Thermoplastic vulcanized rubber as well as auxiliary agent and application thereof

Abstract

The invention belongs to the technical field of thermoplastic vulcanized rubber preparation, and particularly relates to thermoplastic vulcanized rubber and an auxiliary agent and application thereof, the auxiliary agent comprises a heterocyclic compound with a group represented by a formula a in a molecule, and the dielectric constant of the thermoplastic vulcanized rubber can be reduced.

Description

Technical Field

[0001] The present application belongs to the technical field of thermoplastic vulcanized rubber preparation, and specifically relates to thermoplastic vulcanized rubber, its additives and applications. Background Art

[0002] As an important high-performance elastomeric material, thermoplastic vulcanizate (TPV) is widely used in the automotive, electrical and electronics, and construction sectors, combining the elasticity and flexibility of rubber with the reprocessability of plastic. In the automotive industry, particularly in electric vehicles (EVs) and high-voltage systems, TPV is widely used in the manufacture of critical seals (such as wiring harness seals, connector seals, and battery pack seals) and cooling system piping due to its excellent sealing properties, weather resistance, and chemical resistance.

[0003] However, conventional mainstream thermoplastic vulcanizate (TPV) preparation technologies, whether using peroxide or phenolic resin curing systems, generally suffer from a significant technical bottleneck in the production of TPV materials: their dielectric constant (Dk) is typically high, generally greater than 2.5, and some systems may even exceed 3.0. This characteristic stems from their inherent molecular structure: on the one hand, the peroxide curing process may produce polar byproducts, which may cause some molecular chains to become polarized; on the other hand, the phenolic resin curing agent itself and its cross-linking structure contain rigid, polar groups such as benzene rings. These structures are difficult to effectively shield after the cross-linking network is formed, increasing the overall polarity of the material. The dielectric constant is a parameter that measures a material's ability to store electrical energy in an electric field. A higher value means that the material will experience greater dielectric loss when exposed to alternating electric fields (such as high-frequency signal transmission or high-voltage environments).

[0004] This high dielectric constant and high dielectric loss present significant challenges in electric vehicles and high-voltage applications. First, in high-voltage environments (e.g., 600V or 800V and above), high losses can lead to increased heating of the material itself, accelerating material aging and reducing service life. This can also lead to the risk of thermal runaway, threatening system safety. Second, for seals used in coolant lines or for electrical signal transmission, high dielectric constants increase parasitic capacitance, potentially interfering with the efficiency of sensitive electronic signal transmission or increasing the system's reactive power losses. Summary of the Invention

[0005] In a first aspect, the present application provides an auxiliary agent for reducing the dielectric constant of thermoplastic vulcanizate, comprising a compound containing a group represented by formula a in the molecule:

[0006] [Formula a]

[0007]

[0008] Here, * indicates the connection site with the adjacent atom.

[0009] The present application includes at least the following beneficial effects: After dynamic vulcanization of thermoplastic vulcanizate in a phenolic or peroxide system, polar groups or aromatic ring byproducts such as -OH, -CHO, and -OCN are generated. These groups or byproducts have asymmetric structures and high inherent dipole moments, which are the main factors that increase the dielectric constant of thermoplastic vulcanizate materials. The auxiliary agent described in the present application can reduce the dielectric constant of thermoplastic vulcanizate. The reason may be that the structure represented by formula a in the auxiliary agent molecule can undergo a ring-opening reaction during the dynamic vulcanization process of thermoplastic vulcanizate to generate polar molecules containing hydroxyl groups. These polar molecules are prone to forming hydrogen bonds with polar groups or byproducts in the thermoplastic vulcanizate to form a ring structure, which partially offsets the dipole moment in the thermoplastic vulcanizate molecule, thereby reducing the overall molecular dipole moment of the thermoplastic vulcanizate material, reducing the polarization ability, and ultimately achieving a reduction in the dielectric constant.

[0010] In some embodiments, the auxiliary agent includes a compound represented by formula A:

[0011] [Formula A]

[0012]

[0013] Wherein, R1 is a group represented by formula b, formula c or formula d:

[0014] [Formula b]

[0015]

[0016] [Formula c]

[0017]

[0018] [Formula d]

[0019]

[0020] in,

[0021] R2 is H, a substituted alkyl group, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted 3,4-dihydro-2H-1,3-oxazinyl group. When R2 is a substituted or unsubstituted phenyl group or a substituted or unsubstituted 3,4-dihydro-2H-1,3-oxazinyl group, the benzene ring or 3,4-dihydro-2H-1,3-oxazinyl ring is fused to the benzene ring in the main structure of Formula A. R3 is a substituted or unsubstituted alkyl group. R4 is H or a substituted or unsubstituted alkyl group. * indicates the attachment site. This application specifies that the additive meets the above conditions and can further reduce the dielectric constant of the thermoplastic vulcanizate material.

[0022] In some embodiments, the adjuvant comprises one or more of the following compounds:

[0023]

[0024]

[0025]

[0026]

[0027] The present application stipulates that the auxiliary agent meets the above conditions, which can further reduce the dielectric constant of the thermoplastic vulcanized rubber material.

[0028] The second aspect of the present application provides a method for preparing a thermoplastic vulcanizate with a low dielectric constant, comprising dynamic vulcanization, and adding the auxiliary agent described in the first aspect of the present application during the dynamic vulcanization stage.

[0029] The present application does not limit the preparation method of the thermoplastic vulcanized rubber. As an example, the preparation method of the thermoplastic vulcanized rubber may include the following steps:

[0030] Premixing: Rubber, plastic, crosslinking agent, filler and oil are premixed and granulated to obtain premix;

[0031] Dynamic vulcanization: heating the premix and continuously shearing it, adding the auxiliary agent, cross-linking agent, filler and auxiliary oil thereto, extruding and granulating, and obtaining the thermoplastic vulcanized rubber with a low dielectric constant.

