Vulcanized rubber with super-hydrophobic surface and preparation method thereof

Abstract

The invention discloses vulcanized rubber with a super-hydrophobic surface and a preparation method thereof, and relates to the technical field of vulcanized rubber preparation, and the vulcanized rubber is prepared from the following raw materials in parts by weight: 100-110 parts of butyl rubber, 10-20 parts of a hydrophobic modifier, 0.6-0.8 part of dibenzoyl peroxide, 0.7-0.9 part of sulfur, 3-5 parts of stearic acid and 0.5-0.7 part of polyacrylamide. In the preparation process of the vulcanized rubber with the super-hydrophobic surface, polyacrylamide separated out to the surface of vulcanized rubber and zinc oxide particles grown on the surface in situ form a micro-nano composite structure, and the requirement for the super-hydrophobic surface is met. The synthesized hydrophobic modifier is obtained by grafting triazine, thioether and hindered phenol on graphene oxide, the hydrophobicity, oxidation resistance and flame retardance of vulcanized rubber are improved, good surface hydrophobicity can still be maintained after multiple times of abrasion, and the hydrophobic modifier is worthy of popularization.

Description

Technical Field

[0001] The invention relates to the technical field of vulcanized rubber preparation, and in particular to a vulcanized rubber with a super-hydrophobic surface and a preparation method thereof. Background Art

[0002] Superhydrophobic materials refer to materials with a contact angle of more than 150° and a rolling angle of less than 10° between water droplets and the material surface. Superhydrophobic materials are widely used in tableware, medical products, electronic and electrical components, transportation, construction, aerospace and other fields due to their excellent hydrophobicity, anti-icing, anti-fog, anti-pollution, drag reduction and other properties. Currently developed superhydrophobic materials are mainly based on hard matrix materials (such as metals, plastics, etc.), which have low strength and are easily damaged by external forces such as wear. Vulcanized rubber materials have high elasticity. When used as a matrix, they can better utilize their reversible deformation to retain the micro-nano composite structure of the surface and improve the mechanical stability of the superhydrophobic surface.

[0003] Butyl rubber is a synthetic rubber similar to natural rubber. It is synthesized from isobutylene and a small amount of isoprene. It has outstanding air tightness and water tightness and is commonly used to manufacture various rubber products such as inner tubes, steam pipes, water tubes, dam bottom layers, and gaskets. Butyl rubber can be used as a matrix for super-hydrophobic materials. By using appropriate modification methods, butyl rubber can have a super-hydrophobic surface, which is of great significance for expanding its scope of use. However, there are unsaturated double bonds in the molecular chain of butyl rubber, and its oxidation resistance is insufficient. Directly adding small molecule antioxidants has poor compatibility with butyl rubber and cannot effectively improve its oxidation resistance. Butyl rubber is easy to burn under high temperature conditions and there is a potential fire risk. It is necessary to use suitable flame retardants to improve its flame retardant properties.

[0004] Graphene is based on sp 2 Hybrid-connected two-dimensional carbon materials, in which the carbon atoms are arranged in a hexagonal shape similar to a honeycomb, can be used to prepare super-hydrophobic composite materials after being compounded with rubber due to their good hydrophobicity, so that the rubber composite material itself has super-hydrophobic properties. The two-dimensional plane of graphene has extremely high electron cloud density and mechanical strength, and its surface density is higher than that of general inorganic materials. It can be used as an extremely thin "barrier" material that is impermeable to gas molecules. Graphene oxide is an oxidation product of graphene. Compared with graphene, the surface of graphene oxide has more oxygen-containing functional groups such as carboxyl and hydroxyl groups, so it has stronger reactivity. At the same time, due to the carboxyl and hydroxyl groups, the interaction force between graphene oxide sheets is enhanced, and they are easily attracted to each other and agglomerated, which limits the use of graphene oxide in rubber super-hydrophobic materials.

[0005] Therefore, a suitable modification method is needed to improve the oxidation resistance and flame retardancy of butyl rubber, improve the agglomeration phenomenon of graphene oxide, and use the vulcanized butyl rubber as the matrix to obtain a super-hydrophobic vulcanized butyl rubber with excellent oxidation resistance, flame retardancy and other properties, thereby expanding the application scope of butyl rubber, which is of practical significance. Summary of the invention

[0006] In order to solve the above technical problems, the present invention provides a vulcanized rubber with a super-hydrophobic surface and a preparation method thereof.

