CN114843019A - High and low temperature resistant halogen-free flame-retardant cable - Google Patents
High and low temperature resistant halogen-free flame-retardant cable Download PDFInfo
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- CN114843019A CN114843019A CN202210633640.0A CN202210633640A CN114843019A CN 114843019 A CN114843019 A CN 114843019A CN 202210633640 A CN202210633640 A CN 202210633640A CN 114843019 A CN114843019 A CN 114843019A
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- H—ELECTRICITY
- 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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- 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
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/025—Other inorganic material
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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
- H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
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- 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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- 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
- H01B7/22—Metal wires or tapes, e.g. made of steel
- H01B7/228—Metal braid
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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
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- 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
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
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Abstract
The invention relates to the technical field of cables, in particular to a high and low temperature resistant halogen-free flame-retardant cable which comprises an outer sheath, a copper wire woven layer, a flame-retardant heat-preservation sheath, a mica tape layer, cable cores and an FRP (fiber reinforced plastic) reinforced core, wherein each cable core comprises a polyethylene inner sheath and a conductor, the FRP reinforced core is arranged at the center of a plurality of cable cores, and the mica tape layer is coated on the plurality of cable cores.
Description
Technical Field
The invention relates to the technical field of cables, in particular to a high and low temperature resistant halogen-free flame-retardant cable.
Background
The cable has the functions of transmitting electric energy and signals and realizing electromagnetic conversion, the electric power is transmitted by the cable such as a power cable and an overhead line, the signal is transmitted by the cable such as an axial cable, the electromagnetic conversion is realized by the enameled wire, the cable demand is increased with the development of the industry, most of the insulating layers and the sheathing materials of the electric wires and cables belong to organic polymers, and the electric wires and cables are easy to cause combustion under the conditions of high voltage, heat source, certain temperature, oxygen concentration and the like, so the flame retardance is very important. The halogen flame retardant is decomposed when the high polymer is decomposed by heat, and can capture free radicals generated by the degradation reaction of the high polymer material, so that the chain reaction is delayed or terminated, and simultaneously, the released hydrogen halide is a flame-retardant gas, has high density, can cover the surface of the material, plays a role in blocking the surface combustible gas and inhibits combustion.
The halogen flame retardant has the obvious advantages of high flame retardant efficiency, small dosage and low price, but along with the progress of society and the enhancement of environmental protection consciousness, the halogen flame retardant generates a large amount of smoke, corrosive and toxic gases during combustion, so that the application of the halogen flame retardant is limited, and therefore, the halogen-free flame retardant cable which is environment-friendly is especially important to provide.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the technical problems, the invention provides a high-low temperature resistant halogen-free flame-retardant cable.
The adopted technical scheme is as follows:
a high and low temperature resistant halogen-free flame-retardant cable comprises an outer sheath, a copper wire woven layer, a flame-retardant heat-preservation sheath, a mica tape layer, cable cores and an FRP (fiber reinforced plastic) reinforced core, wherein the cable cores comprise polyethylene inner sheaths and conductors, the FRP reinforced core is arranged at the central positions of a plurality of cable cores, and the mica tape layer is coated on the cable cores;
the flame-retardant heat-insulation sheath comprises the following components in parts by weight:
80-100 parts of high-density polyethylene, 30-50 parts of ethylene-octene copolymer, 15-20 parts of carboxyl-terminated liquid nitrile rubber, 10-15 parts of styrene thermoplastic elastomer, 1-3 parts of silane coupling agent, 2-4 parts of epoxy rubber seed oil, 0.5-1 part of turpentine, 0.5-1 part of caged pentaerythritol phosphate, 2-4 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10-20 parts of hollow glass microsphere, 30-40 parts of nano silicon dioxide, 10-20 parts of zinc oxide, 30-40 parts of carbon black, 0.1-0.5 part of crosslinking agent and 0.4-0.6 part of sulfur.
Further, the flame-retardant heat-insulation sheath comprises the following components in parts by weight:
100 parts of high-density polyethylene, 45 parts of ethylene-octene copolymer, 15 parts of carboxyl-terminated liquid nitrile rubber, 15 parts of styrene thermoplastic elastomer, 2 parts of silane coupling agent, 2 parts of epoxy rubber seed oil, 1 part of turpentine, 0.8 part of caged pentaerythritol phosphate, 3 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10 parts of hollow glass microspheres, 35 parts of nano silicon dioxide, 10 parts of zinc oxide, 40 parts of carbon black, 0.48 part of crosslinking agent and 0.5 part of sulfur.
