Flame retardant rubber material and preparation method thereof

Abstract

The present invention relates to the technical field of rubber materials, and proposes a flame retardant rubber material and a preparation method thereof. The flame retardant rubber material comprises the following raw materials by weight: 100 parts of styrene-butadiene rubber, 1 to 3 parts of a vulcanizing agent, 10 to 20 parts of an inorganic flame retardant, 1 to 2 parts of an antioxidant, 20 to 40 parts of a filler, and 5 to 10 parts of an organic flame retardant; the organic flame retardant is vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate. Through the above technical scheme, the problems of poor flame retardancy and low mechanical strength of rubber materials in the related art are solved.

Description

Technical Field

[0001] The invention relates to the technical field of rubber materials, and in particular to a flame retardant rubber material and a preparation method thereof. Background Art

[0002] Rubber material is a kind of high-elastic polymer material. It is widely used in many fields such as automobile, aerospace, construction, electronics, etc. due to its good elasticity, wear resistance, corrosion resistance and insulation. However, ordinary rubber materials are usually flammable. Once a fire occurs, it will burn quickly and release a large amount of heat and toxic gases, posing a serious threat to people's life and property safety. In addition, due to its high elasticity, rubber materials are prone to deformation and cracking during use. They do not have good mechanical strength and cannot ensure reliable sealing, effective shock absorption, and stable transmission. This will cause leakage, equipment damage and other problems, affecting its normal application in many fields. Therefore, the development of a rubber material with high flame retardant properties and high mechanical strength is an urgent problem to be solved. Summary of the invention

[0003] The invention provides a flame retardant rubber material and a preparation method thereof, which solves the problems of poor flame retardant performance and low mechanical strength of the rubber material in the related art.

[0004] The technical solution of the present invention is as follows: The present invention provides a flame retardant rubber material, comprising the following component raw materials in parts by weight: 100 parts of styrene-butadiene rubber, 1 to 3 parts of a vulcanizing agent, 10 to 20 parts of an inorganic flame retardant, 1 to 2 parts of an antioxidant, 20 to 40 parts of a filler, and 5 to 10 parts of an organic flame retardant;

[0005] The organic flame retardant is vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate.

[0006] As a further technical solution, in the vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate, the mass ratio of the vinyl-containing polysiloxane to the 2-(phosphoryloxy)ethyl acrylate is 3 to 5:1;

[0007] The preparation method of vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate comprises the following steps: mixing vinyl-containing polysiloxane and 2-(phosphoryloxy)ethyl acrylate, adding a catalyst, and reacting to obtain an organic flame retardant.

[0008] In the present invention, by regulating the mass ratio of vinyl polysiloxane and 2-(phosphoryloxy)ethyl acrylate, the formation rate of the heat insulating carbon layer and the release rate of the non-combustible gas during the combustion process are adjusted, the synergistic flame retardant effect of the two is fully exerted, and the flame retardant properties and mechanical strength of the rubber material are enhanced.

[0009] The vinyl-containing polysiloxane includes one or more of vinyl-terminated polydimethylsiloxane, vinyl-terminated polymethylvinylsiloxane, and monovinyl-terminated dimethyl (siloxane and polysiloxane), and is preferably vinyl-terminated polymethylvinylsiloxane.

[0010] In the present invention, when the vinyl-containing polysiloxane is vinyl-terminated polymethylvinylsiloxane, the flame retardant property and mechanical strength of the rubber material are further improved.

[0011] As a further technical solution, the catalyst is triethylamine.

[0012] As a further technical solution, the reaction temperature is 60-80° C., and the reaction time is 1-3 hours.

[0013] As a further technical solution, the styrene-butadiene rubber consists of a first styrene-butadiene rubber and a second styrene-butadiene rubber, and the first styrene-butadiene rubber and the second styrene-butadiene rubber have different styrene contents.

[0014] As a further technical solution, the styrene content of the first styrene butadiene rubber is 18wt%, the styrene content of the second styrene butadiene rubber is 40.5wt%, and the mass ratio of the first styrene butadiene rubber to the second styrene butadiene rubber is 1:1-3.

[0015] In the present invention, styrene-butadiene rubber with different styrene contents is selected as raw material, and the flame retardant property and mechanical strength of the rubber material are further improved by adjusting the magnitude of the π-π stacking force formed with the organic flame retardant.

