Antioxidant-grafted MXene / rubber composition, antioxidant-grafted MXene / rubber and preparation method

Abstract

The present invention relates to an antioxidant-grafted MXene / rubber composition, antioxidant-grafted MXene / rubber and a preparation method thereof. The antioxidant-grafted MXene / rubber composition comprises the following components: a rubber matrix, antioxidant-grafted MXene, a reinforcing filler, a vulcanizing agent, and a plasticizer; wherein, the rubber matrix is hydrogenated nitrile rubber; the antioxidant is a long-chain antioxidant; relative to 100 parts by weight of the rubber matrix, the weight parts of the reinforcing filler are 20-100 parts, the weight parts of the antioxidant-grafted MXene are 2-10 parts, the weight parts of the vulcanizing agent are 0.1-5 parts, and the weight parts of the plasticizer are 5-40 parts. The composition selects hydrogenated nitrile rubber with less double bond content and more excellent aging resistance as the matrix material; and the combination of long-chain antioxidant-grafted MXene and flaky reinforcing filler with a larger aspect ratio forms an effective filler network, which is beneficial to improving the oil resistance. The long-chain antioxidant has the function of preventing migration, achieving the effects of aging resistance and migration prevention.

Description

Technical Field

[0001] The present invention belongs to the field of rubber nanocomposites, and specifically relates to an antioxidant-grafted MXene / rubber composition, an antioxidant-grafted MXene / rubber, and a preparation method. Background Art

[0002] Currently, 110kV-750kV oil-filled electrical equipment frequently experiences aging and micro-leakage in rubber seals, posing operational risks. Removing and replacing rubber seals often involves complex processes such as power outages and assembly and disassembly, consuming significant manpower and financial resources. Furthermore, small molecules such as antioxidants contained in traditional rubber seals are susceptible to migration during use due to compatibility issues with the rubber molecular chain, impacting the performance of both the rubber seal and the oil. Therefore, the development of a long-life, aging-resistant, and migration-resistant rubber sealing material is urgently needed.

[0003] Currently, the most commonly used sealing rubber base material is nitrile rubber. Because it contains the polar acrylonitrile component, nitrile rubber's oil resistance increases with increasing acrylonitrile content. However, nitrile rubber also contains butadiene, which has a high content of carbon-carbon double bonds. In actual use, it is prone to aging, cracking, or excessive cross-linking, ultimately resulting in reduced seal elasticity, increased compression set, and decreased sealing performance. Therefore, there is an urgent need to develop oil-resistant sealing rubber based on a rubber with superior aging resistance.

[0004] The presence of a filler network within the rubber matrix not only enhances mechanical properties but also occupies the free volume between rubber molecular chains, reducing the penetration of small gas and liquid molecules and improving sealing performance. However, traditional fillers are primarily spherical carbon black and white carbon black, which form a relatively weak filler network. Furthermore, antioxidants are the most important component in improving the aging life of sealing rubber. Traditional antioxidants have poor compatibility with the rubber matrix. Once a certain component is exceeded, the small antioxidant molecules will migrate out, causing frosting. During use, these small antioxidant molecules will continue to migrate out, ultimately causing a decline in the rubber's aging performance. Simultaneously, these migrated small antioxidant molecules will enter the oil phase, reducing the oil's quality.

[0005] Based on the above research background, existing rubbers have problems such as easy migration of antioxidants, poor oil resistance, and poor aging resistance, which cannot meet sealing requirements. It is urgent to develop a rubber with improved performance. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides an antioxidant-grafted MXene / rubber composition comprising the following components:

[0007] Rubber matrix, antioxidant grafted MXene, reinforcing filler, vulcanizer, plasticizer;

[0008] Among them, the rubber matrix is hydrogenated nitrile rubber; the anti-aging agent in the anti-aging agent grafted MXene is a long-chain anti-aging agent;

[0009] Relative to 100 parts by weight of the rubber matrix, the weight parts of the reinforcing filler are 20-100 parts, the weight parts of the anti-aging agent grafted MXene are 2-10 parts, the weight parts of the vulcanizing agent are 0.1-5 parts, and the weight parts of the plasticizer are 5-40 parts.

[0010] MXene is a new type of two-dimensional material composed of transition metals (such as titanium, molybdenum, vanadium, etc.) and carbon or nitrogen, and its surface often has functional groups such as oxygen (-O), fluorine (-F) or hydroxyl (-OH), etc., with both metal conductivity, hydrophilicity and high mechanical strength.

