CN109979663B - Corrosion-resistant flame-retardant wire and cable and preparation method thereof - Google Patents

Corrosion-resistant flame-retardant wire and cable and preparation method thereof Download PDF

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CN109979663B
CN109979663B CN201910324423.1A CN201910324423A CN109979663B CN 109979663 B CN109979663 B CN 109979663B CN 201910324423 A CN201910324423 A CN 201910324423A CN 109979663 B CN109979663 B CN 109979663B
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corrosion
flame
cable
retardant
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南赞峰
张志坤
王国荣
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Shaanxi Chint Cable Co ltd
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    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • 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
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    • H—ELECTRICITY
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    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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    • H01B9/02—Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
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    • C08K2003/265—Calcium, strontium or barium carbonate
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Abstract

The invention discloses an anti-corrosion flame-retardant wire cable, which comprises a cable body, wherein the cable body comprises a conductor, a shielding layer, a reinforcing layer and an anti-corrosion flame-retardant layer; the anti-corrosion flame-retardant layer mainly comprises the following raw materials in parts by weight: polyimide resin, nitrile rubber, polyimide fiber, composite additive, metallocene low-density polyethylene-butadiene-maleic anhydride copolymer, dioctyl phthalate, polyethylene wax, polyoxyethylene, 3-isocyanatopropyl trimethoxy silane, dicumyl peroxide, modified calcium carbonate, melamine cyanurate and composite cage-type silsesquioxane. The electric wire and cable provided by the invention has the excellent performances of strong corrosion resistance, high flame retardance, strong heat resistance, low smoke, stable performance, long service life and the like. The invention also discloses a preparation method of the anti-corrosion flame-retardant wire and cable.

Description

Corrosion-resistant flame-retardant wire and cable and preparation method thereof
Technical Field
The invention relates to the technical field of wires and cables, in particular to an anti-corrosion flame-retardant wire and cable and a preparation method thereof.
Background
The electric wires and cables are used as main carriers for power transmission and widely applied to the aspects of electrical equipment, lighting circuits, household appliances and the like, and the quality of the electric wires and cables directly affects the engineering quality and the life and property safety of consumers. With the continuous progress of industry and the gradual improvement of safety consciousness, the requirements of different industries on performances such as flame retardance, fire resistance, low smoke, oil resistance, temperature resistance and the like of wires and cables are higher and higher, and corrosion-resistant high-flame-retardance wires and cables are one important point of increasing attention.
Most of the electric wires and cables in the market at present can be divided into a plurality of electric wires and cables such as PVC, PE, PP from the material. Whereas existing wire and cable products have good mechanical properties, shielding properties and flexibility. However, in order to solve the problems that the high and low temperature difference is large, the flame retardant requirement is high, and the communication requirement is strict on important equipment such as aerospace, ships, offshore platforms, petroleum exploration, power plants and the like, the requirements of communication products are continuously changed due to the fact that the demand of the communication products is small, the quality requirement is strict, and the performance is different in occasions, in the use process, water, air and corrosive substances in the external environment easily enter the external conductor along with the time through blowing and insolation, and therefore the cable performance and the corrosion are affected.
Disclosure of Invention
In view of the defects of the prior art, the technical problems to be solved by the invention are to solve the problems of the existing wire and cable, such as the defects of corrosion resistance, flame retardance and short service life, and provide the corrosion-resistant flame-retardant wire and cable and the preparation method thereof, namely the corrosion resistance and flame retardance of the wire and cable are improved, and meanwhile, the wire and cable has the advantages of stable performance, long service life and the like, so that the wire and cable are more beneficial to large-scale popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an anti-corrosion flame-retardant wire and cable comprises a cable body, wherein the cable body comprises a conductor, a shielding layer, a reinforcing layer and an anti-corrosion flame-retardant layer; the anti-corrosion flame-retardant layer is divided into an inner anti-corrosion flame-retardant layer and an outer anti-corrosion flame-retardant layer, the shielding layer is wrapped outside the conductor, the shielding layer is wrapped with an inner anti-corrosion flame-retardant layer, the reinforcing layer is wrapped outside the inner anti-corrosion flame-retardant layer, and the reinforcing layer is wrapped with an outer anti-corrosion flame-retardant layer; the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer are mainly composed of the following raw materials in parts by weight: 100 parts of polyimide resin, 12-30 parts of nitrile rubber, 1-8 parts of polyimide fiber, 2-6 parts of composite additive, 1.5-3.5 parts of metallocene low-density polyethylene-butadiene-maleic anhydride copolymer, 1-10 parts of dioctyl phthalate, 2-7 parts of polyethylene wax, 3.5-4.5 parts of polyoxyethylene, 1.5-6.5 parts of 3-isocyanatopropyl trimethoxysilane, 1-3 parts of dicumyl peroxide, 5-8 parts of modified calcium carbonate, 1-2 parts of melamine cyanurate and 1-8 parts of composite cage-type silsesquioxane. The polyimide resin is used as a main component of the electric wire and cable, has extremely high thermal stability, extremely cold resistance and extremely high temperature resistance, and excellent mechanical properties, and the addition of the polyimide fiber can increase the self-extinguishing effect and the overall strength of the electric wire and cable, and has higher ultraviolet resistance. Through the vulcanization crosslinking and blending reaction of 3-isocyanatopropyl trimethoxysilane, dicumyl peroxide, melamine cyanurate and composite cage-type silsesquioxane with polyimide resin and nitrile rubber, the obtained wire and cable has excellent corrosion resistance and flame retardance.
