CN113652091B - Tensile flame-retardant silicone rubber composition, flame-retardant B1-grade silicone rubber insulated polyolefin sheath control cable and preparation method thereof - Google Patents

Tensile flame-retardant silicone rubber composition, flame-retardant B1-grade silicone rubber insulated polyolefin sheath control cable and preparation method thereof Download PDF

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CN113652091B
CN113652091B CN202110879012.6A CN202110879012A CN113652091B CN 113652091 B CN113652091 B CN 113652091B CN 202110879012 A CN202110879012 A CN 202110879012A CN 113652091 B CN113652091 B CN 113652091B
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silicone rubber
flame
retardant
grade
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CN113652091A (en
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何治新
林珊
柯志欣
刘丽萍
邓树
赵美君
谌小莉
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Guangdong Line Giant Cable Co ltd
Guangzhou Metro Design and Research Institute Co Ltd
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Guangdong Line Giant Cable Co ltd
Guangzhou Metro Design and Research Institute Co Ltd
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    • 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
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    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B13/06—Insulating conductors or cables
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    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
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    • 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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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation
    • H01B7/0291—Disposition of insulation comprising two or more layers of insulation having different electrical properties
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/04—Flexible cables, conductors, or cords, e.g. trailing cables
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/18—Protection against damage caused by wear, mechanical force or pressure; Sheaths; Armouring
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    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
    • H01B7/2825—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable using a water impermeable sheath
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
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Abstract

The invention provides a tensile flame-retardant silicone rubber composition, a flame-retardant B1-grade silicone rubber insulation polyolefin sheath control cable and a preparation method thereof, wherein the tensile flame-retardant silicone rubber composition comprises the following components in parts by weight: 45-75 parts of methyl vinyl silicone rubber; 20-40 parts of silicon dioxide; 10-35 parts of nano-grade active pottery clay; 3-10 parts of hydroxyl siloxane; 5-10 parts of a composite efficient flame retardant; 0.5-3 parts of a crosslinking agent; 0.5-2 parts of a vulcanizing agent. The formula of the tensile flame-retardant silicone rubber composition has high temperature resistance, good ceramic forming performance, B1-grade flame retardance, overload incombustibility, fire resistance and no toxicity.

Description

Tensile flame-retardant silicone rubber composition, flame-retardant B1-grade silicone rubber insulated polyolefin sheath control cable and preparation method thereof
Technical Field
The invention relates to the field of electric wires and cables, in particular to a tensile flame-retardant silicone rubber composition, a flame-retardant B1-grade silicone rubber insulated polyolefin sheath control cable and a preparation method thereof.
Background
Currently, the existing flame-retardant B1-grade control cable on the market is a control cable of WDZB1-KYJYP (WDZB1-KYJY) model, and the main structure and the used materials of the cable are as follows:
the conductor adopts 5-class stranded copper wires; the insulating layer is made of low-smoke halogen-free crosslinked polyethylene; the filling layer is made of flame-retardant halogen-free material; the wrapping layer is made of an environment-friendly flame-retardant mineral material; the inner sheath adopts B1-grade flame-retardant low-smoke halogen-free polyolefin (WDZB1-KYJYP type); the shielding layer is made of thin copper wire braided shielding (WDZB1-KYJYP type); the outer sheath adopts B1-grade flame-retardant low-smoke halogen-free polyolefin.
That is, the insulation layer of this conventional cable is made of a crosslinked polyethylene material. The insulating temperature-resistant grade of the crosslinked polyethylene material is 90 ℃. Meanwhile, the crosslinked polyethylene material has high hardness, is not easy to bend, has poor softness and has high laying difficulty in certain specific places due to crosslinking. Furthermore, crosslinked polyethylene is subject to hydrolysis and crosslinked polyethylene itself is not flame retardant.
Therefore, it is necessary to provide a flexible, high-grade temperature-resistant, water-resistant and moisture-proof cable.
Disclosure of Invention
The invention aims to provide a tensile flame-retardant silicone rubber composition with good tensile strength and flame retardance, a flame-retardant B1-grade silicone rubber insulating polyolefin sheath control cable which is soft, high in temperature resistance grade and waterproof and moistureproof and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the tensile flame-retardant silicone rubber composition comprises the following components in parts by weight:
45-75 parts of methyl vinyl silicone rubber;
20-40 parts of silicon dioxide;
10-35 parts of nano-grade active pottery clay;
3-10 parts of hydroxyl siloxane;
5-10 parts of a composite efficient flame retardant;
0.5-3 parts of a crosslinking agent;
0.5-2 parts of a vulcanizing agent.
