CN114957822A - Flame-retardant corrosion-resistant cable material and preparation method thereof - Google Patents
Flame-retardant corrosion-resistant cable material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant corrosion-resistant cable material and a preparation method thereof, and belongs to the technical field of insulated power cables. Aiming at the characteristics of poor mechanical property, poor flame-retardant effect, weak corrosion resistance and the like of the flame-retardant cable in the prior art, the method takes increasing the density of a system as a starting point to prepare the flame-retardant cable material. Firstly, the 1-butyl-3-methylimidazole chloride modified glass fiber is used, and the modified glass fiber can help the matrix material to keep good mechanical property and thermal stability. Meanwhile, the crosslinking of the polymer into carbon can be promoted, and the effect of blocking heat and gas transmission is achieved through a good carbon layer, so that high-efficiency flame retardance is realized. Meanwhile, the modified aluminum hydroxide particles with polarity can be adsorbed, the flame retardant effect of the matrix is further enhanced, and meanwhile, the nano-grade aluminum hydroxide can promote efficient dispersion of the modified aluminum hydroxide particles under the action of glass fibers, reduce internal defects, improve the overall density of the material, and further improve the strength, flame retardant effect and corrosion resistance of the material.
Description
Technical Field
The invention belongs to the technical field of insulated power cables, and particularly relates to a flame-retardant corrosion-resistant cable material and a preparation method thereof.
Background
The fire is discovered and utilized along with the fire, and is closely related to the development of human civilization. The fire safety is closely related to the life of people, and belongs to the field of public safety. Along with the development of socioeconomic in China, the contradiction that fire fighting work is not suitable for the development of economy and society is more prominent.
The cable material is an important part for protecting the cable from being damaged by the outside, and is generally made of high molecular functional materials. The cable material must be able to protect the inner and outer conductors and the insulation layer of the cable from the effects of environment, weather, acid and hydrolysis, and at present, the main material of the cable material mainly comprises chlorinated polyethylene, chlorosulfonated polyethylene, polyurethane, polyethylene, various natural or synthetic rubbers, and the like.
In recent years, with the development and popularization of the production of living electric wires and cables, the demand of the electric wires and cables is rapidly increased, and with the development of economy, the requirements on materials of the electric wires and cables are higher and higher, and the electric wires and cables are required to have the performances of softness, wear resistance, low temperature resistance and the like. However, the flame-retardant cable is a cable which is used for burning a test sample under a specified test condition, spreading of flame is only in a limited range after a test fire source is removed, and residual flame or residual ignition can be automatically extinguished within a limited time. The basic characteristics are as follows: in the event of a fire, may burn out and fail to operate, but may prevent the spread of the fire. In common, in case of fire, the electric wire can limit the combustion within a local range, does not spread, keeps other various equipment and avoids causing larger loss. Can protect life safety and property safety to a greater extent, so the application is more common.
In the specific application process, the cable material must be capable of resisting sunlight, UV radiation, ozone aging and chemical corrosion, and simultaneously can still ensure or temporarily ensure the normal operation of the cable material under the accidental disaster condition, and along with the frequent occurrence of electrical fire accidents, the flame retardant problem of the electric wire and the cable gradually arouses the attention of all countries in the world.
In the field of cable flame retardance, flame retardance of a cable is generally improved by adding a flame retardant material, an inorganic flame retardant and a filler are flame retardants frequently used, in the actual use process, the addition of the inorganic flame retardant can change the vulcanization performance, the physical and mechanical properties, the thermal properties and the like of rubber materials, and meanwhile, powder materials are extremely easy to agglomerate and directly influence the flame retardant effect of inorganic filler particles; meanwhile, the agglomerated inorganic flame retardant and the filler can cause void defects in the material to a great extent, and further cause the reduction of the overall mechanical property and the corrosion resistance of the cable material. Therefore, how to solve the inherent defects of the existing flame-retardant cable is a technical problem to be solved urgently.
