Vinyl fluorine-containing hyperbranched organic silicon resin modified addition type fluorinated silicone rubber as well as preparation method and application thereof

Abstract

The invention discloses vinyl fluorine-containing hyperbranched organic silicon resin modified addition type fluorinated silicone rubber as well as a preparation method and application thereof, and belongs to the technical field of organic polymer preparation. The modified addition type fluorosilicone rubber is prepared from the following components in parts by weight: 100 parts of vinyl fluorosilicone raw rubber, 0.1 to 40 parts of vinyl fluorine-containing hyperbranched organic silicon resin, 1 to 50 parts of filler, 0.2 to 30 parts of hydrogen-containing silicone oil, 0.01 to 10 parts of inhibitor and 0.01 to 12 parts of platinum catalyst. The vinyl fluorine-containing hyperbranched organic silicon resin is introduced into a fluorosilicone rubber system, and the rheological property and processability of the fluorosilicone rubber can be remarkably improved by utilizing a low-viscosity and highly branched three-dimensional network structure of the vinyl fluorine-containing hyperbranched organic silicon resin, so that the mechanical property and high-temperature resistance of the fluorosilicone rubber are remarkably improved; for example, the tensile strength is maximally improved by over 115%, the bonding strength is maximally improved by over 279%, and high transparency and excellent chemical stability are maintained.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic polymer preparation, and more specifically relates to a vinyl fluorine-containing hyperbranched organic silicon resin modified addition-type fluorosilicone rubber, and a preparation method and application thereof. Background Art

[0002] Fluorosilicone rubber is a specialized synthetic rubber that combines the high-temperature resistance of silicone rubber with the corrosion and oil resistance of fluororubber. It has a wide range of industrial applications. Liquid fluorosilicone rubber can be used as an adhesive for flat / static seals, offering stable and oil-resistant properties, such as in small transformer seals, aircraft fuel tank sealants, and automotive fuel system seals. It also exhibits excellent bonding to aluminum alloys. Fluorosilicone rubber can also be used to produce automotive oil-resistant hoses and seals. In the aerospace industry, its wide temperature range, fuel resistance, and stability offer promising applications in the aviation and aircraft markets.

[0003] At present, fluorosilicone rubber has significant defects in practical applications: insufficient mechanical strength, unable to withstand high-stress environments; difficult to process, requiring special mixing and molding processes, and high processing costs; poor adhesion to other materials, limiting its application in composite materials; weak heat resistance, difficult to maintain a certain strength for a long time in high-temperature environments.

[0004] Vinyl fluorinated hyperbranched silicone resins, a material that combines the excellent properties of both vinyl hyperbranched silicone resins and fluoropolymers, possess a unique, highly branched three-dimensional structure and low viscosity, allowing modified materials to enhance processability. The presence of fluorinated functional groups in their structure provides good compatibility with fluorosilicone rubber. Furthermore, the high content of vinyl functional groups allows for a hydrosilylation reaction with hydrogenated silicone oils, forming a double-crosslinked network upon curing with fluorosilicone rubber. Compared to linear or lightly branched silicone resins, these resins exhibit higher mechanical strength, thermal stability, and chemical stability.

[0005] Patent CN115260546A discloses a method for preparing low-temperature-resistant and aging-resistant fluorosilicone rubber. The method involves mixing modified borosilicone, potassium perfluorobutanesulfonate, ethylene glycol, and water to obtain a suspension. Next, zein, a long-chain dibasic acid, acetone, and water are mixed to obtain an emulsion. Trifluoropropyl chloromethylsilane, a fluorinated alkyne, dipropylene glycol methyl ether, 1,1,3,3,3-pentafluoro-2-trifluoromethylpropyl methyl ether, and perfluoro-n-propyl vinyl ether are mixed and pressurized to obtain a preformed gel. The suspension, emulsion, preformed gel, 2,4,6-trifluoroaniline, and a vulcanizing agent are then mixed and kneaded to obtain the fluorosilicone rubber. The overall preparation process involves numerous steps and is complex, making industrialization challenging.

