CN111430066B - Low-smoke halogen-free 750 ℃ resistant cable - Google Patents

Low-smoke halogen-free 750 ℃ resistant cable Download PDF

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CN111430066B
CN111430066B CN202010073376.0A CN202010073376A CN111430066B CN 111430066 B CN111430066 B CN 111430066B CN 202010073376 A CN202010073376 A CN 202010073376A CN 111430066 B CN111430066 B CN 111430066B
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weight
low
layer
free
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CN111430066A (en
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聂磊
李华斌
谢刚
陈彦
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Hunan Valin Wire and Cable Co Ltd
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Hunan Valin Wire and Cable Co Ltd
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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
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • 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
    • C—CHEMISTRY; METALLURGY
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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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01B13/06—Insulating conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01B13/06—Insulating conductors or cables
    • H01B13/14—Insulating conductors or cables by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01B13/22—Sheathing; Armouring; Screening; Applying other protective layers
    • H01B13/24—Sheathing; Armouring; Screening; Applying other protective layers by extrusion
    • 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
    • H01B7/02—Disposition of insulation
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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
    • 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
    • H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/2806—Protection against damage caused by corrosion
    • 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
    • H01B7/28—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
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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
    • H01B7/29—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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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
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    • C08L2201/22—Halogen free composition
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Abstract

The invention provides a low-smoke halogen-free 750 ℃ resistant cable which sequentially comprises a low-smoke halogen-free flame-retardant polyolefin layer, a non-woven fabric belt, a glass fiber belt, an insulating filling layer and a plurality of cable core units from outside to inside; the preparation method of the low-smoke halogen-free flame-retardant polyolefin layer comprises the following steps: stirring and mixing the basf flame retardant, the 1,3, 5-triazine, the pentaerythritol and the hindered phenol antioxidant in parts by weight; fully stirring the plant cellulose and the magnetite nano particles in the obtained mixture again; and adding the polyolefin and the char forming agent in parts by weight into the obtained mixture, and stirring and extruding by using a double-screw extruder to obtain the low-smoke halogen-free flame-retardant polyolefin layer. The low-smoke halogen-free 750 ℃ resistant cable provided by the invention has good flame retardant property, corrosion resistance and mechanical property, and can reduce the release of toxic and harmful gases; the polyolefin layer prepared by adding the plant cellulose and the magnetite nanoparticles can improve the mechanical property, the antibacterial activity, the elasticity and the compression resistance of the cable.

Description

Low-smoke halogen-free 750 ℃ resistant cable
Technical Field
The invention belongs to the technical field of cables, and particularly relates to a low-smoke halogen-free 750-DEG C-resistant cable.
Background
With the development of modern science and technology, energy and information are indispensable resources, and the transmission of electric energy and information can not be separated from cables, but unsafe cables are also one of important ways for spreading fire. According to incomplete statistics, accidents caused by cables in fire occupy about 35%, and about one third of dead people are suffocated and die due to toxic gas released when the cables are inhaled and burned. Thus, the prevention of cable burning, the prevention of the release of toxic and harmful corrosive gases and fumes has been a problem that must be faced by the cable industry.
The traditional flame-retardant cable protective layer material is mainly selected from halogen-containing materials such as flame-retardant polyvinyl chloride, chlorosulfonated polyethylene and the like to prevent the spread of fire. However, these flame-retardant cables are flammable materials, and the materials release a large amount of toxic and harmful smoke and corrosive gases during combustion, so that the poor light transmission of the gases causes difficulties in fire scene escape and rescue, and the toxic gases easily suffocate people, thus seriously endangering the safety of lives and properties of people.