[0016] As a further technical solution, the vulcanizing agent includes one or more of dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0017] As a further technical solution, the inorganic flame retardant includes one or more of aluminum hydroxide, magnesium hydroxide, and antimony trioxide.

[0018] As a further technical solution, the filler includes one or more of carbon black, clay, and talcum powder.

[0019] As a further technical solution, the antioxidant includes one or more of antioxidant 1135 , antioxidant 1010 , and antioxidant 1076 .

[0020] The present invention also provides a method for preparing a flame retardant rubber material, comprising the following steps:

[0021] S1, weighing the weight parts of styrene-butadiene rubber, inorganic flame retardant, antioxidant, filler, and organic flame retardant, and mixing them to obtain a mixed rubber;

[0022] S2. Mix the rubber mixture with a vulcanizing agent and vulcanize to obtain a flame retardant rubber material.

[0023] As a further technical solution, the mixing temperature is 30-50° C., and the mixing time is 12-36 hours.

[0024] As a further technical solution, the vulcanization temperature is 160-180° C., and the mixing time is 10-20 min.

[0025] The working principle and beneficial effects of the present invention are:

[0026] In the present invention, an organic flame retardant is prepared by modifying 2-(phosphoryloxy)ethyl acrylate with terminal vinyl polymethylvinylsiloxane. During the combustion process, the organic flame retardant can not only promote the formation of a dense carbon layer on the surface of the rubber material, effectively block the transfer of oxygen and heat, and slow down the combustion reaction, but also release non-combustible gas, dilute the surrounding oxygen concentration, reduce the intensity of the combustion reaction, absorb a large amount of heat, reduce the temperature of the surrounding environment, slow down the thermal decomposition rate of rubber, and enhance the oxygen index and tensile strength of the rubber material. DETAILED DESCRIPTION

[0027] 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.

[0028] In the following examples and comparative examples:

[0029] Vinyl-terminated polymethylvinylsiloxane: vinyl content is 1.0wt%, the manufacturer is Shenzhen Jipeng Silicon Fluoride Materials Co., Ltd.;

[0030] Vinyl-terminated polydimethylsiloxane: vinyl content is 0.16±0.02wt%, the manufacturer is Shenzhen Jipeng Silicon Fluoride Materials Co., Ltd.;

[0031] First, styrene-butadiene rubber: styrene content is 18wt%, model is SEBS6014, manufacturer is Borida New Materials Co., Ltd.;

[0032] Second styrene butadiene rubber: styrene content is 40.5wt%, model is SBR1516, manufacturer is Shanghai Cunsi Industrial Co., Ltd.

[0033] Example 1

[0034] Preparation of organic flame retardant: weigh 16 parts of vinyl-terminated polydimethylsiloxane, add 8 parts of 2-(phosphoryloxy)ethyl acrylate, add 0.2 parts of triethylamine, react at a constant temperature of 60°C for 3 hours, and cool to room temperature to obtain the organic flame retardant;

[0035] A method for preparing a flame retardant rubber material comprises the following steps:

[0036] S1, weigh 100 parts of the first styrene-butadiene rubber, 10 parts of aluminum hydroxide, 1 part of antioxidant 1135, 20 parts of carbon black, and 5 parts of organic flame retardant, and mix them at 30° C. for 36 hours to obtain a mixed rubber;

[0037] S2. Mix the mixed rubber with 1 part of dicumyl peroxide and vulcanize at 160°C for 10 minutes to obtain a flame retardant rubber material.

[0038] Example 2

[0039] Preparation of organic flame retardant: weigh 16 parts of vinyl-terminated polydimethylsiloxane, add 8 parts of 2-(phosphoryloxy)ethyl acrylate, add 0.2 parts of triethylamine, react at a constant temperature of 70°C for 2 hours, and cool to room temperature to obtain an organic flame retardant;

[0040] A method for preparing a flame retardant rubber material comprises the following steps:

[0041] S1, weighing 100 parts of the first styrene-butadiene rubber, 15 parts of magnesium hydroxide, 1.5 parts of antioxidant 1010, 30 parts of clay, and 8 parts of organic flame retardant, mixing at 40° C. for 24 hours to obtain a mixed rubber;

[0042] S2. Mix the mixed rubber with 2 parts of di-tert-butyl peroxide and vulcanize at 170°C for 15 minutes to obtain a flame retardant rubber material.

