Corrosion-resistant rubber composite material as well as preparation method and application thereof

Abstract

The invention relates to the field of fluorinated silicone rubber high polymer materials, and discloses a corrosion-resistant rubber composite material as well as a preparation method and application thereof. The preparation method comprises the following steps: preparing a fluorine-containing copolymer A with iodine and double bonds as terminal groups through a free radical step-by-step transfer-addition-termination polymerization reaction, blocking the terminal double bonds to obtain a fluorine-containing copolymer B, and taking the fluorine-containing copolymer B as a macromolecular initiator, initiating the polymerization of methacryloyloxy propyl triisopropoxy silane and glycidyl methacrylate to prepare a fluorine-silicon nano filler modifier; grafting the fluorine-silicon nano filler modifier on the surface of nano aluminum oxide through condensation reaction to obtain modified nano aluminum oxide; fluorosilicone raw rubber, modified nano aluminum oxide and other auxiliaries are mixed and vulcanized together to obtain the corrosion-resistant rubber composite material, and the corrosion-resistant rubber composite material has excellent mechanical properties and corrosion resistance and can be widely applied to the field of corrosion-resistant rubber materials.

Description

Technical Field

[0001] The present invention relates to the field of fluorosilicone rubber polymer materials, and in particular to a corrosion-resistant rubber composite material and a preparation method and application thereof. Background Art

[0002] In the field of rubber composites, although traditional corrosion-resistant materials such as fluororubber and fluorosilicone rubber have certain chemical resistance, they still have significant defects: fluororubber has poor flexibility and is easy to harden at high temperatures, while fluorosilicone rubber has insufficient mechanical strength and limited long-term tolerance to strong acids (such as concentrated sulfuric acid). In addition, conventional nanofillers have weak interfacial bonding with the rubber matrix, resulting in low stress transfer efficiency and easy agglomeration of fillers, which affects the uniformity of the composite material. In the existing technology, although the use of perfluoroether rubber can improve corrosion resistance, it is expensive and the vulcanization process is complicated. Although epoxy-modified rubber can enhance interfacial bonding, the epoxy groups are prone to premature ring opening and crosslinking during the mixing stage, resulting in processing difficulties. Therefore, the development of a new rubber composite material that combines high corrosion resistance, excellent mechanical properties, low cost and easy processing has become a technical problem that urgently needs to be overcome in this field.

[0003] Existing technologies, such as Chinese patent application CN119285958A, disclose a reinforced fluorosilicone rubber composite material and a preparation method thereof. A carbon nanotube / silicon dioxide composite material is prepared and modified with 3-mercaptopropyltriethoxysilane to obtain a composite filler. The composite filler is then added to polyfluorosilicone to prepare a fluorosilicone rubber composite material to improve the mechanical properties of the fluorosilicone rubber. Although the mechanical properties of the fluorosilicone rubber can be improved, the corrosion resistance is not significantly improved.

[0004] Existing technologies, such as Chinese patent application CN119752195A, disclose a high-temperature resistant and corrosion-resistant silicone rubber sealing ring and a preparation method thereof. Silicon-hydrogen groups and double bond structures are introduced into the modified fluorosilicone resin, and complex cyclic, cross-linked and grafted structures are formed by cross-linking with the monomer structure and reinforcing fillers. Ultimately, the chain segment complexity of the hybrid fluorosilicone resin is significantly improved and a large number of fluorine groups are introduced. After mixing with hollow fillers and auxiliary materials and vulcanization, a silicone rubber sealing ring with corrosion resistance is obtained. However, its fluorine groups are unevenly distributed, the local corrosion rate is fast, and the interface bonding between the hollow filler and the fluorosilicone resin relies on physical adsorption, and chemical bonds cannot be formed, making it easy for corrosive media to penetrate. Summary of the Invention

[0005] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a corrosion-resistant rubber composite material and a preparation method and application thereof. The rubber composite material has excellent mechanical properties and corrosion resistance and can be applied to the field of corrosion-resistant rubber materials.

