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

Abstract

The application relates to the field of fluorosilicone rubber high polymer materials, and discloses a corrosion-resistant rubber composite material and a preparation method and application thereof. The preparation method comprises the following steps: a fluorine-containing copolymer A with iodine and double bonds as end groups is prepared through a free radical step-by-step transfer-addition-termination polymerization reaction; the terminal double bonds are capped to obtain a fluorine-containing copolymer B; the fluorine-containing copolymer B is used as a macromolecular initiator to initiate polymerization of methylacryloxypropyl triisopropoxy silane and glycidyl methacrylate, so that a fluorosilicon nano filler modifier is prepared; the fluorosilicon nano filler modifier is grafted on the surface of nano alumina through a condensation reaction to obtain modified nano alumina; and the fluorosilicone rubber, the modified nano alumina and other additives are mixed and vulcanized to obtain the corrosion-resistant rubber composite material, which 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 application relates to the field of fluorosilicone rubber polymer materials, in particular to a corrosion-resistant rubber composite material and a preparation method and application thereof. BACKGROUND

[0002] In the field of rubber composites, traditional corrosion-resistant materials such as fluororubber and fluorosilicone rubber have certain chemical resistance, but still have significant defects: fluororubber has poor flexibility and is prone to hardening at high temperatures, while fluorosilicone rubber has insufficient mechanical strength and limited long-term resistance 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 the fillers, affecting the uniformity of the composite material. In the prior art, the use of perfluoroether rubber can improve corrosion resistance, but the cost is high and the vulcanization process is complex; while epoxy-modified rubber can enhance interfacial bonding, but the epoxy groups are prone to ring-opening crosslinking at the mixing stage, leading to processing difficulties. Therefore, developing a new type of rubber composite material with high corrosion resistance, excellent mechanical properties, low cost and easy processing has become a technical problem that needs to be solved in this field.

[0003] The prior art such as Chinese Patent Application CN119285958A discloses a reinforced fluorosilicone rubber composite material and a preparation method thereof, by preparing a carbon nanotube / silicon dioxide composite material and modifying the composite material with 3-mercaptopropyl triethoxysilane to obtain a composite filler, and adding the composite filler to polyfluorosiloxane to prepare a fluorosilicone rubber composite material, the mechanical properties of the fluorosilicone rubber are improved, but the corrosion resistance is not significantly improved.

[0004] The prior art such as Chinese Patent Application CN119752195A discloses a high-temperature-resistant and corrosion-resistant silicone rubber sealing ring and a preparation method thereof, by introducing silicon-hydrogen groups and double bond structures into the modified fluorosilicone resin, crosslinking with monomer structures and reinforcing fillers to form complex ring, crosslinking and grafting structures, finally significantly improving the complexity of the hybrid fluorosilicone resin segments and introducing a large number of fluorine groups, and mixing with hollow fillers and auxiliary materials for vulcanization, a silicone rubber sealing ring with corrosion resistance is obtained, but the fluorine groups are unevenly distributed, the local corrosion rate is fast, and the interface bonding between the hollow fillers and the fluorosilicone resin relies on physical adsorption and does not form chemical bonds, and the corrosion medium can easily penetrate. SUMMARY

[0005] The present application aims to overcome the shortcomings of the prior art and provide a corrosion-resistant rubber composite material and a preparation method and application thereof, which has excellent mechanical properties and corrosion resistance and can be applied in the field of corrosion-resistant rubber materials.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] A preparation method of a corrosion-resistant rubber composite material, comprising the following steps:

[0008] Step (1), 1,4-diiodoperfluorobutane, 1,5-hexadiene, catalyst sodium iodide, acetone are mixed, 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 taken, vacuum dried to obtain fluorine-containing copolymer A;

[0009] Fluorine-containing copolymer A, perfluoroalkyl iodine, catalyst sodium iodide, acetone are mixed, 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 taken, vacuum dried to obtain fluorine-containing copolymer B;

[0010] Fluorine-containing copolymer B, methyl acryloyl propyl triisopropoxy silane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide are mixed, 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 taken, vacuum dried to obtain fluorine-silicon nano filler modifier;

[0011] Step (2), nanometer aluminum oxide and toluene are mixed and ultrasonically dispersed, then fluorine-silicon nano filler modifier and 1mol / L HCl aqueous solution are added and reacted, after the reaction is completed, centrifuged, washed and dried to obtain an intermediate product;

[0012] The intermediate product, azobis isobutyronitrile and tributyltin hydride are mixed and reacted, after the reaction is completed, centrifuged, washed and dried to obtain modified nanometer aluminum oxide;

[0013] Step (3), fluorine-silicon raw rubber, modified nanometer aluminum oxide and structure control agent hydroxyl silicone oil are mixed and placed in a double roller open mill, mixed, then peroxide diisopropylbenzene and zinc stearate are added and continuously mixed, after the mixing is completed, placed in a mold for vulcanization, after the vulcanization is completed, cooled to room temperature to obtain a corrosion-resistant rubber composite material.

[0014] Preferably, in step (1), when preparing fluorine-containing 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 condition is: under argon atmosphere, 400-410nm wavelength, 34-38mW / cm 2 Light intensity, reaction at room temperature for 4-6h.