Further, the preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding red phosphorus and a dispersing agent into water, stirring to uniformly disperse the red phosphorus, then adding aluminum sulfate, heating to 60-70 ℃, dropwise adding a sodium carbonate solution, adjusting the pH of the system to 10-11, reacting for 2-4h, cooling and filtering the reaction liquid, washing the obtained solid, drying to constant weight to obtain an intermediate, and forming a graphene layer on the surface by adopting a chemical vapor deposition method.
Further, the chemical vapor deposition method comprises placing the intermediate into a CVD chamber, and pre-vacuumizing the chamber to 5 × 10 - 3 Introducing hydrogen with the hydrogen flow rate of 200-250cm below Pa 3 Min, heating to 1000-1020 ℃ under the hydrogen atmosphere, controlling the air pressure of the chamber to be 2-4kPa, and introducing the gas with the flow of 10-15cm after 20-40min 3 Methane at a rate of 200- 3 Argon/min and 500-1000cm 3 And (3) starting to grow graphene by using hydrogen in/min for 3-10min, closing methane and hydrogen after the growth is finished, and naturally cooling to room temperature under the argon atmosphere.
Further, the cross-linking agent comprises dicumyl peroxide and polymaleimide, and the mass ratio of the dicumyl peroxide to the polymaleimide is 5-10: 1.
further, the preparation method of the flame-retardant heat-insulating sheath comprises the following steps:
weighing raw materials in proportion, adding the raw materials into an internal mixer for internal mixing, carrying out hot cutting and air cooling after the internal mixing is finished, adding the obtained granules into a double-roller open mill, heating to 140 ℃ for mixing, carrying out extrusion granulation by a double screw after mixing for 5-8min, preheating for 5-10min without pressurizing in a flat vulcanizing machine at 185 ℃ for 180 ℃, then carrying out heat preservation and pressurization to 10-15MPa and keeping for 5-10min, and finally carrying out die stripping after pressure maintaining and cooling to room temperature.
Further, the outer sheath comprises the following components in parts by weight:
100-120 parts of linear low-density polyethylene, 30-50 parts of EVM rubber, 20-25 parts of polyolefin elastomer, 30-40 parts of nano zinc oxide, 5-10 parts of stearic acid, 50-80 parts of aluminum hydroxide, 40-50 parts of magnesium hydroxide, 1-2 parts of dioctyl adipate, 1-2 parts of dioctyl sebacate, 0.5-1 part of dicumyl peroxide, 1-1 part of light stabilizer GW-5400.5, 62-4 parts of antioxidant 10762 and 1-2 parts of sulfur.
Further, the outer sheath comprises the following components in parts by weight:
110 parts of linear low-density polyethylene, 40 parts of EVM rubber, 25 parts of polyolefin elastomer, 30 parts of nano zinc oxide, 8 parts of stearic acid, 60 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 2 parts of dioctyl adipate, 2 parts of dioctyl sebacate, 1 part of dicumyl peroxide, GW-5400.5 parts of light stabilizer, 10762 parts of antioxidant and 2 parts of sulfur.
Further, the preparation method of the outer sheath comprises the following steps:
weighing raw materials in proportion, adding the raw materials into an internal mixer for internal mixing, carrying out hot cutting and air cooling after the internal mixing is finished, adding the obtained granules into a double-roller open mill, heating to 140 ℃ for mixing, carrying out extrusion granulation by a double screw after mixing for 5-8min, preheating for 5-10min without pressurizing in a flat vulcanizing machine at 185 ℃ for 180 ℃, then carrying out heat preservation and pressurization to 10-15MPa and keeping for 5-10min, and finally carrying out die stripping after pressure maintaining and cooling to room temperature.
Further, the banburying temperature is 120-130 ℃, and the rotor speed of the banbury mixer is 20-30 r/min.