In order to achieve the purpose of fire prevention and flame retardation, high amount of sodium hydroxide or magnesium hydroxide is added into polyethylene or traditional high-efficiency flame retardant is added. The addition of high-content alkali can generate negative effects on the mechanical, physical and rheological properties and the processing capacity of polyolefin, a flame-retardant layer adopted in the manufacturing process is mineral mud formed by mixing magnesium hydroxide and glue, belongs to a semi-conductive structure, an insulating single phase can be punctured to the mineral mud in a place with slightly damaged or thinner insulation, and the problem cannot be solved by only increasing the insulation thickness at present; in the preparation process, the mineral mud is soft in the extrusion process, and sometimes the mineral mud is not very stable in the extrusion process, so that the outer diameter of a cable core is not uniform, the outer diameter of a finished product is not uniform, the selection of a matched die is influenced, the use amount of materials for driving is influenced, and the appearance quality of the cable is also influenced; mineral mud is used as a flame-retardant layer, water is separated out after a long time, and the quality and the service life of the cable are affected to a certain degree.
The traditional high-efficiency flame retardant generally contains halogen, especially bromine, has high flame retardant efficiency, and has good flame retardant effect on high polymer materials after the flame retardant is compounded with antimony trioxide. However, such flame retardants release a large amount of hydrogen halide and smoke during combustion or processing, which causes secondary environmental pollution, and are gradually banned.
Chinese patent 201610171783.9 discloses a magnesium hydroxide flame retardant and a flame retardant polymer for cables, a high flame retardant EVA resin cable material, the raw materials of which include EVA resin, ABS resin, PVC, chlorinated polyethylene, dicumyl peroxide, maleic anhydride, acrylic acid, methacrylic acid, modified magnesium hydroxide, sodium stearate, polyphosphate, low density polyethylene, liquid paraffin, styrene, wood flour, red phosphorus, organic silicon, a flame retardant, a phase solvent and an antioxidant. According to the cable material, the EVA resin is subjected to mixed modification by adding the modified magnesium hydroxide, so that the flame retardant property of the cable is improved.
Disclosure of Invention
Aiming at the defects, the invention provides the low-smoke halogen-free 750-DEG C-resistant cable which effectively reduces toxic and harmful gases released by the cable in the fire process, has good flame retardant property, excellent corrosion resistance and excellent mechanical property.
The invention provides the following technical scheme: a low-smoke halogen-free 750 ℃ resistant cable comprises a low-smoke halogen-free flame-retardant polyolefin layer, a non-woven fabric belt, a glass fiber belt, an insulating filling layer and a plurality of cable core units from outside to inside in sequence; the cable core unit sequentially comprises a ceramic polyolefin insulating layer, a mica tape insulating layer, a phenylenediamine modified graphene oxide layer and a conductor from outside to inside.
The preparation method of the ceramic polyolefin insulating layer comprises the following steps:
1) stirring and mixing 30-40 parts by weight of polyoxyethylene-polyoxypropylene copolymer and 50-60 parts by weight of low-density polyethylene serving as matrix resin, and then adding 5-8 parts by weight of compatilizer, 2-3 parts by weight of POE (polyolefin elastomer) flexibilizer, 1-2 parts by weight of vitrified powder, 2-3 parts by weight of hindered phenol antioxidant and 3-5 parts by weight of lubricant into an open mill at 130-170 ℃ for plasticizing to obtain vitrified polyolefin;
2) and (2) carrying out mould pressing on the ceramic polyolefin obtained in the step 1) on a vulcanization press bed at 170-175 ℃ for 10-20 min to obtain a ceramic polyolefin layer.
As a further improvement of the above technical solution;
the preparation method of the low-smoke halogen-free flame-retardant polyolefin layer comprises the following steps:
1) stirring and mixing 5-10 parts of basf flame retardant, 30-35 parts of 1,3, 5-triazine, 10-14 parts of pentaerythritol and 15-20 parts of hindered phenol antioxidant in parts by weight;
2) adding 5-15 parts by weight of plant cellulose and 10-20 parts by weight of magnetite nanoparticles into the mixture obtained in the step 1), and fully stirring again;
3) adding 40-50 parts by weight of polyolefin and 5-35 parts by weight of char forming agent into the mixture obtained in the step 2), and stirring and extruding by using a double-screw extruder to obtain the low-smoke halogen-free flame-retardant polyolefin layer.
