CN110938252A - B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and preparation method thereof - Google Patents
B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and preparation method thereof Download PDFInfo
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
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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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0869—Acids or derivatives thereof
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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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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
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- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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
Abstract
The invention discloses a B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and a preparation method thereof, wherein the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material comprises the following raw materials: 25-45 parts of ethylene-vinyl acetate copolymer, 25-45 parts of ethylene-butyl acrylate copolymer, 10-25 parts of ultra-low density polyethylene, 5-10 parts of compatilizer, 3-8 parts of lubricant, 0.5-2 parts of antioxidant, 150-200 parts of aluminum hydroxide, 30-70 parts of magnesium hydroxide, 1-5 parts of sepiolite, 3 parts of carbon black master batch and 0.2-1 part of peroxide. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material can ensure that a low-smoke halogen-free cable reaches the B1 combustion grade in GB/T31247, has excellent stress cracking resistance, can be used for large-outer-diameter steel wire or steel-tape armored cables, is soft in texture, excellent in mechanical property and long in service life, and is beneficial to processing and laying of the cables; the preparation is simple and easy to operate.
Description
Technical Field
The invention relates to a B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and a preparation method thereof, belonging to the field of wire and cable materials.
Background
The low-smoke halogen-free flame-retardant cable material meeting the B1 grade flame-retardant requirement in the national standard GB/T31247 is a domestic research hotspot, and is mainly used in important public occasions such as airports, stations, rail transit and the like. Compared with the national standards GB/T19666 and GB/T17651, the test conditions of the GB/T31247 standard are closer to the real fire scene, and the passing difficulty of the test is increased. The cable sheath material for the large-outer-diameter steel wire or steel-tape armored low-smoke halogen-free cable meets the B1-level flame-retardant requirement, and is easy to crack in the use process due to factors such as cable self-weight, high-temperature weather and the like, so that the development of a stress cracking resistant B1-level flame-retardant low-smoke halogen-free cable material is a trend in the future. At present, no relevant report meeting the requirements of B1-grade flame retardant and stress cracking resistant thermoplastic cable material exists at home.
Disclosure of Invention
The invention provides a B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and a preparation method thereof, the obtained cable material meets the requirement of B1-grade combustion performance in GB/T31247, and meanwhile, the stress cracking resistant performance is excellent, and the cable material can be used for large-outer-diameter steel wires or steel-tape-armored low-smoke halogen-free cable outer sheaths.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material comprises the following raw materials:
wherein the weight sum of the ethylene-vinyl acetate, the ethylene-butyl acrylate and the ultra-low density polyethylene is 100 parts; the parts are parts by weight.
Ethylene-vinyl acetate copolymers are referred to as EVA for short. Ultra low density polyethylene is abbreviated VLDPE.
The applicant finds that the integrity and strength of a carbon layer of a material can be greatly improved by adding a small amount of sepiolite into a polyolefin cable material, and the heat release rate is greatly reduced, so that the finished cable can reach the B1 level combustion performance in GB/T31247; the heat resistance of the polyolefin cable material can be improved by adding the ethylene-butyl acrylate, and the high-temperature cracking risk of the low-smoke halogen-free cable material is favorably reduced; the addition of a small amount of dicumyl peroxide is beneficial to forming a micro-crosslinking structure in the processing process of the polyolefin cable material, greatly enhances the acting force among molecular chains, and can ensure that a large-outer-diameter steel wire or steel-tape armored cable is not cracked under the action of external force; compared with other polyethylene, the addition of the ultra-low density polyethylene can greatly improve the mechanical properties of the polyolefin cable material.
In order to further improve the mechanical properties such as strength of the product, the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 20-50%, and the melt index is 2-10 g/10min (190 ℃/2.16 kg).
In order to further improve the heat resistance of the product and avoid cracking, the mass content of butyl acrylate in the ethylene-butyl acrylate copolymer is 15-30%, and the melt index is 2-10 g/10min (190 ℃/2.16 kg).
The heat resistance and the mechanical property of the product are further improved, and the melt index of the ultra-low density polyethylene is 0.5-20 g/10min (190 ℃/2.16 kg).
