Modified hybrid filler, brominated butyl rubber composite material as well as preparation method and application of brominated butyl rubber composite material

Abstract

The invention discloses a modified hybrid filler, a brominated butyl rubber composite material and a preparation method and application thereof. The modified hybrid filler comprises modified graphene, modified carbon black and brominated butyl rubber in a weight ratio of 1: (12-25): (0.02-0.3). The modified graphene is a product obtained by modifying graphene with a silane coupling agent; the modified carbon black is a product obtained by modifying carbon black with a silane coupling agent. When the modified hybrid filler is used for preparing the brominated butyl rubber composite material, the modified graphene and the modified carbon black are uniformly dispersed in the brominated butyl rubber, and meanwhile, the brominated butyl rubber in the modified graphene, the modified carbon black and the modified hybrid filler forms a stable net structure; the modified hybrid filler is promoted to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, so that a compact and stable net-shaped structure is favorably formed in the brominated butyl rubber composite material, and the air tightness of the brominated butyl rubber is further improved.

Description

Technical Field

[0001] The present invention relates to the field of material technology, and more specifically, to a modified hybrid filler, brominated butyl rubber composite material, and a preparation method and application thereof. Background Art

[0002] Gas insulated switchgear (GIS) is an indispensable component of the power system. The equipment encapsulates multiple components including circuit breakers, disconnectors, grounding switches, transformers, lightning arresters, busbars, connecting parts and outgoing terminals in a metal grounded protective shell and is filled with pressurized insulating gas (such as sulfur hexafluoride gas). GIS has been widely used in power facilities such as urban power grids, substations and power stations due to its small footprint, high reliability, simple maintenance and good safety. GIS has extremely strict requirements on sealing during operation, and the gas leakage rate needs to be controlled at an extremely low level, because the leakage of insulating gas caused by sealing failure will not only affect the insulation capacity of GIS, cause electrical failures, and endanger the stable operation of the power grid, but also cause environmental pollution, increase maintenance costs, and reduce the service life of GIS. Therefore, maintaining the high sealing of GIS is an important task in the design, production and operation stages.

[0003] Using sealing rings for sealing is an important measure for GIS to improve its own sealing performance. Bromobutyl rubber is used to prepare GIS sealing rings due to its excellent airtightness. However, during the long-term operation of GIS, especially under complex working conditions such as temperature changes and pressure fluctuations, the sealing rings prepared with bromobutyl rubber have a certain degree of slow gas leakage, which cannot guarantee electrical insulation performance and safe operation. In other words, the airtightness of bromobutyl rubber needs to be improved.

[0004] Therefore, it is of great significance to develop a modified hybrid filler for brominated butyl rubber to improve the air tightness of brominated butyl rubber. Summary of the invention

[0005] The purpose of the present invention is to solve the problem of poor air tightness of brominated butyl rubber in the prior art, and to provide a modified hybrid filler, a brominated butyl rubber composite material, and a preparation method and application thereof.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

[0007] In a first aspect, the present invention provides a modified hybrid filler comprising modified graphene, modified carbon black and brominated butyl rubber in a weight ratio of 1:(12-25):(0.02-0.3);

[0008] The modified graphene is a product of graphene modified by a silane coupling agent;

[0009] The modified carbon black is a product of carbon black modified by a silane coupling agent.

[0010] The invention comprises a modified hybrid filler of modified graphene, modified carbon black and brominated butyl rubber in a specific weight ratio. When used for preparing a brominated butyl rubber composite material, the modified graphene and modified carbon black are uniformly dispersed in the brominated butyl rubber, and the brominated butyl rubber in the modified graphene, modified carbon black and modified hybrid filler forms a stable network structure, and the modified hybrid filler is promoted to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, thereby facilitating the formation of a dense and stable network structure inside the brominated butyl rubber composite material, thereby improving the air tightness of the brominated butyl rubber.

[0011] Specifically, in the modified graphene and / or modified carbon black of the present invention, the presence of the silane coupling agent can not only wrap the graphene and / or carbon black, thereby helping the modified graphene and modified carbon black to be uniformly dispersed in the brominated butyl rubber and not easily agglomerated; and the silane coupling agent can also connect the modified graphene, the modified carbon black and the brominated butyl rubber in the modified hybrid filler through reaction to form a stable network structure, and at the same time promote the modified hybrid filler to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, thereby helping the brominated butyl rubber composite material to form a dense and stable network structure, thereby improving the air tightness of the brominated butyl rubber.

