Flame-retardant rubber hose and preparation method thereof

Abstract

The invention relates to the technical field of rubber materials, and provides a flame-retardant rubber hose and a preparation method thereof. The flame-retardant rubber hose comprises an inner rubber layer, a reinforcing layer and an outer rubber layer, and raw materials of the inner rubber layer and the outer rubber layer respectively and independently comprise the following components in parts by weight: 10-15 parts of MQ silicone rubber, 85-90 parts of nitrile rubber, 3-7 parts of 3-carboxyl-4-hydroxy-acetoacetanilide modified graphene, 35-45 parts of filler, 1-3 parts of an anti-aging agent, 5-10 parts of a plasticizer, 2-5 parts of an activating agent, 1-2 parts of a vulcanizing agent and 0.5-1.5 parts of an accelerant. According to the technical scheme, the problem that the rubber hose in the prior art is insufficient in mechanical property and flame retardant property is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rubber material, in particular, relates to a kind of flame-retardant rubber hose and preparation method thereof. BACKGROUND

[0002] Rubber hose is used to transport gas, liquid, slurry, granular and other flowability material connection hose. Generally made of rubber (natural rubber or synthetic rubber) and fiber or metal material, its structure includes inner rubber layer, reinforcing layer and outer rubber layer, reinforcing layer is actually metal wire reinforcing layer, the purpose is to improve the strength of rubber hose, and reduce the deformation of rubber hose when under internal pressure.

[0003] At present, as the base rubber of rubber hose, there are many kinds, including natural rubber, styrene butadiene rubber, isoprene rubber, butadiene rubber, butyl rubber, chlorobutyl rubber, nitrile rubber, ethylene propylene rubber, silicone rubber and fluorine rubber, etc. Among them, nitrile rubber and silicone rubber are more commonly used, but there are problems of low mechanical properties and insufficient flame retardant properties. SUMMARY

[0004] The present application provides a kind of flame-retardant rubber hose and preparation method thereof, solve the problem of insufficient mechanical properties and flame retardant properties of rubber hose in the related art.

[0005] The technical scheme of the present application is as follows: A kind of flame-retardant rubber hose, including inner rubber layer, reinforcing layer and outer rubber layer, the raw material of the inner rubber layer and the outer rubber layer includes the following components independently: 10~15 parts of MQ silicone rubber, 85~90 parts of nitrile rubber, 3~7 parts of 3-carboxyl-4-hydroxy-acetoacetylphenylamine modified graphene, 35~45 parts of filler, 1~3 parts of antioxidant, 5~10 parts of plasticizer, 2~5 parts of activator, 1~2 parts of vulcanizing agent, 0.5~1.5 parts of accelerator.

[0006] In the present application, silicone rubber can ensure that the rubber hose has good heat resistance, cold resistance, ozone resistance and atmospheric aging resistance and other properties. The silicone rubber may be one or more of MQ silicone rubber, vinyl silicone rubber, phenyl silicone rubber, fluorosilicone rubber, nitrile silicone rubber, preferably MQ silicone rubber.

[0007] Nitrile rubber is an elastomer copolymer generated by monomer butadiene and propylene, in the presence of certain ingredient ratio and emulsifier and other additives and free radical initiation, through emulsion copolymerization. In the present application, the addition of nitrile rubber can ensure that the rubber hose has good oil resistance.

[0008] As a further technical solution, the raw material of the 3-carboxyl-4-hydroxy-acetoacetylphenylamine modified graphene includes graphene and 3-carboxyl-4-hydroxy-acetoacetylphenylamine in a mass ratio of 100:1~5.

[0009] As a further technical solution, the preparation method of the 3-carboxyl-4-hydroxy-acetoacetyl aniline modified graphene comprises the following steps: dispersing graphene in methanol by ultrasonic, adding 3-carboxyl-4-hydroxy-acetoacetyl aniline while stirring, modifying, drying, and obtaining 3-carboxyl-4-hydroxy-acetoacetyl aniline modified graphene.

[0010] In the preparation process of the 3-carboxyl-4-hydroxy-acetoacetyl aniline modified graphene, graphene is first dispersed in methanol by ultrasonic, which can destroy the graphene agglomerates and disperse the graphene agglomerates, and then 3-carboxyl-4-hydroxy-acetoacetyl aniline is added during stirring to modify the graphene and inhibit the re-agglomeration of the graphene in the subsequent use process, thereby improving the dispersibility of the graphene in the rubber hose.

[0011] As a further technical solution, the filler is a vinyl silane modified talc powder.

[0012] As a further technical solution, the raw material of the vinyl silane modified talc powder comprises vinyl silane and talc powder in a mass ratio of 2-7:100.