[0032] This application does not limit the specific types of other raw materials in the thermoplastic vulcanizate. As an example, the rubber includes one or more of EPDM rubber, butyl rubber, silicone rubber, fluororubber, ethylene acrylate rubber, and natural rubber. As an example, the plastic includes one or more of polypropylene, polyethylene, polyamide, polyvinyl chloride, polystyrene, polycarbonate, and polyethylene terephthalate.

[0033] In some embodiments, based on 100 parts by weight of rubber, the amount of the plastic added is 35-150 parts, and the amount of the additive described in the first aspect of this application added is 1-8 parts. This application stipulates that the mass ratio of rubber, plastic, and additive in the thermoplastic vulcanizate meets the above conditions, which is conducive to further reducing the dielectric constant of the thermoplastic vulcanizate.

[0034] The present application does not limit the amount of other ingredients added to the thermoplastic vulcanizate. As an example, the amount of the cross-linking agent added may be 1-4 parts; and / or, the amount of the cross-linking aid added may be 2-4 parts; and / or, the amount of the filler added in the premixing stage may be 15-80 parts, and the total amount of the filler added may be 25-120 parts; and / or, the amount of the auxiliary oil added in the premixing stage may be 25-115 parts, and the total amount of the auxiliary oil added may be 50-225 parts.

[0035] In the examples of the thermoplastic vulcanizate preparation method provided in this application, to improve the uniformity of the thermoplastic vulcanizate composition, the filler and co-oil are added in batches during the premixing and dynamic vulcanization processes. It should be noted that the type or composition of the co-oil added at different stages can be the same or different, and the type or composition of the filler added at different stages can be the same or different. The specific selection can be based on actual needs and is not limited by this application.

[0036] In addition, the present application does not impose any restrictions on the types and combinations of cross-linking agents and cross-linking aids, as long as the purpose of preparing thermoplastic vulcanizate can be achieved.

[0037] As an example, the cross-linking agent may include one or more of a peroxide cross-linking agent and a phenolic resin; the peroxide may include one or more of diisopropyl benzene peroxide, di-tert-butyl peroxyisopropyl benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(2,4-dichlorobenzoyl) peroxide, and di-tert-butyl peroxide.

[0038] As an example, the cross-linking auxiliary agent may include a primary antioxidant, a secondary antioxidant and an accelerator, wherein:

[0039] The primary antioxidant may include one or more of butylated hydroxytoluene, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p-phenylenediamine;

[0040] The auxiliary antioxidant may include one or more of tris[2,4-di-tert-butylphenyl]phosphite, triphenyl phosphite, dilauryl thiodipropionate, and distearyl thiodipropionate;

[0041] The accelerator can include one or more of stannous chloride, zinc oxide, zinc stearate, manganese oxide, zinc bromide, stannous octoate, hexamethylenetetramine, TAIC (triallyl isocyanurate), TMPTMA (trimethylolpropane trimethacrylate), EGDMA (ethylene glycol dimethacrylate), DAP (diallyl phthalate).

[0042] It should be noted that the specific components of the crosslinking aid can be the same or different depending on the type of crosslinking agent.

[0043] As an example, when the crosslinking agent is phenol-formaldehyde resin, the accelerator in the crosslinking aid can be zinc oxide, and can also include one or more of stannous chloride, zinc stearate, manganese oxide, zinc bromide, stannous octoate, hexamethylenetetramine, and an antioxidant can also be added as necessary.

[0044] As an example, when the crosslinking agent is peroxide, an antioxidant needs to be added, and one or more of TAIC, TMPTMA, EGDMA, DAP, zinc oxide, and zinc stearate can also be added as an accelerator.

[0045] It should be noted that when an antioxidant needs to be added in the thermoplastic vulcanizate system, an auxiliary antioxidant is preferably added at the same time for a synergistic effect.

[0046] As an example, the filler includes one or more of calcium carbonate, talc, carbon black, glass fiber, kaolin, and wollastonite.

[0047] As an example, the extender includes one or more of paraffin oil, naphthenic oil, epoxidized soybean oil, and white oil.

[0048] The third aspect of the present application provides a thermoplastic vulcanizate material prepared by the method of the second aspect of the present application.

[0049] The fourth aspect of the present application provides the use of the thermoplastic vulcanizate of the third aspect of the present application in consumer electronics, smart wearable devices, home appliances, batteries, sealing devices, soundproofing devices, water pipes, electric wires and cables, engines, and automobiles. DETAILED DESCRIPTION

[0050] The present application will be described in detail below with reference to specific embodiments. The embodiments shown below do not have any limiting effect on the content of the invention described in the claims. In addition, the entire content of the configuration represented in the following embodiments is not limited to what is necessary as a solution to the invention described in the claims.

[0051] As used herein, the term "comprise" should be interpreted as inclusive and open-ended, rather than exclusive. Specifically, when used in the specification and claims, the term "comprises" and its variations mean including the specified features, steps, or components. These terms should not be interpreted as excluding the presence of other features, steps, or components.

[0052] Whenever a range of values ​​is given herein, that range includes its endpoints, and all individual integers and fractions within that range, and also includes each narrower range formed from all possible combinations of those endpoints and internal integers and fractions therein to form subgroups of the larger group of values ​​within that range to the same extent as if each of those narrower ranges were expressly set forth.

[0053] In a first aspect, the present application provides an auxiliary agent for reducing the dielectric constant of thermoplastic vulcanizate, comprising a compound containing a group represented by formula a in the molecule:

[0054] [Formula a]

[0055]

[0056] Here, * indicates the connection site with the adjacent atom.