Disclosure of Invention
The invention provides a modified flame-retardant corrosion-resistant cable material and a preparation method thereof, aiming at the problems of the flame-retardant cable material in the prior art. The obtained cable material has excellent flame retardant property, ageing resistance and mechanical property.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
the flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 50-80 parts of chloroprene rubber, 20-40 parts of ethylene-vinyl acetate copolymer, 10-20 parts of filler, 12-25 parts of flame-retardant fiber, 5-15 parts of modified flame retardant, 0.1-0.5 part of dipentamethylenethiuram tetrasulfide, 1-3 parts of antioxidant and 1-5 parts of barium stearate.
Further, the VA content of the ethylene-vinyl acetate copolymer is 28-35%, and the melt index is 3.0 g/min.
Further, the filler is one or more of white carbon black, talcum powder or kaolin.
Further, the preparation method of the flame-retardant fiber comprises the following steps: uniformly mixing 10-20g of glass fiber and 30-50g of chlorinated 1-butyl-3-methylimidazole, adding the mixture into 100ml of acetic acid solution with the volume fraction of 5-10%, uniformly dispersing by ultrasonic wave, adding chitosan with the mass of 1-5% of the mixed solution and gamma-aminopropyltriethoxysilane with the mass of 0.3-1%, stirring and mixing for 1-2h at the constant temperature of 70-80 ℃ and the magnetic force of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber.
Further, the modified flame retardant is modified aluminum hydroxide, the aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are mixed according to the mass ratio of 1:1, dispersed in deionized water with the weight being 3-5 times that of the aluminum hydroxide and the 2-carboxyethyl phenyl hypophosphorous acid, sodium dodecyl sulfate with the mass being 1-3% of the mixed liquid is added, ultrasonic dispersion is carried out for 1-3 hours, centrifugal separation and drying are carried out, and the modified flame retardant is obtained.
Further, the median diameter D of the aluminum hydroxide 50 ≈200-300nm。
Further, the antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: uniformly mixing 10-20g of glass fiber and 30-50g of chlorinated 1-butyl-3-methylimidazole, adding the mixture into 100ml of acetic acid solution with the volume fraction of 5-10%, uniformly dispersing by ultrasonic wave, adding chitosan with the mass of 1-5% of the mixed solution and gamma-aminopropyltriethoxysilane with the mass of 0.3-1%, stirring and mixing for 1-2h at the constant temperature of 70-80 ℃ and the magnetic force of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in deionized water with the weight of 3-5 times, adding sodium dodecyl sulfate with the mass of 1-3% of the mixed solution, ultrasonically dispersing for 1-3h, centrifugally separating, and drying to obtain a modified flame retardant;
(3) weighing the raw materials in parts by weight, firstly placing the chloroprene rubber and the ethylene-vinyl acetate copolymer into an internal mixer for mixing for 10-15min, wherein the mixing temperature is 125-130 ℃, and the mixing speed is 200-300 rpm; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 15-30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
Each of the raw materials of the present invention is commercially available.
Aiming at the characteristics of poor mechanical property, poor flame-retardant effect, weak corrosion resistance and the like of the flame-retardant cable in the prior art, the method takes increasing the density of a system as a starting point to prepare the flame-retardant cable material. Firstly, the 1-butyl-3-methylimidazole chloride modified glass fiber is used, and the modified glass fiber can help the matrix material to keep good mechanical property and thermal stability. Meanwhile, the crosslinking of the polymer into carbon can be promoted, and the effect of blocking heat and gas transmission is achieved through a good carbon layer, so that high-efficiency flame retardance is realized. Meanwhile, the modified aluminum hydroxide particles with polarity can be adsorbed, the aluminum hydroxide is adsorbed in the glass fibers after being modified by the 2-carboxyethyl phenyl hypophosphorous acid, the flame retardant effect of the matrix is further enhanced, and meanwhile, the nano-level aluminum hydroxide can promote efficient dispersion of the aluminum hydroxide under the action of the glass fibers, reduce agglomeration of inorganic flame retardants, reduce internal defects of materials, improve the overall density of the materials, and further improve the strength, the flame retardant effect and the corrosion resistance of the materials.