[0012] Preferably, the weight ratio of the modified graphene, modified carbon black and brominated butyl rubber is 1:(12-20):(0.02-0.2).

[0013] More preferably, the weight ratio of the modified graphene, modified carbon black and brominated butyl rubber is 1:(12-20):0.2.

[0014] Preferably, in the modified graphene, the weight ratio of graphene to silane coupling agent is 1:(1-3).

[0015] More preferably, in the modified graphene, the weight ratio of graphene to silane coupling agent is 1:(1.5-2.5).

[0016] More preferably, in the modified graphene, the weight ratio of graphene to silane coupling agent is 1:(1.5-2).

[0017] Preferably, in the modified carbon black, the weight ratio of carbon black to silane coupling agent is 15:(0.3-2).

[0018] More preferably, in the modified carbon black, the weight ratio of carbon black to silane coupling agent is 15:(0.7-1.5).

[0019] More preferably, in the modified carbon black, the weight ratio of carbon black to silane coupling agent is 15:(0.7-1).

[0020] Preferably, the silane coupling agent is at least one of γ-aminopropyltriethoxysilane (KH-550), bis-[3-(triethoxysilyl)propyl]-tetrasulfide (Si-69), 3-mercaptopropyltrimethoxysilane (KH-590), 3-mercaptopropyltriethoxysilane (KH-580), N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane (KH-602), N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (KH-792), and N-(3-trimethoxysilylpropyl)ethylenediamine (TM SPEDA).

[0021] Preferably, the average particle size D of the graphene 50 ≤50μm.

[0022] More preferably, the average particle size D of the graphene 50 ≤10μm.

[0023] Preferably, the average particle size of the carbon black is 10 nm-20 μm.

[0024] More preferably, the average particle size of the carbon black is 10nm-500nm.

[0025] Preferably, the preparation method of the modified graphene is: mixing graphene and a silane coupling agent, heating and reacting to obtain the modified graphene.

[0026] More preferably, the weight ratio of the graphene to the silane coupling agent is 1:(1-3).

[0027] More preferably, the weight ratio of the graphene to the silane coupling agent is 1:(1.5-2.5), specifically 1:(1.5-2).

[0028] More preferably, the heating temperature is 40-60°C.

[0029] More preferably, the reaction time is ≥ 2 h, specifically 2-4 h.

[0030] More preferably, the heating reaction is carried out under the protection of an inert gas.

[0031] More preferably, the graphene is dispersed in a liquid to prepare a graphene suspension before use.

[0032] More preferably, the liquid is at least one of water, ethanol, methanol and acetonitrile.

[0033] More preferably, the dispersion is performed by ultrasonic treatment for 30-60 min.

[0034] More preferably, the silane coupling agent is dissolved in a solvent to prepare a silane coupling agent solution before use.

[0035] More preferably, the solvent is at least one of water, ethanol, methanol and acetonitrile.

[0036] More preferably, the mass concentration of the silane coupling agent solution is 1-5wt%.

[0037] More preferably, after the heating reaction, the product is separated, washed and dried. The separation is achieved by filtering and / or centrifuging; the washing is performed 3-5 times; the washing agent used in the washing is at least one of ethanol and acetone, and the weight ratio of the washing agent to the graphene is (5-10):1.

[0038] Preferably, the preparation method of the modified carbon black is: mixing carbon black and a silane coupling agent, heating and reacting to obtain the modified carbon black.

[0039] More preferably, the weight ratio of the carbon black to the silane coupling agent is 15:(0.3-2).

[0040] More preferably, the weight ratio of the carbon black to the silane coupling agent is 15:(0.7-1.5), specifically 15:(0.7-1).

[0041] More preferably, the heating temperature is 45-55°C.

[0042] More preferably, the reaction time is ≥ 2 h, specifically 2-4 h.

[0043] More preferably, the carbon black is dried before use and then dispersed in an organic solvent to prepare a carbon black suspension.

[0044] More preferably, the drying temperature is 100-150° C., and the drying time is 2-4 hours.