Preferably, the weight part of the methyl vinyl silicone rubber is 50-70 parts.
Preferably, the molecular weight of the methyl vinyl silicone rubber is 35 to 48 ten thousand.
Preferably, in the tensile flame-retardant silicone rubber composition, the mass percentage of the methyl vinyl silicone rubber is greater than or equal to 50%.
Preferably, the mass ratio of the hydroxyl siloxane to the silicon dioxide is 1 to (4-10).
The application also provides a fire-retardant B1 level silicon rubber insulation polyolefin sheath control line of tensile fire-retardant silicon rubber composition preparation, fire-retardant B1 level silicon rubber insulation polyolefin sheath control line includes the wire, the outer cladding of wire has the insulating layer, the insulating layer includes inner insulation layer and outer insulating layer, outer insulating layer adopts tensile fire-retardant silicon rubber composition preparation.
Preferably, the inner insulating layer is prepared from a high-temperature porcelain-forming silicone rubber composition, and the high-temperature porcelain-forming silicone rubber composition comprises the following components in parts by weight:
25-55 parts of methyl vinyl silicone rubber;
20-30 parts of silicon dioxide;
1-5 parts of zinc oxide;
1-5 parts of ferric oxide;
20-40 parts of ceramic powder;
0.1-1 part of a lubricant;
2-8 parts of a processing aid;
0.5-3 parts of a crosslinking agent;
0.3-1.5 parts of vulcanizing agent.
Preferably, the outermost side of the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable is wrapped by an outer sheath;
the inner sheath and the outer sheath are prepared from a low-smoke halogen-free polyolefin composition, and the low-smoke halogen-free polyolefin composition comprises the following components in parts by weight:
15-30 parts of EVA resin;
10-25 parts of PE resin;
45-65 parts of a flame retardant;
0.1-2 parts of antioxidant;
0.3-4 parts of a coupling agent;
3-8 parts of a carbon forming agent;
1-5 parts of a coloring agent.
Preferably, the flame retardant is aluminum hydroxide;
the antioxidant is selected from hindered phenol antioxidants;
the coupling agent is vinyl tri (beta-methoxyethoxy) silane.
The application also provides a preparation method of the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable, which comprises the following steps:
mixing the rubber material at the temperature of less than 80 ℃;
sulphurizing at a temperature of less than 60 ℃:
extruding the wire, wherein the vulcanization temperature of the rubber material is 200-300 ℃, and the extrusion temperature is less than 40 ℃.
Compared with the prior art, the scheme of the invention has the following advantages:
1. the tensile flame-retardant silicone rubber composition adopts methyl vinyl silicone rubber, and has good flexibility, high temperature resistance and good porcelain forming performance. After the nano-level active argil is used for active treatment, the dispersion and combination performance with silica gel can be enhanced, and the strength of the tensile flame-retardant silicone rubber composition is effectively improved. The silica is used as reinforcing filler to enhance the tensile tear strength of the tensile flame-retardant silicone rubber composition. The flame retardant effect is improved by using the composite efficient flame retardant.
2. In the tensile flame-retardant silicone rubber composition, the molecular weight of the methyl vinyl silicone rubber is 35-48 ten thousand, so that the strength of the tensile flame-retardant silicone rubber composition can be effectively ensured.
3. In the tensile flame-retardant silicone rubber composition, the mass percent of the methyl vinyl silicone rubber is more than or equal to 50% so as to ensure the insulation resistance value.
4. In the tensile flame-retardant silicone rubber composition, hydroxyl siloxane is used as a processing aid to improve the organic combination of silicon dioxide molecules and methyl vinyl silicone rubber so as to improve the water resistance.
5. The tensile flame-retardant silicone rubber composition has the flame retardance of grade B1, overload incombustibility, fire resistance, no toxicity and good environmental protection performance.
6. According to the flame-retardant B1-grade silicone rubber insulating polyolefin sheath control cable, the inner insulating layer, the outer insulating layer and the outer sheath all use methyl vinyl silicone rubber as sizing materials, so that the cable has good flexibility and is suitable for laying in various complex or special places.