[0057] After dynamic vulcanization of thermoplastic vulcanizate in phenolic or peroxide system, polar groups or aromatic ring by-products such as -OH, -CHO, and -OCN will be produced. These groups or by-products have asymmetric structures and high inherent dipole moments, which are the main factors for the increase in the dielectric constant of thermoplastic vulcanizate materials. The auxiliary agent described in this application can reduce the dielectric constant of thermoplastic vulcanizate, and the reason may be that: the structure shown in formula a in the auxiliary agent molecule described in this application can react with heat during the dynamic vulcanization process of thermoplastic vulcanizate. The reaction process can refer to reaction formula (I), wherein the oxygen-containing heterocyclic structure is activated by high temperature to open the ring, and the heterocyclic OC bond is cleaved to generate a phenolic hydroxyl group conjugated with the benzene ring. On the one hand, the phenolic hydroxyl group reduces the auxiliary agent's own dipole moment through self-generated intramolecular hydrogen bonds (-OH in the same ring-opening product molecule forms a hydrogen bond with N) and intermolecular hydrogen bonds (-OH in the ring-opening product molecule forms a hydrogen bond with -OH in another ring-opening product molecule); on the other hand, it can form an intermolecular hydrogen bond network with the polar groups of the vulcanization byproducts in the thermoplastic vulcanizate and the polar sites of the rubber phase oxidation. This rearranges the local charge distribution, partially offsets the dipole moment vector, restricts the movement of the polar groups, and suppresses the polarization of the interfacial space charge, thereby reducing the dielectric constant of the thermoplastic vulcanizate material.

[0058]

[0059] In reaction formula I, n is a positive integer, and * represents a connection site with an adjacent atom.

[0060] In some embodiments, the adjuvant comprises a compound represented by Formula A:

[0061] [Formula A]

[0062]

[0063] wherein R1is a group represented by Formula b, Formula c, or Formula d:

[0064] [Formula b]

[0065]

[0066] [Formula c]

[0067]

[0068] [Formula d]

[0069]

[0070] wherein,

[0071] R2is H, substituted alkyl, substituted phenyl, substituted or unsubstituted 3,4-dihydro-2H-1,3-oxazinyl, and when R2is substituted or unsubstituted phenyl, or substituted or unsubstituted 3,4-dihydro-2H-1,3-oxazinyl, the phenyl ring or 3,4-dihydro-2H-1,3-oxazinyl ring is fused to the phenyl ring in the main structure of Formula A; R3is substituted or unsubstituted alkyl; R4is H, or substituted or unsubstituted alkyl; * represents a connection site. The present application limits that the adjuvant satisfies the above conditions, which can further reduce the dielectric constant of the thermoplastic vulcanized rubber material. It should be noted that R 2 The connection with the phenyl ring can be a single bond or a fused connection, etc., and the connection bond between R2and the phenyl ring in Formula A is only schematic and does not constitute a limitation on the type and connection position of the connection bond. In addition, the "fused" described in the present application refers to a chemical structure in which two rings share two adjacent carbon atoms and the bond connecting them.

[0072] In some embodiments, the adjuvant comprises one or more of the following compounds:

[0073]

[0074]

[0075]

[0076]

[0077] The present application specifies that the additive satisfies the above conditions. On the one hand, the nitrogen-oxygen heterocycle can be opened to form -OH during the vulcanization process of the thermoplastic vulcanizate, and then the polarity of the polar groups in the thermoplastic vulcanizate can be partially offset by the formation of hydrogen bonds, thereby reducing the dielectric constant of the thermoplastic vulcanizate material. On the other hand, the additive molecule described in the present application contains at least one aromatic ring, which is conducive to making the overall electron cloud distribution of the additive molecule itself more symmetrical, helping to reduce the dipole moment of the additive ring-opening product itself. Moreover, when the additive contains multiple conjugated rings, the molecular structure rigidity will be increased, and the polar groups (such as -OH generated by the additive ring opening and the polar groups of the thermoplastic vulcanizate vulcanization byproducts) will be restricted from rotating freely in the electric field, making it difficult for orientation polarization to occur and reducing the polarization ability, thereby further reducing the dielectric constant.

[0078] The second aspect of the present application provides a method for preparing a thermoplastic vulcanizate with a low dielectric constant, comprising dynamic vulcanization, and adding the auxiliary agent described in the first aspect of the present application during the dynamic vulcanization stage.

[0079] The present application does not limit the preparation method of the thermoplastic vulcanized rubber. As an example, the preparation method of the thermoplastic vulcanized rubber may include the following steps:

[0080] Premixing: Rubber, plastic, crosslinking agent, filler and oil are premixed and granulated to obtain premix;

[0081] Dynamic vulcanization: heating the premix and continuously shearing it, adding the auxiliary agent, cross-linking agent, filler and auxiliary oil thereto, extruding and granulating, and obtaining the thermoplastic vulcanized rubber with a low dielectric constant.

[0082] This application does not limit the specific types of other raw materials in the thermoplastic vulcanizate. As an example, the rubber includes one or more of EPDM rubber, butyl rubber, silicone rubber, fluororubber, ethylene acrylate rubber, and natural rubber. As an example, the plastic includes one or more of polypropylene, polyethylene, polyamide, polyvinyl chloride, polystyrene, polycarbonate, and polyethylene terephthalate.

[0083] In some embodiments, based on 100 parts by weight of rubber, the amount of the plastic added is 35-150 parts, and the amount of the additive described in the first aspect of this application added is 1-8 parts. This application stipulates that the mass ratio of rubber, plastic, and additive in the thermoplastic vulcanizate meets the above conditions, which is conducive to further reducing the dielectric constant of the thermoplastic vulcanizate.

[0084] The present application does not limit the amount of other ingredients added to the thermoplastic vulcanizate. As an example, the amount of the cross-linking agent added may be 1-4 parts; and / or, the amount of the cross-linking aid added may be 2-4 parts; and / or, the amount of the filler added in the premixing stage may be 15-80 parts, and the total amount of the filler added may be 25-120 parts; and / or, the amount of the auxiliary oil added in the premixing stage may be 25-115 parts, and the total amount of the auxiliary oil added may be 50-225 parts.

[0085] In the examples of the thermoplastic vulcanizate preparation method provided in this application, to improve the uniformity of the thermoplastic vulcanizate composition, the filler and co-oil are added in batches during the premixing and dynamic vulcanization processes. It should be noted that the type or composition of the co-oil added at different stages can be the same or different, and the type or composition of the filler added at different stages can be the same or different. The specific selection can be based on actual needs and is not limited by this application.