[0045] More preferably, the dispersion is performed by ultrasonic treatment for 30-60 min.

[0046] More preferably, the organic solvent is at least one of toluene, ethanol, methanol and acetonitrile.

[0047] More preferably, the silane coupling agent is dissolved in a solvent to prepare a silane coupling agent solution before use.

[0048] More preferably, the solvent is at least one of water, ethanol, methanol and acetonitrile.

[0049] More preferably, the mass concentration of the silane coupling agent solution is 2-6 wt %.

[0050] More preferably, after the heating reaction, the product is separated, washed and dried. The separation is achieved by filtering and / or centrifuging; the washing is performed 2-4 times; the washing agent used in the washing is at least one of ethanol, acetone and water, and the weight ratio of the washing agent to the carbon black is (3-8):1.

[0051] In a second aspect, the present invention provides a method for preparing a modified hybrid filler, comprising:

[0052] The modified graphene, modified carbon black and brominated butyl rubber are mixed and heated for reaction to obtain the modified hybrid filler.

[0053] Preferably, the heating temperature is 60-70°C.

[0054] Preferably, the reaction time is 8-12 hours.

[0055] Preferably, the mixing stirring speed is 200-500 r / min.

[0056] Preferably, the method for preparing the modified hybrid filler comprises: mixing modified graphene, modified carbon black and brominated butyl rubber in a solvent, heating to react, and removing the solvent to obtain the modified hybrid filler.

[0057] More preferably, the solvent is at least one of water, toluene, xylene, dichloromethane, chloroform and n-hexane.

[0058] In the present invention, the method for removing the solvent includes but is not limited to at least one of rotary evaporation, reduced pressure distillation, and freeze drying.

[0059] In a third aspect, the present invention provides an application of a modified hybrid filler in rubber.

[0060] In a fourth aspect, the present invention provides a brominated butyl rubber composite material, which comprises the following components, calculated by weight:

[0061] 90-120 parts of brominated butyl rubber, 60-80 parts of modified hybrid filler, and 1-2 parts of vulcanizing agent.

[0062] Preferably, the brominated butyl rubber composite material comprises the following components, calculated by weight:

[0063] 100-120 parts of brominated butyl rubber, 70-80 parts of modified hybrid filler, and 1.5-2 parts of vulcanizing agent.

[0064] The commonly used vulcanizing agents in the art can be used in the present invention, including but not limited to at least one of N,N'-m-phenylene bismaleimide (HVA-2), N,N'-m-phenylene bismaleimide, N-phenylmaleimide, triallyl cyanurate (TAC), and triallyl isocyanurate (TAiC).

[0065] In a fifth aspect, the present invention provides a method for preparing a brominated butyl rubber composite material, comprising:

[0066] S1. heating and mixing the brominated butyl rubber and the modified hybrid filler to obtain a rubber mixture;

[0067] S2. Mix the mixed rubber and the vulcanizing agent, and perform vulcanization to obtain a brominated butyl rubber composite material.

[0068] Preferably, in step S1, the heating and mixing is performed at a temperature of 50-70°C, a rotation speed of 40-60 r / min, and a time of 5-10 min.

[0069] Preferably, in step S1, after the heating and kneading is completed, the temperature is further raised to 100-120°C.

[0070] Preferably, in step S2, the vulcanization temperature is 185-195°C, the pressure is 6-14 MPa, and the time is 10-15 min.

[0071] In a sixth aspect, the present invention provides an application of a brominated butyl rubber composite material in a gas insulated switchgear.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] The invention comprises a modified hybrid filler of modified graphene, modified carbon black and brominated butyl rubber in a specific weight ratio. When used for preparing a brominated butyl rubber composite material, the modified graphene and modified carbon black are uniformly dispersed in the brominated butyl rubber, and the brominated butyl rubber in the modified graphene, modified carbon black and modified hybrid filler forms a stable network structure, and the modified hybrid filler is promoted to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, thereby facilitating the formation of a dense and stable network structure inside the brominated butyl rubber composite material, thereby improving the air tightness of the brominated butyl rubber.