[0015] Preferably, in the step (1), the mass ratio of the fluorine-containing copolymer A, the perfluorohexyl iodonium, the catalyst sodium iodide, the acetone and the fluorosilicon nanofiller modifier is 1: (0.2-0.4): (0.01-0.02): (10-14); the reaction conditions are: under argon atmosphere, 400-410nm wavelength, 30-32mW / cm 2 The light intensity is 400-410nm, and the reaction is carried out at room temperature for 5-7h.

[0016] Preferably, in the step (1), the mass ratio of the fluorine-containing copolymer B, the methacryloyloxypropyl triisopropoxy silane, the glycidyl methacrylate, the catalyst tetrabutylammonium bromide, the dimethylacetamide and the fluorosilicon nanofiller modifier is 1: (0.3-0.6): (0.1-0.3): (0.01-0.02): (14-18); the reaction conditions are: under argon atmosphere, 400-410nm wavelength, 30-32mW / cm 2 The light intensity is 400-410nm, and the reaction is carried out at room temperature for 14-16h.

[0017] Preferably, in the step (2), the mass ratio of the nanometer alumina, the toluene, the fluorosilicon nanofiller modifier and the HCl in the 1mol / L HCl aqueous solution is 1: (16-20): (0.2-0.4): (0.02-0.04); the reaction conditions are: the reaction is carried out at room temperature for 12-16h.

[0018] Preferably, in the step (2), the mass ratio of the intermediate product, the azobis isobutyronitrile, the tributyltin hydride and the toluene is 1: (0.1-0.2): (1-1.2): (16-20); the reaction conditions are: under argon atmosphere, 75-85℃ temperature, the reaction is carried out for 5-7h.

[0019] Preferably, in the step (3), the mass ratio of the fluorosilicon raw rubber, the modified nanometer alumina, the structure control agent hydroxyl silicone oil, the vulcanizing agent dicumyl peroxide and the lubricant zinc stearate is 100: (10-30): (2-4): (1-2): (0.6-1).

[0020] Preferably, in the step (3), the mixing conditions are: mixing at 55-65℃ temperature for 20-30min; the continuous mixing conditions are: continuous mixing at 55-65℃ temperature for 5-10min; the first stage vulcanization conditions are: first stage vulcanization at 10-14MPa, 160-180℃ temperature for 10-20min; the second stage vulcanization conditions are: second stage vulcanization under vacuum, 190-210℃ temperature for 3-5h.

[0021] Preferably, the corrosion-resistant rubber composite material is prepared by the preparation method of the corrosion-resistant rubber composite material.

[0022] Preferably, the corrosion-resistant rubber composite material is applied in the corrosion-resistant rubber material prepared by the preparation method of the corrosion-resistant rubber composite material.

[0023] Compared with the prior art, the present application has the following beneficial effects:

[0024] The fluorosilicon nanofiller modifier is prepared by polymerization of methylacryloyloxypropyl triisopropoxy silane and glycidyl methacrylate, using the fluorine-containing copolymer B as a macromolecular initiator; the fluorosilicon nanofiller modifier is grafted on the surface of the nano-aluminum oxide through a condensation reaction, forming a fluorinated layer on the surface of the nano-aluminum oxide and introducing an epoxy group, and the iodine group is removed by a tributyltin hydride / azobisisobutyronitrile system, so that the modified nano-aluminum oxide has super-hydrophobic properties, can capture a large amount of air pockets to form an air layer at a solid-liquid interface, and the air layer can effectively prevent the corrosion of corrosive media to the matrix material.

[0025] In addition, the low surface energy characteristics of the fluorine segment repel polar corrosive media (such as acid and alkali), and the epoxy group forms a dense crosslinking network through ring-opening reaction in the subsequent vulcanization process, further preventing the penetration of corrosive factors, and the synergistic corrosion resistance of fluorine atoms and epoxy groups builds a double protective barrier; the epoxy group is ring-opened and crosslinked with the hydroxyl silicone oil and the vulcanizing agent dicumyl peroxide in the vulcanization stage to form an ether bond crosslinking network, building a "hydrophobic barrier-chemical crosslinking" double protection system, improving the compatibility of the modified nano-aluminum oxide and the fluorosilicon rubber, and improving the mechanical properties and vulcanization properties of the fluorosilicon rubber.

[0026] The present application mixes and vulcanizes fluorosilicon raw rubber, modified nano-aluminum oxide and other additives to obtain a corrosion-resistant rubber composite material with excellent mechanical properties and corrosion resistance, which has a broad application prospect in the field of corrosion-resistant rubber materials. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 is a Shore A hardness column chart in the comprehensive performance test of the rubber composite material prepared in examples 1-5 and comparative examples 1-2 in the present application;

[0028] Figure 2 is a tear strength column chart in the comprehensive performance test of the rubber composite material prepared in examples 1-5 and comparative examples 1-2 in the present application;

[0029] Figure 3 is a line graph of acid corrosion mass change rate in the comprehensive performance test of the rubber composite prepared in the examples 1-5 and the comparative examples 1-2 of the present application;

[0030] Figure 4 is a line graph of alkali corrosion mass change rate in the comprehensive performance test of the rubber composite prepared in the examples 1-5 and the comparative examples 1-2 of the present application. DETAILED DESCRIPTION

[0031] The technical solutions in the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0032] Example 1; the present embodiment discloses a preparation method of a corrosion-resistant rubber composite, comprising the following steps:

