Chinese patent CN118325453A: belongs to the field of coating technology, and discloses a method for preparing a water-based metal anti-corrosion coating. The method comprises intercalating zirconium phosphate with an amine substance, and then mixing nanocellulose and the intercalated zirconium phosphate; after the mixture undergoes self-assembly, the zirconium phosphate nanosheets will be wrapped on the surface of the nanocellulose; and then mixing the mixed liquid with a water-based coating to obtain a water-based metal anti-corrosion coating.

[0005] Chinese patent CN118165628A: relates to the technical field of modified alkyd coatings, and discloses an environmentally friendly quick-drying modified alkyd metal anticorrosive coating, which comprises the following components by weight: 500-700 parts of environmentally friendly quick-drying water-based alkyd resin, 20-40 parts of ethylene glycol butyl ether, 0-20 parts of water-based composite drying agent, 0-15 parts of mineral oil defoamer, 4-8 parts of multifunctional additives, 240-280 parts of deionized water, 70-100 parts of rutile titanium dioxide, 5-15 parts of dispersant, 1-3 parts of carbon black, 150-280 parts of barium sulfate, 0-0.2 parts of water-based defoamer, 0-0.4 parts of leveling agent and 3-8 parts of thickener. The environmentally friendly quick-drying water-based alkyd resin includes the following components by weight: 200-260 parts of sulfonated alkyd resin product, 130-160 parts of acrylic acid grafted fatty acid product, 0.2-0.4 parts of hypophosphorous acid solution, 20-40 parts of butanediol, 500-650 parts of deionized water, and 8-12 parts of ammonia water.

[0006] The metal anti-corrosion technology of the above patents and prior art has high cost, complex process, slow film forming speed, poor stability, and the anti-corrosion performance of the metal needs to be further improved. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a method for fluorination film formation inside a device, and the operating steps are as follows:

[0008] S1: Degreasing: Fill the metal equipment with alkali solution so that the inside of the equipment is completely immersed in the alkali solution, and perform ultrasonic cleaning until there is no oil or grease inside the equipment; then drain, wash the residual alkali solution with deionized water, and dry;

[0009] S2: Rust removal: Use 600-mesh water-resistant sand to grind and remove rust from the inside of the equipment;

[0010] S3: Fluorination film formation: 3N pure fluorine gas and 5N pure nitrogen gas are introduced into the equipment, and after heating and pressurizing, the pressure is maintained for a period of time to form a film.

[0011] The flow rate of the 3N pure fluorine gas is 5-10 ml / min, and the flow rate of the 5N pure nitrogen gas is 10-15 ml / min.

[0012] The charging pressure is from -0.05MPa to 0MPa, and the temperature is 80-100°C.

[0013] The pressure holding time is 24-36h.

[0014] The film thickness is 70-100nm.

[0015] The alkali solution is a sodium hydroxide solution with a mass concentration of 5-10%, and a passivation accelerator with a mass percentage of 1-5% of the sodium hydroxide solution.

[0016] The preparation method of the passivation accelerator is:

[0017] In a sealed stirred reactor, nitrogen is introduced to replace the air, 19-38 parts of 10-alkenyl undecyl trihydrosilane, 0.03-0.3 parts of 5,5-divinyl-2,2-bipyridine / molybdenum complex, 9-18 parts of vinyl-1H-tetrazole CAS: 18755-47-0, 200-300 parts of ethanol, and 0.02-0.5 parts of Custer catalyst are added, and the mixture is reacted at 60-70° C. for 60-120 minutes. After the reaction is completed, the ethanol is evaporated under reduced pressure to obtain the passivation promoter.

[0018] The preparation method of the 5,5-divinyl-2,2-bipyridine / molybdenum complex is as follows:

[0019] By weight, 21-42 parts of 5,5-divinyl-2,2-bipyridine, 12-24 parts of molybdenum nitrate, and 200-300 parts of ethanol are mixed, reacted at 40-50° C. for 2-5 hours, ethanol is distilled off, and then dried in a vacuum to obtain the 5,5-divinyl-2,2-bipyridine / molybdenum complex.

