New energy automobile high-temperature-resistant flame-retardant cable material and preparation method thereof

Abstract

The invention discloses a preparation method of a high-temperature-resistant flame-retardant cable material for a new energy automobile, which comprises the following steps: S1, carrying out click chemical reaction on alkynyl phosphate and azido fatty amine to obtain phosphate-1, 2, 3-triazole diamine; s2, carrying out condensation polymerization on the nitrogen-phosphorus-rich polymer and ODOPB to obtain a nitrogen-phosphorus-rich polymer as an additive; s3, uniformly mixing the ethylene-acrylate copolymer and the special rubber, adding the additive, the inorganic filler and the auxiliary agent, and continuously mixing to obtain a mixture; and S4, extruding and granulating to obtain the high-temperature-resistant flame-retardant cable material for the new energy automobile. According to the preparation method disclosed by the invention, the high-temperature resistance and the flame retardant property are improved, and the material has excellent mechanical strength and chemical stability, meanwhile, the long-term durability and reliability of the material under extreme conditions are ensured, and the material is high in overall comprehensive performance and wide in application prospect. The high-standard requirements of new energy automobiles on the cable material in the aspects of safety, durability and functionality can be met.

Description

Technical Field

[0001] The present invention relates to the technical field of new energy vehicles, and in particular to a high temperature resistant flame retardant cable material for new energy vehicles and a preparation method thereof. Background Art

[0002] In the field of new energy vehicles, the selection of cable materials is crucial because they need to withstand extreme temperature changes, chemical corrosion, and mechanical stress throughout the life cycle of the vehicle. Traditional cable materials, such as general-purpose polyethylene and polyvinyl chloride, although low in cost, have obvious deficiencies in high temperature resistance and flame retardancy. Especially in the battery system, motor and control system of new energy vehicles, cable materials need to have higher heat resistance grades and excellent flame retardant properties to ensure the safety and reliability of the vehicle. In addition, with the development of new energy vehicle technology, higher requirements are also placed on the mechanical properties and chemical stability of cable materials. Therefore, the development of a new type of high temperature resistant and flame retardant cable material that can meet these harsh conditions has become an urgent need for the development of the new energy vehicle industry. Although there are some improved cable materials on the market, it is still difficult for them to fully meet the special requirements of new energy vehicles in terms of comprehensive performance, especially in terms of high temperature resistance, flame retardancy and long-term stability. Summary of the invention

[0003] In view of the above shortcomings of the prior art, the present invention provides a method for preparing a high-temperature resistant and flame-retardant cable material for new energy vehicles to solve the deficiencies of traditional cable materials in terms of high temperature resistance, flame retardancy, mechanical strength and chemical stability. This new method for preparing cable materials not only improves the heat resistance and flame retardant effect of the cable material, but also enhances its mechanical strength and chemical corrosion resistance by introducing nitrogen-phosphorus-rich polymers as additives, and selected ethylene-acrylate copolymers and special rubbers as main materials, combined with inorganic fillers and a variety of additives, thereby ensuring the long-term durability and stability of the cable material under the harsh working conditions of new energy vehicles. These improvements make the cable material of the present invention particularly suitable for high-performance application fields such as new energy vehicles, and can maintain its functionality and safety in extreme temperatures and chemical environments, meeting the strict requirements of new energy vehicles for high temperature resistance, flame retardancy, mechanical properties and chemical stability of cable materials.

[0004] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0005] A method for preparing a high temperature resistant flame retardant cable material for new energy vehicles, the preparation method comprising the following steps:

[0006] S1: Under anhydrous and oxygen-free conditions, alkynyl phosphate and azido fatty amine are subjected to a click chemistry reaction in the presence of a catalyst to obtain phosphate-1,2,3-triazole diamine;

[0007] S2: subjecting the phosphate-1,2,3-triazole diamine obtained in step S1 to a polycondensation reaction with ODOPB under certain conditions to obtain a nitrogen- and phosphorus-rich polymer;

[0008] S3: Compounding the main components of the cable material, ethylene-acrylate copolymer and special rubber, in proportion and kneading them evenly, then adding the nitrogen-phosphorus-rich polymer obtained in step S2 as an additive together with the inorganic filler and the auxiliary agent to the main components of the mixed cable material, and continuing to knead them to obtain a mixture;

[0009] S4: Extruding and granulating the mixture obtained in step S3 through a twin-screw extruder under high temperature conditions to obtain the high temperature resistant and flame retardant cable material for new energy vehicles.