The polyethylene wax and the polyoxyethylene are good lubricants and a softener, so that the viscosity can be reduced, the material processing production is facilitated, the production efficiency of the material processing can be improved, the production cost is reduced, and the chemical resistance of the material is better;
the metallocene low-density polyethylene-butadiene-maleic anhydride copolymer is prepared from metallocene low-density polyethylene, butadiene and maleic anhydride by adopting an emulsion graft polymerization method. The metallocene low-density polyethylene-butadiene-maleic anhydride copolymer not only improves the excellent shock resistance of the electric wire and cable, but also can improve the compatibility and the processability of the product.
Preferably, the composite additive consists of the following raw materials in parts by weight: 0.3 to 1 part of conductive carbon black, 0.3 to 0.8 part of nano titanium dioxide, 5 to 8 parts of tri (xylene) phosphate, 1.5 to 2.8 parts of calcium carbonate whisker and 1.5 to 8.8 parts of 4-carboxyphenylboronic acid pinacol ester. The addition of the composite additive can increase the performances of flame retardance, static resistance, corrosion resistance, ultraviolet resistance and the like of the electric wires and the cables, wherein the calcium carbonate whisker not only improves the stability and mechanical properties of each component in the electric wires and the cables, but also plays a role in activation.
Preferably, the composite cage silsesquioxane consists of the following components in mass ratio 1:1 and octaiodopropyl polyhedral oligomeric silsesquioxanes containing ionic liquid. The octanaphthyl cage-type silsesquioxane is obtained through hydrolysis reaction of 1-naphthyl trimethoxysilane.
Preferably, the substituents at 8 vertex angles of the octa-naphthyl cage-type silsesquioxane are naphthyl, and the substituents at 8 vertex angles of the octa-iodopropyl cage-type silsesquioxane are iodopropyl.
Preferably, the octaiodopropyl cage-type silsesquioxane containing the ionic liquid is prepared by the following method:
s1: placing dichloromethane, trimethoxy (iodopropyl) silane and potassium hydroxide into an oil bath, stirring and heating to 110 ℃, adding deionized water, and heating, condensing and refluxing for reaction for 72h at the temperature of 110 ℃;
s2: after the reaction is finished, centrifugally separating a product, cleaning the product by using absolute methanol, and drying the product in vacuum at 50 ℃ for 24 hours to obtain the octaiodopropyl cage-type silsesquioxane;
s3: adding the octaiodopropyl cage-type silsesquioxane obtained in the step S2 into a mixed solution consisting of 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine and toluene, and magnetically stirring at a constant temperature of 60 ℃ for reaction for 24 hours; and then adding ammonium tetrafluoroborate for ion exchange to obtain the octaiodopropyl cage-type silsesquioxane containing the ionic liquid.
The cage-type silsesquioxane containing the ionic liquid prepared by the method has good solubility to organic and inorganic matters, and further synergistically modifies calcium carbonate, so that a polyimide wire and cable reaction system can be carried out under a homogeneous phase condition; by utilizing the excellent properties of non-volatility, high heat resistance, incombustibility and the like of the ionic liquid and combining the material obtained by blending the cage-type silsesquioxane and the polymer, the electric wire and the cable have obvious combustion delaying characteristics, the service temperature is increased, the electric wire and the cable are more suitable for the service environment with large temperature difference at high and low temperatures, the mechanical property and the processing property of the electric wire and the cable are also obviously improved, the manufacturing cost of the electric wire and the cable is reduced, and the service life of the electric wire and the cable is prolonged.