[0020] The Custer catalyst is a commercially available product, CAS: 11057-89-9, and its name is: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (2% xylene).

[0021] Reaction mechanism

[0022] 10-Alkenyl undecyl trihydrosilane is subjected to a hydrosilylation reaction with a 5,5-divinyl-2,2-bipyridine / molybdenum complex, and 10-Alkenyl undecyl trihydrosilane is subjected to a hydrosilylation reaction with vinyl-1H-tetrazolyl to obtain undecyl silane containing a bipyridine / molybdenum complex and a tetrazolyl group.

[0023] Technical Effects

[0024] The present invention provides a method for forming a fluorinated film inside a device. Compared with the prior art, the present invention has the following significant effects:

[0025] 1. Enhanced surface activity: The complex formed by bipyridine and molybdenum has a strong coordination ability and can form a uniform film on the surface of the equipment. This film, as a substrate for the fluorination reaction, can provide more active sites and promote the adsorption and reaction of fluorine gas.

[0026] 2. Chemical reaction catalysis: Tetrazolyl compounds have high chemical reaction activity, which can reduce the activation energy of the fluorination reaction and accelerate the chemical reaction between fluorine gas and the surface of the equipment. This catalytic effect helps to improve the fluorination efficiency and convert fluorine gas into fluorinated membrane more quickly.

[0027] 3. Physical adsorption: The film containing bipyridine / molybdenum complex has a certain physical adsorption capacity, which can adsorb impurities and pollutants on the surface of the equipment and reduce their interference with the fluorination reaction. At the same time, this film can also prevent fluorine gas from directly contacting the surface of the equipment to avoid excessive corrosion or damage.

[0028] 4. Chemical bonding: During the fluorination process, the chemical bonds in bipyridine and molybdenum complexes may react with fluorine gas to form stronger chemical bonding forces. This force helps to strengthen the bonding force between the fluorinated membrane and the equipment surface and improve the firmness of the membrane.

[0029] In summary, the equipment is cleaned before the fluorination film formation inside the equipment by undecylsilane containing bipyridine / molybdenum complex and tetrazolyl. Through the formation of active thin films, providing catalysis, physical adsorption and chemical bonding and other mechanisms, the efficiency of pure fluorine gas fluorination film formation inside the equipment and the firmness of the film are jointly improved. DETAILED DESCRIPTION

[0030] In order to further explain the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with embodiments and comparative examples:

[0031] 1. Acid resistance test: Immerse the entire interior of the device after film formation in a 10% hydrochloric acid solution, heat it to 150°C, soak it at a constant temperature for 24 hours, then take it out and observe its surface;

[0032] 2. Alkali resistance test: After film formation, immerse the entire interior of the device in 10% sodium hydroxide solution, heat it to 150°C, soak it at constant temperature for 24 hours, then take it out and observe its surface.

[0033] Example 1

[0034] A method for forming a fluorinated film inside a device, the operating steps of which are:

[0035] S1: Degreasing: Fill the metal equipment with alkali solution so that the inside of the equipment is completely immersed in the alkali solution, and perform ultrasonic cleaning until there is no oil or grease inside the equipment; then drain, wash the residual alkali solution with deionized water, and dry;

[0036] S2: Rust removal: Use 600-mesh water-resistant sand to grind and remove rust from the inside of the equipment;

[0037] S3: Fluorination film formation: 3N pure fluorine gas and 5N pure nitrogen gas are introduced into the equipment, and after heating and pressurizing, the pressure is maintained for a period of time to form a film.

[0038] The flow rate of the 3N pure fluorine gas is 5 ml / min, and the flow rate of the 5N pure nitrogen gas is 10 ml / min.

[0039] The charging pressure is from -0.05MPa to 0MPa, and the temperature is 80°C.

[0040] The pressure holding time is 24 hours.

[0041] The film thickness is 70nm.

[0042] The alkali solution is a sodium hydroxide solution with a mass concentration of 5%, and a passivation accelerator with a mass percentage of 1% of the sodium hydroxide solution.

