CN114989525B - Flame-retardant cable and preparation method thereof - Google Patents
Flame-retardant cable and preparation method thereof Download PDFInfo
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- CN114989525B CN114989525B CN202210913716.5A CN202210913716A CN114989525B CN 114989525 B CN114989525 B CN 114989525B CN 202210913716 A CN202210913716 A CN 202210913716A CN 114989525 B CN114989525 B CN 114989525B
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
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Abstract
The invention relates to the technical field of cable processing, in particular to a flame-retardant cable and a preparation method thereof, wherein the flame-retardant cable comprises, by weight, 30-60 parts of an ethylene-ethyl acrylate copolymer, 10-20 parts of a flame-retardant polyurethane elastomer, 20-30 parts of polypropylene, 2-8 parts of a compatilizer, 30-60 parts of a flame-retardant additive, 1-3 parts of an antioxidant and 1-3 parts of a lubricant. According to the invention, the flame-retardant additive and the flame-retardant polyurethane elastomer are added into the cable matrix, and the blocking effect of the flame-retardant additive, the flame-retardant effect of the flame-retardant polyurethane elastomer and the synergistic effect of the flame-retardant additive and the flame-retardant polyurethane elastomer are utilized to reinforce the coke residues, so that a compact protective layer can be rapidly formed on the surface of the material, the heat and mass transfer between the cable material and the outside and the exchange between the cable material and the combustible gas are isolated, and the cable has excellent flame-retardant performance.
Description
Technical Field
The invention relates to the technical field of cable processing, in particular to a flame-retardant cable and a preparation method thereof.
Background
The insulation and sheath material of the electric wire and the electric cable is commonly called electric wire and electric cable material, and is called cable material for short, and is widely applied to various fields, and the main material of the cable material used in the market at present is plastic, rubber or nylon, wherein the plastic material is the most widely used. The demand of electric wires and cables has the market of cable materials, and with the large-area upgrading and reconstruction of communication facilities in recent years, the demand of electric wire and cable products is huge, so the demand of the cable materials is increased. The essential component of the cable material that uses the most at present is polyvinyl chloride, and its temperature resistance is relatively poor, uses the life that can shorten the cable material under the higher condition of temperature, contains halogen in the polyvinyl chloride cable material moreover, and the burning of cable material can produce the pollution to the environment, the processing of the later stage cable material of being not convenient for.
With the increasing awareness of people about fire accidents caused by aging of electric wires and cables, the requirements on the environmental friendliness of the electric wires and cables are higher and higher. The harm of toxic smoke generated by halogen combustion to human bodies and the environment is well known, so that low smoke, no halogen, flame retardance, environmental protection, high temperature resistance and the like become the development direction of the wire and cable industry. For example, chinese patent CN2015101317507 discloses a yellowing-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable rubber material and a preparation method thereof, wherein the cable rubber material contains 60-80 parts by weight of polyether polyurethane elastomer; 0.01-5 parts of yellowing resistant agent; 5-15 parts of a phosphorus flame retardant; 10-30 parts of nitrogen flame retardant; 0.01-3 parts of antioxidant. The invention also provides a preparation method of the yellowing-resistant halogen-free flame-retardant thermoplastic polyurethane elastomer cable rubber material; the cable sizing material has good yellowing resistance, the delta YI is less than 1.5, the cable sizing material is in a 0-level non-discoloration grade, the insulating material of the wire has excellent performance in all aspects, the hydrolysis resistance is outstanding, and the flame retardance passes a VW-1 test; however, the oxygen index of the cable rubber is only 32, and although the cable rubber belongs to a first-grade flame-retardant rubber, the flame retardant property of the cable rubber is general in the actual use process and cannot meet the requirement in some special places.
Disclosure of Invention
The invention aims to provide a flame-retardant cable and a preparation method thereof, so as to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a flame-retardant cable comprises, by weight, 30-60 parts of an ethylene-ethyl acrylate copolymer, 10-20 parts of a flame-retardant polyurethane elastomer, 20-30 parts of polypropylene, 2-8 parts of a compatilizer, 30-60 parts of a flame-retardant additive, 1-3 parts of an antioxidant and 1-3 parts of a lubricant.
As a further preferable scheme of the invention, the compatilizer is at least one of maleic anhydride grafted ethylene-vinyl acetate copolymer, maleic anhydride grafted ethylene-octene copolymer and maleic anhydride grafted ethylene-methyl acrylate copolymer;
the antioxidant is selected from 3-5:1 a mixture of 1010 and 168 antioxidants;
the lubricant is at least one of polyethylene wax, ethylene bis-stearic acid amide and calcium stearate.
As a further preferred embodiment of the present invention, the preparation method of the flame retardant polyurethane elastomer is as follows:
firstly, weighing equal amounts of boron nitride and water-soluble ammonium polyphosphate, adding the boron nitride into deionized water, carrying out ultrasonic treatment for 6-10h, standing for 2-5h, taking upper-layer liquid to obtain a boron nitride suspension, adding the water-soluble ammonium polyphosphate into the deionized water, heating to 80-90 ℃, carrying out ultrasonic treatment for 20-30min to obtain an ammonium polyphosphate aqueous solution, adding the boron nitride suspension into the ammonium polyphosphate aqueous solution, reacting for 1-3h, carrying out suction filtration on the obtained product, washing with water, and drying to obtain pretreated boron nitride;
and secondly, dispersing polyester diol and pretreated boron nitride at a high speed for 30-50min at 60-70 ℃, heating to 100-120 ℃, vacuum dehydrating for 2-3h, cooling to 60-70 ℃, then rapidly adding hexamethylene diisocyanate, reacting for 30-50min, heating to 80-90 ℃, preserving heat for 2-3h, stirring and heating the formed prepolymer to 120-130 ℃, vacuum defoaming for 1-5min, then adding a chain extender BDO and a catalyst stannous octoate, rapidly stirring and mixing, pouring into a preheated mold, placing into an oven for heat treatment, and standing at room temperature for 20-25h after the treatment is finished to obtain the flame-retardant polyurethane elastomer.