[0006] In order to achieve the above object, the technical solution adopted by the present invention is as follows: A method for preparing a corrosion-resistant rubber composite material comprises the following steps: Step (1), 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide as a catalyst, and acetone are mixed and reacted. After the reaction is completed, the light is removed, tetrahydrofuran is added to obtain a homogeneous solution, methanol is added, centrifuged, the precipitate is collected, and vacuum dried to obtain a fluorinated copolymer A; Fluorinated copolymer A, perfluorohexyl iodide, sodium iodide catalyst, and acetone were mixed and reacted. After the reaction, the light was removed and tetrahydrofuran was added to obtain a homogeneous solution. Methanol was added and the solution was centrifuged. The precipitate was collected and dried in vacuo to obtain fluorinated copolymer B. The fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and reacted. After the reaction was completed, the light was removed and tetrahydrofuran was added to obtain a homogeneous solution. Methanol was added and the solution was centrifuged. The precipitate was collected and vacuum dried to obtain a fluorosilicone nanofiller modifier. Step (2), mixing nano-alumina and toluene, ultrasonically dispersing, adding fluorosilicone nano-filler modifier and 1 mol / L HCl aqueous solution, reacting, after the reaction is completed, centrifuging, washing, and drying to obtain an intermediate product; The intermediate product, azobisisobutyronitrile, tributyltin hydride and toluene are mixed and reacted. After the reaction is completed, the mixture is centrifuged, washed and dried to obtain modified nano-alumina. Step (3): Mix the fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, place them in a double-roll mill, mix them, add the vulcanizing agent diisopropylbenzene peroxide and the lubricant zinc stearate, continue mixing, and after the mixing is completed, place them in a mold for vulcanization. After the vulcanization is completed, cool them to room temperature to obtain a corrosion-resistant rubber composite material.

[0007] Preferably, in the step (1), when preparing the fluorinated copolymer A, the molar ratio of 1,4-diiodoperfluorobutane and 1,5-hexadiene is 1:(0.8-1); the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide, and acetone is 1:(0.01-0.02):(10-14); the reaction conditions are: in an argon atmosphere, a wavelength of 400-410 nm, and a power of 34-38 mW / cm 2 Incubate under strong light and room temperature for 4-6 hours.

[0008] Preferably, in the step (1), when preparing the fluorinated copolymer B, the mass ratio of the fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:(0.2-0.4):(0.01-0.02):(10-14); the reaction conditions are: in an argon atmosphere, a wavelength of 400-410 nm, and a power of 30-32 mW / cm 2 Incubate under strong light and room temperature for 5-7 hours.

[0009] Preferably, in the step (1), when preparing the fluorosilicone nanofiller modifier, the mass ratio of the fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:(0.3-0.6):(0.1-0.3):(0.01-0.02):(14-18); the reaction conditions are: in an argon atmosphere, a wavelength of 400-410 nm, and a power of 30-32 mW / cm 2 Incubate under strong light and room temperature for 14-16 hours.

[0010] Preferably, in step (2), when preparing the intermediate product, the mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and solute HCl in a 1 mol / L HCl aqueous solution is 1:(16-20):(0.2-0.4):(0.02-0.04); and the reaction conditions are: reaction at room temperature for 12-16 hours.

[0011] Preferably, in step (2), when preparing the modified nano-alumina, the mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:(0.1-0.2):(1-1.2):(16-20); and the reaction conditions are: reaction in an argon atmosphere at a temperature of 75-85°C for 5-7h.

[0012] Preferably, in step (3), when preparing the corrosion-resistant rubber composite material, the mass ratio of fluorosilicone raw rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:(10-30):(2-4):(1-2):(0.6-1).

[0013] Preferably, in step (3), when preparing the corrosion-resistant rubber composite material, the mixing conditions are: mixing at a temperature of 55-65°C for 20-30 minutes; the continued mixing conditions are: continuing mixing at a temperature of 55-65°C for 5-10 minutes; the first-stage vulcanization conditions are: first-stage vulcanization at 10-14 MPa and a temperature of 160-180°C for 10-20 minutes; the second-stage vulcanization conditions are: second-stage vulcanization at a temperature of 190-210°C in vacuum for 3-5 hours.

[0014] Preferably, a corrosion-resistant rubber composite material is prepared using the method for preparing a corrosion-resistant rubber composite material as described above.

[0015] Preferably, a corrosion-resistant rubber composite material prepared by the method for preparing a corrosion-resistant rubber composite material as described above is used in corrosion-resistant rubber materials.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The invention prepares a fluorine-containing copolymer A having terminal groups of iodine and double bonds through a free radical stepwise transfer-addition-termination polymerization reaction, caps the terminal double bonds to obtain a fluorine-containing copolymer B, uses the fluorine-containing copolymer B as a macromolecular initiator to initiate polymerization of methacryloyloxypropyltriisopropoxysilane and glycidyl methacrylate to prepare a fluorine-silicon nanofiller modifier; grafts the fluorine-silicon nanofiller modifier onto the surface of nanoalumina through a condensation reaction, introduces epoxy groups while forming a fluorinated layer on the surface of the nanoalumina, and reduces and removes the iodine groups through a tributyltin hydride / azobisisobutyronitrile system. The obtained modified nanoalumina has a super-hydrophobic property and can capture a large number of air pockets at a solid-liquid interface to form an air layer. The air layer serves as a physical barrier and can effectively prevent corrosion of a base material by a corrosive medium.

