Tear-resistant high-elasticity fluorosilicone rubber and preparation method thereof

Abstract

The invention discloses tear-resistant high-elasticity fluorosilicone rubber and a preparation method thereof. The tear-resistant high-elasticity fluorosilicone rubber is prepared from the following raw materials in parts by weight: 60-70 parts of modified fluorosilicone rubber material, 20-30 parts of filler, 10-20 parts of white carbon black, 5-10 parts of interface modifier, 3-8 parts of vulcanizing agent, 0.8-1.5 parts of anti-aging agent and 1-5 parts of accelerant. Comprising the following steps: S1, putting the modified fluorinated silicone rubber material, the filling agent and the interface modifier into a kneading machine according to the raw materials in parts by weight, and stirring for 10-15 minutes at the temperature of 50-55 DEG C and the rotating speed of 35-50 rpm / min to obtain a premix; s2, putting the premix into an internal mixer for mixing, adding white carbon black, controlling the temperature to be 70-80 DEG C, mixing for 10-15 minutes, adding an anti-aging agent, mixing uniformly, and discharging in the internal mixer to obtain a mixed rubber material; s3, putting the rubber compound into an open mill, adding a vulcanizing agent and an accelerant, controlling the temperature to be 120-145 DEG C, and uniformly mixing to obtain the tear-resistant high-elasticity fluorosilicone rubber.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber products, and in particular to tear-resistant high-elastic fluorosilicone rubber and a preparation method thereof. Background Art

[0002] Fluorosilicone rubber, also known as γ-trifluoropropylmethylpolysiloxane, is a side-chain modified silicone elastomer. Products usually made of fluorosilicone rubber, in addition to the characteristics of general silicone rubber, also have excellent oil resistance, including fuel, engine oil, chemical reagents and solvents. Therefore, fluorosilicone rubber makes up for the lack of oil resistance of ordinary silicone rubber and can be called the "oil fighter" among silicone elastomers. Due to the excellent oil resistance of fluorosilicone rubber and its heat resistance of silicone elastomers, this material is particularly suitable for some applications that require high temperature resistance and fuel resistance, such as seals, hoses, rubber pads, films and impregnated products. It has a wide range of applications in the automotive industry, aerospace industry, petrochemical industry and other fields.

[0003] However, the strength of fluorosilicone rubber vulcanizate is low, and the hot tear strength is even lower, which will cause damage to the fluorosilicone rubber during the demolding process after molding, limiting its processing and use. Therefore, the fluorosilicone rubber needs to be reinforced.

[0004] Chinese patent document CN 106349714A discloses a tear-resistant silicone rubber material for cables, which is prepared by combining fluorosilicone rubber with aliphatic aromatic copolyester materials, adding polypropylene, sodium hexametaphosphate, maleic anhydride, diisopropylbenzene peroxide, tricalcium phosphate, nitrile rubber, pine tar, sodium hydroxymethylcellulose, nano zinc oxide, methyl tributylidene oxime silane, alumina fiber, vinyl triethoxysilane and water, adding each component to a vacuum kneader or internal mixer and mixing evenly, then forming the synthetic rubber through an open mill, and finally adding the formed rubber to a mold containing a vulcanizing agent for vulcanization. In addition to fluorosilicone rubber, the raw materials used in this patent also add a large amount of polyester materials, which will lead to a decrease in the solvent resistance of the material and weaken the advantages of fluorosilicone.

[0005] Chinese patent document CN105199106 A discloses a method for preparing an addition-type liquid fluorosilicone rubber, using D3F, ViD4 and MM with a purity greater than 99.5% as raw materials, mixing them evenly in a certain proportion to obtain vinyl fluorosilicone oil; using vinyl fluorosilicone oil as the base rubber, adding reinforcing agent, crosslinking agent, catalyst, and then kneading, grinding, tableting and other processes to prepare liquid fluorosilicone rubber. Compared with other liquid silicone rubbers with the same process and the same formula, FSR is superior to LSR in terms of insulation performance, hydrophobicity, high temperature resistance and other properties. This method has a short production cycle, the product has good hot tearing performance, is easy to demold, can realize a variety of processing methods such as molding, extrusion, injection molding, and can realize the automated production of materials. The fluorosilicone rubber material prepared by this method is in a liquid flow state. Although a variety of processing methods can be realized, its application will be limited by the constraints of molecular weight and other aspects.