As a further preferable embodiment of the present invention, in the first step, the ratio of boron nitride to deionized water in the boron nitride suspension is (5-10) g: (500-800) mL;
in the ammonium polyphosphate water solution, the proportion of water-soluble ammonium polyphosphate to deionized water is (5-10) g: (100-200) mL;
in the preparation process of the pretreated boron nitride, the boron nitride and the water-soluble ammonium polyphosphate are used in equal amount.
As a further preferable embodiment of the present invention, in the second step, the ratio of the polyester diol, the pretreated boron nitride, the hexamethylene diisocyanate, the chain extender BDO, and the catalyst stannous octoate is (10-15) g: (1.2-1.8) g: (20-26) g: (1-2) g: (0.1-0.5) g;
the preheating temperature of the die is 70-80 ℃;
the heat treatment temperature is 110-120 ℃, and the heat treatment time is 10-15h.
As a further preferable scheme of the invention, the preparation method of the flame retardant additive comprises the following steps:
step one, pretreating composite hydrotalcite to obtain pretreated hydrotalcite, dispersing the pretreated hydrotalcite in a proper amount of deionized water, then magnetically stirring for 20-30min at 80-90 ℃ under a nitrogen atmosphere to obtain pretreated hydrotalcite dispersion liquid, meanwhile, dissolving triazine sulfonate in a proper amount of deionized water with the pH of 6.0-6.5, then rapidly adding the triazine sulfonate into the pretreated hydrotalcite dispersion liquid, violently stirring the mixed liquid at 80-90 ℃ for 8-12h under a nitrogen atmosphere, centrifuging the product, washing the product to be neutral, and drying to obtain intercalation modified composite hydrotalcite;
step two, performing amination modification treatment on the intercalation modified composite hydrotalcite by using KH550 to obtain amination composite hydrotalcite, dispersing the amination composite hydrotalcite in tetrahydrofuran to obtain suspension with the concentration of 10-30g/L, performing ultrasonic treatment for 1-3h, adding hexaamino cyclotriphosphazene and acid-binding agent EDTA into the suspension, stirring and reacting for 8-10h under heating and stirring conditions in a nitrogen environment, filtering and washing a product, and drying to obtain phosphazene grafted composite hydrotalcite;
and step three, adding the phosphazene grafted composite hydrotalcite and distilled water into a container, heating to 70-80 ℃, stirring for 2-5h, adding the single-ion quaternary ammonium salt after uniform dispersion, continuing stirring for 23-28h, filtering the product, repeatedly washing with 80-90 ℃ distilled water, and drying to constant weight to obtain the flame retardant additive.
As a further preferable embodiment of the present invention, in the first step, the preparation method of the composite hydrotalcite is as follows:
step one, at room temperature, dropwise adding an orthophosphoric acid solution into a mixed solution of calcium hydroxide and zinc nitrate hexahydrate, keeping the pH value at 10.5-11.5 by using ammonia water, continuously stirring at 150-200r/min for 18-23h after mixing, then standing for 10-15d, carrying out heat treatment at 125-130 ℃ for 1-3h after centrifugation to obtain modified hydroxyapatite;
step two, mixing the raw materials in a mass ratio of 1:2-6 of modified hydroxyapatite and magnalium hydrotalcite are put into distilled water to obtain mixed suspension, and the mixed suspension is stirred under the assistance of ultrasound and magnetic force, wherein the ultrasound intensity is 0.5-1.5W/cm 2 Magnetic stirring at 500-800r/min, mixing and reacting for 1-5h, centrifuging, cleaning, and drying to obtain the composite hydrotalcite.
As a further preferable scheme of the invention, in the step one, the pretreatment method of the composite hydrotalcite is as follows, the composite hydrotalcite is placed in a muffle furnace, and the temperature is raised to 500-560 ℃ at the rate of 5-10 ℃/min, and the composite hydrotalcite is continuously calcined for 3-6 h;
in the preparation process of the intercalation modified composite hydrotalcite, the mass ratio of the pretreated hydrotalcite to the triazine sulfonate is (2-6): (3-5).
In a further preferred embodiment of the present invention, in the second step, the mass ratio of the aminated composite hydrotalcite, hexaaminocyclotriphosphazene and acid-binding agent EDTA is (10-30): (3-5): (0.8-1.2);
the heating temperature is 65-70 ℃, and the stirring speed is 50-100r/min.