In addition, the inner insulating layer is prepared from a high-temperature porcelain-forming silicon rubber composition, and has high temperature resistance and porcelain forming performance; the outer insulating layer is prepared from the tensile flame-retardant silicone rubber composition, and has high tensile strength performance and high flame retardance; the outer sheath is prepared from a low-smoke halogen-free polyolefin composition, and has the advantages of no toxicity, low smoke, high tensile strength, good wear resistance and the like. The materials of the inner insulating layer, the outer insulating layer and the outer sheath enable the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable to have the advantages of being soft, high in temperature resistance grade, water-resistant and moisture-proof.
7. Although the novel material is used in the flame-retardant B1-grade silicon rubber insulation polyolefin sheath control line, the price of the control line is reduced by about 5 percent compared with that of the traditional B1-grade control cable, and the product performance is far superior to that of the traditional control cable, so that the control line has a huge development prospect.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic structural view of an exemplary embodiment of a flame retardant B1 grade silicone rubber insulated polyolefin jacketed control cable of the present application;
fig. 2 is a schematic structural view of another exemplary embodiment of a flame retardant B1 grade silicone rubber insulated polyolefin jacketed control cable of the present application.
Detailed Description
The embodiments described below with reference to the drawings are illustrative only and should not be construed as limiting the invention. In addition, if a detailed description of the known art is not necessary to show the features of the present invention, it is omitted.
The tensile flame-retardant silicone rubber composition comprises the following components in parts by weight:
45-75 parts of methyl vinyl silicone rubber;
20-40 parts of silicon dioxide;
10-35 parts of nano-grade active pottery clay;
3-10 parts of hydroxyl siloxane;
5-10 parts of a composite efficient flame retardant;
0.5-3 parts of a crosslinking agent;
0.5-2 parts of a vulcanizing agent.
Preferably, the weight part of the methyl vinyl silicone rubber is 50-70 parts.
The tensile flame-retardant silicone rubber composition adopts methyl vinyl silicone rubber, and has good flexibility, high temperature resistance and good porcelain forming performance. After the nano-level active argil is used for active treatment, the dispersion and combination performance with silica gel can be enhanced, and the strength of the tensile flame-retardant silicone rubber composition is effectively improved. The silica is used as reinforcing filler to enhance the tensile tear strength of the tensile flame-retardant silicone rubber composition. The flame retardant effect is improved by using the composite efficient flame retardant.
In one embodiment of the present application, the methyl vinyl silicone rubber has a molecular weight of 35 to 48 ten thousand. In another embodiment of the present application, the methyl vinyl silicone rubber has a molecular weight of 38 to 42 ten thousand. In another embodiment of the present application, the methyl vinyl silicone rubber has a molecular weight of 40 ten thousand. The molecular weight of the methyl vinyl silicone rubber is 35-48 ten thousand, and the strength of the rubber material can be effectively ensured.
In one embodiment of the present application, in the tensile flame-retardant silicone rubber composition, the mass percentage of the methyl vinyl silicone rubber is greater than or equal to 50% to ensure an insulation resistance value.
In one embodiment herein, the mass ratio of the hydroxy siloxane to the silica is 1: 4-10. The hydroxyl siloxane as a processing aid can improve the organic combination of silicon dioxide molecules and methyl vinyl silicone rubber so as to improve the water resistance.
In one embodiment of the present application, the methyl vinyl silicone rubber is polymethylvinylsiloxane.
In one embodiment of the present application, the lubricant is selected from at least one of zinc stearate or calcium stearate.
In one embodiment of the application, the composite high-efficiency flame retardant adopts a material with an oxygen index of more than or equal to 38. The composite efficient flame retardant is used to enable the oxygen index of the material to reach more than 38, and has good flame retardant effect.
In one embodiment of the present application, the crosslinker is a hydrido siloxane. The hydrogen-based siloxane as a crosslinking agent can promote the degree of crosslinking reaction of the silicone rubber, thereby obtaining a material having good physical properties.
In one embodiment of the present application, the sulfiding agent is a platinum sulfiding agent. Platinum is adopted as a vulcanizing agent, belongs to a food-grade vulcanizing agent, and chemical reactants of the platinum are nontoxic and tasteless in the vulcanizing process.
The formula of the tensile flame-retardant silicone rubber composition has high temperature resistance and good porcelain forming performance. Meanwhile, the flame retardant has B1-grade flame retardance, overload incombustibility and fire resistance. And the tensile flame-retardant silicone rubber composition is nontoxic and has good environmental protection performance, and the nontoxicity is mainly reflected in that the tensile flame-retardant silicone rubber composition is silica gel containing silicon, carbon, hydrogen and oxygen. The tensile flame-retardant silicone rubber composition has excellent non-flaming-drip characteristics because of the self-contained vulcanized solid material and ceramic forming property. In addition, it possesses excellent tear resistance.