[0007] The purpose of the present invention can be achieved through the following technical solutions: A vulcanized rubber with a super-hydrophobic surface comprises the following raw materials in parts by weight: 100-110 parts of butyl rubber, 10-20 parts of a hydrophobic modifier, 0.6-0.8 parts of dibenzoyl peroxide, 0.7-0.9 parts of sulfur, 3-5 parts of stearic acid and 0.5-0.7 parts of polyacrylamide; The preparation of the super-hydrophobic vulcanized rubber comprises the following steps: Step S1, mixing butyl rubber and a hydrophobic modifier at 160-170° C. for 1-1.5 h, then adding dibenzoyl peroxide, sulfur and polyacrylamide and continuing mixing for 2-2.5 h, and then thinning through 5-7 times to obtain a vulcanized rubber sheet; Step S2, washing the vulcanized rubber sheet with ethanol, cutting it into small pieces of vulcanized rubber sheet with a specification of 30-35 mm×10-15 mm×1.5-2 mm, immersing the small pieces of vulcanized rubber sheet in an aqueous solution of n-butylamine, stirring and swelling for 3-3.5 hours, transferring them to an ethanol solution of zinc nitrate, stirring and reacting for 5-6 hours, vacuum drying at 50-60° C., transferring them to an isopropanol solution of stearic acid, stirring and reacting at 55-60° C. for 2-3 hours, and then washing with isopropanol and drying to obtain a vulcanized rubber with a super-hydrophobic surface; Furthermore, the aqueous solution of n-butylamine is obtained by mixing n-butylamine and water in a mass ratio of 1 g: 1-2 g, the ethanol solution of zinc nitrate is obtained by mixing zinc nitrate and ethanol in a mass ratio of 1-1.5 g: 10 g, and the volume fraction of ethanol is 95%; the isopropanol solution of stearic acid is obtained by mixing stearic acid and isopropanol in a mass ratio of 3-3.5 g: 100 g; Furthermore, in the preparation process of the vulcanized rubber with super-hydrophobic surface, a sol-gel reaction is used to "in situ grow" zinc oxide particles on the surface of the vulcanized butyl rubber to form a nano-petal-like structure. The good water absorption of polyacrylamide can make the rubber bind water during the swelling reaction, thereby enhancing the sol-gel reaction. At the same time, polyacrylamide has poor compatibility with butyl rubber and will precipitate from the vulcanized rubber to the surface to form a micro-nano rough structure, so that the vulcanized butyl rubber has a surface super-hydrophobic property. The preparation of the hydrophobic modifier comprises the following steps: Step A1, adding graphene oxide to DMF, adding thionyl chloride under stirring, reflux stirring and reacting at 45-55° C. for 24-26 hours to obtain an acyl chloride product; then adding [(4-amino-1,3,5-triazine-2-yl)thio]acetate and potassium carbonate to dimethyl sulfoxide and stirring to obtain a mixed solution 1, then adding the above-mentioned acyl chloride product to dimethyl sulfoxide and stirring to obtain a mixed solution 2, and adding the mixed solution 2 dropwise to the mixed solution 1 under an ice-water bath. After the dropwise addition is completed, the temperature is raised to 40-50° C., stirred at a constant temperature for 8-10 hours, and distilled under reduced pressure to obtain a product containing triazine and thioether; Further, the usage ratio of graphene oxide, DMF, and dichlorothionyl is 1-2 g: 10-15 mL: 50-60 mL; the usage ratio of [(4-amino-1,3,5-triazine-2-yl)thio] methyl acetate, potassium carbonate, and dimethyl sulfoxide in mixed solution 1 is 0.1-0.15 mol: 0.04-0.05 mol: 50-60 mL; the usage ratio of acyl chloride product and dimethyl sulfoxide in mixed solution 2 is 2-4 g: 15-20 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 55-60 mL: 80-100 mL; During the reaction of step A1, the carboxyl groups on the surface of graphene oxide react with thionyl chloride to generate an acyl chloride product; the amino groups of [(4-amino-1,3,5-triazine-2-yl)thio]acetate react with the acyl chloride product to generate a product containing triazine and thioether; Step A2, adding a cyano-containing hindered phenol to tetrahydrofuran, starting stirring, adding Raney nickel and Pd / C, introducing hydrogen, stirring and reacting at normal pressure for 48-50 hours to obtain an amino-containing hindered phenol; Further, the hindered phenol containing a cyano group is selected from one of 3,5-di-tert-butyl-4-hydroxyphenylacetonitrile and 3,5-di-tert-butyl-4-hydroxybenzonitrile, and the amount ratio of the hindered phenol containing a cyano group, tetrahydrofuran, Raney nickel and Pd / C is 0.1-0.15 mol: 60-80 mL: 1.2-1.4 g: 5-7 g; During the reaction of step A2, the cyano group of the cyano-containing hindered phenol is reduced to an amino group to obtain an amino-containing hindered phenol; Step A3, in a protective gas atmosphere, adding the product containing triazine and thioether to methanol, stirring and mixing, heating to 60-70° C., adding hindered phenol containing amino group, and then adding sodium methoxide, stirring and reacting for 24-26 hours to obtain a hydrophobic modifier; Further, the amount ratio of the product containing triazine and thioether, methanol, hindered phenol containing amino group and sodium methoxide is 12-14 g: 80-90 mL: 26-28 g: 0.6-0.8 g; During the reaction of step A3, the methyl ester group in the product containing triazine and thioether undergoes an aminolysis reaction with the amino group of the hindered phenol containing an amino group to obtain a hydrophobic modifier; Beneficial effects of the invention: The invention discloses a vulcanized rubber with a super-hydrophobic surface and a preparation method thereof, wherein the super-hydrophobic surface vulcanized rubber is prepared from raw materials such as butyl rubber, a hydrophobic modifier, dibenzoyl peroxide, sulfur, stearic acid and polyacrylamide. In the preparation process of the super-hydrophobic surface vulcanized rubber, the polyacrylamide precipitated on the surface of the vulcanized rubber forms a micro-nano composite structure with zinc oxide particles "in situ grown" on the surface, thereby meeting the requirements of the super-hydrophobicity of the surface of the vulcanized butyl rubber.