[0006] Chinese patent document CN 104672910A discloses a fluorosilicone rubber for aging-resistant porcelain composite insulators, wherein the fluorosilicone rubber is made of the following materials in parts by weight: 30-40 parts of fluororubber raw rubber, 50-70 parts of silicone rubber compound, 23-41 parts of aluminum hydroxide powder, 5-15 parts of fumed silica, 0.4-1 parts of di-2-pentane vulcanizer, 0.4-4 parts of polytetrafluoroethylene powder, 5-9 parts of anti-aging and heat-resistant additives, 2-5 parts of structure control agents, 3-6 parts of plasticizers, and 6-8 parts of colorants. The present invention also discloses the use of the fluorosilicone rubber for aging-resistant porcelain composite insulators in the preparation of insulator sheds. The tear strength of the prepared insulator sheds is increased by 167% compared with conventional sheds; after artificial light aging treatment, the tensile strength of the fluorosilicone rubber made by this formula remains almost unchanged, while the tensile strength is reduced by 25% relative to silicone rubber. This patent is for the use of fluororubber raw rubber and silicone rubber to obtain fluorosilicone rubber material. Due to the difference in structure, there are certain differences in the compatibility of the two rubbers, which can easily lead to defects in the structure and performance of the product. Summary of the invention

[0007] In order to solve the problems mentioned in the above background technology, the present invention provides a tear-resistant high-elastic fluorosilicone rubber and a preparation method thereof.

[0008] In order to achieve the above object, the present invention adopts the following technical solutions:

[0009] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 60-70 parts of modified fluorosilicone rubber material, 20-30 parts of filler, 10-20 parts of white carbon black, 5-10 parts of interface modifier, 3-8 parts of vulcanizer, 0.8-1.5 parts of antioxidant and 1-5 parts of accelerator.

[0010] Preferably, the preparation method of the modified fluorosilicone rubber material comprises the following steps:

[0011] S1. Add fluororubber and silicone rubber into an internal mixer at a ratio of 1.1:1.2-1.5 for blending, and control the temperature to 75-110°C and the speed to 20-40rpm / min to ensure that the two rubbers are fully mixed;

[0012] S2. gradually adding reinforcing agent, plasticizer and maleic anhydride modifier during the mixing process and ensuring that they are evenly dispersed in the rubber matrix;

[0013] S3. The mixed rubber material is taken out and placed into a mold for preforming. The purpose of preforming is to give the material a preliminary shape to facilitate subsequent vulcanization molding;

[0014] S4. The preformed rubber material is placed in a vulcanizer for high temperature and high pressure vulcanization at 160-180°C for 15-35 minutes;

[0015] During the vulcanization process, cross-linking occurs between the rubber molecular chains to form a three-dimensional network structure, thus giving the material excellent elastic and mechanical properties.

[0016] S5. Wash, dry and grind the vulcanized rubber material to obtain modified fluorosilicone rubber material.

[0017] The silicone rubber described in S1 is phenyl silicone rubber, which is prepared by introducing diphenylsiloxane segments or methylphenylsiloxane segments into the molecular chain of vinyl silicone rubber. The introduction of bulky phenyl groups destroys the regularity of the dimethylsiloxane structure and reduces the crystallization temperature and glass transition temperature of the polymer.

[0018] Preferably, the reinforcing agent is a mixture of carbon black N330 and nano-silicon dioxide, and the mass ratio of the carbon black N330 to the nano-silicon dioxide is 1.8-2.5:1.1.

[0019] Preferably, the plasticizer is di(2-ethylhexyl) phthalate and / or di(2-ethylhexyl) terephthalate.