[0011] Preferably, the hydrogenation degree of the hydrogenated nitrile rubber is 80-100%.

[0012] The hydrogenation degree of the hydrogenated nitrile rubber is 80-100%, which can meet the requirements of sulfur vulcanization, peroxide vulcanization, and the combination of both.

[0013] Preferably, the anti-aging agent grafted MXene is prepared by the following steps:

[0014] Weigh the MXene aqueous dispersion, add a small molecule with a carboxyl or amino group at one end and a thiol group at the other end, stir well and react at a temperature of 80-100 °C for 0.5-8 h. After the reaction, filter, wash, and dry to obtain MXene with a thiol group on the surface;

[0015] Ultrasonically disperse the MXene with a thiol group on the surface in a solvent, add an anti-aging agent, stir well and react at a temperature of 50-100 °C for 1-10 h. After the reaction, filter, wash, and dry to obtain the anti-aging agent grafted MXene.

[0016] Preferably, the small molecule with a carboxyl or amino group at one end and a thiol group at the other end includes one or more of small molecules such as 3-mercaptopropionic acid, mercaptobutyric acid, mercaptohexanoic acid, carboxyl-poly(2-ethyl-2-oxazoline)-thiol, mercaptopropylamine, mercaptobutylamine, and cysteine.

[0017] Preferably, the long chain of the long-chain anti-aging agent is an alkyl chain or a long chain containing other heteroatoms, and contains more than one double bond.

[0018] Preferably, the long-chain anti-aging agent is one or more of BH-F77, AITC-PPD, NDM-6PPD, and CGE-6PPD.

[0019] The antioxidant-grafted MXene first chemically modifies MXene by introducing small molecules with a carboxyl or amino group at one end and a thiol group at the other end. Further, through chemical bonding, a long-chain antioxidant containing a carbon-carbon double bond is chemically grafted onto the surface of MXene. The carboxyl or amino group of the small molecule can react with the hydroxyl groups on the surface of MXene, and the thiol group can react with the carbon-carbon double bond of the antioxidant, resulting in antioxidant-grafted MXene grafted with a long-chain antioxidant, which maximally restricts the migration of the antioxidant, thereby improving the performance of the rubber.

[0020] Preferably, the reinforcing filler is one or more of carbon black, silica, calcium carbonate, clay, graphene, hydrotalcite, and carbon nanotubes.

[0021] Compared with traditional fillers such as spherical carbon black and silica, sheet-like fillers with a larger aspect ratio such as clay, graphene, and hydrotalcite form a weaker filler network. Therefore, constructing a more perfect filler network based on sheet-like fillers is more beneficial for improving oil resistance.

[0022] Preferably, the vulcanizing agent is one or more of sulfur and vulcanization accelerators, di-tert-butyl peroxide, dicumyl peroxide, bis(tert-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0023] Preferably, the plasticizer is one or more of trioctyl trimellitate, dibutyl diglycol adipate, dioctyl sebacate, D810, Aflux25, and liquid nitrile rubber.

[0024] The present invention also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above, comprising the following steps:

[0025] Mix the antioxidant-grafted MXene, hydrogenated nitrile rubber, reinforcing filler, vulcanizing agent, and plasticizer uniformly in a mixing device to obtain a mixed rubber, and fully crosslink the mixed rubber at 150 - 200 °C to obtain antioxidant-grafted MXene / rubber.

[0026] Preferably, the mixing device is one of an internal mixer, an open mill, and a kneader.

[0027] The present invention also provides an antioxidant-grafted MXene / rubber prepared using the composition or the preparation method described above.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] In the selection of the rubber matrix for the antioxidant-grafted MXene / rubber composition of the present invention, hydrogenated nitrile rubber with a lower double bond content and more excellent aging resistance is selected as the matrix material; at the same time, a new type of filler MXene with oil-resistant hydroxyl groups on the surface and excellent oil resistance is selected. Compared with traditional lamellar fillers, MXene is an inorganic particle with more excellent oil resistance and aging resistance, which enhances the ability of the filler network to hinder the penetration of small molecules. At the same time, sheet-shaped reinforcing fillers with a larger aspect ratio are used, and the composed filler network is more conducive to improving oil resistance. The long-chain antioxidant can effectively prevent the migration of the antioxidant, achieving the effects of aging resistance and anti-migration.