As a further preferable scheme of the present invention, in the second step, the amination modification treatment method of the intercalation modified composite hydrotalcite is as follows:
dispersing 5-10g of intercalation modified composite hydrotalcite in 300-500mL of a mixture of distilled water and ethanol according to a volume ratio of 3-4:1 at 50-60 ℃ for 30-50min at 100-160r/min to obtain a suspension, dissolving 1.5-3.5gKH550 in 150-200mL of a mixture of distilled water and ethanol at a volume ratio of 8-9:1 to obtain KH550 solution, slowly adding the KH550 solution into the suspension under the condition of vigorous stirring at 800-1000r/min, adding acetic acid to adjust the pH value to 3-4, continuously carrying out side reaction for 25-30h at 90-95 ℃ and under the nitrogen atmosphere, filtering the obtained product, repeatedly washing with distilled water, and drying at 80-90 ℃ for 20-25h under vacuum to obtain the aminated composite hydrotalcite.
In a further preferred embodiment of the present invention, in step three, the ratio of the phosphazene graft composite hydrotalcite, distilled water and the single-ion type quaternary ammonium salt is (40-100) g: (800-1500) mL: (5-15) g.
In a further preferred embodiment of the present invention, in the third step, the mono-ionic quaternary ammonium salt is any one of a mono-ionic quaternary ammonium salt PAAB and a mono-ionic quaternary ammonium salt PAEAC.
A preparation method of a flame-retardant cable comprises the following steps:
mixing the raw materials, placing the mixture into an internal mixer, carrying out internal mixing for 5-10min at the temperature of 100-150 ℃, then mixing the mixture by using a double-screw extruder, preparing a finished cable material product by using an extruder granulation production line, wherein the extrusion temperature is set to 180-210 ℃, and then pouring the finished cable material product into an extruder to prepare the required flame-retardant cable.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the triazine-based compound is introduced into the interlayer of the hydrotalcite by adopting a roasting recovery method, so that the hydrotalcite can keep a layered structure, the interlayer spacing is increased, the subsequent single-ion type quaternary ammonium salt is favorably dispersed and attached to the interlayer of the hydrotalcite, and meanwhile, triazine-sulfonic acid chains in the triazine-based compound can be decomposed at high temperature to generate coke residues, a good protective layer can be formed on the surface of the material to form a blocking effect, and the material can be effectively isolated from the exchange of external heat mass transferred to combustible gas, so that the material has good flame retardant property; secondly, by utilizing the surface modification performance and the synergistic flame retardant performance of hexa-amino cyclotriphosphazene, the phosphazene is grafted to the surface of the hydrotalcite through a chemical bond, so that on one hand, the compatibility between the hydrotalcite and a polymer can be improved, the hydrotalcite has better dispersibility, the hydrotalcite can be uniformly distributed in a material matrix, and meanwhile, strong interface interaction is generated between the hydrotalcite obtained after grafting modification and the polymer matrix, so that the thermal movement of a polymer chain can be limited, the thermal degradation activation energy of the material is increased, and in addition, the rapid formation of a protective layer on the surface of the material by coke residues can be promoted, so that the flame retardant performance of the material is further improved; in addition, the single-ion quaternary ammonium salt is dispersed and intercalated between layers of the hydrotalcite, so that a protective layer formed by coke residues on the surface of the material can be strengthened, the compactness and hardness of the protective layer structure are improved, the protective layer is not easy to crack, fall off and the like under the action of thermal stress, the protective layer formed by the coke residues can be efficiently and stably attached to the material, and the flame retardant property of the material is further enhanced.
In the invention, zinc ions are utilized to replace part of calcium ions in the hydroxyapatite in a zinc doping mode, so that the performance of the hydroxyapatite is changed, the size and the crystallinity of crystal nuclei of the hydroxyapatite are reduced, the hydroxyapatite is easy to attach to the magnesium-aluminum hydrotalcite to form a compound, and the compatibility between the zinc-doped hydroxyapatite and a polymer is improved, so that the compound hydrotalcite can be uniformly dispersed in a polymer matrix.
According to the invention, ammonium polyphosphate is adopted to modify the surface of boron nitride, and then the boron nitride is introduced into polyurethane, and the boron nitride nanosheets form a lamellar barrier layer in a polyurethane matrix, so that the barrier effect is achieved, the heat transfer path is effectively prolonged, the heat transfer rate is slowed down, and the heat loss in the transfer process is increased, so that the heat and mass transfer efficiency of the material matrix in the outside is reduced, and the flame retardant property of the material matrix can be effectively improved.
According to the invention, the flame-retardant additive and the flame-retardant polyurethane elastomer are added into the cable matrix, and the blocking effect of the flame-retardant additive, the flame-retardant effect of the flame-retardant polyurethane elastomer and the synergistic effect of the flame-retardant additive and the flame-retardant polyurethane elastomer are utilized to reinforce the coke residues, so that a compact protective layer can be rapidly formed on the surface of the material, the heat and mass transfer between the cable material and the outside and the exchange between the cable material and the combustible gas are isolated, and the cable has excellent flame-retardant performance.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a graph showing the effect of the amount of flame retardant additive added on the tensile strength of a cable.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and its several details are capable of modifications and/or changes in various obvious respects, all without departing from the spirit of the present invention.
It should be understood that the process equipment or devices not specifically mentioned in the following examples and experimental examples are conventional in the art.