[0006] Patent CN 109762092A discloses a method for synthesizing a novel low-temperature-resistant fluorosilicone rubber. The method involves adding a chain transfer agent, a vulcanizing monomer, and an initiator to a fluorinated polyether carboxylate, a perfluorobutyl sulfonate, a fluorinated gas-phase monomer, and a fluorinated and silicon-containing monomer, to produce the fluorosilicone rubber through a polymerization reaction. However, the resulting fluorosilicone rubber does not address the technical issue of severe performance degradation after aging.

[0007] Patent CN 118271619A discloses a method for synthesizing ethyl fluorosilicone rubber. The method uses 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane ethyl to synthesize ethyl fluorosilicone rubber through an alkaline ring-opening polymerization reaction. However, the molecular weight of the synthesized fluorosilicone rubber is uncontrollable, and batch stability is poor. Summary of the Invention

[0008] In view of the above-mentioned problems existing in the prior art, the technical problem to be solved by the present invention is to provide a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber, which forms a highly cross-linked double network structure during the curing process, significantly improving the mechanical properties of the fluorosilicone rubber. Another technical problem to be solved by the present invention is to provide a preparation method of the above-mentioned vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber, which is simple and easy to operate. Another technical problem to be solved by the present invention is to provide the application of the above-mentioned vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber in the preparation of automotive oil-resistant hoses and seals, and as an adhesive for flat sealing or static sealing.

[0009] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0010] Disclosed is a vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber, which comprises the following components in parts by weight: 100 parts of vinyl fluorine-containing hyperbranched organosilicon resin, 0.1-40 parts of vinyl fluorine-containing hyperbranched organosilicon resin, 1-50 parts of filler, 0.2-30 parts of hydrogenated silicone oil, 0.01-10 parts of inhibitor, and 0.01-12 parts of platinum catalyst.

[0011] Preferably, the vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber is composed of the following components and proportions by weight: 100 parts of vinyl fluorine-containing hyperbranched organosilicon resin, 5-20 parts of vinyl fluorine-containing hyperbranched organosilicon resin, 15-30 parts of filler, 5-20 parts of hydrogenated silicone oil, 0.2-2 parts of inhibitor, and 0.2-1 part of platinum catalyst.

[0012] Preferably, the structure of the vinyl fluorine-containing hyperbranched silicone resin is:

[0013]

[0014] In the formula, R is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a cyclohexyl group, and R' at different positions in the structural formula is the same or different; R' is a monofluoromethyl group, a trifluoropropyl group, a pentafluorophenylpropyl group, a nonafluorohexyl group, a dodecafluoroheptyl group, a perfluorododecyl group, a tridecafluorooctyl group, a perfluorohexadecyl group or a perfluoroeicosyl group, and R' at different positions in the structural formula is the same or different.

[0015] Preferably, the vinyl fluorine-containing hyperbranched silicone resin has a viscosity of 100 to 1000 mPa·s, a vinyl content of 0 to 10%, and a fluorine content of 0 to 40% in the molecule.

[0016] Preferably, the structure of the hydrogen-containing silicone oil is:

[0017]

[0018] In the formula, R1 is hydroxyl, phenyl, polyalkyl or vinyl, and R2 is hydroxyl, phenyl, polyalkyl or vinyl.

[0019] Preferably, the hydrogenated silicone oil has a viscosity of 10-1000 mPa·s and a hydrogen content of 0.1-20% and is one or more of hydroxyl hydrogenated silicone oil, alkyl hydrogenated silicone oil, phenyl hydrogenated silicone oil, vinyl hydrogenated silicone oil and fluorine hydrogenated silicone oil.

[0020] Preferably, the inhibitor is selected from one or more of 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, pyridine, polydivinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane, tetramethyldivinyldisiloxane, phosphite, organic phosphine, unsaturated amide, alkynyl-containing maleic acid, and alkynyl-containing fumaric acid.

[0021] Preferably, the platinum catalyst is selected from any one of a platinum complex coordinated by methylvinylpolysiloxane, a platinum complex coordinated by diethyl phthalate, and a chloroplatinic acid isopropanol solution.

[0022] Preferably, the filler is selected from one or more of fumed silica, precipitated silica, silica powder, calcium carbonate, kaolin, talc, calcium sulfate, aluminosilicate, diatomaceous earth, aluminum oxide, iron oxide, magnesium hydroxide, titanium dioxide, and organic montmorillonite.