Further, the preparation method of the phenylenediamine modified graphene oxide layer comprises the following steps:
1) dissolving 0.2-0.5 g of graphene oxide in 200-500 ml of distilled water, and stirring uniformly by adopting magnetic stirring to obtain a graphene oxide solution;
2) adding 2-5 g of p-phenylenediamine into 200-500 ml of N, N-dimethylformamide solution, and stirring uniformly by adopting magnetic stirring to obtain p-phenylenediamine colloidal solution;
3) mixing the graphene oxide solution obtained in the step 1) with the p-phenylenediamine colloidal solution obtained in the step 2), and heating under reflux for 12-15 h in an oil bath at 80-100 ℃ in an oxygen-free environment of nitrogen;
4) filtering the mixture obtained in the step 3), and cleaning the mixture for 2 to 3 times by using an acetone solution to obtain p-phenylenediamine modified graphene oxide nanoparticles;
5) putting the p-phenylenediamine modified graphene oxide nanoparticles obtained in the step 4) into a double-screw extruder to be stirred and extruded to obtain the p-phenylenediamine modified graphene oxide layer.
Further, the charring agent is a combination of a triazine charring agent and an acid source charring agent, and the weight part ratio of the triazine charring agent to the acid source charring agent is (1:1.5) - (1: 3).
Further, the acid source charring agent is ammonium polyphosphate.
Further, the triazine charring agent is an ethylenediamine triazine charring agent.
Further, the mica tape insulating layer is formed by overlapping, wrapping and covering two layers of mica tapes.
Further, the preparation method of the ceramic polyolefin insulating layer comprises the following steps:
furthermore, the covering rate of the glass fiber tape on the insulating filling layer is 10-15%.
Further, the insulating filling layer is an inorganic rope or a glass fiber rope.
Further, the plant celluloseIs one or more of sisal cellulose, flax cellulose or corn cellulose. The magnetite nanoparticles are Fe3O4、Fe2O3Or one or more of FeO.
The invention has the beneficial effects that:
1) the distance between the insulating filling layer and the low-smoke halogen-free flame-retardant polyolefin layer is increased structurally through the non-woven fabric belt and the glass fiber belt, so that the speed of temperature spreading to a core cable core unit during flame combustion is further ensured, and the flame-retardant efficiency is improved; the insulating filling layer can ensure that the cable does not support combustion when a fire disaster and flame combustion happen, and the structural requirements of the fire-resistant cable are met. The ceramic polyolefin insulating layer that every cable core unit adopted can crust when receiving flame high temperature, can not burn like crosslinked polyethylene, still can play insulating effect after the crust, through adding the mica tape insulating layer, phenylenediamine modified oxidation graphite alkene layer has further improved the fire resistance and the corrosion resisting property of every cable core unit between conductor and ceramic polyolefin insulating layer, guaranteed the normal transmission of cable internal current, can not inside because corrode the back, conductor contact between the cable core unit, lead to conflagration or circuit fault that the short circuit caused.
2) Plant cellulose and magnetite nanoparticles are added in the preparation process of the low-smoke halogen-free flame-retardant polyolefin layer of the cable, so that the mechanical property and antibacterial activity of the low-smoke halogen-free 750 ℃ resistant cable can be effectively improved, the elasticity and compression resistance of the cable are effectively improved, the cable is not easy to crack and break, and the corrosion of external rainwater and microorganisms is effectively resisted. Meanwhile, different flame retardants are added and mixed in the process of preparing the low-smoke halogen-free flame-retardant polyolefin layer, so that the flame retardant property of the polyolefin layer is enhanced, and the added hindered phenol antioxidant can enhance the defect that the cable is easy to deteriorate and soften due to the resistance of the polyolefin layer to external ultraviolet oxidation, high-temperature oxidation and oxidative gas oxidation, so that the service life of the cable is prolonged, and the performance of the cable protection in the using process of electric leakage and short circuit is improved.
