CN110591275A - 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for automobile wire - Google Patents
150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for automobile wire Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
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- 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
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
- C08K2003/3036—Sulfides of zinc
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- C08K2201/004—Additives being defined by their length
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention relates to a 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for automobile wires, which is characterized by comprising the following raw material components in percentage by weight: 50-80 parts of polypropylene, 10-35 parts of styrene-ethylene-butylene-styrene segmented copolymer, 10-15 parts of compatilizer, 60-100 parts of stearic acid modified aluminum hydroxide, 10-30 parts of melamine cyanurate, 10-30 parts of basic magnesium sulfate whisker, 3-5 parts of antioxidant, 0.1-0.8 part of copper resisting agent, 0.5-2.0 parts of zinc sulfide, 2-5 parts of silicone master batch and 0.5-1.2 parts of lubricant.
Description
Technical Field
The invention relates to a cable material, in particular to a 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for an automobile wire.
Background
Automobile manufacturing has become the backbone industry of national economy in China, driving the development of a large number of supporting industries. The automobile wire is one of important components of automobile electrical appliances, is different from a common wire cable and is specially designed for the requirements of automobiles, and because the inside of an automobile is a very complicated small environment and has various complicated conditions such as vibration, friction, ozone, oil stain, high heat, cold, electromagnetic radiation and the like, the automobile wire is required to have various functions such as heat resistance, cold resistance, wear resistance, oil resistance, interference resistance and the like, and the requirements on the automobile wire are continuously increased along with the continuous change of the functions of the automobile.
Most of cable materials for automobile lines on the market at present are halogen-containing flame retardant, the cost is greatly increased along with the rapid increase of the price of antimony trioxide and bromine flame retardants in recent years, the cable materials are not environment-friendly enough, a large amount of black smoke is generated during the combustion of the halogen-containing flame retardants, common wires resistant to 125 ℃ and 150 ℃ are produced by irradiation crosslinking materials, and if thermoplastic materials capable of reaching the same temperature resistant grade are used instead, the production flow is greatly simplified, and the production efficiency is improved. Therefore, from the perspective of cost and environmental protection, development and promotion of thermoplastic low-cost low-smoke halogen-free flame-retardant automobile lines are imperative, and the prospect is wide. At present, thermoplastic polypropylene materials for automobile lines with the temperature of 125 ℃ are developed by a few manufacturers, but thermoplastic polypropylene materials for automobile lines with the temperature of 150 ℃ are not disclosed. CN02806324 discloses an insulating material for electric wire and cable, which can resist 150 ℃ high temperature, but its flame retardant property needs to be further improved; CN201611102565 discloses a high temperature resistant halogen-free flame retardant thermoplastic elastomer cable material which can resist 125 ℃ and can not be used for a long time at 150 ℃; CN105219006 discloses a halogen-free flame-retardant heat-resistant weather-resistant polypropylene nano-composite insulating material for automobile wires and a preparation process thereof, wherein the insulating material can resist temperature of 105 ℃; CN 106543626 discloses a high-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene material for 125 ℃ automobile wires, a preparation method and application thereof, which can not resist high temperature of 150 ℃, and CN201811219942 discloses a self-crosslinking oil-resistant polypropylene halogen-free material capable of resisting room temperature of 150 ℃ and a preparation method thereof, but the polypropylene material does not resist aging under the condition of copper.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for an automobile wire, which has the advantages of low smoke, no halogen, oil resistance, copper-containing high-temperature aging resistance, scratch and abrasion resistance, low cost, no precipitation and frost spraying phenomenon, no need of irradiation crosslinking and capability of producing a D-type wire meeting the ISO6722 standard.
The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire comprises the following raw material components in percentage by weight:
further, the polypropylene (PP) is impact-resistant block copolymerization polypropylene, the melt index of the polypropylene is 1.4-2.2 g/10min under the condition of 190 ℃ multiplied by 5kg, and the density of the polypropylene is 0.90-0.95 g/cm3。
Further, the weight ratio of styrene to butadiene in the styrene-ethylene-butylene-styrene block copolymer (SEBS) is (60-70): (30-40).
Further, the compatilizer is one or a mixture of more than two of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted ethylene-vinyl acetate copolymer, the grafting rate of the compatilizer is 0.5-1.5%, and the melt index of the compatilizer under the condition of 190 ℃ multiplied by 5kg is 0.2-2.0 g/10 min.
Further, the particle size of stearic acid-modified aluminum hydroxide (ATH) is 1.5 to 2.0 μm.
Further, Melamine Cyanurate (MCA) has a particle size of 2.5 to 3.5 μm.
Further, the chemical component of the basic magnesium sulfate whisker is MgSO4·5Mg(OH)2·3H2O, which is a needle-like fiber structure, has a diameter D of less than 2 μm, a length L of 3.5 to 120 μm, and an aspect ratio L/D of 8 to 70.