Advantageous effects
(1) The invention takes the chloroprene rubber and the ethylene-vinyl acetate copolymer as the base materials, has good working performance and excellent stability, and obviously enhances the insulating property and the heat resistance;
(2) the chitosan, the gamma-aminopropyltriethoxysilane and the chlorinated 1-butyl-3-methylimidazole modified glass fiber enhance the aggregate force of the glass fiber and a substrate and improve the flame retardant property at the same time; the nano magnesium hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are compounded to prepare the modified flame retardant for use, and the 2-carboxyethyl phenyl hypophosphorous acid compound is decomposed into micromolecular PO at high temperature in the combustion process 2 PO and HPO, which react with H and OH formed in the combustion process and are then interruptedThe flame retardance of the combustion reaction chain is realized, the uniform dispersion of free radicals can be promoted due to the existence of the glass fiber, and the flame retardance effect is further enhanced by the nano magnesium hydroxide; therefore, the flame-retardant fibers and the modified flame retardant act synergistically to realize efficient flame retardance of the material;
(3) the cable material disclosed by the invention is compact in structure, has good mechanical properties and corrosion resistance on the basis of high-efficiency flame retardance, is suitable for various severe environments, and has a wide application prospect.
Drawings
FIG. 1 is an SEM image of the internal structure of the materials of example 3 and comparative examples 1-5.
Detailed Description
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
Example 1
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 50 parts of chloroprene rubber, 20 parts of ethylene-vinyl acetate copolymer, 10 parts of filler, 12 parts of flame-retardant fiber, 5 parts of modified flame retardant, 0.1 part of dipentamethylenethiuram tetrasulfide, 1 part of antioxidant and 1 part of barium stearate.
The VA content of the ethylene-vinyl acetate copolymer is 28-35%, and the melt index is 3.0 g/min.
The filler is white carbon black.
The preparation method of the flame-retardant fiber comprises the following steps: uniformly mixing 10g of glass fiber and 30g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 5 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 1 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 0.3 percent of the mass of the mixed solution, magnetically stirring and mixing for 1 hour at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber.
The modified flame retardant is modified aluminum hydroxide, the aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are mixed according to the mass ratio of 1:1, and then dispersed in deionized water with the weight of 3 times, sodium dodecyl sulfate with the mass of 1% of the mixed solution is added, ultrasonic dispersion is carried out for 1h, centrifugal separation is carried out, and drying is carried out, so that the modified flame retardant is obtained.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: uniformly mixing 10g of glass fiber and 30g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 5 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 1 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 0.3 percent of the mass of the mixed solution, magnetically stirring and mixing for 1 hour at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in deionized water of which the weight is 3 times that of the mixture, adding sodium dodecyl sulfate of which the mass is 1% of that of the mixture, performing ultrasonic dispersion for 1 hour, performing centrifugal separation and drying to obtain a modified flame retardant;
(3) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 10min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 15min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
Example 2
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 60 parts of chloroprene rubber, 30 parts of ethylene-vinyl acetate copolymer, 15 parts of filler, 18 parts of flame-retardant fiber, 10 parts of modified flame retardant, 0.3 part of dipentamethylenethiuram tetrasulfide, 2 parts of antioxidant and 3 parts of barium stearate.
The ethylene-vinyl acetate copolymer has a VA content of 28-35% and a melt index of 3.0 g/min.
The filler is talcum powder.
The preparation method of the flame-retardant fiber comprises the following steps: uniformly mixing 15g of glass fiber and 40g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 8 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 3 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 0.6 percent of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber.