[0023] A method for preparing the vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0024] 1) Weighing vinyl fluorosilicone rubber, vinyl fluorine-containing hyperbranched silicone resin, filler, hydrogen-containing silicone oil, inhibitor, and platinum catalyst according to parts by weight;

[0025] 2) adding vinyl fluorine-containing hyperbranched organosilicon resin and filler to the vinyl fluorosilicone rubber weighed in step 1) and mixing them evenly, then adding hydrogenated silicone oil and mixing them evenly to obtain a rubber sample;

[0026] 3) adding an inhibitor and a platinum catalyst to the rubber sample obtained in step 2), and stirring the mixture to obtain a modified rubber material;

[0027] 4) pre-curing the modified rubber obtained in step 3) at 40-80° C. for 1-8 hours, and then curing at 80-140° C. for 1-8 hours to obtain vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber.

[0028] The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber is used in the preparation of automotive oil-resistant hoses and seals, and as an adhesive for plane sealing or static sealing.

[0029] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0030] 1) The present invention uses vinyl fluorine-containing hyperbranched silicone resin as a modifier. Because it contains a high proportion of fluorine-containing functional groups, it conforms to the principle of similar compatibility with fluorosilicone rubber, has good compatibility, and has high transparency after curing;

[0031] 2) The present invention introduces a vinyl fluorine-containing hyperbranched silicone resin into a fluorosilicone rubber system, utilizing its low viscosity and highly branched three-dimensional network structure to significantly improve the rheological properties and processability of the fluorosilicone rubber, resulting in better fluidity during processing. The modified material forms a highly cross-linked double network structure during the curing process, significantly improving the mechanical properties and high-temperature resistance of the fluorosilicone rubber. The tensile strength is increased by up to 115%, the bonding strength is increased by up to 279%, and the hardness can reach up to 53, while maintaining high transparency and excellent chemical stability.

[0032] 3) The present invention introduces vinyl groups into the vinyl fluorine-containing hyperbranched silicone resin, which can participate in the hydrosilylation reaction to form a higher degree of crosslinking and a more stable three-dimensional network structure. This makes the performance of the material more controllable. The conditions of the hydrosilylation reaction between the hydrogenated silicone oil and the vinyl functional groups can be regulated according to actual needs, thereby customizing the final performance of the material to meet different application requirements.

[0033] 4) The present invention has the advantages of simple preparation process and significantly improved performance, and can be widely used in aerospace, automotive fuel system seals, electronic component packaging and other fields with high requirements for heat resistance and mechanical strength. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1The figure is a reaction equation diagram for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to the present invention;

[0035] Figure 2 The physical pictures of samples prepared in Examples 1-3 and Comparative Example 1;

[0036] Figure 3 Graph showing shear test results of samples prepared in Examples 1-6 and Comparative Example 1;

[0037] Figure 4 Water contact angle diagrams of samples prepared in Examples 1-6 and Comparative Example 1;

[0038] Figure 5 Thermogravimetric curves of samples prepared in Examples 1-3 and Comparative Example 1 under a nitrogen atmosphere;

[0039] Figure 6 This is a physical picture of the samples prepared in Examples 1-2 and Comparative Example 1 after aging at 300°C for 24 hours. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention will be further described below in conjunction with specific examples. In the following examples, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art. In the examples, if specific conditions are not specified, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are all conventional products that can be purchased commercially.

[0041] The performance testing methods used in the following examples are as follows:

[0042] 1. Tensile strength test: The rubber was tested for tensile strength using an Instron 5967 universal tensile testing machine.

[0043] 2. Shear strength test: The rubber is tested for shear strength using an Instron 5967 universal tensile testing machine.

[0044] 3. Hardness test: Use the SHS-1 Shore A hardness tester of Deens Company to test the hardness of rubber;

[0045] 4. Thermogravimetric analysis: Thermogravimetric analysis was performed using a STA449F3 thermogravimetric-differential scanning calorimetric simultaneous analyzer (Netzche, Germany).

[0046] 5. Water contact angle: The water contact angle test was performed using an OSA60 Optical Surface Analyzer water contact angle tester.

