Flame-retardant rubber hose for automobile and preparation method of flame-retardant rubber hose

Abstract

The invention discloses a flame-retardant rubber hose for an automobile and a preparation method of the flame-retardant rubber hose, and relates to the technical field of automobile parts. The silane coupling agent is utilized to modify mica, chemical and physical adsorption between mica and active groups on silane molecules is promoted under the assistance of a ball milling process, and cyclotriphosphazene derivatives are subjected to a grafting reaction on the surface of mica through the silane coupling agent, so that the mechanical property of rubber is indirectly enhanced; the preparation method comprises the following steps: mixing a matrix with silicon rubber, potassium oxide and polydiphenyl siloxane to obtain a flame retardant, blending the flame retardant with silicon rubber, potassium oxide and polydiphenyl siloxane, in a high-temperature combustion state, enabling the matrix to form a hard ceramic phase so as to enhance the flame retardance and high temperature resistance, and finally, carrying out irradiation treatment under a vacuum condition so as to obtain the flame-retardant composite material. Hydrogen in phenyl and methyl equilateral groups in the matrix is extracted to generate benzene, so that the high temperature resistance and the mechanical property of the matrix are enhanced.

Description

Technical Field

[0001] The invention relates to the technical field of vehicle parts, in particular to a flame-retardant rubber hose for automobiles and a preparation method thereof. Background Art

[0002] High speed, safety, comfort, energy saving and environmental protection are the goals of modern automobile performance. Rubber hoses for automobiles are mainly used in three major parts: chassis, engine and body, including rubber hoses for seven systems: oil, gas, drive, control, brake, cooling and heating.

[0003] Rubber can generally only withstand temperatures around 200°C, and its own oxygen index is low. It will produce black smoke when burning, and the amount of smoke is large, because rubber contains rich organic components, such as methyl and vinyl, which will produce a lot of smoke when burning. The combustion temperature of rubber is relatively high, and a large amount of heat will be released when burning, so there will be obvious flames during the combustion process. At the same time, the combustion speed of rubber is relatively fast, and the combustion surface is relatively flat. The combustion products of rubber mainly include carbon monoxide, nitrogen oxides, etc. These products will cause certain pollution to the environment during the combustion process, especially some toxic gases, which will cause harm to human health. Rubber is prone to dripping during the combustion process, and these drippings may cause the spread of fire and increase the risk of fire. Therefore, it is particularly necessary to prepare a flame-retardant rubber hose for automobiles. Summary of the invention

[0004] The object of the present invention is to provide a flame retardant rubber hose for automobile and a preparation method thereof, so as to solve the problems existing in the prior art.

[0005] In order to solve the above technical problems, the present invention provides the following technical solution: a flame-retardant rubber hose for automobiles, wherein the flame-retardant rubber hose for automobiles is prepared by blending a flame retardant, silicone rubber, potassium oxide and polydiphenylsiloxane.

[0006] Furthermore, the flame retardant is prepared by ball milling mica, a silane coupling agent and a cyclotriphosphazene derivative.

[0007] Furthermore, a method for preparing a flame-retardant rubber hose for automobiles comprises the following preparation steps:

[0008] (1) Mix a silane coupling agent, deionized water, and anhydrous ethanol, stir at 20 to 50° C. and 50 to 120 rpm for 10 to 40 minutes, adjust the solution pH to 4 to 5 with acetic acid, add mica powder, cool to room temperature, and perform ball milling for 20 to 40 minutes, add a cyclotriphosphazene derivative, and perform ball milling again for 30 to 70 minutes, wash with deionized water for 3 to 8 times, and dry at 50 to 90° C. for 4 to 8 hours to obtain a flame retardant;

[0009] (2) Wrap the silicone rubber on a double roller with a roller gap of 2 to 4 mm, add polydiphenylsiloxane and hydroxy silicone oil in turn for mixing at a temperature of 60°C for 10 to 20 min, then adjust the roller gap to 1 to 2 mm and the temperature to 150°C, add potassium oxide and flame retardant, mix for 20 to 50 min, and extrude at a temperature of 180°C under a vacuum of 10 -4 Pa, electron beam irradiation treatment was carried out to obtain a flame retardant rubber hose for automobiles.

[0010] Furthermore, the silane coupling agent in step (1) is vinyltriethoxysilane.

[0011] Furthermore, the cyclotriphosphazene derivative in step (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

[0012] Furthermore, the process parameters of the ball milling in step (1) are as follows: the ball milling medium is zirconium silicate, the ball-to-material ratio is 4 to 10:1, and the rotation speed is 800 to 1350 rpm.