The invention has the beneficial effects that:
the invention provides a high and low temperature resistant halogen-free flame-retardant cable, an outer sheath and a flame-retardant heat-insulating sheath play a role in protecting a conductor together, wherein linear low-density polyethylene in the outer sheath is formed by copolymerizing ethylene and a small amount of alpha-olefin on a linear ethylene main chain, has a molecular structure of a very short comonomer branched chain, is non-toxic, tasteless and odorless, has higher softening temperature and melting temperature, and good heat resistance and cold resistance, EVM rubber has good performances of low smoke, zero halogen and flame retardance, a polyolefin elastomer has the characteristics of small density, large bending, high low-temperature impact resistance, easiness in processing, reusability and the like, after the polyolefin elastomer is added, the impact resistance and the processing performance of the outer sheath can be improved, the linear low-density polyethylene, the EVM rubber and the polyolefin elastomer have good compatibility, and the addition of dioctyl adipate and dioctyl sebacate can further improve the low-temperature resistance and the mechanical strength of the outer sheath, the high-density polyethylene in the flame-retardant heat-insulation sheath has good high-temperature resistance, excellent tensile strength and creep property, the flexibility, tensile skin strength and tear strength of the flame-retardant heat-insulation sheath are improved after the ethylene-octene copolymer is added, the polarity of a sizing material can be increased after the carboxyl-terminated liquid nitrile rubber is added, the intermolecular force is improved, the carboxyl can react with an epoxy group on epoxy rubber seed oil to play a role in toughening and modifying, the caged pentaerythritol phosphate can be compatible with the aluminum hydroxide/graphene microencapsulated red phosphorus to play a role in synergistic flame retardance, and a composite capsule layer formed by the aluminum hydroxide and the graphene improves the stability and the flame retardance of the cable.
Drawings
FIG. 1 is a schematic structural diagram of a halogen-free flame-retardant cable capable of resisting high and low temperatures according to the present invention;
the reference numbers in the figures represent respectively:
1-outer sheath, 2-copper wire braided layer, 3-flame-retardant heat-insulating sheath, 4-mica tape layer, 5-polyethylene inner sheath, 6-conductor and 7-FRP reinforced core.
Detailed Description
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1:
referring to fig. 1, the high and low temperature resistant halogen-free flame retardant cable comprises an outer sheath (1), a copper wire woven layer (2), a flame retardant and heat preservation sheath (3), a mica tape layer (4), a cable core and an FRP reinforced core (7), wherein the cable core comprises a polyethylene inner sheath (5) and a conductor (6), the FRP reinforced core (7) is arranged at the center of a plurality of cable cores, and the mica tape layer (4) is coated on the plurality of cable cores;
the flame-retardant heat-insulation sheath (3) comprises the following components in parts by weight:
100 parts of high-density polyethylene, 45 parts of ethylene-octene copolymer, 15 parts of carboxyl-terminated liquid nitrile rubber, 15 parts of styrene thermoplastic elastomer, kh-5502 parts of silane coupling agent, 2 parts of epoxy rubber seed oil, 1 part of turpentine, 0.8 part of caged pentaerythritol phosphate, 3 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10 parts of hollow glass microsphere, 35 parts of nano silicon dioxide, 10 parts of zinc oxide, 40 parts of carbon black, 0.4 part of dicumyl peroxide, 0.08 part of polymaleimide and 0.5 part of sulfur.
The preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding 180g of red phosphorus and 5g of dispersant NNO into 500mL of water, stirring to uniformly disperse the red phosphorus, adding 35g of aluminum sulfate, heating to 70 ℃, dropwise adding 10 wt% of sodium carbonate solution, adjusting the pH of the system to 11, reacting for 4 hours, cooling and filtering the reaction solution, washing the obtained solid, drying to constant weight to obtain an intermediate, putting the intermediate into a CVD (chemical vapor deposition) chamber, and pre-vacuumizing the chamber to 5 x 10 -3 Introducing hydrogen gas with a flow rate of 250cm below Pa 3 Min, heating to 1020 ℃ under hydrogen atmosphere, keeping the air pressure of the chamber at 4kPa, and introducing the gas at a flow of 15cm after 40min 3 Methane,/min, 250cm 3 Argon/min and 1000cm 3 Hydrogen gas of/min, starting to grow graphene, wherein the growth time is 10min, closing methane and hydrogen after the growth is finished, and carrying out argon atmosphereNaturally cooling to room temperature.
The preparation method of the flame-retardant heat-insulating sheath (3) comprises the following steps:
weighing raw materials in proportion, adding the raw materials into an internal mixer for internal mixing at the internal mixing temperature of 130 ℃ and the rotor speed of the internal mixer of 30r/min, carrying out hot cutting and air cooling after the internal mixing is finished, adding the obtained granules into a double-roll open mill, heating to 140 ℃, carrying out extrusion granulation by a double screw after the mixing is carried out for 8min, preheating for 10min without pressurization in a flat vulcanizing machine at the temperature of 185 ℃, carrying out heat preservation and pressurization to 12MPa and keeping for 8min, and carrying out die stripping after the pressure is maintained and the temperature is reduced to room temperature.