[0030] The preparation method of the antioxidant-grafted MXene / rubber of the present invention is simple in operation and mild in reaction conditions, and is suitable for wide promotion. Detailed implementation manners

[0031] The following embodiments are provided to better further understand the present invention, which are not limited to the best implementation manner, and do not limit the content and protection scope of the present invention. Any product obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with those of other existing technologies and being the same as or similar to the present invention falls within the protection scope of the present invention.

[0032] For those not specifying specific experimental steps or conditions in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in the art can be followed.

[0033] Example 1

[0034] This example provides an antioxidant-grafted MXene / rubber composition, including the following components:

[0035] 100 parts of hydrogenated nitrile rubber with 80% hydrogenation degree, 40 parts of reinforcing filler, 7 parts of antioxidant-grafted MXene, 1 part of vulcanizing agent, and 5 parts of plasticizer. The reinforcing filler is carbon black; the vulcanizing agent is sulfur and vulcanization accelerator; the plasticizer is dioctyl sebacate; the antioxidant is BH-F77 long-chain antioxidant.

[0036] The vulcanization accelerator is a common vulcanization accelerator used in combination with sulfur. In this example, the following examples and comparative examples, the vulcanization accelerator is MBTS.

[0037] The antioxidant-grafted MXene is prepared through the following steps:

[0038] (1) 3-mercaptopropionic acid (molar ratio of terminal functional groups 1:2) was added to the MXene aqueous dispersion, stirred thoroughly, and reacted at 80 °C for 6 h. After the reaction, the product was obtained by filtration and further washed three times with deionized water. The product was dried in a vacuum oven for 10 h to obtain MXene with thiol groups on its surface;

[0039] (2) The MXene platelet particles with thiol groups on their surface were further ultrasonically dispersed in ethanol, and the long-chain antioxidant BH-F77 was added. After thorough stirring, the mixture was reacted at 60 °C for 8 h. After the reaction, the product was obtained by filtration and further washed five times with ethanol. The product was dried in a vacuum oven for 6 h to obtain MXene grafted with the long-chain antioxidant BH-F77.

[0040] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0041] 100 parts of hydrogenated nitrile rubber with 80% hydrogenation degree, 40 parts of carbon black, 7 parts of MXene grafted with the long-chain antioxidant BH-F77, 1 part of sulfur and vulcanization accelerator, and 5 parts of dioctyl sebacate were kneaded evenly in a mixer to obtain a kneaded rubber compound. Further, the kneaded rubber compound was fully crosslinked at 170 °C to obtain a composite material of MXene grafted with the long-chain antioxidant BH-F77 / hydrogenated nitrile rubber.

[0042] Comparative Example 1

[0043] This comparative example provides a rubber, and its preparation method is as follows:

[0044] 100 parts of nitrile rubber, 40 parts of carbon black, 5 parts of MXene, 1 part of sulfur and vulcanization accelerator, 2 parts of small molecule antioxidant 4020, 5 parts of dioctyl sebacate, etc. were kneaded evenly in a mixer to obtain a kneaded rubber compound. The kneaded rubber compound was fully crosslinked at 170 °C to obtain a composite material of small molecule antioxidant 4020 / MXene / hydrogenated nitrile rubber.

[0045] Example 2

[0046] This example provides an antioxidant-grafted MXene / rubber composition, which includes the following components:

[0047] 100 parts of hydrogenated nitrile rubber with 85% hydrogenation degree, 50 parts of reinforcing filler, 8 parts of antioxidant-grafted MXene, 2 parts of vulcanizing agent, and 6 parts of plasticizer. The reinforcing filler is silica, the vulcanizing agent is sulfur and vulcanization accelerator; the plasticizer is trioctyl trimellitate; the antioxidant is the long-chain antioxidant AITC-PPD.