[0013] Furthermore, in step (1), the mass ratio of the silane coupling agent, deionized water, anhydrous ethanol, mica powder, and cyclotriphosphazene derivative is 1:1:10-20:1-3:0.5-1.

[0014] Furthermore, the silicone rubber in step (2) is methyl vinyl silicone rubber.

[0015] Furthermore, the process parameters of the electron beam irradiation in step (2) are: the irradiation dose is 40 to 160 kGy.

[0016] Furthermore, in step (2), the mass ratio of the silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide and flame retardant is 100:5-10:1-5:20:20-40.

[0017] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0018] The present invention utilizes a silane coupling agent to modify mica, and with the assistance of a ball milling process, increases the number of chemical reaction points on the surface of the mica and improves its activity, thereby promoting chemical and physical adsorption between mica and active groups on silane molecules. Subsequently, the silane coupling agent is used to cause a grafting reaction of the cyclotriphosphazene derivative on the surface of the mica, and under the action of mechanical force, the binding force between the cyclotriphosphazene derivative and the mica is greatly enhanced, resulting in an intercalation effect, thereby improving the stability of both, and at the same time enhancing the dispersibility of the mica in the rubber matrix, thereby indirectly enhancing the mechanical properties of the rubber and enabling the matrix to achieve a stronger flame retardant property. , and then as a flame retardant, it is blended with silicone rubber, potassium oxide, and polydiphenylsiloxane. Under high-temperature combustion, the potassium oxide is melted and filled between the mica particles and the silica powder degraded from the silicone rubber matrix at high temperature, playing a connecting role, and finally forming a dense, continuous and hard ceramic phase, thereby enhancing the flame retardancy and high-temperature resistance of the matrix. Finally, it is irradiated and, under vacuum conditions, hydrogen from the phenyl and methyl equilateral groups in the matrix is ​​extracted to generate benzene, which triggers the subsequent intrachain cyclization reaction under the hydrogenated group, enhancing the stability of the matrix structure, thereby improving the high-temperature resistance and mechanical properties of the rubber. DETAILED DESCRIPTION

[0019] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. 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.

[0020] In order to more clearly illustrate the method provided by the present invention, the following examples are used to describe in detail the various index testing methods of the flame-retardant rubber hose for automobiles prepared in the following examples are as follows:

[0021] Mechanical properties: The same size of the embodiment and the comparative example were taken to test their tensile strength according to GB / T528, and after heat aging treatment, the tensile strength was tested again.

[0022] Flame retardancy: The same size of the embodiment and the comparative example were tested for limiting oxygen index (LOI) according to GB / T2406.2.

[0023] Example 1

[0024] (1) Vinyl triethoxysilane, deionized water and anhydrous ethanol are mixed, stirred at 20° C. and 50 rpm for 10 min, acetic acid is used to adjust the solution pH to 4, mica powder is added, cooled to room temperature, and ball milling is performed, wherein the process parameters are as follows: the ball milling medium is zirconium silicate, the ball-to-material ratio is 4:1, the rotation speed is 800 rpm, the time is 20 min, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, ball milling is performed again for 30 min, the mixture is washed with deionized water for 3 times, and dried at 50° C. for 4 h to obtain a flame retardant; the mass ratio of vinyl triethoxysilane, deionized water, anhydrous ethanol, mica powder and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1:10:1:0.5;

[0025] (2) Wrap methyl vinyl silicone rubber on a double roller with a roller gap of 2 mm, add polydiphenylsiloxane and hydroxy silicone oil in turn for mixing at 60°C for 10 min, then adjust the roller gap to 1 mm and the temperature to 150°C, add potassium oxide and flame retardant, mix for 20 min, and extrude at 180°C under a vacuum of 10 -4 Pa, electron beam irradiation treatment is carried out with an irradiation dose of 40 kGy to obtain a flame-retardant rubber hose for automobiles; the mass ratio of the methyl vinyl silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide and flame retardant is 100:5:1:20:20.

[0026] Example 2

[0027] (1) Vinyl triethoxysilane, deionized water and anhydrous ethanol are mixed, stirred at 35° C. and 85 rpm for 25 min, acetic acid is used to adjust the solution pH to 4.5, mica powder is added, cooled to room temperature, and ball milling is performed, wherein the process parameters are as follows: the ball milling medium is zirconium silicate, the ball-to-material ratio is 7:1, the rotation speed is 1000 rpm, the time is 30 min, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, ball milling is performed again for 50 min, the mixture is washed with deionized water for 6 times, and dried at 70° C. for 6 h to obtain a flame retardant; the mass ratio of vinyl triethoxysilane, deionized water, anhydrous ethanol, mica powder and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1:15:2:0.75;

[0028] (2) Wrap the methyl vinyl silicone rubber on a double roller with a roller gap of 3 mm, add polydiphenylsiloxane and hydroxy silicone oil in turn for mixing at a temperature of 60°C for 15 min, then adjust the roller gap to 1.5 mm and the temperature to 150°C, add potassium oxide and flame retardant, mix for 35 min, and extrude at a temperature of 180°C. -4Pa, electron beam irradiation treatment is carried out with an irradiation dose of 100 kGy to obtain a flame-retardant rubber hose for automobiles; the mass ratio of the methyl vinyl silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide and flame retardant is 100:7.5:3:20:30.

