CN113896979A - High-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition and preparation method and application thereof - Google Patents

High-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition and preparation method and application thereof Download PDF

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CN113896979A
CN113896979A CN202111290577.7A CN202111290577A CN113896979A CN 113896979 A CN113896979 A CN 113896979A CN 202111290577 A CN202111290577 A CN 202111290577A CN 113896979 A CN113896979 A CN 113896979A
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low
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resistant thermoplastic
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王登辉
王志豪
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Suzhou Baima New Material Co ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators 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
    • H01B3/44Insulators 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
    • H01B3/441Insulators 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
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224Magnesium hydroxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • C08L2203/202Applications use in electrical or conductive gadgets use in electrical wires or wirecoating

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Physics & Mathematics (AREA)
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Abstract

The invention provides a high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition, and a preparation method and application thereof. The high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition comprises the following raw materials: 10-15 parts of ethylene-vinyl acetate copolymer, 8-12 parts of toughening agent, 10-15 parts of rubber resin, 60-70 parts of magnesium hydroxide, 3-5 parts of silicon shell forming agent, 1-1.5 parts of coupling aid, 1.5-2.5 parts of antioxidant, 0.4-0.6 part of lubricant and 1.5-2 parts of high molecular weight silicone master batch. The invention also provides a preparation method of the composition, and a low-smoke low-halogen flame-retardant polyolefin wire and cable prepared from the composition.

