CN110903647A - Ultrahigh-voltage flame-retardant cable material and preparation method thereof - Google Patents
Ultrahigh-voltage flame-retardant cable material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of an ultrahigh-voltage flame-retardant cable material, which comprises the following steps: step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol and carboxyl-terminated polyurethane, step S2, preparation of an intermediate, step S3, modification of a polyurethane-based polycondensate, and step S4, and cable material forming. The invention also discloses the ultrahigh-voltage flame-retardant cable material prepared by the preparation method of the ultrahigh-voltage flame-retardant cable material. The ultrahigh-voltage flame-retardant cable material disclosed by the invention is excellent in comprehensive performance, excellent in flame retardance and insulativity, good in performance stability, long in service life, and safe and environment-friendly in production and use processes.
Description
Technical Field
The invention relates to the technical field of power cables, in particular to an ultrahigh-voltage flame-retardant cable material and a preparation method thereof.
Background
In recent years, with the progress of science and technology and the development of society, the electric power industry in China develops rapidly, the operating voltage level of a power grid system is continuously improved, and the network scale is gradually enlarged. The ultrahigh or extra-high voltage transmission network is a framework and a core of a smart power grid which is fully created by a national power grid, the extra-high voltage transmission network can greatly improve the transmission capacity of the national power grid and reduce the long-distance power transmission loss, but the higher voltage level and the direct current transmission provide great challenges for the safety and reliability of cable materials widely applied to electrical equipment. The high-performance cable material is the technical core and key for forming high-voltage and extra-high-voltage power transmission and transformation equipment and networks, and the electrical performance of the high-performance cable material is directly related to the voltage level and safety of the whole power transmission network.
The flame retardance is an important index of the performance of the ultrahigh-voltage cable material, and along with the enhancement of safety consciousness and environmental protection consciousness, people have higher and higher requirements on the flame retardance and the smoke generation amount during combustion of the ultrahigh-voltage cable material. Not only is it required to be flame retardant, but also it is required to ensure that personnel can escape safely in case of fire. In addition, because the voltage that the superhigh pressure cable bore is high, when the cable run normally transmitted electricity, there was the distribution electric charge in the space, in order to guarantee the safety of personnel around the cable, the insulation of superhigh pressure cable material is one order of magnitude higher than ordinary cable material.
The ultrahigh-voltage cable material with larger use amount in the prior art is a polyolefin material added with a flame retardant, and the material is light in weight, free of halogen, excellent in electrical insulation performance and chemical corrosion resistance, low in price and easy to mold and process, but due to poor flame resistance, when the ultrahigh-voltage cable material is made into a cable for use, the ultrahigh-voltage cable material is often burnt under the conditions of high pressure, heating, discharging and the like to cause fire, is not extinguished after being separated from the fire, forms molten drops with fire to ignite other objects around, and causes the expansion of the fire scale.
Therefore, the ultrahigh-voltage flame-retardant cable material which has excellent comprehensive performance, good flame retardance and insulativity and good performance stability, is safe and environment-friendly to use, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the ultrahigh-voltage cable industry.
