CN113912930A - Halogen-free flame-retardant polyolefin cable sheath material and preparation method and application thereof - Google Patents

Halogen-free flame-retardant polyolefin cable sheath material and preparation method and application thereof Download PDF

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CN113912930A
CN113912930A CN202111270889.1A CN202111270889A CN113912930A CN 113912930 A CN113912930 A CN 113912930A CN 202111270889 A CN202111270889 A CN 202111270889A CN 113912930 A CN113912930 A CN 113912930A
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weight
parts
sheath material
cable sheath
polyolefin
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于德宝
华占红
丛晓飞
张中云
郑建平
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Suzhou Hengli Communications Material Co Ltd
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Suzhou Hengli Communications Material Co Ltd
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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
    • 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
    • C08L23/06—Polyethene
    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
    • C08K2003/2293—Oxides; Hydroxides of metals of nickel
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
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    • C08L2207/062—HDPE

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Abstract

The invention provides a halogen-free flame-retardant polyolefin cable sheath material and a preparation method and application thereof, wherein the polyolefin cable sheath material comprises a combination of ethylene vinyl acetate copolymer, polyolefin resin, a flame retardant, silane, dicumyl peroxide and nickel oxide in specific parts; silane and nickel oxide are added in the preparation raw materials for matching, so that combustion and crusting of the flame retardant can be promoted, the polyolefin cable sheath material generates little heat and smoke during combustion, and has good flame retardant property; and the dicumyl peroxide and dicumyl peroxide in specific parts are further added into the raw materials, so that the local crosslinking between the ethylene-vinyl acetate copolymer and the polyolefin resin can be effectively prevented, and the flame retardant property and the mechanical property of the polyolefin cable sheath material are further improved.

Description

Halogen-free flame-retardant polyolefin cable sheath material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of cables, and particularly relates to a halogen-free flame-retardant polyolefin cable sheath material and a preparation method and application thereof.
Background
With the rapid development of the domestic electric wire and cable industry, the demand on the polyolefin semi-conductive sheath material is more and more, however, the manufacturing technology of the polyolefin semi-conductive sheath material is not mature at present, only a few families can produce the polyolefin semi-conductive sheath material at home, and most products depend on import. When the ultrahigh voltage cable of 110kV or above is manufactured, the outer sheath of the ultrahigh voltage cable is made of a material with larger insulation resistance, and when multipoint continuous grounding cannot be realized, dangerous voltage is formed on the sheath at a position far away from the place, so that the safe operation of the cable can be endangered, and the ultrahigh voltage power cable needs to adopt a semi-conductive outer sheath; the sheath material has a vital influence on heat release and smoke release, but the cable structure, the selection of insulating materials, the selection of filling and the presence or absence of armor have a great influence on the cable test result, the general insulation requirement has certain flame retardance, and flame-retardant wrapping treatment is required before extruding the sheath, so that the influence of internal combustible substances on heat release and smoke release is reduced; the combustible matter does not fall in the combustion process, the carbon forming property is required, the expansion phenomenon exists in the material combustion process due to the fact that carbon dioxide and water vapor are released in the material combustion process, and the combustible matter falls due to the fact that cracks exist after the material expands and the material expands under the action of gravity.
CN102863686A discloses a semiconductive low-smoke halogen-free flame-retardant polyolefin sheath material and a preparation method thereof, wherein the semiconductive polyolefin sheath material comprises the following raw materials in parts by weight: 60-100 parts of polyolefin resin, 40-80 parts of conductive carbon black, 20-40 parts of a flame retardant, 1-5 parts of a dispersing agent, 0.1-3 parts of stearate, 0.1-3 parts of a silane coupling agent, 5-20 parts of a lubricating agent, 2-8 parts of a wetting agent, 3-10 parts of an antioxidant and 0-3 parts of an anti-ultraviolet agent, wherein the dispersing agent is oleamide, erucamide or a mixture of the oleamide and the erucamide. The improved special semiconductive polyolefin sheath material for the extra-high voltage cable has the advantages of excellent comprehensive performance, particularly conductivity and flame retardant performance, lower cost and the like.