[0043] Example 3

[0044] Preparation of organic flame retardant: weigh 16 parts of vinyl-terminated polydimethylsiloxane, add 8 parts of 2-(phosphoryloxy)ethyl acrylate, add 0.2 parts of triethylamine, react at a constant temperature of 80°C for 1 hour, and cool to room temperature to obtain the organic flame retardant;

[0045] A method for preparing a flame retardant rubber material comprises the following steps:

[0046] S1, weigh 100 parts of the first styrene-butadiene rubber, 20 parts of antimony trioxide, 2 parts of antioxidant 1076, 40 parts of talcum powder, and 10 parts of organic flame retardant, and mix them at 50° C. for 12 hours to obtain a mixed rubber;

[0047] S2. Mix the mixed rubber with 3 parts of 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane and vulcanize at 180° C. for 20 minutes to obtain a flame retardant rubber material.

[0048] Example 4

[0049] Compared with Example 1, the difference of Example 4 is that 16 parts of vinyl-terminated polydimethylsiloxane are replaced by an equal amount of vinyl-terminated polymethylvinylsiloxane.

[0050] Example 5

[0051] Compared with Example 1, the difference of Example 5 is that 16 parts of the vinyl-terminated polydimethylsiloxane are replaced by an equal amount of monovinyl-terminated dimethyl (siloxane and polysiloxane).

[0052] Example 6

[0053] Compared with Example 4, Example 6 is different in that 16 parts of vinyl-terminated polymethylvinylsiloxane and 8 parts of 2-(phosphoryloxy)ethyl acrylate are replaced with 18 parts of vinyl-terminated polymethylvinylsiloxane and 6 parts of 2-(phosphoryloxy)ethyl acrylate.

[0054] Example 7

[0055] Compared with Example 4, Example 7 is different in that 16 parts of vinyl-terminated polymethylvinylsiloxane and 8 parts of 2-(phosphoryloxy)ethyl acrylate are replaced with 20 parts of vinyl-terminated polymethylvinylsiloxane and 4 parts of 2-(phosphoryloxy)ethyl acrylate.

[0056] Example 8

[0057] Compared with Example 4, Example 8 is different in that 16 parts of vinyl-terminated polymethylvinylsiloxane and 8 parts of 2-(phosphoryloxy)ethyl acrylate are replaced with 21 parts of vinyl-terminated polymethylvinylsiloxane and 3 parts of 2-(phosphoryloxy)ethyl acrylate.

[0058] Example 9

[0059] Compared with Example 4, the difference of Example 9 is that 100 parts of the first styrene butadiene rubber are replaced by an equal amount of the second styrene butadiene rubber.

[0060] Example 10

[0061] Compared with Example 7, Example 10 is different in that 100 parts of the first styrene butadiene rubber are replaced by 60 parts of the first styrene butadiene rubber and 40 parts of the second styrene butadiene rubber.

[0062] Embodiment 11

[0063] Compared with Example 7, Example 11 is different in that 100 parts of the first styrene butadiene rubber are replaced by 50 parts of the first styrene butadiene rubber and 50 parts of the second styrene butadiene rubber.

[0064] Example 12

[0065] Compared with Example 7, the difference of Example 12 is that 100 parts of the first styrene butadiene rubber are replaced by 25 parts of the first styrene butadiene rubber and 75 parts of the second styrene butadiene rubber.

[0066] Example 13

[0067] Compared with Example 7, Example 13 is different in that 100 parts of the first styrene butadiene rubber are replaced by 20 parts of the first styrene butadiene rubber and 80 parts of the second styrene butadiene rubber.

[0068] Comparative Example 1

[0069] Compared with Example 1, Comparative Example 1 is different in that only 2-(phosphoryloxy)ethyl acrylate is added.

[0070] The flame retardant rubber materials prepared in Examples 1 to 13 and Comparative Example 1 were tested according to the following method:

[0071] 1. Oxygen index: Test the oxygen index of the sample according to the test method specified in GB / T 2406.2-2009 "Determination of combustion behavior by oxygen index method Part 2: Room temperature test".

[0072] 2. Tensile strength: Test the tensile strength of the sample according to the test method specified in GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber".