Example 1
A flame-retardant cable comprises, by weight, 30 parts of an ethylene-ethyl acrylate copolymer, 10 parts of a flame-retardant polyurethane elastomer, 20 parts of polypropylene, 2 parts of a compatilizer, 30 parts of a flame-retardant additive, 1 part of an antioxidant and 1 part of a lubricant;
wherein the compatilizer is maleic anhydride grafted ethylene-vinyl acetate copolymer;
the antioxidant is prepared from the following components in percentage by mass of 3:1 of a mixture of 1010 antioxidant and 168 antioxidant;
the lubricant is polyethylene wax;
the preparation method of the flame-retardant cable comprises the following steps:
mixing the raw materials, placing the mixture into an internal mixer, carrying out internal mixing at 100 ℃ for 5min, then mixing the mixture by using a double-screw extruder, preparing a finished cable material by using an extruder granulation production line, setting the extrusion temperature to be 180 ℃, and then pouring the finished cable material into an extruder to prepare the required flame-retardant cable.
The preparation method of the flame retardant additive comprises the following steps:
step one, placing composite hydrotalcite in a muffle furnace, heating to 500 ℃ at a speed of 5 ℃/min, continuously calcining for 3h to obtain pre-treated hydrotalcite, dispersing 2g of the pre-treated hydrotalcite in 500mL of deionized water, then magnetically stirring for 20min at 80 ℃ under a nitrogen atmosphere to obtain a pre-treated hydrotalcite dispersion liquid, simultaneously dissolving 3g of triazine sulfonate in 70mL of deionized water with a pH value of 6.0, then rapidly adding the triazine sulfonate into the pre-treated hydrotalcite dispersion liquid, violently stirring the mixed liquid for 8h at 80 ℃ under the nitrogen atmosphere at 1500r/min, centrifuging the product, washing to be neutral, and drying for 20h at 60 ℃ to obtain intercalation modified composite hydrotalcite;
step two, dispersing 5g of intercalation modified composite hydrotalcite in 300mL of a mixture of distilled water and ethanol according to a volume ratio of 3:1 at 50 ℃ for 30min with constant stirring at 100r/min, to give a suspension, 1.5g kh550 was dissolved in 150mL of a solvent mixture of distilled water and ethanol in a volume ratio of 8:1 to obtain a KH550 solution, slowly adding the KH550 solution into the suspension under the vigorous stirring of 800r/min, adding acetic acid to adjust the pH to 3, continuously carrying out side reaction for 25 hours at 90 ℃ and under the nitrogen atmosphere, filtering the obtained product, repeatedly washing the product with distilled water, and drying the product for 20 hours at 80 ℃ under vacuum to obtain aminated composite hydrotalcite;
dispersing 10g of aminated composite hydrotalcite in tetrahydrofuran to obtain suspension with the concentration of 10g/L, carrying out ultrasonic treatment for 1h by 200W, adding 3g of hexaaminocyclophosphazene and 0.8g of acid-binding agent EDTA into the suspension, stirring and reacting for 8h at 65 ℃ and 50r/min in a nitrogen environment, filtering and washing a product, and drying at 80 ℃ for 10h to obtain phosphazene grafted composite hydrotalcite;
step four, adding 40g of phosphazene grafted composite hydrotalcite and 800mL of distilled water into a container, heating to 70 ℃, stirring for 2 hours at 500r/min, adding 5g of single-ion type quaternary ammonium salt PAAB after uniform dispersion, continuing stirring for 23 hours, filtering the product, repeatedly washing with 80 ℃ distilled water, and drying at 70 ℃ under vacuum to constant weight to obtain the flame retardant additive.
The preparation method of the composite hydrotalcite comprises the following steps:
step one, at room temperature, dropwise adding an orthophosphoric acid solution into a mixed solution of calcium hydroxide and zinc nitrate hexahydrate, keeping the pH value at 10.5 by using ammonia water, continuously stirring for 18h at 150r/min after mixing, standing for 10d, and carrying out heat treatment for 1h at 125 ℃ after centrifugation to obtain modified hydroxyapatite;
step two, mixing the raw materials in a mass ratio of 1:2, placing the modified hydroxyapatite and the magnalium hydrotalcite in distilled water to obtain mixed suspension, and stirring under the assistance of ultrasound and magnetic force, wherein the ultrasound intensity is 0.5W/cm 2 And (3) mixing and reacting for 1h at a magnetic stirring speed of 500r/min, centrifugally separating, cleaning and drying to obtain the composite hydrotalcite.
The preparation method of the flame-retardant polyurethane elastomer comprises the following steps:
step one, adding 5g of boron nitride into 500mL of deionized water, carrying out ultrasonic treatment at 200W for 6h, standing for 2h, taking upper-layer liquid to obtain a boron nitride suspension, adding 5g of water-soluble ammonium polyphosphate into 100mL of deionized water, heating to 80 ℃, carrying out ultrasonic treatment at 200W for 20min to obtain an ammonium polyphosphate aqueous solution, adding the boron nitride suspension into the ammonium polyphosphate aqueous solution, reacting for 1h, carrying out suction filtration on the obtained product, washing with water, and drying to obtain pretreated boron nitride;
and secondly, dispersing 10g of polyester diol and 1.2g of pretreated boron nitride at 60 ℃ at a high speed of 8000r/min for 30min, heating to 100 ℃ for vacuum dehydration for 2h, cooling to 60 ℃, then rapidly adding 20g of hexamethylene diisocyanate, reacting for 30min, heating to 80 ℃, preserving heat for 2h, heating the formed prepolymer to 120 ℃ under the stirring condition of 100r/min, carrying out vacuum defoaming for 1min, then adding 1g of chain extender BDO and 0.1g of catalyst stannous octoate, rapidly stirring and mixing, pouring into a mold preheated to 70 ℃, placing into a 110 ℃ oven for heat treatment for 10h, and standing at room temperature for 20h after the treatment is finished to obtain the flame-retardant polyurethane elastomer.
