CN114106479B - High-performance cable material for vehicles and preparation method thereof - Google Patents

High-performance cable material for vehicles and preparation method thereof Download PDF

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CN114106479B
CN114106479B CN202111491041.1A CN202111491041A CN114106479B CN 114106479 B CN114106479 B CN 114106479B CN 202111491041 A CN202111491041 A CN 202111491041A CN 114106479 B CN114106479 B CN 114106479B
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cable material
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CN114106479A (en
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吕琦
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C08L23/36—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with compounds containing nitrogen, e.g. by nitration
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

Abstract

The invention discloses a high-performance automotive cable material and a preparation method thereof, and relates to the technical field of cable materials. The invention prepares the self-made flame retardant from melamine and phenyl phosphoryl dichloride, and prepares the modified polyethylene through ultraviolet irradiation with polyethylene, so that the modified polyethylene can form a compact carbon layer when burning, thereby achieving the effects of flame retardance and smoke suppression; blending the modified polyethylene, the self-made additive, the ethylene-octene copolymer and other fillers to prepare a cable material; the self-made additive is prepared from acetonitrile dimethyl pyrazole tetrazine, methyl aldehyde nitrobenzoate and cyclooctene, and an ultraviolet absorbing group is introduced, so that the ultraviolet shielding performance of the cable material is realized, and the molecular chain segments at damaged parts can be subjected to chain scission recombination, so that the self-repairing performance is realized. The high-performance cable material for the vehicle, which is prepared by the invention, has the effects of flame retardance, self-repairing and ultraviolet shielding.

Description

High-performance cable material for vehicles and preparation method thereof
Technical Field
The invention relates to the technical field of cable materials, in particular to a high-performance automotive cable material and a preparation method thereof.
Background
The new energy automobile industry in the new era is responsible for the double tasks of industry transformation and upgrading and protecting the atmosphere environment, and greatly drives the industrial development of related accessories such as cables for electric automobiles, and various cable manufacturers and certification institutions invest a great deal of effort in the research and development of the cables for electric automobiles.
With the development of the cable industry, the requirements of people on the use performances of the cable, such as safety, aesthetic property and the like, are higher and higher, and the improvement of the traditional cable material is a fundamental way for improving the use performances of the cable.
Disclosure of Invention
The invention aims to provide a high-performance cable material for a vehicle and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme: the high-performance cable material for the vehicle is characterized by mainly comprising, by weight, 70-100 parts of modified polyethylene, 60-90 parts of ethylene-octene copolymer, 10-20 parts of self-made additive, 40-60 parts of talcum powder, 10-15 parts of calcium carbonate, 30-50 parts of calcined clay and 10-20 parts of paraffin-based rubber oil.
Further, the modified polyethylene is prepared from polyethylene and a self-made flame retardant.
Further, the self-made flame retardant is prepared from melamine and phenyl phosphoryl dichloride.
Further, the self-made additive is prepared from para-acetonitrile dimethyl pyrazole tetrazine, methyl aldehyde nitrobenzoate and cyclooctene.
Further, the high-performance automotive cable material comprises the following raw material components in parts by weight: 90 parts of modified polyethylene, 60 parts of ethylene-octene copolymer, 15 parts of self-made additive, 50 parts of talcum powder, 12 parts of calcium carbonate, 40 parts of calcined clay and 20 parts of paraffin-based rubber oil.