Preferably, the volume ratio of the dichloromethane, the trimethoxy (isopropyl) silane, the potassium hydroxide and the deionized water is 100:5 to 12:0.1 to 1:1 to 10.
Preferably, the molar ratio of the ammonium tetrafluoroborate and the 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine to the octaiodopropyl polyhedral oligomeric silsesquioxane is 1.1 to 1.3:1.1 to 1.3:1, wherein the volume and mass ratio of toluene to 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine is 3-10: 1ml/g.
Preferably, the shielding layer is an aluminum-plastic composite belt shielding layer, and the reinforcing layer is a glass fiber and carbon fiber composite reinforcing layer.
Preferably, the modified calcium carbonate is cage-type silsesquioxane modified calcium carbonate, and the preparation method thereof is as follows:
s1: adding coarse calcium carbonate powder into a grinder, adding a modifier consisting of 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate and melamine cyanurate, wherein the adding amount of the modifier is 1-5% of the weight of the coarse calcium carbonate powder, and grinding to obtain fine calcium carbonate powder with the particle size of 300-500 meshes; the mass ratio of the 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate to the melamine cyanurate is 0.5:1 to 2;
s2: adding the calcium carbonate fine powder into a high-speed stirrer, adding a secondary modifier consisting of octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane and polystyrene, wherein the addition amount of the secondary modifier is 1.5-2.5% of the weight of the calcium carbonate fine powder, stirring and mixing uniformly at a high speed, drying and grinding to 600-800 meshes, and sieving to obtain the modified calcium carbonate. The mass ratio of the octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane to the polystyrene is 1-10: 1.
correspondingly, the preparation method of the anti-corrosion flame-retardant wire and cable mainly comprises the steps of preparing cable materials of an inner anti-corrosion flame-retardant layer and an outer anti-corrosion flame-retardant layer, wherein the two layers of the cable materials are identical, and the preparation method comprises the following steps: and (3) mixing according to the formula, adding the mixed materials into a double-roll open mill for melt blending, wherein the mixing temperature is 120-130 ℃, the mixing time is 8-15 minutes, cutting the lower sheet after uniform blending, and then transferring the cut lower sheet to a flat vulcanizing machine for tabletting and forming, wherein the forming temperature is 155-165 ℃, the time is 8-10 minutes, and the pressure is 15MPa, so that the cable material of the required inner anti-corrosion flame-retardant layer and the required outer anti-corrosion flame-retardant layer can be prepared.
The invention has the beneficial effects that:
the electric wire and cable provided by the invention is provided with the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer, and through multiple arrangement, the anti-corrosion and flame-retardant properties of the product are improved, and the properties of the product exceed those of commercial products; meanwhile, the raw materials used for preparation are halogen-free substances, so that the electric wire and cable have excellent environmental protection performance;
according to the invention, the compatibility, the dispersibility and the processing fluidity of the calcium carbonate can be improved by adding the modified calcium carbonate, and the modified calcium carbonate contains active groups and a polyimide wire and cable reaction system to form a network structure, so that the calcium carbonate has good compatibility with polyimide resin, nitrile rubber and a composite additive, the interfacial adhesion of the polyimide wire and cable reaction system is improved, the mechanical property and the corrosion resistance and flame retardance of wires and cables are further improved, and the service life of the wires and cables is prolonged;
the octaiodopropyl cage-type silsesquioxane containing the ionic liquid prepared by the invention cooperates with the octanaphtyl cage-type silsesquioxane, the composite additive, the modified calcium carbonate and the organic polymer to ensure that the prepared wire and cable has high chemical bond bonding strength of organic and inorganic components, stable performance and long service life, thereby ensuring that the anti-corrosion flame-retardant layer has the use effects of strong corrosion resistance, high flame retardance, strong heat resistance and low smoke.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
An anti-corrosion flame-retardant wire and cable comprises a cable body, wherein the cable body comprises a conductor, a shielding layer, a reinforcing layer and an anti-corrosion flame-retardant layer; the anti-corrosion flame-retardant layer is divided into an inner anti-corrosion flame-retardant layer and an outer anti-corrosion flame-retardant layer, the shielding layer is wrapped outside the conductor, the shielding layer is wrapped with an inner anti-corrosion flame-retardant layer, the reinforcing layer is wrapped outside the inner anti-corrosion flame-retardant layer, and the reinforcing layer is wrapped with an outer anti-corrosion flame-retardant layer; the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer are mainly composed of the following raw materials in parts by weight: 100 parts of polyimide resin, 12 parts of nitrile rubber, 1 part of polyimide fiber, 2 parts of composite additive, 1.5 parts of metallocene low-density polyethylene-butadiene-maleic anhydride copolymer, 1 part of dioctyl phthalate, 2 parts of polyethylene wax, 3.5 parts of polyoxyethylene, 1.5 parts of 3-isocyanatopropyl trimethoxysilane, 1 part of dicumyl peroxide, 5 parts of modified calcium carbonate, 1 part of melamine cyanurate and 1 part of composite cage-type silsesquioxane.