[0010] In the preparation process of the high temperature resistant flame retardant cable material for new energy vehicles of the present invention, steps S1 and S2 achieve a significant improvement in material performance by introducing specific functional groups. In step S1, through a click chemistry reaction under anhydrous and oxygen-free conditions, alkynyl phosphate and azido fatty amine react under the action of a catalyst to generate phosphate-1,2,3-triazole diamine. In this process, the combination of alkynes and azides forms a stable triazole ring. At the same time, the introduction of phosphate groups provides additional polarity for the material, enhances the interaction between the material and the substrate, and helps to improve the flame retardant properties of the material. These characteristics make the material stable in a high temperature environment, enhancing its heat resistance and chemical stability.

[0011] In step S2, the phosphate ester-1,2,3-triazole diamine obtained in step S1 is further reacted with ODOPB (10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide) through a condensation reaction to obtain a nitrogen-phosphorus-rich polymer. As a phosphorus-containing compound, the introduction of the phosphaphenanthrene functional group of ODOPB can increase the phosphorus content in the material. The phosphorus element can produce phosphoric acid during thermal decomposition, thereby improving the flame retardant properties of the material. The formation of the nitrogen-phosphorus polymer not only improves the flame retardant properties of the material, but also enhances the thermal stability and mechanical properties of the material, which is crucial for the application of cable materials in new energy vehicles, especially under high temperature and mechanical stress environments. The nitrogen-phosphorus-rich polymer synthesized by steps S1 and S2 makes the prepared cable material not only have excellent high temperature resistance and flame retardant properties, but also have good mechanical strength and durability, meeting the high performance requirements of new energy vehicles for cable materials.

[0012] As a preferred technical solution, the general structural formula of the alkynyl phosphate is as follows:

[0013] In the formula, R1 is methyl, ethyl or propyl; R2 is an alkane group of 1 or 2 carbon atoms.

[0014] As a preferred technical solution, the azido fatty amine is at least one of 2-azidoethylamine, 3-azido-1-propylamine, and 4-azidobutylamine.

[0015] As a preferred technical solution, in step S2, the reaction conditions of the polycondensation reaction are: under the protection of an inert atmosphere, the reaction temperature is controlled to be 180-250° C., the reaction pressure is 0.1-1 bar, the reaction time is 2-10 hours, and an organic tin compound is selected as a catalyst. The organic tin compound is at least one of dibutyltin dilaurate, stannous octoate, dibutyltin didodecylsulfide, and dibutyltin diacetate.

[0016] As a preferred technical solution, the ethylene-acrylic acid ester copolymer is at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene butyl acrylate copolymer (EBA).

[0017] As a preferred technical solution, the special rubber is at least one of silicone rubber, fluororubber and fluorosilicone rubber.

[0018] As a preferred technical solution, the inorganic filler is at least one of white carbon black, magnesium hydroxide, aluminum hydroxide, zinc borate and zinc phosphate.

[0019] As a preferred technical solution, the auxiliary agent is at least one of a plasticizer, a stabilizer, a wetting agent, an antioxidant, a crosslinking agent, and a vulcanizing agent.

[0020] As a preferred technical solution, the plasticizer is at least one of dibutyl phthalate, dioctyl phthalate, and diisobutyl phthalate.

[0021] As a preferred technical solution, the stabilizer is at least one of calcium stearate, zinc stearate, magnesium stearate, epoxy soybean oil, and bisphenol A.

[0022] As a preferred technical solution, the wetting agent is at least one of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, and polyoxyethylene sorbitan monostearate.

[0023] As a preferred technical solution, the antioxidant is at least one of antioxidant 168, antioxidant 1010, antioxidant 1076, antioxidant 626, and antioxidant 3114.

[0024] As a preferred technical solution, the cross-linking agent is at least one of dibenzoyl peroxide, a dibenzoyl peroxide-benzophenone mixture, and dicumyl peroxide.

[0025] As a preferred technical solution, the vulcanizing agent is at least one of 2-mercaptobenzothiazole, 2,2'-dibenzoylbis(N-phenylamine), and tetramethylthiodiphenylamine.

[0026] As a preferred technical solution, the mass ratio of the ethylene-acrylic ester copolymer, the special rubber, the additive, the inorganic filler and the auxiliary agent is 40-60:25-45:1-7:3-9:5-15.

[0027] Another aspect of the present invention is to provide a high temperature resistant and flame retardant cable material for new energy vehicles, wherein the cable material is prepared by the preparation method of the high temperature resistant and flame retardant cable material for new energy vehicles as described above.