[0043] The preparation method of the passivation accelerator is:

[0044] In a closed stirred reactor, nitrogen was introduced to replace the air, 19 g of 10-alkenyl undecyl trihydrosilane, 0.03 g of 5,5-divinyl-2,2-bipyridine / molybdenum complex, 9 g of vinyl-1H-tetrazole CAS: 18755-47-0, 200 g of ethanol, and 0.02 g of Custer catalyst were added and mixed, and reacted at 60° C. for 60 minutes. After the reaction was completed, ethanol was evaporated under reduced pressure to obtain the passivation promoter.

[0045] The preparation method of the 5,5-divinyl-2,2-bipyridine / molybdenum complex is as follows:

[0046] 21 g of 5,5-divinyl-2,2-bipyridine, 12 g of molybdenum nitrate, and 200 g of ethanol were mixed, reacted at 40° C. for 2 hours, ethanol was distilled off, and then dried in a vacuum to obtain the 5,5-divinyl-2,2-bipyridine / molybdenum complex.

[0047] The Custer catalyst is a commercially available product, CAS: 11057-89-9, and its name is: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (2% xylene).

[0048] Example 2

[0049] A method for forming a fluorinated film inside a device, the operating steps of which are:

[0050] S1: Degreasing: Fill the metal equipment with alkali solution so that the inside of the equipment is completely immersed in the alkali solution, and perform ultrasonic cleaning until there is no oil or grease inside the equipment; then drain, wash the residual alkali solution with deionized water, and dry;

[0051] S2: Rust removal: Use 600-mesh water-resistant sand to grind and remove rust from the inside of the equipment;

[0052] S3: Fluorination film formation: 3N pure fluorine gas and 5N pure nitrogen gas are introduced into the equipment, and after heating and pressurizing, the pressure is maintained for a period of time to form a film.

[0053] The flow rate of the 3N pure fluorine gas is 6 ml / min, and the flow rate of the 5N pure nitrogen gas is 12 ml / min.

[0054] The charging pressure is from -0.05MPa to 0MPa, and the temperature is 85°C.

[0055] The pressure holding time is 28 hours.

[0056] The film thickness is 80nm.

[0057] The alkali solution is a sodium hydroxide solution with a mass concentration of 6%, and a passivation accelerator with a mass percentage of 2% of the sodium hydroxide solution.

[0058] The preparation method of the passivation accelerator is:

[0059] In a closed stirred reactor, nitrogen was introduced to replace the air, 25 g of 10-alkenyl undecyl trihydrosilane, 0.1 g of 5,5-divinyl-2,2-bipyridine / molybdenum complex, 12 g of vinyl-1H-tetrazole CAS: 18755-47-0, 240 g of ethanol, and 0.2 g of Custer catalyst were added and mixed, and the mixture was reacted at 65° C. for 80 minutes. After the reaction was completed, the ethanol was evaporated under reduced pressure to obtain the passivation promoter.

[0060] The preparation method of the 5,5-divinyl-2,2-bipyridine / molybdenum complex is as follows:

[0061] 28 g of 5,5-divinyl-2,2-bipyridine, 16 g of molybdenum nitrate, and 240 g of ethanol were mixed, reacted at 45° C. for 3 hours, ethanol was distilled off, and then dried in a vacuum to obtain the 5,5-divinyl-2,2-bipyridine / molybdenum complex.

[0062] The Custer catalyst is a commercially available product, CAS: 11057-89-9, and its name is: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (2% xylene).

[0063] Example 3

[0064] A method for forming a fluorinated film inside a device, the operating steps of which are:

[0065] S1: Degreasing: Fill the metal equipment with alkali solution so that the inside of the equipment is completely immersed in the alkali solution, and perform ultrasonic cleaning until there is no oil or grease inside the equipment; then drain, wash the residual alkali solution with deionized water, and dry;

[0066] S2: Rust removal: Use 600-mesh water-resistant sand to grind and remove rust from the inside of the equipment;

[0067] S3: Fluorination film formation: 3N pure fluorine gas and 5N pure nitrogen gas are introduced into the equipment, and after heating and pressurizing, the pressure is maintained for a period of time to form a film.