[0029] Example 3

[0030] (1) Vinyl triethoxysilane, deionized water and anhydrous ethanol are mixed, stirred at 50° C. and 120 rpm for 40 min, acetic acid is used to adjust the solution pH to 5, mica powder is added, cooled to room temperature, and ball milling is performed, wherein the process parameters are as follows: the ball milling medium is zirconium silicate, the ball-to-material ratio is 10:1, the rotation speed is 1350 rpm, the time is 40 min, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is added, ball milling is performed again for 70 min, the mixture is washed with deionized water for 8 times, and dried at 90° C. for 8 h to obtain a flame retardant; the mass ratio of vinyl triethoxysilane, deionized water, anhydrous ethanol, mica powder and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 1:1:20:3:1;

[0031] (2) Wrap methyl vinyl silicone rubber on a double roller with a roller gap of 4 mm, add polydiphenylsiloxane and hydroxy silicone oil in turn for mixing at 60°C for 20 min, then adjust the roller gap to 2 mm and the temperature to 150°C, add potassium oxide and flame retardant, mix for 50 min, and extrude at 180°C under a vacuum of 10 -4 Pa, electron beam irradiation treatment is carried out with an irradiation dose of 160 kGy to obtain a flame-retardant rubber hose for automobiles; the mass ratio of the methyl vinyl silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide and flame retardant is 100:10:5:20:40.

[0032] Comparative Example 1

[0033] The difference between Comparative Example 1 and Example 2 is that step (1) is different. Step (1) is changed to: vinyl triethoxysilane, deionized water and anhydrous ethanol are mixed, stirred at 35°C and 85rpm for 25min, the pH of the solution is adjusted to 4.5 with acetic acid, mica powder is added, cooled to room temperature, and ball milling is performed. The process parameters are as follows: the ball milling medium is zirconium silicate, the ball-to-material ratio is 7:1, the rotation speed is 1000rpm, the time is 30min, washed with deionized water 6 times, and dried at 70°C for 6h to obtain a flame retardant; the mass ratio of the vinyl triethoxysilane, deionized water, anhydrous ethanol and mica powder is 1:1:15:2; the remaining steps are the same as Example 2.

[0034] Comparative Example 2

[0035] The difference between Comparative Example 2 and Example 2 is that there is no step (1), and step (2) is changed to: wrap methyl vinyl silicone rubber on a double roller with a roller gap of 3 mm, add polydiphenylsiloxane and hydroxy silicone oil in sequence for mixing at a temperature of 60° C. for 15 min, then adjust the roller gap to 1.5 mm and the temperature to 150° C., add potassium oxide, mica powder, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, mix for 35 min, and extrude to form the product at an extrusion temperature of 180° C. and a vacuum degree of 10 -4 Pa, electron beam irradiation treatment is carried out, the irradiation dose is 100 kGy, and a flame retardant rubber hose for automobile is obtained; the mass ratio of the methyl vinyl silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide, mica powder, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is 100:7.5:3:20:20:10; the remaining steps are the same as Example 2.

[0036] Comparative Example 3

[0037] The difference between Comparative Example 3 and Example 2 is that step (2) is different. Step (2) is changed to: wrap methyl vinyl silicone rubber on a double roller with a roller gap of 3 mm, add polydiphenylsiloxane and hydroxy silicone oil in sequence for mixing at a temperature of 60°C for 15 min, then adjust the roller gap to 1.5 mm and the temperature to 150°C, add flame retardant, mix for 35 min, extrude and form at a temperature of 180°C, and place under a vacuum of 10 -4 Pa, electron beam irradiation treatment is carried out with an irradiation dose of 100 kGy to obtain a flame-retardant rubber hose for automobiles; the mass ratio of the methyl vinyl silicone rubber, polydiphenylsiloxane, hydroxy silicone oil and flame retardant is 100:7.5:3:30; the remaining steps are the same as in Example 2.