[0033] Step (1), mixing 1,4-diiodoperfluorobutane, 1,5-hexadiene, catalyst sodium iodide and acetone, reacting under the condition of argon atmosphere, 410 nm wavelength, 38 mW / cm 2 light intensity, normal temperature for 4 h, after the reaction is completed, removing the light, adding four times the mass of tetrahydrofuran to the reaction, obtaining a homogeneous solution, adding five times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, vacuum drying at 40℃ for 20 h, obtaining fluorine-containing copolymer A;

[0034] wherein, the molar ratio of 1,4-diiodoperfluorobutane and 1,5-hexadiene is 1:1; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide and acetone is 1:0.02:14;

[0035] mixing fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide and acetone, reacting under the condition of argon atmosphere, 410 nm wavelength, 32 mW / cm 2 light intensity, normal temperature for 5 h, after the reaction is completed, removing the light, adding four times the mass of tetrahydrofuran to the reaction, obtaining a homogeneous solution, adding five times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, vacuum drying at 40℃ for 20 h, obtaining fluorine-containing copolymer B;

[0036] wherein, the mass ratio of fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide and acetone is 1:0.4:0.02:14;

[0037] The fluorine-containing copolymer B, methacryloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide are mixed, and the mixture is reacted under an argon atmosphere, at a wavelength of 410 nm, and at a power of 32 mW / cm 2 The light is removed after the reaction is completed, four times the mass of tetrahydrofuran is added to the reaction mixture to obtain a homogeneous solution, five times the mass of methanol is added to the homogeneous solution, and the mixture is centrifuged to obtain a precipitate, which is dried under vacuum at a temperature of 40℃ for 20 h to obtain the fluorosilicon nano filler modifier;

[0038] The mass ratio of the fluorine-containing copolymer B, methacryloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, and dimethylacetamide is 1:0.6:0.3:0.02:18.

[0039] In step (2), the nano-alumina and toluene are mixed and ultrasonically dispersed for 10 min, the fluorosilicon nano filler modifier and 1 mol / L HCl aqueous solution are added, and the mixture is reacted at room temperature for 16 h. After the reaction is completed, the mixture is centrifuged to obtain a precipitate, which is washed with toluene for 5 times, and the precipitate is dried at a temperature of 120℃ for 2 h to obtain an intermediate product.

[0040] The mass ratio of the nano-alumina, toluene, fluorosilicon nano filler modifier, and 1 mol / L HCl aqueous solution is 1:20:0.4:0.04.

[0041] In step (3), the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene are mixed and reacted under an argon atmosphere at a temperature of 85℃ for 5 h. After the reaction is completed, the mixture is centrifuged to obtain a precipitate, which is washed with toluene for 5 times, and the precipitate is dried at a temperature of 120℃ for 2 h to obtain modified nano-alumina.

[0042] The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.2:1.2:20.

[0043] In step (3), the fluorosilicon raw rubber, modified nano-alumina, and structure control agent hydroxyl silicone oil are mixed and placed in a two-roll open mill, and the mixture is mixed at a temperature of 65℃ for 20 min. The vulcanizing agent dicumyl peroxide and the lubricant zinc stearate are added, and the mixture is continuously mixed at a temperature of 65℃ for 5 min. After the mixing is completed, the mixture is placed in a mold and subjected to one-stage vulcanization at a pressure of 14 MPa and a temperature of 180℃ for 10 min, and two-stage vulcanization under vacuum at a temperature of 210℃ for 3 h. After the vulcanization is completed, the mixture is cooled to room temperature to obtain a corrosion-resistant rubber composite material.

[0044] The mass ratio of the fluorosilicon raw rubber, modified nano-alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide, and lubricant zinc stearate is 100:30:4:2:1.

[0045] Example 2; this example discloses a method for preparing a corrosion resistant rubber composite material, comprising the following steps:

[0046] Step (1), mixing 1,4-diiodoperfluorobutane, 1,5-hexadiene, catalyst sodium iodide, acetone, under argon atmosphere, 400nm wavelength, 34mW / cm 2 light intensity, reacting for 6h at room temperature, after the reaction, removing the light, adding four times the mass of tetrahydrofuran to the reaction, obtaining a homogeneous solution, adding three times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, vacuum drying at 30℃ for 24h, obtaining fluorine-containing copolymer A;

[0047] wherein, the molar ratio of 1,4-diiodoperfluorobutane and 1,5-hexadiene is 1:0.8; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide, and acetone is 1:0.01:10;

[0048] Mixing fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide, acetone, under argon atmosphere, 400nm wavelength, 30mW / cm 2 light intensity, reacting for 7h at room temperature, after the reaction, removing the light, adding four times the mass of tetrahydrofuran to the reaction, obtaining a homogeneous solution, adding three times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, vacuum drying at 30℃ for 24h, obtaining fluorine-containing copolymer B;

[0049] wherein, the mass ratio of fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide, and acetone is 1:0.2:0.01:10;

[0050] Mixing fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxy silane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide, under argon atmosphere, 400nm wavelength, 30mW / cm 2 light intensity, reacting for 16h at room temperature, after the reaction, removing the light, adding four times the mass of tetrahydrofuran to the reaction, obtaining a homogeneous solution, adding three times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, vacuum drying at 30℃ for 24h, obtaining fluorine-silicon nano filler modifier;

[0051] wherein, the mass ratio of fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxy silane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide is 1:0.3:0.1:0.01:14;