[0048] The antioxidant-grafted MXene is prepared through the following steps:

[0049] (1)Add mercaptobutyric acid (molar ratio of terminal functional groups 1:3) to the MXene aqueous dispersion, stir well and react at 90 °C for 8 h. After the reaction, filter to obtain the product, and further wash it 4 times with deionized water. Dry the product in a vacuum oven for 8 h to obtain MXene with thiol groups on the surface;

[0050] (2)Further ultrasonically disperse the MXene with thiol groups on the surface in a mixed solution of methanol and ethanol, add the AITC-PPD long-chain antioxidant, stir well and react at 70 °C for 10 h. After the reaction, filter to obtain the product, and further wash it 3 times with the mixed solution of methanol and ethanol. Dry the product in a vacuum oven for 5 h to obtain AITC-PPD long-chain antioxidant grafted MXene;

[0051] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0052] Mix 100 parts of hydrogenated nitrile rubber with 85% hydrogenation degree, 50 parts of silica, 8 parts of AITC-PPD long-chain antioxidant grafted MXene, 2 parts of sulfur and vulcanization accelerator, 6 parts of trioctyl trimellitate, etc. in a mixer to obtain a mixed rubber. Further crosslink the mixed rubber at 175 °C to obtain an AITC-PPD long-chain antioxidant grafted MXene / hydrogenated nitrile rubber composite.

[0053] Comparative Example 2

[0054] This comparative example provides a rubber, and its preparation method is as follows:

[0055] Mix 100 parts of nitrile rubber, 50 parts of silica, 6 parts of MXene, 2 parts of small molecule antioxidant 4010NA, 2 parts of sulfur and vulcanization accelerator, 6 parts of trioctyl trimellitate, etc. in a mixer to obtain a mixed rubber.

[0056] Crosslink the mixed rubber at 175 °C to obtain a small molecule antioxidant 4010NA / MXene / hydrogenated nitrile rubber composite.

[0057] Example 3

[0058] This example provides an antioxidant-grafted MXene / rubber composition, which includes the following components:

[0059] 100 parts of hydrogenated nitrile rubber with 90% hydrogenation degree, 55 parts of reinforcing filler, 7 parts of antioxidant-grafted MXene, 3 parts of vulcanizing agent, 6 parts of plasticizer. The reinforcing filler is calcium carbonate; the vulcanizing agent is sulfur and vulcanization accelerator; the plasticizer is dibutyl diglycol adipate; the antioxidant is NDM-6PPD long-chain antioxidant.

[0060] The antioxidant-grafted MXene is prepared by the following steps:

[0061] (1) Mercaptohexanoic acid (molar ratio of terminal functional groups 1:2.5) is added to the MXene aqueous dispersion, stirred well and reacted at a temperature of 85 °C for 5 h. After the reaction is completed, the product is obtained by filtration and further washed 3 times with deionized water. The product is dried in a vacuum oven for 7 h to obtain MXene with thiol groups on its surface;

[0062] (2) The MXene with thiol groups on its surface is further ultrasonically dispersed in dimethyl sulfoxide, and the NDM-6PPD long-chain antioxidant is added. Stir well and react at a temperature of 80 °C for 6 h. After the reaction is completed, the product is obtained by filtration and further washed 6 times with dimethyl sulfoxide. The product is dried in a vacuum oven for 4 h to obtain NDM-6PPD long-chain antioxidant-grafted MXene. This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0063] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0064] 100 parts of hydrogenated nitrile rubber with 90% hydrogenation degree, 55 parts of calcium carbonate, 7 parts of NDM-6PPD long-chain antioxidant-grafted MXene, 3 parts of sulfur and vulcanization accelerator, and 6 parts of dibutyl diglycol adipate are kneaded evenly in a mixer to obtain a kneaded rubber. Further, the kneaded rubber is fully crosslinked at 185 °C to obtain an NDM-6PPD long-chain antioxidant-grafted MXene / hydrogenated nitrile rubber composite.

[0065] Comparative Example 3

[0066] This comparative example provides a rubber, and its preparation method is as follows:

[0067] 100 parts of nitrile rubber, 55 parts of calcium carbonate, 5 parts of MXene, 2 parts of small molecule antioxidant RD, 3 parts of sulfur and vulcanization accelerator, 6 parts of dibutyl diglycol adipate, etc. are kneaded evenly in a mixer to obtain a kneaded rubber.

[0068] The kneaded rubber is fully crosslinked at 185 °C to obtain a small molecule antioxidant RD / MXene / hydrogenated nitrile rubber composite.

[0069] Example 4

[0070] This example provides an antioxidant-grafted MXene / rubber composition, which includes the following components:

[0071] 100 parts of hydrogenated nitrile rubber with 90% hydrogenation degree, 40 parts of reinforcing filler, 8 parts of antioxidant-grafted MXene, 2.5 parts of vulcanizing agent, and 10 parts of plasticizer. The reinforcing filler is clay; the antioxidant is CGE-6PPD long-chain antioxidant; the vulcanizing agent is dicumyl peroxide; the plasticizer is Aflux25.