[0038] Comparative Example 4

[0039] The difference between Comparative Example 4 and Example 2 is that step (2) is different. Step (2) is changed to: wrap the methyl vinyl silicone rubber on a double roller with a roller gap of 3 mm, add polydiphenylsiloxane and hydroxy silicone oil in sequence for mixing, the temperature is 60°C, the time is 15 min, and then adjust the roller gap to 1.5 mm and the temperature to 150°C, add potassium oxide and flame retardant, mix for 35 min, and extrude at an extrusion temperature of 180°C to obtain a flame retardant rubber hose for automobiles; the mass ratio of the methyl vinyl silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide and flame retardant is 100:7.5:3:20:30; the remaining steps are the same as Example 2.

[0040] Effect example

[0041] Table 1 below shows the performance analysis results of the flame-retardant rubber hoses for automobiles using Examples 1 to 3 of the present invention and Comparative Examples 1 to 4.

[0042] Table 1

[0043]

[0044]

[0045] From the comparison of the experimental data of the embodiment and the comparative example in Table 1, it can be found that the present invention uses a silane coupling agent to modify mica, and with the assistance of a ball milling process, the surface activity of mica is improved, and the chemical and physical adsorption of mica and silane is promoted. Then, the silane coupling agent is used to make the cyclotriphosphazene derivative undergo a grafting reaction on the surface of the mica, and under the action of mechanical force, the binding force between the cyclotriphosphazene derivative and the mica is enhanced, the stability of both is improved, and the dispersibility of the mica in the rubber matrix is ​​enhanced, thereby enhancing the mechanical properties of the base tube. Then, as a flame retardant, it is blended with silicone rubber, potassium oxide, and polydiphenylsiloxane. Under high temperature, the molten potassium oxide plays a connecting role in the matrix and fills between the mica particles and the silicon dioxide powder degraded by the silicone rubber matrix at high temperature, thereby enhancing the flame retardancy and high temperature resistance. Finally, irradiation treatment is carried out, and under vacuum conditions, hydrogen in the phenyl and methyl equilateral groups in the matrix is ​​extracted to generate benzene, thereby enhancing the stability of the matrix structure, thereby improving the high temperature resistance and mechanical properties of the rubber.

[0046] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations within the meaning and scope of the equivalent elements of the claims be included in the invention. Any marking in a claim should not be considered as limiting the claim to which it relates.

Claims

1. A flame-retardant rubber hose for automobiles, characterized in that: The flame-retardant rubber hose for automobiles is prepared by blending flame retardant, silicone rubber, potassium oxide and polydiphenylsiloxane.

2. The flame-retardant rubber hose for automobiles according to claim 1, characterized in that: The flame retardant is prepared by ball milling mica, a silane coupling agent and a cyclotriphosphazene derivative.

3. A method for preparing a flame-retardant rubber hose for automobiles, characterized in that: The method comprises the following preparation steps: (1) Mix a silane coupling agent, deionized water, and anhydrous ethanol, stir at 20 to 50° C. and 50 to 120 rpm for 10 to 40 minutes, adjust the solution pH to 4 to 5 with acetic acid, add mica powder, cool to room temperature, and perform ball milling for 20 to 40 minutes, add a cyclotriphosphazene derivative, and perform ball milling again for 30 to 70 minutes, wash with deionized water for 3 to 8 times, and dry at 50 to 90° C. for 4 to 8 hours to obtain a flame retardant; (2) Wrap the silicone rubber on a double roller with a roller gap of 2 to 4 mm, add polydiphenylsiloxane and hydroxy silicone oil in turn for mixing at a temperature of 60°C for 10 to 20 min, then adjust the roller gap to 1 to 2 mm and the temperature to 150°C, add potassium oxide and flame retardant, mix for 20 to 50 min, and extrude at a temperature of 180°C under a vacuum of 10 -4 Pa, electron beam irradiation treatment was carried out to obtain a flame retardant rubber hose for automobiles.

4. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The silane coupling agent in step (1) is vinyltriethoxysilane.

5. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The cyclotriphosphazene derivative in step (1) is 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

6. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The process parameters of the ball milling in step (1) are as follows: the ball milling medium is zirconium silicate, the ball-to-material ratio is 4 to 10:1, and the rotation speed is 800 to 1350 rpm.

7. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The mass ratio of the silane coupling agent, deionized water, anhydrous ethanol, mica powder and cyclotriphosphazene derivative in step (1) is 1:1:10-20:1-3:0.5-1.

8. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The silicone rubber in step (2) is methyl vinyl silicone rubber.

9. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The process parameters of the electron beam irradiation in step (2) are as follows: the irradiation dose is 40 to 160 kGy.

10. The method for preparing a flame-retardant rubber hose for automobile according to claim 3, characterized in that: The mass ratio of the silicone rubber, polydiphenylsiloxane, hydroxy silicone oil, potassium oxide and flame retardant in step (2) is 100:5-10:1-5:20:20-40.

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