Further, the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168 and an antioxidant DLTP, and the mass ratio of the antioxidant 1010 to the antioxidant 168 to the antioxidant DLTP is 2-4: 1-3.
Further, the copper inhibitor is N.N-bis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine, and preferably, the copper inhibitor is MD-1024.
Further, the particle size of the zinc sulfide is 0.3 to 1.0 μm.
Furthermore, the mass content of the effective component silicone in the silicone master batch is 50 percent, and the molecular weight of siloxane in the silicone master batch is 80-120 ten thousand.
Further, the lubricant is one or two of PE wax, EVA wax, calcium stearate and zinc stearate.
Preferably, the 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire comprises the following raw material components in percentage by weight:
more preferably, the 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire comprises the following raw material components in percentage by weight:
further, the preparation method of the 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire comprises the following steps:
uniformly mixing the raw material components, and then carrying out extrusion granulation in a double-screw extrusion granulator to obtain master batches of the thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire with the temperature resistance of 150 ℃; the temperature of the twin-screw extrusion granulator is set as follows: the first zone is 165 +/-5 ℃, the second zone is 170 +/-5 ℃, the third zone is 180 +/-5 ℃, the fourth zone is 190 +/-5 ℃, the fifth zone is 200 +/-5 ℃, and the head and the die are 210 +/-5 ℃.
The invention also provides a preparation method of the automobile wire, and the thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire with the temperature resistance of 150 ℃ comprises the following steps:
the master batches of the 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire are used for producing wire rods in a wire and cable extruding machine, and are extruded at the temperature of 160-170 ℃ in a first area, 180-190 ℃ in a second area, 190-200 ℃ in a third area, 200-210 ℃ in a fourth area and 195-205 ℃ in a machine head, so that the conductor wire core is coated with the extrusion material, and the automobile wire is obtained.
Further, the diameter of the conductor wire core is 1.07mm, and the diameter of the manufactured wire is 1.67 mm.
By the scheme, the invention at least has the following advantages:
1. the cable material can meet the temperature resistance of 150 ℃ without irradiation crosslinking, simplifies the production process of a wire manufacturer, and greatly improves the production efficiency of wires.
2. The zinc sulfide and the copper resisting agent are matched in the formula of the cable material, so that the catalytic aging of copper ions is inhibited in a synergistic manner, the dosage of the copper resisting agent is reduced, and the problem of precipitation caused by adding too much copper resisting agent is avoided.
3. The basic magnesium sulfate whisker is used in the formula of the cable material, so that the compactness, wear resistance and flame retardant property of the material are improved.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a preferred embodiment of the present invention and is described in detail below.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Examples
The components of the 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire in the embodiments 1-3 are shown in table 1, and for comparison, the components of the cable material in the comparative examples 1-3 are also shown in table 1.
TABLE 1 composition of the different cable materials (the amount of each component is in parts by weight)
The compatilizer is one or the mixture of more than two of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted ethylene-vinyl acetate copolymer, the grafting rate of the compatilizer is 0.5-1.5%, and the melt index of the compatilizer under the condition of 190 ℃ multiplied by 5kg is 0.2-2.0 g/10 min.
The master batch of the 150 ℃ thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile line is produced by using the raw materials consisting of the components in the table 1, and the steps are as follows:
the raw material components are put into a high-speed mixer for mixing, and then put into a double-screw extruder for extrusion and granulation. The temperature of the twin-screw extruder is set as follows: the first cylinder area is 165 +/-5 ℃, the second cylinder area is 170 +/-5 ℃, the third cylinder area is 180 +/-5 ℃, the fourth cylinder area is 190 +/-5 ℃, the fifth cylinder area is 200 +/-5 ℃, and the head and the die are 210 +/-5 ℃.
The master batches are further utilized to prepare the automobile wire, the master batches are used for producing the automobile wire rod in a wire and cable extruding machine, the automobile wire rod is extruded at the temperature of 160-170 ℃ in the first area, 180-190 ℃ in the second area, 190-200 ℃ in the third area, 200-210 ℃ in the fourth area and 195-205 ℃ of a machine head, the automobile wire rod is coated on the conductor wire core, the diameter of the conductor wire core is 1.07mm, and the diameter of the manufactured automobile wire rod is 1.67 mm.