[0086] In addition, the present application does not impose any restrictions on the types and combinations of cross-linking agents and cross-linking aids, as long as the purpose of preparing thermoplastic vulcanizate can be achieved.

[0087] As an example, the cross-linking agent may include one or more of a peroxide cross-linking agent and a phenolic resin; the peroxide may include one or more of diisopropyl benzene peroxide, di-tert-butyl peroxyisopropyl benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(2,4-dichlorobenzoyl) peroxide, and di-tert-butyl peroxide.

[0088] As an example, the cross-linking auxiliary agent may include a primary antioxidant, a secondary antioxidant and an accelerator, wherein:

[0089] The primary antioxidant may include one or more of butylated hydroxytoluene, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, and N-phenyl-N'-isopropyl-p-phenylenediamine;

[0090] The auxiliary antioxidant may include one or more of tris[2,4-di-tert-butylphenyl]phosphite, triphenyl phosphite, dilauryl thiodipropionate, and distearyl thiodipropionate;

[0091] The accelerator can include one or more of stannous chloride, zinc oxide, zinc stearate, manganese oxide, zinc bromide, stannous octoate, hexamethylenetetramine, TAIC (triallyl isocyanurate), TMPTMA (trimethylolpropane trimethacrylate), EGDMA (ethylene glycol dimethacrylate), DAP (diallyl phthalate).

[0092] It should be noted that the specific components of the crosslinking aid can be the same or different depending on the type of crosslinking agent.

[0093] As an example, when the crosslinking agent is phenol-formaldehyde resin, the accelerator in the crosslinking aid can be zinc oxide, and can also include one or more of stannous chloride, zinc oxide, zinc stearate, manganese oxide, zinc bromide, stannous octoate, hexamethylenetetramine, and an antioxidant can also be added as necessary.

[0094] As an example, when the crosslinking agent is peroxide, an antioxidant needs to be added, and one or more of TAIC, TMPTMA, EGDMA, DAP, zinc oxide, and zinc stearate can also be added as an accelerator.

[0095] It should be noted that when an antioxidant needs to be added in the thermoplastic vulcanized rubber system, an auxiliary antioxidant is preferably added at the same time for a synergistic effect.

[0096] As an example, the filler includes one or more of calcium carbonate, talc, carbon black, glass fiber, kaolin, and wollastonite.

[0097] As an example, the extender includes one or more of paraffin oil, naphthenic oil, epoxidized soybean oil, and white oil.

[0098] The third aspect of the present application provides a thermoplastic vulcanized rubber material prepared by the method of the second aspect of the present application.

[0099] The fourth aspect of the present application provides the use of the thermoplastic vulcanized rubber of the third aspect of the present application in consumer electronics, smart wearable devices, home appliances, batteries, sealing devices, soundproofing devices, water pipes, electric wires and cables, engines, and automobiles.

[0100] In order to make the technical problems, technical solutions and beneficial effects solved by the embodiments of the present application clearer, the following will be further described in detail with embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and in no way limits the present application and its applications. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without creative labor fall within the scope of the present application.

[0101] Embodiment 1

[0102] A method for preparing 2-(2H-benzo[e][1,3]oxazin-3(4H)-yl)-N-methylethan-1-amine (I-1), with the reaction formula referring to the following formula, comprises the following steps:

[0103]

[0104] (1) Add 2 parts (by mole, the same below) of phenol to chloroform solvent, adjust the amount of solvent to make the phenol concentration 0.5 mol / L, adjust the solution temperature to 50°C, and stir the reaction for 10 minutes.

[0105] (2) Add 5 parts of formaldehyde to the solution after the reaction in (1), heat it to 60°C at a heating rate of not less than 10°C / min, and continue stirring to react for 5 minutes.

[0106] (3) Add 2 parts of N-methylethylenediamine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 10°C / min, and continue stirring for 5 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 200-250 rpm.

[0107] (4) After the reaction is completed, the reaction system is filtered to obtain a solid substance, which is washed and purified and then dried at normal pressure and 80° C. for 5 h to obtain a solid product.

[0108] In this application, the prepared product was characterized by first using infrared spectroscopy to determine the presence of the desired main structure (i.e., the structure represented by formula a) in the target product, and then further purified by nuclear magnetic resonance NMR to detect the solid product. 1 H NMR, 13 C NMR, and then compared with the NMR spectrum of the target product simulated by ChemDraw software to verify whether the prepared product is the target product. After verification by the above method, it was confirmed that the solid product prepared in this example is the target substance 2-(2H-benzo[e][1,3]oxazin-3(4H)-yl)-N-methylethan-1-amine (I-1). The following examples and comparative examples all use the above method to verify the product structure, and will not be repeated in this application.

[0109] Example 2

[0110] A method for preparing 3-(pyrrolidin-3-yl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (I-2), with the reaction formula referring to the following formula, comprises the following steps:

[0111]

[0112] (1) Add 2 parts (by mole, the same below) of phenol to toluene solvent, adjust the amount of solvent to make the phenol concentration 0.7 mol / L, adjust the solution temperature to 60°C, and stir the reaction for 20 minutes.

[0113] (2) Add 8 parts of formaldehyde to the solution after the reaction in (1), heat it to 80°C at a heating rate of not less than 10°C / min, and continue stirring to react for 10 minutes.

[0114] (3) Add 2 parts of 3-aminopyrrolidine to the solution after the reaction in (2), heat the mixture to 120°C at a heating rate of not less than 10°C / min, and continue stirring for 5 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 300-350 rpm.

[0115] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 3-(pyrrolidin-3-yl)-3,4-dihydro-2H-benzo[e][1,3]oxazine (I-2).