Referring to fig. 1 and 2, the present application further provides a flame retardant B1 grade silicone rubber insulated polyolefin sheath control wire prepared from the tensile flame retardant silicone rubber composition, the flame retardant B1 grade silicone rubber insulated polyolefin sheath control wire comprises a wire, an insulating layer is coated outside the wire, the insulating layer comprises an inner insulating layer 5 and an outer insulating layer 6, and the outer insulating layer 6 is prepared from the tensile flame retardant silicone rubber composition.
In one embodiment of the present application, the inner insulating layer 5 is prepared from a high-temperature porcelain-forming silicone rubber composition comprising the following components in parts by weight:
25-55 parts of methyl vinyl silicone rubber;
20-30 parts of silicon dioxide;
1-5 parts of zinc oxide;
1-5 parts of ferric oxide;
20-40 parts of ceramic powder;
0.1-1 part of lubricant;
2-8 parts of a processing aid;
0.5-3 parts of a crosslinking agent;
0.3-1.5 parts of vulcanizing agent.
The high-temperature porcelain-forming silicon rubber composition adopts methyl vinyl silicon rubber, so that the high-temperature porcelain-forming silicon rubber composition has good flexibility. In one embodiment of the present application, the methyl vinyl silicone rubber is a gas phase process produced polymethylvinylsiloxane. In one embodiment of the present application, the methyl vinyl silicone rubber has a molecular weight of 35 to 48 ten thousand. In another embodiment of the present application, the methyl vinyl silicone rubber has a molecular weight of 38 to 42 ten thousand. In another embodiment of the present application, the methyl vinyl silicone rubber has a molecular weight of 40 ten thousand. The molecular weight of the methyl vinyl silicone rubber is 35-48 ten thousand, and the strength of the rubber material can be effectively ensured. In one embodiment of the application, in the high-temperature porcelain-forming silicone rubber composition, the mass percentage of the methyl vinyl silicone rubber is less than or equal to 50%, so that the porcelain forming effect can be effectively ensured.
In the high-temperature porcelain-forming silicon rubber composition, the silicon dioxide is used as reinforcing filler, so that the tensile and tear strength of the high-temperature porcelain-forming silicon rubber composition can be enhanced.
The high-temperature porcelain-forming silicon rubber composition is added with zinc oxide and iron oxide, so that the temperature required by porcelain forming can be reduced. The porcelainized layer has certain strength through the combined action of zinc oxide, iron oxide and silicon dioxide. In one embodiment of the present application, the mass ratio of the zinc oxide to the iron oxide to the silicon dioxide is (1-4) to (23-28). In another embodiment of the present application, the mass ratio of zinc oxide, iron oxide and silicon dioxide is 1: (13-15).
The ceramic powder is nano-scale ceramic powder and is selected from one or more of calcium silicate, diatomite, mullite, quartz powder, alumina, bauxite, wollastonite, magnesium hydroxide, zinc borate, mica and other raw materials. In one embodiment of the present application, the ceramifying powder is calcium silicate. The low-melting-point composite porcelain powder can improve the porcelain forming speed and effect, and a hard insulating ceramic layer is quickly formed instead of burnt ash to fall off during combustion, so that the high-temperature porcelain-forming silicon rubber composition has fire resistance.
In one embodiment of the present application, the lubricant is selected from at least one of zinc stearate or calcium stearate. The zinc stearate and the calcium stearate are used as processing lubricants to improve the processing extrudability of the cable.
In one embodiment of the present application, the processing aid is a hydroxy siloxane. The hydroxyl siloxane as a processing aid can organically combine silicon dioxide molecules with the methyl vinyl silicone rubber, so that the water resistance is improved.
In one embodiment of the present application, the crosslinker is a hydrido siloxane. The hydrogen-based siloxane as a crosslinking agent can promote the degree of crosslinking reaction of the silicone rubber, thereby obtaining a material having good physical properties.
In one embodiment of the present application, the sulfiding agent is a platinum sulfiding agent. Platinum is adopted as a vulcanizing agent, belongs to a food-grade vulcanizing agent, and chemical reactants of the platinum are nontoxic and tasteless in the vulcanizing process.