In order to further ensure the uniformity of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and further promote the synergistic effect among the components, the compatilizer is PE-g-MAH or POE-g-MAH, wherein in the PE-g-MAH, the melt index of PE is 0.5-10 g/10 min; in the POE-g-MAH, the melt index of POE is 2-10 g/10min (190 ℃/2.16 kg). PE-g-MAH refers to maleic anhydride grafted on polyethylene, and POE-g-MAH refers to maleic anhydride grafted on polyethylene oxide.
In order to further promote the synergistic effect between the components and improve the material processing performance, the lubricant is preferably stearic acid, silicone master batch, PE wax or EVA wax. PE is polyethylene, EVA is ethylene-vinyl acetate copolymer.
In order to further improve the weather resistance of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material and promote the improvement of the mechanical property of the cable material, the antioxidant is a mixture of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of (1-1.5) to (1-0.5).
In order to further improve the flame retardant property of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material, preferably, the particle size of the aluminum hydroxide is 0.5-5 mu m, and the surface of the aluminum hydroxide is treated by stearic acid, vinyl silane or titanate.
In order to further improve the flame retardant property of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material, preferably, the particle size of magnesium hydroxide is 0.5-5 mu m, and the surface of the magnesium hydroxide is treated by stearic acid, vinyl silane or titanate.
In order to further improve the comprehensive performance of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material, the mass ratio of magnesium hydroxide to aluminum hydroxide in the inorganic filler is preferably 1: 3.
In order to further improve the flame retardant property of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material, especially ensure the integrity and the flame retardance of a carbon layer of a polyolefin cable material, preferably, the particle size of the sepiolite is 1-100 nm.
According to the preparation method of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material, after dicumyl peroxide, aluminum hydroxide and magnesium hydroxide are uniformly mixed, the obtained mixture, an ethylene-vinyl acetate copolymer, an ethylene-butyl acrylate copolymer, ultra-low density polyethylene, a compatilizer, a lubricant, an antioxidant, carbon black master batches and sepiolite are sequentially added into a kneader for kneading, and then extrusion granulation is carried out through a double-stage unit; wherein the discharging temperature of the kneading machine is 155-165 ℃, the kneading time is 15-16min, and the upper top plug is lifted up once every 2-3min in the kneading process to ensure that the materials are uniformly mixed; the temperature ranges of the double screw and the single screw in the double-stage unit are both 105-135 ℃.
The prior art is referred to in the art for techniques not mentioned in the present invention.
The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material can ensure that a low-smoke halogen-free cable reaches the B1 combustion grade in GB/T31247, has excellent stress cracking resistance, can be used for large-outer-diameter steel wire or steel-tape armored cables, is soft in texture, excellent in mechanical property and long in service life, and is beneficial to processing and laying of the cables; the preparation is simple and easy to operate.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In each example, the raw material components of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material are shown in table 1, and the parts are parts by weight.
Table 1 raw material components of stress cracking resistant thermoplastic low-smoke halogen-free cable material of examples 1-5B 1
In each case, the ethylene-vinyl acetate copolymer was acoma EVA 2803; the ethylene-butyl acrylate copolymer is repsol EBA 1770; the ultra-low density polyethylene is three wells SP 0540; the compatilizer is 588P of DuPont; the silicone master batch is Qiagen KJ-A01; the antioxidant is prepared from the following components in a mass ratio of 1: 1; the model of the aluminum hydroxide is Nabaltec 60CD, and the model of the magnesium hydroxide is Yabao H5; sepiolite is clay 80T; the carbon BLACK masterbatch is BLACK MAX HCB 70.
The preparation method of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material in each embodiment comprises the following steps: accurately weighing dicumyl peroxide, aluminum hydroxide and magnesium hydroxide according to the proportion shown in Table 1, mixing uniformly, adding the obtained mixture, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer, ultra-low density polyethylene, compatilizer, lubricant, antioxidant, carbon black master batch and sepiolite into a kneading machine in sequence, kneading, and then extruding and granulating by a double-stage unit; wherein the discharging temperature of the kneading machine is 155-165 ℃, the kneading time is 15-16min, and the upper top plug is lifted up once every 2-3min in the kneading process to ensure that the materials are uniformly mixed; the temperature ranges of the double screw and the single screw in the double-stage unit are both 105-135 ℃.