[0008] The synthesized hydrophobic modifier is obtained by grafting triazine, thioether and hindered phenol on graphene oxide, and has good stability. The grafted triazine, thioether and hindered phenol are not easy to migrate and fail in the matrix; after the modification, the agglomeration phenomenon of graphene oxide itself is improved, and it can better play its hydrophobic and "barrier" role, giving the vulcanized butyl rubber its own excellent hydrophobicity, which is conducive to maintaining the surface hydrophobicity after repeated wear; the triazine ring decomposes during the combustion process to produce non-combustible gases such as ammonia and nitrogen to dilute the combustible gas in the gas phase, and also has a certain The smoke suppression effect, together with the dense carbon layer with barrier effect formed by graphene oxide in the solid phase during combustion, prevents further combustion and makes up for the deficiency of large amount of smoke generated during the flame retardant process of graphene oxide, thus making the vulcanized rubber and vulcanized butyl rubber have excellent flame retardancy; hindered phenol can terminate the chain reaction of peroxyl radicals participating in oxidative degradation and avoid the oxidative degradation of vulcanized butyl rubber, while thioether group can reduce and decompose hydrogen peroxide to make up for the deficiency of hindered phenol, hindered phenol and thioether group produce intramolecular synergy and significantly improve the oxidation resistance of vulcanized rubber. DETAILED DESCRIPTION

