Modified fluorine-containing vinyl silicone oil and preparation method thereof

Abstract

The invention provides modified fluorine-containing vinyl silicone oil and a preparation method thereof. The silicone oil comprises the following raw materials in percentage by mass: 45-54% of modified vinyl silicone oil, 14-21% of hydrogen-containing silicone oil, 30-35% of modified white carbon black, 0.1-0.5% of an inhibitor and 0.1-0.5% of a catalyst. The silicone oil provided by the invention has good hydrophobicity and light transmission, the invention provides a preparation method of the modified fluorine-containing vinyl silicone oil which can be accurately terminated and has high yield, and the modified fluorine-containing vinyl silicone oil can be widely applied to the field of coatings of underwater equipment and has better commercial application value.

Description

Technical Field

[0001] The present invention relates to the field of coatings for underwater equipment, in particular to the field of modified vinyl silicone oil used as coatings for underwater equipment, and particularly to a modified fluorine-containing vinyl silicone oil and a preparation method thereof. Background Art

[0002] Silicone oil is a type of organopolysiloxane product, consisting of a polymer with Si—O bonds as the main chain and organic groups connected by silicon atoms in the side chains. It exhibits excellent film-forming properties, low surface energy, heat resistance, biocompatibility, hydrophobicity, electrical insulation, and chemical inertness. Due to its excellent physical and chemical properties, silicone oil products are now widely used in various fields such as chemical industry, shipbuilding, and medicine.

[0003] To further expand their application, a growing number of researchers are focusing on modifying silicone fluids. Introducing different functional groups into silicone molecules can impart novel functional properties to silicone products. Long-chain alkyl-modified silicone fluids are formed by replacing some of the methyl groups in the polysiloxane side chains with long-chain alkyl groups. The addition of long-chain alkyl groups imparts improved mold release, lipophilicity, lubricity, defoaming, and anti-stick properties to silicone fluids, broadening their application range. Vinyl silicone fluids are composed of vinyl groups and silanol bonds. Vinyl-terminated silicone fluids, in particular, possess the properties of silicone fluids, as well as strong reactivity, lack of dangling segments, and improved compatibility with other materials. However, currently modified fluorinated vinyl silicone fluids face common preparation difficulties, such as poor end-capping, poor reaction controllability, vinyl synthesis on the side chains, and poor yields. Furthermore, silica is often added as a reinforcing agent during the synthesis of vinyl silicone fluids. However, poor dispersion of silica in the system can reduce the optical transparency of the silicone fluid.

[0004] Therefore, there is an urgent need on the market for a modified fluorinated vinyl silicone oil with high hydrophobicity and light transmittance, as well as a preparation method that can accurately cap the end and has a high yield. Summary of the Invention

[0005] In response to the problems existing in the prior art, the present invention modifies vinyl silicone oil as the main component, and then adds hydrogen-containing silicone oil and modified white carbon black to prepare a modified fluorine-containing vinyl silicone oil. The obtained vinyl silicone oil has the advantages of high hydrophobicity and light transmittance, and solves the problems of inaccurate end-capping and low yield of traditional vinyl silicone oil.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0007] On the one hand, the present invention provides a modified fluorine-containing vinyl silicone oil, which includes the following raw materials in percentage by mass: 45-54% of modified vinyl silicone oil, 14-21% of hydrogen-containing silicone oil, 30-35% of modified white carbon black, 0.1%-0.5% of inhibitor, and 0.1%-0.5% of catalyst, with the total percentage by mass being 100%.

[0008] In some embodiments of the present invention, the structural formula of the modified vinyl silicone oil is as follows:

[0009]

[0010] Among them, R F is a fluorinated alkyl group; R1 is a long-chain alkane; R2 is an ether group; the value of n1 is 2-10; the value of n2 is 7-15; and the value of n3 is 3-8.

[0011] In some embodiments of the present invention, the fluorinated alkyl group is trifluoropropyl or heptadecafluorodecyl.

[0012] Preferably, the fluorinated alkyl group is heptadecafluorodecyl.