[0020] Preferably, the mass ratio of the reinforcing agent, the plasticizer and the maleic anhydride modifier is (1.5-2):(1.2-1.5):1.1.

[0021] Preferably, the filler is prepared by compounding amino-modified multi-walled carbon nanotubes, nano-boehmite powder and graphene oxide in a mass ratio of 1.3:(1.5-2):(2-2.5).

[0022] The outer diameter of the amino-modified multi-walled carbon nanotubes is 8-15 nm, and the length is 30-50 μm;

[0023] The average particle size of the nano-boehmite powder is 10-20 nm;

[0024] The average particle size of the graphene oxide is 100-200 nm.

[0025] Preferably, the interface modifier is at least one of γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and bis-[γ-(triethoxysilyl)propyl]tetrasulfide.

[0026] Preferably, the vulcanizing agent is at least one of ZIMAG29 / 43, vulcanizing agent DCP and vulcanizing agent bisphenol AF.

[0027] Preferably, the antioxidant is at least one of antioxidant RD and antioxidant MD;

[0028] The accelerator is at least one of accelerator DM, accelerator D and accelerator TS.

[0029] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0030] S1. According to the weight of the raw materials, the modified fluorosilicone rubber material, filler and interface modifier are put into a kneader and stirred at 50-55 ° C and 35-50 rpm / min for 10-15min to obtain a premix;

[0031] S2. The premix is ​​put into an internal mixer for mixing, and white carbon is added, the temperature is controlled at 70-80 ° C, mixed for 10-15 minutes, and then an antioxidant is added and mixed until uniform after the internal mixer is discharged to obtain a mixed rubber compound;

[0032] S3. Put the mixed rubber into an open mixer, add vulcanizing agent and accelerator, control the temperature at 120-145°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0033] Compared with the prior art, the present invention has the following beneficial effects:

[0034] 1. The present invention can obtain a high-performance elastomeric material by modifying fluorosilicone rubber. In the preparation process of the modified fluorosilicone rubber material, the mixture of carbon black N330 and nano-silicon dioxide can not only reinforce the main material, but also make the vulcanized rubber material have good elasticity and low dynamic multiple; when carbon black N330 and nano-silicon dioxide are mixed and used, a complementary reinforcement system can be formed, carbon black provides high wear resistance, and nano-silicon dioxide can improve the flexibility and heat resistance of the rubber and enhance the overall mechanical properties of the material.

[0035] 2. In the preparation process of the modified fluorosilicone rubber material of the present invention, by adding a reinforcing agent, a plasticizer and a maleic anhydride modifier in a mass ratio of (1.5-2):(1.2-1.5):1.1, the mechanical properties, processing properties and chemical resistance of the rubber can be significantly improved; wherein the plasticizer can reduce the glass transition temperature of the fluorosilicone rubber, so that it still maintains good elasticity and flexibility in a low temperature environment, and can reduce the viscosity of the rubber, improve its processing properties, and make it easier to operate during the blending and molding process; and maleic anhydride is a chemical substance with strong polarity, which can react with the active groups on the rubber molecular chain, such as the fluorine atoms in the fluororubber or the silicon-oxygen bonds in the silicone rubber, to form chemical bonds, thereby enhancing the compatibility between the fluororubber and the silicone rubber.

[0036] 3. In the preparation process of the present invention, by adding a filler prepared by compounding amino multi-walled carbon nanotubes, nano-boehmite powder and graphene oxide in a mass ratio of 1.3:(1.5-2):(2-2.5), the resilience of the rubber can be effectively improved; wherein the amino multi-walled carbon nanotubes, nano-boehmite powder and graphene oxide all have ultrafine nano-scale particle sizes, and the finer the particles, the better the rubber reinforcement effect, and the three have a synergistic effect, and have a good dispersion effect in the rubber, can effectively reduce the hysteresis of the rubber under dynamic motion, improve the resilience of the rubber, and reduce the dynamic multiple, and have a high social use value and application prospect. DETAILED DESCRIPTION

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are 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.