[0009] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention. Example 1

[0010] A hydrophobic modifier, the preparation of which comprises the following steps: Step A1, add graphene oxide (supplier: Xianfeng Nano, item number: 102740) to DMF, add dichlorothionyl under stirring, reflux and stir at 45°C for 24 hours to obtain an acyl chloride product; then add [(4-amino-1,3,5-triazine-2-yl)thio]acetate and potassium carbonate to dimethyl sulfoxide and stir to obtain a mixed solution 1, then add the above-mentioned acyl chloride product to dimethyl sulfoxide and stir to obtain a mixed solution 2, under an ice water bath, add the mixed solution 2 dropwise to the mixed solution 1, after the addition is complete, heat to 40°C, stir at a constant temperature for 8 hours, and distill under reduced pressure, that is, A product containing triazine and thioether is obtained; the usage ratio of graphene oxide, DMF, and dichlorothionyl is 1 g: 10 mL: 50 mL; the usage ratio of [(4-amino-1,3,5-triazine-2-yl)thio] methyl acetate, potassium carbonate, and dimethyl sulfoxide in mixed solution 1 is 0.1 mol: 0.04 mol: 50 mL; the usage ratio of acyl chloride product and dimethyl sulfoxide in mixed solution 2 is 2 g: 15 mL; the usage ratio of mixed solution 1 and mixed solution 2 is 55 mL: 80 mL; Step A2, adding 3,5-di-tert-butyl-4-hydroxybenzeneacetonitrile to tetrahydrofuran, starting stirring, adding Raney nickel and Pd / C, introducing hydrogen, stirring and reacting at normal pressure for 48 hours to obtain an amino-containing hindered phenol; the amount ratio of 3,5-di-tert-butyl-4-hydroxybenzeneacetonitrile, tetrahydrofuran, Raney nickel and Pd / C is 0.1 mol: 60 mL: 1.2 g: 5 g; Step A3. In a nitrogen atmosphere, add the product containing triazine and thioether to methanol, stir and mix, heat to 60°C, add hindered phenol containing amino group, then add sodium methoxide, stir and react for 24 hours to obtain a hydrophobic modifier; the amount ratio of the product containing triazine and thioether, methanol, hindered phenol containing amino group and sodium methoxide is 12g:80mL:26g:0.6g. Example 2

[0011] A hydrophobic modifier, the preparation of which comprises the following steps: Step A1, add graphene oxide (supplier: Xianfeng Nano, item number: 102740) to DMF, add dichlorothionyl under stirring, reflux and stir at 50°C for 25h to obtain an acyl chloride product; then add [(4-amino-1,3,5-triazine-2-yl)thio]acetate and potassium carbonate to dimethyl sulfoxide and stir to obtain a mixed solution 1, then add the above-mentioned acyl chloride product to dimethyl sulfoxide and stir to obtain a mixed solution 2, under an ice-water bath, add the mixed solution 2 dropwise to the mixed solution 1, after the addition is complete, heat to 45°C, stir at a constant temperature for 9h, and distill under reduced pressure to obtain Products containing triazine and thioether; the ratio of graphene oxide, DMF, and dichlorothionyl is 1.5g:12mL:55mL; the ratio of [(4-amino-1,3,5-triazine-2-yl)thio]acetate, potassium carbonate, and dimethyl sulfoxide in mixed solution 1 is 0.12mol:0.045mol:55mL; the ratio of acyl chloride product and dimethyl sulfoxide in mixed solution 2 is 3g:17mL; the ratio of mixed solution 1 to mixed solution 2 is 58mL:90mL; Step A2, adding 3,5-di-tert-butyl-4-hydroxybenzeneacetonitrile to tetrahydrofuran, starting stirring, adding Raney nickel and Pd / C, introducing hydrogen, stirring and reacting at normal pressure for 49 hours to obtain an amino-containing hindered phenol; the amount ratio of 3,5-di-tert-butyl-4-hydroxybenzeneacetonitrile, tetrahydrofuran, Raney nickel and Pd / C is 0.12 mol: 70 mL: 1.3 g: 6 g; Step A3. In a nitrogen atmosphere, add the product containing triazine and thioether to methanol, stir and mix, heat to 65°C, add hindered phenol containing amino group, then add sodium methoxide, stir and react for 25 hours to obtain a hydrophobic modifier; the amount ratio of the product containing triazine and thioether, methanol, hindered phenol containing amino group and sodium methoxide is 13g:85mL:27g:0.7g. Example 3