[0017] In addition, the low surface energy characteristics of the fluorine chain segment repels polar corrosive media (such as acids and alkalis), and the epoxy group forms a dense cross-linked network through a ring-opening reaction in the subsequent vulcanization process, further blocking the penetration of corrosive factors. The synergistic corrosion resistance of fluorine atoms and epoxy groups constructs a double protection barrier; during the vulcanization stage, the epoxy group undergoes ring-opening cross-linking with the structure control agent hydroxyl silicone oil and the vulcanizing agent diisopropyl peroxide to form an ether bond cross-linking network, constructing a "hydrophobic barrier-chemical cross-linking" dual protection system, improving the compatibility of modified nano-alumina and fluorosilicone rubber, and enhancing the mechanical properties and vulcanization properties of fluorosilicone rubber.

[0018] The present invention mixes fluorosilicone raw rubber, modified nano-alumina and other additives together and vulcanizes them to obtain a corrosion-resistant rubber composite material with excellent mechanical properties and corrosion resistance, and has broad application prospects in the field of corrosion-resistant rubber materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 1 is a histogram of Shore A hardness in comprehensive performance tests of the rubber composite materials prepared in Examples 1-5 and Comparative Examples 1-2 of the present invention; Figure 2 The tear strength histogram of the rubber composite materials prepared by Examples 1-5 and Comparative Examples 1-2 in the comprehensive performance test of the present invention is shown; Figure 3 is a line graph of the acid corrosion mass change rate in the comprehensive performance test of the rubber composite materials prepared by Examples 1-5 and Comparative Examples 1-2 of the present invention; Figure 4 It is a broken line graph of the alkali corrosion mass change rate in the comprehensive performance test of the rubber composite materials prepared by Examples 1-5 and Comparative Examples 1-2 of the present invention. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0021] Example 1: This example discloses a method for preparing a corrosion-resistant rubber composite material, comprising the following steps: Step (1): 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide catalyst, and acetone were mixed and heated in an argon atmosphere at a wavelength of 410 nm and a power of 38 mW / cm 2 The mixture was reacted under high-intensity light and room temperature for 4 hours. After the reaction, the light was removed and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (5 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 40°C for 20 hours to obtain a fluorinated copolymer A. The molar ratio of 1,4-diiodoperfluorobutane to 1,5-hexadiene is 1:1; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide, and acetone is 1:0.02:14; Fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone were mixed and heated in an argon atmosphere at a wavelength of 410 nm and a power of 32 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 5 hours. After the reaction was completed, the light was removed, and tetrahydrofuran (3 times the mass of the reactants) was added to obtain a homogeneous solution. Methanol (5 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 40°C for 20 hours to obtain a fluorinated copolymer B. The mass ratio of fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.4:0.02:14; Fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and heated in an argon atmosphere at a wavelength of 410 nm and a temperature of 32 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 14 hours. After the reaction, the light was removed and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (5 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 40°C for 20 hours to obtain a fluorosilicone nanofiller modifier. The mass ratio of fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.6:0.3:0.02:18; Step (2): nano-alumina and toluene are mixed, ultrasonically dispersed for 10 minutes, a fluorosilicone nanofiller modifier and a 1 mol / L HCl aqueous solution are added, and the mixture is reacted at room temperature for 16 hours. After the reaction is completed, the mixture is centrifuged, the precipitate is taken, and toluene twice the mass of the precipitate is added to wash the mixture 5 times, and the mixture is dried at 120°C for 2 hours to obtain an intermediate product; The mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and HCl in a 1 mol / L HCl aqueous solution is 1:20:0.4:0.04; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted under an argon atmosphere at 85°C for 5 hours. After the reaction, the mixture was centrifuged and the precipitate was taken out. The mixture was washed five times with toluene twice the mass of the precipitate and dried at 120°C for 2 hours to obtain modified nano-alumina. The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.2:1.2:20; Step (3), mixing fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a two-roll open mill, mixing at 65°C for 20 minutes, adding a vulcanizing agent diisopropylbenzene peroxide and a lubricant zinc stearate, and continuing to mix at 65°C for 5 minutes. After the mixing is completed, the mixture is placed in a mold and vulcanized at 14 MPa and 180°C for 10 minutes in a first stage, and vulcanized at 210°C in a vacuum for 3 hours in a second stage. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:30:4:2:1.