The formula of the high-temperature porcelain-forming silicon rubber composition has high temperature resistance and good porcelain forming performance. Meanwhile, the flame retardant has B1-grade flame retardance, overload incombustibility and fire resistance. And the high-temperature porcelain-forming silicon rubber composition is nontoxic and has good environmental protection performance, and the nontoxicity is mainly reflected by silica gel containing silicon, carbon, hydrogen and oxygen. The high-temperature porcelain-forming silicone rubber composition has excellent non-dripping characteristics because of the self-contained vulcanization solidifying material and porcelain-forming property. In addition, it possesses excellent tear resistance.
In an embodiment of the application, the outermost side of the flame-retardant B1-grade silicon rubber insulated polyolefin sheath control cable is wrapped by an outer sheath 4, the outer sheath 4 is prepared from a low-smoke halogen-free polyolefin composition, and the low-smoke halogen-free polyolefin composition comprises the following components in parts by weight:
15-30 parts of EVA resin;
10-25 parts of PE resin;
45-65 parts of a flame retardant;
0.1-2 parts of an antioxidant;
0.3-4 parts of a coupling agent;
3-8 parts of a carbonizing agent;
1-5 parts of a coloring agent.
In another embodiment of the application, in the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable, the outer periphery of a conductor cluster consisting of a plurality of conductors is wrapped by the inner sheath 3, and the outermost side of the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable is wrapped by the outer sheath 4. The inner sheath 3 and the outer sheath 4 are both prepared from the low-smoke halogen-free polyolefin composition.
The EVA resin and the PE resin are base materials of the low-smoke halogen-free polyolefin composition, the EVA resin can be used as a main structure of the strength of the low-smoke halogen-free polyolefin composition, and the PE resin mainly provides processability and structural strength.
In one embodiment of the present application, the flame retardant is aluminum hydroxide. The aluminum hydroxide is used as a flame retardant and is matched with other materials for use, so that the oxygen index of the cable is not lower than 40 when the low-smoke halogen-free polyolefin composition is used for preparing a finished cable, and the integral flame retardant effect of the cable can be effectively improved.
In one embodiment herein, the antioxidant is selected from hindered phenolic antioxidants. In one embodiment of the present application, the antioxidant is any one or more of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, 2, 6-tert-butyl-4-methylphenol, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide. In one embodiment of the application, the antioxidant adopts pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, which can improve the ageing resistance and temperature resistance of the low-smoke halogen-free polyolefin composition.
In one embodiment herein, the coupling agent is vinyltris (β -methoxyethoxy) silane. The vinyl tri (beta-methoxyethoxy) silane can effectively combine with inorganic molecules such as aluminum hydroxide and the like and organic polymers such as EVA resin and PE resin, thereby forming a stable structure and improving the overall performance.
The addition of the char forming agent enables the low-smoke halogen-free polyolefin composition to have certain crusting property during combustion, further improves flame retardance and simultaneously does not generate burning dripping particles. In the embodiment of the application, the carbon forming agent is any one or more of hexachlorocyclotriphosphazene, anhydrous sodium acetate, o-allylphenol, phenol and pentaerythritol ester alcohol.
In one embodiment of the present application, the low smoke zero halogen polyolefin composition comprises the following components in parts by weight:
15-30 parts of EVA resin;
10-25 parts of PE resin;
45-65 parts of aluminum hydroxide;
0.1-2 parts of pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate;
0.3-4 parts of vinyl tri (beta-methoxyethoxy) silane;
3-8 parts of a carbon forming agent;
1-5 parts of carbon black.
Wherein, the carbon black is used as a coloring agent to prepare a black product, and simultaneously, the product has the ultraviolet resistance. When the color cable product is prepared, the color powder is used, and simultaneously, the UV stabilizer is used together.
The application also provides a preparation method of the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable, which comprises the following steps:
mixing the rubber material at the temperature of less than 80 ℃;
sulphurizing at a temperature of less than 60 ℃:
extruding the wire, wherein the vulcanization temperature of the rubber material is 200-300 ℃, and the extrusion temperature is less than 40 ℃.
Specifically, in the process of controlling the cable by the flame-retardant B1-grade silicon rubber insulating polyolefin sheath, the temperature in the rubber mixing process is controlled to be lower than 80 ℃; controlling the temperature to be lower than 60 ℃ in the vulcanizing process, and controlling the time to be less than 3 min; the vulcanizing temperature of the rubber material is controlled between 200 ℃ and 300 ℃ during the extrusion of the wire.
The effects of the tensile flame retardant silicone rubber composition and the flame retardant B1 grade silicone rubber insulated polyolefin sheathed control cable of the present application are demonstrated below by several examples and comparative examples of flame retardant B1 grade silicone rubber insulated polyolefin sheathed control cables.