The composite additive consists of the following raw materials in parts by weight: 0.3 part of conductive carbon black, 0.3 part of nano titanium dioxide, 5 parts of tri (xylene) phosphate, 1.5 parts of calcium carbonate whisker and 1.5 parts of 4-carboxyphenylboronic acid pinacol ester.
The composite cage type silsesquioxane comprises the following components in percentage by mass: 1 and octaiodopropyl polyhedral oligomeric silsesquioxanes containing ionic liquid.
The substituents at 8 vertex angles of the octa-naphthyl cage-type silsesquioxane are naphthyl, and the substituents at 8 vertex angles of the octa-iodopropyl cage-type silsesquioxane are iodopropyl.
The octaiodopropyl cage-type silsesquioxane containing the ionic liquid is prepared by the following method:
s1: placing dichloromethane, trimethoxy (iodopropyl) silane and potassium hydroxide into an oil bath, stirring and heating to 110 ℃, adding deionized water, and heating, condensing and refluxing for reaction for 72h at the temperature of 110 ℃;
s2: after the reaction is finished, centrifugally separating a product, cleaning the product by using absolute methanol, and drying the product in vacuum at 50 ℃ for 24 hours to obtain the octaiodopropyl cage-type silsesquioxane;
s3: adding the octaiodopropyl cage-type silsesquioxane obtained in the step S2 into a mixed solution consisting of 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine and toluene, and magnetically stirring at a constant temperature of 60 ℃ for reaction for 24 hours; and then adding ammonium tetrafluoroborate for ion exchange to obtain the octaiodopropyl cage-type silsesquioxane containing the ionic liquid.
The volume ratio of the dichloromethane to the trimethoxy (iodopropyl) silane to the potassium hydroxide to the deionized water is 100:5:0.1:1.
the molar ratio of the ammonium tetrafluoroborate and the 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine to the octaiodopropyl polyhedral oligomeric silsesquioxane is 1.1:1.1:1, volume and mass ratio of toluene to 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine 3:1ml/g.
The shielding layer is an aluminum-plastic composite belt shielding layer, and the reinforcing layer is a glass fiber and carbon fiber composite reinforcing layer.
The modified calcium carbonate is cage-type silsesquioxane modified calcium carbonate, and the preparation method thereof is as follows:
s1: adding coarse calcium carbonate powder into a grinder, adding a modifier consisting of 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate and melamine cyanurate, wherein the adding amount of the modifier is 1% of the weight of the coarse calcium carbonate powder, and grinding to obtain fine calcium carbonate powder with the particle size of 300 meshes; the mass ratio of the 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate to the melamine cyanurate is 0.5:1, a step of;
s2: adding the calcium carbonate fine powder into a high-speed stirrer, adding a secondary modifier consisting of octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane and polystyrene, wherein the addition amount of the secondary modifier is 1.5% of the weight of the calcium carbonate fine powder, stirring and mixing uniformly at a high speed, drying and grinding to 600 meshes, and sieving to obtain the modified calcium carbonate. The mass ratio of the octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane to the polystyrene is 1:1.
correspondingly, the preparation method of the anti-corrosion flame-retardant wire and cable mainly comprises the steps of preparing cable materials of an inner anti-corrosion flame-retardant layer and an outer anti-corrosion flame-retardant layer, wherein the two layers of the cable materials are identical, and the preparation method comprises the following steps: and (3) mixing according to the formula, adding the mixed materials into a double-roll open mill for melt blending, wherein the mixing temperature is 120 ℃, the mixing time is 8 minutes, cutting a lower sheet after uniform blending, transferring the cut lower sheet onto a flat vulcanizing machine for tabletting and forming, wherein the forming temperature is 155 ℃, the time is 8 minutes, and the pressure is 15MPa, so that the cable material of the required inner anti-corrosion flame-retardant layer and the required outer anti-corrosion flame-retardant layer can be prepared.