[0052] Step (2), the nano-alumina, toluene were mixed, ultrasonic dispersion for 5 min, the fluorine silicon nano filler modifier, 1 mol / L HCl aqueous solution, reaction for 12 h at room temperature, after the reaction, centrifugal, take the precipitate, the precipitate was washed with 4 times the mass of toluene for 3 times, dried at 100 DEG C temperature for 4 h, the intermediate product was obtained;

[0053] The mass ratio of nano-alumina, toluene, fluorine silicon nano filler modifier, 1 mol / L HCl aqueous solution, HCl solute in 1:16:0.2:0.02;

[0054] The intermediate product, azobisisobutyronitrile, tributyltin hydride, toluene were mixed, reaction for 7 h in argon atmosphere, 75 DEG C temperature, after the reaction, centrifugal, take the precipitate, the precipitate was washed with 4 times the mass of toluene for 3 times, dried at 100 DEG C temperature for 4 h, the modified nano-alumina was obtained;

[0055] The mass ratio of intermediate product, azobisisobutyronitrile, tributyltin hydride, toluene was 1:0.1:1:16;

[0056] Step (3), the fluorine silicon raw rubber, modified nano-alumina, structure control agent hydroxyl silicone oil were mixed, placed in a two roll mill, mixing for 30 min at 55 DEG C temperature, the vulcanizing agent dicumyl peroxide, lubricant zinc stearate were added, continue to mix for 10 min at 55 DEG C temperature, after mixing, placed in a mold, one stage vulcanization for 20 min at 10 MPa, 160 DEG C temperature, two stage vulcanization for 5 h under vacuum, 190 DEG C temperature, after vulcanization, cooled to room temperature, the corrosion resistant rubber composite material was obtained;

[0057] The mass ratio of fluorine silicon raw rubber, modified nano-alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide, lubricant zinc stearate was 100:10:2:1:0.6.

[0058] Embodiment 3; the present embodiment discloses a kind of preparation methods of corrosion resistant rubber composite material, comprising the following steps:

[0059] Step (1), 1, 4-diiodine perfluorobutane, 1, 5-hexadiene, catalyst sodium iodide, acetone were mixed, reaction for 4.5 h under argon atmosphere, 408 nm wavelength, 37 mW / cm 2 Light intensity illumination, room temperature, after the reaction, remove illumination, the homogeneous solution was obtained by adding 3 times the mass of tetrahydrofuran to the reaction mass, 5 times the mass of methanol was added to the homogeneous solution, centrifugal, take the precipitate, vacuum dried at 38 DEG C temperature for 21 h, the fluorine-containing copolymer A was obtained;

[0060] The molar ratio of 1,4-diiodoperfluorobutane and 1,5-hexadiene is 1:0.95; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide and acetone is 1:0.02:13;

[0061] The fluorine-containing copolymer A, perfluorohexyl iodocane, catalyst sodium iodide and acetone are mixed, and the mixture is irradiated under an argon atmosphere, at a wavelength of 408 nm and an intensity of 32 mW / cm 2 The reaction is carried out at room temperature for 5.5 h under light irradiation, after the reaction is completed, the light is removed, 3 times the mass of tetrahydrofuran is added to the reaction mixture to obtain a homogeneous solution, 5 times the mass of methanol is added to the homogeneous solution, centrifugation is carried out, and the precipitate is obtained, which is dried under vacuum at a temperature of 38℃ for 21 h to obtain the fluorine-containing copolymer B;

[0062] The mass ratio of the fluorine-containing copolymer A, perfluorohexyl iodocane, catalyst sodium iodide and acetone is 1:0.35:0.02:13;

[0063] The fluorine-containing copolymer B, methyl methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide and dimethylacetamide are mixed, and the mixture is irradiated under an argon atmosphere, at a wavelength of 408 nm and an intensity of 32 mW / cm 2 The reaction is carried out at room temperature for 14.5 h under light irradiation, after the reaction is completed, the light is removed, 3 times the mass of tetrahydrofuran is added to the reaction mixture to obtain a homogeneous solution, 5 times the mass of methanol is added to the homogeneous solution, centrifugation is carried out, and the precipitate is obtained, which is dried under vacuum at a temperature of 38℃ for 21 h to obtain the fluorosilicon nano filler modifier;

[0064] The mass ratio of the fluorine-containing copolymer B, methyl methacryloyloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide and dimethylacetamide is 1:0.5:0.25:0.02:17;

[0065] In step (2), the nano alumina and toluene are mixed and ultrasonically dispersed for 9 min, and then the fluorosilicon nano filler modifier and 1 mol / L HCl aqueous solution are added, and the mixture is reacted at room temperature for 15 h, after the reaction is completed, centrifugation is carried out, and the precipitate is obtained, which is washed with toluene for 5 times with 2 times the mass of toluene, and then dried at a temperature of 115℃ for 2 h to obtain an intermediate product;

[0066] The mass ratio of the nano alumina, toluene, fluorosilicon nano filler modifier and HCl in 1 mol / L HCl aqueous solution is 1:19:0.35:0.035;

[0067] The intermediate product, azobis isobutyronitrile, tributyltin hydride and toluene are mixed, and the mixture is reacted under an argon atmosphere at a temperature of 82℃ for 5.5 h, after the reaction is completed, centrifugation is carried out, and the precipitate is obtained, which is washed with toluene for 5 times with 2 times the mass of toluene, and then dried at a temperature of 115℃ for 2 h to obtain the modified nano alumina;