[0074] Specifically, in the modified graphene and / or modified carbon black of the present invention, the presence of the silane coupling agent can not only wrap the graphene and / or carbon black, thereby helping the modified graphene and modified carbon black to be uniformly dispersed in the brominated butyl rubber and not easily agglomerated; and the silane coupling agent can also connect the modified graphene, the modified carbon black and the brominated butyl rubber in the modified hybrid filler through reaction to form a stable network structure, and at the same time promote the modified hybrid filler to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, thereby helping the brominated butyl rubber composite material to form a dense and stable network structure, thereby improving the air tightness of the brominated butyl rubber. DETAILED DESCRIPTION

[0075] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0076] The experimental methods in the following examples without specifying specific conditions are generally carried out according to conventional conditions in the art or according to conditions recommended by the manufacturer; the raw materials, reagents, etc. used, unless otherwise specified, are all raw materials and reagents that can be obtained from commercial channels such as conventional markets.

[0077] In each embodiment and comparative example of the present invention, the use of reagents is as follows:

[0078] Graphene, SE1430, average particle size D 50 <10μm, Changzhou Sixth Element Materials Technology Co., Ltd.;

[0079] Carbon black, N774, Cabot, USA;

[0080] Bromobutyl rubber, BIIR2828, Shandong Chambord Petrochemical Co., Ltd.;

[0081] Curing agent, N,N'-phenylene bismaleimide (HVA-2), PDM-100, Xianyang Sanjing Technology Co., Ltd.

[0082] Example 1

[0083] This embodiment provides a modified hybrid filler, comprising modified graphene, modified carbon black and brominated butyl rubber in a weight ratio of 1:20:0.2;

[0084] The modified graphene is a product of graphene modified by silane coupling agent γ-aminopropyltriethoxysilane (KH-550); the modified carbon black is a product of carbon black modified by silane coupling agent γ-aminopropyltriethoxysilane (KH-550); in the modified graphene, the weight ratio of graphene to the silane coupling agent KH-550 is 1:2; in the modified carbon black, the weight ratio of carbon black to the silane coupling agent KH-550 is 15:1;

[0085] The preparation method of the modified graphene is:

[0086] S1. Add graphene to deionized water and disperse it by ultrasonic treatment for 30 min to obtain a graphene suspension for standby use; the weight ratio of graphene to deionized water is 1:100;

[0087] S2. γ-aminopropyltriethoxysilane (KH-550) was added to a mixed solution of ethanol and water in a volume ratio of 1:1, and stirred to dissolve to obtain a silane coupling agent solution with a mass concentration of 5wt%;

[0088] S3. Under nitrogen protection, the graphene suspension was slowly added dropwise to the silane coupling agent solution to mix, and after the addition was completed, the mixture was heated to 50° C. for reaction for 4 h, the product was separated by centrifugation, washed three times with ethanol, the weight ratio of ethanol to graphene was 5:1, and dried in a vacuum oven at 55° C. to obtain modified graphene;

[0089] Wherein, the weight ratio of graphene to silane coupling agent KH-550 is 1:2;

[0090] The preparation method of the modified carbon black is:

[0091] (1) drying carbon black at 120° C. for 4 h to remove moisture and impurities, then adding the carbon black to toluene and dispersing the carbon black by ultrasonic treatment for 30 min to obtain a carbon black suspension for later use; the weight ratio of carbon black to toluene is 1:20;

[0092] (2) adding γ-aminopropyltriethoxysilane (KH-550) to a mixed solution of ethanol and water in a volume ratio of 1:1, stirring and dissolving, to obtain a silane coupling agent solution with a mass concentration of 6 wt%;

[0093] (3) slowly dropping the carbon black suspension into the silane coupling agent solution to mix, heating to 50° C. to react for 4 h after the dropping is completed, separating the product by centrifugation, washing with ethanol three times, the weight ratio of ethanol to carbon black being 5:1, and drying in a vacuum oven at 60° C. to obtain modified carbon black;

[0094] Among them, the weight ratio of carbon black to silane coupling agent KH-550 is 15:1;

[0095] The preparation method of the modified hybrid filler comprises:

[0096] In deionized water solvent, the modified graphene, modified carbon black and brominated butyl rubber were mixed at a stirring speed of 300 r / min for 3 minutes, heated at 60° C. for reaction for 8 hours, and the solvent was removed by rotary evaporation to obtain a modified hybrid filler.