Example 2
The anti-corrosion flame-retardant wire and cable of the embodiment is basically similar to the embodiment 1 in wire and cable structure, raw material composition and preparation method thereof, and is mainly different in that the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer are mainly composed of the following raw materials in parts by weight: 100 parts of polyimide resin, 21 parts of nitrile rubber, 5 parts of polyimide fiber, 4 parts of composite additive, 2.5 parts of metallocene low-density polyethylene-butadiene-maleic anhydride copolymer, 5 parts of dioctyl phthalate, 4 parts of polyethylene wax, 4 parts of polyoxyethylene, 4.8 parts of 3-isocyanatopropyl trimethoxysilane, 2 parts of dicumyl peroxide, 6 parts of modified calcium carbonate, 1.6 parts of melamine cyanurate and 5 parts of composite cage-type silsesquioxane.
Example 3
The anti-corrosion flame-retardant wire and cable of the embodiment is basically similar to the embodiment 1 in wire and cable structure, raw material composition and preparation method thereof, and is mainly different in that the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer are mainly composed of the following raw materials in parts by weight: 100 parts of polyimide resin, 30 parts of nitrile rubber, 8 parts of polyimide fiber, 6 parts of composite additive, 3.5 parts of metallocene low-density polyethylene-butadiene-maleic anhydride copolymer, 10 parts of dioctyl phthalate, 7 parts of polyethylene wax, 4.5 parts of polyoxyethylene, 6.5 parts of 3-isocyanatopropyl trimethoxysilane, 3 parts of dicumyl peroxide, 8 parts of modified calcium carbonate, 2 parts of melamine cyanurate and 8 parts of composite cage-type silsesquioxane.
Example 4
The anti-corrosion flame-retardant wire and cable is basically similar to the wire and cable in embodiment 1 in structure, raw material composition and preparation method thereof, and is mainly different in that the composite additive consists of the following raw materials in parts by weight: 1 part of conductive carbon black, 0.8 part of nano titanium dioxide, 8 parts of tri (xylene) phosphate, 2.8 parts of calcium carbonate whisker and 8.8 parts of 4-carboxyphenylboronic acid pinacol ester.
Example 5
The anti-corrosion flame-retardant wire and cable of the embodiment is basically similar to the embodiment 1 in wire and cable structure, raw material composition and preparation method thereof, and is mainly different in that the modified calcium carbonate is cage-type silsesquioxane modified calcium carbonate, and the preparation method thereof is as follows:
s1: adding coarse calcium carbonate powder into a grinder, adding a modifier consisting of 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate and melamine cyanurate, wherein the addition amount of the modifier is 5% of the weight of the coarse calcium carbonate powder, and grinding to obtain fine calcium carbonate powder with the particle size of 500 meshes; the mass ratio of the 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate to the melamine cyanurate is 0.5:2;
s2: adding the calcium carbonate fine powder into a high-speed stirrer, adding a secondary modifier consisting of octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane and polystyrene, wherein the addition amount of the secondary modifier is 2.5% of the weight of the calcium carbonate fine powder, stirring and mixing uniformly at a high speed, drying and grinding to 800 meshes, and sieving to obtain the modified calcium carbonate. The mass ratio of the octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane to the polystyrene is 10:1.
example 6
The anti-corrosion flame-retardant wire and cable is basically similar to the wire and cable in embodiment 1 in structure, raw material composition and preparation method thereof, and is mainly different in that the composite additive consists of the following raw materials in parts by weight: 0.5 part of conductive carbon black, 0.6 part of nano titanium dioxide, 7 parts of tri (xylene) phosphate, 1.8 parts of calcium carbonate whisker and 5.8 parts of 4-carboxyphenylboronic acid pinacol ester.