The outer sheath (1) comprises the following components in parts by weight:
110 parts of linear low-density polyethylene, 40 parts of EVM rubber, 25 parts of polyolefin elastomer, 30 parts of nano zinc oxide, 8 parts of stearic acid, 60 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 2 parts of dioctyl adipate, 2 parts of dioctyl sebacate, 1 part of dicumyl peroxide, GW-5400.5 parts of light stabilizer, 10762 parts of antioxidant and 2 parts of sulfur.
The outer sheath (1) is prepared by the following method:
weighing raw materials in proportion, adding the raw materials into an internal mixer for internal mixing at the internal mixing temperature of 120 ℃ and the rotor speed of the internal mixer of 30r/min, carrying out hot cutting and air cooling after the internal mixing is finished, adding the obtained granules into a double-roll open mill, heating to 135 ℃, carrying out mixing for 6min, carrying out twin-screw extrusion granulation, preheating for 8min in a flat vulcanizing machine at the temperature of 185 ℃ without pressurizing, carrying out heat preservation and pressurization to 15MPa and keeping for 8min, and carrying out pressure preservation and cooling to room temperature and then carrying out die stripping.
Example 2:
referring to fig. 1, the high and low temperature resistant halogen-free flame retardant cable comprises an outer sheath (1), a copper wire woven layer (2), a flame retardant and heat preservation sheath (3), a mica tape layer (4), a cable core and an FRP reinforced core (7), wherein the cable core comprises a polyethylene inner sheath (5) and a conductor (6), the FRP reinforced core (7) is arranged at the center of a plurality of cable cores, and the mica tape layer (4) is coated on the plurality of cable cores;
the flame-retardant heat-insulation sheath (3) comprises the following components in parts by weight:
80 parts of high-density polyethylene, 30 parts of ethylene-octene copolymer, 15 parts of carboxyl-terminated liquid nitrile rubber, 10 parts of styrene thermoplastic elastomer, kh-5501 parts of silane coupling agent, 2 parts of epoxy rubber seed oil, 0.5 part of turpentine, 0.5 part of caged pentaerythritol phosphate, 2 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10 parts of hollow glass microsphere, 30 parts of nano silicon dioxide, 10 parts of zinc oxide, 30 parts of carbon black, 0.4 part of dicumyl peroxide, 0.08 part of polymaleimide and 0.4 part of sulfur.
The preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding 180g of red phosphorus and 5g of dispersant NNO into 500mL of water, stirring to uniformly disperse the red phosphorus, adding 35g of aluminum sulfate, heating to 60 ℃, dropwise adding 10 wt% of sodium carbonate solution, adjusting the pH of the system to 10, reacting for 2 hours, cooling and filtering the reaction liquid, washing the obtained solid, drying to constant weight to obtain an intermediate, putting the intermediate into a CVD (chemical vapor deposition) chamber, and pre-vacuumizing the chamber to 5 x 10 -3 Introducing hydrogen gas with a flow rate of 200cm below Pa 3 Min, heating to 1000 deg.C under hydrogen atmosphere, 2kPa of chamber pressure, and introducing 10cm of flow rate after 20min 3 Methane per min, 200cm 3 Argon/min and 500cm 3 And (3) starting to grow graphene by using hydrogen in/min for 3min, closing methane and hydrogen after the growth is finished, and naturally cooling to room temperature under the argon atmosphere.
The preparation method of the flame-retardant heat-insulating sheath (3) is the same as that of the embodiment 1.
The outer sheath comprises the following components in parts by weight:
100 parts of linear low-density polyethylene, 30 parts of EVM rubber, 20 parts of polyolefin elastomer, 30 parts of nano zinc oxide, 5 parts of stearic acid, 50 parts of aluminum hydroxide, 40 parts of magnesium hydroxide, 1 part of dioctyl adipate, 1 part of dioctyl sebacate, 0.5 part of dicumyl peroxide, GW-5400.5 parts of light stabilizer, 10762 parts of antioxidant and 1 part of sulfur.
The outer jacket (1) was prepared in the same manner as in example 1.