CN102295796A discloses a cable sheath material and a manufacturing method thereof, which mainly solves the defects of the prior conductive polyolefin sheath material for ultrahigh voltage, such as large pollution, unstable volume resistivity and the like. The invention provides a conductive polyolefin sheath material for an ultra-high voltage cable sheath, which comprises the following raw materials of 65-85 wt% of polyolefin resin and 15-35 wt% of conductive master batches, wherein the conductive master batches comprise the following components in percentage by weight: 5-15% of thermoplastic elastomer, 5-15% of ethylene copolymer, 20-40% of conductive carbon black a, 10-30% of conductive carbon black b, 10-40% of dispersant, 1-20% of antioxidant and 1-10% of processing aid. The conductive polyolefin sheath material for the ultra-high voltage cable sheath can be widely applied to the outer sheath of the ultra-high voltage cable.
CN107141575A discloses a compression-resistant thermoplastic low-smoke halogen-free flame-retardant polyolefin sheath material and a preparation method thereof, wherein the sheath material comprises the following components in parts by weight: 30-50 parts of ethylene-vinyl acetate copolymer resin, 10-30 parts of polyolefin elastomer, 5-25 parts of linear low-density polyethylene, 5-15 parts of functionalized polyolefin resin, 140-180 parts of flame retardant, 5-25 parts of functional filler, 1-3 parts of surface modifier, 0.5-2 parts of antioxidant and 1.5-9 parts of processing aid. Firstly, the preparation method of the sheath material does not need crosslinking, and has low manufacturing cost and high production efficiency; secondly, the sheath material is easy to extrude and mold and has higher compression resistance; and thirdly, the sheath material has good wear resistance, excellent mechanical property and excellent high and low temperature resistance.
However, the flame retardant and the synergistic flame retardant used in the sheathing material provided by the prior art at the present stage are all non-polar materials, but the resin is a polar material, so that the compatibility between the materials is poor, and in order to meet the flame retardant requirement, a large amount of flame retardant needs to be added, so that the resin and the flame retardant cannot be uniformly fused, and meanwhile, the cracking resistance of the material is obviously reduced due to the large amount of the flame retardant.
Therefore, the development of a polyolefin cable sheath material with excellent flame retardant property and excellent cracking resistance is a technical problem to be solved urgently in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a halogen-free flame-retardant polyolefin cable sheath material and a preparation method and application thereof, wherein the polyolefin cable sheath material comprises a combination of ethylene vinyl acetate copolymer, polyolefin resin, a flame retardant, silane, dicumyl peroxide and nickel oxide in specific parts, and the obtained polyolefin cable sheath material has excellent mechanical properties and aging properties on the premise of higher flame retardance through mutual matching of the components, and is suitable for larger-size cables.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a halogen-free flame-retardant polyolefin cable sheath material, which comprises the following components in parts by weight:
Figure BDA0003328715430000031
the ethylene vinyl acetate copolymer may be 5 parts by weight 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
The polyolefin resin may be 6 parts by weight, 9 parts by weight, 12 parts by weight, 15 parts by weight, 18 parts by weight, 21 parts by weight, 24 parts by weight, 27 parts by weight, or the like.
The flame retardant may be 5 parts by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, 70 parts by weight, 80 parts by weight, 90 parts by weight, 100 parts by weight, or the like.
The silane may be 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9 parts by weight, or the like.
The dicumyl peroxide may be 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or 0.9 parts by weight, etc.
The nickel oxide can be 0.3, 0.5, 0.7, 0.9, 1.1, 1.3, 1.5, 1.7, or 1.9 parts by weight, or the like.
The polyolefin cable sheath material provided by the invention comprises the combination of ethylene vinyl acetate copolymer, polyolefin resin, a flame retardant, silane, dicumyl peroxide and nickel oxide in specific parts; the silane can be coated on the inner surface of the oxide to treat the surface of the oxide, the nickel oxide treated by the silane has high catalytic efficiency, can catalyze and promote the combustion and crusting of the flame retardant, and can also be coated with an organic film on the surface of the flame retardant, so that an invisible bridge is formed between the flame retardant and a resin base material, and the flame retardant performance and the mechanical performance of the polyolefin cable sheath material are improved; in addition, dicumyl peroxide (DCP) is added, so that the polyolefin resin base material and the ethylene-vinyl acetate copolymer base material in the DCP have better micro-crosslinking effect, and the flame retardant property and the thermal shock resistance of the polyolefin cable sheath material can be further greatly improved in the micro-crosslinking state of the resin base material; the silane can pre-melt the DCP, so that the DCP is better dispersed in a system and the local crosslinking condition occurs in the placed system; the polyolefin cable sheath material obtained by adopting the formula realizes higher flame retardance under the condition of less addition amount of the flame retardant, meanwhile, the thermal shock resistance of the polyolefin cable sheath material is improved due to the micro-crosslinking structure, and a cable prepared by adopting the polyolefin cable sheath material as a sheath has excellent flame retardance, aging resistance and cracking resistance.