Further, the preparation method of the high-performance automotive cable material is characterized by mainly comprising the following preparation steps:
(1) Placing melamine and chloroform with the mass of 5.4 times of that of the melamine into a three-neck flask, placing the three-neck flask into an ice bath pot at the temperature of 0 ℃, adding phenyl phosphoryl dichloride with the mass of 0.8 times of that of the melamine, adding sodium hydroxide with the mass fraction of 12% until the pH value of the solution is 7-8, separating liquid after reaction for 6 hours, steaming for 3-4 min at the temperature of 60 ℃ under the speed of 200rpm, and washing with deionized water for 3-4 times to obtain a self-made flame retardant;
(2) Under the nitrogen atmosphere, soaking polyethylene in a self-made flame retardant/methanol solution with the mass ratio of 4.5 times of that of the polyethylene to the self-made flame retardant/methanol solution being 1:4, placing the polyethylene in an ultraviolet crosslinking reactor after soaking for 24 hours, and obtaining the modified polyethylene with the irradiation time of 10-15 minutes;
(3) Adding acetonitrile dimethyl pyrazole tetrazine and ethanol with the mass of 19.2 times of that of the acetonitrile dimethyl pyrazole tetrazine into a three-neck flask, heating to 78 ℃ in an oil bath while stirring at the speed of 150rpm, adding methyl aldehyde nitrobenzoate/ethanol solution with the mass of 12.4 times of that of the acetonitrile dimethyl pyrazole tetrazine, wherein the mass ratio of the methyl aldehyde nitrobenzoate to the ethanol in the methyl aldehyde nitrobenzoate/ethanol solution is 1:12.1, adding glacial acetic acid with the mass of 1.02 times of that of the acetonitrile dimethyl pyrazole tetrazine, stirring at the same speed for 3 hours at the temperature of 78 ℃, cooling to room temperature, and adding cyclooctene with the mass of 1.8 times of that of the acetonitrile dimethyl pyrazole tetrazine, and reacting for 2 hours to obtain a self-made additive;
(4) Plasticating the modified polyethylene and the ethylene-octene copolymer in an internal mixer with the formula amount of 70-80 ℃ and the speed of 40rpm for 2-3 min, adding the self-made additive and the paraffin-based rubber oil with the formula amount of 1-2 min, adding the calcium carbonate, the calcined clay and the talcum powder with the formula amount of 100-130 ℃ for 2-3 min, placing the materials on an open mill for 1-2 times, placing the materials on a glue placing device for 2-3 times, calendaring the materials to form sheets with the thickness of 0.23mm, cooling to room temperature, conveying the materials to a continuous vulcanization rubber extruder, and extruding the materials to obtain the high-performance automotive cable material. .
Further, the ultraviolet light wavelength of the ultraviolet light crosslinking reactor in the step (2) is 254nm, and the irradiation distance is 20-30 cm.
Further, the preparation method of the para acetonitrile dimethyl pyrazole tetrazine in the step (3) comprises the following steps:
a. adding distilled water with the mass of the triaminoguanidine hydrochloride and the triaminoguanidine hydrochloride being 5 times into a three-neck flask, heating to 75 ℃ while stirring at the speed of 200rpm, dropwise adding an acetylacetone-ethanol mixed solution at the speed of 1-2 mL/min, controlling the mass ratio of acetylacetone to ethanol in the acetylacetone-ethanol mixed solution to be 1:1.13, controlling the reaction temperature to be 75 ℃, stirring at the same speed for 4 hours, cooling to room temperature, carrying out suction filtration, and drying at room temperature for 8 hours to obtain the dimethyl pyrazole tetrazine;
b. adding dimethyl pyrazole tetrazine and sodium nitrite with the mass of 0.32 times of that of the dimethyl pyrazole tetrazine into a three-neck flask, adding distilled water-ethanol solution with the mass of 89.5 times of that of the dimethyl pyrazole tetrazine, wherein the mass ratio of distilled water to ethanol in the distilled water-ethanol solution is 1:1.8, stirring uniformly, adding diethyl ether-glacial acetic acid with the mass of 10.9 times of that of the dimethyl pyrazole tetrazine at the speed of 0.3-0.5 mL/min, wherein the mass ratio of diethyl ether to glacial acetic acid in the diethyl ether-glacial acetic acid is 1:6.62, performing suction filtration after reacting for 12 hours, washing for 10-12 times by using absolute ethanol, and drying at room temperature for 6 hours to obtain tetrazine oxide;
c. adding tetrazine oxide and acetonitrile with the mass of 8.73 times of that of the tetrazine oxide into a round bottom flask, placing the round bottom flask in an ice-water bath at 0 ℃, dropwise adding hydrazine hydrate with the mass of 0.2 times of that of the tetrazine oxide while stirring at the speed of 200rpm, reacting for 1h, filtering, and drying at room temperature for 12h to obtain the para-acetonitrile dimethyl pyrazole tetrazine.
Further, the revolving speed of the open mill in the step (4) is 20rpm, the diameter of a screw is 163mm, and the roll gap is 0.5mm; the glue placing amplitude of the glue placing device is 90mm, and the distance between the press rolls is 72mm; the screw diameter of the continuous vulcanization rubber extruder is 90mm, the vapor pressure is 2.0MPa, and the temperature is 200 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the cable material for the vehicle by using the modified polyethylene and the self-made additive, so that the cable material has the effects of flame retardance, self-repairing and ultraviolet shielding.