[0013] As a further technical solution, the preparation method of the vinyl silane modified talc powder comprises the following steps: dispersing talc powder in an ethanol aqueous solution by ultrasonic, adding vinyl silane for modification, filtering, washing the product, drying, and obtaining the vinyl silane modified talc powder.

[0014] As a further technical solution, the talc powder in the vinyl silane modified talc powder is a silica coated talc powder.

[0015] In the present application, by coating silica on the surface of the talc powder, the modification effect of the vinyl silane on the filler is improved, and the mechanical properties and flame retardant properties of the rubber hose are further improved.

[0016] As a further technical solution, the silica coated talc powder is prepared by a water bath method.

[0017] As a further technical solution, the preparation method of the silica coated talc powder comprises the following steps: mixing talc powder, cetyltrimethylammonium bromide, urea and water, uniformly dispersing by ultrasonic, adding isopropyl alcohol, toluene and tetraethyl orthosilicate, performing water bath reaction, centrifugal separation, washing the product, drying, and heat treatment to obtain the silica coated talc powder.

[0018] The present application also proposes a preparation method of a flame-retardant rubber hose, which is used for preparing the flame-retardant rubber hose and comprises the following steps: S1, mixing the raw materials of the inner rubber layer, extruding, rubberizing to obtain the inner rubber layer; S2, after setting the metal wire reinforcing layer outside the inner rubber layer, obtaining the reinforcing layer; S3, mixing the raw materials of the outer rubber layer, extruding, coating outside the reinforcing layer to obtain the outer rubber layer, vulcanizing to obtain the flame-retardant rubber hose.

[0019] The working principle and beneficial effects of the present application are as follows: In the present application, 3-carboxyl-4-hydroxy-acetoacetanilide is added to modify graphene. The graphene not only has high strength, but also has good flame-retardant effect, which can give the rubber hose certain strength and flame-retardant property. At the same time, the graphene is surface-functionalized and modified by 3-carboxyl-4-hydroxy-acetoacetanilide. The functional groups in 3-carboxyl-4-hydroxy-acetoacetanilide form hydrogen bonds with graphene to realize non-covalent bond modification of graphene. The graphene body structure and excellent performance are maintained, and the dispersibility of graphene in the rubber hose is improved, so that the mechanical properties and flame-retardant properties of the rubber hose are improved. DETAILED DESCRIPTION

[0020] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0021] The parameters of the raw materials in the following examples and comparative examples are as follows: MQ silicone rubber: model DR-101, purchased from Ningbo Daoruo Silicone Co., Ltd.; Nitrile rubber: Lanhua nitrile rubber 3305; Graphene: industrial-grade graphene powder; Talc: 1250 mesh; The preparation method of silica-coated talc is as follows: 30 parts of talc, 30 parts of CTAB and 18 parts of urea were added to 900 parts of deionized water, and then ultrasonic dispersion was carried out. After uniform dispersion, 27.6 parts of isopropanol, 900 parts of toluene and 30 parts of tetraethyl orthosilicate were added in sequence. After stirring at 200 rpm for 5 min, the temperature was raised to 70℃ and reacted for 16 h. After centrifugal separation, the product was washed with ethanol, dried at 110℃, and calcined at 550℃ in air atmosphere for 2 h to obtain silica-coated talc.

[0022] Example 1 A flame-retardant rubber hose comprises an inner rubber layer, a reinforcing layer and an outer rubber layer, the raw materials of the inner rubber layer and the outer rubber layer respectively comprise the following components by weight: MQ silicone rubber 10 parts, nitrile rubber 90 parts, 3-carboxy-4-hydroxy-acetoacetanilide modified graphene 3 parts, talc 35 parts, antioxidant RD 1 part, dibutyl phthalate 5 parts, stearic acid 1 part, zinc stearate 1 part, sulfur 1 part, accelerator CZ 1.5 parts; 3-carboxy-4-hydroxy-acetoacetanilide modified graphene is prepared as follows: 10 parts of graphene are ultrasonically dispersed in 20 parts of methanol, the ultrasonic power is 200 W, the ultrasonic frequency is 30 kHz, the ultrasonic temperature is 30℃, the ultrasonic time is 20 min, after uniform dispersion, 0.1 parts of 3-carboxy-4-hydroxy-acetoacetanilide is added while stirring at a speed of 300 rpm, stirring for 1.5 h for modification, drying to obtain 3-carboxy-4-hydroxy-acetoacetanilide modified graphene; A method for preparing a flame-retardant rubber hose is as follows: S1, after mixing the raw materials of the inner rubber layer, extruding and rubberizing, the inner rubber layer is obtained; S2, after weaving a metal wire reinforcing layer on the outer side of the inner rubber layer, the reinforcing layer is obtained; S3, after mixing the raw materials of the outer rubber layer, extruding and coating on the outer side of the reinforcing layer, the outer rubber layer is obtained, vulcanization is carried out to obtain the flame-retardant rubber hose.