[0013] In some embodiments of the present invention, the long chain alkane is C 10 -C 14 ; The ether group is polyglycol ether.

[0014] In some embodiments of the present invention, the method for preparing the modified vinyl silicone oil comprises the following steps:

[0015] (1) adding a long-chain alkoxysiloxane to a strong alkaline solution and hydrolyzing it at a temperature of 80-90° C. to obtain a reaction product 1, which is set aside;

[0016] (2) adding a fluorinated cyclosiloxane monomer, vinyl polyglycol ether, a catalyst, and a strong base solution to the reaction product 1 obtained in step (1), stirring at 140-150° C. for 2.5-3.5 hours, keeping the temperature, then cooling and filtering to obtain a reaction product 2 for later use;

[0017] (3) Adding a capping agent to the reaction product 2 obtained in step (2) and stirring, thereby obtaining the modified vinyl silicone oil.

[0018] Preferably, the long-chain alkoxysiloxane is a trialkoxysiloxane or a dialkoxysiloxane, including but not limited to n-undecylmethyldiethoxysilane, n-dodecylmethyldiethoxysilane, n-tridecylmethyldiethoxysilane, n-dodecylmethyltriethoxysilane, and n-tetradecylmethyltriethoxysilane; the fluorinated cyclosiloxane monomer is heptafluorodecyltrimethoxysilane or heptafluorodecyltriethoxysilane; the vinyl polyglycol ether is vinyl diethylene glycol ether or vinyl triethylene glycol ether; the catalyst is a platinum catalyst; and the strong alkaline solutions in steps (1) and (2) are both NaOH or KOH.

[0019] More preferably, the mass ratio of the long-chain alkoxysiloxane, the fluorinated cyclosiloxane monomer and the vinyl polyglycol ether is 1:(4-8):(1-2.5); the mass ratio of the end-capping agent and the long-chain alkoxysiloxane is (0.9%-6.0%):1.

[0020] In some embodiments of the present invention, the structural formula of the capping agent is as follows:

[0021]

[0022] Wherein, R1 and R2 are both -CH3 or -CH2CH3.

[0023] Preferably, the end-capping agent is allyl(diethylamino)dimethylsilane, that is, R1 and R2 are both -CH2CH3.

[0024] In the present invention, silicone oil has good heat resistance, hydrophobicity, low surface tension, antioxidant, non-toxic and other properties, and is favored by scholars. In order to further expand its scope of application, people synthesize various modified silicone oils by introducing different functional groups on the silicone molecule to give silicone products new functional properties. Vinyl silicone oil, especially terminal vinyl, has good reactivity and compatibility. Fluorine-containing silicone oil has the dual properties of silicone and organic fluorine, with excellent weather resistance, high and low stability, chemical stability and water and oil resistance. Long-chain alkane silicone oil has good lipophilicity, lubricity, defoaming and anti-sticking properties. In order to obtain better performance and a wider range of applications, people are in urgent need of preparing a modified silicone oil that combines terminal vinyl silicone oil, fluorine-containing silicone oil and long-chain alkyl silicone oil. However, there are still defects in the technical theory. On the one hand, due to the strong polarity of the fluorine-containing silicone oil structure, it is not compatible with vinyl silicone oil. On the other hand, the method for preparing terminal vinyl silicone oil is still immature, which can easily lead to problems such as poor end-capping effect and poor reaction controllability. On the one hand, the applicant added a specific vinyl polyglycol ether during the hydrolysis and condensation process of the fluorinated cyclosiloxane monomer and the long-chain alkoxysiloxane, so that the synthesized modified silicone oil contains an ether bond structure, thereby improving the compatibility of silicon in the system; on the other hand, by selecting a capping agent having a Si-N bond and a vinyl structure, the high activity of the Si-OH bond reaction in the intermediate structure of the synthetic silicone oil and the Si-N bond in the capping agent is utilized to make the weakly alkaline Si-N (R1) (R2) and the weakly acidic Si-OH structure react rapidly, thereby quickly and efficiently preparing a terminal vinyl-modified fluorinated silicone oil with good hydrophobic properties.