Preferably, the ethylene vinyl acetate copolymer of step (1) comprises a combination of EVA and EVM.
Preferably, the content of EVA in the polyolefin cable sheath material is 1 to 30 parts by weight, such as 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, 26 parts by weight, or 28 parts by weight.
Preferably, the content of the EVM in the polyolefin cable sheath material is 1 to 20 parts by weight, for example, 2 parts by weight, 4 parts by weight, 6 parts by weight, 8 parts by weight, 10 parts by weight, 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, or the like.
Preferably, the polyolefin resin includes a combination of a linear low density polyethylene resin, a high density polyethylene resin, and a POE elastomer.
As a preferred technical scheme, the base material resin of the polyolefin cable sheath material provided by the invention comprises the combination of EVA, EVM, linear low-density polyethylene resin, high-density polyethylene resin and POE (polyolefin elastomer), so that the polyolefin cable sheath material has excellent mechanical properties, and meanwhile, the flame retardant can be well fused with the base material resin, so that the mechanical properties and the flame retardant property of the polyolefin cable sheath material are further improved.
Preferably, the content of the linear low density polyethylene resin in the polyolefin cable sheath material is 1 to 10 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight.
Preferably, the content of the high-density polyethylene resin in the polyolefin cable sheath material is 1 to 10 parts by weight, for example, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight.
Preferably, the content of the POE elastomer in the polyolefin cable sheath material is 1 to 10 parts by weight, such as 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, or 9 parts by weight.
Preferably, the flame retardant comprises a combination of magnesium hydroxide, aluminum hydroxide and montmorillonite clay.
Preferably, the content of the magnesium hydroxide in the polyolefin cable sheath material is 1 to 50 parts by weight, such as 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
Preferably, the content of the aluminum hydroxide in the polyolefin cable sheath material is 1 to 50 parts by weight, such as 5 parts by weight, 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight, or the like.
Preferably, the content of montmorillonite in the polyolefin cable sheath material is 0.1-5 parts by weight, such as 0.5 part by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight or 4.5 parts by weight.
Preferably, the mass ratio of the magnesium hydroxide to the aluminum hydroxide to the montmorillonite is 1 (0.5-1.5) to 0.1-0.5.
The mass ratio of the magnesium hydroxide to the aluminum hydroxide is 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3 or 1:1.4, and the like.
The mass ratio of the magnesium hydroxide to the montmorillonite is 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45 or 1:0.5, and the like.
According to the preferable technical scheme, when the flame retardant comprises the combination of magnesium hydroxide, aluminum hydroxide and montmorillonite in a mass ratio of 1 (0.5-1.5) to (0.1-0.5), the obtained polyolefin cable sheath material has the most excellent flame retardant property, the peak value of the heat release rate, the total heat release amount and the combustion growth rate index of the polyolefin cable sheath material during combustion are lower under the fire condition, the oxygen consumption rate in the air is reduced due to low heat release, and the safety is improved.
Preferably, the polyolefin cable sheath material further comprises a compatilizer and/or an antioxidant.
Preferably, the content of the compatibilizer in the polyolefin cable sheath material is 1 to 5 parts by weight, such as 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, or 4.5 parts by weight.
Preferably, the antioxidant is contained in the polyolefin cable sheath material in an amount of 0.1 to 1 part by weight, for example, 0.2 part by weight, 0.3 part by weight, 0.4 part by weight, 0.5 part by weight, 0.6 part by weight, 0.7 part by weight, 0.8 part by weight, or 0.9 part by weight.