[0028] The present invention selects ethylene-acrylate copolymer and special rubber as the main components of the cable material, so that the cable material of the present invention has the excellent properties of ethylene-acrylate copolymer and special rubber, and further compounding inorganic fillers such as white carbon black, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc phosphate, etc., not only enhances the mechanical strength and heat resistance of the cable material, but also helps to improve the flame retardant performance of the cable material; through the addition of plasticizers, stabilizers, wetting agents, antioxidants, crosslinking agents, vulcanizing agents and other additives, the processing performance, stability and aging resistance of the cable material of the present invention are improved, ensuring the long-term durability and reliability of the cable material in complex environments. These comprehensive characteristics make the cable material of the present invention particularly suitable for high-performance application fields such as new energy vehicles, and can maintain its functionality and safety in extreme temperatures and chemical environments, meeting the strict requirements of new energy vehicles for high temperature resistance, flame retardancy, mechanical properties and chemical stability of cable materials.

[0029] Beneficial effects of the present invention:

[0030] The preparation method of the high temperature resistant flame retardant cable material for new energy vehicles of the present invention not only achieves high temperature resistance and excellent flame retardant properties, but also improves the comprehensive performance of the material by innovatively introducing a polymer rich in nitrogen and phosphorus as an additive in the material formula and preparation method. The material formula and preparation method of the present invention not only enhance the mechanical strength and heat resistance of the cable material, but also maintain the processability and flexibility of the material, which helps to improve the application reliability and safety of the cable material in new energy vehicles.

[0031] In general, the high temperature resistant and flame retardant cable material for new energy vehicles of the present invention not only has excellent high temperature resistance and outstanding flame retardant effect, but also has good mechanical properties and chemical stability, which can meet the high performance requirements of new energy vehicles for cable materials in extreme temperature and chemical environments. DETAILED DESCRIPTION

[0032] The following description is used to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are only examples, and those skilled in the art may think of other obvious variations.

[0033] Example 1

[0034] The preparation method of the high temperature resistant flame retardant cable material for new energy vehicles of this embodiment comprises the following steps:

[0035] Step S1: Under anhydrous and oxygen-free conditions, 50 g of ethyl diprop-2-ynyl phosphate and 60 g of 2-azidoethylamine are subjected to a click chemistry reaction in the presence of 0.5 g of copper acetate (Cu(I)OAc) (as a catalyst). The reaction is carried out at room temperature (about 25°C) and stirred continuously until the reaction is completed. The reaction lasts for 2 hours to obtain phosphate-1,2,3-triazole diamine. In order to improve the reaction efficiency and selectivity, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) can be added as a ligand in an amount of 0.5 g.

[0036] Step S2: 55 g of the phosphate-1,2,3-triazole diamine obtained in step S1 and 30 g of ODOPB (i.e., 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide) are subjected to polycondensation under certain conditions to obtain a polymer rich in nitrogen and phosphorus. The polycondensation reaction is carried out under the protection of an inert atmosphere, the reaction temperature is controlled to be 200° C., the reaction pressure is 0.5 bar, the reaction time is 5 hours, and dibutyltin dilaurate is selected as a catalyst in an amount of 0.1% of the total reactant mass.

[0037] Step S3: 200 g of ethylene-methyl acrylate copolymer (EMA), the main component of the cable material, and 150 g of silicone rubber are compounded in proportion and mixed evenly. During the mixing process, EMA and silicone rubber are first mixed at a temperature of 80° C. for 2 hours to ensure that the two are fully compatible; then 20 g of the nitrogen-phosphorus-rich polymer obtained in step S2 is added as an additive to the main component of the mixed cable material; in addition, 30 g of inorganic filler aluminum hydroxide and the following weight of auxiliary agents are added: 10 g of plasticizer dibutyl phthalate, 5 g of stabilizer calcium stearate, 2 g of wetting agent polyoxyethylene sorbitan monolaurate, 3 g of antioxidant 1010, 2 g of crosslinking agent dibenzoyl peroxide and 1 g of vulcanizing agent 2-mercaptobenzothiazole. After continuing to mix for 4 hours, a uniform mixture is obtained.

[0038] Step S4: Add the mixture obtained in step S3 into a twin-screw extruder with a rotation speed of 60 rpm and an extrusion temperature of 120-160° C. for melt mixing, and then sequentially perform extrusion, drawing, air cooling, pelletizing and drying processes to obtain the high temperature resistant and flame retardant cable material for new energy vehicles.

