CN110862595A - Super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and preparation method thereof - Google Patents

Super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and preparation method thereof Download PDF

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CN110862595A
CN110862595A CN201911271313.XA CN201911271313A CN110862595A CN 110862595 A CN110862595 A CN 110862595A CN 201911271313 A CN201911271313 A CN 201911271313A CN 110862595 A CN110862595 A CN 110862595A
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黄春美
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Abstract

The inventionRelates to the technical field of super-hydrophobic magnetic rubber materials, and discloses a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and a preparation method thereof, wherein the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material comprises the following formula raw materials: hydrogenated nitrile rubber, graphene oxide and nano SiO2Composite material, modified nano ferrite composite material, plasticizer, activator, accelerator, anti-aging agent, reinforcing agent carbon black and vulcanizing agent sublimed sulfur. The super-hydrophobic modified hydrogenated nitrile-butadiene rubber magnetic composite material and the preparation method thereof, nanometer SiO2The nano SiO is avoided when the nano SiO is uniformly loaded in the Al-Fe double-metal hydroxide layered structure2Agglomeration and caking are performed, the ageing resistance of the rubber material is improved, the damping performance and the magnetic performance of the rubber material are enhanced by the ferromagnetic ferrite composite material, and the thirteen-fluorine octyl triethoxysilane modifies the SiO2The isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate modified ferrite composite material enhances the hydrophobic property of the rubber material.

Description

Super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and preparation method thereof
Technical Field
The invention relates to the technical field of super-hydrophobic magnetic rubber materials, in particular to a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and a preparation method thereof.
Background
The rubber is a high-elasticity polymer material with reversible deformation, is rich in elasticity at room temperature, can generate larger deformation under the action of small external force, and can recover the original shape after the external force is removed, the rubber belongs to a completely amorphous polymer, the glass transition temperature of the rubber is low, the molecular weight of the rubber is often very large, the rubber material is mainly divided into nitrile rubber, silicon rubber, fluororubber, polysulfide rubber, polyurethane rubber and the like, and the rubber material has wide application in the fields of transportation, agriculture and forestry water conservancy, military and national defense, civil construction, electrical communication and the like.
The hydrogenated nitrile rubber is a highly saturated elastomer material obtained by carrying out special hydrotreatment on nitrile rubber, has good oil resistance, heat resistance, chemical corrosion resistance and higher compression permanent deformation resistance, has the characteristics of high strength, high tearing performance and the like, is a rubber material with excellent comprehensive performance, has poor hydrophobic performance and low wear resistance, is easy to wear in the long-term use process, and reduces the service life of the hydrogenated nitrile rubber.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and a preparation method thereof, which solve the problem of poor hydrophobic property of a hydrogenated nitrile rubber material and solve the problems of low wear resistance and easy wear service life of the hydrogenated nitrile rubber.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a super-hydrophobic modified hydrogenated nitrile-butadiene rubber magnetic composite material and its preparing process are disclosed, which includesThe formula comprises the following raw materials in parts by weight: 42-58 parts of hydrogenated nitrile rubber, 2-5 parts of graphene oxide and 5-8 parts of nano SiO215-18 parts of modified nano ferrite composite material, 1.5-3 parts of plasticizer DBP (dibutyl phthalate), 2-3 parts of activating agent, 0.2-0.5 part of accelerating agent and 0.3-1 part of anti-aging agent DNP (dibutyl phthalate)N,N' -di (β -naphthyl) p-phenylenediamine), 15-18 parts of carbon black as a reinforcing agent and 1-1.5 parts of sublimed sulfur as a vulcanizing agent.
Preferably, the plasticizer is DBP (dibutyl phthalate), the activator is zinc oxide, the accelerator is stearic acid, and the anti-aging agent is DNP (N,N' -di (β -naphthyl) p-phenylenediamine), the vulcanizing agent is sublimed sulfur, and the reinforcing agent is carbon black
Preferably, the preparation method of the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material comprises the following steps:
(1) placing 42-58 parts of hydrogenated nitrile rubber into a two-roll plasticator for plastication for 10-20 min, and then adding 5-8 parts of nano SiO22-5 parts of graphene oxide, 15-18 parts of modified nano ferrite composite material, 1.5-3 parts of plasticizer DBP (dibutyl phthalate), 2-3 parts of activator zinc oxide, 0.2-0.5 part of accelerator stearic acid and 0.3-1 part of antioxidant DNP (dibutyl phthalate)N,N' -di (β -naphthyl) p-phenylenediamine) and 15-18 parts of carbon black as a reinforcing agent are mixed for 5-8 hours at the temperature of 80-100 ℃, and then 1-1.5 parts of vulcanizing agent sublimed sulfur is added for mixing for 6-8 hours.