[0068] Wherein the mass ratio of intermediate product, azobisisobutyronitrile, tributyltin hydride, toluene is 1:0.2:1.15:19;

[0069] Step (3), the fluorosilicone raw rubber, modified nano alumina, structure control agent hydroxyl silicone oil are mixed, placed in a two-roll open mill, mixed at 62 DEG C for 22 min, the vulcanizing agent dicumyl peroxide, lubricant zinc stearate are added, and mixed at 62 DEG C for 6 min, after mixing, placed in a mold, one-stage vulcanization at 13 MPa, 175 DEG C for 12 min, two-stage vulcanization under vacuum, 205 DEG C for 3.5 h, after vulcanization, cooled to room temperature, to obtain a corrosion-resistant rubber composite material;

[0070] Wherein the mass ratio of fluorosilicone raw rubber, modified nano alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide, lubricant zinc stearate is 100:25:3.5:1.8:0.9.

[0071] Embodiment 4; the present embodiment discloses a preparation method of a corrosion-resistant rubber composite material, comprising the following steps:

[0072] Step (1), 1, 4-diiodoperfluorobutane, 1, 5-hexadiene, catalyst sodium iodide, acetone are mixed, under argon atmosphere, 405 nm wavelength, 36 mW / cm 2 Light intensity, normal temperature, reaction for 5 h, after the reaction, remove the light, add 3 times the mass of the reaction of tetrahydrofuran to obtain a homogeneous solution, add 4 times the mass of the homogeneous solution of methanol, centrifugal, take the precipitate, vacuum drying at 35 DEG C for 22 h, to obtain fluorine-containing copolymer A;

[0073] Wherein the molar ratio of 1, 4-diiodoperfluorobutane, 1, 5-hexadiene is 1:0.9; the mass ratio of 1, 4-diiodoperfluorobutane, catalyst sodium iodide, acetone is 1:0.015:12;

[0074] Fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide, acetone are mixed, under argon atmosphere, 405 nm wavelength, 31 mW / cm 2 Light intensity, normal temperature, reaction for 6 h, after the reaction, remove the light, add 3 times the mass of the reaction of tetrahydrofuran to obtain a homogeneous solution, add 4 times the mass of the homogeneous solution of methanol, centrifugal, take the precipitate, vacuum drying at 35 DEG C for 22 h, to obtain fluorine-containing copolymer B;

[0075] Wherein the mass ratio of fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide, acetone is 1:0.3:0.015:12;

[0076] The fluorine-containing copolymer B, methacryloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide are mixed, and the mixture is reacted under an argon atmosphere, at a wavelength of 405 nm, and a power of 31 mW / cm 2 The light is removed after the reaction is completed, four times the mass of tetrahydrofuran is added to the homogeneous solution, four times the mass of methanol is added to the homogeneous solution, and the precipitate is obtained by centrifugation. The precipitate is dried under vacuum at a temperature of 35℃ for 22 hours to obtain the fluorosilicon nano filler modifier.

[0077] The mass ratio of the fluorine-containing copolymer B, methacryloxypropyl triisopropoxysilane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide is 1:0.45:0.2:0.015:16.

[0078] In step (2), the nano-alumina and toluene are mixed and ultrasonically dispersed for 7 minutes. The fluorosilicon nano filler modifier and 1 mol / L HCl aqueous solution are added and reacted at room temperature for 14 hours. After the reaction is completed, the precipitate is obtained by centrifugation. The precipitate is washed with toluene four times, and the intermediate product is obtained by drying at a temperature of 110℃ for 3 hours.

[0079] The mass ratio of the nano-alumina, toluene, fluorosilicon nano filler modifier, and solute HCl in the 1 mol / L HCl aqueous solution is 1:18:0.3:0.03.

[0080] In step (3), the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene are mixed and reacted under an argon atmosphere at a temperature of 80℃ for 6 hours. After the reaction is completed, the precipitate is obtained by centrifugation. The precipitate is washed with toluene four times, and the modified nano-alumina is obtained by drying at a temperature of 110℃ for 3 hours.

[0081] The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene is 1:0.15:1.1:18.

[0082] In step (3), the fluorosilicon raw rubber, modified nano-alumina, and structure control agent hydroxyl silicone oil are mixed and placed in a two-roll open mill for mixing at a temperature of 60℃ for 25 minutes. The vulcanizing agent dicumyl peroxide and lubricant zinc stearate are added and the mixing is continued at a temperature of 60℃ for 7 minutes. After the mixing is completed, the mixture is placed in a mold for one-stage vulcanization at a pressure of 12 MPa and a temperature of 170℃ for 15 minutes. The two-stage vulcanization is carried out under vacuum at a temperature of 200℃ for 4 hours. After the vulcanization is completed, the temperature is lowered to room temperature to obtain the corrosion-resistant rubber composite material.

[0083] The mass ratio of the fluorosilicon raw rubber, modified nano-alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide, and lubricant zinc stearate is 100:20:3:1.5:0.8.