[0097] Examples 2-5 and Comparative Examples 1-5

[0098] Examples 2-5 and Comparative Examples 1-5 provide different modified hybrid fillers, which differ from Example 1 in that the weight ratios of modified graphene, modified carbon black and brominated butyl rubber are different, and the rest are consistent with Example 1, as shown in the following table:

[0099] Table 1 Weight ratio of modified graphene, modified carbon black and brominated butyl rubber in Examples 1-5 and Comparative Examples 1-5

[0100]

[0101]

[0102] Examples 6-8 and Comparative Example 6

[0103] Examples 6-8 and Comparative Example 6 provide different modified hybrid fillers, which differ from Example 1 in that the weight ratio of graphene to silane coupling agent in the preparation method of modified graphene is different, and the rest is consistent with Example 1, as shown in the following table:

[0104] Table 2 Weight ratio of graphene to silane coupling agent in the preparation method of modified graphene in Examples 1, 6-8 and Comparative Example 6

[0105] Weight ratio of graphene to silane coupling agent Example 1 1:2 Example 6 1:1.5 Example 7 1:3 Example 8 1:1 Comparative Example 6 1:0

[0106] Examples 9-11 and Comparative Example 7

[0107] Examples 9-11 and Comparative Example 7 provide different modified hybrid fillers, which differ from Example 1 in that the weight ratio of carbon black to silane coupling agent in the preparation method of the modified carbon black is different, and the rest is consistent with Example 1, as shown in the following table:

[0108] Table 3 Weight ratio of carbon black to silane coupling agent in the preparation method of modified carbon black in Examples 1, 9-11 and Comparative Example 7

[0109]

[0110]

[0111] Example 12

[0112] This embodiment provides a modified hybrid filler, which differs from Embodiment 1 in that 3-mercaptopropyltriethoxysilane (KH-580) is used instead of γ-aminopropyltriethoxysilane (KH-550), and the rest is consistent with Embodiment 1.

[0113] Comparative Example 8

[0114] This comparative example provides a modified hybrid filler, which differs from Example 1 in that graphene is used instead of modified graphene, and carbon black is used instead of modified carbon black, and the rest is consistent with Example 1.

[0115] Application Example 1

[0116] This application example provides a brominated butyl rubber composite material, which includes the following components by weight:

[0117] 100 parts of brominated butyl rubber, 70 parts of the modified hybrid filler prepared in Example 1, and 1.5 parts of a vulcanizing agent (HVA-2);

[0118] The preparation method of the brominated butyl rubber composite material comprises:

[0119] S1. Mixing was performed using an internal mixer at 70°C and 60 r / min. First, bromobutyl rubber was added and mixed for 1 min. Then, the modified hybrid filler was added in 3 times. The interval between each addition was 1 min. The whole mixing process took 7 min. Then, the temperature was raised to 120°C and the rubber was discharged to obtain a mixed rubber.

[0120] S2. The mixed rubber was rolled out on an open mixing mill with the roller distance maintained at 2 mm. The vulcanizing agent (HVA-2) was added and stirred evenly. The mixed rubber was rolled out and transferred to a vulcanizing machine. The mixed rubber was vulcanized at 190°C and 10 MPa for 10 min to obtain a brominated butyl rubber composite material.

[0121] Application Example 2-12

[0122] Application Examples 2-12 provide different brominated butyl rubber composite materials, which differ from Application Example 1 in that Application Examples 2-12 use the modified hybrid fillers prepared in Examples 2-12 to replace the modified hybrid fillers prepared in Example 1, respectively, and the rest are consistent with Application Example 1.

[0123] Application Example 13

[0124] This application example provides a brominated butyl rubber composite material, which includes the following components by weight:

[0125] 90 parts of brominated butyl rubber, 60 parts of the modified hybrid filler prepared in Example 1, and 1 part of a vulcanizing agent (HVA-2);

[0126] The preparation method of the above brominated butyl rubber composite material is consistent with that of Application Example 1.

[0127] Application Example 14

[0128] This application example provides a brominated butyl rubber composite material, which includes the following components by weight:

[0129] 120 parts of brominated butyl rubber, 80 parts of the modified hybrid filler prepared in Example 1, and 2 parts of a vulcanizing agent (HVA-2);

[0130] The preparation method of the above brominated butyl rubber composite material is consistent with that of Application Example 1.