(2) The material is subjected to thin-pass plastication through a milling machine to carry out thin-pass process, then the blanking process is carried out, the material is placed in a flat vulcanizing machine, the pressure is increased to 20-25 MPa, the vulcanization is carried out at the temperature of 150-160 ℃ for 30-50 min, the material is cooled to the room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material is prepared.
Preferably, the nano SiO2The composite material is Al-Fe layered double hydroxide-modified SiO2The preparation method of the composite material comprises the following steps:
(1) adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxysilane, placing the solution in a bathHeating to 80-90 deg.C in warm water bath, stirring at constant speed, reflux reacting for 15-20 hr, cooling to room temperature, concentrating under reduced pressure to remove solvent, washing solid product with appropriate amount of ethanol solvent, and drying to obtain modified nanometer SiO2。
(2) Adding a proper amount of sodium carbonate solution with the mass fraction of 5-8% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2Adding sodium hydroxide, adjusting the pH value of the solution to 8-10, uniformly stirring the solution at 10-20 ℃ for reaction for 3-5 h, standing the solution for 5-8 h, removing the solvent from the solution by a high-speed centrifuge, washing a solid product by using a proper amount of distilled water, and fully drying to prepare the Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material.
Preferably, the nano SiO in the step (1)2And tridecafluorooctyltriethoxysilane in a molar ratio of 8-10: 1.
Preferably, the FeCl is added in the step (2)3、AlCl3And modified nano SiO2The mass ratio of the three components is 2.4-2.6:1: 70-80.
Preferably, the modified nano ferrite composite material is a modified nano strontium ferrite-cobalt ferrite composite material, and the preparation method comprises the following steps:
(1) adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2After stirring and dissolving, adding polyethylene glycol and sodium citrate, stirring uniformly, then adding sodium hydroxide, adjusting the pH value of the solution to 11-12, heating the solution to 90-100 ℃, stirring at a constant speed and refluxing for 6-8 h, evaporating and concentrating the solution, cooling and crystallizing, washing a solid product by using a proper amount of distilled water, fully drying, then placing the solid product in a resistance furnace, heating at the rate of 5-10 ℃/min, and carrying out heat preservation and calcination at the temperature of 1050 and 1100 ℃ for 4-6 h, wherein the calcined product is the nano strontium ferrite-cobalt ferrite composite material.
(2) Adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, placing the reaction bottle in a constant temperature water bath kettle, heating to 50-60 ℃, stirring at a constant speed for reaction for 4-6 h, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material.
Preferably, Fe (NO) in said step (1)3)3、SrCl2、CoCl2Polyethylene glycol and sodium citrate, wherein the mass of the five materials is 122-128:9-10.5:1:35-40: 140-150.
Preferably, the mass ratio of the nano strontium ferrite-cobalt ferrite composite material in the step (2) to the isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate is 45-50: 1.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and the preparation method thereof use nano SiO2The composite material formed by the composite material and Al-Fe layered double hydroxide is used as a reinforcing agent, has excellent mechanical property, and enables the nano SiO to be prepared by an in-situ growth method2The nano SiO is avoided when the nano SiO is uniformly loaded in the layered structure of the Al-Fe layered double hydroxide2Agglomeration and agglomeration to form large particles, and increase the content of SiO nanoparticles2The modified nano SiO double hydroxide has dispersibility in hydrogenated nitrile rubber, and the layered structure of the Al-Fe layered double hydroxide has good elastic modulus and tensile property, so that the elastic buffer is improved in the deformation process of the rubber material, the tensile strength and the bending strength of the rubber material are enhanced, and the modified nano SiO is used for modifying the rubber material2The composite material has strong oxidation resistance, and the ageing resistance of the rubber material is improved.
The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and the preparation method thereof have the advantages that the modified nano strontium ferrite-cobalt ferrite composite material is high in resistivity, large in coercive force and strong in magnetism, the damping performance and the magnetic performance of the rubber material are enhanced, the graphene oxide is doped with the rubber material, the graphene oxide has excellent conductivity, the electric magnetic field strength inside the rubber material is enhanced, and under the combined action of the two, the prepared high-damping magnetic hydrogenated nitrile rubber material can be applied to various fields such as electromagnetic shielding material systems and magnetic shape memory materials, the application range of the hydrogenated nitrile rubber is widened, and the practicability of the rubber material is improved.