[0025] In some embodiments of the present invention, the hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%.

[0026] Preferably, the hydrogen-containing silicone oil is methyl low-hydrogen silicone oil, model number CJ-1100. Low-hydrogen silicone oil has good weather resistance and hydrophobicity, and has a good cross-linking effect.

[0027] The present invention does not impose any special restrictions on the source of the hydrogen-containing silicone oil, which can be purchased from commercial sources, including but not limited to Zhejiang Chuangji Organic Silicone Materials Co., Ltd.

[0028] In some embodiments of the present invention, the method for preparing the modified silica comprises the following steps:

[0029] ① Add silica to anhydrous ethanol, stir and mix, and ultrasonicate to obtain a suspension for later use;

[0030] ② Add butyl titanate to the suspension of step ① under heating conditions of 50-70°C, stir, add isopropyl alcohol, stir, adjust the pH, react for 4-5 hours, wash, filter, dry, and calcine to obtain silica-titanium dioxide composite particles;

[0031] ③ Add the ionic liquid to the silica-titanium dioxide composite particles, add anhydrous ethanol, react in a constant temperature water bath, and dry to obtain modified silica.

[0032] Preferably, the preparation method of the modified silica comprises the following steps:

[0033] ① Add white carbon black to 70-100 ml of anhydrous ethanol, stir and mix, and ultrasonicate for 20-40 minutes to obtain a suspension for later use;

[0034] ② Add butyl titanate to the suspension of step ① under heating conditions of 50-70°C, stir for 5-15 minutes, add 5-15 ml of isopropyl alcohol, stir for 5-10 minutes, add dilute nitric acid solution to adjust the pH to 2-5, react for 4-5 hours, wash, filter, dry at 100-120°C for 10-20 minutes, and then calcine in a muffle furnace at 550-650°C for 2-3 hours, and grind to obtain white carbon black-titanium dioxide composite particles;

[0035] ③ Add the ionic liquid to the silica-titanium dioxide composite particles, add anhydrous ethanol, react in a constant temperature water bath, dry and grind to obtain modified silica.

[0036] More preferably, the mass ratio of white carbon black to butyl titanate is 1:(5-9); the mass ratio of white carbon black to ionic liquid is 1:(15-20); the average particle size of white carbon black is 20-40 nm, and the specific surface area is 200-250 m 2 / g; the average particle size of the white carbon black-titanium dioxide composite particles is 300-500nm; the average particle size of the modified white carbon black is 400-600nm.

[0037] The present invention does not impose any special restrictions on the source of the white carbon black, which can be purchased commercially, including but not limited to Hubei Huifu Nanomaterials Co., Ltd.

[0038] In some embodiments of the present invention, the ionic liquid is 1-allyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium hexafluorophosphate. The ionic liquid selected in the present invention has good stability and excellent reinforcement effect, and can significantly improve the mechanical properties of the composite material.

[0039] Silica, a commonly used reinforcing agent in modified silicone oil systems, offers high-temperature resistance, hydrophobicity, and excellent mechanical properties. However, it suffers from poor dispersibility and prone to secondary aggregation, which reduces the light transmittance of the modified silicone oil. The present invention, by introducing butyl titanate to synthesize silica-titanium dioxide composite particles, ensures complete grafting of titanium dioxide and silica. This not only enhances the reinforcing role of silica in the modified silicone oil system to a certain extent, imparting excellent high-temperature resistance, hydrophobicity, and antioxidant properties to the modified silicone oil, but also effectively increases the light transmittance of silica in the modified silicone oil system by introducing titanium dioxide, which has excellent optical properties. The applicant further selects a specific ionic liquid to surface-modify the silica-titanium dioxide composite particles. The ionic liquid reacts with the silica particles to produce a hydrogen-bonded polymer, which reduces the ability of the particles to aggregate, thereby improving agglomeration and enhancing dispersibility. Furthermore, the hydrogen-containing silicone oil, as a good crosslinking agent, effectively resolves the agglomeration problem of silica, thereby improving the light transmittance of the modified silicone oil.