[0131] Comparative Application Examples 1-8

[0132] Comparative Application Examples 1-8 provide different brominated butyl rubber composite materials, which differ from Application Example 1 in that Comparative Application Examples 1-8 use the modified hybrid fillers prepared in Comparative Examples 1-8 to replace the modified hybrid fillers prepared in Example 1, respectively, and the rest are consistent with Application Example 1.

[0133] Comparative Application Example 9

[0134] This comparative application example provides a brominated butyl rubber composite material, which includes the following components in parts by weight:

[0135] 100 parts of brominated butyl rubber, 70 parts of hybrid filler, 1.5 parts of vulcanizing agent (HVA-2);

[0136] The hybrid filler comprises a graphene mixture, a carbon black mixture and brominated butyl rubber in a weight ratio of 1:20:0.2; the graphene mixture comprises graphene and a silane coupling agent γ-aminopropyltriethoxysilane (KH-550) in a weight ratio of 1:2; the carbon black mixture comprises carbon black and a silane coupling agent γ-aminopropyltriethoxysilane (KH-550) in a weight ratio of 15:1;

[0137] The preparation method of the brominated butyl rubber composite material comprises:

[0138] S1. Mixing was performed using an internal mixer at 70°C and 60 r / min. First, brominated butyl rubber was added and mixed for 1 min. Then, all the components of the hybrid filler (including graphene, carbon black, silane coupling agent KH-550 and brominated butyl rubber) were added in 3 times. The interval between each addition was 1 min. The whole mixing process took 7 min. Then, the temperature was raised to 120°C and the rubber was discharged to obtain a mixed rubber.

[0139] S2. The mixed rubber was rolled out on an open mixing mill with the roller distance maintained at 2 mm. The vulcanizing agent (HVA-2) was added and stirred evenly. The mixed rubber was rolled out and transferred to a vulcanizing machine. The mixed rubber was vulcanized at 190°C and 10 MPa for 10 min to obtain a brominated butyl rubber composite material.

[0140] Performance Testing

[0141] The performance tests of the brominated butyl rubber composite materials of each application example and comparative application example are as follows:

[0142] (1) Air tightness test experiment

[0143] The brominated butyl rubber composite material was made into a sample with a length of 150 mm, a width of 120 mm, and a height of 2 mm. Then, according to Appendix A (pressure sensor method) of GB / T1038.1-2022 standard, sulfur hexafluoride SF6 gas was used as the test gas for the experiment, and the corresponding gas permeability coefficient [unit: cm 3 cm / (cm 2 ·s·Pa)];

[0144] The smaller the gas permeability coefficient, the better the air tightness of the bromobutyl rubber composite material;

[0145] (2) Compression set test

[0146] According to GB / T 7759.1-2015 standard, the brominated butyl rubber composite material was made into a type B specimen for experiment, wherein the type B specimen was aged with hot air in an aging box at 120°C for 70h; and the corresponding compression set (%) was calculated;

[0147] The smaller the compression set, the better the durability of the bromobutyl rubber composite material;

[0148] (3) Tensile strength test

[0149] According to GB / T 528-2009 standard, the brominated butyl rubber composite material was made into a dumbbell-shaped specimen of type 1 for testing, and the corresponding tensile strength (unit: MPa) was calculated;

[0150] The experimental results are shown in the following table:

[0151] Table 4 Performance test results of brominated butyl rubber composite materials in various application examples and comparative application examples

[0152]

[0153]

[0154] As can be seen from Table 4, the modified hybrid filler of the present invention including modified graphene, modified carbon black and brominated butyl rubber in a specific weight ratio is used to prepare a brominated butyl rubber composite material, so that the modified graphene and modified carbon black are uniformly dispersed in the brominated butyl rubber, and the brominated butyl rubber in the modified graphene, modified carbon black and modified hybrid filler forms a stable network structure, and promotes the modified hybrid filler to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, thereby helping to form a dense and stable network structure inside the brominated butyl rubber composite material, thereby improving the air tightness of the brominated butyl rubber.