The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material uses tridecafluorooctyltriethoxysilane modified SiO with strong hydrophobicity2The isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate modified ferrite composite material greatly reduces the hydrophilicity of the ferrite composite material and a rubber material, enables the rubber material to have excellent hydrophobic property, and simultaneously improves the SiO of an inorganic material2Compatibility and dispersibility between the composite and ferrite composites and hydrogenated nitrile rubber.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material comprises the following formula raw materials in parts by weight: 42-58 parts of hydrogenated nitrile rubber, 2-5 parts of graphene oxide and 5-8 parts of nano SiO215-18 parts of modified nano ferrite composite material, 1.5-3 parts of plasticizer DBP (dibutyl phthalate), 2-3 parts of activating agent, 0.2-0.5 part of accelerating agent and 0.3-1 part of anti-aging agent DNP (dibutyl phthalate)N,N' -di (β -naphthyl) p-phenylenediamine), 15-18 parts of reinforcing agent carbon black, 1-1.5 parts of vulcanizing agent sublimed sulfur, a plasticizer DBP (dibutyl phthalate), an activator zinc oxide, a promoter stearic acid and an anti-aging agent DNP (sodium dodecyl benzene sulfonate) ((DNP) ((B))N,N' -di (β -naphthyl) p-phenylenediamine), the vulcanizing agent is sublimed sulfur, and the reinforcing agent is carbon black.
Nano SiO2The composite material is Al-Fe layered double hydroxide-modified SiO2The preparation method of the composite material comprises the following steps:
(1) adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxySilane with the mass molar ratio of the two substances being 8-10:1, placing the solution in a constant-temperature water bath kettle, heating to 80-90 ℃, stirring at a constant speed for reflux reaction for 15-20 h, cooling the solution to room temperature, carrying out reduced pressure concentration to remove the solvent, washing the solid product with a proper amount of ethanol solvent, and fully drying to prepare the modified nano SiO2。
(2) Adding a proper amount of sodium carbonate solution with the mass fraction of 5-8% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2Adding sodium hydroxide, adjusting the pH value of the solution to 8-10, uniformly stirring the solution at 10-20 ℃ for reaction for 3-5 h, standing the solution for 5-8 h, removing the solvent from the solution by a high-speed centrifuge, washing a solid product by using a proper amount of distilled water, and fully drying to prepare the Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material.
The modified nanometer ferrite composite material is a modified nanometer strontium ferrite-cobalt ferrite composite material, and the preparation method comprises the following steps:
(1) adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2After stirring and dissolving, adding polyethylene glycol and sodium citrate, wherein the mass of the five materials is 122-.
(2) Adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, wherein the mass ratio of the two is 45-50:1, placing the reaction bottle in a constant-temperature water bath kettle, heating to 50-60 ℃, uniformly stirring for reaction for 4-6 h, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material.
The preparation method of the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material comprises the following steps:
(1) placing 42-58 parts of hydrogenated nitrile rubber into a two-roll plasticator for plastication for 10-20 min, and then adding 5-8 parts of nano SiO22-5 parts of graphene oxide, 15-18 parts of modified nano ferrite composite material, 1.5-3 parts of plasticizer DBP (dibutyl phthalate), 2-3 parts of activator zinc oxide, 0.2-0.5 part of accelerator stearic acid and 0.3-1 part of antioxidant DNP (dibutyl phthalate)N,N' -di (β -naphthyl) p-phenylenediamine) and 15-18 parts of carbon black as a reinforcing agent are mixed for 5-8 hours at the temperature of 80-100 ℃, and then 1-1.5 parts of vulcanizing agent sublimed sulfur is added for mixing for 6-8 hours.
(2) The material is subjected to thin-pass plastication through a milling machine to carry out thin-pass process, then the blanking process is carried out, the material is placed in a flat vulcanizing machine, the pressure is increased to 20-25 MPa, the vulcanization is carried out at the temperature of 150-160 ℃ for 30-50 min, the material is cooled to the room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material is prepared.