[0023] Example 2 A flame-retardant rubber hose comprises an inner rubber layer, a reinforcing layer and an outer rubber layer, the raw materials of the inner rubber layer and the outer rubber layer respectively comprise the following components by weight: MQ silicone rubber 15 parts, nitrile rubber 85 parts, 3-carboxy-4-hydroxy-acetoacetanilide modified graphene 7 parts, talc 45 parts, antioxidant M 3 parts, dioctyl phthalate 10 parts, stearic acid 3 parts, zinc stearate 2 parts, sulfur 2 parts, accelerator TMU 0.5 parts; 3-carboxy-4-hydroxy-acetoacetanilide modified graphene is prepared as follows: 10 parts of graphene are ultrasonically dispersed in 20 parts of methanol, the ultrasonic power is 300 W, the ultrasonic frequency is 20 kHz, the ultrasonic temperature is 35℃, the ultrasonic time is 15 min, after uniform dispersion, 0.5 parts of 3-carboxy-4-hydroxy-acetoacetanilide is added while stirring at a speed of 400 rpm, stirring for 2 h for modification, drying to obtain 3-carboxy-4-hydroxy-acetoacetanilide modified graphene; A method for preparing a flame-retardant rubber hose is as follows: S1, after mixing the raw materials of the inner rubber layer, extruding and rubberizing, the inner rubber layer is obtained; S2, after weaving a metal wire reinforcing layer on the outer side of the inner rubber layer, the reinforcing layer is obtained; S3, mixing the raw material of the outer rubber layer, extruding, and coating the outer side of the reinforcing layer to obtain the outer rubber layer, and vulcanizing to obtain the flame-retardant rubber hose.

[0024] Example 3 The difference from Example 1 is that the talc powder is replaced with an equal amount of vinyl silane modified talc powder. The preparation method of the vinyl silane modified talc powder is as follows: 100 parts of talc powder are ultrasonically dispersed in 1000 parts of an ethanol aqueous solution with a mass ratio of 3:1, the ultrasonic power is 150 W, the ultrasonic frequency is 20 kHz, the ultrasonic temperature is 35°C, and the ultrasonic time is 10 min. After uniform dispersion, 2 parts of vinyl silane KH-171 is added for modification at 50°C for 10 h, filtered, washed, and dried to obtain the vinyl silane modified talc powder.

[0025] Example 4 The difference from Example 2 is that the talc powder is replaced with an equal amount of vinyl silane modified talc powder. The preparation method of the vinyl silane modified talc powder is as follows: 100 parts of talc powder are ultrasonically dispersed in 1000 parts of an ethanol aqueous solution with a mass ratio of 3:1, the ultrasonic power is 150 W, the ultrasonic frequency is 20 kHz, the ultrasonic temperature is 35°C, and the ultrasonic time is 10 min. After uniform dispersion, 2 parts of vinyl silane KH-171 is added for modification at 50°C for 10 h, filtered, washed, and dried to obtain the vinyl silane modified talc powder.

[0026] Example 5 The difference from Example 1 is that the talc powder is replaced with an equal amount of vinyl silane modified silica coated talc powder. The preparation method of the vinyl silane modified silica coated talc powder is as follows: 100 parts of silica coated talc powder are ultrasonically dispersed in 1000 parts of an ethanol aqueous solution with a mass ratio of 3:1, the ultrasonic power is 150 W, the ultrasonic frequency is 20 kHz, the ultrasonic temperature is 35°C, and the ultrasonic time is 10 min. After uniform dispersion, 5 parts of vinyl silane KH-171 is added for modification at 50°C for 10 h, filtered, washed, and dried to obtain the vinyl silane modified silica coated talc powder.

[0027] Example 6 The difference from Example 2 is that the talc powder is replaced with an equal amount of vinyl silane modified silica coated talc powder. The preparation method of the vinyl silane modified silica coated talc powder is as follows: 100 parts of the silica-coated talc powder was dispersed in 1000 parts of an ethanol water solution with a mass ratio of 3:1 by ultrasonic dispersion, the ultrasonic power was 200 W, the ultrasonic frequency was 20 kHz, the ultrasonic temperature was 30℃, and the ultrasonic time was 15 min, after uniform dispersion, 7 parts of vinyl silane KH-171 was added for modification at 50℃ for 10 h, then the product was filtered, washed and dried to obtain the vinyl silane modified silica-coated talc powder.