The modified flame retardant is modified aluminum hydroxide, the aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are mixed according to the mass ratio of 1:1, dispersed in deionized water of 5 times of the weight, added with sodium dodecyl sulfate accounting for 2% of the mass of the mixed solution, ultrasonically dispersed for 3 hours, centrifugally separated and dried to obtain the modified flame retardant.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: uniformly mixing 15g of glass fiber and 40g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of acetic acid solution with the volume fraction of 8%, uniformly dispersing by ultrasonic wave, adding chitosan with the mass of 3% of the mixed solution and gamma-aminopropyltriethoxysilane with the mass of 0.6% of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in 5 times of deionized water, adding sodium dodecyl sulfate accounting for 2% of the mass of the mixed solution, performing ultrasonic dispersion for 3 hours, performing centrifugal separation, and drying to obtain a modified flame retardant;
(3) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
Example 3
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 80 parts of chloroprene rubber, 40 parts of ethylene-vinyl acetate copolymer, 20 parts of filler, 25 parts of flame-retardant fiber, 15 parts of modified flame retardant, 0.5 part of dipentamethylenethiuram tetrasulfide, 3 parts of antioxidant and 5 parts of barium stearate.
The ethylene-vinyl acetate copolymer has a VA content of 28-35% and a melt index of 3.0 g/min.
The filler is kaolin.
The preparation method of the flame-retardant fiber comprises the following steps: uniformly mixing 20g of glass fiber and 50g of chlorinated 1-butyl-3-methylimidazole, adding the mixture into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan and 1% of gamma-aminopropyltriethoxysilane which account for 5% of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at a speed of 200r/min, centrifuging, and drying by a vacuum freeze dryer to obtain the flame-retardant fiber.
The modified flame retardant is modified aluminum hydroxide, aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are mixed according to the mass ratio of 1:1, dispersed in deionized water with the weight being 3 times that of the mixture, added with sodium dodecyl sulfate accounting for 3% of the mass of the mixture, ultrasonically dispersed for 3 hours, centrifugally separated and dried to obtain the modified flame retardant.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: uniformly mixing 20g of glass fiber and 50g of chlorinated 1-butyl-3-methylimidazole, adding the mixture into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan and 1% of gamma-aminopropyltriethoxysilane which account for 5% of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at a speed of 200r/min, centrifuging, and drying by a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in 5 times of deionized water, adding sodium dodecyl sulfate accounting for 3% of the mass of the mixed solution, performing ultrasonic dispersion for 3 hours, performing centrifugal separation, and drying to obtain a modified flame retardant;
(3) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
Comparative example 1
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 80 parts of chloroprene rubber, 40 parts of ethylene-vinyl acetate copolymer, 20 parts of filler, 25 parts of flame-retardant fiber, 15 parts of modified flame retardant, 0.5 part of dipentamethylenethiuram tetrasulfide, 3 parts of antioxidant and 5 parts of barium stearate.
The ethylene-vinyl acetate copolymer has a VA content of 28-35% and a melt index of 3.0 g/min.
The filler is kaolin.
The flame-retardant fiber is glass fiber.
The modified flame retardant is modified aluminum hydroxide, the aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are mixed according to the mass ratio of 1:1, and then dispersed in deionized water with the weight of 3 times that of the aluminum hydroxide and the 2-carboxyethyl phenyl hypophosphorous acid, sodium dodecyl sulfate with the mass of 3% of the mixed solution is added, ultrasonic dispersion is carried out for 3 hours, centrifugal separation and drying are carried out, and the modified flame retardant is obtained.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in 5 times of deionized water, adding sodium dodecyl sulfate accounting for 3% of the mass of the mixed solution, performing ultrasonic dispersion for 3 hours, performing centrifugal separation, and drying to obtain a modified flame retardant;
(2) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
This comparative example is similar in part to example 3 in the raw materials and preparation method, except that all modifications of the glass fiber are not performed, i.e., the glass fiber is directly used.
Comparative example 2
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 80 parts of chloroprene rubber, 40 parts of ethylene-vinyl acetate copolymer, 20 parts of filler, 25 parts of flame-retardant fiber, 15 parts of flame retardant, 0.5 part of dipentamethylenethiuram tetrasulfide, 3 parts of antioxidant and 5 parts of barium stearate.