[0038] Unless otherwise specified, the raw materials used in the present invention are all conventional products purchased from the market.

[0039] Preparation Example 1

[0040] The preparation method of the modified fluorosilicone rubber material comprises the following steps:

[0041] S1. 11 g of fluororubber and 12 g of phenyl silicone rubber were added to an internal mixer for blending, and the temperature was controlled at 75 ° C and the speed was 20 rpm / min to ensure that the two rubbers were fully mixed;

[0042] S2. 15 g reinforcing agent, 12 g di(2-ethylhexyl) phthalate and 11 g maleic anhydride modifier were gradually added during the mixing process to ensure that they were uniformly dispersed in the rubber matrix;

[0043] The reinforcing agent is a mixture of carbon black N330 and nano-silicon dioxide, and the mass ratio of the carbon black N330 to the nano-silicon dioxide is 1.8:1.1;

[0044] S3. The mixed rubber material is taken out and placed into a mold for preforming. The purpose of preforming is to give the material a preliminary shape to facilitate subsequent vulcanization molding;

[0045] S4. The preformed rubber material is placed in a vulcanizer for high temperature and high pressure vulcanization at 160°C for 15 minutes;

[0046] S5. Wash, dry and grind the vulcanized rubber material to obtain modified fluorosilicone rubber material.

[0047] Preparation Example 2

[0048] The preparation method of the modified fluorosilicone rubber material comprises the following steps:

[0049] S1. 11 g of fluororubber and 13.5 g of phenyl silicone rubber were added to an internal mixer for blending, and the temperature was controlled at 85 ° C and the speed was 30 rpm / min to ensure that the two rubbers were fully mixed;

[0050] S2. 18 g reinforcing agent, 15 g di(2-ethylhexyl) terephthalate and 11 g maleic anhydride modifier were gradually added during the mixing process to ensure that they were uniformly dispersed in the rubber matrix;

[0051] The reinforcing agent is a mixture of carbon black N330 and nano-silicon dioxide, and the mass ratio of the carbon black N330 to the nano-silicon dioxide is 2.1:1.1;

[0052] S3. The mixed rubber material is taken out and placed into a mold for preforming. The purpose of preforming is to give the material a preliminary shape to facilitate subsequent vulcanization molding;

[0053] S4. The preformed rubber material is placed in a vulcanizer for high temperature and high pressure vulcanization at 160°C for 15 minutes;

[0054] S5. Wash, dry and grind the vulcanized rubber material to obtain modified fluorosilicone rubber material.

[0055] Preparation Example 3

[0056] The preparation method of the modified fluorosilicone rubber material comprises the following steps:

[0057] S1. 11 g of fluororubber and 15 g of phenyl silicone rubber were added to an internal mixer for blending, and the temperature was controlled at 85 ° C and the speed was 30 rpm / min to ensure that the two rubbers were fully mixed;

[0058] S2. 20 g reinforcing agent, 15 g di(2-ethylhexyl) terephthalate and 11 g maleic anhydride modifier were gradually added during the mixing process to ensure that they were uniformly dispersed in the rubber matrix;

[0059] The reinforcing agent is a mixture of carbon black N330 and nano-silicon dioxide, and the mass ratio of the carbon black N330 to the nano-silicon dioxide is 2.5:1.1;

[0060] S3. The mixed rubber material is taken out and placed into a mold for preforming. The purpose of preforming is to give the material a preliminary shape to facilitate subsequent vulcanization molding;

[0061] S4. The preformed rubber material is placed in a vulcanizer for high temperature and high pressure vulcanization at 180°C for 35 minutes;

[0062] S5. Wash, dry and grind the vulcanized rubber material to obtain modified fluorosilicone rubber material.