In a second aspect, the present invention provides a method for preparing the polyolefin cable sheath material according to the first aspect, the method comprising: and banburying the ethylene-vinyl acetate copolymer, the polyolefin resin, the flame retardant, dicumyl peroxide, nickel oxide, optional compatilizer and optional antioxidant to obtain the polyolefin cable sheath material.
Preferably, the banburying temperature is 100-200 ℃, such as 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃ or 190 ℃.
Preferably, the banburying time is 10-30 min, such as 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min or 28 min.
In a third aspect, the invention provides a cable, wherein a sheath of the cable is prepared from the polyolefin cable sheath material according to the first aspect.
Preferably, the thickness of the sheath is 1-3 mm, such as 1.2mm, 1.4mm, 1.6mm, 1.8mm, 2mm, 2.2mm, 2.4mm, 2.6mm, or 2.8mm, etc.
Preferably, the cable includes any one of a subway cable, an optical-electrical composite cable, a railway cable, or a communication power line.
Compared with the prior art, the invention has the following beneficial effects:
the halogen-free flame-retardant polyolefin cable sheath material provided by the invention is prepared by adding a combination of ethylene vinyl acetate copolymer, polyolefin resin, a flame retardant, silane, dicumyl peroxide and nickel oxide in a specific part into a preparation raw material; the silane is used for carrying out surface treatment on the nickel oxide, so that the catalytic effect of the nickel oxide is improved, and the effect of catalyzing and promoting combustion and crusting of the flame retardant by the nickel oxide is more excellent; DCP is added to promote the micro-crosslinking effect of the resin base material, so that the flame retardant property and the thermal shock resistance of the polyolefin cable sheath material are further greatly improved in a micro-crosslinking state; specifically, the vertical flame spread of the polyolefin cable sheath material provided by the invention is 367-424 mm, and is less than 425mm, so that the requirement is met; the total smoke release is 3.5-5.0 m2(ii) a The tensile strength is 11.8-12.8 MPa; and the cracking resistance of 135 ℃ multiplied by 1h can pass, so that the cable sheath material is very suitable for being used as a sheath material of a larger-size cable.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The halogen-free flame-retardant polyolefin cable sheath material comprises the following components in parts by weight:
Figure BDA0003328715430000081
the preparation method of the polyolefin cable sheath material comprises the following steps:
(1) mixing silane (silane 172) and DCP at 50 ℃ for 2min to obtain a mixture;
(2) mixing magnesium hydroxide, aluminum hydroxide and nickel oxide for 1min, then adding the mixture obtained in the step (1), and stirring for 5min at 110 ℃ to obtain a surface treatment material;
(3) and (3) internally mixing EVA (Taiwan plastics industry, 7470M), EVM (vinyl ester rubber of Langsheng acid, EVM700), LLDPE (Zhejiang petrochemical industry, 7042), POE (Sabike, 5070D), compatilizer (Henry material, N5T01), antioxidant (Korean pine original, AT10), montmorillonite and the surface treatment material obtained in the step (2) in an internal mixer AT 175 ℃ for 10min to obtain the polyolefin cable sheath material.
Example 2
The halogen-free flame-retardant polyolefin cable sheath material comprises the following components in parts by weight:
Figure BDA0003328715430000091
Figure BDA0003328715430000101
the preparation method is the same as that of example 1.
Example 3
The halogen-free flame-retardant polyolefin cable sheath material comprises the following components in parts by weight:
Figure BDA0003328715430000102
the preparation method is the same as that of example 1.
Example 4
The halogen-free flame-retardant polyolefin cable sheath material is different from the material in the embodiment 1 in that the addition amount of magnesium hydroxide is 100 parts by weight, aluminum hydroxide is not added, and other components, the use amount and the preparation method are the same as those in the embodiment 1.
Example 5
The halogen-free flame-retardant polyolefin cable sheath material is different from the material in the embodiment 1 in that the addition amount of aluminum hydroxide is 100 parts by weight, magnesium hydroxide is not added, and other components, the use amount and the preparation method are the same as those in the embodiment 1.
Example 6
A halogen-free flame-retardant polyolefin cable sheath material is different from that of example 1 in that the addition amount of magnesium hydroxide is 51.25 parts by weight, the addition amount of aluminum hydroxide is 51.25 parts by weight, montmorillonite is not added, and other components, the use amounts and the preparation method are the same as those of example 1.