[0116] Example 3

[0117] A method for preparing 1,2-bis(2H-benzo[e][1,3]oxazin-3(4H)-yl)ethane (I-4), with the reaction formula referring to the following formula, comprises the following steps:

[0118]

[0119] (1) Add 4 parts (by mole, the same below) of phenol to chloroform solvent, adjust the amount of solvent to make the phenol concentration 0.8 mol / L, adjust the solution temperature to 50°C, and stir the reaction for 15 minutes.

[0120] (2) Add 16 parts of formaldehyde to the solution after the reaction in (1), heat it to 60°C at a heating rate of not less than 10°C / min, and continue stirring to react for 10 minutes.

[0121] (3) Add 2 parts of N-methylethylenediamine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 10°C / min, and continue stirring for 5 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 200-250 rpm.

[0122] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at 90°C under normal pressure for 5 hours to obtain the target product 1,2-bis(2H-benzo[e][1,3]oxazin-3(4H)-yl)ethane (I-4).

[0123] Example 4

[0124] A method for preparing 2,2'-(4,9-dihydrobenzo[1,2-e:4,5-e']bis([1,3]oxazine)-3,8(2H,7H)-diyl)bis(N-methylethan-1-amine (II-1) is provided. The reaction formula is as follows, and the method comprises the following steps:

[0125]

[0126] (1) Add 2 parts (by mole, the same below) of hydroquinone to chloroform solvent, adjust the amount of solvent to make its concentration 0.5 mol / L, adjust the solution temperature to 50°C, and stir the reaction for 10 minutes.

[0127] (2) Add 16 parts of formaldehyde to the solution after the reaction in (1), heat it to 60°C at a heating rate of not less than 10°C / min, and continue stirring to react for 10 minutes.

[0128] (3) Add 4 parts of N-methylethylenediamine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 10°C / min, and continue stirring for 5 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 200-250 rpm.

[0129] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 2,2'-(4,9-dihydrobenzo[1,2-e:4,5-e']bis([1,3]oxazine)-3,8(2H,7H)-diyl)bis(N-methylethyl-1-amine (II-1).

[0130] Example 5

[0131] A method for preparing 2,2'-(propane-2,2-diylbis(2H-benzo[e][1,3]oxazine-6,3(4H)-diyl))bis(N-methylethan-1-amine) (III-1) is provided. The reaction formula is as follows, and the method comprises the following steps:

[0132]

[0133] (1) Add 2 parts (by mole, the same below) of 4,4'-(propane-2,2-diyl)diphenol to tetrahydrofuran solvent, adjust the amount of solvent to make its concentration 0.2 mol / L, adjust the solution temperature to 50°C, and stir the reaction for 30 minutes.

[0134] (2) Add 15 parts of formaldehyde to the solution after the reaction in (1), heat it to 70°C at a heating rate of about 10°C / min, and continue stirring and reacting for 10 minutes.

[0135] (3) Add 4 parts of N-methylethylenediamine to the solution after the reaction in (2), heat it to 100°C at a heating rate of about 10°C / min, and continue stirring for 8 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 100-150 rpm.

[0136] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 2,2'-(propane-2,2-diylbis(2H-benzo[e][1,3]oxazine-6,3(4H)-diyl))bis(N-methylethyl-1-amine) (III-1).

[0137] Example 6

[0138] A method for preparing 6,6'-(propane-2,2-diyl)bis(3-(pyrrolidin-3-yl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) (III-3) is provided, wherein the reaction formula is as follows and the method comprises the following steps:

[0139]

[0140] (1) Add 2 parts (by mole, the same below) of 4,4'-(propane-2,2-diyl)diphenol to tetrahydrofuran solvent, adjust the amount of solvent to make its concentration 0.2 mol / L, adjust the solution temperature to 50°C, and stir the reaction for 30 minutes.

[0141] (2) Add 15 parts of formaldehyde to the solution after the reaction in (1), heat it to 70°C at a heating rate of about 10°C / min, and continue stirring and reacting for 10 minutes.

[0142] (3) Add 4 parts of pyrrolidine-3-amine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of about 10°C / min, and continue stirring for 8 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 100-150 rpm.

[0143] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 6,6'-(propane-2,2-diyl)bis(3-(pyrrolidin-3-yl)-3,4-dihydro-2H-benzo[e][1,3]oxazine) (III-3).

[0144] Example 7

[0145] A method for preparing N-methyl-2-(1H-naphtho[1,2-e][1,3]oxazin-2(3H)-yl)ethan-1-amine (IV-1), the reaction formula of which is as follows, comprises the following steps:

[0146]

[0147] (1) Add 2 parts (by mole, the same below) of naphthalene-2-ol to dichloromethane solvent, adjust the amount of solvent to make its concentration 0.1 mol / L, adjust the solution temperature to 40°C, and stir the reaction for 5 minutes.

[0148] (2) Add 5 parts of formaldehyde to the solution after the reaction in (1), heat it to 80°C at a heating rate of not less than 20°C / min, and continue stirring to react for 5 minutes.

[0149] (3) Add 2 parts of N-methylethylenediamine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 20°C / min, and continue stirring for 3 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 350-400 rpm.

[0150] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product N-methyl-2-(1H-naphtho[1,2-e][1,3]oxazin-2(3H)-yl)ethan-1-amine (IV-1).

[0151] Example 8

[0152] A method for preparing 1,2-bis(1H-naphtho[1,2-e][1,3]oxazin-2(3H)-yl)ethane (IV-4) comprises the following steps:

[0153]

[0154] (1) Add 4 parts (by mole, the same below) of naphthalene-2-ol to dichloromethane solvent, adjust the amount of solvent to make its concentration 0.1 mol / L, adjust the solution temperature to 40°C, and stir the reaction for 5 minutes.

[0155] (2) Add 16 parts of formaldehyde to the solution after the reaction in (1), heat it to 80°C at a heating rate of not less than 20°C / min, and continue stirring to react for 5 minutes.

[0156] (3) Add 2 parts of N-methylethylenediamine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 20°C / min, and continue stirring for 3 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 350-400 rpm.