Description

High-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition and preparation method and application thereof
Technical Field
The invention relates to a composition, in particular to a high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition for wires and cables and a preparation method thereof, belonging to the technical field of compositions.
Background
With the rapid development of the overall economy of China, the use environment and conditions of the electric wire and the cable continuously put forward hard requirements, and due to the vast territory of China and the continuous expansion of various industries, the use of the electric wire and the cable in different fields is also a new challenge. The service conditions of the electric wire and the electric cable are mainly determined by the working environment temperature and the service position.
The existing low-temperature resistant thermoplastic wire and cable materials have the following problems:
(1) the common thermoplastic wire and cable material has low temperature resistance of-25 ℃ and special low temperature resistance of-45 ℃;
(2) the common thermoplastic low-smoke halogen-free material has lower flame retardant grade, generally the bundled materials pass through the C class, and the bundled materials A and B are less.
Disclosure of Invention
In order to solve the above technical problems, an object of the present invention is to provide a wire and cable having good low temperature resistance and excellent flame retardant effect.
In order to achieve the technical purpose, the invention firstly provides a high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition, which comprises the following raw materials: 10-15 parts of ethylene-vinyl acetate copolymer, 8-12 parts of toughening agent, 10-15 parts of rubber resin, 60-70 parts of magnesium hydroxide, 3-5 parts of silicon shell forming agent, 1-1.5 parts of coupling aid, 1.5-2.5 parts of antioxidant, 0.4-0.6 part of lubricant and 1.5-2 parts of high molecular weight silicone master batch.
In a specific embodiment of the invention, the high flame-retardant low-temperature resistant thermoplastic low-smoke halogen-free flame-retardant composition comprises the following raw materials: 12-15 parts of ethylene vinyl acetate copolymer, 9-12 parts of toughening agent, 10-13 parts of rubber resin, 60-67 parts of magnesium hydroxide, 3-5 parts of silicon shell forming agent, 1-1.5 parts of coupling aid, 1.5-2.5 parts of antioxidant, 0.4-0.6 part of lubricant and 1.5-2 parts of high molecular weight silicone master batch.
According to the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition, the low-temperature-resistant type of the cable material is enhanced on the premise that the basic performance of the cable is not changed by the prepared material through the rubber resin, the EVA with high VA content, the magnesium hydroxide by a chemical method and the silicon shell forming agent, and the flame-retardant grade of the material is improved on the premise that the basic performance of the material is not changed.
In a specific embodiment of the invention, the VA content of the ethylene vinyl acetate copolymer used is 40% to 80%. Specifically, the ethylene-vinyl acetate copolymer is EVM with VA content of 40% -80%.
In a specific embodiment of the invention, the adopted toughening agent is a POE and EPDM mixed grafting material.
In one embodiment of the present invention, the rubber resin is ethylene propylene diene monomer.
In one embodiment of the present invention, the magnesium hydroxide used is chemically surface treated magnesium hydroxide. Such as S-7 of the japanese god island.
In one embodiment of the present invention, the silicon based crusting agent used was Clay20 (produced by hakuba).
In one embodiment of the present invention, the coupling aid used is a silane coupling agent 172.
In one embodiment of the present invention, the antioxidant is a bisphenol-based or an ammonia-based antioxidant. Such as antioxidant 1010 and/or DSTP.
In one embodiment of the invention, the lubricant used is a PE grafted wax.
In one embodiment of the present invention, the high molecular weight silicone masterbatch is 80 ten thousand molecular weight silicone masterbatch.
The invention also provides a preparation method of the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition, which comprises the following steps:
mixing materials by a high-order mixing roll, heating and banburying by a banbury mixer, feeding by a double-step cone, shearing and discharging by double screws, extruding the mixed materials by single screws, granulating by a granulator, collecting by a fan and a storage bin, cooling materials by a vibrating screen, collecting and subpackaging by a large storage bin, and plastically packaging materials by a vacuum machine to obtain the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition.
In order to achieve the technical purpose, the invention also provides a low-smoke low-halogen flame-retardant polyolefin wire and cable, which is prepared from the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition.
According to the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition, the ethylene-vinyl acetate copolymer with high VA content and the lubricant are used, so that the fluidity in the wire and cable processing is increased, and the mechanical strength and the low-temperature resistance of a wire and a cable are improved to a certain extent; the low-temperature resistance of the material is greatly improved through the rubber resin; the addition of the toughening agent improves the mechanical and physical properties of the material on one hand and promotes the compatibility of the resin material on the other hand; the magnesium hydroxide is subjected to surface treatment by a chemical method, so that the flame retardant effect of the material is improved; the integrity of a protective layer on the surface of the material during combustion is improved and the flame retardant property of the material is enhanced through the silicon-based shell forming agent; the addition of the coupling agent promotes the dispersion of the powder material in the resin; the thermal aging and the thermal stability of the material are improved through an antioxidant; the fluidity of the material is improved and the extrusion effect of the material is increased by the silicone master batch with high molecular weight.
The wire and cable prepared from the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition improves the low-temperature-resistant stability of the material by mixing EVM and rubber resin; by adding the silicone master batch with high molecular weight, the fluidity and the extrusion processing rate of the material are increased, and the grinding material accumulation of the material in the extrusion processing can be reduced; the flame retardant grade of the material can be enhanced through the flame retardant and the shell forming agent; the material is a low-smoke halogen-free material, so that the national environmental protection requirement is met. Tensile strength after irradiation: not less than 10.0 MPa; elongation at break: not less than 150%; oxygen index: more than or equal to 38 percent; the specific gravity of the material is as follows: 1.55 plus or minus 0.03; aging conditions are as follows: short-term aging: the performance retention rate at 110 ℃ for 240h is more than or equal to 75 percent; low temperature resistant catalytic test: the experimental temperature is-65 ℃, and the test is carried out; flame retardant rating: bundles a or B (tested according to the wire gauge).