[0012] A hydrophobic modifier, the preparation of which comprises the following steps: Step A1, add graphene oxide (supplier: Xianfeng Nano, item number: 102740) to DMF, add dichlorothionyl under stirring, reflux and stir at 55°C for 26 hours to obtain an acyl chloride product; then add [(4-amino-1,3,5-triazine-2-yl)thio]acetate and potassium carbonate to dimethyl sulfoxide and stir to obtain a mixed solution 1, then add the above-mentioned acyl chloride product to dimethyl sulfoxide and stir to obtain a mixed solution 2, under an ice-water bath, add the mixed solution 2 dropwise to the mixed solution 1, after the addition is complete, heat to 50°C, stir at a constant temperature for 10 hours, and distill under reduced pressure to obtain to a product containing triazine and thioether; the amount ratio of graphene oxide, DMF, and dichlorothionyl is 2g:15mL:60mL; the amount ratio of [(4-amino-1,3,5-triazine-2-yl)thio]acetate, potassium carbonate, and dimethyl sulfoxide in mixed solution 1 is 0.15mol:0.05mol:60mL; the amount ratio of acyl chloride product and dimethyl sulfoxide in mixed solution 2 is 4g:20mL; the amount ratio of mixed solution 1 to mixed solution 2 is 60mL:100mL; Step A2, adding 3,5-di-tert-butyl-4-hydroxybenzonitrile to tetrahydrofuran, starting stirring, adding Raney nickel and Pd / C, introducing hydrogen, stirring and reacting for 50 hours at normal pressure to obtain an amino-containing hindered phenol; the amount ratio of 3,5-di-tert-butyl-4-hydroxybenzonitrile, tetrahydrofuran, Raney nickel and Pd / C is 0.15 mol: 80 mL: 1.4 g: 7 g; Step A3. In a nitrogen atmosphere, add the product containing triazine and thioether to methanol, stir and mix, heat to 70°C, add hindered phenol containing amino group, then add sodium methoxide, stir and react for 26 hours to obtain a hydrophobic modifier; the amount ratio of the product containing triazine and thioether, methanol, hindered phenol containing amino group and sodium methoxide is 14g:90mL:28g:0.8g. Example 4

[0013] A vulcanized rubber with a super-hydrophobic surface comprises the following raw materials in parts by weight: 100 parts of butyl rubber, 10 parts of a hydrophobic modifier, 0.6 parts of dibenzoyl peroxide, 0.7 parts of sulfur, 3 parts of stearic acid and 0.5 parts of polyacrylamide; The preparation of the super-hydrophobic vulcanized rubber comprises the following steps: Step S1, mixing butyl rubber (supplier: Shandong Lier New Materials Co., Ltd.) and the hydrophobic modifier obtained in Example 1 at 160° C. for 1 h, then adding dibenzoyl peroxide, sulfur and polyacrylamide (supplier: Wujiang Hailan Chemical Co., Ltd.) and continuing to mix for 2 h, and then thinning through 5 times to obtain a vulcanized rubber sheet; Step S2, after washing the vulcanized rubber sheet with ethanol, cutting it into small pieces of vulcanized rubber sheet with a specification of 30mm×10mm×1.5mm, immersing the small pieces of vulcanized rubber sheet in an aqueous solution of n-butylamine, stirring and swelling for 3-3.5h, transferring them to an ethanol solution of zinc nitrate, stirring and reacting for 5h, vacuum drying at 50°C, transferring them to an isopropanol solution of stearic acid, stirring and reacting at 55°C for 2h, and then washing and drying with isopropanol to obtain a vulcanized rubber with a super-hydrophobic surface; the aqueous solution of n-butylamine is obtained by mixing n-butylamine and water in a mass ratio of 1g:1g, the ethanol solution of zinc nitrate is obtained by mixing zinc nitrate and ethanol in a mass ratio of 1g:10g; the volume fraction of the ethanol is 95%; the isopropanol solution of stearic acid is obtained by mixing stearic acid and isopropanol in a mass ratio of 3g:100g. Example 5

[0014] A vulcanized rubber with a super-hydrophobic surface comprises the following raw materials in parts by weight: 105 parts of butyl rubber, 15 parts of a hydrophobic modifier, 0.7 parts of dibenzoyl peroxide, 0.8 parts of sulfur, 4 parts of stearic acid and 0.6 parts of polyacrylamide; The preparation of the super-hydrophobic vulcanized rubber comprises the following steps: Step S1, mixing butyl rubber (supplier: Shandong Lier New Materials Co., Ltd.) and the hydrophobic modifier obtained in Example 1 at 165° C. for 1.2 h, then adding dibenzoyl peroxide, sulfur and polyacrylamide (supplier: Wujiang Hailan Chemical Co., Ltd.) and continuing to mix for 2.3 h, and then thinning 6 times to obtain a vulcanized rubber sheet; Step S2, after washing the vulcanized rubber sheet with ethanol, cutting it into small pieces of vulcanized rubber sheet with a specification of 32mm×12mm×1.8mm, immersing the small pieces of vulcanized rubber sheet in an aqueous solution of n-butylamine, stirring and swelling for 3-3.5h, transferring them to an ethanol solution of zinc nitrate, stirring and reacting for 5.5h, vacuum drying at 55°C, transferring them to an isopropanol solution of stearic acid, stirring and reacting at 58°C for 2.5h, and then washing and drying with isopropanol to obtain a vulcanized rubber with a super-hydrophobic surface; the aqueous solution of n-butylamine is obtained by mixing n-butylamine and water in a mass ratio of 1g:1.5g, the ethanol solution of zinc nitrate is obtained by mixing zinc nitrate and ethanol in a mass ratio of 1.2g:10g; the volume fraction of the ethanol is 95%; the isopropanol solution of stearic acid is obtained by mixing stearic acid and isopropanol in a mass ratio of 3.2g:100g. Example 6