[0063] Example 1

[0064] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 60 parts of the modified fluorosilicone rubber material prepared in Preparation Example 1, 20 parts of a filler, 10 parts of white carbon black, 5 parts of an interface modifier, 3 parts of a vulcanizer, 0.8 parts of an antioxidant, and 1 part of an accelerator.

[0065] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0066] S1. According to the weight proportions of the raw materials, the modified fluorosilicone rubber material, filler and γ-chloropropyltrimethoxysilane prepared in Preparation Example 1 were put into a kneader and stirred at 50°C at a speed of 35 rpm / min for 10 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder, and graphene oxide compounded in a mass ratio of 1.3:1.5:2;

[0067] The amino-modified multi-walled carbon nanotube has an outer diameter of 8 nm and a length of 30 μm;

[0068] The average particle size of the nano-boehmite powder is 10 nm;

[0069] The average particle size of the graphene oxide is 100 nm.

[0070] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 70 ° C, mixed for 10 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0071] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent ZIMAG29 / 43 and the accelerator DM, control the temperature at 120°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0072] Example 2

[0073] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 60 parts of the modified fluorosilicone rubber material prepared in Preparation Example 2, 20 parts of a filler, 10 parts of white carbon black, 5 parts of an interface modifier, 3 parts of a vulcanizer, 0.8 parts of an antioxidant, and 1 part of an accelerator.

[0074] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0075] S1. According to the weight proportions of the raw materials, the modified fluorosilicone rubber material, filler and γ-aminopropyltriethoxysilane prepared in Preparation Example 2 were put into a kneader and stirred at 52°C at a speed of 45 rpm / min for 15 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder, and graphene oxide compounded in a mass ratio of 1.3:1.8:2.1;

[0076] The amino-modified multi-walled carbon nanotube has an outer diameter of 8 nm and a length of 30 μm;

[0077] The average particle size of the nano-boehmite powder is 10 nm;

[0078] The average particle size of the graphene oxide is 100 nm.

[0079] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 70 ° C, mixed for 10 minutes, and then the antioxidant MD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0080] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent DCP and the accelerator DM, control the temperature at 120°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0081] Example 3

[0082] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 60 parts of the modified fluorosilicone rubber material prepared in Preparation Example 3, 20 parts of a filler, 10 parts of white carbon black, 5 parts of an interface modifier, 3 parts of a vulcanizer, 0.8 parts of an antioxidant, and 1 part of an accelerator.

[0083] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0084] S1. According to the weight proportion of the raw materials, the modified fluorosilicone rubber material, filler and vinyl triethoxysilane prepared in Preparation Example 3 were put into a kneader and stirred at 52 ° C. at a speed of 45 rpm / min for 15 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder, and graphene oxide compounded in a mass ratio of 1.3:2:2.5;

[0085] The amino-modified multi-walled carbon nanotube has an outer diameter of 8 nm and a length of 30 μm;

[0086] The average particle size of the nano-boehmite powder is 10 nm;

[0087] The average particle size of the graphene oxide is 100 nm.

[0088] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 70 ° C, mixed for 10 minutes, and then the antioxidant MD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0089] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent DCP and the accelerator DM, control the temperature at 120°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0090] Example 4

[0091] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 65 parts of the modified fluorosilicone rubber material prepared in Preparation Example 1, 25 parts of a filler, 15 parts of white carbon black, 7 parts of an interface modifier, 5 parts of a vulcanizer, 1 part of an antioxidant, and 3 parts of an accelerator.

[0092] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0093] S1. According to the weight proportions of the raw materials, the modified fluorosilicone rubber material, filler and γ-aminopropyltriethoxysilane prepared in Preparation Example 1 were put into a kneader and stirred at 50°C at a speed of 35 rpm / min for 10 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder, and graphene oxide compounded in a mass ratio of 1.3:1.5:2;

[0094] The amino-modified multi-walled carbon nanotube has an outer diameter of 10 nm and a length of 40 μm;

[0095] The average particle size of the nano-boehmite powder is 15 nm;

[0096] The average particle size of the graphene oxide is 150 nm.