[0073] The test results are shown in the following table:

[0074] Table 1 Performance test results of flame retardant rubber materials prepared in Examples 1 to 13 and Comparative Example 1

[0075]

[0076] Compared with Comparative Example 1, Examples 1 to 3 add an organic flame retardant modified by vinyl-terminated polydimethylsiloxane, Example 4 adds an organic flame retardant modified by vinyl-terminated polymethylvinylsiloxane, and Example 5 adds an organic flame retardant modified by monovinyl-terminated dimethyl (siloxane and polysiloxane). As a result, the oxygen index and tensile strength of Examples 1 to 5 are better than those of Comparative Example 1, indicating that the addition of organic flame retardants modified by vinyl-containing polysiloxane can improve the flame retardant properties and mechanical strength of rubber materials. In Examples 1 to 5, the oxygen index and tensile strength of Example 4 are better than those of Examples 1 to 3 and Example 5, indicating that the flame retardant properties and mechanical strength of the rubber material with the addition of organic flame retardants modified by vinyl-terminated polymethylvinylsiloxane are better.

[0077] Compared with Example 4, Examples 6 to 8 added different mass ratios of terminal vinyl polymethylvinyl siloxane and 2-(phosphoryloxy)ethyl acrylate. As a result, the oxygen index and tensile strength of Examples 6 and 7 were better than those of Examples 4 and 8, indicating that when the mass ratio of terminal vinyl polymethylvinyl siloxane and 2-(phosphoryloxy)ethyl acrylate was 3 to 5:1, the flame retardant properties and mechanical strength of the obtained rubber material were better.

[0078] Compared with Examples 7 and 9, Examples 10 to 13 simultaneously add the first styrene butadiene rubber and the second styrene butadiene rubber. As a result, the oxygen index and tensile strength of Examples 10 to 13 are better than those of Examples 7 and 9, indicating that the first styrene butadiene rubber and the second styrene butadiene rubber play a synergistic role and can further improve the flame retardant properties and mechanical strength of the rubber material. In Examples 10 to 13, the first styrene butadiene rubber and the second styrene butadiene rubber are added in different mass ratios. As a result, the oxygen index and tensile strength of Examples 11 and 12 are better than those of Examples 10 and 13, indicating that when the mass ratio of the first styrene butadiene rubber to the second styrene butadiene rubber is 1:1 to 3, the flame retardant properties and mechanical strength of the obtained rubber material are better.

[0079] The above are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the protection scope of the present invention.

Claims

1. A flame retardant rubber material, characterized in that: The invention comprises the following raw materials in parts by weight: 100 parts of styrene-butadiene rubber, 1 to 3 parts of a vulcanizing agent, 10 to 20 parts of an inorganic flame retardant, 1 to 2 parts of an antioxidant, 20 to 40 parts of a filler, and 5 to 10 parts of an organic flame retardant; the organic flame retardant is vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate; In the vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate, the mass ratio of the vinyl-containing polysiloxane to the 2-(phosphoryloxy)ethyl acrylate is 3 to 5:1; The preparation method of the vinyl-containing polysiloxane-modified 2-(phosphoryloxy)ethyl acrylate comprises the following steps: mixing the vinyl-containing polysiloxane and 2-(phosphoryloxy)ethyl acrylate, adding a catalyst, and reacting to obtain an organic flame retardant; The styrene-butadiene rubber is composed of a first styrene-butadiene rubber and a second styrene-butadiene rubber, and the first styrene-butadiene rubber and the second styrene-butadiene rubber have different styrene contents; The styrene content of the first styrene butadiene rubber is 18 wt %, the styrene content of the second styrene butadiene rubber is 40.5 wt %, and the mass ratio of the first styrene butadiene rubber to the second styrene butadiene rubber is 1:1-3.

2. A flame retardant rubber material according to claim 1, characterized in that: The vinyl-containing polysiloxane includes one or both of vinyl-terminated polydimethylsiloxane and vinyl-terminated polymethylvinylsiloxane.

3. The flame retardant rubber material according to claim 1, characterized in that: The vulcanizing agent includes one or more of dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

4. The flame retardant rubber material according to claim 1, characterized in that: The inorganic flame retardant includes one or more of aluminum hydroxide, magnesium hydroxide, and antimony trioxide.

5. The flame retardant rubber material according to claim 1, characterized in that: The filler includes one or more of carbon black, clay, and talc.

6. The flame retardant rubber material according to claim 1, characterized in that: The antioxidant includes one or more of antioxidant 1135 , antioxidant 1010 , and antioxidant 1076 .

7. The method for preparing a flame retardant rubber material according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1, weighing the weight parts of styrene-butadiene rubber, inorganic flame retardant, antioxidant, filler, and organic flame retardant, and mixing them to obtain a mixed rubber; S2. Mix the rubber mixture with a vulcanizing agent and vulcanize to obtain a flame retardant rubber material.

Images