[0068] The flow rate of the 3N pure fluorine gas is 8 ml / min, and the flow rate of the 5N pure nitrogen gas is 14 ml / min.

[0069] The charging pressure is from -0.05MPa to 0MPa, and the temperature is 95°C.

[0070] The pressure holding time is 32 hours.

[0071] The film thickness is 90nm.

[0072] The alkali solution is a sodium hydroxide solution with a mass concentration of 8%, and a passivation accelerator with a mass percentage of 4% of the sodium hydroxide solution.

[0073] The preparation method of the passivation accelerator is:

[0074] In a closed stirred reactor, nitrogen was introduced to replace the air, 35 g of 10-alkenyl undecyl trihydrosilane, 0.2 g of 5,5-divinyl-2,2-bipyridine / molybdenum complex, 15 g of vinyl-1H-tetrazole CAS: 18755-47-0, 280 g of ethanol, and 0.4 g of Custer catalyst were added and mixed, and the mixture was reacted at 65° C. for 100 minutes. After the reaction was completed, the ethanol was evaporated under reduced pressure to obtain the passivation promoter.

[0075] The preparation method of the 5,5-divinyl-2,2-bipyridine / molybdenum complex is as follows:

[0076] 38 g of 5,5-divinyl-2,2-bipyridine, 20 g of molybdenum nitrate, and 280 g of ethanol were mixed, reacted at 45° C. for 4 hours, ethanol was distilled off, and then dried in a vacuum to obtain the 5,5-divinyl-2,2-bipyridine / molybdenum complex.

[0077] The Custer catalyst is a commercially available product, CAS: 11057-89-9, and its name is: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (2% xylene).

[0078] Example 4

[0079] A method for forming a fluorinated film inside a device, the operating steps of which are:

[0080] S1: Degreasing: Fill the metal equipment with alkali solution so that the inside of the equipment is completely immersed in the alkali solution, and perform ultrasonic cleaning until there is no oil or grease inside the equipment; then drain, wash the residual alkali solution with deionized water, and dry;

[0081] S2: Rust removal: Use 600-mesh water-resistant sand to grind and remove rust from the inside of the equipment;

[0082] S3: Fluorination film formation: 3N pure fluorine gas and 5N pure nitrogen gas are introduced into the equipment, and after heating and pressurizing, the pressure is maintained for a period of time to form a film.

[0083] The flow rate of the 3N pure fluorine gas is 10 ml / min, and the flow rate of the 5N pure nitrogen gas is 15 ml / min.

[0084] The charging pressure is from -0.05MPa to 0MPa, and the temperature is 100°C.

[0085] The pressure holding time is 36 hours.

[0086] The film thickness is 100 nm.

[0087] The alkali solution is a sodium hydroxide solution with a mass concentration of 10%, and a passivation accelerator with a mass percentage of 5% of the sodium hydroxide solution.

[0088] The preparation method of the passivation accelerator is:

[0089] In a closed stirred reactor, nitrogen was introduced to replace the air, 38 g of 10-alkenyl undecyl trihydrosilane, 0.3 g of 5,5-divinyl-2,2-bipyridine / molybdenum complex, 18 g of vinyl-1H-tetrazole CAS: 18755-47-0, 300 g of ethanol, and 0.5 g of Custer catalyst were added and mixed, and reacted at 70° C. for 120 minutes. After the reaction was completed, ethanol was evaporated under reduced pressure to obtain the passivation promoter.

[0090] The preparation method of the 5,5-divinyl-2,2-bipyridine / molybdenum complex is as follows:

[0091] 42 g of 5,5-divinyl-2,2-bipyridine, 24 g of molybdenum nitrate, and 300 g of ethanol were mixed, reacted at 50° C. for 5 hours, ethanol was distilled off, and then dried in a vacuum to obtain the 5,5-divinyl-2,2-bipyridine / molybdenum complex.