[0097] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 70 ° C, mixed for 10 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0098] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent ZIMAG29 / 43 and the accelerator DM, control the temperature at 120°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0099] Example 5

[0100] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 65 parts of the modified fluorosilicone rubber material prepared in Preparation Example 2, 25 parts of a filler, 15 parts of white carbon black, 7 parts of an interface modifier, 5 parts of a vulcanizer, 1 part of an antioxidant, and 3 parts of an accelerator.

[0101] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0102] S1. According to the weight proportions of the raw materials, the modified fluorosilicone rubber material, filler and bis-[γ-(triethoxysilyl)propyl] tetrasulfide prepared in Preparation Example 2 were put into a kneader and stirred at 55° C. at a speed of 45 rpm / min for 10 min to obtain a premix; wherein the filler is amino-modified multi-walled carbon nanotubes, nano-boehmite powder and graphene oxide, which are compounded in a mass ratio of 1.3:1.5:2;

[0103] The amino-modified multi-walled carbon nanotube has an outer diameter of 10 nm and a length of 40 μm;

[0104] The average particle size of the nano-boehmite powder is 15 nm;

[0105] The average particle size of the graphene oxide is 150 nm.

[0106] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 75 ° C, mixed for 15 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0107] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent ZIMAG29 / 43 and the accelerator DM, control the temperature at 120°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0108] Example 6

[0109] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 65 parts of the modified fluorosilicone rubber material prepared in Preparation Example 3, 25 parts of a filler, 15 parts of white carbon black, 7 parts of an interface modifier, 5 parts of a vulcanizer, 1 part of an antioxidant, and 3 parts of an accelerator.

[0110] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0111] S1. According to the weight proportion of the raw materials, the modified fluorosilicone rubber material, filler and vinyl trimethoxysilane prepared in Preparation Example 3 were put into a kneader and stirred at 55°C at a speed of 35 rpm / min for 10 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder and graphene oxide compounded in a mass ratio of 1.3:1.8:2.5;

[0112] The amino-modified multi-walled carbon nanotube has an outer diameter of 10 nm and a length of 40 μm;

[0113] The average particle size of the nano-boehmite powder is 15 nm;

[0114] The average particle size of the graphene oxide is 150 nm.

[0115] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 75 ° C, mixed for 10 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0116] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent bisphenol AF and the accelerator DM, control the temperature at 130°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0117] Example 7

[0118] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 70 parts of the modified fluorosilicone rubber material prepared in Preparation Example 1, 30 parts of a filler, 20 parts of white carbon black, 10 parts of an interface modifier, 8 parts of a vulcanizer, 1.5 parts of an antioxidant, and 5 parts of an accelerator.

[0119] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0120] S1. According to the weight proportions of the raw materials, the modified fluorosilicone rubber material, filler and γ-chloropropyltrimethoxysilane prepared in Preparation Example 1 were put into a kneader and stirred at 50°C at a speed of 35 rpm / min for 10 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder, and graphene oxide compounded in a mass ratio of 1.3:1.8:2.2;

[0121] The amino-modified multi-walled carbon nanotube has an outer diameter of 8 nm and a length of 30 μm;

[0122] The average particle size of the nano-boehmite powder is 10 nm;

[0123] The average particle size of the graphene oxide is 100 nm.

[0124] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 70 ° C, mixed for 10 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0125] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent ZIMAG29 / 43 and the accelerator DM, control the temperature at 120°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0126] Example 8

[0127] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 70 parts of the modified fluorosilicone rubber material prepared in Preparation Example 2, 30 parts of a filler, 20 parts of white carbon black, 10 parts of an interface modifier, 8 parts of a vulcanizer, 1.5 parts of an antioxidant, and 5 parts of an accelerator.