Firstly, modified polyethylene is prepared from polyethylene and self-made flame retardant; the self-made flame retardant is prepared by utilizing the reaction of amino groups of melamine and chloride ions of phenyl phosphoryl dichloride, and then is polymerized with free radicals generated by irradiated polyethylene, and the self-made flame retardant is grafted into a polyethylene molecular chain to prepare modified polyethylene; when the modified polyethylene burns, a self-made flame retardant forms a compact carbon layer on the surface of the modified polyethylene, so that the burning is prevented from further occurrence, the discharge of dense smoke generated by the burning is restrained from outwards, the flame retardant and smoke suppression effects are achieved, and the phosphorus-containing structure of the phenylphosphoryl dichloride has a catalytic effect on the thermal decomposition of melamine, so that the pyrolysis temperature is reduced, the char formation is advanced, and the carbon layer can be formed in a short time after the burning to achieve the flame retardant effect; in addition, the imino groups of the modified polyethylene can react with hydrophilic groups of the cable conductor, so that the interface combination of the imino groups and the cable conductor is improved, a uniform protective layer can be formed on the surface of the conductor, the occurrence of aggregation phases is reduced, and the electrical performance of the cable is improved.
Secondly, preparing a self-made additive from para-acetonitrile dimethyl pyrazole tetrazine, methyl aldehyde nitrobenzoate and cyclooctene; the acetonitrile group of acetonitrile dimethylpyrazole tetrazine reacts with the aldehyde group of aldehyde methyl nitrobenzoate to generate chromophore cyano, and a color assisting group ester group is introduced, so that the cable material can absorb ultraviolet light under the combined action of the chromophore cyano and the aldehyde group, a tautomer is formed, the ultraviolet shielding function of the cable material is realized, and meanwhile, a plurality of hydrophobic nitro groups are introduced, so that the waterproof performance of the cable material is improved; then the self-made additive is prepared by diene addition reaction with the unsaturated bond of the cyclooctene, after the cable material is damaged, the tetrazinyl and the cyclooctene in the damaged part are subjected to inverse reaction by heat energy generated by ultraviolet light absorption, chemical bonds are broken, the damage is prevented from being aggravated, the reaction is carried out again after the temperature is reduced to the room temperature, and the damaged part is repaired, so that the cable material has a self-repairing effect; the imino group of the modified polyethylene reacts with the ester group of the self-made additive, the self-made additive contains cyano groups with higher mediating constants, the insulating property of the modified polyethylene is effectively improved, and the two react together, so that the ultraviolet shielding effect of the cable material is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order to more clearly illustrate the method provided by the invention, the following examples are used for describing the method for testing each index of the high-performance automotive cable material manufactured in the following examples as follows:
flame retardancy: the combustion grade of the SMC molding compounds was determined by the vertical combustion method, with reference to the IPC-TM-650 test method.
Smoke suppression properties: the smoke density was tested according to the national standard GB/T8627.
Self-repairability: preparing a 30mm multiplied by 5mm multiplied by 1mm strip-shaped sample from the material, cutting the sample into two sections by using a knife, then mutually contacting two ends of a wound, observing and measuring the initial cross-sectional area of the wound by using a laser confocal microscope, waiting for 2 hours at room temperature, completely self-healing the sample, observing and measuring the cross-sectional areas of the wound of four samples by using the laser confocal microscope, and calculating the self-healing efficiency.
Ultraviolet shielding property: a test lamp box was made of ultraviolet rays, a white glass of a 10X 10cm mouth-mounted sample was formed on the opposite side of the lamp box, the number of transmitted ultraviolet rays was measured by an ultraviolet ray tester, and the ultraviolet ray transmittance was calculated, and the ultraviolet ray transmittance=transmitted light intensity/incident light intensity×100%, thereby determining the shielding effect of the cable material on ultraviolet rays.
Example 1
The high-performance cable material for the vehicle mainly comprises the following components in parts by weight: 90 parts of modified polyethylene, 60 parts of ethylene-octene copolymer, 15 parts of self-made additive, 50 parts of talcum powder, 12 parts of calcium carbonate, 40 parts of calcined clay and 20 parts of paraffin-based rubber oil.