The modified calcium carbonate is cage-type silsesquioxane modified calcium carbonate, and the preparation method thereof is as follows:
s1: adding coarse calcium carbonate powder into a grinder, adding a modifier consisting of 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate and melamine cyanurate, wherein the adding amount of the modifier is 3% of the weight of the coarse calcium carbonate powder, and grinding to obtain fine calcium carbonate powder with the particle size of 400 meshes; the mass ratio of the 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate to the melamine cyanurate is 0.5:1.5;
s2: adding the calcium carbonate fine powder into a high-speed stirrer, adding a secondary modifier consisting of octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane and polystyrene, wherein the addition amount of the secondary modifier is 2.2% of the weight of the calcium carbonate fine powder, stirring and mixing uniformly at a high speed, drying and grinding to 700 meshes, and sieving to obtain the modified calcium carbonate. The mass ratio of the octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane to the polystyrene is 6:1.
comparative example 1
The comparative anti-corrosion flame-retardant wire and cable is basically similar to the wire and cable structure, the raw material composition and the preparation method thereof in example 1, and is mainly different in that the raw material composition of the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer is not added with composite cage-type silsesquioxane.
Comparative example 2
The comparative anti-corrosion flame-retardant wire and cable is basically similar to the wire and cable structure, the raw material composition and the preparation method thereof in example 1, and is mainly different in that modified calcium carbonate and composite cage-type silsesquioxane are not added in the raw material composition of the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer.
Comparative example 3
The comparative anti-corrosion flame-retardant wire and cable is basically similar to example 1 in wire and cable structure, raw material composition and preparation method thereof, and is mainly different in that no composite additive is added in the raw material composition of the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer.
Comparative example 4
The comparative anti-corrosion flame-retardant wire and cable is basically similar to example 1 in wire and cable structure, raw material composition and preparation method thereof, and is mainly different in that metallocene low-density polyethylene-butadiene-maleic anhydride copolymer is not added in the raw material composition of the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer.
The electric wires and cables prepared in examples 1 to 6 and comparative examples 1 to 4 and commercial electric wires and cables were subjected to performance test as comparative example 5, and the performance results thereof are shown in table 1:
TABLE 1
Oxygen index Tensile strength, MPa Elongation at break% Corrosion resistance
Example 1 68 48 302 No corrosion on surface
Example 2 67 47 305 No corrosion on surface
Example 3 71 49 311 No corrosion on surface
Example 4 66 52 298 No corrosion on surface
Example 5 69 51 304 No corrosion on surface
Example 6 70 48 310 No corrosion on surface
Comparative example 1 61 43 285 Severe corrosion of surface
Comparative example 2 48 32 261 Severe corrosion of surface
Comparative example 3 62 39 275 Slight corrosion of surface
Comparative example 4 64 35 229 Slight corrosion of surface
Comparative example 5 38 25 186 Severe corrosion of surface
The wires and cables of examples 1 to 6 and comparative examples 1 to 5 were immersed in the etchant under the same conditions for 168 hours, and taken out to observe the surface corrosion.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made therein without departing from the spirit and scope of the invention, which is defined by the appended claims.

Claims (5)

1. An anti-corrosion flame-retardant wire and cable comprises a cable body, wherein the cable body comprises a conductor, a shielding layer, a reinforcing layer and an anti-corrosion flame-retardant layer; the anti-corrosion flame-retardant coating is characterized by comprising an inner anti-corrosion flame-retardant coating and an outer anti-corrosion flame-retardant coating, wherein the shielding layer is wrapped outside the conductor, the shielding layer is wrapped with an inner anti-corrosion flame-retardant coating, the reinforcing layer is wrapped outside the inner anti-corrosion flame-retardant coating, and the reinforcing layer is wrapped with an outer anti-corrosion flame-retardant coating; the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer are mainly composed of the following raw materials in parts by weight: 100 parts of polyimide resin, 12-30 parts of nitrile rubber, 1-8 parts of polyimide fiber, 2-6 parts of composite additive, 1.5-3.5 parts of metallocene low-density polyethylene-butadiene-maleic anhydride copolymer, 1-10 parts of dioctyl phthalate, 2-7 