Example 7
The halogen-free flame-retardant polyolefin cable sheath material is different from the material in the embodiment 1 in that the addition amount of magnesium hydroxide is 70 parts by weight, the addition amount of aluminum hydroxide is 30 parts by weight, and other components, the use amounts and the preparation method are the same as those in the embodiment 1.
Example 8
The halogen-free flame-retardant polyolefin cable sheath material is different from the material in the embodiment 1 in that the adding amount of aluminum hydroxide is 70 parts by weight, the adding amount of magnesium hydroxide is 30 parts by weight, and other components, the using amount and the preparation method are the same as those in the embodiment 1.
Example 9
A halogen-free flame-retardant polyolefin cable sheath material is different from that of example 1 in that the addition amount of aluminum hydroxide is 51 parts by weight, the addition amount of magnesium hydroxide is 51 parts by weight, the addition amount of montmorillonite is 0.5 part by weight, and other components, the use amounts and the preparation method are the same as those of example 1.
Comparative example 1
A halogen-free flame-retardant polyolefin cable sheath material is different from that in example 1 in that no nickel oxide is added, and other components, the using amount and the preparation method are the same as those in example 1.
Comparative example 2
A halogen-free flame-retardant polyolefin cable sheath material, which is different from the material in example 1 in that no silane is added, and other components, the using amount and the preparation method are the same as those in example 1.
Comparative example 3
A halogen-free flame-retardant polyolefin cable sheath material is different from that of example 1 in that no DCP is added, and other components, the using amount and the preparation method are the same as those of example 1.
And (3) performance testing:
(1) smoke density: testing according to a testing method provided by GB/T8323-1987;
(2) tensile strength: testing according to the testing method provided by GBT 528-2009;
(3) cracking resistance: the test was carried out according to the test method provided in GB/T32129-2015.
The polyolefin cable sheath materials provided in examples 1 to 9 and comparative examples 1 to 3 were tested according to the above test method, and the test results are shown in table 1:
TABLE 1
Figure BDA0003328715430000121
Figure BDA0003328715430000131
As can be seen from the data in Table 1, the polyolefin cable sheath material provided by the invention has excellent flame retardant property and mechanical property.
Specifically, the smoke density of the polyolefin cable sheath material provided by the embodiments 1 to 9 is 85 to 98, and the smoke density is less than 100, so that the requirement is met; the tensile strength is 11.8-12.8 MPa; and the cracking resistance can be passed at 135 ℃ for 1 h.
Comparing example 1 with comparative example 1, it can be seen that the smoke density of the polyolefin cable sheath material obtained without adding nickel oxide is as high as 106, which indicates that the smoke release amount is high, the heat release amount is high, and the vertical flame spread is longer because the flame retardant cannot be promoted to burn and crust without adding nickel oxide.
Comparing example 1 with comparative example 2, it can be seen that the smoke density of the polyolefin cable sheath material obtained in comparative example 2 is as high as 107; meanwhile, the tensile strength and the cracking resistance are greatly reduced in tests, because no silica gel is added, an effective bridge cannot be formed between the flame retardant and the base material resin, and the mechanical property and the flame retardant property of the material are greatly reduced.
Comparing example 1 with comparative example 3, it can be seen that the smoke density of the polyolefin cable sheath material of comparative example 3 has a flame as high as 107; meanwhile, the tensile strength and the anti-cracking performance are greatly reduced, because no DCP is added, the base material resin is easy to form over-crosslinking, and the mechanical performance and the flame retardant performance of the material are greatly reduced.
Further comparing examples 1 and 4 to 9, it can be seen that the flame retardancy of the polyolefin sheathing compound obtained by either one of the three flame retardants is absent or the amount of one of the flame retardants is not within the predetermined range is reduced.
The applicant states that the present invention is illustrated by the above examples to provide a halogen-free flame retardant polyolefin cable sheath material, and a preparation method and application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The halogen-free flame-retardant polyolefin cable sheath material is characterized by comprising the following components in parts by weight:
Figure FDA0003328715420000011
2. the polyolefin cable sheath material according to claim 1, wherein the ethylene vinyl acetate copolymer of step (1) comprises a combination of EVA and EVM;
preferably, the content of EVA in the polyolefin cable sheath material is 1-30 parts by weight;
preferably, the content of the EVM in the polyolefin cable sheath material is 1-20 parts by weight.