Detailed Description
Examples and comparative examples are shown in table 1.
TABLE 1
Figure BDA0003334547250000031
Wherein the ethylene-vinyl acetate copolymer is EVM with VA content of 40%. The toughening agent is a POE and EPDM mixed grafting material. The rubber resin is ethylene propylene diene monomer. The magnesium hydroxide surface-treated by a chemical method is S-7 of Japan God island. The silicon based cruster was Clay 20. The coupling aid is a silane coupling agent 172. The antioxidant is antioxidant 1010 and DSTP. The lubricant is PE grafted wax. The high molecular weight silicone master batch is a silicone master batch with the molecular weight of 80 ten thousand.
The preparation method of the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition comprises the following steps:
mixing materials by a high-order mixing roll, heating and banburying by a banbury mixer, feeding by a double-step cone, shearing and discharging by double screws, extruding the mixed materials by single screws, granulating by a granulator, collecting by a fan and a storage bin, cooling materials by a vibrating screen, collecting and subpackaging by a large storage bin, and plastically packaging materials by a vacuum machine to obtain the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition.
The above examples and comparative examples were tested and the results are shown in table 2.
TABLE 2
Figure BDA0003334547250000041
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. A high flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition comprises the following raw materials: 10-15 parts of ethylene-vinyl acetate copolymer, 8-12 parts of toughening agent, 10-15 parts of rubber resin, 60-70 parts of magnesium hydroxide, 3-5 parts of silicon shell forming agent, 1-1.5 parts of coupling aid, 1.5-2.5 parts of antioxidant, 0.4-0.6 part of lubricant and 1.5-2 parts of high molecular weight silicone master batch.
2. The high flame retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1, wherein the raw material composition of the high flame retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition comprises: 12-15 parts of ethylene vinyl acetate copolymer, 9-12 parts of toughening agent, 10-13 parts of rubber resin, 60-67 parts of magnesium hydroxide, 3-5 parts of silicon shell forming agent, 1-1.5 parts of coupling aid, 1.5-2.5 parts of antioxidant, 0.4-0.6 part of lubricant and 1.5-2 parts of high molecular weight silicone master batch.
3. The high flame-retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1 or 2, wherein the VA content of the ethylene vinyl acetate copolymer is 40-80%;
preferably, the ethylene-vinyl acetate copolymer is EVM with VA content of 40% -80%.
4. The high flame-retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1 or 2, wherein the toughening agent is a POE and EPDM mixed grafting material;
preferably, the rubber resin is ethylene propylene diene monomer.
5. The high flame retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1 or 2, wherein the magnesium hydroxide is chemically surface treated magnesium hydroxide, such as S-7 of the japanese island;
preferably, the silicon based shell-forming agent is Clay 20.
6. The high flame-retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1 or 2, wherein the coupling aid is a silane coupling agent 172;
preferably, the antioxidant is a bisphenol and an aminic antioxidant, such as antioxidant 1010 and/or DSTP.
7. The high flame retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1 or 2, wherein the lubricant is PE grafted wax.
8. The high flame-retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition according to claim 1 or 2, wherein the high molecular weight silicone master batch is a silicone master batch with a molecular weight of 80 ten thousand.
9. A method for preparing the high flame retardant low temperature resistant thermoplastic low smoke zero halogen flame retardant composition of any one of claims 1 to 8, which comprises the following steps:
mixing materials by a high-order mixing roll, heating and banburying by a banbury mixer, feeding by a double-step cone, shearing and discharging by double screws, extruding the mixed materials by single screws, granulating by a granulator, collecting by a fan and a storage bin, cooling materials by a vibrating screen, collecting and subpackaging by a large storage bin, and plastically packaging materials by a vacuum machine to obtain the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition.
10. A low-smoke low-halogen flame-retardant polyolefin wire and cable, which is prepared from the high-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition as claimed in any one of claims 1 to 8.
CN202111290577.7A 2021-11-02 2021-11-02 High-flame-retardant low-temperature-resistant thermoplastic low-smoke halogen-free flame-retardant composition and preparation method and application thereof Pending CN113896979A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115926349A (en) * 2022-11-28 2023-04-07 苏州铂玛新材料有限公司 Soft high-temperature-resistant halogen-free low-smoke high-flame-retardant polyolefin material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101914236A (en) * 2010-08-19 2010-12-15 王进 Irradiation crosslinking halogen-free high flame-retardant cable material and preparation method thereof
CN110791011A (en) * 2019-11-11 2020-02-14 南通林格橡塑制品有限公司 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and preparation method thereof
CN110845783A (en) * 2019-11-14 2020-02-28 苏州铂玛新材料有限公司 Low-smoke halogen-free flame-retardant polyolefin wire material for B1-grade wire distribution and preparation method thereof
CN112708186A (en) * 2020-12-28 2021-04-27 苏州铂玛新材料有限公司 Irradiation crosslinking super-flexible bending-resistant wear-resistant low-smoke halogen-free composition and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101914236A (en) * 2010-08-19 2010-12-15 王进 Irradiation crosslinking halogen-free high flame-retardant cable material and preparation method thereof
CN110791011A (en) * 2019-11-11 2020-02-14 南通林格橡塑制品有限公司 150 ℃ irradiation crosslinking low-smoke halogen-free flame-retardant elastomer cable material and preparation method thereof
CN110845783A (en) * 2019-11-14 2020-02-28 苏州铂玛新材料有限公司 Low-smoke halogen-free flame-retardant polyolefin wire material for B1-grade wire distribution and preparation method thereof
CN112708186A (en) * 2020-12-28 2021-04-27 苏州铂玛新材料有限公司 Irradiation crosslinking super-flexible bending-resistant wear-resistant low-smoke halogen-free composition and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115926349A (en) * 2022-11-28 2023-04-07 苏州铂玛新材料有限公司 Soft high-temperature-resistant halogen-free low-smoke high-flame-retardant polyolefin material and preparation method and application thereof

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