The preparation method of the high-performance automotive cable material mainly comprises the following preparation steps:
(1) Placing melamine and chloroform with the mass of 5.4 times of that of the melamine into a three-neck flask, placing the three-neck flask into an ice bath pot at the temperature of 0 ℃, adding phenyl phosphoryl dichloride with the mass of 0.8 times of that of the melamine, adding sodium hydroxide with the mass fraction of 12% until the pH value of the solution is 7, separating liquid after reaction for 6 hours, steaming for 4 minutes at the temperature of 60 ℃ under the speed of 200rpm, and washing with deionized water for 4 times to obtain a self-made flame retardant;
(2) Under the nitrogen atmosphere, soaking polyethylene in a self-made flame retardant/methanol solution with the mass ratio of 4.5 times of that of the polyethylene to the self-made flame retardant/methanol solution being 1:4, placing the polyethylene in an ultraviolet crosslinking reactor after soaking for 24 hours, and obtaining the modified polyethylene with the irradiation time being 12 minutes;
(3) Adding acetonitrile dimethyl pyrazole tetrazine and ethanol with the mass of 19.2 times of that of the acetonitrile dimethyl pyrazole tetrazine into a three-neck flask, heating to 78 ℃ in an oil bath while stirring at the speed of 150rpm, adding methyl aldehyde nitrobenzoate/ethanol solution with the mass of 12.4 times of that of the acetonitrile dimethyl pyrazole tetrazine, wherein the mass ratio of the methyl aldehyde nitrobenzoate to the ethanol in the methyl aldehyde nitrobenzoate/ethanol solution is 1:12.1, adding glacial acetic acid with the mass of 1.02 times of that of the acetonitrile dimethyl pyrazole tetrazine, stirring at the same speed for 3 hours at the temperature of 78 ℃, cooling to room temperature, and adding cyclooctene with the mass of 1.8 times of that of the acetonitrile dimethyl pyrazole tetrazine, and reacting for 2 hours to obtain a self-made additive;
(4) Plasticating the modified polyethylene and the ethylene-octene copolymer according to the formula amount in an internal mixer with the speed of 40rpm at 77 ℃ for 3min, adding the self-made additive and the paraffin-based rubber oil according to the formula amount, mixing for 2min at 110 ℃, adding the calcium carbonate, the calcined clay and the talcum powder according to the formula amount, mixing for 3min at 125 ℃, placing the mixture on an open mill for 2 times, placing the mixture on a glue placing device for 3 times, calendaring the mixture to obtain sheets with the thickness of 0.23mm, cooling the sheets to the room temperature, conveying the sheets to a continuous vulcanization rubber extruder, and extruding the sheets to obtain the high-performance cable material for the vehicle.
Further, the ultraviolet light wavelength of the ultraviolet light crosslinking reactor in the step (2) is 254nm, and the irradiation distance is 26cm.
Further, the preparation method of the para acetonitrile dimethyl pyrazole tetrazine in the step (3) comprises the following steps:
a. adding distilled water with the mass of the triaminoguanidine hydrochloride and the triaminoguanidine hydrochloride being 5 times into a three-neck flask, heating to 75 ℃ while stirring at the speed of 200rpm, dropwise adding an acetylacetone-ethanol mixed solution at the speed of 1.3mL/min, controlling the mass ratio of acetylacetone to ethanol in the acetylacetone-ethanol mixed solution to be 1:1.13, controlling the reaction temperature to be 75 ℃, stirring at the same speed for 4 hours, cooling to room temperature, carrying out suction filtration, and drying at room temperature for 8 hours to obtain the dimethyl pyrazole tetrazine;
b. adding dimethyl pyrazole tetrazine and sodium nitrite with the mass of 0.32 times of that of the dimethyl pyrazole tetrazine into a three-neck flask, adding distilled water and ethanol solution with the mass of 89.5 times of that of the dimethyl pyrazole tetrazine into the three-neck flask, uniformly stirring, adding diethyl ether-glacial acetic acid with the mass of 10.9 times of that of the dimethyl pyrazole tetrazine into the distilled water and ethanol solution at the speed of 0.4mL/min, wherein the mass ratio of diethyl ether to glacial acetic acid is 1:6.62, performing suction filtration after reacting for 12 hours, washing for 12 times by using absolute ethanol, and drying at room temperature for 6 hours to obtain tetrazine oxide;
c. adding tetrazine oxide and acetonitrile with the mass of 8.73 times of that of the tetrazine oxide into a round bottom flask, placing the round bottom flask in an ice-water bath at 0 ℃, dropwise adding hydrazine hydrate with the mass of 0.2 times of that of the tetrazine oxide while stirring at the speed of 200rpm, reacting for 1h, filtering, and drying at room temperature for 12h to obtain the para-acetonitrile dimethyl pyrazole tetrazine.