Example 2
A flame-retardant cable comprises, by weight, 50 parts of an ethylene-ethyl acrylate copolymer, 15 parts of a flame-retardant polyurethane elastomer, 25 parts of polypropylene, 5 parts of a compatilizer, 45 parts of a flame-retardant additive, 2 parts of an antioxidant and 2 parts of a lubricant;
wherein the compatilizer is maleic anhydride grafted ethylene-octene copolymer;
the antioxidant is prepared from the following components in percentage by mass of 4:1 of a mixture of 1010 antioxidant and 168 antioxidant;
the lubricant is ethylene bis stearamide;
the preparation method of the flame-retardant cable comprises the following steps:
mixing the raw materials, placing the mixture into an internal mixer, carrying out internal mixing at 120 ℃ for 8min, then carrying out mixing by using a double-screw extruder, preparing a finished cable material by using an extruder granulation production line, setting the extrusion temperature to be 200 ℃, and then pouring the finished cable material into an extruder to prepare the required flame-retardant cable.
The preparation method of the flame retardant additive comprises the following steps:
step one, placing composite hydrotalcite in a muffle furnace, heating to 520 ℃ at the temperature of 7 ℃/min, continuously calcining for 5h to obtain pre-treated hydrotalcite, dispersing 3g of the pre-treated hydrotalcite in 700mL of deionized water, then magnetically stirring for 25min at the temperature of 85 ℃ under the nitrogen atmosphere to obtain a pre-treated hydrotalcite dispersion liquid, simultaneously dissolving 4g of triazine sulfonate in 100mL of deionized water with the pH of 6.2, then rapidly adding the triazine sulfonate into the pre-treated hydrotalcite dispersion liquid, violently stirring the mixed liquid for 10h at the temperature of 85 ℃ under the nitrogen atmosphere at 2000r/min, centrifuging the product, washing to be neutral, and drying for 23h at the temperature of 70 ℃ to obtain the intercalation modified composite hydrotalcite;
step two, dispersing 7g of intercalation modified composite hydrotalcite in 400mL of distilled water and ethanol according to the volume ratio of 3.5:1 at 55 ℃ for 40min with continuous stirring at 130r/min, to give a suspension, 2.5g kh550 was dissolved in 170mL of a solution of ethanol in water, distilled water and ethanol in a volume ratio of 8.5:1 to obtain a KH550 solution, slowly adding the KH550 solution into the suspension under vigorous stirring at 900r/min, adding acetic acid to adjust the pH to 3.5, continuously carrying out side reaction for 28h at 92 ℃ and under a nitrogen atmosphere, filtering the obtained product, repeatedly washing with distilled water, and drying at 85 ℃ for 23h under vacuum to obtain aminated composite hydrotalcite;
dispersing 20g of aminated composite hydrotalcite in tetrahydrofuran to obtain a suspension with the concentration of 20g/L, carrying out ultrasonic treatment for 2h by 250W, adding 4g of hexaaminocyclophosphazene and 1g of acid-binding agent EDTA into the suspension, stirring and reacting for 9h at 68 ℃ and 70r/min in a nitrogen environment, filtering and washing a product, and drying at 85 ℃ for 12h to obtain phosphazene grafted composite hydrotalcite;
and step four, adding 60g of phosphazene grafted composite hydrotalcite and 1200mL of distilled water into a container, heating to 75 ℃, stirring for 3h at 550r/min, adding 10g of single-ion type quaternary ammonium salt PAAB after uniform dispersion, continuing stirring for 25h, filtering a product, repeatedly washing with 85 ℃ distilled water, and drying at 75 ℃ in vacuum to constant weight to obtain the flame retardant additive.
The preparation method of the composite hydrotalcite comprises the following steps:
step one, at room temperature, dropwise adding an orthophosphoric acid solution into a mixed solution of calcium hydroxide and zinc nitrate hexahydrate, keeping the pH value at 11 by using ammonia water, continuously stirring for 20 hours at a speed of 170r/min after mixing, then standing for 12d, carrying out heat treatment for 2 hours at a temperature of 126 ℃ after centrifugation to obtain modified hydroxyapatite;
step two, mixing the raw materials in a mass ratio of 1:5, placing the modified hydroxyapatite and the magnesium aluminum hydrotalcite in distilled water to obtain mixed suspension, and stirring under the assistance of ultrasound and magnetic force, wherein the ultrasound intensity is 1W/cm 2 And (3) mixing and reacting for 3h at the magnetic stirring speed of 600r/min, centrifugally separating, cleaning and drying to obtain the composite hydrotalcite.