[0022] Example 2: This example discloses a method for preparing a corrosion-resistant rubber composite material, comprising the following steps: Step (1) 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide catalyst and acetone were mixed and heated in an argon atmosphere at a wavelength of 400 nm and a temperature of 34 mW / cm 2 The mixture was reacted under high-intensity light and room temperature for 6 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 30°C for 24 hours to obtain a fluorinated copolymer A. The molar ratio of 1,4-diiodoperfluorobutane to 1,5-hexadiene is 1:0.8; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide, and acetone is 1:0.01:10; Fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone were mixed and heated in an argon atmosphere at a wavelength of 400 nm and a power of 30 mW / cm2 The mixture was reacted under high-intensity light and room temperature for 7 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 30°C for 24 hours to obtain a fluorinated copolymer B. The mass ratio of fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.2:0.01:10; Fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and heated in an argon atmosphere at a wavelength of 400 nm and a temperature of 30 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 16 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 30°C for 24 hours to obtain a fluorosilicone nanofiller modifier. The mass ratio of fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.3:0.1:0.01:14; Step (2): nano-alumina and toluene were mixed and ultrasonically dispersed for 5 minutes, a fluorosilicone nanofiller modifier and a 1 mol / L HCl aqueous solution were added, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was taken and washed three times with toluene 4 times the mass of the precipitate. The mixture was dried at 100°C for 4 hours to obtain an intermediate product. The mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and HCl in a 1 mol / L HCl aqueous solution is 1:16:0.2:0.02; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted under an argon atmosphere at 75°C for 7 hours. After the reaction was completed, the mixture was centrifuged and the precipitate was taken out. The mixture was washed three times with toluene 4 times the mass of the precipitate and dried at 100°C for 4 hours to obtain modified nano-alumina. The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.1:1:16; Step (3), mixing fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a double-roll mill, mixing at 55°C for 30 minutes, adding a vulcanizing agent, diisopropylbenzene peroxide, and a lubricant, zinc stearate, and continuing to mix at 55°C for 10 minutes. After the mixing is completed, the mixture is placed in a mold and vulcanized at 10 MPa and 160°C for 20 minutes in a first stage, and vulcanized at 190°C in a vacuum for 5 hours in a second stage. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:10:2:1:0.6.

[0023] Example 3: This example discloses a method for preparing a corrosion-resistant rubber composite material, comprising the following steps: Step (1): 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide catalyst, and acetone were mixed and heated in an argon atmosphere at a wavelength of 408 nm and a power of 37 mW / cm 2 The reaction was carried out under high-intensity light and room temperature for 4.5 hours. After the reaction was completed, the light was removed, and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (5 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 38°C for 21 hours to obtain a fluorinated copolymer A. The molar ratio of 1,4-diiodoperfluorobutane to 1,5-hexadiene is 1:0.95; the mass ratio of 1,4-diiodoperfluorobutane to catalyst sodium iodide to acetone is 1:0.02:13; Fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone were mixed and heated in an argon atmosphere at a wavelength of 408 nm and a power of 32 mW / cm 2 The reaction was carried out under high-intensity light and room temperature for 5.5 hours. After the reaction was completed, the light was removed, and tetrahydrofuran (3 times the mass of the reactants) was added to obtain a homogeneous solution. Methanol (5 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 38°C for 21 hours to obtain a fluorinated copolymer B. The mass ratio of fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.35:0.02:13; Fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and heated in an argon atmosphere at a wavelength of 408 nm and a power of 32 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 14.5 hours. After the reaction, the light was removed and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (5 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 38°C for 21 hours to obtain a fluorosilicone nanofiller modifier. The mass ratio of fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.5:0.25:0.02:17; Step (2): nano-alumina and toluene were mixed and ultrasonically dispersed for 9 minutes, a fluorosilicone nanofiller modifier and a 1 mol / L HCl aqueous solution were added, and the mixture was reacted at room temperature for 15 hours. After the reaction, the mixture was centrifuged, and the precipitate was taken and washed five times with toluene twice the mass of the precipitate. The mixture was dried at 115°C for 2 hours to obtain an intermediate product. The mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and HCl in a 1 mol / L HCl aqueous solution is 1:19:0.35:0.035; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted under an argon atmosphere at 82°C for 5.5 hours. After the reaction, the mixture was centrifuged and the precipitate was taken out. The mixture was washed five times with toluene twice the mass of the precipitate and dried at 115°C for 2 hours to obtain modified nano-alumina. The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.2:1.15:19; Step (3), mixing fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a double-roll open mill, mixing at 62°C for 22 minutes, adding a vulcanizing agent diisopropylbenzene peroxide and a lubricant zinc stearate, and continuing to mix at 62°C for 6 minutes. After the mixing is completed, the mixture is placed in a mold and vulcanized at 13 MPa and 175°C for 12 minutes in a first stage, and vulcanized at 205°C in a vacuum for 3.5 hours in a second stage. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:25:3.5:1.8:0.9.