parts of polyethylene wax, 3.5-4.5 parts of polyoxyethylene, 1.5-6.5 parts of 3-isocyanatopropyl trimethoxysilane, 1-3 parts of dicumyl peroxide, 5-8 parts of modified calcium carbonate, 1-2 parts of melamine cyanurate and 1-8 parts of composite cage-type silsesquioxane; the composite additive consists of the following raw materials in parts by weight: 0.3 to 1 part of conductive carbon black, 0.3 to 0.8 part of nano titanium dioxide, 5 to 8 parts of tri (xylene) phosphate, 1.5 to 2.8 parts of calcium carbonate whisker and 1.5 to 8.8 parts of 4-carboxyphenylboronic acid pinacol ester; the composite cage type silsesquioxane comprises the following components in percentage by mass: 1 and octaiodopropyl cage-type silsesquioxane containing ionic liquid; the substituents of 8 vertex angles of the octa-naphthyl cage-type silsesquioxane are naphthyl, and the substituents of 8 vertex angles of the octa-iodopropyl cage-type silsesquioxane are iodopropyl;
the octaiodopropyl cage-type silsesquioxane containing the ionic liquid is prepared by the following method:
s1: placing dichloromethane, trimethoxy (iodopropyl) silane and potassium hydroxide into an oil bath, stirring and heating to 110 ℃, adding deionized water, and heating, condensing and refluxing for reaction for 72h at the temperature of 110 ℃;
s2: after the reaction is finished, centrifugally separating a product, cleaning the product by using absolute methanol, and drying the product in vacuum at 50 ℃ for 24 hours to obtain the octaiodopropyl cage-type silsesquioxane;
s3: adding the octaiodopropyl cage-type silsesquioxane obtained in the step S2 into a mixed solution consisting of 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine and toluene, and magnetically stirring at a constant temperature of 60 ℃ for reaction for 24 hours; then adding ammonium tetrafluoroborate for ion exchange to obtain octaiodopropyl cage-type silsesquioxane containing ionic liquid;
the modified calcium carbonate is cage-type silsesquioxane modified calcium carbonate, and the preparation method thereof is as follows:
s1: adding coarse calcium carbonate powder into a grinder, adding a modifier consisting of 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate and melamine cyanurate, wherein the adding amount of the modifier is 1-5% of the weight of the coarse calcium carbonate powder, and grinding to obtain fine calcium carbonate powder with the particle size of 300-500 meshes; the mass ratio of the 2-hydroxy-3- [3- (trimethoxysilyl) propoxy ] propyl acrylate to the melamine cyanurate is 0.5:1 to 2;
s2: adding the calcium carbonate fine powder into a high-speed stirrer, adding a secondary modifier consisting of octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane and polystyrene, wherein the addition amount of the secondary modifier is 1.5-2.5% of the weight of the calcium carbonate fine powder, stirring and mixing uniformly at a high speed, drying and grinding to 600-800 meshes, and sieving to obtain the modified calcium carbonate; the mass ratio of the octaN- (hydroxyethyl) -N-methylaminopropyl cage-shaped silsesquioxane to the polystyrene is 1-10: 1.
2. the corrosion-resistant flame-retardant wire and cable of claim 1, wherein the volume ratio of methylene chloride, trimethoxy (iodopropyl) silane, potassium hydroxide and deionized water is 100:5 to 12:0.1 to 1:1 to 10.
3. The corrosion-resistant flame-retardant wire and cable of claim 1, wherein the molar ratio of the ammonium tetrafluoroborate and 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine to the octaiodopropyl polyhedral oligomeric silsesquioxane is from 1.1 to 1.3:1.1 to 1.3:1, wherein the volume and mass ratio of toluene to 1- (3- (trifluoromethyl) pyridin-2-yl) piperazine is 3-10: 1ml/g.
4. The corrosion-resistant flame-retardant wire and cable of claim 1, wherein the shielding layer is an aluminum-plastic composite tape shielding layer, and the reinforcing layer is a glass fiber and carbon fiber composite reinforcing layer.
5. The method for preparing the anti-corrosion flame-retardant wire and cable according to claim 1, wherein the cable material mainly comprises an inner anti-corrosion flame-retardant layer and an outer anti-corrosion flame-retardant layer, and the two layers of the cable material are consistent, and the specific preparation method comprises the following steps: the cable material for the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer is prepared by mixing the raw materials in parts by weight according to the method of claim 1, adding the prepared materials into a double-roll open mill for melt blending, wherein the mixing temperature is 120-130 ℃, the mixing time is 8-15 minutes, cutting a lower sheet after blending uniformly, transferring the lower sheet to a flat vulcanizing machine for tabletting and forming, the forming temperature is 155-165 ℃, the time is 8-10 minutes, and the pressure is 15MPa, so that the cable material for the inner anti-corrosion flame-retardant layer and the outer anti-corrosion flame-retardant layer is prepared.
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