First, a flame-retardant B1-grade silicone rubber insulation polyolefin sheath control cable includes an inner insulation layer 5 and an outer insulation layer 6 of insulation layers, and an inner sheath 3 and an outer sheath 4, and examples and comparative examples of different component formulations are sequentially referred to tables 1 to 3 depending on the structure of the cable.
Table 1B 1 grade silicone rubber insulating polyolefin jacket examples and comparative examples of the formulation of the components of the outer insulating layer of control cables
Figure GDA0003589523300000101
Table 2B 1 examples and comparative examples of component formulations of silicone rubber insulating polyolefin jacket control cable inner insulation layer
Figure GDA0003589523300000102
Figure GDA0003589523300000111
Table 3B 1 grade silicone rubber insulating polyolefin sheath examples and comparative examples of inner and outer sheaths of control cables
Figure GDA0003589523300000112
Several examples and comparative examples of flame retardant grade B1 silicone rubber insulated polyolefin sheath control cables were obtained by combining the above examples and comparative examples of different materials with the corresponding structures of flame retardant grade B1 silicone rubber insulated polyolefin sheath control cables, as shown in table 4:
table 4B 1 grade silicone rubber insulated polyolefin sheathed control cable examples and comparative examples
Figure GDA0003589523300000121
The effect of the flame retardant B1 grade silicone rubber insulated polyolefin jacket control cable of the examples and comparative examples is verified in the following respects.
And (3) softness testing: and (3) performing an elastic modulus test, wherein the test standard is ASTM D790-03, the test conditions are 25 +/-2 ℃ and the elastic modulus standard is 2.5-4.2 Mpa.
Tensile strength: the tensile strength was tested by means of a tensile machine. According to the requirement of GB12706.1-2008 standard, the tensile strength standard of the low-smoke halogen-free cable is 9.0MPa, the tensile strength exceeds the standard requirement value, and the surface wire has excellent tensile capacity.
Fire resistance: fire resistance tests were conducted on the fire retardant B1 grade silicone rubber insulated polyolefin sheathed control cables of the examples and comparative examples to simulate the burning of the wire in a fire situation. Taking a cable with the length of 100cm, fixing the cable in a combustion test box, carrying out a combustion test with the test standard of BS6387-2013, the flame temperature of 950 ℃, and the combustion temperature of 3H, and detecting whether the cable is short-circuited. If the cable does not have the short circuit phenomenon, the cable can persist for 3 hours in a fire disaster and the short circuit phenomenon can not occur, and secondary damage to the environment and personal safety can not be caused.
Temperature resistance, insulation, water resistance and moisture resistance: 10M of insulated core wire is taken and put into a constant temperature water tank to see whether the insulated core wire meets the requirement of the insulated water boiling at 60 ℃ and 400h 2000M omega km.
And (3) wear resistance test: the simulation cable generates friction with other objects in the laying process, so that the cable body cannot be damaged. The main method comprises the following steps: and repeatedly scraping and grinding the wire rod for 10000 times on a grinding-resistant machine, and checking whether the wire rod sheath is worn through.
The results of the performance measurements are shown in table 5.
TABLE 5
Figure GDA0003589523300000131
Figure GDA0003589523300000141
Known from Shanghai:
first, the flame-retardant B1-grade silicone rubber insulated polyolefin sheath control cables of examples a1, a2, and A3 of the present application have better flexibility and higher tensile strength than comparative examples a1 (the molecular weight of the methyl vinyl silicone rubber used for the outer insulating layer 6 is about 50 ten thousand) and comparative examples a2 (the mass percentage ratio of the methyl vinyl silicone rubber in the tensile flame-retardant silicone rubber composition used for the outer insulating layer 6 is less than 50%). Meanwhile, compared with the common cable of the comparative example A3 (the tensile flame-retardant silicone rubber composition adopted by the outer insulating layer 6 does not contain the nano-scale activated clay in the proportion of the application), the control cable with the flame-retardant B1-grade silicone rubber insulating polyolefin sheath has obviously higher tensile strength. The control cable of the flame-retardant B1 grade silicone rubber insulating polyolefin sheath does not meet the insulating poaching requirement of 60 ℃ 400h 2000M omega km compared with the control cable of the comparative example A4 (the mass ratio of the hydroxyl siloxane and the silicon dioxide in the tensile flame-retardant silicone rubber composition adopted by the outer insulating layer 6 is not in the ratio range defined by the application). Meanwhile, the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable has good softness, good tensile strength, good fire resistance and excellent insulating water-resistant and moisture-proof performances.