Example 3:
referring to fig. 1, the high and low temperature resistant halogen-free flame retardant cable comprises an outer sheath (1), a copper wire woven layer (2), a flame retardant and heat preservation sheath (3), a mica tape layer (4), a cable core and an FRP reinforced core (7), wherein the cable core comprises a polyethylene inner sheath (5) and a conductor (6), the FRP reinforced core (7) is arranged at the center of a plurality of cable cores, and the mica tape layer (4) is coated on the plurality of cable cores;
the flame-retardant heat-insulation sheath (3) comprises the following components in parts by weight:
100 parts of high-density polyethylene, 30 parts of ethylene-octene copolymer, 20 parts of carboxyl-terminated liquid nitrile rubber, 10 parts of styrene thermoplastic elastomer, kh-5503 parts of silane coupling agent, 2 parts of epoxy rubber seed oil, 1 part of turpentine, 0.5 part of caged pentaerythritol phosphate, 4 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10 parts of hollow glass microsphere, 40 parts of nano silicon dioxide, 10 parts of zinc oxide, 40 parts of carbon black, 0.4 part of dicumyl peroxide, 0.08 part of polymaleimide and 0.4 part of sulfur.
The preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding 180g of red phosphorus and 5g of dispersant NNO into 500mL of water, stirring to uniformly disperse the red phosphorus, adding 35g of aluminum sulfate, heating to 70 ℃, dropwise adding 10 wt% of sodium carbonate solution, adjusting the pH of the system to 10, reacting for 4 hours, cooling the reaction solution, performing suction filtration, washing the obtained solid, drying to constant weight to obtain an intermediate, placing the intermediate into a CVD (chemical vapor deposition) chamber, and pre-vacuumizing the chamber to 5 x 10 -3 Introducing hydrogen gas with a flow rate of 200cm below Pa 3 Min, heating to 1020 ℃ under hydrogen atmosphere, keeping the air pressure of the chamber at 2kPa, and introducing 10cm of flow after 40min 3 Methane,/min, 250cm 3 Argon/min and 500cm 3 And (3) starting to grow graphene by using hydrogen in/min for 10min, closing methane and hydrogen after the growth is finished, and naturally cooling to room temperature under the argon atmosphere.
The preparation method of the flame-retardant heat-insulating sheath (3) is the same as that of the embodiment 1.
The outer sheath comprises the following components in parts by weight:
100 parts of linear low-density polyethylene, 50 parts of EVM rubber, 20 parts of polyolefin elastomer, 40 parts of nano zinc oxide, 5 parts of stearic acid, 80 parts of aluminum hydroxide, 40 parts of magnesium hydroxide, 2 parts of dioctyl adipate, 1 part of dioctyl sebacate, 1 part of dicumyl peroxide, GW-5400.5 parts of light stabilizer, 10764 parts of antioxidant and 1 part of sulfur.
The outer jacket (1) was prepared in the same manner as in example 1.
Example 4:
referring to fig. 1, the high and low temperature resistant halogen-free flame retardant cable comprises an outer sheath (1), a copper wire woven layer (2), a flame retardant and heat preservation sheath (3), a mica tape layer (4), a cable core and an FRP reinforced core (7), wherein the cable core comprises a polyethylene inner sheath (5) and a conductor (6), the FRP reinforced core (7) is arranged at the center of a plurality of cable cores, and the mica tape layer (4) is coated on the plurality of cable cores;
the flame-retardant heat-insulation sheath (3) comprises the following components in parts by weight:
80 parts of high-density polyethylene, 50 parts of ethylene-octene copolymer, 15 parts of carboxyl-terminated liquid nitrile rubber, 15 parts of styrene thermoplastic elastomer, kh-5501 parts of silane coupling agent, 4 parts of epoxy rubber seed oil, 0.5 part of turpentine, 1 part of caged pentaerythritol phosphate, 2 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 20 parts of hollow glass microsphere, 30 parts of nano silicon dioxide, 20 parts of zinc oxide, 30 parts of carbon black, 0.4 part of dicumyl peroxide, 0.08 part of polymaleimide and 0.6 part of sulfur.
The preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding 180g of red phosphorus and 5g of dispersant NNO into 500mL of water, stirring to uniformly disperse the red phosphorus, then adding 35g of aluminum sulfate, heating to 60 ℃, dropwise adding 10 wt% of sodium carbonate solution, adjusting the pH value of the system to 11, reacting for 2 hours, cooling and filtering reaction liquid, washing obtained solid, drying to constant weight to obtain an intermediate, putting the intermediate into a CVD (chemical vapor deposition) chamber, pre-vacuumizing the chamber to 5 multiplied by 10 -3 Introducing hydrogen gas with a flow rate of 250cm below Pa 3 Min, heating to 1000 deg.C under hydrogen atmosphere, chamber pressure of 4kPa, and introducing flow of 15cm after 20min 3 Methane per min, 200cm 3 Argon/min and 1000cm 3 Hydrogen gas of/min, starting to grow graphene, wherein the growth time is 3min, closing methane and hydrogen gas after the growth is finished, and introducing argon gasNaturally cooling to room temperature under the atmosphere.