[0047] The present application provides a reaction equation for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition type fluorosilicone rubber, such as Figure 1 As shown, vinyl fluorine-containing hyperbranched silicone resin is blended with vinyl fluorine silicone rubber and hydrogen-containing silicone oil, and then a platinum catalyst is added to catalyze the temperature increase and cross-linking and curing to obtain a modified addition-type fluorine silicone rubber.

[0048] Example 1

[0049] A method for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0050] 1) Add 5 parts of vinyl fluorine-containing hyperbranched silicone resin to 100 parts of vinyl fluorosilicone rubber, then add 10 parts of silicon powder and 5 parts of calcium carbonate and mix well, then add 15 parts of alkyl hydrogen silicone oil and mix well to obtain a rubber sample;

[0051] 2) adding 0.2 parts of 3,5-dimethyl-1-hexyn-3-ol, 0.2 parts of 3-methyl-1-pentyn-3-ol, and 0.5 parts of a platinum complex catalyst coordinated with methylvinyl polysiloxane to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0052] 3) The modified rubber obtained in step 2) was pre-cured at 80°C for 2 hours and then cured at 130°C for 4 hours to obtain a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber. Figure 2 shown.

[0053] Example 2

[0054] A method for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0055] 1) Add 5 parts of vinyl fluorine-containing hyperbranched silicone resin to 100 parts of vinyl fluorosilicone rubber, then add 10 parts of fumed silica and 10 parts of aluminum oxide and mix well, then add 20 parts of vinyl hydrogenated silicone oil and mix well to obtain a rubber sample;

[0056] 2) adding 0.05 parts of tetravinyltetramethylcyclotetrasiloxane, 0.2 parts of tetramethyldivinyldisiloxane, and 0.3 parts of chloroplatinic acid isopropyl alcohol catalyst to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0057] 3) The modified rubber obtained in step 2) was pre-cured at 40°C for 1 hour and then cured at 150°C for 4 hours to obtain a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber. Figure 2 shown.

[0058] Example 3

[0059] A method for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0060] 1) adding 10 parts of vinyl fluorine-containing hyperbranched silicone resin to 100 parts of vinyl fluorosilicone rubber, then adding 10 parts of aluminosilicate and 15 parts of diatomaceous earth and mixing evenly, then adding 20 parts of fluorine-containing and hydrogen-containing silicone oil and mixing evenly to obtain a rubber sample;

[0061] 2) adding 0.02 parts of polydivinyltetramethyldisiloxane, 0.3 parts of organic phosphine, and 0.2 parts of a platinum complex coordinated with diethyl phthalate to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0062] 3) The modified rubber obtained in step 2) was pre-cured at 70°C for 5 hours and then cured at 110°C for 4 hours to obtain a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber. Figure 2 shown.

[0063] Example 4

[0064] A method for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0065] 1) adding 20 parts of vinyl fluorine-containing hyperbranched silicone resin to 100 parts of vinyl fluorosilicone rubber, then adding 20 parts of magnesium hydroxide and 10 parts of titanium dioxide and mixing evenly, then adding 10 parts of fluorine-containing and hydrogen-containing silicone oil and mixing evenly to obtain a rubber sample;

[0066] 2) adding 0.5 parts of 1-ethynylcyclohexanol and 0.5 parts of chloroplatinic acid isopropanol solution to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0067] 3) The modified rubber obtained in step 2) is pre-cured at 60° C. for 3 h and then cured at 140° C. for 6 h to obtain a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber.

[0068] Example 5

[0069] A method for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0070] 1) adding 15 parts of vinyl fluorine-containing hyperbranched silicone resin to 100 parts of vinyl fluorosilicone rubber, then adding 15 parts of precipitated silica and 15 parts of calcium sulfate and mixing them evenly, and then adding 15 parts of hydroxyl hydrogen silicone oil and mixing them evenly to obtain a rubber sample;

[0071] 2) adding 0.05 parts of acetylenic group-containing maleic acid and 0.25 parts of a platinum complex coordinated by methylvinyl polysiloxane to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0072] 3) The modified rubber obtained in step 2) is pre-cured at 50° C. for 2 h and then cured at 120° C. for 3 h to obtain a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber.