[0128] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0129] S1. According to the weight proportions of the raw materials, the modified fluorosilicone rubber material, filler and vinyl triethoxysilane prepared in Preparation Example 2 were put into a kneader and stirred at 55°C at a speed of 50 rpm / min for 15 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder and graphene oxide compounded in a mass ratio of 1.3:1.8:2.2;

[0130] The amino-modified multi-walled carbon nanotube has an outer diameter of 8 nm and a length of 30 μm;

[0131] The average particle size of the nano-boehmite powder is 10 nm;

[0132] The average particle size of the graphene oxide is 100 nm.

[0133] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 80 ° C, mixed for 15 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0134] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent ZIMAG29 / 43 and the accelerator DM, control the temperature at 145°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0135] Example 9

[0136] A tear-resistant high-elastic fluorosilicone rubber comprises the following raw materials in parts by weight: 70 parts of the modified fluorosilicone rubber material prepared in Preparation Example 3, 30 parts of a filler, 20 parts of white carbon black, 10 parts of an interface modifier, 8 parts of a vulcanizer, 1.5 parts of an antioxidant, and 5 parts of an accelerator.

[0137] A method for preparing tear-resistant high-elastic fluorosilicone rubber, further comprising the following steps:

[0138] S1. According to the weight proportion of the raw materials, the modified fluorosilicone rubber material, filler and γ-aminopropyltrimethoxysilane prepared in Preparation Example 3 were put into a kneader and stirred at 50°C at a speed of 35 rpm / min for 10 min to obtain a premix; wherein the filler is amino multi-walled carbon nanotubes, nano-boehmite powder, and graphene oxide compounded in a mass ratio of 1.3:2:2.5;

[0139] The amino-modified multi-walled carbon nanotubes have an outer diameter of 15 nm and a length of 45 μm;

[0140] The average particle size of the nano-boehmite powder is 15 nm;

[0141] The average particle size of the graphene oxide is 180 nm.

[0142] S2. The premix was put into an internal mixer for mixing, and white carbon was added, the temperature was controlled at 80 ° C, mixed for 15 minutes, and then the antioxidant RD was added and mixed until uniform after the internal mixer was discharged to obtain a mixed rubber compound;

[0143] S3. Put the mixed rubber into an open mixer, add the vulcanizing agent bisphenol AF and the accelerator DM, control the temperature at 140°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

[0144] Comparative Example 1

[0145] The difference between this comparative example and Example 1 is that the modified fluorosilicone rubber material prepared in Preparation Example 1 is replaced by ordinary commercially available fluorosilicone rubber material purchased from Shuyang Yimei Fluorine New Material Technology Co., Ltd., model LS5-2040 / 60.

[0146] Comparative Example 2

[0147] The difference between this comparative example and Example 1 is that during the preparation process of the modified fluorosilicone rubber material in Preparation Example 1, no reinforcing agent is added.

[0148] Comparative Example 3

[0149] The difference between this comparative example and Example 1 is that during the preparation process of the modified fluorosilicone rubber material in Preparation Example 1, no plasticizer is added.

[0150] Comparative Example 4

[0151] The difference between this comparative example and Example 1 is that in the preparation process of the modified fluorosilicone rubber material in Preparation Example 1, no maleic anhydride modifier is added.

[0152] Comparative Example 5

[0153] The difference between this comparative example and Example 1 is that no filler is added.

[0154] Comparative Example 6

[0155] The difference between this comparative example and Example 1 is that the filler is an amino-modified multi-walled carbon nanotube, and the amino-modified multi-walled carbon nanotube has an outer diameter of 8 nm and a length of 30 μm.

[0156] The tear-resistant high-elastic fluorosilicone rubbers obtained in Examples 1-9 and Comparative Examples 1-6 were tested for tensile strength, elongation at break, and tear strength. The results are shown in Table 1:

[0157] Tensile strength and elongation at break: According to GB / T 528-2009 standard, the tensile strength and elongation at break of high-performance rubber products are tested;

[0158] Tear strength: According to GB / T 529-2008 standard, the tear strength of high-performance rubber products is tested;

[0159] Resilience test: According to GB / T 1681-2009 standard, the resilience of high-performance rubber products is tested;

[0160] Table 1

[0161]

[0162]

[0163] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A tear-resistant high-elastic fluorosilicone rubber, characterized in that: The invention comprises the following raw materials in parts by weight: 60-70 parts of modified fluorosilicone rubber material, 20-30 parts of filler, 10-20 parts of white carbon black, 5-10 parts of interface modifier, 3-8 parts of vulcanizer, 0.8-1.5 parts of antioxidant and 1-5 parts of accelerator.