The preparation method of the flame-retardant polyurethane elastomer comprises the following steps:
step one, adding 7g of boron nitride into 700mL of deionized water, carrying out 250W ultrasonic treatment for 8h, standing for 3h, taking upper-layer liquid to obtain a boron nitride suspension, adding 7g of water-soluble ammonium polyphosphate into 150mL of deionized water, heating to 85 ℃, carrying out 250W ultrasonic treatment for 25min to obtain an ammonium polyphosphate aqueous solution, adding the boron nitride suspension into the ammonium polyphosphate aqueous solution, reacting for 2h, carrying out suction filtration on the obtained product, washing with water, and drying to obtain pretreated boron nitride;
and step two, dispersing 12g of polyester diol and 1.5g of pretreated boron nitride at 65 ℃ at a high speed of 9000r/min for 40min, heating to 110 ℃ for vacuum dehydration for 2.5h, cooling to 65 ℃, then rapidly adding 23g of hexamethylene diisocyanate, reacting for 40min, heating to 85 ℃, keeping the temperature for reaction for 2.5h, heating the formed prepolymer to 125 ℃ under the stirring condition of 120r/min, defoaming for 3min in vacuum, then adding 1.5g of chain extender BDO and 0.3g of catalyst stannous octoate, rapidly stirring and mixing, pouring into a mold preheated to 75 ℃, placing into a 115 ℃ oven for heat treatment for 12h, standing at room temperature for 23h after the treatment is finished, and obtaining the flame-retardant polyurethane elastomer.
Example 3
A flame-retardant cable comprises, by weight, 60 parts of an ethylene-ethyl acrylate copolymer, 20 parts of a flame-retardant polyurethane elastomer, 30 parts of polypropylene, 8 parts of a compatilizer, 60 parts of a flame-retardant additive, 3 parts of an antioxidant and 3 parts of a lubricant;
wherein the compatilizer is maleic anhydride grafted ethylene-methyl acrylate copolymer;
the antioxidant is prepared from the following components in percentage by mass: 1 of a mixture of 1010 antioxidant and 168 antioxidant;
the lubricant is calcium stearate;
the preparation method of the flame-retardant cable comprises the following steps:
mixing the raw materials, placing the mixture into an internal mixer, carrying out internal mixing for 10min at the temperature of 150 ℃, then carrying out mixing by using a double-screw extruder, preparing a finished cable material by using an extruder granulation production line, setting the extrusion temperature to be 210 ℃, and then pouring the finished cable material into an extruder to prepare the required flame-retardant cable.
The preparation method of the flame retardant additive comprises the following steps:
step one, placing composite hydrotalcite in a muffle furnace, heating to 560 ℃ at a rate of 10 ℃/min, continuously calcining for 6h to obtain pre-treated hydrotalcite, dispersing 6g of the pre-treated hydrotalcite in 800mL of deionized water, then magnetically stirring for 30min at a temperature of 90 ℃ under a nitrogen atmosphere to obtain a pre-treated hydrotalcite dispersion liquid, simultaneously dissolving 5g of triazine sulfonate in 120mL of deionized water with a pH value of 6.5, then rapidly adding the triazine sulfonate into the pre-treated hydrotalcite dispersion liquid, violently stirring the mixed liquid for 12h at a temperature of 90 ℃ under a nitrogen atmosphere at 3000r/min, centrifuging the product, washing to be neutral, and drying for 25h at a temperature of 80 ℃ to obtain intercalated modified composite hydrotalcite;
step two, dispersing 10g of intercalation modified composite hydrotalcite in 500mL of distilled water and ethanol according to the volume ratio of 4:1 at 60 ℃ for 50min with continuous stirring at 160r/min, to give a suspension, 3.5gkh550 was dissolved in 200mL of a solvent mixture of distilled water and ethanol in a volume ratio of 9:1 to obtain KH550 solution, slowly adding the KH550 solution into the suspension under the vigorous stirring of 1000r/min, adding acetic acid to adjust the pH to 4, continuously performing side reaction for 30 hours at 95 ℃ and under the nitrogen atmosphere, filtering the obtained product, repeatedly washing with distilled water, and drying at 90 ℃ for 25 hours under vacuum to obtain aminated composite hydrotalcite;
dispersing 30g of aminated composite hydrotalcite in tetrahydrofuran to obtain a suspension with the concentration of 30g/L, carrying out ultrasonic treatment for 3h by 300W, then adding 5g of hexaaminocyclophosphazene and 1.2g of acid-binding agent EDTA into the suspension, stirring and reacting for 10h at 70 ℃ and 100r/min in a nitrogen environment, filtering and washing a product, and drying for 15h at 90 ℃ to obtain phosphazene grafted composite hydrotalcite;
and step four, adding 100g of phosphazene grafted composite hydrotalcite and 1500mL of distilled water into a container, heating to 80 ℃, stirring for 5h at 600r/min, adding 15g of single-ion type quaternary ammonium salt PAAB after uniform dispersion, continuing stirring for 28h, filtering the product, repeatedly washing with 90 ℃ distilled water, and drying at 80 ℃ in vacuum to constant weight to obtain the flame retardant additive.
The preparation method of the composite hydrotalcite comprises the following steps:
step one, at room temperature, dropwise adding an orthophosphoric acid solution into a mixed solution of calcium hydroxide and zinc nitrate hexahydrate, keeping the pH value at 11.5 by using ammonia water, continuously stirring at 200r/min for 23 hours after mixing, standing for 15 days, and carrying out heat treatment at 130 ℃ for 3 hours after centrifuging to obtain modified hydroxyapatite;
step two, mixing the raw materials in a mass ratio of 1:6, placing the modified hydroxyapatite and the magnalium hydrotalcite in distilled water to obtain mixed suspension, and stirring under the assistance of ultrasound and magnetic force, wherein the ultrasound intensity is 1.5W/cm 2 And (3) mixing and reacting for 5 hours at a magnetic stirring speed of 800r/min, centrifugally separating, cleaning and drying to obtain the composite hydrotalcite.