Disclosure of Invention
The invention aims to solve the problems and provides an ultrahigh-voltage flame-retardant cable material and a preparation method thereof, wherein the preparation method is simple and easy to implement, has rich raw material sources and low price, is suitable for large-scale production, and has higher popularization and use values; the prepared ultrahigh-voltage flame-retardant cable material is excellent in comprehensive performance, good in flame retardance and insulativity, good in performance stability, long in service life, and safe and environment-friendly in production and use processes.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an ultrahigh-voltage flame-retardant cable material comprises the following steps:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, carboxyl-terminated polyurethane, N-diisopropylethylamine and 4-dimethylaminopyridine in a high-boiling point solvent to form a solution, adding the solution into a reaction kettle, replacing air in the kettle with nitrogen or inert gas, reacting at 130-150 ℃ under normal pressure for 3-5 hours, adding a catalyst into the reaction system, heating to 240-500 ℃, performing polycondensation reaction at 500Pa under 300-500 ℃ for 15-20 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying at 80-90 ℃ in a vacuum drying oven to constant weight to obtain a polyurethane-based polycondensate;
step S2, preparation of intermediate: dissolving 4-chlorobenzoic acid and 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in an organic solvent, adding 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 15-20 hours at 30-40 ℃ in a dark room, and then removing the solvent by rotary evaporation to obtain an intermediate;
step S3, modified polyurethane-based polycondensate: adding the intermediate prepared in the step S2, the polyurethane-based polycondensate prepared in the step S1 and an alkaline catalyst into a three-necked bottle connected with a water separator, adding N, N-dimethylformamide and toluene into the three-necked bottle, heating a reaction system to 120-140 ℃, stirring the mixture for reaction for 3-5 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating the reaction system in water, washing the product for 3-5 times by using ethanol, and finally drying the product in a vacuum drying oven at the temperature of 80-90 ℃ until the weight is constant to obtain the modified polyurethane-based polycondensate;
step S4, cable material molding: and (4) adding the modified polyurethane-based polycondensate prepared in the step S3, polyamide fibers, nano silicon powder and a coupling agent into a double-screw extruder, extruding, molding and pelletizing to obtain the ultrahigh-voltage cable material.
Further, in the step S1, the ratio of the amounts of the 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol, the carboxyl-terminated polyurethane, the N, N-diisopropylethylamine, the 4-dimethylaminopyridine, the high boiling point solvent and the catalyst is 1:1:0.6:0.3 (8-12): 0.5.
further, the high boiling point solvent is selected from at least one of dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the catalyst is at least one of thiophosphonate, thiophosphoramide and phosphorous acid; the inert gas is one of helium, neon and argon.
Further, in the step S2, the mass ratio of the 4-chlorobenzoic acid, the 3- [ bis (4-fluorophenyl) phosphoryl ] aniline, the organic solvent and the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline is 1:2.1 (10-15): 0.2-0.4.
Further, the organic solvent is at least one of dichloromethane, tetrahydrofuran and acetone.
Further, in step S3, the mass ratio of the intermediate, the polyurethane-based polycondensate, the basic catalyst, the N, N-dimethylformamide and the toluene is 1 (3-5): 0.2-0.4): 12-20): 5-8.
Preferably, the alkaline catalyst is at least one of sodium carbonate, potassium hydroxide and sodium hydroxide.
Furthermore, in the step S4, the mass ratio of the modified polyurethane-based polycondensate, the polyamide fiber, the nano silicon powder and the coupling agent is 1 (0.2-0.4) to 0.1 (0.02-0.04).
The coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
Further, the extrusion molding specifically comprises the following temperature control parameters: the material supply section is 160-.
Further, the ultrahigh-voltage flame-retardant cable material is prepared by the preparation method of the ultrahigh-voltage flame-retardant cable material.
Adopt the produced beneficial effect of above-mentioned technical scheme to lie in:
(1) the ultrahigh-voltage flame-retardant cable material provided by the invention is simple and feasible in preparation method, rich in raw material source, low in price, suitable for large-scale production and high in popularization and use value.
(2) The ultrahigh-voltage flame-retardant cable material provided by the invention overcomes the technical defects that the traditional cable material is poor in comprehensive performance, the flame retardance and the insulativity need to be further improved, the performance stability is poor, and the environmental pollution is large in the using and production processes, and has the advantages of excellent comprehensive performance, good flame retardance and insulativity, good performance stability, long service life, and safety and environmental protection in the producing and using processes.