[0015] A vulcanized rubber with a super-hydrophobic surface comprises the following raw materials in parts by weight: 110 parts of butyl rubber, 20 parts of a hydrophobic modifier, 0.8 parts of dibenzoyl peroxide, 0.9 parts of sulfur, 5 parts of stearic acid and 0.7 parts of polyacrylamide; The preparation of the super-hydrophobic vulcanized rubber comprises the following steps: Step S1, mixing butyl rubber (supplier: Shandong Lier New Materials Co., Ltd.) and the hydrophobic modifier obtained in Example 1 at 170° C. for 1.5 h, then adding dibenzoyl peroxide, sulfur and polyacrylamide (supplier: Wujiang Hailan Chemical Co., Ltd.) and continuing to mix for 2.5 h, and then thinning 7 times to obtain a vulcanized rubber sheet; Step S2, after washing the vulcanized rubber sheet with ethanol, cutting it into small pieces of vulcanized rubber sheet with a specification of 35mm×15mm×2mm, immersing the small pieces of vulcanized rubber sheet in an aqueous solution of n-butylamine, stirring and swelling for 3.5 hours, transferring them to an ethanol solution of zinc nitrate, stirring and reacting for 6 hours, vacuum drying at 60°C, transferring them to an isopropanol solution of stearic acid, stirring and reacting at 60°C for 3 hours, and then washing and drying with isopropanol to obtain a vulcanized rubber with a super-hydrophobic surface; the aqueous solution of n-butylamine is obtained by mixing n-butylamine and water in a mass ratio of 1g:2g, the ethanol solution of zinc nitrate is obtained by mixing zinc nitrate and ethanol in a mass ratio of 1.5g:10g; the volume fraction of the ethanol is 95%; the isopropanol solution of stearic acid is obtained by mixing stearic acid and isopropanol in a mass ratio of 3.5g:100g.

[0016] Comparative Example 1 Compared with Example 6, the hydrophobic modifier used was replaced with a product containing triazine and thioether, that is, no hindered phenol was introduced into the hydrophobic modifier, and the rest was exactly the same as Example 6 to obtain a vulcanized rubber with a super-hydrophobic surface.

[0017] Comparative Example 2 Compared with Example 6, the [(4-amino-1,3,5-triazine-2-yl)thio]acetic acid methyl ester used in the preparation of the hydrophobic modifier was replaced with 2-(4,6-diamino-1,3,5-triazine-2-yl)ethyl-2-methyl-2-acrylate, and no thioether was introduced into the hydrophobic modifier. The rest was exactly the same as in Example 6, and a vulcanized rubber with a super-hydrophobic surface was obtained.

[0018] Comparative Example 3 Compared with Example 6, the [(4-amino-1,3,5-triazine-2-yl)thio]acetate methyl ester used in the preparation process of the hydrophobic modifier is replaced with product 1, and triazine is not introduced into the hydrophobic modifier. The rest is completely the same as Example 6 to obtain a vulcanized rubber with a super-hydrophobic surface. Preparation of Product 1: Add 2-[(2-cyanoethyl)thio]acetate methyl ester to tetrahydrofuran, start stirring, add Raney nickel and Pd / C, pass hydrogen, and stir the reaction at normal pressure for 48-50h to obtain Product 1; the amount ratio of 2-[(2-cyanoethyl)thio]acetate, tetrahydrofuran, Raney nickel and Pd / C is 0.1mol:65mL:1.28g:5.6g.