[0072] The antioxidant-grafted MXene is prepared by the following steps:

[0073] (1) Add mercaptopropylamine (molar ratio of terminal functional groups 1:5) to the MXene aqueous dispersion, stir well and react at a temperature of 85 °C for 10 h. After the reaction, filter to obtain the product, and further wash it 5 times with deionized water. The product is dried in a vacuum oven for 5 h to obtain MXene with thiol groups on the surface;

[0074] (2) Further ultrasonically disperse the MXene with thiol groups on the surface in N-methylpyrrolidone, add CGE-6PPD long-chain antioxidant, stir well and react at a temperature of 65 °C for 6 h. After the reaction, filter to obtain the product, and further wash it 3 times with N-methylpyrrolidone. The product is dried in a vacuum oven for 4 h to obtain CGE-6PPD long-chain antioxidant-grafted MXene;

[0075] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0076] Mix 100 parts of hydrogenated nitrile rubber with 90% hydrogenation degree, 40 parts of clay, 8 parts of CGE-6PPD long-chain antioxidant-grafted MXene, 2.5 parts of dicumyl peroxide, 10 parts of Aflux25, etc. in a mixer until evenly mixed to obtain a mixed rubber. Further crosslink the mixed rubber at 175 °C to obtain a CGE-6PPD long-chain antioxidant-grafted MXene / hydrogenated nitrile rubber composite.

[0077] Comparative Example 4

[0078] Mix 100 parts of nitrile rubber, 40 parts of clay, 5 parts of MXene platelet particles, 3 parts of small molecule antioxidant D, 2.5 parts of dicumyl peroxide, 10 parts of Aflux25, etc. in a mixer until evenly mixed to obtain a mixed rubber.

[0079] Crosslink the mixed rubber at 175 °C to obtain a small molecule antioxidant D / MXene / hydrogenated nitrile rubber composite.

[0080] Example 5

[0081] This example provides an antioxidant-grafted MXene / rubber composition, including the following components:

[0082] 100 parts of hydrogenated nitrile rubber with 95% hydrogenation degree, 50 parts of reinforcing filler, 10 parts of antioxidant-grafted MXene, 3 parts of vulcanizing agent, and 5 parts of plasticizer. The reinforcing filler is hydrotalcite; the antioxidant is BH-F77 long-chain antioxidant; the vulcanizing agent is 2,5-dimethyl-2,5-di-tert-butylperoxyhexane; the plasticizer is liquid nitrile rubber.

[0083] The antioxidant-grafted MXene is prepared by the following steps:

[0084] (1) Add cysteine (molar ratio of terminal functional groups 1:3) to the MXene aqueous dispersion, stir well and react at a temperature of 85 °C for 8 h. After the reaction is completed, the product is obtained by filtration and further washed 5 times with deionized water. The product is dried in a vacuum oven for 8 h to obtain MXene with thiol groups on the surface;

[0085] (2) Further ultrasonically disperse the MXene with thiol groups on the surface in dimethylformamide, add BH-F77 long-chain antioxidant, stir well and react at a temperature of 70 °C for 10 h. After the reaction is completed, the product is obtained by filtration and further washed 3 times with dimethylformamide. The product is dried in a vacuum oven for 5 h to obtain BH-F77 long-chain antioxidant-grafted MXene;

[0086] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0087] Mix 100 parts of hydrogenated nitrile rubber with 95% hydrogenation degree, 50 parts of hydrotalcite, 10 parts of BH-F77 long-chain antioxidant-grafted MXene, 3 parts of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 5 parts of liquid nitrile rubber, etc. in a mixer until evenly mixed to obtain a mixed rubber. Further crosslink the mixed rubber at 180 °C to obtain a BH-F77 long-chain antioxidant-grafted MXene / hydrogenated nitrile rubber composite.

[0088] Comparative Example 5

[0089] Mix 100 parts of nitrile rubber, 50 parts of hydrotalcite, 7 parts of MXene platelet particles, 3 parts of small molecule antioxidant MB, 3 parts of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 5 parts of liquid nitrile rubber, etc. in a mixer until evenly mixed to obtain a mixed rubber.

[0090] Crosslink the mixed rubber at 180 °C to obtain a small molecule antioxidant MB / MXene / hydrogenated nitrile rubber composite.