3) In the preparation process of the low-smoke halogen-free polyolefin layer, the triazine charring agent and the acid source charring agent are used together, so that the defect that the charring agent with a single component is high in water solubility and low in thermal stability caused by easy migration is effectively overcome, and the thermal stability of the polyolefin layer is ensured. And meanwhile, a halogen-containing flame retardant is not adopted in the preparation process, so that a large amount of hydrogen halide and smoke released in the combustion or processing process is effectively avoided, and secondary pollution to the environment is avoided.
4) By preparing phenylenediamine-modified graphene oxide nanoparticles and preparing phenylenediamine-modified graphene layers, the pi orbitals of the adopted graphene oxide form a dense delocalized electron cloud, and then gaps in the aromatic ring of the graphene oxide are blocked, so that a repulsive field to reactive atoms or molecules is generated, and the intrinsic impermeability to most molecules is formed. The geometrical pores of the graphene lattice are 0.064nm, theoretically preventing the formation of small molecules such as helium (0.208nm) and hydrogen (0.314nm), which makes graphene oxide possess passivation properties to protect the internal metals from oxidation and corrosion, even in harsh electrochemical environments. In addition, the graphene modified by phenylenediamine can effectively ensure the affinity to metals and inorganic substances, so that the technical problem of poor adhesion force which often causes delamination in application is solved, and the stacked phenylenediamine modified graphene layer can be used as a diffusion barrier between an internal conductor and a reactive chemical substance.
5) The invention adopts the insulating material as the filling material of the insulating filling layer, the problem of single-phase breakdown can not occur directly even in the place with slight damage or thinness of the insulation, and the insulation of other phases is isolated from the insulation; because the cable is filled with inorganic ropes or glass fiber ropes, the outer diameter of the formed cable is more round compared with mineral mud, the outer diameter of a finished product is also more round, and the outer diameter is also more stable; compared with the mineral mud material in the prior art, the ceramic polyolefin insulating layer adopted by the cable core unit is safer and more stable, is directly ceramic during combustion, and has more advantages in fire resistance and insulating property; the extrusion of the contrast mineral mud of extruding at preparation cable Guo Hengzhong pottery polyolefin is more convenient, directly can go on the PVC extruder, and productivity and cost of labor contrast mineral mud all can be little a lot.
Drawings
The invention will be described in more detail hereinafter on the basis of embodiments and with reference to the accompanying drawings.
Wherein:
fig. 1 is a schematic cross-sectional view of a low-smoke halogen-free 750 ℃ resistant cable provided in embodiment 1 of the present invention;
fig. 2 is a schematic cross-sectional view of a low-smoke halogen-free 750 ℃ resistant cable provided in embodiment 2 of the present invention;
fig. 3 is a schematic cross-sectional view of a low-smoke halogen-free 750 ℃ resistant cable provided in embodiment 3 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The used Pasteur flame retardant is Melapur200-70, and is purchased from Kyon chemical Co., Ltd; the hindered phenol antioxidant is one of CHEMNOX1010, CHEMNOX1098, CHEMNOX1076, CHEMNOX168 or CHEMNOX DLTP, and is purchased from Nanjing Hualimng chemical company Limited. 1,3, 5-triazine is purchased from Dalianzuril chemical Co., Ltd, and other chemical reagents are commercially available.
Example 1
As shown in fig. 1, the low-smoke halogen-free 750 ℃ resistant cable provided in this embodiment includes, in order from outside to inside, a low-smoke halogen-free flame-retardant polyolefin layer 1, a non-woven fabric tape 2, a glass fiber tape 3, an insulating filling layer 4, and five cable core units 5; each cable core unit 5 sequentially comprises a ceramic polyolefin insulating layer 5-1, a mica tape insulating layer 5-2, a phenylenediamine modified graphene oxide layer 5-3 and a conductor 5-4 from outside to inside. Wherein the mica tape insulating layer 5-2 is composed of a layer of 0.10mm mica tape 5-2, the lapping rate of the glass fiber tape 3 on the insulating filling layer 4 is 10%, and the insulating filling layer 4 is an inorganic rope.