Example 1:
(1) preparation of modified Nano SiO2Component 1: adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxysilane with the mass molar ratio of 8:1, placing the solution in a constant temperature water bath kettle, heating to 80 ℃, stirring at a constant speed and refluxing for reaction for 15 hours, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product by using a proper amount of ethanol solvent, and fully drying to prepare the modified nano SiO2And (3) component 1.
(2) Preparation of nano SiO2Composite material 1: adding a proper amount of sodium carbonate solution with the mass fraction of 5% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2The component 1 is added with sodium hydroxide according to the mass ratio of 2.4:1:70, the pH value of the solution is adjusted to 8, the solution is stirred at a constant speed at 10 ℃ for reaction for 3 hours, and the solution is allowed to standStanding for 5h, removing solvent from the solution by a high-speed centrifuge, washing the solid product with appropriate amount of distilled water, and fully drying to obtain Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material 1.
(3) Preparing a nano strontium ferrite-cobalt ferrite composite material 1: adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2After stirring and dissolving, adding polyethylene glycol and sodium citrate, wherein the mass ratio of the five components is 122:9:1:35:140, stirring uniformly, adding sodium hydroxide, adjusting the pH value of the solution to 11, heating the solution to 90 ℃, stirring at a constant speed and refluxing for reaction for 6 hours, evaporating and concentrating the solution, cooling and crystallizing, washing a solid product with a proper amount of distilled water, fully drying, placing in a resistance furnace, heating at the rate of 5 ℃/min, and carrying out heat preservation and calcination for 4 hours at 1050 ℃, wherein the calcined product is the nano strontium ferrite-cobalt ferrite composite material 1.
(4) Preparing a modified nano ferrite composite material 1: adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material 1 and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, wherein the mass ratio of the two is 45:1, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 4 hours, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material 1.
(5) Preparing a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 1: placing 58 parts of hydrogenated nitrile rubber into a two-roll plasticator for plastication for 10 min, and then adding 5 parts of nano SiO21 part of composite material, 2 parts of graphene oxide, 15 parts of modified nano ferrite composite material 1 part, 1.5 parts of plasticizer DBP (dibutyl phthalate), 2 parts of activator zinc oxide, 0.2 part of accelerator stearic acid and 0.3 part of antioxidant DNP (dibutyl phthalate)N,N' -di (β -naphthyl) p-phenylenediamine) and 15 parts of carbon black as reinforcing agent are mixed for 5 hours at the temperature of 80 ℃, 1 part of vulcanizing agent is added for subliming sulfur and mixed for 6 hours, the materials are subjected to thin-pass process by thin-pass plastication method through a mill, and then the blanking process is carried outPlacing the material in a flat vulcanizing machine, pressurizing to 20 MPa, vulcanizing at 150 ℃ for 30 min, and cooling the material to room temperature to prepare the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 1.
Example 2:
(1) preparation of modified Nano SiO2And (2) component: adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxysilane with the mass molar ratio of 10:1, placing the solution in a constant temperature water bath kettle, heating to 90 ℃, stirring at a constant speed and refluxing for reaction for 15 hours, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product by using a proper amount of ethanol solvent, and fully drying to prepare the modified nano SiO2And (3) component 2.
(2) Preparation of nano SiO2Composite material 2: adding a proper amount of sodium carbonate solution with the mass fraction of 5% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2The mass ratio of the component 2 to the component 2 is 2.4:1:75, sodium hydroxide is added, the pH value of the solution is adjusted to 10, the solution is stirred at a constant speed at 20 ℃ for reaction for 3 hours, the solution is kept stand for 5 hours, then the solution is passed through a high-speed centrifuge to remove the solvent, a proper amount of distilled water is used for washing a solid product, and the solid product is fully dried to prepare the Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material 2.
(3) Preparing a nano strontium ferrite-cobalt ferrite composite material 2: adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2After stirring and dissolving, adding polyethylene glycol and sodium citrate, wherein the mass ratio of the five components is 126:10.5:1:38:145, stirring uniformly, adding sodium hydroxide, adjusting the pH value of the solution to 11, heating the solution to 100 ℃, stirring at a constant speed and refluxing for reaction for 6 hours, evaporating and concentrating the solution, cooling and crystallizing, washing a solid product with a proper amount of distilled water, fully drying, placing in a resistance furnace, heating at a speed of 10 ℃/min, and carrying out heat preservation and calcination for 4 hours at 1050 ℃, wherein the calcined product is the nano strontium ferrite-cobalt ferrite composite material 2.