[0019] Comparative Example 4 Compared with Example 6, the hydrophobic modifier was replaced with unmodified graphene oxide, and the rest was exactly the same as Example 6 to obtain a vulcanized rubber with a super-hydrophobic surface.

[0020] The following is a further effect test on the vulcanized rubber with super-hydrophobic surface prepared by the present invention, and the test results are as follows.

[0021] In order to test the vulcanized rubber with a super-hydrophobic surface prepared by the present invention, the super-hydrophobic vulcanized rubber obtained in Examples 4-6 and Comparative Examples 1-4 was subjected to a linear abrasion test in Item 2.4 of the paper "In-situ Growth of ZnO Nanoflowers on Silicone Rubber Surface to Construct a Stable Super-hydrophobic Surface", and the contact angle after 220 wears was measured to evaluate the super-hydrophobicity; the tensile strength of the super-hydrophobic vulcanized rubber was tested at 25°C with a tensile rate of 500 mm / min with reference to GB / T528-2008, and then the tensile strength was tested after oxygen aging for 18 days in an air oven at 80°C to evaluate the oxidation resistance; the limiting oxygen index was measured with reference to GB / T10707-2008, and the smoke density was measured with reference to GB / T8627-2007 to evaluate the flame retardancy; the results are recorded in Table 1; Table 1: Test results Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Contact angle after 220 wears (°) 158 159 162 161 162 161 156 Tensile strength (MPa) 14.9 15.1 15.4 15.3 15.4 15.3 15.0 Change rate of tensile strength after oxygen aging for 18 days (%) -16 -15 -13 -22 -19 -13 -45 Limiting oxygen index (%) 36 37 39 38 39 29 24 Smoke density (index ≤ 75SDR) 53 55 52 52 53 61 65 According to the data in Table 1, the vulcanized rubber of the surface super-hydrophobic of the present invention has strong super-hydrophobicity, oxidation resistance, flame retardancy. Embodiment 6 is compared with comparative example 1, and hindered phenol is not introduced in the hydrophobic modifier, and it is not possible to cooperate with thioether for anti-oxidation, and the oxidation resistance of vulcanized rubber decreases. Embodiment 6 is compared with comparative example 2, and thioether is not introduced in the hydrophobic modifier, and it is not possible to cooperate with hindered phenol for anti-oxidation, and the oxidation resistance of vulcanized rubber decreases. Embodiment 6 is compared with comparative example 3, and triazine is not introduced in the hydrophobic modifier, and it is not possible to cooperate with graphene oxide for flame retardancy, and oxygen index decreases, and the smoke amount during combustion can not be reduced, and smoke density increases. Comparison of Example 6 with Comparative Example 4 shows that when only graphene oxide is used as a hydrophobic modifier, the agglomeration phenomenon of graphene oxide is not improved, and the hydrophobicity of the vulcanized rubber itself cannot be effectively improved. The contact angle after 200 wears decreases slightly; it cannot cooperate with triazine for flame retardancy, the oxygen index decreases significantly, and the amount of smoke during combustion cannot be reduced. The smoke density increases and the flame retardancy decreases; and there is no synergistic antioxidant effect of hindered phenol and thioether, and the antioxidant property decreases.

[0022] The above contents are merely examples and explanations of the concept of the present invention. The technicians in this technical field may make various modifications or additions to the specific embodiments described or replace them in a similar manner. As long as they do not deviate from the concept of the invention or exceed the scope defined by the claims, they should all fall within the protection scope of the present invention.

Claims

1. A vulcanized rubber having a super-hydrophobic surface, characterized in that: The invention comprises the following raw materials in parts by weight: 100-110 parts of butyl rubber, 10-20 parts of hydrophobic modifier, 0.6-0.8 parts of dibenzoyl peroxide, 0.7-0.9 parts of sulfur, 3-5 parts of stearic acid and 0.5-0.7 parts of polyacrylamide; The preparation of the hydrophobic modifier comprises the following steps: Step A1, adding graphene oxide to DMF, reacting with dichlorothionyl to obtain an acyl chloride product; then adding [(4-amino-1,3,5-triazine-2-yl)thio]acetate methyl ester and potassium carbonate to dimethyl sulfoxide and stirring to obtain a mixed solution 1, then adding the above-mentioned acyl chloride product to dimethyl sulfoxide and stirring to obtain a mixed solution 2, and under an ice-water bath, adding the mixed solution 2 dropwise to the mixed solution 1, stirring to react to obtain a product containing triazine and thioether; Step A2, adding a cyano-containing hindered phenol to tetrahydrofuran, adding Raney nickel and Pd / C, introducing hydrogen, and stirring the mixture under normal pressure to react to obtain an amino-containing hindered phenol; Step A3: In a protective gas atmosphere, add the product containing triazine and thioether into methanol and stir to mix, then add hindered phenol containing amino group, then add sodium methoxide, stir to react and obtain a hydrophobic modifier.