[0092] The Custer catalyst is a commercially available product, CAS: 11057-89-9, and its name is: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (2% xylene).

[0093] Comparative Example 1

[0094] No passivation accelerator was added, and the rest was the same as in Example 1.

[0095] Comparative Example 2

[0096] The other steps were the same as in Example 1 except that the 5,5-divinyl-2,2-bipyridine / molybdenum complex was not added.

[0097] Comparative Example 3

[0098] The other steps were the same as in Example 1 except that vinyl-1H-tetrazole was not added.

[0099] The experimental results of the acid resistance test agent and the alkali resistance test are shown in Table 1.

[0100] Table 1

[0101]

[0102] Through the analysis of the above embodiments and comparative examples, the interior of the device treated by the present invention has excellent acid and alkali resistance.

[0103] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A method for forming a fluorinated film inside a device, the operating steps of which are: S1: Degreasing: Fill the metal equipment with alkali solution so that the inside of the equipment is completely immersed in the alkali solution, and perform ultrasonic cleaning until there is no oil or grease inside the equipment; then drain, wash the residual alkali solution with deionized water, and dry; S2: Rust removal: Use 600-mesh water-resistant sand to grind and remove rust from the inside of the equipment; S3: Fluorination film formation: 3N pure fluorine gas and 5N pure nitrogen gas are introduced into the equipment, and after heating and pressurizing, the pressure is maintained for a period of time to form a film; The alkali solution is a sodium hydroxide solution with a mass concentration of 5-10%, and a passivation accelerator with a mass percentage of 1-5% of the sodium hydroxide solution; The passivation accelerator is prepared by reacting 10-alkenyl undecyl trihydrosilane, 5,5-divinyl-2,2-bipyridine / molybdenum complex and vinyl-1H-tetrazole.

2. The method for forming a fluorinated film inside a device according to claim 1, characterized in that: The flow rate of the 3N pure fluorine gas is 5-10 ml / min, and the flow rate of the 5N pure nitrogen gas is 10-15 ml / min.

3. The method for forming a fluorinated film inside a device according to claim 1, characterized in that: The charging pressure is from -0.05MPa to 0MPa, and the temperature is 80-100°C.

4. The method for forming a fluorinated film inside a device according to claim 1, characterized in that: The pressure holding time is 24-36h.

5. The method for forming a fluorinated film inside a device according to claim 1, characterized in that: The film thickness is 70-100nm.

6. The method for forming a fluorinated film inside a device according to claim 1, characterized in that: The alkali solution is a sodium hydroxide solution with a mass concentration of 5-10%, and a passivation accelerator with a mass percentage of 1-5% of the sodium hydroxide solution.

7. A method for forming a fluorinated film inside a device according to claim 6, characterized in that: The preparation method of the passivation accelerator is: In a sealed stirred reactor, nitrogen is introduced to replace the air, 19-38 parts of 10-alkenyl undecyl trihydrosilane, 0.03-0.3 parts of 5,5-divinyl-2,2-bipyridine / molybdenum complex, 9-18 parts of vinyl-1H-tetrazole, 200-300 parts of ethanol, and 0.02-0.5 parts of Custer catalyst are added and mixed, and the mixture is reacted at 60-70° C. for 60-120 minutes. After the reaction is completed, the ethanol is evaporated under reduced pressure to obtain the passivation promoter.

8. The method for forming a fluorinated film inside a device according to claim 7, characterized in that: The preparation method of the 5,5-divinyl-2,2-bipyridine / molybdenum complex is as follows: By weight, 21-42 parts of 5,5-divinyl-2,2-bipyridine, 12-24 parts of molybdenum nitrate, and 200-300 parts of ethanol are mixed, reacted at 40-50° C. for 2-5 hours, ethanol is distilled off, and then dried in a vacuum to obtain the 5,5-divinyl-2,2-bipyridine / molybdenum complex.

9. The method for forming a fluorinated film inside a device according to claim 7, characterized in that: The Custer catalyst is a commercially available product, and its name is: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (2% xylene).

Images