[0073] Example 6

[0074] A method for preparing vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber comprises the following steps:

[0075] 1) Add 20 parts of vinyl fluorine-containing hyperbranched silicone resin to 100 parts of vinyl fluorosilicone rubber, then add 15 parts of kaolin and 15 parts of iron oxide and mix well, then add 5 parts of fluorine-containing and hydrogen-containing silicone oil, and mix well to obtain a rubber sample;

[0076] 2) adding 2 parts of 2-methyl-3-butyn-2-ol and 1 part of a platinum complex coordinated with methylvinyl polysiloxane to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0077] 3) The modified rubber obtained in step 2) is pre-cured at 80° C. for 4 h and then cured at 100° C. for 2 h to obtain a vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber.

[0078] Comparative Example 1

[0079] Preparation of fluorosilicone rubber:

[0080] 1) Add 10 parts of fumed silica and 10 parts of aluminum oxide to 100 parts of vinyl fluorosilicone rubber and mix well. Then add 5 parts of fluorine-containing and hydrogen-containing silicone oil and mix well to obtain a rubber sample.

[0081] 2) adding 2 parts of 2-methyl-3-butyn-2-ol and 1 part of a platinum complex coordinated with methylvinyl polysiloxane to the rubber sample obtained in step 1), and stirring uniformly to obtain a modified rubber material;

[0082] 3) The modified rubber obtained in step 2) was pre-cured at 60°C for 5 hours and then cured at 120°C for 3 hours to obtain fluorosilicone rubber. Figure 2 shown.

[0083] Example 7

[0084] The tensile strength, elongation at break, and Shore A hardness of the samples prepared in Examples 1-6 and Comparative Example 1 were tested. The tensile test method was based on ASTM D1708, and the mass change rate was the mass change rate after immersion in ASTM 3# for 72 hours. The results are shown in Table 1.

[0085] Table 1 Performance test results of samples prepared in Examples 1-6 and Comparative Example 1

[0086]

[0087] As can be seen from Table 1, the tensile strength, elongation at break and hardness of the addition-type fluorosilicone rubber modified by the vinyl fluorine-containing hyperbranched silicone resin prepared by the present invention are significantly improved compared with those in Comparative Example 1. Compared with Comparative Example 1, the tensile strength is increased by more than 115% at the highest, and the water resistance is greatly improved. By conducting an oil resistance test on the rubber, it was found that the quality changes of each group of fluorosilicone rubber were at a relatively low level. The mass change rate of the fluorosilicone rubber modified by the vinyl fluorine-containing hyperbranched silicone resin is lower than that of the unmodified group, and is significantly reduced in Example 3. This shows that the vinyl fluorine-containing hyperbranched silicone resin has greatly improved the oil resistance of fluorosilicone rubber.

[0088] Depend on Figure 2 It can be seen that the cured vinyl fluorine-containing hyperbranched silicone resin modified fluorosilicone rubber prepared by the present invention has high transparency and good flexibility, while the fluorosilicone rubber not modified by the fluorine-containing hyperbranched silicone resin is yellowish brown as a whole and has low transparency.

[0089] Depend on Figure 3 It can be seen that the vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber prepared by the present invention is mixed and evenly applied to the middle of the aluminum alloy plate with a thickness of 100 μm. After pressing and curing, the shear strength test is carried out. It can be seen that the vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber has a significantly improved bonding strength to the aluminum alloy. Compared with Comparative Example 1, the strength is increased by more than 279%.

[0090] Depend on Figure 4 It can be seen that the vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber prepared in Examples 1-6 of the present invention has good hydrophobicity, and the water contact angle is increased by more than 10° compared with Comparative Example 1, and the maximum water contact angle reaches 120.0°.

[0091] Depend on Figure 5 It can be seen that under a nitrogen environment, the initial thermal decomposition temperature (95%) of the vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber prepared in Examples 1-3 of the present invention all exceeds 400°C, has good high temperature resistance, and compared with Comparative Example 1, the residual weight is significantly improved.

[0092] Depend on Figure 6It can be seen that after the heat aging test at 300°C for 24 hours, the comparative example 1 has decomposed and liquefied, while the addition-type fluorosilicone rubber modified by the vinyl fluorine-containing hyperbranched silicone resin still has good morphology retention and significantly improved temperature resistance.