The preparation method of the flame-retardant polyurethane elastomer comprises the following steps:
adding 10g of boron nitride into 800mL of deionized water, carrying out ultrasonic treatment at 300W for 10h, standing for 5h, taking upper-layer liquid to obtain a boron nitride suspension, adding 10g of water-soluble ammonium polyphosphate into 200mL of deionized water, heating to 90 ℃, carrying out ultrasonic treatment at 300W for 30min to obtain an ammonium polyphosphate aqueous solution, adding the boron nitride suspension into the ammonium polyphosphate aqueous solution, reacting for 3h, carrying out suction filtration on the obtained product, washing with water, and drying to obtain pretreated boron nitride;
and secondly, dispersing 15g of polyester diol and 1.8g of pretreated boron nitride at 70 ℃ at a high speed of 10000r/min for 50min, heating to 120 ℃ for vacuum dehydration for 3h, cooling to 70 ℃, then rapidly adding 26g of hexamethylene diisocyanate, reacting for 50min, heating to 90 ℃, preserving heat for reaction for 3h, heating the formed prepolymer to 130 ℃ under the stirring condition of 150r/min, carrying out vacuum defoaming for 5min, then adding 2g of chain extender BDO and 0.5g of catalyst stannous octoate, rapidly stirring and mixing, pouring into a mold preheated to 80 ℃, placing into a 120 ℃ oven for heat treatment for 15h, and standing at room temperature for 25h after treatment is finished to obtain the flame-retardant polyurethane elastomer.
Comparative example 1: this comparative example is essentially the same as example 1 except that it does not contain a flame retardant polyurethane elastomer.
Comparative example 2: this comparative example is essentially the same as example 1 except that no flame retardant additive is included.
Comparative example 3: this comparative example is essentially the same as example 1 except that magnesium aluminum hydrotalcite was used in place of the composite hydrotalcite during the flame retardant additive preparation.
Test experiment 1:
the performance of the cables of examples 1 to 3 and comparative examples 1 to 3 was measured using the cables of examples 1 to 3 and CN2015101317507 of the prior art and the cable of example 1 of CN2015101317507 as a technical standard, and the performance of the cables of examples 1 to 3 and comparative examples 1 to 3 was measured using the test result of the cable of example 1 of CN2015101317507 of the prior art as a technical standard, and the results are as follows.
TABLE 1 oxygen index test
Technical standard | Example 1 | Example 2 | Example 3 | |
Oxygen index% | 32 | 38 | 42 | 41 |
Technical standard | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Oxygen index% | 32 | 33 | 28 | 35 |
Table 2 tensile strength testing
Technical standard | Example 1 | Example 2 | Example 3 | |
Tensile strength MPa | 22.1 | 26.5 | 28.7 | 27.3 |
Technical standard | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Tensile strength MPa | 22.1 | 20.3 | 23.5 | 24.6 |
TABLE 3 aging test (113. + -. 2 ℃ X168 h)
Technical standard | Example 1 | Example 2 | Example 3 | |
Tensile Strength (percent defective) | 93.2% | 96.7 | 97.5 | 97.1 |
Technical standard | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Tensile Strength (percent defective) | 93.2% | 89.1 | 94.3 | 95.2 |
TABLE 4 Heat distortion test (121. + -. 2 ℃ C.. Times.1h, 400g)
Technical standard | Example 1 | Example 2 | Example 3 | |
Appearance condition | Without cracking | Without cracking | Without cracking | Without cracking |
Technical standard | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Appearance condition | Without cracking | Few cracks | Few cracks | Few cracks |
The test results in the table show that the cable provided by the invention has excellent flame retardant property and mechanical strength, and the loss rate of the mechanical property is low in a high-temperature environment, so that the normal use requirement can be still met.
Test experiment 2:
based on example 1, the effect of different addition amounts of the flame retardant additive on the tensile strength of the cable is compared, as shown in fig. 1, and as can be seen from fig. 1, the tensile strength of the cable is gradually increased with the increase of the addition amount of the flame retardant additive, but when the addition amount of the flame retardant additive exceeds a certain value, the tensile strength of the cable tends to decrease.