The VA content of the ethylene-vinyl acetate copolymer is 28-35%, and the melt index is 3.0 g/min.
The filler is kaolin.
The preparation method of the flame-retardant fiber comprises the following steps: uniformly mixing 20g of glass fiber and 50g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 5 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 1 percent of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber.
The flame retardant is aluminum hydroxide.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: uniformly mixing 20g of glass fiber and 50g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 5 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 1 percent of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
This comparative example is similar in part to example 3 in the raw materials and preparation method except that the flame retardant aluminum hydroxide is used, i.e., the subsequent modification of the flame retardant is not performed.
Comparative example 3
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 80 parts of chloroprene rubber, 40 parts of ethylene-vinyl acetate copolymer, 20 parts of filler, 25 parts of flame-retardant fiber, 15 parts of flame retardant, 0.5 part of dipentamethylenethiuram tetrasulfide, 3 parts of antioxidant and 5 parts of barium stearate.
The ethylene-vinyl acetate copolymer has a VA content of 28-35% and a melt index of 3.0 g/min.
The filler is kaolin.
The flame-retardant fiber is glass fiber.
The flame retardant is aluminum hydroxide.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
This comparative example is similar in part to example 3 in the raw materials and preparation method except that the glass fiber and the flame retardant aluminum hydroxide are used as they are.
Comparative example 4
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 80 parts of chloroprene rubber, 40 parts of ethylene-vinyl acetate copolymer, 20 parts of filler, 25 parts of flame-retardant fiber, 15 parts of modified flame retardant, 0.5 part of dipentamethylenethiuram tetrasulfide, 3 parts of antioxidant and 5 parts of barium stearate.
The ethylene-vinyl acetate copolymer has a VA content of 28-35% and a melt index of 3.0 g/min.
The filler is kaolin.
The preparation method of the flame-retardant fiber comprises the following steps: adding 20g of glass fiber into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic, adding chitosan accounting for 5 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 1 percent of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at a speed of 200r/min, centrifuging, and drying by a vacuum freeze dryer to obtain the flame-retardant fiber.
The modified flame retardant is modified aluminum hydroxide, the aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid are mixed according to the mass ratio of 1:1, and then dispersed in deionized water with the weight of 3 times that of the aluminum hydroxide and the 2-carboxyethyl phenyl hypophosphorous acid, sodium dodecyl sulfate with the mass of 3% of the mixed solution is added, ultrasonic dispersion is carried out for 3 hours, centrifugal separation and drying are carried out, and the modified flame retardant is obtained.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: adding 20g of glass fiber into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic, adding chitosan and 1% of gamma-aminopropyltriethoxysilane which are 5% of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at a speed of 200r/min, centrifuging, and drying by a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in 5 times of deionized water, adding sodium dodecyl sulfate accounting for 3% of the mass of the mixed solution, performing ultrasonic dispersion for 3 hours, performing centrifugal separation, and drying to obtain a modified flame retardant;
(3) weighing the raw materials according to the parts by weight, firstly placing the chloroprene rubber and the ethylene-vinyl acetate copolymer into an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
In this comparative example, the raw materials and preparation method were the same as in example 3 except that the flame-retardant fiber was not modified with 1-butyl-3-methylimidazole chloride, i.e., 1-butyl-3-methylimidazole chloride was not added during the preparation of the flame-retardant fiber.
Comparative example 5
The flame-retardant corrosion-resistant cable material is prepared from the following raw materials: 80 parts of chloroprene rubber, 40 parts of ethylene-vinyl acetate copolymer, 20 parts of filler, 25 parts of flame-retardant fiber, 15 parts of modified flame retardant, 0.5 part of dipentamethylenethiuram tetrasulfide, 3 parts of antioxidant and 5 parts of barium stearate.
The ethylene-vinyl acetate copolymer has a VA content of 28-35% and a melt index of 3.0 g/min.
The filler is kaolin.
The preparation method of the flame-retardant fiber comprises the following steps: uniformly mixing 20g of glass fiber and 50g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 5 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 1 percent of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber.