[0157] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 1,2-bis(1H-naphtho[1,2-e][1,3]oxazin-2(3H)-yl)ethane (IV-4).

[0158] Example 9

[0159] A method for preparing 3-(1-methylpyrrolidin-3-yl)-3,4-dihydro-2H-naphtho[2,1-e][1,3]oxazine (V-3), with the reaction formula referring to the following formula, comprises the following steps:

[0160]

[0161] (1) Add 4 parts (by mole, the same below) of naphthalene-1-ol to xylene solvent, adjust the amount of solvent to make its concentration 0.1 mol / L, adjust the solution temperature to 60°C, and stir the reaction for 10 minutes.

[0162] (2) Add 10 parts of formaldehyde to the solution after the reaction in (1), heat it to 80°C at a heating rate of not less than 20°C / min, and continue stirring to react for 5 minutes.

[0163] (3) Add 2 parts of 1-methylpyrrolidin-3-amine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 20°C / min, and continue stirring for 3 hours. Steps (1) to (3) all utilize continuous mechanical double-paddle stirring, and the stirring speed is controlled at 350-400 rpm.

[0164] After the reaction, the reaction system was filtered and washed with a pure solvent to obtain a precipitated product, which was then dried at 90°C under normal pressure for 5 h to obtain the target product 3-(1-methylpyrrolidin-3-yl)-3,4-dihydro-2H-naphtho[2,1-e][1,3]oxazine (V-3).

[0165] Example 10

[0166] A method for preparing 3,9-di(pyrrolidin-3-yl)-2,3,4,8,9,10-hexahydronaphtho[1,2-e:5,6-e']bis([1,3]oxazine) (VI-2) is provided. The reaction formula is as follows, and the method comprises the following steps:

[0167]

[0168] (1) Add 2 parts (by mole, the same below) of naphthalene-2,6-diol to chloroform solvent, adjust the amount of solvent to make its concentration 0.1 mol / L, adjust the solution temperature to 60°C, and stir the reaction for 15 minutes.

[0169] (2) Add 10 parts of formaldehyde to the solution after the reaction in (1), heat it to 80°C at a heating rate of not less than 20°C / min, and continue stirring to react for 10 minutes.

[0170] (3) Add 4 parts of pyrrolidine-3-amine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 20°C / min, and continue stirring for 3 hours. Steps (1) to (3) all use continuous mechanical double-paddle stirring, and the stirring speed is controlled at 350-400 rpm.

[0171] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 3,9-di(pyrrolidin-3-yl)-2,3,4,8,9,10-hexahydronaphtho[1,2-e:5,6-e']bis([1,3]oxazine) (VI-2).

[0172] Example 11

[0173] A method for preparing 2,8-bis(1-methylpyrrolidin-3-yl)-1,2,3,7,8,9-hexahydronaphtho[2,1-e:6,5-e']bis([1,3]oxazine) (VII-3) is provided. The reaction formula is as follows, and the method comprises the following steps:

[0174]

[0175] (1) Add 2 parts (by mole, the same below) of naphthalene-1,5-diol to toluene solvent, adjust the amount of solvent to make its concentration 0.1 mol / L, adjust the solution temperature to 60°C, and stir the reaction for 20 minutes.

[0176] (2) Add 10 parts of formaldehyde to the solution after the reaction in (1), heat it to 80°C at a heating rate of not less than 20°C / min, and continue stirring to react for 10 minutes.

[0177] (3) Add 4 parts of 1-methylpyrrolidin-3-amine to the solution after the reaction in (2), heat the mixture to 100°C at a heating rate of not less than 20°C / min, and continue stirring for 3 hours. Steps (1) to (3) all utilize continuous mechanical double-paddle stirring, and the stirring speed is controlled at 350-400 rpm.

[0178] After the reaction is completed, the reaction system is filtered and washed with a pure solvent to obtain a precipitated product, which is then dried at normal pressure and 90°C for 5 hours to obtain the target product 2,8-bis(1-methylpyrrolidin-3-yl)-1,2,3,7,8,9-hexahydronaphtho[2,1-e:6,5-e']bis([1,3]oxazine) (VII-3).

[0179] Application Example 1

[0180] A method for preparing a thermoplastic vulcanized rubber comprises the following steps:

[0181] (1) Premixing: Under the conditions of high temperature heating at 210°C and continuous shearing of the extruder, 100 parts (by mass, the same below) of EPDM rubber, 100 parts of polypropylene plastic, 2 parts of primary antioxidant butylated hydroxytoluene, 1 part of secondary antioxidant triphenyl phosphite, 1 part of TAIC accelerator, 5 parts of carbon black filler, and 15 parts of calcium carbonate filler are added to 50 parts of paraffin oil, and premix particles are obtained by extrusion granulation, and dried for use;

[0182] (2) Dynamic vulcanization: The premix particles were placed into an extruder with continuous shearing at 200°C, and 2 parts of dicumyl peroxide crosslinker, 1 part of compound I-1, 50 parts of paraffin oil, and 15 parts of calcium carbonate filler were added for dynamic vulcanization. The mixture was then extruded and granulated to obtain a thermoplastic vulcanized rubber.

[0183] Application Example 2

[0184] The only difference between this application example and application example 1 is that the amount of compound I-1 added is 3 parts, and the other conditions are the same.

[0185] Application Example 3

[0186] The only difference between this application example and application example 1 is that the amount of compound I-1 added is 5 parts, and the other conditions are the same.

[0187] Application Example 4

[0188] The only difference between this application example and application example 1 is that the amount of compound I-1 added is 8 parts, and the other conditions are the same.

[0189] Application Example 5-12

[0190] The only difference between Application Examples 5-12 and Application Example 3 is that Compound I-1 is replaced by Compounds I-4, II-1, II-3, III-3, IV-2, V-4, VI-2, and VII-3, respectively, and the other conditions are the same.

[0191] Application Example 13

[0192] The only difference between this application example and application example 3 is that EPDM rubber is replaced by natural rubber, and the other conditions are the same.