[0084] Example 5; this example discloses a method for preparing a corrosion resistant rubber composite, comprising the following steps:

[0085] Step (1), mixing 1,4-diiodoperfluorobutane, 1,5-hexadiene, catalyst sodium iodide, acetone, under argon atmosphere, 402 nm wavelength, 35 mW / cm 2 light intensity, reacting for 5.5 h at room temperature, after the reaction is completed, removing the light, adding four times the mass of tetrahydrofuran to the reactants, obtaining a homogeneous solution, adding three times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, and vacuum drying the precipitate at 32°C for 23 h to obtain fluorine-containing copolymer A;

[0086] wherein 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;

[0087] mixing fluorine-containing copolymer A, perfluorohexyl iodide, catalyst sodium iodide, acetone, under argon atmosphere, 402 nm wavelength, 30 mW / cm 2 light intensity, reacting for 6.5 h at room temperature, after the reaction is completed, removing the light, adding four times the mass of tetrahydrofuran to the reactants, obtaining a homogeneous solution, adding three times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, and vacuum drying the precipitate at 32°C for 23 h to obtain fluorine-containing copolymer B;

[0088] wherein the mass ratio of fluorine-containing copolymer A to perfluorohexyl iodide to catalyst sodium iodide to acetone is 1:0.25:0.01:11;

[0089] mixing fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxy silane, glycidyl methacrylate, catalyst tetrabutylammonium bromide, dimethylacetamide, under argon atmosphere, 402 nm wavelength, 30 mW / cm 2 light intensity, reacting for 15.5 h at room temperature, after the reaction is completed, removing the light, adding four times the mass of tetrahydrofuran to the reactants, obtaining a homogeneous solution, adding three times the mass of methanol to the homogeneous solution, centrifuging, taking the precipitate, and vacuum drying the precipitate at 32°C for 23 h to obtain fluorine-silicon nano filler modifier;

[0090] wherein the mass ratio of fluorine-containing copolymer B to methacryloyloxypropyl triisopropoxy silane to glycidyl methacrylate to catalyst tetrabutylammonium bromide to dimethylacetamide is 1:0.4:0.15:0.01:15;

[0091] Step (2), the nano-alumina, toluene were mixed, ultrasonic dispersion 6 min, the fluorine silicon nano filler modifier, 1 mol / L HCl aqueous solution, reaction 13 h at room temperature, after the reaction, centrifugal, take the precipitate, the precipitate was washed with toluene 4 times the mass 3 times, dried at 105 DEG C temperature 4 h, obtained intermediate product;

[0092] The mass ratio of the nano-alumina, toluene, fluorine silicon nano filler modifier, 1 mol / L HCl aqueous solution, HCl solute in 1:17:0.25:0.025;

[0093] The intermediate product, azobisisobutyronitrile, tributyltin hydride, toluene were mixed, reaction 6.5 h in argon atmosphere, 78 DEG C temperature, after the reaction, centrifugal, take the precipitate, the precipitate was washed with toluene 4 times the mass 3 times, dried at 105 DEG C temperature 4 h, obtained modified nano-alumina;

[0094] The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride, toluene was 1:0.1:1.05:17;

[0095] Step (3), the fluorine silicon raw rubber, modified nano-alumina, structure control agent hydroxyl silicone oil were mixed, placed in a double roll mill, mixing 28 min at 58 DEG C temperature, the vulcanizing agent dicumyl peroxide, lubricant zinc stearate were added, continue to mix 9 min at 58 DEG C temperature, after mixing, placed in a mold at 11 MPa, 165 DEG C temperature one stage vulcanization 18 min, vacuum, 195 DEG C temperature two stage vulcanization 4.5 h, after vulcanization, the temperature was lowered to room temperature, obtained corrosion resistant rubber composite material;

[0096] The mass ratio of the fluorine silicon raw rubber, modified nano-alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide, lubricant zinc stearate was 100:15:2.5:1.2:0.7.

[0097] Comparative example 1; the present comparative example discloses a kind of preparation method of rubber composite material, comprising the following steps:

[0098] Step (1), 1,4-diiodine perfluorobutane, 1,5-hexadiene, catalyst sodium iodide, acetone were mixed, reaction 6 h in argon atmosphere, 400 nm wavelength, 34 mW / cm 2 Light intensity illumination, room temperature, after the reaction, remove illumination, the precipitate was washed with toluene 4 times the mass 3 times, dried at 105 DEG C temperature 4 h, obtained intermediate product;

[0099] The molar ratio of 1,4-diiodoperfluorobutane and 1,5-hexadiene is 1:0.8; the mass ratio of 1,4-diiodoperfluorobutane, catalyst sodium iodide and acetone is 1:0.01:10;

[0100] The fluorine-containing copolymer A, perfluorohexyl iodocane, catalyst sodium iodide and acetone are mixed, and the mixture is reacted under an argon atmosphere, at a wavelength of 400 nm and an intensity of 30 mW / cm 2 The reaction is carried out under light irradiation at room temperature for 7 h, and after the reaction is completed, the light irradiation is removed, 2 times the mass of tetrahydrofuran is added to the reaction mixture to obtain a homogeneous solution, 3 times the mass of methanol is added to the homogeneous solution, and the mixture is centrifuged to obtain a precipitate, which is dried under vacuum at a temperature of 30℃ for 24 h to obtain the fluorine-containing copolymer B;

[0101] The mass ratio of the fluorine-containing copolymer A, perfluorohexyl iodocane, catalyst sodium iodide and acetone is 1:0.2:0.01:10;