3. The polyolefin cable sheath material according to claim 1 or 2, wherein the polyolefin resin comprises a combination of a linear low density polyethylene resin, a high density polyethylene resin and a POE elastomer;
preferably, the content of the linear low-density polyethylene resin in the polyolefin cable sheath material is 1-10 parts by weight;
preferably, the content of the high-density polyethylene resin in the polyolefin cable sheath material is 1-10 parts by weight;
preferably, the content of the POE elastomer in the polyolefin cable sheath material is 1-10 parts by weight.
4. The polyolefin cable sheath material according to any one of claims 1 to 3, wherein the flame retardant comprises a combination of magnesium hydroxide, aluminum hydroxide and montmorillonite;
preferably, the content of the magnesium hydroxide in the polyolefin cable sheath material is 1-50 parts by weight;
preferably, the content of the aluminum hydroxide in the polyolefin cable sheath material is 1-50 parts by weight;
preferably, the content of montmorillonite in the polyolefin cable sheath material is 0.1-5 parts by weight;
preferably, the mass ratio of the magnesium hydroxide to the aluminum hydroxide to the montmorillonite is 1 (0.5-1.5) to 0.1-0.5.
5. The polyolefin cable sheath material according to any one of claims 1 to 4, wherein the polyolefin cable sheath material further comprises a compatibilizer and/or an antioxidant;
preferably, the content of the compatilizer in the polyolefin cable sheath material is 1-5 parts by weight;
preferably, the content of the antioxidant in the polyolefin cable sheath material is 0.1-1 part by weight.
6. A preparation method of the polyolefin cable sheath material as claimed in any one of claims 1 to 5, wherein the preparation method comprises the following steps: and banburying the ethylene-vinyl acetate copolymer, the polyolefin resin, the flame retardant, dicumyl peroxide, nickel oxide, optional compatilizer and optional antioxidant to obtain the polyolefin cable sheath material.
7. The preparation method according to claim 6, wherein the banburying temperature is 100-200 ℃;
preferably, the banburying time is 10-30 min.
8. A cable, characterized in that the sheath of the cable is prepared by using the polyolefin cable sheath material according to any one of claims 1 to 5.
9. The cable of claim 8, wherein the sheath has a thickness of 1 to 3 mm.
10. A cable according to claim 8 or 9, wherein the cable comprises any one of a subway cable, an optical-electrical composite cable, a railway cable or a telecommunication power line.
CN202111270889.1A 2021-10-29 2021-10-29 Halogen-free flame-retardant polyolefin cable sheath material and preparation method and application thereof Pending CN113912930A (en)

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CN107419173A (en) * 2017-07-07 2017-12-01 安徽同盛环件股份有限公司 A kind of corrosion-resisting alloy steel ring and its production technology
CN107418038A (en) * 2017-05-10 2017-12-01 江苏益帆高分子材料有限公司 Electric cable with large cross-section resistance to cracking low-smoke halogen-free polyolefin protective cover material and preparation method thereof
CN109110772A (en) * 2018-02-13 2019-01-01 公安部天津消防研究所 A kind of preparation method of carried metal organo montmorillonite

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CN106995546A (en) * 2016-11-28 2017-08-01 中广核三角洲（苏州）高聚物有限公司 Electric cable with large cross-section resistance to cracking low-smoke halogen-free polyolefin protective cover material and preparation method thereof
CN107418038A (en) * 2017-05-10 2017-12-01 江苏益帆高分子材料有限公司 Electric cable with large cross-section resistance to cracking low-smoke halogen-free polyolefin protective cover material and preparation method thereof
CN107419173A (en) * 2017-07-07 2017-12-01 安徽同盛环件股份有限公司 A kind of corrosion-resisting alloy steel ring and its production technology
CN109110772A (en) * 2018-02-13 2019-01-01 公安部天津消防研究所 A kind of preparation method of carried metal organo montmorillonite

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Publication number Priority date Publication date Assignee Title
CN116453739A (en) * 2023-04-07 2023-07-18 北京市昆仑线缆制造有限公司 Special photovoltaic new energy cable
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