(3) The base material of the ultrahigh-voltage flame-retardant cable material is prepared from a polycondensate formed by polycondensation of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol and carboxyl-terminated polyurethane, and the ultrahigh-voltage flame-retardant cable material has excellent weather resistance and elasticity of a polyurethane material and can improve other comprehensive properties of the material; the pteridine structure on the side chain is beneficial to improving the weather resistance and the ultraviolet aging resistance of the material, and also greatly improves the insulativity and the flame retardance; by modifying the polycondensate and introducing the structure containing the fluorine phenylphosphine, the flame retardance and the mechanical property of the material are improved, so that the material has excellent comprehensive performance, good weather resistance and long service life; the main molecular chain is of a polyamide structure, the compatibility with the added polyamide fiber is good, and the mechanical property of the material can be enhanced by adding the polyamide fiber; the addition of the nano silicon powder can improve the mechanical property of the cable material through a dispersion strengthening mechanism on one hand, and is beneficial to improving the insulating property of the material on the other hand; the coupling agent is added, so that the nano silicon powder can be uniformly dispersed, the compatibility of the nano silicon powder and the polymer base material is improved, the components form an organic whole, the comprehensive performance of the material is improved, the performance stability is better, and the service life is longer.
Detailed Description
In order to make the technical solutions of the present invention better understood and make the above features, objects, and advantages of the present invention more comprehensible, the present invention is further described with reference to the following examples. The examples are intended to illustrate the invention only and are not intended to limit the scope of the invention.
Wherein, the raw materials related in the examples are all purchased commercially.
Example 1
A preparation method of an ultrahigh-voltage flame-retardant cable material comprises the following steps:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 1kg of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, 1kg of carboxyl-terminated polyurethane, 0.6kg of N, N-diisopropylethylamine and 0.3kg of 4-dimethylaminopyridine in 8kg of dimethyl sulfoxide to form a solution, adding the solution into a reaction kettle, replacing the air in the kettle with nitrogen, reacting at 130 ℃ under normal pressure for 3 hours, adding 0.5kg of thiophosphonate into the reaction system, heating to 240 ℃, carrying out polycondensation reaction under 300Pa for 15 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 3 times, and finally placing in a vacuum drying oven at 80 ℃ for drying to constant weight to obtain a polyurethane-based polycondensate;
step S2, preparation of intermediate: dissolving 1kg of 4-chlorobenzoic acid and 2.1kg of 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in 10kg of dichloromethane, adding 0.2kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 15 hours in a dark room at 30 ℃, and then performing rotary evaporation to remove the solvent to obtain an intermediate;
step S3, modified polyurethane-based polycondensate: adding 1kg of the intermediate prepared in the step S2, 3kg of the polyurethane-based polycondensate prepared in the step S1 and 0.2kg of sodium carbonate into a three-necked bottle connected with a water separator, adding 12kg of N, N-dimethylformamide and 5kg of toluene into the three-necked bottle, heating a reaction system to 120 ℃, stirring the mixture under the protection of nitrogen for reaction for 3 hours, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating the reaction system in water, washing the product for 3 times by using ethanol, and finally drying the product in a vacuum drying oven at 80 ℃ until the weight is constant to obtain the modified polyurethane-based polycondensate;
step S4, cable material molding: adding 1kg of modified polyurethane-based polycondensate prepared in the step S3, 0.2kg of polyamide fiber, 0.1kg of nano silicon powder and 0.02kg of silane coupling agent KH5500 to a double-screw extruder, extruding and molding, and pelletizing to obtain an ultrahigh-voltage cable material; the extrusion molding specifically comprises the following temperature control parameters: the feeding section is 160 ℃, the compression section is 175 ℃, the head temperature is 190 ℃, the neck mold temperature is 190 ℃, the production speed is controlled to be 260m/min, and the screw rotating speed is controlled to be 50 r/min.
An ultrahigh-voltage flame-retardant cable material is prepared by adopting the preparation method of the ultrahigh-voltage flame-retardant cable material.