[0102] The fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxy silane, catalyst tetrabutylammonium bromide and dimethylacetamide are mixed, and the mixture is reacted under an argon atmosphere, at a wavelength of 400 nm and an intensity of 30 mW / cm 2 The reaction is carried out under light irradiation at room temperature for 16 h, and after the reaction is completed, the light irradiation is removed, 2 times the mass of tetrahydrofuran is added to the reaction mixture to obtain a homogeneous solution, 3 times the mass of methanol is added to the homogeneous solution, and the mixture is centrifuged to obtain a precipitate, which is dried under vacuum at a temperature of 30℃ for 24 h to obtain the fluorosilicon nano filler modifier;

[0103] The mass ratio of the fluorine-containing copolymer B, methacryloyloxypropyl triisopropoxy silane, catalyst tetrabutylammonium bromide and dimethylacetamide is 1:0.3:0.01:14;

[0104] In step (2), the nano-alumina and toluene are mixed and ultrasonically dispersed for 5 min, and then the fluorosilicon nano filler modifier and 1 mol / L HCl aqueous solution are added, and the mixture is reacted at room temperature for 12 h, and after the reaction is completed, the mixture is centrifuged to obtain a precipitate, which is washed with toluene 4 times its mass and dried at a temperature of 100℃ for 4 h to obtain an intermediate product;

[0105] The mass ratio of the nano-alumina, toluene, fluorosilicon nano filler modifier and 1 mol / L HCl aqueous solution is 1:16:0.2:0.02;

[0106] The intermediate product, azobisisobutyronitrile, tributyltin hydride and toluene are mixed, and the mixture is reacted under an argon atmosphere at a temperature of 75℃ for 7 h, and after the reaction is completed, the mixture is centrifuged to obtain a precipitate, which is washed with toluene 4 times its mass and dried at a temperature of 100℃ for 4 h to obtain the modified nano-alumina;

[0107] The mass ratio of the intermediate product, azobisisobutyronitrile, tributyltin hydride and toluene is 1:0.1:1:16.

[0108] Step (3), the fluorosilicone raw rubber, modified nano alumina, structure control agent hydroxyl silicone oil are mixed, placed in a double roller open mill, mixed at 55 DEG C for 30 min, the vulcanizing agent dicumyl peroxide, lubricant zinc stearate are added, and mixed at 55 DEG C for 10 min, after mixing, placed in a mold, one stage vulcanization at 10 MPa, 160 DEG C for 20 min, two stage vulcanization under vacuum, 190 DEG C for 5 h, after vulcanization, cooling to room temperature, the corrosion resistant rubber composite material is obtained.

[0109] The mass ratio of the fluorosilicone raw rubber, modified nano alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide and lubricant zinc stearate is 100:10:2:1:0.6.

[0110] Comparative Example 2; the present comparative example discloses a preparation method of a rubber composite material, comprising the following steps:

[0111] Step (1), the fluorosilicone raw rubber, nano alumina, structure control agent hydroxyl silicone oil are mixed, placed in a double roller open mill, mixed at 55 DEG C for 30 min, the vulcanizing agent dicumyl peroxide, lubricant zinc stearate are added, and mixed at 55 DEG C for 10 min, after mixing, placed in a mold, one stage vulcanization at 10 MPa, 160 DEG C for 20 min, two stage vulcanization under vacuum, 190 DEG C for 5 h, after vulcanization, cooling to room temperature, the corrosion resistant rubber composite material is obtained.

[0112] The mass ratio of the fluorosilicone raw rubber, nano alumina, structure control agent hydroxyl silicone oil, vulcanizing agent dicumyl peroxide and lubricant zinc stearate is 100:10:2:1:0.6.

[0113] 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 iodopane was from Shanghai Xiangna Chemical Technology Co., Ltd., CAS No.: 355-43-1; methacryloyloxypropyltriisopropoxysilane 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 sourced from Shanghai Siyan Biotechnology Co., Ltd., CAS No.: 1643-19-2; dimethylacetamide was sourced from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No.: 127-19-5; nano-alumina was sourced from Shanghai Aladdin Biochemical Technology Co., Ltd., particle size: 30nm, CAS No.: 1344-28-1; toluene was sourced from Wuxi Jiaxi Chemical Co., Ltd., CAS No.: 108-88-3; azobisisobutyronitrile was sourced from Jinan Century Tongda Chemical Co., Ltd., CAS No.: 78- 67-1; Tributyltin hydride is from Wuhan Xinyang Ruihe Chemical Technology Co., Ltd., CAS No.: 688-73-3; Fluorosilicone raw rubber is from Jining Sanshi Biotechnology Co., Ltd., item number: SS-K22; Hydroxysilicone oil is from Hubei Enxing Biotechnology Co., Ltd., CAS No.: 70131-67-8; Dicumyl peroxide is from Jiangsu Daoming Chemical Co., Ltd., CAS No.: 80-43-3; Zinc stearate is from Shanghai Maclean Biochemical Technology Co., Ltd., CAS No.: 557-05-1.

[0114] Test case

[0115] (1) Comprehensive performance test

[0116] The rubber composite materials prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to comprehensive performance tests. Specific test results are shown in Table 1.