[0028] Comparative Example 1 The difference from Example 1 is that the 3-carboxyl-4-hydroxy-acetoacetanilide modified graphene is replaced by an equal amount of graphene.

[0029] The outer rubber layer of the flame-retardant rubber hose was subjected to the following performance tests: (1) Mechanical properties: the tensile strength was tested according to the method in GB / T 528-2009, the test sample was a 1A dumbbell-shaped sample with a thickness of 3 mm; (2) Flame-retardant properties: the oxygen index was tested according to the method in GB / T 10707-2008; The test results are recorded in Table 1.

[0030] Table 1 Performance test results of the flame-retardant rubber hose

[0031] As can be seen from Table 1, the tensile strength of the flame-retardant rubber hose provided by the present application is above 23.5 MPa, and the oxygen index is above 32.3%, which has good mechanical properties and flame-retardant properties. In addition, the tensile strength and oxygen index of the flame-retardant rubber hose obtained in Examples 1-6 are higher than those of Comparative Example 1, which indicates that the graphene modified by 3-carboxyl-4-hydroxy-acetoacetanilide improves the mechanical properties and flame-retardant properties of the rubber hose.

[0032] The above is only a preferred embodiment of the present application, and is not intended to limit the present application, any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A flame-retardant rubber hose, comprising an inner rubber layer, a reinforcing layer, and an outer rubber layer, characterized in that, The raw materials of the inner and outer rubber layers each independently include the following components in parts by weight: 10-15 parts of MQ silicone rubber, 85-90 parts of nitrile rubber, 3-7 parts of 3-carboxy-4-hydroxy-acetylacetanilide modified graphene, 35-45 parts of filler, 1-3 parts of antioxidant, 5-10 parts of plasticizer, 2-5 parts of activator, 1-2 parts of vulcanizing agent, and 0.5-1.5 parts of accelerator.

2. The flame-retardant rubber hose according to claim 1, characterized in that, The raw materials for the 3-carboxy-4-hydroxy-acetoacetanilide-modified graphene include graphene and 3-carboxy-4-hydroxy-acetoacetanilide in a mass ratio of 100:1~5.

3. The flame-retardant rubber hose according to claim 1, characterized in that, The preparation method of the 3-carboxy-4-hydroxy-acetylacetanilide modified graphene includes the following steps: ultrasonically dispersing graphene in methanol, adding 3-carboxy-4-hydroxy-acetylacetanilide while stirring, modifying, and drying to obtain 3-carboxy-4-hydroxy-acetylacetanilide modified graphene.

4. The flame-retardant rubber hose according to claim 1, characterized in that, The filler is vinylsilane-modified talc.

5. The flame-retardant rubber hose according to claim 4, characterized in that, The raw materials for the vinylsilane-modified talc powder include vinylsilane and talc powder in a mass ratio of 2~7:

100.

6. A flame-retardant rubber hose according to claim 4, characterized in that, The preparation method of the vinylsilane-modified talc powder includes the following steps: ultrasonically dispersing talc powder in an ethanol aqueous solution, adding vinylsilane for modification, filtering, washing the product, and drying to obtain vinylsilane-modified talc powder.

7. A flame-retardant rubber hose according to claim 4, characterized in that, The talc in the vinylsilane-modified talc is silica-coated talc.

8. A flame-retardant rubber hose according to claim 7, characterized in that, The silica-coated talc powder was prepared by a water bath method.

9. A flame-retardant rubber hose according to claim 7, characterized in that, The preparation method of silica-coated talc includes the following steps: talc powder, hexadecyltrimethylammonium bromide, urea and water are mixed and ultrasonically dispersed evenly; isopropanol, toluene and tetraethyl orthosilicate are added; a water bath reaction is carried out; centrifugation is performed; the product is washed, dried and heat-treated to obtain silica-coated talc powder.

10. A method for preparing a flame-retardant rubber hose, used to prepare the flame-retardant rubber hose according to any one of claims 1 to 9, characterized in that, Includes the following steps: S1. After mixing the raw materials for the inner rubber layer, extrude and coat them with rubber to obtain the inner rubber layer. S2. After providing a metal wire reinforcing layer on the outside of the inner adhesive layer, a reinforcing layer is obtained; S3. After mixing the raw materials for the outer rubber layer, extrude them and coat the outside of the reinforcing layer to obtain the outer rubber layer. Then vulcanize the outer rubber layer to obtain a flame-retardant rubber hose.

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