The modified flame retardant is modified aluminum hydroxide, the modified aluminum hydroxide is mixed according to the mass ratio of 1:1, and then is dispersed in deionized water with the weight being 3 times that of the modified aluminum hydroxide, sodium dodecyl sulfate with the mass being 3% of that of the mixed solution is added, ultrasonic dispersion is carried out for 3 hours, centrifugal separation is carried out, and drying is carried out, so that the modified flame retardant is obtained.
The median diameter D of the aluminum hydroxide 50 ≈200-300nm。
The antioxidant is antioxidant 1010.
A preparation method of a flame-retardant corrosion-resistant cable material comprises the following steps:
(1) preparing flame-retardant fibers: uniformly mixing 20g of glass fiber and 50g of 1-butyl-3-methylimidazole chloride, adding the mixture into 100ml of 10 volume percent acetic acid solution, uniformly dispersing by ultrasonic wave, adding chitosan accounting for 5 percent of the mass of the mixed solution and gamma-aminopropyltriethoxysilane accounting for 1 percent of the mass of the mixed solution, magnetically stirring and mixing for 2 hours at the constant temperature of 70-80 ℃ at the speed of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: dispersing aluminum hydroxide in deionized water of which the weight is 5 times that of the aluminum hydroxide, adding sodium dodecyl sulfate of which the mass is 3% of that of the mixed solution, performing ultrasonic dispersion for 3 hours, performing centrifugal separation and drying to obtain a modified flame retardant;
(3) weighing the raw materials in parts by weight, firstly placing chloroprene rubber and ethylene-vinyl acetate copolymer in an internal mixer for mixing for 15min, wherein the mixing temperature is 125-; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
This comparative example is similar to example 3 in part for the raw materials and preparation method except that 2-carboxyethylphenyl phosphinic acid is not added as a flame retardant.
Performance testing
Mechanical properties: testing according to GB/T1040-2006;
testing by a cone calorimeter: the test was carried out according to ASTM 1356-90 and ISO5660-1:2005, with specimen dimensions of 100mm X3 mm and a thermal radiation intensity of 50kW/m 2 ；
An oxygen index (LOI) is obtained by cutting an IV type sample according to GBT 2406.2-2009, introducing oxygen and nitrogen mixed gas at the temperature of (23+2) DEG, and testing, wherein the length of the sample is 140mm, the width of the sample is (6.5 soil 0.5) mm, and the thickness of the sample is (3 soil 0.25) mm;
vertical burning performance: testing according to GB/T2408-2008, wherein the size of the sample is 125mm multiplied by 13mm multiplied by 3mm, and 5 sample strips are taken as a group for testing each numbered sample;
the volume resistivity is tested according to GB/T1410-2006, the thickness of a sample is (1.0 mm 0.1) mm, and the test voltage is l kV;
the dielectric strength is tested according to GB/T1408.1-2006, is carried out at the temperature of (20 Shi 2), symmetrical electrodes are adopted, the diameter of each electrode is 25mm, and the radius of an arc at the edge of each electrode is 2.5 mm;
table 1 results of performance testing
TABLE 2 vertical Combustion and Cone calorimeter test results
As can be seen from the data in tables 1-2, the cable materials of examples 1-3 of the present invention exhibit better mechanical properties and flame retardant properties, while comparative example 1/3/4 in which the fiber modification means is changed and comparative example 2/3/5 in which the flame retardant composition is changed both exhibit different reductions in flame retardant properties, mechanical properties and insulation properties, which are caused by the loss of the synergy between the flame retardant fiber and the modified flame retardant, the failure of the flame retardant to interact with the glass fiber, resulting in matrix defects and the reduction in material density. It can also be seen from the internal electron microscopic image of the material test that the material of the example 3 of the invention is uniform in density, while the comparative examples all show different degrees of holes and gaps.