2. The tear-resistant high-elastic fluorosilicone rubber according to claim 1, characterized in that: The preparation method of the modified fluorosilicone rubber material comprises the following steps: S1. Add fluororubber and silicone rubber into an internal mixer at a ratio of 1.1:1.2-1.5 for blending, and control the temperature to 75-110°C and the speed to 20-40rpm / min to ensure that the two rubbers are fully mixed; S2. gradually adding reinforcing agent, plasticizer and maleic anhydride modifier during the mixing process and ensuring that they are evenly dispersed in the rubber matrix; S3. The mixed rubber material is taken out and placed into a mold for preforming. The purpose of preforming is to give the material a preliminary shape to facilitate subsequent vulcanization molding; S4. The preformed rubber material is placed in a vulcanizer for high temperature and high pressure vulcanization at 160-180°C for 15-35 minutes; S5. Wash, dry and grind the vulcanized rubber material to obtain modified fluorosilicone rubber material.

3. The tear-resistant high-elastic fluorosilicone rubber according to claim 2, characterized in that: The reinforcing agent is a mixture of carbon black N330 and nano silicon dioxide, and the mass ratio of the carbon black N330 to the nano silicon dioxide is 1.8-2.5:1.

1.

4. The tear-resistant high-elastic fluorosilicone rubber according to claim 2, characterized in that: The plasticizer is di(2-ethylhexyl) phthalate and / or di(2-ethylhexyl) terephthalate.

5. The tear-resistant high-elastic fluorosilicone rubber according to claim 2, characterized in that: The mass ratio of the reinforcing agent, the plasticizer and the maleic anhydride modifier is (1.5-2):(1.2-1.5):1.

1.

6. The tear-resistant high-elastic fluorosilicone rubber according to claim 1, characterized in that: The filler is prepared by compounding amino multi-walled carbon nanotubes, nano-scale boehmite powder and graphene oxide in a mass ratio of 1.3:(1.5-2):(2-2.5).

7. The tear-resistant high-elastic fluorosilicone rubber according to claim 1, characterized in that: The interface modifier is at least one of γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, and bis-[γ-(triethoxysilyl)propyl]tetrasulfide.

8. The tear-resistant high-elastic fluorosilicone rubber according to claim 1, characterized in that: The vulcanizing agent is at least one of ZIMAG29 / 43, vulcanizing agent DCP and vulcanizing agent bisphenol AF.

9. The tear-resistant high-elastic fluorosilicone rubber according to claim 1, characterized in that: The antioxidant is at least one of antioxidant RD and antioxidant MD; The accelerator is at least one of accelerator DM, accelerator D and accelerator TS.

10. A method for preparing tear-resistant high-elastic fluorosilicone rubber, preparing the tear-resistant high-elastic fluorosilicone rubber as claimed in any one of claims 1 to 9, characterized in that: The following steps are also included: S1. According to the weight of the raw materials, the modified fluorosilicone rubber material, filler and interface modifier are put into a kneader and stirred at 50-55 ° C and 35-50 rpm / min for 10-15min to obtain a premix; S2. The premix is ​​put into an internal mixer for mixing, and white carbon is added, the temperature is controlled at 70-80 ° C, mixed for 10-15 minutes, and then an antioxidant is added and mixed until uniform after the internal mixer is discharged to obtain a mixed rubber compound; S3. Put the mixed rubber into an open mixer, add vulcanizing agent and accelerator, control the temperature at 120-145°C, mix evenly, and obtain tear-resistant high-elastic fluorosilicone rubber.

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