The performance test data of the 150 ℃ thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire prepared in the examples 1-3 and the comparative examples 1-3 are shown in table 2 (reference standard GB/T32129-:
TABLE 2 Performance test results for different cable materials
The test performance results of the 150 ℃ thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire obtained in the examples 1 to 3 and the comparative examples 1 to 3 used as the wire with the wall thickness of 0.3mm are shown in the following table 3 (reference standard ISO6722-2011, QC/T730-2005):
TABLE 3 results of testing the properties of various wires
As can be seen from the test data in tables 2 and 3, the copper resisting agent 1024 and the zinc sulfide both have the effect of inhibiting the catalytic aging of copper ions, and have a certain synergistic effect between the copper resisting agent 1024 and the zinc sulfide, but the copper resisting agent is added with more copper ions and is separated out, but the zinc sulfide is not separated out; the dosage of the silicone master batch is increased, the scratch resistance of the product is improved, and the addition of the basic magnesium sulfate whisker is helpful for flame retardance and scratch resistance. As can be seen from the technical indexes of the examples 1 to 3 in tables 2 and 3, the 150 ℃ thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire has excellent physical and mechanical properties, copper aging resistance, oil resistance, high temperature resistance, low temperature (-40 ℃) resistance and scratch and abrasion resistance.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire is characterized by comprising the following raw material components in percentage by weight:
2. according to claim 1The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire is characterized in that: the polypropylene is impact-resistant block copolymerization polypropylene, the melt index of the polypropylene is 1.4-2.2 g/10min under the condition of 190 ℃ multiplied by 5kg, and the density of the polypropylene is 0.90-0.95 g/cm3。
3. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wires according to claim 1, which is characterized in that: the styrene-ethylene-butylene-styrene block copolymer comprises (60-70) of styrene and butadiene in weight ratio: (30-40).
4. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wires according to claim 1, which is characterized in that: the compatilizer is one or a mixture of more than two of maleic anhydride grafted polyethylene, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted ethylene-vinyl acetate copolymer, the grafting rate of the compatilizer is 0.5-1.5%, and the melt index of the compatilizer under the condition of 190 ℃ multiplied by 5kg is 0.2-2.0 g/10 min.
5. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wires according to claim 1, which is characterized in that: the antioxidant is a mixture of an antioxidant 1010, an antioxidant 168 and an antioxidant DLTP, and the mass ratio of the antioxidant 1010 to the antioxidant 168 to the antioxidant DLTP is 2-4: 1-3.
6. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wires according to claim 1, which is characterized in that: the copper resisting agent is N, N-bis [ beta (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl ] hydrazine.
7. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wires according to claim 1, which is characterized in that: the lubricant is one or two of PE wax, EVA wax, calcium stearate and zinc stearate.
8. The 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wires according to claim 1, which is characterized in that: the basic magnesium sulfate whisker is of a needle-shaped fiber structure, the diameter D of the basic magnesium sulfate whisker is less than 2 mu m, the length L of the basic magnesium sulfate whisker is 3.5-120 mu m, and the length-diameter ratio L/D of the basic magnesium sulfate whisker is 8-70.
9. The 150 ℃ resistant thermoplastic low-smoke zero-halogen flame-retardant polypropylene cable material for the automobile wires according to any one of claims 1 to 8, characterized in that the preparation method comprises the following steps:
uniformly mixing the raw material components, and then carrying out extrusion granulation in a double-screw extrusion granulator to obtain master batches of the thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire with the temperature resistance of 150 ℃; the temperature of the twin-screw extrusion granulator is set as follows: the first zone is 165 +/-5 ℃, the second zone is 170 +/-5 ℃, the third zone is 180 +/-5 ℃, the fourth zone is 190 +/-5 ℃, the fifth zone is 200 +/-5 ℃, and the head and the die are 210 +/-5 ℃.
10. The preparation method of the automobile wire is characterized in that the thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire with the temperature resistance of 150 ℃ in claim 9 is adopted, and comprises the following steps:
the master batches of the 150 ℃ resistant thermoplastic low-smoke halogen-free flame-retardant polypropylene cable material for the automobile wire are used for producing wire rods in a wire and cable extruding machine, and are extruded at the temperature of 160-170 ℃ in a first area, 180-190 ℃ in a second area, 190-200 ℃ in a third area, 200-210 ℃ in a fourth area and 195-205 ℃ in a machine head, so that the conductor wire core is coated with the extrusion material, and the automobile wire is obtained.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982155A (en) * | 2019-12-24 | 2020-04-10 | 远东电缆有限公司 | Halogen-free phosphorus-free flame-retardant thermoplastic alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100160514A1 (en) * | 2006-06-21 | 2010-06-24 | Stephane David | Plastic comprising zinc sulphide |
| JP2010254886A (en) * | 2009-04-28 | 2010-11-11 | Sumitomo Wiring Syst Ltd | Insulating composition |
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2019
- 2019-10-09 CN CN201910955051.2A patent/CN110591275A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100160514A1 (en) * | 2006-06-21 | 2010-06-24 | Stephane David | Plastic comprising zinc sulphide |
| JP2010254886A (en) * | 2009-04-28 | 2010-11-11 | Sumitomo Wiring Syst Ltd | Insulating composition |
Non-Patent Citations (1)
| Title |
|---|
| 天津化工研究院: "《无机盐工业手册 第二版 上册》", 31 January 1996 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110982155A (en) * | 2019-12-24 | 2020-04-10 | 远东电缆有限公司 | Halogen-free phosphorus-free flame-retardant thermoplastic alloy and preparation method thereof |
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Application publication date: 20191220 |
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