Further, the revolving speed of the open mill in the step (4) is 20rpm, the diameter of a screw is 163mm, and the roll gap is 0.5mm; the glue placing amplitude of the glue placing device is 90mm, and the distance between the press rolls is 72mm; the screw diameter of the continuous vulcanization rubber extruder is 90mm, the vapor pressure is 2.0MPa, and the temperature is 200 ℃.
Example 2
The high-performance cable material for the vehicle mainly comprises the following components in parts by weight: 90 parts of polyethylene, 60 parts of ethylene-octene copolymer, 15 parts of homemade additive, 50 parts of talcum powder, 12 parts of calcium carbonate, 40 parts of calcined clay and 20 parts of paraffin-based rubber oil.
The preparation method of the high-performance automotive cable material mainly comprises the following preparation steps:
(1) Adding acetonitrile dimethyl pyrazole tetrazine and ethanol with the mass of 19.2 times of that of the acetonitrile dimethyl pyrazole tetrazine into a three-neck flask, heating to 78 ℃ in an oil bath while stirring at the speed of 150rpm, adding methyl aldehyde nitrobenzoate/ethanol solution with the mass of 12.4 times of that of the acetonitrile dimethyl pyrazole tetrazine, wherein the mass ratio of the methyl aldehyde nitrobenzoate to the ethanol in the methyl aldehyde nitrobenzoate/ethanol solution is 1:12.1, adding glacial acetic acid with the mass of 1.02 times of that of the acetonitrile dimethyl pyrazole tetrazine, stirring at the same speed for 3 hours at the temperature of 78 ℃, cooling to room temperature, and adding cyclooctene with the mass of 1.8 times of that of the acetonitrile dimethyl pyrazole tetrazine, and reacting for 2 hours to obtain a self-made additive;
(2) Plasticizing polyethylene and ethylene-octene copolymer according to formula amount in an internal mixer at 77 ℃ and speed of 40rpm for 3min, adding self-made additive and paraffin-based rubber oil according to formula amount, mixing at 110 ℃ for 2min, adding calcium carbonate, calcined clay and talcum powder according to formula amount, mixing at 125 ℃ for 3min, placing on an open mill for 2 times, placing on a glue placing device for 3 times, calendaring to obtain sheets with thickness of 0.23mm, cooling to room temperature, conveying to a continuous vulcanization rubber extruder, extruding, and obtaining the high-performance cable material for the vehicle.
Further, the preparation method of the para acetonitrile dimethyl pyrazole tetrazine in the step (1) comprises the following steps:
a. adding distilled water with the mass of the triaminoguanidine hydrochloride and the triaminoguanidine hydrochloride being 5 times into a three-neck flask, heating to 75 ℃ while stirring at the speed of 200rpm, dropwise adding an acetylacetone-ethanol mixed solution at the speed of 1.3mL/min, controlling the mass ratio of acetylacetone to ethanol in the acetylacetone-ethanol mixed solution to be 1:1.13, controlling the reaction temperature to be 75 ℃, stirring at the same speed for 4 hours, cooling to room temperature, carrying out suction filtration, and drying at room temperature for 8 hours to obtain the dimethyl pyrazole tetrazine;
b. adding dimethyl pyrazole tetrazine and sodium nitrite with the mass of 0.32 times of that of the dimethyl pyrazole tetrazine into a three-neck flask, adding distilled water and ethanol solution with the mass of 89.5 times of that of the dimethyl pyrazole tetrazine into the three-neck flask, uniformly stirring, adding diethyl ether-glacial acetic acid with the mass of 10.9 times of that of the dimethyl pyrazole tetrazine into the distilled water and ethanol solution at the speed of 0.4mL/min, wherein the mass ratio of diethyl ether to glacial acetic acid is 1:6.62, performing suction filtration after reacting for 12 hours, washing for 12 times by using absolute ethanol, and drying at room temperature for 6 hours to obtain tetrazine oxide;
c. adding tetrazine oxide and acetonitrile with the mass of 8.73 times of that of the tetrazine oxide into a round bottom flask, placing the round bottom flask in an ice-water bath at 0 ℃, dropwise adding hydrazine hydrate with the mass of 0.2 times of that of the tetrazine oxide while stirring at the speed of 200rpm, reacting for 1h, filtering, and drying at room temperature for 12h to obtain the para-acetonitrile dimethyl pyrazole tetrazine.