The preparation method of the low-smoke halogen-free flame-retardant polyolefin layer comprises the following steps:
1) stirring and mixing 5 parts of basf flame retardant, 30 parts of 1,3, 5-triazine, 10 parts of pentaerythritol and 15 parts of hindered phenol antioxidant CHEMNOX1010 in parts by weight;
2) adding 5 parts by weight of sisal cellulose and 10 parts by weight of Fe into the mixture obtained in the step 1)3O4Fully stirring the magnetite nanoparticles again;
3) adding 40 parts by weight of polyolefin and 5 parts by weight of char forming agent into the mixture obtained in the step 2), wherein the char forming agent is a mixture of ammonium polyphosphate and ethylenediamine triazine char forming agent according to the weight part ratio of 1:1.5, and stirring and extruding by using a double-screw extruder to obtain the low-smoke halogen-free flame-retardant polyolefin layer.
The preparation method of the phenylenediamine modified graphene oxide layer comprises the following steps:
1) dissolving 0.2g of graphene oxide in 200ml of distilled water, and fully and uniformly stirring by adopting magnetic stirring to obtain a graphene oxide solution;
2) adding 2g of p-phenylenediamine into 200ml of N, N-dimethylformamide solution, and stirring uniformly by adopting magnetic stirring to obtain p-phenylenediamine colloidal solution;
3) mixing the graphene oxide solution obtained in the step 1) with the p-phenylenediamine colloidal solution obtained in the step 2), and heating under reflux for 12 hours in an oil bath at 80 ℃ in a nitrogen oxygen-free environment;
4) filtering the mixture obtained in the step 3), and cleaning for 2 times by using an acetone solution to obtain p-phenylenediamine modified graphene oxide nanoparticles;
5) putting the p-phenylenediamine modified graphene oxide nanoparticles obtained in the step 4) into a double-screw extruder for stirring and extruding to obtain the p-phenylenediamine modified graphene oxide layer.
The preparation method of the ceramic polyolefin insulating layer comprises the following steps:
1) stirring and mixing 30 parts by weight of polyoxyethylene-polyoxypropylene copolymer and 50 parts by weight of low-density polyethylene as matrix resin, adding 5 parts by weight of maleic anhydride, 2 parts by weight of POE (polyolefin elastomer) toughening agent, 1 part by weight of vitrified powder, 2 parts by weight of hindered phenol antioxidant CHEMNOX1010 and 3 parts by weight of lubricant-zinc stearate, and plasticizing on a mill at 130 ℃ to obtain vitrified polyolefin;
2) and (2) carrying out mould pressing on the ceramic polyolefin obtained in the step 1) on a vulcanization press bed at 170 ℃ for 10min to obtain a ceramic polyolefin layer.
Example 2
As shown in fig. 2, the low-smoke halogen-free 750 ℃ resistant cable provided in this embodiment includes, from outside to inside, a low-smoke halogen-free flame-retardant polyolefin layer 1, a non-woven fabric tape 2, a glass fiber tape 3, an insulating filling layer 4, and four cable core units 5 in sequence; each cable core unit 5 sequentially comprises a ceramic polyolefin insulating layer 5-1, a mica tape insulating layer 5-2, a phenylenediamine modified graphene oxide layer 5-3 and a conductor 5-4 from outside to inside. The mica tape insulating layer 5-2 is composed of two layers of mica tapes, namely a mica tape 5-21 and a mica tape 5-22, the thicknesses of the two layers of mica tapes are 0.12mm and 0.15mm respectively, the overlapping rate of the glass fiber tapes on the insulating filling layer is 12%, and the insulating filling layer is a glass fiber rope.