Example 2
A preparation method of an ultrahigh-voltage flame-retardant cable material comprises the following steps:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 1kg of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, 1kg of carboxyl-terminated polyurethane, 0.6kg of N, N-diisopropylethylamine and 0.3kg of 4-dimethylaminopyridine in 9kg of N, N-dimethylformamide to form a solution, adding the solution into a reaction kettle, replacing the air in the kettle with helium, reacting at 135 ℃ under normal pressure for 3.5 hours, adding 0.5kg of thiophosphoramide into a reaction system, heating to 250 ℃, performing polycondensation reaction at 350Pa for 17 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 4 times, and finally drying at 83 ℃ in a vacuum drying oven to constant weight to obtain a polyurethane-based polycondensate;
step S2, preparation of intermediate: dissolving 1kg of 4-chlorobenzoic acid and 2.1kg of 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in 12kg of tetrahydrofuran, adding 0.25kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 16.5 hours in a dark room at 32 ℃, and then removing the solvent by rotary evaporation to obtain an intermediate;
step S3, modified polyurethane-based polycondensate: adding 1kg of the intermediate prepared in the step S2, 3.5kg of the polyurethane-based polycondensate prepared in the step S1 and 0.25kg of potassium carbonate into a three-neck flask connected with a water separator, adding 14kg of N, N-dimethylformamide and 6kg of toluene into the three-neck flask, heating the reaction system to 125 ℃, stirring the mixture for reaction for 3.5 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating the reaction system in water, washing the product for 4 times by using ethanol, and finally drying the product in a vacuum drying oven at 83 ℃ to constant weight to obtain the modified polyurethane-based polycondensate;
step S4, cable material molding: adding 1kg of modified polyurethane-based polycondensate prepared in the step S3, 0.25kg of polyamide fiber, 0.1kg of nano silicon powder and 0.025kg of silane coupling agent KH5600.025kg into a double-screw extruder, extruding and molding, and pelletizing to obtain an ultrahigh-pressure cable material; the extrusion molding specifically comprises the following temperature control parameters: the feeding section is 163 ℃, the compression section is 177 ℃, the head temperature is 192 ℃, the neck mold temperature is 193 ℃, the production speed is 270m/min, and the screw rotating speed is 55 r/min.
An ultrahigh-voltage flame-retardant cable material is prepared by adopting the preparation method of the ultrahigh-voltage flame-retardant cable material.
Example 3
A preparation method of an ultrahigh-voltage flame-retardant cable material comprises the following steps:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 1kg of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, 1kg of carboxyl-terminated polyurethane, 0.6kg of N, N-diisopropylethylamine and 0.3kg of 4-dimethylaminopyridine in 10kg of N-methylpyrrolidone to form a solution, adding the solution into a reaction kettle, replacing the air in the kettle with neon, reacting at the normal pressure for 4 hours at 140 ℃, adding 0.5kg of phosphorous acid into the reaction system, heating to 255 ℃, carrying out polycondensation reaction for 17.5 hours at 400Pa, cooling to room temperature, adjusting to the normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and finally drying at the temperature of 85 ℃ in a vacuum drying oven to constant weight to obtain a polyurethane-based polycondensate;
step S2, preparation of intermediate: dissolving 1kg of 4-chlorobenzoic acid and 2.1kg of 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in 13kg of acetone, adding 0.3kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 18 hours at 35 ℃ in a dark room, and then performing rotary evaporation to remove the solvent to obtain an intermediate;
step S3, modified polyurethane-based polycondensate: adding 1kg of the intermediate prepared in the step S2, 4kg of the polyurethane-based polycondensate prepared in the step S1 and 0.3kg of potassium hydroxide into a three-necked bottle connected with a water separator, adding 17kg of N, N-dimethylformamide and 6.5kg of toluene into the three-necked bottle, heating the reaction system to 130 ℃, stirring the mixture for reaction for 4 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating the reaction system in water, washing the product for 4 times by using ethanol, and finally drying the product in a vacuum drying oven at 85 ℃ to constant weight to obtain the modified polyurethane-based polycondensate;
step S4, cable material molding: adding 1kg of modified polyurethane-based polycondensate prepared in the step S3, 0.3kg of polyamide fiber, 0.1kg of nano silicon powder and KH5700.03kg of silane coupling agent into a double-screw extruder for extrusion molding and pelletizing to obtain an ultrahigh-voltage cable material; the extrusion molding specifically comprises the following temperature control parameters: the feeding section is 165 ℃, the compression section is 179 ℃, the head temperature is 195 ℃, the neck mold temperature is 196 ℃, the production speed is 290m/min, and the screw rotating speed is 60 r/min.