[0117] Table 1

[0118]

[0119] The testing of each indicator in Table 1 is based on the following standards: Shore A hardness is determined by GB / T

[0120] The indentation hardness of vulcanized or thermoplastic rubber is determined according to GB / T 531.1-2008 "Test Method for Indentation Hardness of Vulcanized or Thermoplastic Rubber - Part 1: Shore Hardness Tester Method (Shore Hardness)"; the tear strength is determined according to GB / T 529-2008 "Determination of Tear Strength of Vulcanized or Thermoplastic Rubber (Pants-shaped, Right-angled and Crescent-shaped Specimens)"; the acid corrosion mass change rate and alkali corrosion mass change rate are determined according to ASTM D471-2016 "Standard Test Methods for Rubber Properties - Liquid Effects", 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 for both.

[0121] As can be seen from the test results in Table 1, the rubber composite material prepared by this invention has excellent mechanical properties and corrosion resistance.

[0122] In Comparative Example 1, glycidyl methacrylate was not polymerized and epoxy groups were not introduced during the preparation of the fluorosilicone nanofiller modifier. As a result, it could not undergo ring-opening crosslinking with the structure control agent hydroxyl silicone oil and the vulcanizing agent dicumyl peroxide during the vulcanization stage. At the same time, it lacked the synergistic corrosion resistance effect with the fluorine segments. The mechanical properties and corrosion resistance of the resulting rubber composite material were reduced. Therefore, the Shore A hardness and tear strength of Comparative Example 1 were lower than those of the Example, while the acid corrosion mass change rate and alkali corrosion mass change rate were higher than those of the Example.

[0123] In Comparative Example 2, the nano-alumina was not modified during the preparation of the rubber composite material, and fluorine segments and epoxy groups were not introduced. The nano-alumina was directly used as a filler to be mixed and vulcanized with fluorosilicone raw rubber. The resulting rubber composite material was ordinary fluorosilicone rubber. Furthermore, the interfacial bonding between the nano-alumina and the rubber matrix was weak, and it was prone to agglomeration, which affected the uniformity of the composite material and led to a reduction in its mechanical properties and corrosion resistance. Therefore, the Shore A hardness and tear strength of Comparative Example 2 were lower than those of the Example, while the acid corrosion mass change rate and alkali corrosion mass change rate were higher than those of the Example.

[0124] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a corrosion-resistant rubber composite material, characterized in that, Includes the following steps: Step (1): Mix 1,4-diiodoperfluorobutane, 1,5-hexadiene, catalyst, and acetone, react, and after the reaction is completed, perform post-treatment to obtain fluorinated copolymer A; Fluorinated copolymer A, perfluorohexyl iodide, catalyst, and acetone were mixed and reacted. After the reaction was completed, post-treatment was performed to obtain fluorinated copolymer B. Fluorinated copolymer B, methacryloxypropyltriisopropoxysilane, glycidyl methacrylate, catalyst, and dimethylacetamide were mixed and reacted. After the reaction was completed, post-treatment was performed to obtain a fluorosilicone nanofiller modifier. Step (2): Mix nano-alumina and toluene, disperse by ultrasonication, add fluorosilicone nanofiller modifier and HCl aqueous solution, react, and after the reaction is completed, perform post-treatment to obtain intermediate product; The intermediate product, azobisisobutyronitrile, tributyltin hydride, and toluene were mixed and reacted. After the reaction was completed, post-treatment was performed to obtain modified nano-alumina. Step (3): Mix fluorosilicone raw rubber, modified nano alumina, and additives, knead, and vulcanize to obtain 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 to 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: argon atmosphere, 400-410 nm wavelength, 34-38 mW / cm². 2 Under intense light and at room temperature, react 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 iodoalkane, sodium iodide, and acetone is 1:(0.2-0.4):(0.01-0.02):(10-14); the reaction conditions are: argon atmosphere, 400-410 nm wavelength, 30-32 mW / cm². 2 Under intense light and at room temperature, react 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): In the preparation of fluorosilicone nanofiller modifiers: the catalyst is tetrabutylammonium bromide; the mass ratio of fluorinated copolymer B, methacryloyloxypropyltriisopropoxysilane, 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: argon atmosphere, 400-410nm wavelength, 30-32mW / cm². 2 Under light intensity and at room temperature, react 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 solute HCl in nano alumina, toluene, fluorosilicone nanofiller modifier and 1 mol / L HCl aqueous solution is 1:(16-20):(0.2-0.4):(0.02-0.04); the reaction conditions for preparing the intermediate product are: reacting at room temperature for 12-16 h.

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 intermediate product, azobisisobutyronitrile, tributyltin hydride and toluene is 1:(0.1-0.2):(1-1.2):(16-20); the reaction conditions for preparing modified nano-alumina are: reaction at 75-85℃ for 5-7 hours under an argon atmosphere.

7. The method for preparing a corrosion-resistant rubber composite material according to claim 1, characterized in that, In step (3): the additives include structure control agent, vulcanizing agent and lubricant, wherein the structure control agent is hydroxyl silicone oil, the vulcanizing agent is diisopropylbenzene peroxide and the lubricant is zinc stearate; the mass ratio of fluorosilicone raw rubber, modified nano alumina, hydroxyl silicone oil, diisopropylbenzene 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 step (3), the mixing conditions are: mixing at 55-65℃ for 20-30 minutes; the vulcanization conditions are: vulcanization at 10-14MPa and 160-180℃ for 10-20 minutes, and vulcanization at vacuum and 190-210℃ for 3-5 hours.

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

10. An application of the corrosion-resistant rubber composite material as described in claim 9 in corrosion-resistant rubber materials.

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