(4) Preparing a modified nano ferrite composite material 2: adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material 2 and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, wherein the mass ratio of the two is 50:1, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 6 hours, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material 2.
(5) Preparing a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 2: placing 55 parts of hydrogenated nitrile rubber into a double-roller plasticator for plastication for 20 min, and then adding 6 parts of nano SiO22 parts of composite material, 2.5 parts of graphene oxide, 16.2 parts of modified nano ferrite composite material 2 parts of plasticizer DBP (dibutyl phthalate), 2.3 parts of activator zinc oxide, 0.3 part of accelerator stearic acid and 0.5 part of antioxidant DNP (dibutyl phthalate)N,N' -bis (β -naphthyl) p-phenylenediamine) and 16 parts of reinforcing agent carbon black are mixed for 5 hours at the temperature of 80 ℃, 1.2 parts of vulcanizing agent is added for subliming sulfur, mixing is carried out for 8 hours, the materials are subjected to thin-pass plastication through a mill, then the blanking process is carried out, the materials are placed in a flat plate vulcanizing machine, the pressure is increased to 25 MPa, vulcanization is carried out for 30 minutes at the temperature of 160 ℃, the materials are cooled to room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 2 is prepared.
Example 3:
(1) preparation of modified Nano SiO2And (3) component: adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxysilane with the mass molar ratio of 10:1, placing the solution in a constant temperature water bath kettle, heating to 80 ℃, stirring at a constant speed and refluxing for 20 hours, cooling the solution to room temperature, decompressing and concentrating to remove the solvent, washing the solid product by using a proper amount of ethanol solvent, and fully drying to prepare the modified nano SiO2And (3) component.
(2) Preparation of nano SiO2Composite material 3: adding a proper amount of sodium carbonate solution with the mass fraction of 8% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2And (3) adding sodium hydroxide, adjusting the pH value of the solution to 8, uniformly stirring the solution at 20 ℃ for 5 hours, standing the solution for 8 hours, removing the solvent from the solution by using a high-speed centrifuge, washing a solid product by using a proper amount of distilled water, and fully drying to prepare the Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material 3.
(3) Preparing a nano strontium ferrite-cobalt ferrite composite material 3: adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2Stirring to dissolve, then adding polyethylene glycol and sodium citrate, wherein the mass ratio of the five components is 122:9:1:40:140, stirring uniformly, then adding sodium hydroxide, adjusting the pH value of the solution to 11, heating the solution to 100 ℃, stirring at a constant speed and refluxing for reaction for 8 hours, evaporating and concentrating the solution, cooling and crystallizing, washing a solid product with a proper amount of distilled water, fully drying, then placing in a resistance furnace, heating at the rate of 5 ℃/min, and carrying out heat preservation and calcination for 4 hours at the temperature of 1100 ℃, wherein the calcination product is the nano strontium ferrite-cobalt ferrite composite material 3.
(4) Preparing a modified nano ferrite composite material 3: adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material 3 and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, wherein the mass ratio of the two is 50:1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 4 hours, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material 3.
(5) Preparing a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 3: 50 parts of hydrogenated nitrile rubber are placed in a double-roll plasticator for plastication for 10 min, and then 6.5 parts of nano SiO are added23 parts of composite material, 3.5 parts of graphene oxide, 16.8 parts of modified nano ferrite composite material 3, 2.3 parts of plasticizer DBP (dibutyl phthalate), 2.5 parts of activator zinc oxide, 0.4 part of accelerator stearic acid and 0.6 part of antioxidant DNP (dibutyl phthalate)N,N' -bis (β -naphthyl) p-phenylenediamine) and 16.1 parts of reinforcing agent carbon black are mixed for 8 hours at the temperature of 100 ℃, 1.3 parts of vulcanizing agent sublimed sulfur is added for mixing for 8 hours, the materials are subjected to thin-pass plastication through a mill for thin-pass process, then the blanking process is carried out, the materials are placed in a flat-plate vulcanizing machine, the pressure is increased to 20 MPa, the vulcanization is carried out for 30 minutes at the temperature of 160 ℃, the materials are cooled to the room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 3 is prepared.
Example 4:
(1) preparation of modified Nano SiO2And (4) component: adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxysilane with the mass molar ratio of 9:1, placing the solution in a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed and refluxing for 18 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of ethanol solvent, and fully drying to prepare the modified nano SiO2And (4) component.