[0039] Example 2

[0040] The preparation method of the high temperature resistant flame retardant cable material for new energy vehicles of this embodiment comprises the following steps:

[0041] Step S1: Under anhydrous and oxygen-free conditions, 50 g of ethyl diprop-2-ynyl phosphate and 68 g of 3-azido-1-propylamine are subjected to a click chemistry reaction in the presence of 0.5 g of copper acetate (Cu(I)OAc) (as a catalyst). The reaction is carried out at room temperature (about 25°C) and stirred continuously until the reaction is completed. The reaction lasts for 2 hours to obtain phosphate-1,2,3-triazole diamine. In order to improve the reaction efficiency and selectivity, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) can be added as a ligand in an amount of 0.5 g.

[0042] Step S2: 55 g of the phosphate-1,2,3-triazole diamine obtained in step S1 and 30 g of ODOPB (i.e., 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide) are subjected to polycondensation under certain conditions to obtain a polymer rich in nitrogen and phosphorus. The polycondensation reaction is carried out under the protection of an inert atmosphere, the reaction temperature is controlled to be 180° C., the reaction pressure is 0.3 bar, the reaction time is 8 hours, and dibutyltin dilaurate is selected as a catalyst in an amount of 0.1% of the total reactant mass.

[0043] Step S3: 225 g of ethylene-methyl methacrylate copolymer (EMMA) as the main component of the cable material and 175 g of silicone rubber are mixed in proportion and kneaded evenly. During the kneading process, EMMA and silicone rubber are firstly kneaded at a temperature of 80°C for 3 hours to ensure that the two are fully compatible; then 35 g of the nitrogen-phosphorus-rich polymer obtained in step S2 is added as an additive to the main component of the kneaded cable material; in addition, 45 g of inorganic filler zinc borate and the following weight of auxiliary agents are added: 10 g of plasticizer dioctyl phthalate, 10 g of stabilizer zinc stearate, 5 g of wetting agent polyoxyethylene sorbitan monopalmitate, 10 g of antioxidant 1076, 10 g of crosslinking agent diisopropyl peroxide and 5 g of vulcanizing agent 2,2'-dibenzoylbis(N-aniline). After continuing to knead for 5 hours, a uniform mixture is obtained.

[0044] Step S4: Add the mixture obtained in step S3 into a twin-screw extruder with a rotation speed of 60 rpm and an extrusion temperature of 120-160° C. for melt mixing, and then sequentially perform extrusion, drawing, air cooling, pelletizing and drying processes to obtain the high temperature resistant and flame retardant cable material for new energy vehicles.

[0045] Example 3

[0046] The preparation method of the high temperature resistant flame retardant cable material for new energy vehicles of this embodiment comprises the following steps:

[0047] Step S1: Under anhydrous and oxygen-free conditions, 50 g of ethyl diprop-2-ynyl phosphate and 75 g of 4-azidobutylamine are subjected to a click chemistry reaction in the presence of 0.5 g of copper acetate (Cu(I)OAc) (as a catalyst). The reaction is carried out at room temperature (about 25°C) and stirred continuously until the reaction is completed. The reaction lasts for 2 hours to obtain phosphate-1,2,3-triazole diamine. In order to improve the reaction efficiency and selectivity, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) can be added as a ligand in an amount of 0.5 g.

[0048] Step S2: 55 g of the phosphate-1,2,3-triazole diamine obtained in step S1 and 30 g of ODOPB (i.e., 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide) are subjected to polycondensation under certain conditions to obtain a polymer rich in nitrogen and phosphorus. The polycondensation reaction is carried out under the protection of an inert atmosphere, the reaction temperature is controlled to be 250° C., the reaction pressure is 1 bar, the reaction time is 3 hours, and dibutyltin dilaurate is selected as a catalyst in an amount of 0.1% of the total reactant mass.

[0049] Step S3: 250 g of ethylene-ethyl acrylate copolymer (EEA), the main component of the cable material, and 125 g of silicone rubber are compounded in proportion and mixed evenly. During the mixing process, EEA and silicone rubber are first mixed at a temperature of 80° C. for 3 hours to ensure that the two are fully compatible; then 15 g of the nitrogen-phosphorus-rich polymer obtained in step S2 is added as an additive to the main component of the mixed cable material; in addition, 40 g of inorganic filler white carbon black and the following weight of auxiliary agents are added: 15 g of plasticizer diisobutyl phthalate, 10 g of stabilizer bisphenol A, 5 g of wetting agent polyoxyethylene sorbitan monostearate, 5 g of antioxidant 626, 5 g of crosslinking agent diisopropyl peroxide, and 5 g of vulcanizing agent tetramethylthiodiphenylamine. After continuing to mix for 5 hours, a uniform mixture is obtained.