[0024] Example 4: This example discloses a method for preparing a corrosion-resistant rubber composite material, comprising the following steps: Step (1): 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide catalyst, and acetone were mixed and heated in an argon atmosphere at a wavelength of 405 nm and a power of 36 mW / cm 2 The mixture was reacted under high-intensity light and room temperature for 5 hours. After the reaction, the light was removed and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (4 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 35°C for 22 hours to obtain a fluorinated copolymer A. The molar ratio of 1,4-diiodoperfluorobutane to 1,5-hexadiene is 1:0.9; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide, and acetone is 1:0.015:12; Fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone were mixed and heated in an argon atmosphere at a wavelength of 405 nm and a power of 31 mW / cm 2 The mixture was reacted under high-intensity light and room temperature for 6 hours. After the reaction, the light was removed and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (4 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 35°C for 22 hours to obtain a fluorinated copolymer B. The mass ratio of fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.3:0.015:12; Fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and heated in an argon atmosphere at a wavelength of 405 nm and a power of 31 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 15 hours. After the reaction, the light was removed and tetrahydrofuran (3 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (4 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 35°C for 22 hours to obtain a fluorosilicone nanofiller modifier. The mass ratio of fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.45:0.2:0.015:16; Step (2): nano-alumina and toluene were mixed and ultrasonically dispersed for 7 minutes, and a fluorosilicone nanofiller modifier and a 1 mol / L HCl aqueous solution were added. The mixture was reacted at room temperature for 14 hours. After the reaction, the mixture was centrifuged and the precipitate was taken. The precipitate was washed four times with toluene 3 times the mass of the precipitate, and dried at 110°C for 3 hours to obtain an intermediate product. The mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and HCl in a 1 mol / L HCl aqueous solution is 1:18:0.3:0.03; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted under an argon atmosphere at 80°C for 6 hours. After the reaction, the mixture was centrifuged and the precipitate was taken out. The mixture was washed four times with toluene 3 times the mass of the precipitate and dried at 110°C for 3 hours to obtain modified nano-alumina. The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.15:1.1:18; Step (3), mixing fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a double-roll mill, mixing at 60°C for 25 minutes, adding a vulcanizing agent, diisopropylbenzene peroxide, and a lubricant, zinc stearate, and continuing to mix at 60°C for 7 minutes. After mixing, placing the mixture in a mold and vulcanizing at 12 MPa and 170°C for 15 minutes, and vulcanizing the mixture in a vacuum at 200°C for 4 hours. After the vulcanization is completed, cooling the mixture to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:20:3:1.5:0.8.

[0025] Example 5: This example discloses a method for preparing a corrosion-resistant rubber composite material, comprising the following steps: Step (1): 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide catalyst, and acetone were mixed and heated in an argon atmosphere at a wavelength of 402 nm and a power of 35 mW / cm 2 The reaction was carried out under high-intensity light and room temperature for 5.5 hours. After the reaction was completed, the light was removed, and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 32°C for 23 hours to obtain fluorinated copolymer A. The molar ratio of 1,4-diiodoperfluorobutane to 1,5-hexadiene is 1:0.85; the mass ratio of 1,4-diiodoperfluorobutane to catalyst sodium iodide to acetone is 1:0.01:11; Fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone were mixed and heated in an argon atmosphere at a wavelength of 402 nm and a power of 30 mW / cm 2 The reaction was carried out under high-intensity light and room temperature for 6.5 hours. After the reaction was completed, the light was removed, and tetrahydrofuran (2 times the mass of the reactants) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 32°C for 23 hours to obtain fluorinated copolymer B. The mass ratio of fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.25:0.01:11; Fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and heated in an argon atmosphere at a wavelength of 402 nm and a temperature of 30 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 15.5 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 32°C for 23 hours to obtain a fluorosilicone nanofiller modifier. The mass ratio of fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.4:0.15:0.01:15; Step (2): nano-alumina and toluene were mixed and ultrasonically dispersed for 6 minutes, a fluorosilicone nanofiller modifier and a 1 mol / L HCl aqueous solution were added, and the mixture was reacted at room temperature for 13 hours. After the reaction, the mixture was centrifuged, and the precipitate was taken and washed three times with toluene 4 times the mass of the precipitate. The mixture was dried at 105°C for 4 hours to obtain an intermediate product. The mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and HCl in a 1 mol / L HCl aqueous solution is 1:17:0.25:0.025; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted under an argon atmosphere at 78°C for 6.5 hours. After the reaction, the mixture was centrifuged and the precipitate was taken out. The mixture was washed three times with toluene 4 times the mass of the precipitate and dried at 105°C for 4 hours to obtain modified nano-alumina. The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.1:1.05:17; Step (3), mixing fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a two-roll open mill, mixing at 58°C for 28 minutes, adding a vulcanizing agent diisopropylbenzene peroxide and a lubricant zinc stearate, and continuing to mix at 58°C for 9 minutes. After the mixing is completed, the mixture is placed in a mold and vulcanized at 11 MPa and 165°C for 18 minutes in a first stage, and vulcanized at 195°C in a vacuum for 4.5 hours in a second stage. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:15:2.5:1.2:0.7.