The preparation method of the low-smoke halogen-free flame-retardant polyolefin layer comprises the following steps:
1) stirring and mixing 8 parts by weight of BASF flame retardant, 33 parts by weight of 1,3, 5-triazine, 12 parts by weight of pentaerythritol and 18 parts by weight of hindered phenol antioxidant CHEMNOX DLTP;
2) adding 10 parts by weight of corn cellulose and 15 parts by weight of Fe into the mixture obtained in the step 1)2O3Fully stirring the magnetite nanoparticles again;
3) adding 45 parts by weight of polyolefin and 20 parts by weight of a char forming agent into the mixture obtained in the step 2), wherein the char forming agent is a mixture of ammonium polyphosphate and ethylenediamine triazine char forming agent according to a weight ratio of 1:2, and stirring and extruding by using a double-screw extruder to obtain the low-smoke halogen-free flame-retardant polyolefin layer.
The preparation method of the phenylenediamine modified graphene oxide layer comprises the following steps:
1) dissolving 0.35g of graphene oxide in 350ml of distilled water, and fully and uniformly stirring by adopting magnetic stirring to obtain a graphene oxide solution;
2) adding 3.5g of p-phenylenediamine into 350ml of N, N-dimethylformamide solution, and stirring uniformly by adopting magnetic stirring to obtain p-phenylenediamine colloidal solution;
3) mixing the graphene oxide solution obtained in the step 1) with the p-phenylenediamine colloidal solution obtained in the step 2), and heating under reflux for 14h in a 90 ℃ oil bath in a nitrogen oxygen-free environment;
4) filtering the mixture obtained in the step 3), and cleaning for 3 times by using an acetone solution to obtain p-phenylenediamine modified graphene oxide nanoparticles;
5) putting the p-phenylenediamine modified graphene oxide nanoparticles obtained in the step 4) into a double-screw extruder for stirring and extruding to obtain the p-phenylenediamine modified graphene oxide layer.
The preparation method of the ceramic polyolefin insulating layer comprises the following steps:
1) stirring and mixing 35 parts by weight of polyoxyethylene-polyoxypropylene copolymer and 55 parts by weight of low-density polyethylene as matrix resin, adding 6.5 parts by weight of ABS-g-MAH, 2.5 parts by weight of POE toughening agent, 1.5 parts by weight of vitrified powder, 2.5 parts by weight of hindered phenol antioxidant CHEMNOX1098 and 4 parts by weight of lubricant-zinc stearate, and plasticizing on an open mill at 150 ℃ to obtain vitrified polyolefin;
2) and (2) carrying out mould pressing on the ceramic polyolefin obtained in the step 1) on a vulcanization press bed at 172 ℃ for 15min to obtain a ceramic polyolefin layer.
Example 3
As shown in fig. 3, the low-smoke halogen-free 750 ℃ resistant cable provided in this embodiment includes, in order from outside to inside, a low-smoke halogen-free flame-retardant polyolefin layer 1, a non-woven fabric tape 2, a glass fiber tape 3, an insulating filling layer 4, and five cable core units 5; each cable core unit 5 sequentially comprises a ceramic polyolefin insulating layer 5-1, a mica tape insulating layer 5-2, a phenylenediamine modified graphene oxide layer 5-3 and a conductor 5-4 from outside to inside. The mica tape insulating layer 5-2 is composed of two layers of mica tapes, namely a mica tape 5-21 and a mica tape 5-22, the thicknesses of the two layers of mica tapes are respectively 0.20mm, the overlapping rate of the glass fiber tape 3 on the insulating filling layer 4 is 15%, and the insulating filling layer 4 is an inorganic rope.
The preparation method of the low-smoke halogen-free flame-retardant polyolefin layer comprises the following steps:
1) stirring and mixing 10 parts of basf flame retardant, 35 parts of 1,3, 5-triazine, 14 parts of pentaerythritol and 20 parts of hindered phenol antioxidant CHEMNOX1076 in parts by weight;
2) adding 15 parts by weight of flax cellulose and 20 parts by weight of FeO magnetite nanoparticles into the mixture obtained in the step 1), and fully stirring again;
3) adding 50 parts by weight of polyolefin and 35 parts by weight of a char forming agent into the mixture obtained in the step 2), wherein the char forming agent is a mixture of ammonium polyphosphate and ethylenediamine triazine char forming agent according to a weight ratio of 1:3, and stirring and extruding by using a double-screw extruder to obtain the low-smoke halogen-free flame-retardant polyolefin layer.