Further, the revolving speed of the open mill in the step (2) is 20rpm, the diameter of a screw is 163mm, and the roll gap is 0.5mm; the glue placing amplitude of the glue placing device is 90mm, and the distance between the press rolls is 72mm; the screw diameter of the continuous vulcanization rubber extruder is 90mm, the vapor pressure is 2.0MPa, and the temperature is 200 ℃.
Example 3
The high-performance cable material for the vehicle mainly comprises the following components in parts by weight: 90 parts of modified polyethylene, 60 parts of ethylene-octene copolymer, 50 parts of talcum powder, 12 parts of calcium carbonate, 40 parts of calcined clay and 20 parts of paraffin-based rubber oil.
The preparation method of the high-performance automotive cable material mainly comprises the following preparation steps:
(1) Placing melamine and chloroform with the mass of 5.4 times of that of the melamine into a three-neck flask, placing the three-neck flask into an ice bath pot at the temperature of 0 ℃, adding phenyl phosphoryl dichloride with the mass of 0.8 times of that of the melamine, adding sodium hydroxide with the mass fraction of 12% until the pH value of the solution is 7, separating liquid after reaction for 6 hours, steaming for 4 minutes at the temperature of 60 ℃ under the speed of 200rpm, and washing with deionized water for 4 times to obtain a self-made flame retardant;
(2) Under the nitrogen atmosphere, soaking polyethylene in a self-made flame retardant/methanol solution with the mass ratio of 4.5 times of that of the polyethylene to the self-made flame retardant/methanol solution being 1:4, placing the polyethylene in an ultraviolet crosslinking reactor after soaking for 24 hours, and obtaining the modified polyethylene with the irradiation time being 12 minutes;
(3) Plasticating the modified polyethylene and the ethylene-octene copolymer according to the formula amount in an internal mixer with the speed of 40rpm at 77 ℃ for 3min, adding the paraffin-based rubber oil according to the formula amount, mixing for 2min at 110 ℃, adding the calcium carbonate, the calcined clay and the talcum powder according to the formula amount, mixing for 3min at 125 ℃, placing the materials on an open mill for 2 times, placing the materials on a glue placing device for 3 times, calendaring the materials to obtain sheets with the thickness of 0.23mm, cooling the sheets to the room temperature, sending the sheets to a continuous vulcanization rubber extruder, and extruding the sheets to obtain the high-performance cable material for the vehicle.
Further, the ultraviolet light wavelength of the ultraviolet light crosslinking reactor in the step (2) is 254nm, and the irradiation distance is 26cm.
Further, the revolving speed of the open mill in the step (3) is 20rpm, the diameter of a screw is 163mm, and the roll gap is 0.5mm; the glue placing amplitude of the glue placing device is 90mm, and the distance between the press rolls is 72mm; the screw diameter of the continuous vulcanization rubber extruder is 90mm, the vapor pressure is 2.0MPa, and the temperature is 200 ℃.
Comparative example
The high-performance cable material for the vehicle mainly comprises the following components in parts by weight: 90 parts of polyethylene, 60 parts of ethylene-octene copolymer, 50 parts of talcum powder, 12 parts of calcium carbonate, 40 parts of calcined clay and 20 parts of paraffin-based rubber oil.
The preparation method of the high-performance automotive cable material mainly comprises the following preparation steps: plasticizing polyethylene and ethylene-octene copolymer according to formula amount in an internal mixer at 77 ℃ and speed of 40rpm for 3min, adding paraffin-based rubber oil according to formula amount, mixing at 110 ℃ for 2min, adding calcium carbonate, calcined clay and talcum powder according to formula amount, mixing at 125 ℃ for 3min, placing on an open mill for 2 times, placing on a glue placing device for 3 times, calendaring to obtain sheets with thickness of 0.23mm, cooling to room temperature, sending to a continuous vulcanization rubber extruder, extruding to obtain the high-performance cable material for the vehicle.
Further, the rotating speed of the open mill is 20rpm, the diameter of a screw is 163mm, and the roll gap is 0.5mm; the glue placing amplitude of the glue placing device is 90mm, and the distance between the press rolls is 72mm; the screw diameter of the continuous vulcanization rubber extruder is 90mm, the vapor pressure is 2.0MPa, and the temperature is 200 ℃.