And (3) detection: the pellets obtained in each example were pressed into tablets on a press at 175 ℃ for 10min under a pressure of 15MPa and a sample thickness of 1mm, and after standing at room temperature for 16h, the conventional properties were tested, and the resulting materials were soft in texture, as shown in Table 2. The reference standard of the mechanical property test method is GB/T1040, the reference standard of Shore hardness is GB/T2411, and the reference standard of B1 combustion test is GB/T31247.
Table 2 shows the properties of the products obtained in each example
Claims (9)
1. The utility model provides a B1 level stress cracking resistance type thermoplasticity low smoke and zero halogen cable material which characterized in that: the raw materials comprise the following components:
wherein the weight sum of the ethylene-vinyl acetate, the ethylene-butyl acrylate and the ultra-low density polyethylene is 100 parts; the parts are parts by weight.
2. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material as claimed in claim 1, wherein: the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is 20-50%, and the melt index is 2-10 g/10 min.
3. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material as claimed in claim 1 or 2, wherein: the mass content of the butyl acrylate in the ethylene-butyl acrylate copolymer is 15-30%, and the melt index is 2-10 g/10 min.
4. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material as claimed in claim 1 or 2, wherein: the melt index of the ultra-low density polyethylene is 0.5-20 g/10 min.
5. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material as claimed in claim 1 or 2, wherein: the compatilizer is PE-g-MAH or POE-g-MAH, wherein in the PE-g-MAH, the melt index of PE is 0.5-10 g/10 min; in the POE-g-MAH, the melt index of POE is 2-10 g/10 min.
6. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material as claimed in claim 1 or 2, wherein: the lubricant is stearic acid, silicone master batch, PE wax or EVA wax.
7. The B1-grade stress cracking resistant thermoplastic low-smoke zero-halogen cable material as claimed in claim 1 or 2, wherein the antioxidant is a mixture of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of (1-1.5) to (1-0.5).
8. The B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material as claimed in claim 1 or 2, wherein: the particle size of the aluminum hydroxide is 0.5-5 mu m, and the surface of the aluminum hydroxide is treated by stearic acid, vinyl silane or titanate; the particle size of the magnesium hydroxide is 0.5-5 mu m, and the surface of the magnesium hydroxide is treated by stearic acid, vinyl silane or titanate; the particle size of the sepiolite is 1-100 nm.
9. The preparation method of the B1-grade stress cracking resistant thermoplastic low-smoke halogen-free cable material of any one of claims 1-8, characterized in that: after dicumyl peroxide, aluminum hydroxide and magnesium hydroxide are mixed uniformly, the obtained mixture, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer, ultra-low density polyethylene, compatilizer, lubricant, antioxidant, carbon black master batch and sepiolite are added into a kneader in sequence for kneading, and then are extruded and granulated by a double-stage unit; wherein the discharge temperature of the kneading machine is 155-165 ℃, the kneading time is 15-16min, and the upper plug is lifted once every 2-3min in the kneading process; the temperature setting ranges of the double screw and the single screw in the double-stage unit are both 105-135 ℃.
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| CN111621085A (en) * | 2020-07-04 | 2020-09-04 | 上海方之德新材料有限公司 | B1-grade special high-flame-retardant low-smoke halogen-free cable material and preparation method thereof |
| CN112662042A (en) * | 2020-12-21 | 2021-04-16 | 常州市沃科科技有限公司 | B1-grade low-smoke halogen-free cable sheath material and preparation method thereof |
| CN112940388A (en) * | 2021-02-04 | 2021-06-11 | 江苏上上电缆集团新材料有限公司 | B2-grade low-smoke halogen-free polyolefin cable material and preparation method thereof |
| CN115873332A (en) * | 2022-08-16 | 2023-03-31 | 江苏上上电缆集团新材料有限公司 | Long-life environment-friendly polyolefin insulating material, preparation method and application in flexible energy storage cable |
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| CN111621085A (en) * | 2020-07-04 | 2020-09-04 | 上海方之德新材料有限公司 | B1-grade special high-flame-retardant low-smoke halogen-free cable material and preparation method thereof |
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| CN115873332A (en) * | 2022-08-16 | 2023-03-31 | 江苏上上电缆集团新材料有限公司 | Long-life environment-friendly polyolefin insulating material, preparation method and application in flexible energy storage cable |
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