[0091] Example 6

[0092] This example provides an antioxidant-grafted MXene / rubber composition, including the following components:

[0093] 100 parts of hydrogenated nitrile rubber with 99% hydrogenation degree, 10 parts of reinforcing filler, 7 parts of antioxidant-grafted MXene, 2 parts of vulcanizing agent, and 5 parts of plasticizer. The reinforcing filler is graphene, the vulcanizing agent is dicumyl peroxide; the plasticizer is D810; the antioxidant is NDM-6PPD long-chain antioxidant.

[0094] The antioxidant-grafted MXene is prepared through the following steps:

[0095] (1) Add carboxyl-poly(2-ethyl-2-oxazoline)-thiol (molar ratio of terminal functional groups 1:3) to the MXene aqueous dispersion, stir well and react at a temperature of 100 °C for 0.5 h. After the reaction, filter to obtain the product, and further wash it 5 times with deionized water. The product is dried in a vacuum oven for 8 h to obtain MXene with thiol groups on the surface;

[0096] (2) Further ultrasonically disperse the MXene with thiol groups on the surface in dimethylformamide, add NDM-6PPD long-chain antioxidant, stir well and react at a temperature of 100 °C for 1 h. After the reaction, filter to obtain the product, and further wash it 3 times with dimethylformamide. The product is dried in a vacuum oven for 5 h to obtain NDM-6PPD long-chain antioxidant-grafted MXene;

[0097] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0098] Mix 100 parts of hydrogenated nitrile rubber with 100% hydrogenation degree, 10 parts of graphene, 7 parts of NDM-6PPD long-chain antioxidant-grafted MXene, 2 parts of dicumyl peroxide, and 5 parts of D810 evenly in a mixer to obtain a mixed rubber. Further crosslink the mixed rubber at 200 °C to obtain an NDM-6PPD long-chain antioxidant-grafted MXene / hydrogenated nitrile rubber composite material.

[0099] Example 7

[0100] This example provides an antioxidant-grafted MXene / rubber composition, including the following components:

[0101] 100 parts of hydrogenated nitrile rubber with 100% hydrogenation degree, 20 parts of reinforcing filler, 10 parts of antioxidant-grafted MXene, 5 parts of vulcanizing agent, and 10 parts of plasticizer. The reinforcing filler is carbon nanotubes, the vulcanizing agent is bis(tert-butylperoxy)diisopropylbenzene; the plasticizer is dibutyl diglycol adipate; the antioxidant is CGE-6PPD long-chain antioxidant.

[0102] The antioxidant-grafted MXene is prepared through the following steps:

[0103] (1) Mercaptobutylamine (molar ratio of terminal functional groups 1:3) was added to the MXene aqueous dispersion, stirred well and reacted at 80 °C for 8 h. After the reaction, the product was obtained by filtration and further washed 5 times with deionized water. The product was dried in a vacuum oven for 8 h to obtain MXene with thiol groups on its surface;

[0104] (2) The MXene with thiol groups on its surface was further ultrasonically dispersed in dimethylformamide, and the CGE-6PPD long-chain antioxidant was added. After stirring well and reacting at 50 °C for 10 h, the product was obtained by filtration and further washed 3 times with dimethylformamide. The product was dried in a vacuum oven for 5 h to obtain CGE-6PPD long-chain antioxidant grafted MXene;

[0105] This example also provides a method for preparing antioxidant-grafted MXene / rubber using the composition described above:

[0106] 100 parts of 100% hydrogenated hydrogenated nitrile rubber, 20 parts of carbon nanotubes, 10 parts of CGE-6PPD long-chain antioxidant grafted MXene, 5 parts of ditert-butyl peroxide diisopropylbenzene, and 10 parts of dibutyl diglycol adipate were kneaded uniformly in a mixer to obtain a kneaded rubber. Further, the kneaded rubber was fully crosslinked at 150 °C to obtain a CGE-6PPD long-chain antioxidant grafted MXene / hydrogenated nitrile rubber composite.

[0107] Experimental Example

[0108] The aging resistance performance and migration performance of the long-chain antioxidant grafted MXene / hydrogenated nitrile rubber composites prepared in Examples 1-7 and the ordinary small-molecule antioxidant MXene / hydrogenated nitrile rubber composites prepared in Comparative Examples 1-5 were tested, and the test results are shown in Table 1.