[0040] In some embodiments of the present invention, the inhibitor is ethynylcyclohexanol or methylbutynol.

[0041] In some embodiments of the present invention, the catalyst is a platinum catalyst or a palladium catalyst.

[0042] Preferably, the catalyst is a platinum catalyst.

[0043] The present invention does not impose any special restrictions on the source of the platinum catalyst, which can be purchased from commercial sources, including but not limited to Zijun Chemical Co., Ltd.

[0044] Another aspect of the present invention further provides a method for preparing the modified fluorine-containing vinyl silicone oil described in the above technical solution, comprising the following steps:

[0045] S1. Add modified silica to modified vinyl silicone oil and stir for 30-60 min to obtain a mixture for later use;

[0046] S2. Add hydrogen-containing silicone oil, inhibitor and catalyst to the mixture of step S1 in sequence, stir evenly, and remove bubbles in vacuo to obtain the hydrophobic long-chain alkane-terminated vinyl silicone oil.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] (1) The present invention modifies the vinyl silicone oil with long-chain alkyl, fluorine-containing silicone oil and ether bonds, effectively improving the compatibility of fluorine-containing silicone oil and vinyl silicone oil, and modifies the reinforcing agent white carbon black with titanium dioxide and ionic liquid to ensure that the modified fluorine-containing vinyl silicone oil has good hydrophobicity and light transmittance.

[0049] (2) The end-capping agent selected in the present invention improves the efficiency and accuracy of synthesizing the terminal vinyl modified fluorine-containing silicone oil, so that the obtained modified fluorine-containing vinyl silicone oil has a higher yield.

[0050] (3) In the present invention, titanium dioxide grafting modification and ionic liquid surface modification are performed on silica, which effectively solves the problem of poor dispersion of silica in the modified silicone oil system, thereby ensuring that the modified fluorine-containing vinyl silicone oil has good light transmittance.

[0051] (4) The modified fluorine-containing vinyl silicone oil prepared by the present invention can be widely used in the coating field of underwater equipment and has good commercial application value. DETAILED DESCRIPTION

[0052] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are illustrative of the present invention and are intended only to illustrate the present invention and are not intended to limit the present invention. Other combinations and various modifications within the scope of the present invention may be made without departing from the spirit or scope of the present invention.

[0053] In the following examples, except for modified vinyl silicone oil and modified white carbon black, the other compound monomers and related reagents used can be purchased from the market. Among them, the hydrogen-containing silicone oil is methyl low-hydrogen silicone oil, model CJ-1100, purchased from Zhejiang Chuangji Silicone Materials Co., Ltd.; the average particle size of white carbon black is 30nm, and the specific surface area is 200-250m 2 / g, purchased from Hubei Huifu Nanomaterials Co., Ltd.; platinum catalyst was purchased from Zijun Chemical Co., Ltd.

[0054] The structural formula of modified vinyl silicone oil is as follows:

[0055]

[0056] The synthetic method of modified vinyl silicone oil A comprises the following steps:

[0057] (1) 5 g of n-dodecylmethyltriethoxysilane was added to 30 ml of 2 mol / L NaOH solution and hydrolyzed at 85° C. to obtain reaction product 1 for later use;

[0058] (2) adding 30 g of heptafluorodecyltrimethoxysilane, 8.5 g of vinyl diethylene glycol ether, 2 g of platinum catalyst and 30 ml of NaOH solution to the reaction product 1 in step (1), stirring at 145 ° C for 3 h, keeping the temperature for 30 min, cooling to room temperature, filtering and obtaining the reaction product 2 for later use;

[0059] (3) Add 1.5 g of allyl(diethylamino)dimethylsilane to the reaction product 2 in step (2) and stir for 30 minutes to obtain the modified vinyl silicone oil.

[0060] The synthesis method of modified vinyl silicone oil B is the same as that of modified vinyl silicone oil A, except that the masses of heptadecafluorodecyltrimethoxysilane, vinyl diethylene glycol ether and allyl (diethylamino) dimethylsilane in the modified vinyl silicone oil are 50 g, 15 g and 0.025 g, respectively.