The tensile flame-retardant silicone rubber composition adopts the methyl vinyl silicone rubber, the molecular weight of the methyl vinyl silicone rubber is kept between 35 and 48 million, the mass percent of the methyl vinyl silicone rubber is more than or equal to 50%, and meanwhile, the hydroxyl siloxane is added as a processing aid to improve the organic combination of the silicon dioxide molecules and the methyl vinyl silicone rubber, so that when the tensile flame-retardant silicone rubber composition is used for preparing cables, the cables with good tensile strength and good flexibility can be prepared, and the tensile flame-retardant silicone rubber composition has the advantages of temperature resistance, B1-level flame retardance and fire resistance.
Second, the flame retardant B1 grade silicone rubber insulated polyolefin sheath control cables of examples B1, B2, and B3 in the present application have better flexibility and higher tensile strength than the conventional cables of comparative example B1 (the molecular weight of the methyl vinyl silicone rubber used for the inner insulating layer 5 is about 50 ten thousand), comparative example B2 (the mass percentage ratio of the methyl vinyl silicone rubber in the high temperature porcelain-forming silicone rubber composition used for the inner insulating layer 5 exceeds 50%), and comparative example B3 (the high temperature porcelain-forming silicone rubber composition used for the inner insulating layer 5 does not contain the zinc oxide and the iron oxide in the present application ratio). Meanwhile, the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable has good softness, good tensile strength, good fire resistance and excellent insulating water-resistant and moisture-proof performances.
The high-temperature porcelain-forming silicone rubber composition adopts the methyl vinyl silicone rubber, the molecular weight of the methyl vinyl silicone rubber is kept between 35 and 48 million, the mass percent of the methyl vinyl silicone rubber is less than or equal to 50 percent, and meanwhile, the zinc oxide and the iron oxide are added, so that when the high-temperature porcelain-forming silicone rubber composition is used for preparing cables, the cables with good tensile strength and flexibility can be prepared, and the high-temperature porcelain-forming silicone rubber composition has the advantages of good temperature resistance, B1-level flame retardance and fire resistance.
Third, the flame retardant B1 grade silicone rubber insulated polyolefin sheathed control cables of examples C1, C2, and C3 of the present application have better flexibility, abrasion resistance, and higher tensile strength than the conventional cables of comparative example C1 (the compound in the low smoke zero halogen polyolefin compositions used for the inner sheath 3 and the outer sheath 4 is a conventional flame retardant low smoke zero halogen polyolefin of WDZB1-KYJYP type) and comparative example C3 (the low smoke zero halogen polyolefin compositions used for the inner sheath 3 and the outer sheath 4 do not contain vinyltris (β -methoxyethoxy) silane in the ratio of the present application). Compared with the comparative example C2 (the low-smoke halogen-free polyolefin composition adopted by the inner sheath 3 and the outer sheath 4 does not contain the tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionic acid pentaerythritol ester in the proportion of the application), the flame-retardant B1 grade silicon rubber insulating polyolefin sheath control cable does not meet the insulating water boiling requirement of 60 ℃ and 400h 2000M omega km, and has better flexibility and better wear resistance. Meanwhile, the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable has good softness, good tensile strength, good fire resistance, better wear resistance and excellent insulating water-resistant and moisture-proof performances.
The description above shows that the low smoke zero halogen polyolefin composition of the present application, by adopting the base material in which the EVA resin and the PE resin are low smoke zero halogen polyolefin composition, simultaneously, pentaerythrityl tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate is added to improve the ageing resistance and temperature resistance of the low-smoke halogen-free polyolefin composition, and vinyl tri (beta-methoxyethoxy) silane is added to effectively combine with inorganic molecules such as aluminum hydroxide and the like, and organic polymers such as EVA resin and PE resin to form a stable structure, so that the overall performance of the low-smoke halogen-free polyolefin composition is improved, therefore, when the low-smoke halogen-free polyolefin composition is used for preparing cables, the cables with good tensile strength, good flexibility and good wear resistance can be prepared, and the low-smoke halogen-free polyolefin composition has the advantages of good temperature resistance, B1-grade flame retardance and fire resistance.