It should be noted that the above-mentioned embodiments are only some of the preferred modes for implementing the invention, and not all of them. Obviously, all other embodiments obtained by persons of ordinary skill in the art based on the above-mentioned embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
Claims (8)
1. The flame-retardant corrosion-resistant cable material is characterized by being prepared from the following raw materials: 50-80 parts of chloroprene rubber, 20-40 parts of ethylene-vinyl acetate copolymer, 10-20 parts of filler, 12-25 parts of flame-retardant fiber, 5-15 parts of modified flame retardant, 0.1-0.5 part of dipentamethylenethiuram tetrasulfide, 1-3 parts of antioxidant and 1-5 parts of barium stearate.
2. The flame retardant and corrosion resistant cable material according to claim 1, wherein said ethylene-vinyl acetate copolymer has a VA content of 28 to 35% and a melt index of 3.0 g/min.
3. The flame-retardant corrosion-resistant cable material according to claim 1, wherein the filler is one or more of white carbon black, talc powder or kaolin.
4. The flame retardant corrosion resistant cable material according to claim 1, wherein the flame retardant fiber is prepared by a method comprising: uniformly mixing 10-20g of glass fiber and 30-50g of chlorinated 1-butyl-3-methylimidazole, adding the mixture into 100ml of acetic acid solution with the volume fraction of 5-10%, uniformly dispersing by ultrasonic wave, adding chitosan with the mass of 1-5% of the mixed solution and gamma-aminopropyltriethoxysilane with the mass of 0.3-1%, stirring and mixing for 1-2h at the constant temperature of 70-80 ℃ and the magnetic force of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber.
5. The flame-retardant corrosion-resistant cable material according to claim 1, wherein the modified flame retardant is modified aluminum hydroxide, and the specific preparation method comprises: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in deionized water with the weight of 3-5 times, adding sodium dodecyl sulfate with the mass of 1-3% of the mixed solution, ultrasonically dispersing for 1-3h, centrifugally separating, and drying to obtain the modified flame retardant.
6. The flame retardant corrosion resistant cable material of claim 5 wherein said aluminum hydroxide has a median particle diameter D 50 ≈200-300nm。
7. The flame retardant corrosion resistant cable material of claim 1 wherein said antioxidant is antioxidant 1010.
8. A method for preparing the flame retardant, corrosion resistant cable material of any one of claims 1 to 7, comprising the steps of:
(1) preparing flame-retardant fibers: uniformly mixing 10-20g of glass fiber and 30-50g of chlorinated 1-butyl-3-methylimidazole, adding the mixture into 100ml of acetic acid solution with the volume fraction of 5-10%, uniformly dispersing by ultrasonic wave, adding chitosan with the mass of 1-5% of the mixed solution and gamma-aminopropyltriethoxysilane with the mass of 0.3-1%, stirring and mixing for 1-2h at the constant temperature of 70-80 ℃ and the magnetic force of 200r/min, centrifuging, and drying in a vacuum freeze dryer to obtain the flame-retardant fiber;
(2) preparing a modified flame retardant: mixing aluminum hydroxide and 2-carboxyethyl phenyl hypophosphorous acid according to the mass ratio of 1:1, dispersing in deionized water with the weight of 3-5 times, adding sodium dodecyl sulfate with the mass of 1-3% of the mixed solution, ultrasonically dispersing for 1-3h, centrifugally separating, and drying to obtain a modified flame retardant;
(3) weighing the raw materials in parts by weight, firstly placing the chloroprene rubber and the ethylene-vinyl acetate copolymer into an internal mixer for mixing for 10-15min, wherein the mixing temperature is 125-130 ℃, and the mixing speed is 200-300 rpm; after complete melting, adding the filler, the flame-retardant fiber, the modified flame retardant, the dipentamethylenethiuram tetrasulfide, the antioxidant and the barium stearate, continuously mixing for 15-30min at the mixing speed of 700-800rpm, and then extruding and granulating by an extruder.
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| CN116262846A (en) * | 2022-12-05 | 2023-06-16 | 浙江万马股份有限公司 | Flame-retardant insulating material for cables and preparation method thereof |
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