An ultrahigh-voltage flame-retardant cable material is prepared by adopting the preparation method of the ultrahigh-voltage flame-retardant cable material.
Example 4
A preparation method of an ultrahigh-voltage flame-retardant cable material comprises the following steps:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 1kg of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, 1kg of carboxyl-terminated polyurethane, 0.6kg of N, N-diisopropylethylamine and 0.3kg of 4-dimethylaminopyridine in 11kg of high boiling point solvent to form a solution, adding the solution into a reaction kettle, replacing the air in the kettle with argon, reacting at 145 ℃ under normal pressure for 4.5 hours, adding 0.5kg of catalyst into the reaction system, heating to 265 ℃, carrying out polycondensation reaction at 460Pa for 19 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 5 times, and finally drying at 88 ℃ in a vacuum drying oven to constant weight to obtain a polyurethane-based polycondensate; the high-boiling-point solvent is formed by mixing dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone according to the mass ratio of 1:3: 2; the catalyst is formed by mixing thiophosphonate, thiophosphoryl amide and phosphorous acid according to the mass ratio of 1:3: 5;
step S2, preparation of intermediate: dissolving 1kg of 4-chlorobenzoic acid and 2.1kg of 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in 14.5kg of organic solvent, adding 0.35kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 19 hours at 38 ℃ in a dark room, and then removing the solvent by rotary evaporation to obtain an intermediate; the organic solvent is formed by mixing dichloromethane, tetrahydrofuran and acetone according to the mass ratio of 2:4: 1;
step S3, modified polyurethane-based polycondensate: adding 1kg of the intermediate prepared in the step S2, 4.8kg of the polyurethane-based polycondensate prepared in the step S1 and 0.38kg of an alkaline catalyst into a three-neck flask connected with a water separator, adding 19kg of N, N-dimethylformamide and 7.5kg of toluene into the three-neck flask, heating the reaction system to 137 ℃, stirring and reacting for 4.8 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating in water, washing the product for 5 times by using ethanol, and finally drying the product in a vacuum drying oven at 88 ℃ to constant weight to obtain the modified polyurethane-based polycondensate; the alkaline catalyst is formed by mixing sodium carbonate, potassium hydroxide and sodium hydroxide according to the mass ratio of 1:1:3: 5;
step S4, cable material molding: adding 1kg of modified polyurethane-based polycondensate prepared in the step S3, 0.38kg of polyamide fiber, 0.1kg of nano silicon powder and 0.038kg of coupling agent into a double-screw extruder for extrusion molding and pelletizing to obtain an ultrahigh-pressure cable material; the coupling agent is formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 2:1: 3; the extrusion molding specifically comprises the following temperature control parameters: the feeding section is 168 ℃, the compression section is 183 ℃, the head temperature is 199 ℃, the neck mold temperature is 199 ℃, the production speed is controlled to be 300m/min, and the screw rotating speed is controlled to be 65 r/min.
An ultrahigh-voltage flame-retardant cable material is prepared by adopting the preparation method of the ultrahigh-voltage flame-retardant cable material.