The preparation method of the phenylenediamine modified graphene oxide layer comprises the following steps:
1) dissolving 0.5g of graphene oxide in 500ml of distilled water, and fully and uniformly stirring by adopting magnetic stirring to obtain a graphene oxide solution;
2) adding 5g of p-phenylenediamine into 500ml of N, N-dimethylformamide solution, and stirring uniformly by adopting magnetic stirring to obtain p-phenylenediamine colloidal solution;
3) mixing the graphene oxide solution obtained in the step 1) with the p-phenylenediamine colloidal solution obtained in the step 2), and heating under reflux for 15h in a 100 ℃ oil bath in a nitrogen oxygen-free environment;
4) filtering the mixture obtained in the step 3), and cleaning for 3 times by using an acetone solution to obtain p-phenylenediamine modified graphene oxide nanoparticles;
5) putting the p-phenylenediamine modified graphene oxide nanoparticles obtained in the step 4) into a double-screw extruder for stirring and extruding to obtain the p-phenylenediamine modified graphene oxide layer.
The preparation method of the ceramic polyolefin insulating layer comprises the following steps:
1) stirring and mixing 40 parts by weight of polyoxyethylene-polyoxypropylene copolymer and 60 parts by weight of low-density polyethylene serving as matrix resin, adding 8 parts by weight of PE-g-ST, 3 parts by weight of POE toughening agent, 2 parts by weight of vitrified powder, 3 parts by weight of hindered phenol antioxidant CHEMNOX168 and 5 parts by weight of lubricant-polyethylene wax, and plasticizing on an open mill at 170 ℃ to obtain vitrified polyolefin;
2) carrying out mould pressing on the ceramic polyolefin obtained in the step 1) for 20min on a vulcanization press bed at 175 ℃ to obtain a ceramic polyolefin layer.
Comparative test example
The cable prepared by the cable material prepared in example 1 of Chinese patent 201610171783.9 and the cables prepared in the examples 1 to 3 are subjected to flame retardant property, corrosion resistance and mechanical property detection. Adopting a PX-01-005 oxygen index analyzer of Sonx instruments Ltd, Suzhou, controlling the flow of oxygen-nitrogen mixed gas through a knob, keeping the flow constant at 10L/min, adjusting the oxygen concentration to be within the range of 25% -50%, igniting an aviation cable by using an igniter after the gas flow and the oxygen concentration are stable, and recording the combustion duration, the combustion length and the lowest combustion oxygen concentration of the cable; GB/T2423.17-2008 & section 2 of environmental test of electronic and electrical products: test methods test Ka: the insulation performance of the prepared cable is detected by a basic test method of salt spray; according to JB/T10696.5-2007 part 5 of test method for mechanical and physical and chemical properties of electric wires and cables: the corrosion expanded test method detects the corrosion expanded area of the cable material to reflect the corrosion resistance of the cable material; GB/T2951 + 2008 general test method for insulation and sheath materials of cables and optical cables, part 11 of thickness and external dimension measurement mechanical property test, and part 12 of general test method for insulation and sheath materials of cables and optical cables, part 12 of thermal aging test: the test method of method 2 in oven aging detects the heat resistance of the cable material and the mechanical properties after heat treatment. The results are shown in Table 1.