The above description is only an example and an experimental example of the present invention, and is not intended to limit the scope of the present invention, and all the equivalent structures or equivalent flow transformations made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (6)
1. The flame-retardant cable is characterized by comprising 30-60 parts by weight of ethylene-ethyl acrylate copolymer,
10-20 parts of flame-retardant polyurethane elastomer, 20-30 parts of polypropylene, 2-8 parts of compatilizer, 30-60 parts of flame-retardant additive, 1-3 parts of antioxidant and 1-3 parts of lubricant;
the preparation method of the flame-retardant polyurethane elastomer comprises the following steps:
firstly, weighing equal amounts of boron nitride and water-soluble ammonium polyphosphate, adding the boron nitride into deionized water, carrying out ultrasonic treatment for 6-10h, standing for 2-5h, taking upper-layer liquid to obtain a boron nitride suspension, adding the water-soluble ammonium polyphosphate into the deionized water, heating to 80-90 ℃, carrying out ultrasonic treatment for 20-30min to obtain an ammonium polyphosphate aqueous solution, adding the boron nitride suspension into the ammonium polyphosphate aqueous solution, reacting for 1-3h, carrying out suction filtration on the obtained product, washing with water, and drying to obtain pretreated boron nitride;
dispersing polyester diol and pretreated boron nitride at a high speed for 30-50min at 60-70 ℃, heating to 100-120 ℃, vacuum dehydrating for 2-3h, cooling to 60-70 ℃, then rapidly adding hexamethylene diisocyanate, reacting for 30-50min, heating to 80-90 ℃, preserving heat for 2-3h, stirring and heating the formed prepolymer to 120-130 ℃, vacuum defoaming for 1-5min, then adding a chain extender BDO and a catalyst stannous octoate, rapidly stirring and mixing, pouring into a preheated mold, placing into an oven for heat treatment, and standing at room temperature for 20-25h after the treatment is finished to obtain a flame-retardant polyurethane elastomer;
the preparation method of the flame retardant additive comprises the following steps:
firstly, pretreating the composite hydrotalcite to obtain pretreated hydrotalcite, dispersing the pretreated hydrotalcite in a proper amount of deionized water, then magnetically stirring for 20-30min at 80-90 ℃ under a nitrogen atmosphere to obtain pretreated hydrotalcite dispersion liquid, simultaneously dissolving triazine sulfonate in a proper amount of deionized water with the pH of 6.0-6.5, then rapidly adding the triazine sulfonate into the pretreated hydrotalcite dispersion liquid, violently stirring the mixed liquid at 80-90 ℃ for 8-12h under a nitrogen atmosphere, centrifuging the product, washing to neutrality, and drying to obtain the intercalation modified composite hydrotalcite;
in the first step, the preparation method of the composite hydrotalcite is as follows:
firstly, at room temperature, dropwise adding an orthophosphoric acid solution into a mixed solution of calcium hydroxide and zinc nitrate hexahydrate, keeping the pH value at 10.5-11.5 by using ammonia water, continuously stirring for 18-23h at 150-200r/min after mixing, then standing for 10-15d, carrying out heat treatment for 1-3h at 125-130 ℃ after centrifugation, and obtaining modified hydroxyapatite;
secondly, mixing the components in a mass ratio of 1:2-6 of modified hydroxyapatite and magnesium-aluminum hydrotalcite are placed in distilled water to obtain mixed suspension, under the assistance of ultrasonic and magnetic stirring, wherein the ultrasonic intensity is 0.5-1.5W/cm < 2 >, the magnetic stirring speed is 500-800r/min, the mixed suspension is subjected to mixing reaction for 1-5h, centrifugal separation is carried out, and composite hydrotalcite is obtained after cleaning and drying;
the pretreatment method of the composite hydrotalcite comprises the following steps of putting the composite hydrotalcite into a muffle furnace, heating to 500-560 ℃ at a speed of 5-10 ℃/min, and continuously calcining for 3-6 hours;
step two, performing amination modification treatment on the intercalation modified composite hydrotalcite by using KH550 to obtain amination composite hydrotalcite, dispersing the amination composite hydrotalcite in tetrahydrofuran to obtain suspension with the concentration of 10-30g/L, performing ultrasonic treatment for 1-3h, adding hexaamino cyclotriphosphazene and an acid-binding agent EDTA into the suspension, stirring and reacting for 8-10h under heating and stirring conditions in a nitrogen environment, filtering and washing a product, and drying to obtain phosphazene grafted composite hydrotalcite;
and step three, adding the phosphazene grafted composite hydrotalcite and distilled water into a container, heating to 70-80 ℃, stirring for 2-5h, adding the single-ion quaternary ammonium salt after uniform dispersion, continuing stirring for 23-28h, filtering the product, repeatedly washing with 80-90 ℃ distilled water, and drying to constant weight to obtain the flame retardant additive.
2. A flame retardant cable according to claim 1, wherein in step one, in the boron nitride suspension,
the ratio of boron nitride to deionized water is (5-10) g: (500-800) mL;
in the ammonium polyphosphate water solution, the proportion of water-soluble ammonium polyphosphate to deionized water is (5-10) g: (100-200) mL;
in the preparation process of the pretreated boron nitride, the boron nitride and the water-soluble ammonium polyphosphate are used in equal amount.
3. The flame retardant cable of claim 1 wherein in step two, the polyester diol is pretreated
The proportion of boron nitride, hexamethylene diisocyanate, chain extender BDO and catalyst stannous octoate is (10-15) g: (1.2-1.8) g: (20-26) g: (1-2) g: (0.1-0.5) g;
the preheating temperature of the die is 70-80 ℃;
the heat treatment temperature is 110-120 ℃, and the heat treatment time is 10-15h.
4. The flame-retardant cable according to claim 1, wherein in the first step, the intercalated modified composite hydrotalcite is prepared by pre-treating hydrotalcite and triazine sulfonate in a mass ratio of (2-6): (3-5).
5. The flame-retardant cable according to claim 1, wherein in the second step, the mass ratio of the aminated composite hydrotalcite to the hexaaminocyclophosphazene to the acid-binding agent EDTA is (10-30): (3-5): (0.8-1.2); the heating temperature is 65-70 ℃, and the stirring speed is 50-100r/min.
6. The flame-retardant cable according to claim 1, wherein the proportions of the phosphazene-grafted composite hydrotalcite, distilled water and the single-ion type quaternary ammonium salt in step three are (40-100) g: (800-1500) mL: (5-15) g.
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