[0193] Application Example 14

[0194] The only difference between this application example and application example 3 is that polypropylene plastic is replaced by polyurethane, and the other conditions are the same.

[0195] Application Example 15

[0196] The only difference between this application example and application example 3 is that EPDM rubber is replaced by ethylene acrylate rubber and polypropylene plastic is replaced by polyethylene, and the other conditions are the same.

[0197] Application Example 16

[0198] The only difference between this application example and application example 3 is that the dicumyl peroxide crosslinker is replaced by brominated p-octylphenolformaldehyde vulcanized resin SP-1055 crosslinker and the accelerator is replaced by zinc oxide. The other conditions are the same.

[0199] Comparative Example 1

[0200] The difference between this comparative example and application example 3 is that compound I-1 is not added, and the other conditions are the same.

[0201] Comparative Example 2

[0202] The difference between this comparative example and application example 16 is that compound I-1 is not added, and the other conditions are the same.

[0203] Comparative Example 3

[0204] The difference between this comparative example and application example 3 is that compound I-1 is replaced with 2-(benzo[d]oxazol-3(2H)-yl)-N-methylethan-1-amine (I-1'), and the other conditions are the same. The preparation method of compound I-1' is as follows:

[0205]

[0206] (1) 1 part (molar fraction, the same below) of o-aminophenol and 1 part of anhydrous potassium carbonate were added to a toluene / water (volume ratio 3:1) mixed solvent, with the concentration of o-aminophenol controlled at 2.5 mol / L. About 0.1 part of tetrabutylammonium bromide was added as a phase transfer catalyst, and the mixture was stirred at room temperature until completely dissolved.

[0207] (2) Raise the temperature to 90°C and slowly add 1.1 parts of 2-chloroethanol dropwise. The addition time is controlled at about 35 minutes. After the addition is completed, raise the temperature to 110°C and reflux for 4 hours.

[0208] (3) The reaction solution was cooled to room temperature and separated, retaining the upper toluene phase; 0.3 parts of anhydrous magnesium sulfate was added thereto, stirred for 30 minutes, and then filtered; the filtrate was distilled under reduced pressure at 85°C / -0.09 MPa to collect the intermediate product;

[0209] (4) Dissolve 1 part of the intermediate product in anhydrous ethanol to a concentration of 4 mol / L, and introduce 2 parts of methylamine gas; cool to 10°C, slowly introduce 1.1 parts of ethylene oxide gas, and then raise the temperature to 20°C for 3 hours;

[0210] (5) Maintaining the temperature at 25°C, add 1.2 parts of sodium borohydride in 6 portions (15 min interval between each addition). After addition, raise the temperature to 50°C and react for 3 h.

[0211] (6) After the reaction was completed, the mixture was cooled to room temperature and 10 wt% dilute hydrochloric acid was slowly added dropwise until no bubbles were generated. The ethanol was then removed by distillation under reduced pressure and the pH was adjusted to 10 with 20% sodium hydroxide solution. The mixture was extracted three times with dichloromethane, and the organic phases were combined, dried over anhydrous magnesium sulfate for 30 min, and filtered. The filtrate was concentrated under reduced pressure to obtain compound I-1'.

[0212] The key parameters of Application Examples 1-16 and Comparative Examples 1-3 of the present application and the dielectric constant test data of the prepared thermoplastic vulcanizate are shown in Table 1, wherein the ambient temperature for the dielectric constant test is 23° C., and the test method refers to the standard ASTM D150.

[0213] Table 1

[0214] serial number rubber plastic crosslinking agent Types of additives Additive content (parts) Dielectric constant Application Example 1 EPDM Polypropylene Dicumyl peroxide I-1 1 1.8 Application Example 2 EPDM Polypropylene Dicumyl peroxide I-1 3 1.7 Application Example 3 EPDM Polypropylene Dicumyl peroxide I-1 5 1.6 Application Example 4 EPDM Polypropylene Dicumyl peroxide I-1 8 1.4 Application Example 5 EPDM Polypropylene Dicumyl peroxide I-4 5 1.5 Application Example 6 EPDM Polypropylene Dicumyl peroxide II-1 5 1.6 Application Example 7 EPDM Polypropylene Dicumyl peroxide II-3 5 1.3 Application Example 8 EPDM Polypropylene Dicumyl peroxide III-3 5 1.4 Application Example 9 EPDM Polypropylene Dicumyl peroxide IV-2 5 1.5 Application Example 10 EPDM Polypropylene Dicumyl peroxide V-4 5 1.4 Application Example 11 EPDM Polypropylene Dicumyl peroxide VI-2 5 1.5 Application Example 12 EPDM Polypropylene Dicumyl peroxide VII-3 5 1.3 Application Example 13 natural rubber Polypropylene Dicumyl peroxide I-1 5 1.5 Application Example 14 EPDM polyurethane Dicumyl peroxide I-1 5 1.4 Application Example 15 Ethylene acrylic rubber polyethylene Dicumyl peroxide I-1 5 1.4 Application Example 16 EPDM Polypropylene SP-1055 I-1 5 1.3 Comparative Example 1 EPDM Polypropylene Dicumyl peroxide / / 2.8 Comparative Example 2 EPDM Polypropylene SP-1055 / / 2.6 Comparative Example 3 EPDM Polypropylene Dicumyl peroxide I-1' 5 2.8

[0215] As can be seen from Table 1, the compounds described herein can effectively reduce the dielectric constant of thermoplastic vulcanizates, regardless of whether they are cross-linked with a peroxide or phenolic resin. Furthermore, while the structure of I-1' in Comparative Example 3 is similar to that of compound I-1, its oxazole ring is relatively stable and does not undergo a ring-opening reaction to form -OH at temperatures around 150°C. Therefore, it is unable to reduce the polarity of the thermoplastic vulcanizate by forming hydrogen bonds during the vulcanization process, and thus is unable to reduce the dielectric constant of the thermoplastic vulcanizate.