[0026] Comparative Example 1: This comparative example discloses a method for preparing a rubber composite material, comprising the following steps: Step (1) 1,4-diiodoperfluorobutane, 1,5-hexadiene, sodium iodide catalyst and acetone were mixed and heated in an argon atmosphere at a wavelength of 400 nm and a temperature of 34 mW / cm 2 The mixture was reacted under high-intensity light and room temperature for 6 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 30°C for 24 hours to obtain a fluorinated copolymer A. The molar ratio of 1,4-diiodoperfluorobutane to 1,5-hexadiene is 1:0.8; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide, and acetone is 1:0.01:10; Fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone were mixed and heated in an argon atmosphere at a wavelength of 400 nm and a power of 30 mW / cm 2 The mixture was reacted under high-intensity light and room temperature for 7 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum-dried at 30°C for 24 hours to obtain a fluorinated copolymer B. The mass ratio of fluorinated copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.2:0.01:10; Fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, catalyst tetrabutylammonium bromide, and dimethylacetamide were mixed and heated in an argon atmosphere at a wavelength of 400 nm and a temperature of 30 mW / cm 2 The mixture was subjected to light irradiation and reaction at room temperature for 16 hours. After the reaction, the light was removed and tetrahydrofuran (2 times the mass of the reactant) was added to obtain a homogeneous solution. Methanol (3 times the mass of the homogeneous solution) was added and centrifuged. The precipitate was collected and vacuum dried at 30°C for 24 hours to obtain a fluorosilicone nanofiller modifier. The mass ratio of fluorinated copolymer B, methacryloxypropyltriisopropoxysilane, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.3:0.01:14; Step (2): nano-alumina and toluene were mixed and ultrasonically dispersed for 5 minutes, a fluorosilicone nanofiller modifier and a 1 mol / L HCl aqueous solution were added, and the mixture was reacted at room temperature for 12 hours. After the reaction was completed, the mixture was centrifuged, and the precipitate was taken and washed three times with toluene 4 times the mass of the precipitate. The mixture was dried at 100°C for 4 hours to obtain an intermediate product. The mass ratio of nano-alumina, toluene, fluorosilicone nano-filler modifier, and HCl in a 1 mol / L HCl aqueous solution is 1:16:0.2:0.02; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted under an argon atmosphere at 75°C for 7 hours. After the reaction was completed, the mixture was centrifuged and the precipitate was taken out. The mixture was washed three times with toluene 4 times the mass of the precipitate and dried at 100°C for 4 hours to obtain modified nano-alumina. The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.1:1:16; Step (3), mixing fluorosilicone rubber, modified nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a double-roll mill, mixing at 55°C for 30 minutes, adding a vulcanizing agent, diisopropylbenzene peroxide, and a lubricant, zinc stearate, and continuing to mix at 55°C for 10 minutes. After the mixing is completed, the mixture is placed in a mold and vulcanized at 10 MPa and 160°C for 20 minutes in a first stage, and vulcanized at 190°C in a vacuum for 5 hours in a second stage. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, modified nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:10:2:1:0.6.

[0027] Comparative Example 2: This comparative example discloses a method for preparing a rubber composite material, comprising the following steps: Step (1), mixing fluorosilicone rubber, nano-alumina, and structure control agent hydroxy silicone oil, placing the mixture in a two-roll open mill, mixing at 55°C for 30 minutes, adding a vulcanizing agent diisopropylbenzene peroxide and a lubricant zinc stearate, and continuing to mix at 55°C for 10 minutes. After the mixing is completed, the mixture is placed in a mold and vulcanized at 10 MPa and 160°C for 20 minutes in a first stage, and vulcanized at 190°C in a vacuum for 5 hours in a second stage. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material; Among them, the mass ratio of fluorosilicone rubber, nano-alumina, structure control agent hydroxy silicone oil, vulcanizing agent diisopropylbenzene peroxide, and lubricant zinc stearate is 100:10:2:1:0.6.