The preparation method of the flame-retardant heat-insulating sheath (3) is the same as that of the embodiment 1.
The outer sheath comprises the following components in parts by weight:
120 parts of linear low-density polyethylene, 30 parts of EVM rubber, 25 parts of polyolefin elastomer, 30 parts of nano zinc oxide, 10 parts of stearic acid, 50 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 1 part of dioctyl adipate, 2 parts of dioctyl sebacate, 0.5 part of dicumyl peroxide, GW-5401 parts of light stabilizer, 10762 parts of antioxidant and 2 parts of sulfur.
The outer jacket (1) was prepared in the same manner as in example 1.
Example 5:
referring to fig. 1, the high and low temperature resistant halogen-free flame retardant cable comprises an outer sheath (1), a copper wire woven layer (2), a flame retardant and heat preservation sheath (3), a mica tape layer (4), a cable core and an FRP reinforced core (7), wherein the cable core comprises a polyethylene inner sheath (5) and a conductor (6), the FRP reinforced core (7) is arranged at the center of a plurality of cable cores, and the mica tape layer (4) is coated on the plurality of cable cores;
the flame-retardant heat-insulation sheath (3) comprises the following components in parts by weight:
90 parts of high-density polyethylene, 40 parts of ethylene-octene copolymer, 15 parts of carboxyl-terminated liquid nitrile rubber, 10 parts of styrene thermoplastic elastomer, kh-5502.5 parts of silane coupling agent, 4 parts of epoxy rubber seed oil, 0.5 part of turpentine, 1 part of caged pentaerythritol phosphate, 2 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 15 parts of hollow glass microsphere, 40 parts of nano silicon dioxide, 10 parts of zinc oxide, 35 parts of carbon black, 0.4 part of dicumyl peroxide, 0.08 part of polymaleimide and 0.6 part of sulfur.
The preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding 180g of red phosphorus and 5g of dispersant NNO into 500mL of water, stirring to uniformly disperse the red phosphorus, adding 35g of aluminum sulfate, heating to 70 ℃, dropwise adding 10 wt% of sodium carbonate solution, adjusting the pH of the system to 10, reacting for 3 hours, cooling the reaction solution, performing suction filtration, washing the obtained solid, drying to constant weight to obtain an intermediate, and putting the intermediate into a CVD (chemical vapor deposition) cavityIn the chamber, the chamber is pre-evacuated to 5X 10 -3 Introducing hydrogen gas with a flow rate of 250cm below Pa 3 Min, heating to 1020 ℃ under hydrogen atmosphere, keeping the air pressure in the chamber at 3kPa, and introducing 15cm of flow after 40min 3 Methane,/min, 250cm 3 Argon/min and 800cm 3 And (3) starting to grow graphene by using hydrogen in/min for 5min, closing methane and hydrogen after the growth is finished, and naturally cooling to room temperature under the argon atmosphere.
The preparation method of the flame-retardant heat-insulating sheath (3) is the same as that of the embodiment 1.
The outer sheath comprises the following components in parts by weight:
120 parts of linear low-density polyethylene, 40 parts of EVM rubber, 25 parts of polyolefin elastomer, 35 parts of nano zinc oxide, 10 parts of stearic acid, 60 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 1 part of dioctyl adipate, 2 parts of dioctyl sebacate, 1 part of dicumyl peroxide, 5401 parts of light stabilizer GW-5401 parts, 10763 parts of antioxidant and 2 parts of sulfur.
The outer jacket (1) was prepared in the same manner as in example 1.
Comparative example 1:
basically the same as example 1, except that the flame-retardant insulation sheath (3) does not contain carboxyl-terminated liquid nitrile rubber.
Comparative example 2:
basically the same as example 1, except that the flame-retardant heat-insulating sheath (3) does not contain epoxy rubber seed oil.
Comparative example 3:
basically the same as example 1, except that the flame-retardant and heat-insulating sheath (3) does not contain aluminum hydroxide/graphene microencapsulated red phosphorus.