[0216] In the second step of dynamic vulcanization in the above application examples and comparative examples, the thermoplastic vulcanized rubber melt samples were taken for infrared testing. Among them, the samples of application examples 1-16 all showed obvious hydrogen bond characteristic peaks (the formation of intramolecular H bonds was in the infrared 3500-3000cm -1 The wavelength band will form a wide absorption peak, and the formation of intermolecular H bonds is in the infrared 3600-3500cm -1The wave band forms a relatively wide absorption peak. The thermoplastic vulcanized rubber samples of Examples 1-16 all have a characteristic peak of hydrogen bond at 3400-3200 cm -1 The wave band forms a relatively wide absorption peak. The thermoplastic vulcanized rubber samples of Examples 1-16 all have a characteristic peak of hydrogen bond at 3400-3200 cm

[0217] In the examples, application examples and comparative examples of the present application, the reaction raw materials (such as the raw materials for preparing the auxiliary agent) and production raw materials (such as the crosslinking agent, antioxidant, rubber, plastic, processing aid and the like used for preparing the thermoplastic vulcanized elastomer) are all commercially available raw materials, and the specific source thereof is not limited in the present application.

[0218] It should be noted that, due to the limited space, the preparation methods and application effects of all the compounds recorded in the present application are not listed one by one. However, the present application is not limited to the above-mentioned embodiments. The above-mentioned embodiments are only examples, and the embodiments having the same technical idea and playing the same role within the scope of the technical solutions of the present application are all included in the technical scope of the present application. In addition, within the scope of the main idea of the present application, various modifications of the embodiments that can be thought of by those skilled in the art, other ways constructed by combining part of the constituent elements of the embodiments are also included in the scope of the present application.

Claims

1. An additive for reducing the dielectric constant of thermoplastic vulcanizate, characterized in that: Included are compounds containing a group represented by formula a in the molecule: [Formula a] Wherein, * indicates the attachment site.

2. The auxiliary agent according to claim 1, characterized in that Including compounds represented by formula A: [Formula A] Wherein, R1 is a group represented by formula b, formula c or formula d: [Formula b] [Formula c] [Formula d] in, R2 is H, substituted alkyl, substituted or unsubstituted phenyl, or substituted or unsubstituted 3,4-dihydro-2H-1,3-oxazinyl, and when R2 is substituted or unsubstituted phenyl, or substituted or unsubstituted 3,4-dihydro-2H-1,3-oxazinyl, the benzene ring or 3,4-dihydro-2H-1,3-oxazinyl ring is fused with the benzene ring in formula A; R3 is a substituted or unsubstituted alkyl group; R4 is H, or substituted or unsubstituted alkyl; * indicates the attachment site.

3. The auxiliary agent according to claim 1 or 2, characterized in that Contains one or more of the following compounds:

4. A method for preparing a thermoplastic vulcanizate with a low dielectric constant, comprising dynamic vulcanization, characterized in that: The auxiliary agent according to any one of claims 1 to 3 is added during the dynamic vulcanization stage.

5. The method according to claim 4, characterized in that The following steps are involved: Premixing: Rubber, plastic, crosslinking agent, filler and oil are premixed and granulated to obtain premix; Dynamic vulcanization: heating the premix and continuously shearing it, adding the auxiliary agent, cross-linking agent, filler and auxiliary oil thereto, extruding and granulating, and obtaining the thermoplastic vulcanized rubber with a low dielectric constant.

6. The method according to claim 5, characterized in that The rubber includes one or more of EPDM rubber, butyl rubber, silicone rubber, fluororubber, ethylene acrylate rubber, and natural rubber; and / or, The plastic includes one or more of polypropylene, polyethylene, polyamide, polyvinyl chloride, polystyrene, polycarbonate, and polyethylene terephthalate.

7. The method according to claim 5 or 6, characterized in that Based on 100 parts by mass of the rubber, the added amount of the plastic is 35-150 parts, and the added amount of the auxiliary agent is 1-8 parts.

8. The method according to claim 7, characterized in that One or more of the following conditions are met: The amount of the cross-linking agent added is 1-4 parts; The amount of the cross-linking aid added is 2-4 parts; The amount of the filler added in the premixing stage is 15-80 parts, and / or the total amount of the filler added is 25-120 parts; The amount of the auxiliary oil added in the premixing stage is 25-115 parts, and / or the total amount of the auxiliary oil added is 50-225 parts; The cross-linking agent includes one or more of a peroxide cross-linking agent and a phenolic resin; the peroxide includes one or more of dicumyl peroxide, di-tert-butyl peroxyisopropylbenzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, di(2,4-dichlorobenzoyl) peroxide, and di-tert-butyl peroxide; The crosslinking aid includes a primary antioxidant, an auxiliary antioxidant and an accelerator; the primary antioxidant includes butylated hydroxytoluene, pentaerythritol tetrakis (3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate), β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N-phenyl-N'-1,3-dimethylbutyl-p-phenylenediamine, N-phenyl- One or more of N'-isopropyl-p-phenylenediamine; and / or, the auxiliary antioxidant includes one or more of tris[2,4-di-tert-butylphenyl]phosphite, triphenyl phosphite, dilauryl thiodipropionate, and distearyl thiodipropionate; and / or, the accelerator includes one or more of stannous chloride, zinc oxide, zinc stearate, manganese oxide, zinc bromide, stannous octoate, hexamethylenetetramine, TAIC, TMPTMA, EGDMA, and DAP; The filler includes one or more of calcium carbonate, talc, carbon black, glass fiber, kaolin, and wollastonite; The auxiliary oil includes one or more of paraffin oil, naphthenic oil, epoxidized soybean oil, and white oil.

9. A thermoplastic vulcanizate prepared by the method according to any one of claims 4 to 8.

10. Use of the thermoplastic vulcanizate according to claim 9 in consumer electronics, smart wearable devices, home appliances, batteries, sealing devices, silencers, water pipes, wires and cables, engines, and automobiles.

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