(2) Preparation of nano SiO2The composite material 4: adding a proper amount of sodium carbonate solution with the mass fraction of 6% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2And (4) adding sodium hydroxide, adjusting the pH value of the solution to 9, uniformly stirring the solution at 15 ℃ for reaction for 4 hours, standing the solution for 7 hours, removing the solvent from the solution by using a high-speed centrifuge, washing a solid product by using a proper amount of distilled water, and fully drying to prepare the Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material 4.
(3) Preparing a nano strontium ferrite-cobalt ferrite composite material 4: adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2Stirring for dissolving, adding polyethylene glycol and sodium citrate (the mass ratio of the five is 125:10:1:38: 145), stirring uniformly, adding sodium hydroxide, adjusting the pH value of the solution to 11, heating the solution to 95 ℃, stirring at a constant speed for reflux reaction for 7 hours, evaporating the solution, and performing reflux reaction on the solution at a constant speedConcentrating, cooling and crystallizing, washing the solid product with a proper amount of distilled water, fully drying, placing in a resistance furnace, heating at the rate of 8 ℃/min, and calcining at 1080 ℃ for 5 hours in a heat preservation way, wherein the calcined product is the nano strontium ferrite-cobalt ferrite composite material 4.
(4) Preparing a modified nano ferrite composite material 4: adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material 4 and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, wherein the mass ratio of the two is 48:1, placing the reaction bottle in a constant-temperature water bath kettle, heating to 55 ℃, stirring at a constant speed for reaction for 5 hours, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material 4.
(5) Preparing a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 4: placing 47 parts of hydrogenated nitrile rubber into a double-roller plasticator for plastication for 15 min, and then adding 7 parts of nano SiO25 parts of composite material, 4 parts of graphene oxide, 17 parts of modified nano ferrite composite material 1, 2.6 parts of plasticizer DBP (dibutyl phthalate), 2.8 parts of activator zinc oxide, 0.4 part of accelerator stearic acid and 0.8 part of antioxidant DNP (dibutyl phthalate)N,N' -bis (β -naphthyl) p-phenylenediamine) and 17 parts of carbon black as a reinforcing agent are mixed for 6 hours at the temperature of 90 ℃, 1.4 parts of vulcanizing agent is added to sublimate sulfur, mixing is carried out for 7 hours, the materials are subjected to a thin-pass plastication process through a mill, then a blanking process is carried out, the materials are placed in a flat-plate vulcanizing machine, the pressure is increased to 22 MPa, vulcanization is carried out for 40 minutes at the temperature of 155 ℃, the materials are cooled to room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 4 is prepared.
Example 5:
(1) preparation of modified Nano SiO2And (5) component: adding a proper amount of ethanol solvent into a reaction bottle, and then adding nano SiO2And tridecafluorooctyltriethoxysilane with the mass molar ratio of 10:1, placing the solution in a constant temperature water bath kettle, heating to 90 ℃, stirring at a constant speed and refluxing for 20 hours, cooling the solution to room temperature, concentrating under reduced pressure to remove the solvent, washing the solid product with a proper amount of ethanol solvent, fully drying, and preparing the finished productPreparing to obtain modified nano SiO2And (5) component.
(2) Preparation of nano SiO2And (3) composite material 5: adding a proper amount of sodium carbonate solution with the mass fraction of 8% into a reaction bottle, and adding FeCl while stirring3And AlCl3After stirring and dissolving, adding modified nano SiO2And (5) adding sodium hydroxide, adjusting the pH value of the solution to 10, uniformly stirring the solution at 20 ℃ for 5 hours, standing the solution for 8 hours, removing the solvent from the solution by using a high-speed centrifuge, washing a solid product by using a proper amount of distilled water, and fully drying to prepare the Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material 5.
(3) Preparing a nano strontium ferrite-cobalt ferrite composite material 5: adding appropriate amount of distilled water into the reaction flask, and adding Fe (NO)3)3、SrCl2And CoCl2After stirring and dissolving, adding polyethylene glycol and sodium citrate, wherein the mass ratio of the five components is 128:10.5:1:40:150, stirring uniformly, adding sodium hydroxide, adjusting the pH value of the solution to 12, heating the solution to 100 ℃, stirring at a constant speed and refluxing for reaction for 8 hours, evaporating and concentrating the solution, cooling and crystallizing, washing a solid product with a proper amount of distilled water, fully drying, placing in a resistance furnace, heating at a speed of 10 ℃/min, and performing heat preservation and calcination for 6 hours at 1100 ℃, wherein the calcination product is the nano strontium ferrite-cobalt ferrite composite material 5.