2. A super-hydrophobic vulcanized rubber according to claim 1, characterized in that: In step A1, the usage ratio of graphene oxide, DMF and dithionyl chloride is 1-2 g: 10-15 mL: 50-60 mL.

3. A super-hydrophobic vulcanized rubber according to claim 1, characterized in that: In step A1, the usage ratio of [(4-amino-1,3,5-triazine-2-yl)thio]acetate, potassium carbonate and dimethyl sulfoxide in mixed solution 1 is 0.1-0.15 mol: 0.04-0.05 mol: 50-60 mL; the usage ratio of acyl chloride product and dimethyl sulfoxide in mixed solution 2 is 2-4 g: 15-20 mL.

4. A super-hydrophobic vulcanized rubber according to claim 1, characterized in that: In step A1, the usage ratio of mixed solution 1 and mixed solution 2 is 55-60 mL:80-100 mL.

5. A super-hydrophobic vulcanized rubber according to claim 1, characterized in that: In step A2, the hindered phenol containing a cyano group is selected from one of 3,5-di-tert-butyl-4-hydroxybenzeneacetonitrile and 3,5-di-tert-butyl-4-hydroxybenzonitrile, and the amount ratio of the hindered phenol containing a cyano group, tetrahydrofuran, Raney nickel and Pd / C is 0.1-0.15 mol: 60-80 mL: 1.2-1.4 g: 5-7 g.

6. A super-hydrophobic vulcanized rubber according to claim 1, characterized in that: In step A3, the amount ratio of the product containing triazine and thioether, methanol, hindered phenol containing amino group and sodium methoxide is 12-14g:80-90mL:26-28g:0.6-0.8g.

7. A method for preparing a vulcanized rubber having a super-hydrophobic surface according to any one of claims 1 to 6, characterized in that: The steps include: Step S1, mixing butyl rubber and a hydrophobic modifier at 160-170° C. for 1-1.5 h, then adding dibenzoyl peroxide, sulfur and polyacrylamide and continuing mixing for 2-2.5 h, and then thinning through 5-7 times to obtain a vulcanized rubber sheet; Step S2, washing the vulcanized rubber sheet with ethanol, cutting it into small pieces of vulcanized rubber sheet, immersing the small pieces of vulcanized rubber sheet in an aqueous solution of n-butylamine, stirring and swelling for 3-3.5 hours, transferring them to an ethanol solution of zinc nitrate, stirring and reacting for 5-6 hours, vacuum drying at 50-60° C., transferring them to an isopropanol solution of stearic acid, stirring and reacting at 55-60° C. for 2-3 hours, and then washing with isopropanol and drying to obtain a vulcanized rubber with a super-hydrophobic surface.

8. A method for preparing a vulcanized rubber with a super-hydrophobic surface according to claim 7, characterized in that: The specifications of the vulcanized rubber block in step S2 are 30-35 mm×10-15 mm×1.5-2 mm; the isopropanol solution of stearic acid is obtained by mixing stearic acid and isopropanol in a mass ratio of 3-3.5 g:100 g.

9. A method for preparing a vulcanized rubber with a super-hydrophobic surface according to claim 7, characterized in that: The aqueous solution of n-butylamine in step S2 is obtained by mixing n-butylamine and water in a mass ratio of 1 g:1-2 g.

10. The method for preparing a vulcanized rubber with a super-hydrophobic surface according to claim 7, characterized in that: The ethanol solution of zinc nitrate in step S2 is obtained by mixing zinc nitrate and ethanol in a mass ratio of 1-1.5 g:10 g; the volume fraction of ethanol used in step S2 is 95%.