[0050] Step S4: Add the mixture obtained in step S3 into a twin-screw extruder with a rotation speed of 60 rpm and an extrusion temperature of 120-160° C. for melt mixing, and then sequentially perform extrusion, drawing, air cooling, pelletizing and drying processes to obtain the high temperature resistant and flame retardant cable material for new energy vehicles.

[0051] Comparative Example 1

[0052] The raw material composition and preparation steps of the preparation method of the high-temperature resistant and flame-retardant cable material for new energy vehicles in this comparative example are basically the same as those in Example 1, except that, in the preparation method of this comparative example, the nitrogen and phosphorus-rich polymer prepared in step S2 is not added.

[0053] The performance of the high temperature resistant flame retardant cable materials for new energy vehicles prepared in Examples 1 to 3 and Comparative Example 1 was tested, and the performance results are shown in Table 1:

[0054] Among them, the testing basis: tensile strength and elongation at break are GB / T 2951.11; the change rate of tensile strength after hot air aging is GB / T 2951.12; the depth of thermal deformation indentation is GB / T 2951.31; the thermal shock test is GB / T 2951.31; the thermal stability test time is GB / T 2951.32; the change rate of tensile strength in acid and alkali resistance test is GB / T 2951.21; and the flame retardant performance is UL1581. Table 1

[0055] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions only describe the principles of the present invention. The present invention may be subject to various changes and improvements without departing from the spirit and scope of the present invention, and these changes and improvements fall within the scope of the present invention claimed.

Claims

1. A method for preparing a high temperature resistant flame retardant cable material for new energy vehicles, characterized in that: The preparation method comprises the following steps: S1: Under anhydrous and oxygen-free conditions, alkynyl phosphate and azido fatty amine are subjected to a click chemistry reaction in the presence of a catalyst to obtain phosphate-1,2,3-triazole diamine; S2: subjecting the phosphate-1,2,3-triazole diamine obtained in step S1 to a polycondensation reaction with ODOPB under certain conditions to obtain a nitrogen- and phosphorus-rich polymer; S3: Compounding the main components of the cable material, ethylene-acrylate copolymer and special rubber, in proportion and kneading them evenly, then adding the nitrogen-phosphorus-rich polymer obtained in step S2 as an additive together with the inorganic filler and the auxiliary agent to the main components of the mixed cable material, and continuing to knead them to obtain a mixture; S4: Extruding and granulating the mixture obtained in step S3 through a twin-screw extruder under high temperature conditions to obtain the high temperature resistant and flame retardant cable material for new energy vehicles.

2. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The general structural formula of the alkynyl phosphate is as follows: In the formula, R1 is methyl, ethyl or propyl; R2 is an alkane group of 1 or 2 carbon atoms.

3. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The azido fatty amine is at least one of 2-azidoethylamine, 3-azido-1-propylamine and 4-azidobutylamine.

4. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: In step S2, the reaction conditions of the polycondensation reaction are: under the protection of an inert atmosphere, the reaction temperature is controlled to be 180-250° C., the reaction pressure is 0.1-1 bar, the reaction time is 2-10 hours, and an organic tin compound is selected as a catalyst.

5. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The ethylene-acrylic acid ester copolymer is at least one of ethylene-methyl acrylate copolymer (EMA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), and ethylene butyl acrylate copolymer (EBA).

6. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The special rubber is at least one of silicone rubber, fluororubber and fluorosilicone rubber.

7. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The inorganic filler is at least one of white carbon black, magnesium hydroxide, aluminum hydroxide, zinc borate and zinc phosphate.

8. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The auxiliary agent is at least one of a plasticizer, a stabilizer, a wetting agent, an antioxidant, a crosslinking agent, and a vulcanizing agent.

9. The method for preparing the high temperature resistant flame retardant cable material for new energy vehicles according to claim 1, characterized in that: The mass ratio of the ethylene-acrylic ester copolymer, the special rubber, the additive, the inorganic filler and the auxiliary agent is 40-60:25-45:1-7:3-9:5-15.

10. A high temperature resistant flame retardant cable material for new energy vehicles, characterized in that: The cable material is prepared by the method for preparing the high temperature resistant and flame retardant cable material for new energy vehicles as claimed in any one of claims 1 to 9.

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