(4) Preparing a modified nano ferrite composite material 5: adding ethanol solvent into a reaction bottle, then adding the nano strontium ferrite-cobalt ferrite composite material 5 and titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate, wherein the mass ratio of the two is 50:1, placing the reaction bottle into a constant-temperature water bath kettle, heating to 60 ℃, stirring at a constant speed for reaction for 6 hours, washing a solid product by using the ethanol solvent, and fully drying to prepare the modified nano ferrite composite material 5.
(5) Preparing a super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 5: plasticating 42 parts of hydrogenated nitrile-butadiene rubber in a two-roll plasticator for 20 min, and then adding 8 parts of nano SiO25 parts of composite material, 5 parts of graphene oxide, 18 parts of modified nano ferrite composite material 5 parts of plasticizer DBP (dibutyl phthalate), 3 parts of activator zinc oxide, 0.5 part of accelerator stearic acid and 1 part of antioxidant DNP (sodium dodecyl phthalate)N,N' -bis (β -naphthyl) p-phenylenediamine) and 18 parts of reinforcing agent carbon black are mixed for 8 hours at the temperature of 100 ℃, 1.5 parts of vulcanizing agent is added for subliming sulfur for mixing for 8 hours, the materials are subjected to thin-pass plastication through a mill for thin-pass process, then the blanking process is carried out, the materials are placed in a flat-plate vulcanizing machine and pressurized to 25 MPa, vulcanization is carried out for 50 minutes at the temperature of 160 ℃, the materials are cooled to room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material 5 is prepared.
In summary, the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material and the preparation method thereof use nano SiO2The composite material formed by the composite material and Al-Fe layered double hydroxide is used as a reinforcing agent, has excellent mechanical property, and enables the nano SiO to be prepared by an in-situ growth method2The nano SiO is avoided when the nano SiO is uniformly loaded in the layered structure of the Al-Fe layered double hydroxide2Agglomeration and agglomeration to form large particles, and increase the content of SiO nanoparticles2The modified nano SiO double hydroxide has dispersibility in hydrogenated nitrile rubber, and the layered structure of the Al-Fe layered double hydroxide has good elastic modulus and tensile property, so that the elastic buffer is improved in the deformation process of the rubber material, the tensile strength and the bending strength of the rubber material are enhanced, and the modified nano SiO is used for modifying the rubber material2The composite material has strong oxidation resistance, and the ageing resistance of the rubber material is improved.
The modified nano strontium ferrite-cobalt ferrite composite material is high in resistivity, large in coercive force and strong in magnetism, the damping performance and the magnetic performance of a rubber material are enhanced, the rubber material is doped with graphene oxide, the graphene oxide has excellent conductivity, the electric magnetic field intensity inside the rubber material is enhanced, and under the combined action of the graphene oxide and the rubber material, the prepared high-damping magnetic hydrogenated nitrile butadiene rubber material can be applied to various fields such as electromagnetic shielding material systems and magnetic shape memory materials, the application range of the hydrogenated nitrile butadiene rubber is widened, and the practicability of the rubber material is improved.
Thirteen-fluorine octyl triethoxysilane with strong hydrophobicity is used for modifying SiO2The isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate modified ferrite composite material greatly reduces the hydrophilicity of the ferrite composite material and a rubber material, enables the rubber material to have excellent hydrophobic property, and simultaneously improves the SiO of an inorganic material2Compatibility and dispersibility between the composite and ferrite composites and hydrogenated nitrile rubber.

Claims (9)

1. The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material comprises the following formula raw materials in parts by weight, and is characterized in that: 42-58 parts of hydrogenated nitrile rubber, 2-5 parts of graphene oxide and 5-8 parts of nano SiO215-18 parts of modified nano ferrite composite material, 1.5-3 parts of plasticizer DBP (dibutyl phthalate), 2-3 parts of activating agent, 0.2-0.5 part of accelerating agent and 0.3-1 part of anti-aging agent DNP (dibutyl phthalate)N,N' -di (β -naphthyl) p-phenylenediamine), 15-18 parts of carbon black as a reinforcing agent and 1-1.5 parts of sublimed sulfur as a vulcanizing agent.