[0061] The synthesis method of modified silica A comprises the following steps:

[0062] ① Add 3g of white carbon black to 80ml of anhydrous ethanol, stir and mix, and ultrasonicate for 30min to obtain a suspension for later use;

[0063] ② Add 21 g of butyl titanate to the suspension of step ① under heating conditions of 60°C, stir for 10 minutes, add 10 ml of isopropanol, stir for 8 minutes, add dilute nitric acid solution to adjust the pH to 3.0, react for 4.5 hours, wash, filter, dry at 110°C for 15 minutes, and calcine in a muffle furnace at 600°C for 2.5 hours. Grind to obtain white carbon black-titanium dioxide composite particles;

[0064] ③ Add 54g of 1-allyl-3-methylimidazole chloride to the silica-titanium dioxide composite particles, add 40ml of anhydrous ethanol, react in a constant temperature water bath at 60°C for 30min, dry and grind to obtain modified silica.

[0065] The average particle size of the silica-titanium dioxide composite particles is 400 nm; the average particle size of the modified silica is 500 nm.

[0066] The synthesis method of modified silica B is the same as that of modified silica A, except that the mass of 1-allyl-3-methylimidazole chloride in the modified silica is 30 g.

[0067] Example 1

[0068] A modified fluorine-containing vinyl silicone oil comprises the following raw materials in percentage by mass: 49.5% of modified vinyl silicone oil A, 17.5% of hydrogen-containing silicone oil, 32.5% of modified silica A, 0.25% of ethynyl cyclohexanol, and 0.25% of a platinum catalyst.

[0069] The preparation method of the modified fluorine-containing vinyl silicone oil in this embodiment comprises the following steps:

[0070] S1. Add modified silica to modified vinyl silicone oil and stir for 45 minutes to obtain a mixture for later use;

[0071] S2. Add hydrogenated silicone oil, ethynyl cyclohexanol and platinum catalyst to the mixture of step S1 in sequence, stir for 30 minutes, and remove bubbles in vacuo to obtain the modified fluorine-containing vinyl silicone oil.

[0072] Example 2

[0073] A modified fluorine-containing vinyl silicone oil comprises the following raw materials in percentage by mass: 49.5% of modified vinyl silicone oil A, 20.3% of hydrogen-containing silicone oil, 30% of modified silica A, 0.1% of ethynyl cyclohexanol, and 0.1% of a platinum catalyst.

[0074] The preparation method of the modified fluorine-containing vinyl silicone oil in this embodiment comprises the following steps:

[0075] S1. Add modified silica to modified vinyl silicone oil and stir for 30 min to obtain a mixture for later use;

[0076] S2. Add hydrogenated silicone oil, ethynyl cyclohexanol and platinum catalyst to the mixture of step S1 in sequence, stir for 30 minutes, and remove bubbles in vacuo to obtain the modified fluorine-containing vinyl silicone oil.

[0077] Example 3

[0078] A modified fluorine-containing vinyl silicone oil comprises the following raw materials in percentage by mass: 49.5% of modified vinyl silicone oil A, 14.5% of hydrogen-containing silicone oil, 35% of modified white carbon black A, 0.5% of ethynyl cyclohexanol, and 0.5% of a platinum catalyst.

[0079] The preparation method of the modified fluorine-containing vinyl silicone oil in this embodiment comprises the following steps:

[0080] S1. Add modified silica to modified vinyl silicone oil and stir for 60 min to obtain a mixture for later use;

[0081] S2. Add hydrogenated silicone oil, ethynyl cyclohexanol and platinum catalyst to the mixture of step S1 in sequence, stir for 30 minutes, and remove bubbles in vacuo to obtain the modified fluorine-containing vinyl silicone oil.