Effect example
The following table 1 gives the results of performance analysis of the high performance automotive cable materials employing examples 1 to 3 of the present invention and comparative examples.
TABLE 1
Example 1 Example 2 Example 3 Comparative example
Flame retardant rating V-0 HB V-0 HB
Smoke density 24.8 70.1 24.7 75.9
Self-healing efficiency (%) 98.79 97.99 11.08 10.46
Ultraviolet light transmittance (%) 10.77 25.68 80.17 85.97
From the comparison of the experimental data of the embodiment 1 and the comparative example, the melamine and phenyl phosphoryl dichloride modified polyethylene are used in the product, so that the flame retardant effect of the polyethylene can be effectively improved, the smoke discharge amount is reduced, and the smoke suppression effect is achieved; the self-made additive can enable the cable material to have ultraviolet light absorption performance, light shielding performance and excellent self-repairing performance; from comparison of experimental data of example 1 and example 2, it can be found that a dense carbon layer cannot be formed when a cable burns without using self-made flame retardant modified polyethylene, so that the flame retardance and smoke suppression of the cable material are reduced, no auxiliary color groups such as amino groups are contained, and the ultraviolet shielding performance is reduced; from comparison of experimental data in example 1 and example 3, it can be found that, without using self-made additives, chromophore cyano groups and color assisting group ester groups cannot be introduced into the product, so that the cable material cannot absorb ultraviolet light, the ultraviolet shielding function of the cable material is affected, and the damaged molecular chain segments of the cable material are difficult to break and recombine, so that the damaged parts cannot be repaired by themselves, and the cable material does not have a self-repairing effect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.

Claims (5)

1. The high-performance cable material for the vehicle is characterized by mainly comprising, by weight, 70-100 parts of modified polyethylene, 60-90 parts of ethylene-octene copolymer, 10-20 parts of self-made additive, 40-60 parts of talcum powder, 10-15 parts of calcium carbonate, 30-50 parts of calcined clay and 10-20 parts of paraffin-based rubber oil;
the high-performance automotive cable material is prepared by the following method:
(1) Placing melamine and chloroform with the mass of 5.4 times of that of the melamine into a three-neck flask, placing the three-neck flask into an ice bath pot at the temperature of 0 ℃, adding phenyl phosphoryl dichloride with the mass of 0.8 times of that of the melamine, adding sodium hydroxide with the mass fraction of 12% until the pH value of the solution is 7-8, reacting for 6 hours, separating liquid, steaming for 3-4 minutes at the temperature of 60 ℃ and at the speed of 200rpm, and washing with deionized water for 3-4 times to obtain a self-made flame retardant;
(2) Under the nitrogen atmosphere, soaking polyethylene in a self-made flame retardant/methanol solution with the mass ratio of 4.5 times of that of the polyethylene, wherein the mass ratio of the self-made flame retardant to the methanol in the self-made flame retardant/methanol solution is 1:4, soaking for 24 hours, and then placing the polyethylene in an ultraviolet crosslinking reactor, wherein the irradiation time is 10-15 min, so as to obtain modified polyethylene;
(3) Adding acetonitrile dimethyl pyrazole tetrazine and ethanol with the mass of 19.2 times of that of the acetonitrile dimethyl pyrazole tetrazine into a three-neck flask, heating to 78 ℃ in an oil bath while stirring at the speed of 150rpm, adding methyl aldehyde nitrobenzoate/ethanol solution with the mass of 12.4 times of that of the acetonitrile dimethyl pyrazole tetrazine, wherein the mass ratio of the methyl aldehyde nitrobenzoate to the ethanol in the methyl aldehyde nitrobenzoate/ethanol solution is 1:12.1, adding glacial acetic acid with the mass of 1.02 times of that of the acetonitrile dimethyl pyrazole tetrazine, stirring at the same speed for 3 hours at the temperature of 78 ℃, cooling to room temperature, and adding cyclooctene with the mass of 1.8 times of that of the acetonitrile dimethyl pyrazole tetrazine, and reacting for 2 hours to obtain a self-made additive;
(4) Plasticating the modified polyethylene and the ethylene-octene copolymer in an internal mixer with the formula amount of 70-80 ℃ and the speed of 40rpm for 2-3 min, adding the self-made additive and the paraffin-based rubber oil with the formula amount of 1-2 min at the temperature of 100-130 ℃, adding the calcium carbonate, the calcined clay and the talcum powder with the formula amount of 2-3 min at the temperature of 100-130 ℃, placing the mixture on an open mill for thin ventilation for 1-2 times, placing the mixture on a glue placing device for 2-3 times, calendaring to obtain sheets with the thickness of 0.23mm, cooling to room temperature, conveying the sheets to a continuous vulcanization rubber extruder, and extruding to obtain the high-performance cable material for the vehicle.