[0093] 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 vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber, characterized in that: The invention is composed of the following components in proportion by weight: 100 parts of vinyl fluorosilicone rubber, 0.1-40 parts of vinyl fluorine-containing hyperbranched organic silicone resin, 1-50 parts of filler, 0.2-30 parts of hydrogenated silicone oil, 0.01-10 parts of inhibitor and 0.01-12 parts of platinum catalyst.

2. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 1, characterized in that: The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber is composed of the following components in parts by weight: 100 parts of vinyl fluorine-containing hyperbranched organosilicon resin, 5-20 parts of vinyl fluorine-containing hyperbranched organosilicon resin, 15-30 parts of filler, 5-20 parts of hydrogenated silicone oil, 0.2-2 parts of inhibitor, and 0.2-1 part of platinum catalyst.

3. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 1, characterized in that: The structure of the vinyl fluorine-containing hyperbranched silicone resin is: In the formula, R is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group or a cyclohexyl group, and R' at different positions in the structural formula is the same or different; R' is a monofluoromethyl group, a trifluoropropyl group, a pentafluorophenylpropyl group, a nonafluorohexyl group, a dodecafluoroheptyl group, a perfluorododecyl group, a tridecafluorooctyl group, a perfluorohexadecyl group or a perfluoroeicosyl group, and R' at different positions in the structural formula is the same or different.

4. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 3, characterized in that: The vinyl fluorine-containing hyperbranched organic silicon resin has a viscosity of 100 to 1000 mPa·s, a vinyl content of 0 to 10%, and a fluorine content of 0 to 40%.

5. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 1, characterized in that: The hydrogenated silicone oil has a viscosity of 10-1000 mPa·s and a hydrogen content of 0.1-20%, and is selected from one or more of hydroxyl hydrogenated silicone oil, alkyl hydrogenated silicone oil, phenyl hydrogenated silicone oil, vinyl hydrogenated silicone oil and fluorine hydrogenated silicone oil.

6. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 1, characterized in that: The inhibitor is selected from one or more of 2-methyl-3-butyn-2-ol, 1-ethynylcyclohexanol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentyn-3-ol, pyridine, polydivinyltetramethyldisiloxane, tetravinyltetramethylcyclotetrasiloxane, tetramethyldivinyldisiloxane, phosphite, organic phosphine, unsaturated amide, alkynyl-containing maleic acid, and alkynyl-containing fumaric acid.

7. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 1, characterized in that: The platinum catalyst is selected from any one of a platinum complex coordinated by methylvinylpolysiloxane, a platinum complex coordinated by diethyl phthalate, and a chloroplatinic acid isopropanol solution.

8. The vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to claim 1, characterized in that: The filler is selected from one or more of fumed silica, precipitated silica, silica powder, calcium carbonate, kaolin, talc, calcium sulfate, aluminosilicate, diatomaceous earth, aluminum oxide, iron oxide, magnesium hydroxide, titanium dioxide, and organic montmorillonite.

9. A method for preparing a vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to any one of claims 1 to 8, characterized in that: The following steps are involved: 1) Weighing vinyl fluorosilicone rubber, vinyl fluorine-containing hyperbranched silicone resin, filler, hydrogen-containing silicone oil, inhibitor, and platinum catalyst according to parts by weight; 2) adding vinyl fluorine-containing hyperbranched organosilicon resin and filler to the vinyl fluorosilicone rubber weighed in step 1) and mixing them evenly, then adding hydrogenated silicone oil and mixing them evenly to obtain a rubber sample; 3) adding an inhibitor and a platinum catalyst to the rubber sample obtained in step 2), and stirring the mixture to obtain a modified rubber material; 4) pre-curing the modified rubber obtained in step 3) at 40-80° C. for 1-8 hours, and then curing at 80-140° C. for 1-8 hours to obtain vinyl fluorine-containing hyperbranched silicone resin modified addition-type fluorosilicone rubber.

10. Use of the vinyl fluorine-containing hyperbranched organosilicon resin modified addition-type fluorosilicone rubber according to any one of claims 1 to 8 in the preparation of automotive oil-resistant hoses and seals, and as an adhesive for flat sealing or static sealing.

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