TABLE 1
Figure BDA0002377832060000121
While the invention has been described with reference to a preferred embodiment, various modifications may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In particular, the technical features mentioned in the embodiments can be combined in any way as long as there is no structural conflict. It is intended that the invention not be limited to the particular embodiments disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (8)

1. A low-smoke halogen-free 750 ℃ resistant cable is characterized by comprising a low-smoke halogen-free flame-retardant polyolefin layer (1), a non-woven fabric belt (2), a glass fiber belt (3), an insulating filling layer (4) and a plurality of cable core units (5) from outside to inside in sequence; the cable core unit (5) sequentially comprises a ceramic polyolefin insulating layer (5-1), a mica tape insulating layer (5-2), a phenylenediamine modified graphene oxide layer (5-3) and a conductor (5-4) from outside to inside;
the preparation method of the ceramic polyolefin insulating layer comprises the following steps:
1) stirring and mixing 30-40 parts by weight of polyoxyethylene-polyoxypropylene copolymer and 50-60 parts by weight of low-density polyethylene serving as matrix resin, and then adding 5-8 parts by weight of compatilizer, 2-3 parts by weight of POE (polyolefin elastomer) flexibilizer, 1-2 parts by weight of vitrified powder, 2-3 parts by weight of hindered phenol antioxidant and 3-5 parts by weight of lubricant into an open mill at 130-170 ℃ for plasticizing to obtain vitrified polyolefin;
2) carrying out mould pressing on the ceramic polyolefin obtained in the step 1) on a vulcanization press bed at 170-175 ℃ for 10-20 min to obtain a ceramic polyolefin layer;
the preparation method of the low-smoke halogen-free flame-retardant polyolefin layer comprises the following steps:
1) stirring and mixing 5-10 parts of basf flame retardant, 30-35 parts of 1,3, 5-triazine, 10-14 parts of pentaerythritol and 15-20 parts of hindered phenol antioxidant in parts by weight;
2) adding 5-15 parts by weight of plant cellulose and 10-20 parts by weight of magnetite nanoparticles into the mixture obtained in the step 1), and fully stirring again;
3) adding 40-50 parts by weight of polyolefin and 5-35 parts by weight of char forming agent into the mixture obtained in the step 2), and stirring and extruding by using a double-screw extruder to obtain the low-smoke halogen-free flame-retardant polyolefin layer.
2. The low-smoke halogen-free 750 ℃ resistant cable according to claim 1, wherein the preparation method of the phenylenediamine modified graphene oxide layer (5-3) comprises the following steps:
1) dissolving 0.2-0.5 g of graphene oxide in 200-500 ml of distilled water, and stirring uniformly by adopting magnetic stirring to obtain a graphene oxide solution;
2) adding 2-5 g of p-phenylenediamine into 200-500 ml of N, N-dimethylformamide solution, and stirring uniformly by adopting magnetic stirring to obtain p-phenylenediamine colloidal solution;
3) mixing the graphene oxide solution obtained in the step 1) with the p-phenylenediamine colloidal solution obtained in the step 2), and heating under reflux for 12-15 h in an oil bath at 80-100 ℃ in an oxygen-free environment of nitrogen;
4) filtering the mixture obtained in the step 3), and cleaning the mixture for 2 to 3 times by using an acetone solution to obtain p-phenylenediamine modified graphene oxide nanoparticles;
5) putting the p-phenylenediamine modified graphene oxide nanoparticles obtained in the step 4) into a double-screw extruder to be stirred and extruded to obtain the p-phenylenediamine modified graphene oxide layer.
3. The low-smoke halogen-free 750 ℃ resistant cable according to claim 1, wherein the char-forming agent is a combination of a triazine char-forming agent and an acid-derived char-forming agent, and the weight ratio of the triazine char-forming agent to the acid-derived char-forming agent is (1:1.5) - (1: 3).
4. The low smoke, zero halogen and 750 ℃ resistant cable according to claim 3, wherein the acid source char forming agent is ammonium polyphosphate.
5. The low smoke, zero halogen and 750 ℃ resistant cable according to claim 3, wherein the triazine char-forming agent is an ethylenediamine triazine char-forming agent.
6. A low smoke zero halogen 750 ℃ resistant cable as claimed in any one of claims 1-5 wherein said mica tape insulating layer is formed by two layers of mica tape overlapping lapping covers.
7. A low smoke zero halogen 750 ℃ resistant cable as claimed in any one of claims 1-5, wherein the cover ratio of the glass fiber tape to the insulating filling layer is 10% -15%.
8. The low smoke zero halogen 750 ℃ resistant cable according to any one of claims 1-5, wherein the insulating filling layer is an inorganic rope or a glass fiber rope.
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