2. The high-performance automotive cable material of claim 1 wherein the high-performance automotive cable material comprises the following raw material components in parts by weight: 90 parts of modified polyethylene, 60 parts of ethylene-octene copolymer, 15 parts of self-made additive, 50 parts of talcum powder, 12 parts of calcium carbonate, 40 parts of calcined clay and 20 parts of paraffin-based rubber oil.
3. The high-performance automotive cable material of claim 1 wherein the ultraviolet light wavelength of the ultraviolet light crosslinking reactor in the step (2) is 254nm, and the irradiation distance is 20-30 cm.
4. The high-performance automotive cable material of claim 1 wherein the preparation method of para-acetonitrile dimethylpyrazole tetrazine in step (3) comprises:
a. adding the triaminoguanidine hydrochloride and distilled water with the mass 5 times of that of the triaminoguanidine hydrochloride into a three-neck flask, heating to 75 ℃ while stirring at the speed of 200rpm, dropwise adding an acetylacetone-ethanol mixed solution at the speed of 1-2 mL/min, controlling the mass ratio of acetylacetone to ethanol in the acetylacetone-ethanol mixed solution to be 1:1.13, controlling the reaction temperature to be 75 ℃, stirring at the same speed for 4 hours, cooling to room temperature, carrying out suction filtration, and drying at room temperature for 8 hours to obtain the dimethyl pyrazole tetrazine;
b. adding dimethyl pyrazole tetrazine and sodium nitrite with the mass of 0.32 times of that of the dimethyl pyrazole tetrazine into a three-neck flask, adding distilled water and ethanol solution with the mass of 89.5 times of that of the dimethyl pyrazole tetrazine into the three-neck flask, wherein the mass ratio of distilled water to ethanol in the distilled water and ethanol solution is 1:1.8, uniformly stirring, adding diethyl ether-glacial acetic acid with the mass of 10.9 times of that of the dimethyl pyrazole tetrazine at the speed of 0.3-0.5 mL/min, wherein the mass ratio of diethyl ether to glacial acetic acid in the diethyl ether-glacial acetic acid is 1:6.62, performing suction filtration after reacting for 12 hours, washing for 10-12 times by using absolute ethanol, and drying at room temperature for 6 hours to obtain tetrazine oxide;
c. adding tetrazine oxide and acetonitrile with the mass of 8.73 times of that of the tetrazine oxide into a round bottom flask, placing the round bottom flask in an ice-water bath at 0 ℃, dropwise adding hydrazine hydrate with the mass of 0.2 times of that of the tetrazine oxide while stirring at the speed of 200rpm, reacting for 1h, filtering, and drying at room temperature for 12h to obtain the para-acetonitrile dimethyl pyrazole tetrazine.
5. The high-performance automotive cable material of claim 1 wherein the speed of rotation of the open mill in step (4) is 20rpm, the screw diameter is 163mm, and the roll gap is 0.5mm; the glue placing amplitude of the glue placing device is 90mm, and the distance between the press rolls is 72mm; the screw diameter of the continuous vulcanization rubber extruder is 90mm, the vapor pressure is 2.0MPa, and the temperature is 200 ℃.
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CN110885488A (en) * 2019-12-05 2020-03-17 广东安拓普聚合物科技有限公司 Ultraviolet light irradiation low-smoke halogen-free cable material and preparation method thereof

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CN105237865A (en) * 2015-10-21 2016-01-13 上海至正道化高分子材料股份有限公司 Ultraviolet light cross-linking color low-smoke halogen-free flame-retardant cable material, cable product and preparation method of cable material
CN106496570A (en) * 2016-10-25 2017-03-15 太原理工大学 A kind of hyperbranched poly phosphamide carbon forming agent of phosphorus-nitrogen containing and benzene ring structure and preparation method thereof
CN108384054A (en) * 2018-03-13 2018-08-10 重庆理工大学 Double-N- phenyl -3- amino-melamine-diphenylphosphoryl the amine of fire retardant and its preparation and application
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