[0028] In the above examples and comparative examples: 1,4-diiodoperfluorobutane was from Shanghai Xiangna Chemical Technology Co., Ltd., CAS No.: 375-50-8; 1,5-hexadiene was from Shanghai Xuntian Technology Co., Ltd., CAS No.: 592-42-7; sodium iodide was from Jiangsu Runfeng Synthetic Technology Co., Ltd., CAS No.: 7681-82-5; acetone was from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 67-64-1; tetrahydrofuran was from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 109-99-9; methanol was from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 67-56-1; perfluorohexyl iodide was from Shanghai Xiangna Chemical Technology Co., Ltd., CAS No.: 355-43-1; methacryloyloxypropyl triisopropoxysilane was from Shanghai Tangui New Materials Technology Co., Ltd., CAS No.: 80750-05-6; glycidyl methacrylate was from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 106-91-2; tetrabutyl bromide Ammonium chloride was obtained from Shanghai Siyan Biotechnology Co., Ltd., CAS No.: 1643-19-2; dimethylacetamide was obtained from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 127-19-5; nano-alumina was obtained from Shanghai Aladdin Biochemical Technology Co., Ltd., particle size: 30 nm, CAS No.: 1344-28-1; toluene was obtained from Wuxi Jiaxi Chemical Co., Ltd., CAS No.: 108-88-3; azobisisobutyronitrile was obtained from Jinan Century Tongda Chemical Co., Ltd., CAS No.: 78- 67-1; tributyltin hydride was from Wuhan Xinyang Ruihe Chemical Technology Co., Ltd., CAS No.: 688-73-3; fluorosilicone rubber was from Jining Sanshi Biotechnology Co., Ltd., item No.: SS-K22; hydroxy silicone oil was from Hubei Enxing Biotechnology Co., Ltd., CAS No.: 70131-67-8; diisopropyl peroxide was from Jiangsu Daoming Chemical Co., Ltd., CAS No.: 80-43-3; zinc stearate was from Shanghai MacLean Biochemical Technology Co., Ltd., CAS No.: 557-05-1.

[0029] Test example (1) Comprehensive performance test Comprehensive performance tests were conducted on the rubber composite materials prepared in Examples 1-5 and Comparative Examples 1-2. Specific test results are shown in Table 1: Table 1 The tests of various indicators in Table 1 are based on the following standards: Shore A hardness is determined by GB / T The test results are as follows: 531.1-2008 "Rubber, vulcanized or thermoplastic—Test method for indentation hardness—Part 1: Shore durometer method (Shore hardness)"; tear strength is determined according to GB / T 529-2008 "Rubber, vulcanized or thermoplastic—Determination of tear strength (trouser-shaped, rectangular and crescent-shaped specimens)"; acid corrosion mass change rate and alkaline corrosion mass change rate are determined according to ASTM D471-2016 "Standard test method for rubber properties. Effect of liquids", where the acidic medium is a 10wt% H2SO4 aqueous solution and the alkaline medium is a 10wt% NaOH aqueous solution, and the test time is 72h.

[0030] According to the test results in Table 1, it can be seen that the rubber composite material prepared in the present invention has excellent mechanical properties and corrosion resistance.

[0031] In the preparation of the fluorosilicone nanofiller modifier in Comparative Example 1, glycidyl methacrylate was not polymerized, and no epoxy group was introduced. Therefore, ring-opening crosslinking with the structure control agent hydroxy silicone oil and the vulcanizing agent diisopropylbenzene peroxide could not occur during the vulcanization stage. At the same time, the synergistic corrosion resistance effect with the fluorine chain segment was lacking. The mechanical properties and corrosion resistance of the obtained rubber composite material were reduced. Therefore, the Shore A hardness and tear strength of Comparative Example 1 were lower than those of the embodiment, and the acid corrosion mass change rate and the alkali corrosion mass change rate were larger than those of the embodiment.

[0032] In the preparation of the rubber composite material in Comparative Example 2, the nano-alumina was not modified, and fluorine segments and epoxy groups were not introduced. The nano-alumina was directly used as a filler for mixing and vulcanization with the fluorosilicone raw rubber. The obtained rubber composite material was ordinary fluorosilicone rubber, and the interface bonding between the nano-alumina and the rubber matrix was weak and easy to agglomerate, which affected the uniformity of the composite material and caused its mechanical properties and corrosion resistance to be reduced. Therefore, the Shore A hardness and tear strength of Comparative Example 2 were smaller than those of the embodiment, and the acid corrosion mass change rate and the alkali corrosion mass change rate were larger than those of the embodiment.