[0109] Table 1 Test Results

[0110]

[0111] It can be seen from the data in the table that, compared with each comparative example, in the examples, due to the use of highly hydrogenated HNBR, there are almost no carbon-carbon double bonds (C=C) in the molecular structure, so it has a higher saturation. This structure endows HNBR with more excellent heat resistance, ozone resistance, chemical corrosion resistance and mechanical properties; and the use of long-chain antioxidant grafted MXene and flaky reinforcing fillers with a larger aspect ratio together form an effective filler network. The long-chain antioxidant has the function of preventing migration, ultimately improving the retention rate of tensile strength after aging and reducing the mass change rate of the dried sample after immersion in oil, achieving the effects of aging resistance and anti-migration of the sealing material.

[0112] The above are only embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention are included within the scope of the claims of the present invention pending approval.

Claims

1. An antioxidant grafted MXene / rubber composition, characterized in that, Includes the following components: Rubber matrix, antioxidant grafted MXene, reinforcing filler, vulcanizer, plasticizer; Wherein, the rubber matrix is hydrogenated nitrile rubber; the antioxidant in the antioxidant-grafted MXene is a long-chain antioxidant; Relative to 100 parts by weight of the rubber matrix, the weight of the reinforcing filler is 20 to 100 parts, the weight of the antioxidant-grafted MXene is 2 to 10 parts, the weight of the vulcanizing agent is 0.1 to 5 parts, and the weight of the plasticizer is 5 to 40 parts; The antioxidant-grafted MXene is prepared by the following steps: Weigh the MXene aqueous dispersion, add a small molecule containing a carboxyl or amino group at one end and a thiol group at the other end, stir thoroughly, and react at 80-100°C for 0.5-8 hours. After the reaction, filter, wash, and dry to obtain MXene with thiol groups on the surface. Ultrasonic dispersion of the MXene containing thiol groups on the surface in a solvent, adding an antioxidant, fully stirring and reacting at a temperature of 50-100° C. for 1-10 hours, filtering, washing, and drying after the reaction to obtain the antioxidant-grafted MXene; The long chain of the long-chain antioxidant is an alkyl chain or a long chain containing other heteroatoms and contains one or more double bonds.

2. The antioxidant grafted MXene / rubber composition according to claim 1, wherein The hydrogenation degree of the hydrogenated nitrile rubber is 80-100%.

3. The antioxidant grafted MXene / rubber composition according to claim 1, wherein The small molecules containing a carboxyl group or an amino group at one end and a thiol group at the other end include one or more of 3-mercaptopropionic acid, mercaptobutyric acid, mercaptohexanoic acid, carboxyl-poly(2-ethyl-2-oxazoline)-thiol, mercaptopropylamine, mercaptobutylamine, and cysteine small molecules.

4. The antioxidant grafted MXene / rubber composition according to claim 1, characterized in that, The long-chain antioxidant is one or more of BH-F77, AITC-PPD, NDM-6PPD, and CGE-6PPD.

5. The antioxidant grafted MXene / rubber composition according to claim 1, characterized in that The reinforcing filler is one or more of carbon black, silicon dioxide, calcium carbonate, clay, graphene, hydrotalcite, and carbon nanotubes.

6. The antioxidant grafted MXene / rubber composition according to claim 1, wherein The vulcanizing agent is one or more of sulfur and a vulcanization accelerator, di-tert-butyl peroxide, diisopropylbenzene peroxide, di-tert-butyl diisopropylbenzene peroxide, and 2,5-dimethyl-2,5-di-tert-butyl peroxide hexane.

7. The antioxidant grafted MXene / rubber composition according to claim 1, wherein, The plasticizer is one or more of trioctyl trimellitate, dibutyl diglyceride adipate, dioctyl sebacate, D810, Aflux25, and liquid nitrile rubber.

8. A method for preparing an antioxidant-grafted MXene / rubber using the composition according to any one of claims 1 to 7, characterized in that, The following steps are involved: The antioxidant grafted MXene, hydrogenated nitrile rubber, reinforcing filler, vulcanizing agent, and plasticizer are uniformly mixed in a mixing device to obtain a rubber compound; The rubber mixture is fully cross-linked at 150-200° C. to obtain an antioxidant-grafted MXene / rubber.

9. The method according to claim 8, characterized in that, The mixing equipment is one of an internal mixer, an open mixer and a kneader.

10. An antioxidant-grafted MXene / rubber prepared by the method according to any one of claims 8 to 9.

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