[0082] Example 4

[0083] A modified fluorine-containing vinyl silicone oil comprises the following raw materials in percentage by mass: 46% of modified vinyl silicone oil A, 21% of hydrogen-containing silicone oil, 32.5% of modified white carbon black A, 0.2% of ethynyl cyclohexanol, and 0.3% of a platinum catalyst.

[0084] The preparation method of the modified fluorine-containing vinyl silicone oil in this example is the same as that in Example 1.

[0085] Example 5

[0086] A modified fluorine-containing vinyl silicone oil comprises the following raw materials in percentage by mass: 53% of modified vinyl silicone oil A, 14% of hydrogen-containing silicone oil, 32.5% of modified white carbon black A, 0.3% of ethynyl cyclohexanol, and 0.2% of a platinum catalyst.

[0087] The preparation method of the modified fluorine-containing vinyl silicone oil in this example is the same as that in Example 1.

[0088] Example 6

[0089] The present invention provides a modified fluorine-containing vinyl silicone oil and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that the modified vinyl silicone oil A is replaced by an equal amount of modified vinyl silicone oil B.

[0090] Example 7

[0091] The present invention provides a modified fluorine-containing vinyl silicone oil and a preparation method thereof. The specific implementation manner is the same as that of Example 1, except that modified silica B replaces modified silica A in equal amounts.

[0092] Comparative Example 1

[0093] This embodiment provides a modified fluorine-containing vinyl silicone oil and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that commercially available conventional vinyl silicone oil is used instead of the modified vinyl silicone oil.

[0094] Vinyl silicone oil was purchased from Shanghai Guiyou New Material Technology Co., Ltd.

[0095] Comparative Example 2

[0096] This embodiment provides a modified fluorine-containing vinyl silicone oil and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that white carbon black is used instead of modified white carbon black.

[0097] Performance Testing

[0098] The hydrophobicity, light transmittance and yield of the vinyl silicone oils described in Examples 1-8 and Comparative Examples 1-2 were tested. The test results are shown in Table 1.

[0099] (1) Hydrophobicity

[0100] The hydrophobicity is determined by testing the water contact angle of the coating formed by coating the synthetic modified silicone oil on the tinplate sheet. A water contact angle greater than 150° is considered superhydrophobic, a water contact angle greater than 90° and less than 150° is considered hydrophobic, and a water contact angle less than 90° is considered hydrophilic.

[0101] (2) Light transmittance

[0102] Light transmittance is determined by testing light transmittance, with reference to standard GB T 2410-2008.

[0103] (3) Yield

[0104] Yield refers to the percentage of the target product generated based on the reaction amount without feed, and is determined by the following equation: Yield of modified fluorinated vinyl silicone oil = (amount of modified vinyl silicone oil generated / amount of reactant fed) × 100%.

[0105] Table 1

[0106] Group Water contact angle Transmittance% Yield % Example 1 160.5° 100％ 99.9％ Example 2 159.7° 99.8％ 99.6％ Example 3 158.5° 99.6％ 99.5％ Example 4 159.2° 99.4％ 99.4％ Example 5 156.4° 99.2％ 99.3％ Example 6 135.7° 93.5％ 87.1％ Example 7 145.5° 88.2％ 94.5％ Comparative Example 1 115.2° 83.5％ 81.9％ Comparative Example 2 128.5° 75.5％ 85.1％

[0107] As can be seen from the data in Table 1, the modified silicone oils in Examples 1-8 of the present invention have the characteristics of good hydrophobicity, excellent light transmittance and high yield as a whole. Among them, Example 6 changes the ratio of the main components in the modified vinyl silicone oil, so that the structure of the modified vinyl silicone oil is different to a certain extent, the by-products are too many, and it is impossible to achieve good hydrophobicity and yield, and the light transmittance is reduced, but the effect is not significant; Example 7 changes the amount of ion solution added in the modified silica. It can be seen from the results that the quality of the ion solution is controlled within a suitable range, and the modified silicone oil synthesized by the present invention can have good light transmittance; Comparative Examples 1 and 2 respectively use commercially available conventional vinyl silicone oil and a separate silica material to replace the modified vinyl silicone oil and modified silica synthesized in the present invention, respectively. Tests show that the hydrophobicity, light transmittance and yield of the prepared modified silicone oil all show poor results.