In conclusion, the tensile flame-retardant silicone rubber composition has good flexibility, temperature resistance and high tensile strength, and also has B1-grade flame retardance, overload incombustibility, flame resistance and no toxicity. Meanwhile, in the flame-retardant B1-grade silicon rubber insulation polyolefin sheath control cable, the inner insulation layer 5 is prepared from a high-temperature porcelain-forming silicon rubber composition, and has high temperature resistance and porcelain forming performance; the outer insulating layer 6 is prepared from a tensile flame-retardant silicone rubber composition, and has high tensile strength performance and high flame retardance; the outer sheath 4 is prepared from a low-smoke halogen-free polyolefin composition, and has the advantages of no toxicity, low smoke, high tensile strength, good wear resistance and the like. The inner insulating layer 5, the outer insulating layer 6 and the outer sheath 4 all use methyl vinyl silicone rubber as sizing materials, so that the cable has good flexibility and is suitable for laying in various complex or special places. The materials of the inner insulating layer 5, the outer insulating layer 6 and the outer sheath 4 enable the flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable to have the advantages of softness, high temperature resistance grade, water resistance and moisture resistance.
The foregoing is only a partial embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. The flame-retardant B1-grade silicon rubber insulating polyolefin sheath control cable is characterized by comprising a lead, wherein an insulating layer is coated outside the lead, the insulating layer comprises an inner insulating layer and an outer insulating layer, and the outer insulating layer is prepared from a tensile flame-retardant silicon rubber composition;
the tensile flame-retardant silicone rubber composition comprises the following components in parts by weight:
45-75 parts of methyl vinyl silicone rubber;
20-40 parts of silicon dioxide;
10-35 parts of nano-grade active pottery clay;
3-10 parts of hydroxyl siloxane;
5-10 parts of a composite efficient flame retardant;
0.5-3 parts of a crosslinking agent;
0.5-2 parts of a vulcanizing agent;
the molecular weight of the methyl vinyl silicone rubber is 35-48 ten thousand;
the mass percentage of the methyl vinyl silicone rubber is more than or equal to 50 percent;
the composite high-efficiency flame retardant is used for enabling the oxygen index of the material to reach more than 38.
2. The flame retardant B1-grade silicone rubber-insulated polyolefin sheath control cable of claim 1, wherein the weight part of the methyl vinyl silicone rubber in the tensile flame retardant silicone rubber composition is 50-70 parts.
3. The flame retardant B1-grade silicone rubber-insulated polyolefin sheath control cable according to claim 1, wherein the tensile flame retardant silicone rubber composition has a mass ratio of hydroxyl siloxane to silica of 1 (4-10).
4. The flame-retardant B1-grade silicone rubber-insulated polyolefin sheath control cable according to claim 1, wherein the inner insulating layer is prepared from a high-temperature porcelain-forming silicone rubber composition comprising the following components in parts by weight:
25-55 parts of methyl vinyl silicone rubber;
20-30 parts of silicon dioxide;
1-5 parts of zinc oxide;
1-5 parts of ferric oxide;
20-40 parts of ceramic powder;
0.1-1 part of lubricant;
2-8 parts of a processing aid;
0.5-3 parts of a crosslinking agent;
0.3-1.5 parts of vulcanizing agent.
5. The flame retardant grade B1 silicone rubber insulated polyolefin sheath control cable of claim 1, wherein the outermost side of the flame retardant grade B1 silicone rubber insulated polyolefin sheath control cable is wrapped with an outer sheath;
the outer sheath is prepared from a low-smoke halogen-free polyolefin composition, and the low-smoke halogen-free polyolefin composition comprises the following components in parts by weight:
15-30 parts of EVA resin;
10-25 parts of PE resin;
45-65 parts of a flame retardant;
0.1-2 parts of antioxidant;
0.3-4 parts of a coupling agent;
3-8 parts of a carbon forming agent;
1-5 parts of a coloring agent.
6. The flame retardant B1 grade silicone rubber insulated polyolefin jacket control cable of claim 5, wherein:
the flame retardant in the low-smoke halogen-free polyolefin composition is aluminum hydroxide;
the antioxidant is selected from hindered phenol antioxidants;
the coupling agent is vinyl tri (beta-methoxyethoxy) silane.
7. The method for preparing the flame-retardant B1-grade silicone rubber insulated polyolefin sheath control cable according to any one of claims 1-6, comprising the following steps:
mixing the rubber material at the temperature of less than 80 ℃;
sulphurizing at a temperature of less than 60 ℃:
extruding the wire, wherein the vulcanization temperature of the rubber material is 200-300 ℃, and the extrusion temperature is less than 40 ℃.
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