[0033] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a corrosion-resistant rubber composite material, characterized in that: The following steps are involved: Step (1), mixing 1,4-diiodoperfluorobutane, 1,5-hexadiene, a catalyst, and acetone, reacting, and after the reaction is completed, post-treating to obtain a fluorinated copolymer A; The fluorinated copolymer A, perfluorohexyl iodide, a catalyst, and acetone are mixed and reacted, and after the reaction, post-processed to obtain the fluorinated copolymer B; The fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, a catalyst, and dimethylacetamide are mixed and reacted, and after the reaction is completed, post-processed to obtain a fluorosilicone nanofiller modifier; Step (2), mixing nano-alumina and toluene, ultrasonically dispersing, adding fluorosilicone nano-filler modifier and HCl aqueous solution, reacting, and after the reaction is completed, post-processing to obtain an intermediate product; The intermediate product, azobisisobutyronitrile, tributyltin hydride and toluene are mixed and reacted, and after the reaction is completed, post-processed to obtain modified nano-alumina; Step (3): mixing the fluorosilicone raw rubber, modified nano-alumina and additives, kneading and vulcanizing to obtain a corrosion-resistant rubber composite material.

2. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In step (1): In the preparation of fluorinated copolymer A, the catalyst is sodium iodide; the molar ratio of 1,4-diiodoperfluorobutane and 1,5-hexadiene is 1:(0.8-1); the mass ratio of 1,4-diiodoperfluorobutane, sodium iodide, and acetone is 1:(0.01-0.02):(10-14); the reaction conditions are: in an argon atmosphere, a wavelength of 400-410 nm, and a power of 34-38 mW / cm 2 Incubate under strong light and room temperature for 4-6 hours.

3. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In step (1): In the preparation of fluorinated copolymer B, the catalyst is sodium iodide; the mass ratio of fluorinated copolymer A, perfluorohexyl iodide, sodium iodide, and acetone is 1:(0.2-0.4):(0.01-0.02):(10-14); the reaction conditions are: in an argon atmosphere, a wavelength of 400-410 nm, and a power of 30-32 mW / cm 2 Incubate under strong light and room temperature for 5-7 hours.

4. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In step (1): When preparing a fluorosilicone nanofiller modifier, the catalyst is tetrabutylammonium bromide; the mass ratio of fluorinated copolymer B, methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, tetrabutylammonium bromide, and dimethylacetamide is 1:(0.3-0.6):(0.1-0.3):(0.01-0.02):(14-18); the reaction conditions are: in an argon atmosphere, at a wavelength of 400-410 nm and a power of 30-32 mW / cm 2 Incubate under strong light and room temperature for 14-16 hours.

5. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In step (2), the HCl aqueous solution is a 1 mol / L HCl aqueous solution; the mass ratio of nano-alumina, toluene, fluorosilicone nanofiller modifier, and solute HCl in the 1 mol / L HCl aqueous solution is 1:(16-20):(0.2-0.4):(0.02-0.04); when preparing the intermediate product, the reaction conditions are: reaction at room temperature for 12-16 hours.

6. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In step (2), the mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:(0.1-0.2):(1-1.2):(16-20); when preparing the modified nano-alumina, the reaction conditions are: reacting in an argon atmosphere at a temperature of 75-85°C for 5-7 hours.

7. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In the step (3), the auxiliary agents include a structure control agent, a vulcanizing agent, and a lubricant, wherein the structure control agent is hydroxy silicone oil, the vulcanizing agent is dicumyl peroxide, and the lubricant is zinc stearate; the mass ratio of fluorosilicone rubber, modified nano-alumina, hydroxy silicone oil, dicumyl peroxide, and zinc stearate is 100:(10-30):(2-4):(1-2):(0.6-1).

8. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that: In the step (3), the mixing conditions are: mixing at a temperature of 55-65°C for 20-30 minutes; the vulcanization conditions are: first-stage vulcanization at 10-14 MPa and a temperature of 160-180°C for 10-20 minutes, and second-stage vulcanization at a temperature of 190-210°C in vacuum for 3-5 hours.

9. A corrosion-resistant rubber composite material prepared by the method for preparing a corrosion-resistant rubber composite material according to any one of claims 1 to 8.

10. Use of the corrosion-resistant rubber composite material according to claim 9 in corrosion-resistant rubber materials.

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