Example 5
A preparation method of an ultrahigh-voltage flame-retardant cable material comprises the following steps:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 1kg of 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, 1kg of carboxyl-terminated polyurethane, 0.6kg of N, N-diisopropylethylamine and 0.3kg of 4-dimethylaminopyridine in 12kg of N, N-dimethylformamide to form a solution, adding the solution into a reaction kettle, replacing the air in the kettle with nitrogen, reacting at the normal pressure of 150 ℃ for 5 hours, adding 0.5kg of thiophosphonate into the reaction system, heating to 270 ℃, carrying out polycondensation reaction at the pressure of 500Pa for 20 hours, cooling to room temperature, adjusting to the normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 6 times, and finally drying at the temperature of 90 ℃ in a vacuum drying oven to constant weight to obtain a polyurethane-based polycondensate;
step S2, preparation of intermediate: dissolving 1kg of 4-chlorobenzoic acid and 2.1kg of 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in 15kg of tetrahydrofuran, adding 0.4kg of 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 20 hours at 40 ℃ in a dark room, and then performing rotary evaporation to remove the solvent to obtain an intermediate;
step S3, modified polyurethane-based polycondensate: adding 1kg of the intermediate prepared in the step S2, 5kg of the polyurethane-based polycondensate prepared in the step S1 and 0.4kg of sodium hydroxide into a three-neck flask connected with a water separator, adding 20kg of N, N-dimethylformamide and 8kg of toluene into the three-neck flask, heating a reaction system to 140 ℃, stirring the mixture for reaction for 5 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating the reaction system in water, washing the product for 5 times by using ethanol, and finally drying the product in a vacuum drying oven at 90 ℃ until the weight is constant to obtain the modified polyurethane-based polycondensate;
step S4, cable material molding: adding 1kg of modified polyurethane-based polycondensate prepared in the step S3, 0.4kg of polyamide fiber, 0.1kg of nano silicon powder and 0.04kg of silane coupling agent KH5600.04kg into a double-screw extruder, extruding, molding and granulating to obtain an ultrahigh-pressure cable material; the extrusion molding specifically comprises the following temperature control parameters: the feeding section is 170 ℃, the compression section is 185 ℃, the head temperature is 200 ℃, the neck mold temperature is 200 ℃, the production speed is controlled to be 310m/min, and the screw rotating speed is controlled to be 70 r/min.
An ultrahigh-voltage flame-retardant cable material is prepared by adopting the preparation method of the ultrahigh-voltage flame-retardant cable material.
Comparative example 1
This example provides an extra-high voltage flame retardant cable material, which is substantially the same in formulation and preparation method as example 1, except that the polyurethane-based polycondensate is not modified.
Comparative example 2
The present example provides an ultra-high voltage flame retardant cable material, which has a formulation and a preparation method substantially the same as those of example 1, except that no polyamide fiber is added.
Comparative example 3
The present example provides an ultrahigh pressure flame retardant cable material, the formulation and the preparation method of which are substantially the same as those of example 1, except that no nano silicon powder is added.
Comparative example 4
The present example provides an ultra-high voltage flame-retardant cable material, and the formula and preparation method thereof are the same as those in example 1 of the chinese patent CN 105949553A.
The samples obtained in examples 1 to 5 and comparative examples 1 to 4 were subjected to the relevant performance tests, and the test results are shown in Table 1.
TABLE 1
As can be seen from table 1, the ultrahigh-voltage flame-retardant cable material disclosed in the embodiment of the invention has more excellent mechanical properties, flame retardancy and insulation properties.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The preparation method of the ultrahigh-voltage flame-retardant cable material is characterized by comprising the following steps of:
step S1, condensation polymerization of 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol and carboxyl-terminated polyurethane: dissolving 3,3' - (2, 4-diamino-6, 7-pteridine diyl) diphenol, carboxyl-terminated polyurethane, N-diisopropylethylamine and 4-dimethylaminopyridine in a high-boiling point solvent to form a solution, adding the solution into a reaction kettle, replacing air in the kettle with nitrogen or inert gas, reacting at 130-150 ℃ under normal pressure for 3-5 hours, adding a catalyst into the reaction system, heating to 240-500 ℃, performing polycondensation reaction at 500Pa under 300-500 ℃ for 15-20 hours, cooling to room temperature, adjusting to normal pressure, precipitating in water, washing the precipitated polymer with ethanol for 3-6 times, and finally drying at 80-90 ℃ in a vacuum drying oven to constant weight to obtain a polyurethane-based polycondensate;
step S2, preparation of intermediate: dissolving 4-chlorobenzoic acid and 3- [ bis (4-fluorophenyl) phosphoryl ] aniline in an organic solvent, adding 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline, stirring and reacting for 15-20 hours at 30-40 ℃ in a dark room, and then removing the solvent by rotary evaporation to obtain an intermediate;
step S3, modified polyurethane-based polycondensate: adding the intermediate prepared in the step S2, the polyurethane-based polycondensate prepared in the step S1 and an alkaline catalyst into a three-necked bottle connected with a water separator, adding N, N-dimethylformamide and toluene into the three-necked bottle, heating a reaction system to 120-140 ℃, stirring the mixture for reaction for 3-5 hours under the protection of nitrogen, removing water and toluene generated in the reaction process through the water separator, cooling the reaction system to room temperature after the reaction is finished, precipitating the reaction system in water, washing the product for 3-5 times by using ethanol, and finally drying the product in a vacuum drying oven at the temperature of 80-90 ℃ until the weight is constant to obtain the modified polyurethane-based polycondensate;
step S4, cable material molding: and (4) adding the modified polyurethane-based polycondensate prepared in the step S3, polyamide fibers, nano silicon powder and a coupling agent into a double-screw extruder, extruding, molding and pelletizing to obtain the ultrahigh-voltage cable material.