[0155] Specifically, in the modified graphene and / or modified carbon black of the present invention, the presence of the silane coupling agent can not only wrap the graphene and / or carbon black, thereby helping the modified graphene and modified carbon black to be uniformly dispersed in the brominated butyl rubber and not easily agglomerated; and the silane coupling agent can also connect the modified graphene, the modified carbon black and the brominated butyl rubber in the modified hybrid filler through reaction to form a stable network structure, and at the same time promote the modified hybrid filler to be uniformly dispersed in the brominated butyl rubber of the brominated butyl rubber composite material, thereby helping the brominated butyl rubber composite material to form a dense and stable network structure, thereby improving the air tightness of the brominated butyl rubber.

[0156] Meanwhile, the compression permanent deformation of the brominated butyl rubber composite material of the present invention is ≤20%, indicating that it has good durability, which not only means that the brominated butyl rubber composite material of the present invention has a long service life, but also means that the sealing ring prepared by using the brominated butyl rubber composite material of the present invention can still maintain good air tightness after long-term pressure use, so that the GIS can operate stably for a long time.

[0157] In addition, the tensile strength of the brominated butyl rubber composite material of the present invention is ≥9.5 MPa, indicating that the brominated butyl rubber composite material has good mechanical properties.

[0158] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A modified hybrid filler, characterized in that: The invention comprises modified graphene, modified carbon black and brominated butyl rubber in a weight ratio of 1:(12-25):(0.02-0.3); The modified graphene is a product of graphene modified by a silane coupling agent; The modified carbon black is a product of carbon black modified by a silane coupling agent.

2. The modified hybrid filler according to claim 1, characterized in that: Including at least one of the following (1)-(4): (1) The weight ratio of the modified graphene, modified carbon black and brominated butyl rubber is 1:(12-20):(0.02-0.2); (2) In the modified graphene, the weight ratio of graphene to silane coupling agent is 1:(1-3); (3) In the modified carbon black, the weight ratio of carbon black to silane coupling agent is 15:(0.3-2); (4) The silane coupling agent is at least one of γ-aminopropyltriethoxysilane, bis-[3-(triethoxysilyl)propyl]-tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and N-(3-trimethoxysilylpropyl)ethylenediamine.

3. The modified hybrid filler according to claim 2, characterized in that: Including at least one of the following (1)-(3): (1) The weight ratio of the modified graphene, the modified carbon black and the brominated butyl rubber is 1:(12-20):0.2; (2) In the modified graphene, the weight ratio of graphene to silane coupling agent is 1:(1.5-2.5); (3) In the modified carbon black, the weight ratio of carbon black to silane coupling agent is 15:(0.7-1.5).

4. The modified hybrid filler according to claim 3, characterized in that: Include at least one of the following (1)-(2): (1) In the modified graphene, the weight ratio of graphene to silane coupling agent is 1:(1.5-2); (2) In the modified carbon black, the weight ratio of carbon black to silane coupling agent is 15:(0.7-1).

5. The modified hybrid filler according to claim 1, characterized in that: Include at least one of the following (1)-(2): (1) The preparation method of the modified graphene is: mixing graphene and a silane coupling agent, heating and reacting, thereby obtaining the modified graphene; (2) The preparation method of the modified carbon black is: mixing carbon black and a silane coupling agent, heating and reacting to obtain the modified carbon black.

6. The method for preparing the modified hybrid filler according to any one of claims 1 to 5, characterized in that: include: The modified graphene, modified carbon black and brominated butyl rubber are mixed and heated for reaction to obtain the modified hybrid filler.

7. Use of the modified hybrid filler as claimed in any one of claims 1 to 5 in rubber.

8. A brominated butyl rubber composite material, characterized in that: Calculated by weight, it includes the following components: 90-120 parts of brominated butyl rubber, 60-80 parts of the modified hybrid filler as claimed in any one of claims 1 to 5, and 1-2 parts of a vulcanizing agent.

9. The method for preparing the brominated butyl rubber composite material according to claim 8, characterized in that: include: S1. heating and mixing the brominated butyl rubber and the modified hybrid filler to obtain a rubber mixture; S2. Mix the mixed rubber and the vulcanizing agent, and perform vulcanization to obtain a brominated butyl rubber composite material.

10. Use of the brominated butyl rubber composite material as claimed in claim 8 in a gas insulated switchgear.

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