Comparative example 4:
basically the same as example 1, except that the flame-retardant and heat-insulating sheath (3) is formed by substituting aluminum hydroxide microencapsulated red phosphorus for aluminum hydroxide/graphene microencapsulated red phosphorus.
The preparation method of the aluminum hydroxide microencapsulated red phosphorus comprises the following steps:
adding 180g of red phosphorus and 5g of dispersant NNO into 500mL of water, stirring to uniformly disperse the red phosphorus, then adding 35g of aluminum sulfate, heating to 70 ℃, dropwise adding 10 wt% of sodium carbonate solution, adjusting the pH of the system to 11, reacting for 4 hours, cooling the reaction liquid, performing suction filtration, washing the obtained solid, and drying to constant weight.
And (3) performance testing:
the cables prepared in examples 1-5 and comparative examples 1-4 of the invention are used as samples, and the test is carried out by referring to GB/T3048.8-2007 method for testing the electrical properties of electric wires and cables;
and (3) placing the sample in a ventilation and heat aging oven at 100 ℃ for 1d, then placing the sample in a refrigerator at-5 ℃ for 1d, repeating the above steps for 60d, and then applying an alternating current of 5.0kV for 24h, wherein the test is passed if no electric arc or breakdown occurs.
The test results are shown in table 1 below:
table 1:
the flame-retardant heat-insulating sheath prepared in the examples 1 to 5 and the comparative examples 1 to 4 of the invention is subjected to performance test, and the results are shown in the following table 2:
table 2:
as can be seen from the above tables 1 and 2, the cable prepared by the invention has the advantages of flame retardance, heat insulation, excellent high and low temperature cycle resistance and wide market application prospect.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A high and low temperature resistant halogen-free flame-retardant cable is characterized by comprising an outer sheath, a copper wire woven layer, a flame-retardant heat-preservation sheath, a mica tape layer, cable cores and an FRP (fiber reinforced plastic) reinforced core, wherein the cable cores comprise polyethylene inner sheaths and conductors, the FRP reinforced core is arranged at the central positions of a plurality of cable cores, and the mica tape layer is coated on the cable cores;
the flame-retardant heat-insulation sheath comprises the following components in parts by weight:
80-100 parts of high-density polyethylene, 30-50 parts of ethylene-octene copolymer, 15-20 parts of carboxyl-terminated liquid nitrile rubber, 10-15 parts of styrene thermoplastic elastomer, 1-3 parts of silane coupling agent, 2-4 parts of epoxy rubber seed oil, 0.5-1 part of turpentine, 0.5-1 part of caged pentaerythritol phosphate, 2-4 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10-20 parts of hollow glass microsphere, 30-40 parts of nano silicon dioxide, 10-20 parts of zinc oxide, 30-40 parts of carbon black, 0.1-0.5 part of crosslinking agent and 0.4-0.6 part of sulfur.
2. The halogen-free flame-retardant cable capable of resisting high and low temperatures according to claim 1, wherein the flame-retardant heat-insulating sheath comprises the following components in parts by weight:
100 parts of high-density polyethylene, 45 parts of ethylene-octene copolymer, 15 parts of carboxyl-terminated liquid nitrile rubber, 15 parts of styrene thermoplastic elastomer, 2 parts of silane coupling agent, 2 parts of epoxy rubber seed oil, 1 part of turpentine, 0.8 part of caged pentaerythritol phosphate, 3 parts of aluminum hydroxide/graphene microencapsulated red phosphorus, 10 parts of hollow glass microspheres, 35 parts of nano silicon dioxide, 10 parts of zinc oxide, 40 parts of carbon black, 0.48 part of crosslinking agent and 0.5 part of sulfur.
3. The high and low temperature resistant halogen-free flame retardant cable according to claim 1, wherein the preparation method of the aluminum hydroxide/graphene microencapsulated red phosphorus comprises the following steps:
adding red phosphorus and a dispersing agent into water, stirring to uniformly disperse the red phosphorus, then adding aluminum sulfate, heating to 60-70 ℃, dropwise adding a sodium carbonate solution, adjusting the pH of the system to 10-11, reacting for 2-4h, cooling and filtering the reaction liquid, washing the obtained solid, drying to constant weight to obtain an intermediate, and forming a graphene layer on the surface by adopting a chemical vapor deposition method.