2. The preparation method of the ultrahigh-voltage flame-retardant cable material according to claim 1, wherein in the step S1, the mass ratio of the 3,3' - (2, 4-diamino-6, 7-pteridinediyl) diphenol, the carboxyl-terminated polyurethane, the N, N-diisopropylethylamine, the 4-dimethylaminopyridine, the high-boiling-point solvent and the catalyst is 1:1:0.6:0.3 (8-12): 0.5.
3. The method for preparing an ultrahigh pressure flame-retardant cable material according to claim 1, wherein the high boiling point solvent is at least one selected from dimethyl sulfoxide, N-dimethylformamide and N-methylpyrrolidone; the catalyst is at least one of thiophosphonate, thiophosphoramide and phosphorous acid; the inert gas is one of helium, neon and argon.
4. The method for preparing the ultrahigh-pressure flame-retardant cable material as claimed in claim 1, wherein the mass ratio of the 4-chlorobenzoic acid, the 3- [ bis (4-fluorophenyl) phosphoryl ] aniline, the organic solvent and the 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline in the step S2 is 1:2.1 (10-15): 0.2-0.4.
5. The preparation method of an ultrahigh-pressure flame-retardant cable material according to claim 1, wherein the organic solvent is at least one of dichloromethane, tetrahydrofuran and acetone.
6. The method of claim 1, wherein the intermediate, the polyurethane-based polycondensate, the basic catalyst, the N, N-dimethylformamide and the toluene are mixed in the step S3 in a mass ratio of 1 (3-5) to (0.2-0.4) to (12-20) to (5-8).
7. The preparation method of the ultrahigh-pressure flame-retardant cable material according to claim 1, wherein the basic catalyst is at least one of sodium carbonate, potassium hydroxide and sodium hydroxide.
8. The preparation method of the ultrahigh-pressure flame-retardant cable material according to claim 1, wherein the mass ratio of the modified polyurethane-based polycondensate, the polyamide fibers, the nano silicon powder and the coupling agent in step S4 is 1 (0.2-0.4) to 0.1 (0.02-0.04); the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
9. The preparation method of the ultrahigh-pressure flame-retardant cable material according to claim 1, wherein the extrusion molding specifically comprises the following temperature control parameters: the material supply section is 160-.
10. An ultra-high voltage flame-retardant cable material prepared by the method for preparing an ultra-high voltage flame-retardant cable material according to any one of claims 1 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113362987A (en) * | 2021-07-01 | 2021-09-07 | 铜陵兢强电子科技股份有限公司 | Aluminum-based electromagnetic flat wire for transformer and manufacturing method |
| CN116396610A (en) * | 2023-05-22 | 2023-07-07 | 江苏发安建设工程有限公司 | Flame-retardant cable wire material and preparation method thereof |
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2019
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113362987A (en) * | 2021-07-01 | 2021-09-07 | 铜陵兢强电子科技股份有限公司 | Aluminum-based electromagnetic flat wire for transformer and manufacturing method |
| CN116396610A (en) * | 2023-05-22 | 2023-07-07 | 江苏发安建设工程有限公司 | Flame-retardant cable wire material and preparation method thereof |
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