2. The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material as claimed in claim 1, wherein: the plasticizer is DBP (dibutyl phthalate), the activating agent is zinc oxide, the accelerating agent is stearic acid, and the anti-aging agent is DNP (dimethyl benzene phthalate)N,N' -di (β -naphthyl) p-phenylenediamine), the vulcanizing agent is sublimed sulfur, and the reinforcing agent is carbon black.
3. The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material as claimed in claim 1, wherein: the preparation method of the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material comprises the following steps:
(1) placing 42-58 parts of hydrogenated nitrile rubber into a two-roll plasticator for plastication for 10-20 min, and then adding 5-8 parts of nano SiO22-5 parts of graphene oxide, 15-18 parts of modified nano ferrite composite material, 1.5-3 parts of plasticizer DBP (dibutyl phthalate), and 2-3 parts of composite materialActivator zinc oxide, 0.2-0.5 part of accelerator stearic acid, 0.3-1 part of antioxidant DNP (N,N' -di (β -naphthyl) p-phenylenediamine) and 15-18 parts of carbon black as a reinforcing agent are mixed for 5-8 hours at the temperature of 80-100 ℃, and then 1-1.5 parts of vulcanizing agent sublimed sulfur is added for mixing for 6-8 hours;
(2) the material is subjected to thin-pass plastication through a milling machine to carry out thin-pass process, then the blanking process is carried out, the material is placed in a flat vulcanizing machine, the pressure is increased to 20-25 MPa, the vulcanization is carried out at the temperature of 150-160 ℃ for 30-50 min, the material is cooled to the room temperature, and the super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material is prepared.
4. The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material as claimed in claim 1, wherein: the nano SiO2The composite material is Al-Fe layered double hydroxide-modified SiO2The preparation method of the composite material comprises the following steps:
(1) adding nano SiO into ethanol solvent2And tridecafluorooctyltriethoxysilane, heating the solution to 80-90 ℃, reacting for 15-20 h, cooling the solution to room temperature, concentrating under reduced pressure, washing a solid product, and drying to prepare the modified nano SiO2;
(2) Adding FeCl into a sodium carbonate solution with the mass fraction of 5-8%3、AlCl3And modified nano SiO2Adding sodium hydroxide, adjusting pH to 8-10, reacting at 10-20 deg.C for 3-5 h, standing for 5-8 h, removing solvent by high speed centrifuge, washing solid product, and drying to obtain Al-Fe layered double hydroxide-modified SiO2The composite material is nano SiO2A composite material.
5. Nano-SiO according to claim 42A composite material characterized by: the nano SiO in the step (1)2And tridecafluorooctyltriethoxysilane in a molar ratio of 8-10: 1.
6. The method of claim 4Nano SiO2A composite material characterized by: FeCl is added in the step (2)3、AlCl3And modified nano SiO2The mass ratio of the three components is 2.4-2.6:1: 70-80.
7. The super-hydrophobic modified hydrogenated nitrile rubber magnetic composite material as claimed in claim 1, wherein: the modified nanometer ferrite composite material is a modified nanometer strontium ferrite-cobalt ferrite composite material, and the preparation method comprises the following steps:
(1) adding Fe (NO) to distilled water3)3、SrCl2、CoCl2Adding sodium hydroxide into the solution, adjusting the pH value of the solution to 11-12, carrying out reflux reaction for 6-8 h at the temperature of 90-100 ℃, carrying out evaporation concentration on the solution, cooling and crystallizing, washing a solid product by using a proper amount of distilled water, fully drying the solid product, placing the solid product in a resistance furnace, carrying out heat preservation and calcination for 4-6 h at the temperature of 1050-1100 ℃, wherein the calcined product is a nano strontium ferrite-cobalt ferrite composite material;
(2) adding the nano strontium ferrite-cobalt ferrite composite material and a titanate coupling agent isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate into an ethanol solvent, reacting for 4-6 h at 50-60 ℃, washing a solid product, and drying to prepare the modified nano ferrite composite material.
8. The modified nano-ferrite composite of claim 7, wherein: fe (NO) in the step (1)3)3、SrCl2、CoCl2Polyethylene glycol and sodium citrate, wherein the mass of the five materials is 122-128:9-10.5:1:35-40: 140-150.
9. The modified nano-ferrite composite of claim 7, wherein: the mass ratio of the nano strontium ferrite-cobalt ferrite composite material in the step (2) to isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate is 45-50: 1.
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