4. The halogen-free high and low temperature resistant flame retardant cable of claim 3 wherein the chemical vapor deposition process comprises placing the intermediate into a CVD chamber, and pre-evacuating the chamber to 5 x 10 -3 Introducing hydrogen with the hydrogen flow rate of 200-250cm below Pa 3 Min, heating to 1000-1020 ℃ under the hydrogen atmosphere, controlling the air pressure of the chamber to be 2-4kPa, and introducing the gas with the flow of 10-15cm after 20-40min 3 Methane at a rate of 200- 3 Argon/min and 500-1000cm 3 And (3) starting to grow graphene by using hydrogen in/min for 3-10min, closing methane and hydrogen after the growth is finished, and naturally cooling to room temperature under the argon atmosphere.
5. The high and low temperature resistant halogen-free flame retardant cable according to claim 1, wherein the cross-linking agent comprises dicumyl peroxide and polymaleimide, and the mass ratio of dicumyl peroxide to polymaleimide is 5-10: 1.
6. the halogen-free flame-retardant cable capable of resisting high and low temperatures according to claim 1, wherein the flame-retardant heat-insulating sheath is prepared by the following steps:
weighing raw materials in proportion, adding the raw materials into an internal mixer for internal mixing, carrying out hot cutting and air cooling after the internal mixing is finished, adding the obtained granules into a double-roller open mill, heating to 140 ℃ for mixing, carrying out extrusion granulation by a double screw after mixing for 5-8min, preheating for 5-10min without pressurizing in a flat vulcanizing machine at 185 ℃ for 180 ℃, then carrying out heat preservation and pressurization to 10-15MPa and keeping for 5-10min, and finally carrying out die stripping after pressure maintaining and cooling to room temperature.
7. The halogen-free flame retardant cable of claim 1, wherein the outer sheath comprises the following components in parts by weight:
100-120 parts of linear low-density polyethylene, 30-50 parts of EVM rubber, 20-25 parts of polyolefin elastomer, 30-40 parts of nano zinc oxide, 5-10 parts of stearic acid, 50-80 parts of aluminum hydroxide, 40-50 parts of magnesium hydroxide, 1-2 parts of dioctyl adipate, 1-2 parts of dioctyl sebacate, 0.5-1 part of dicumyl peroxide, 1-1 part of light stabilizer GW-5400.5, 10762-4 parts of antioxidant and 1-2 parts of sulfur.
8. The halogen-free flame retardant cable of claim 7, wherein the outer sheath comprises the following components in parts by weight:
110 parts of linear low-density polyethylene, 40 parts of EVM rubber, 25 parts of polyolefin elastomer, 30 parts of nano zinc oxide, 8 parts of stearic acid, 60 parts of aluminum hydroxide, 50 parts of magnesium hydroxide, 2 parts of dioctyl adipate, 2 parts of dioctyl sebacate, 1 part of dicumyl peroxide, GW-5400.5 parts of light stabilizer, 10762 parts of antioxidant and 2 parts of sulfur.
9. The halogen-free flame retardant cable of claim 7, wherein the outer sheath is prepared by the following steps:
weighing raw materials in proportion, adding the raw materials into an internal mixer for internal mixing, carrying out hot cutting and air cooling after the internal mixing is finished, adding the obtained granules into a double-roller open mill, heating to 140 ℃ for mixing, carrying out extrusion granulation by a double screw after mixing for 5-8min, preheating for 5-10min without pressurizing in a flat vulcanizing machine at 185 ℃ for 180 ℃, then carrying out heat preservation and pressurization to 10-15MPa and keeping for 5-10min, and finally carrying out die stripping after pressure maintaining and cooling to room temperature.
10. The high and low temperature resistant halogen-free flame retardant cable of claim 9, wherein the banburying temperature is 120-.
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| CN201812508U (en) * | 2010-08-09 | 2011-04-27 | 扬州市红旗电缆制造有限公司 | Fire-fighting corrosion-resistant and weather-proof armored cable for offshore oil platform |
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| CN102040789A (en) * | 2009-10-16 | 2011-05-04 | 青岛汉缆股份有限公司 | Formula of durable cable sheath material |
| CN201812508U (en) * | 2010-08-09 | 2011-04-27 | 扬州市红旗电缆制造有限公司 | Fire-fighting corrosion-resistant and weather-proof armored cable for offshore oil platform |
| CN204117661U (en) * | 2014-07-07 | 2015-01-21 | 江苏中辰电缆有限公司 | A kind of fire-retardant cable of resistance to mud used for oil platform |
| CN107337859A (en) * | 2017-08-31 | 2017-11-10 | 远东电缆有限公司 | Oil-immersed pump electric power cable oil resistant EP rubbers sheath material and preparation method thereof |
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