[0108] The above embodiments are only for illustrating the technical concept and features of the present invention. Its purpose is to enable people familiar with this technology to understand the content of the present invention and implement it. It cannot be used to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A modified fluorine-containing vinyl silicone oil, characterized in that: The silicone oil comprises the following raw materials in percentage by mass: 45-54% of modified vinyl silicone oil, 14-21% of hydrogenated silicone oil, 30-35% of modified white carbon black, 0.1%-0.5% of inhibitor, and 0.1%-0.5% of catalyst, with the total percentage by mass being 100%.

2. The modified fluorine-containing vinyl silicone oil according to claim 1, characterized in that The structural formula of the modified vinyl silicone oil is as follows: Among them, R F is a fluorinated alkyl group; R1 is a long-chain alkane; R2 is an ether group; the value of n1 is 2-10; the value of n2 is 7-15; and the value of n3 is 3-8.

3. The modified fluorine-containing vinyl silicone oil according to claim 2, characterized in that The fluorine-containing alkyl group is a trifluoropropyl group or a heptadecafluorodecyl group.

4. The modified fluorine-containing vinyl silicone oil according to claim 2, characterized in that The long chain alkane is C 10 -C 14 ; The ether group is polyglycol ether.

5. The modified fluorine-containing vinyl silicone oil according to claim 2, characterized in that The preparation method of the modified vinyl silicone oil comprises the following steps: (1) adding a long-chain alkoxysiloxane to a strong alkaline solution and hydrolyzing it at a temperature of 80-90° C. to obtain a reaction product 1, which is set aside; (2) adding a fluorinated cyclosiloxane monomer, vinyl polyglycol ether, a catalyst, and a strong base solution to the reaction product 1 obtained in step (1), stirring at 140-150° C. for 2.5-3.5 hours, keeping the temperature, then cooling and filtering to obtain a reaction product 2 for later use; (3) Adding a capping agent to the reaction product 2 obtained in step (2), stirring, and obtaining a modified vinyl silicone oil.

6. The modified fluorine-containing vinyl silicone oil according to claim 5, characterized in that The structural formula of the capping agent is as follows: Wherein, R1 and R2 are both -CH3 or -CH2CH3; and the fluorine-containing cyclosiloxane monomer is heptadecafluorodecyltrimethoxysilane or heptadecafluorodecyltriethoxysilane.

7. The modified fluorine-containing vinyl silicone oil according to claim 1, characterized in that The hydrogen content of the hydrogen-containing silicone oil is 0.05-0.2%.

8. The modified fluorine-containing vinyl silicone oil according to claim 1, characterized in that The preparation method of the modified silica comprises the following steps: ① Add white carbon black to anhydrous ethanol, stir and mix, and ultrasonicate to obtain a suspension for later use; ② Add butyl titanate to the suspension obtained in step ① under heating conditions of 50-70° C., stir, then add isopropyl alcohol, stir, adjust the pH, react for 4-5 hours, wash, filter, dry, and calcine to obtain white carbon black-titanium dioxide composite particles; ③ Add the ionic liquid to the silica-titanium dioxide composite particles obtained in step ②, add anhydrous ethanol, react in a constant temperature water bath, and dry to obtain modified silica.

9. The modified fluorine-containing vinyl silicone oil according to claim 8, characterized in that The ionic liquid is 1-allyl-3-methylimidazolium chloride or 1-butyl-3-methylimidazolium hexafluorophosphate.

10. A method for preparing the modified fluorine-containing vinyl silicone oil according to any one of claims 1 to 9, characterized in that: The following steps are involved: S1. Add modified silica to modified vinyl silicone oil and stir for 30-60 min to obtain a mixture for later use; S2. Add hydrogen-containing silicone oil, inhibitor and catalyst to the mixture obtained in step S1 in sequence, stir evenly, and remove bubbles in vacuo to obtain the modified fluorine-containing vinyl silicone oil.

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