CN108277548B - Graphene polyester flame-retardant fiber and preparation method thereof - Google Patents
Graphene polyester flame-retardant fiber and preparation method thereof Download PDFInfo
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- CN108277548B CN108277548B CN201810040880.3A CN201810040880A CN108277548B CN 108277548 B CN108277548 B CN 108277548B CN 201810040880 A CN201810040880 A CN 201810040880A CN 108277548 B CN108277548 B CN 108277548B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
Abstract
The invention provides a graphene polyester flame-retardant fiber, which comprises 1.5-3.5% of graphene, 6.1-6.5cN/dtex of dry breaking strength and 31-33% of limiting oxygen index; the invention also provides a preparation method of the graphene polyester flame-retardant fiber, which comprises the steps of preparing the silicon dioxide-graphene composite porous material, preparing the graphene dispersion turbid liquid, preparing the mixed functional master batch, carrying out melt spinning, cooling and forming, and drafting. The graphene polyester flame-retardant fiber prepared by the invention has the advantages that the content of graphene is 1.5-3.5%, the dry breaking strength is 6.1-6.5cN/dtex, the elongation at break is 6.0-7.3%, the dry heat shrinkage at 200 ℃ is lower than 0.8-1.2%, and the limiting oxygen index is up to 31-33%; the graphene terylene flame-retardant fiber has low melt shrinkage rate when meeting high temperature, and the melt shrinkage rate is less than 2-3% within 20 minutes at the ignition point temperature of 500-600 ℃.
Description
Technical Field
The invention relates to a polyester fiber, in particular to a graphene polyester flame-retardant fiber and a preparation method thereof, belonging to the technical field of textiles.
Background
The terylene is a synthetic fiber variety with the largest world output and the most extensive application, and accounts for more than 60 percent of the world synthetic fiber output.
The graphene has high conductivity, is a material with the minimum resistivity in the world, and can be added into a fiber material to improve the conductivity of the fiber; graphene also has antibacterial, flame retardant and radiation resistant properties, and can impart different functions to fiber products.
The graphene polyester flame-retardant fiber prepared by the prior art has the following defects:
(1) in order to reduce the influence of graphene on the mechanical property and spinnability of the fiber, the addition amount of graphene in the fiber is generally small, so that the strength and the flame retardance of the graphene polyester flame-retardant fiber prepared by the prior art are low, and the flame retardance of the fiber can be improved by adding a flame retardant additionally.
(2) The graphene polyester flame-retardant fiber prepared by the prior art has the problems of high-temperature melting shrinkage, melting, dripping and scalding.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a graphene polyester flame-retardant fiber and a preparation method thereof, so as to realize the following purposes:
(1) the prepared graphene polyester flame-retardant fiber is high in strength and good in flame retardant property;
(2) the prepared graphene polyester flame-retardant fiber is not molten and shrunk when meeting high temperature.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
the graphene polyester flame-retardant fiber comprises 1.5-3.5% of graphene, 6.1-6.5cN/dtex of dry breaking strength and 31-33% of limiting oxygen index.
The following is a further improvement of the above technical solution:
the fiber has a melt shrinkage rate of less than 2-3% within 20 minutes at an ignition point temperature of 500-600 ℃.
The preparation method of the graphene polyester flame-retardant fiber comprises the steps of preparing a silicon dioxide-graphene composite porous material, preparing a graphene dispersion turbid liquid, preparing a mixed functional master batch, carrying out melt spinning, cooling and forming, and drafting.
The preparation method of the silicon dioxide-graphene composite porous material comprises the following steps:
adding graphene with the particle size of 300-500 nm into 30-40% sodium silicate aqueous solution according to the mass of 6-10% of that of produced dry silicic acid, adding sodium bicarbonate, fully stirring for 2-3 hours, slowly heating to 50-60 ℃ within 50-70 minutes, preserving heat, ultrasonically treating for 2-3 hours by ultrasonic waves, slowly adding dilute sulfuric acid while stirring at the speed of 30-40 rpm, and adjusting the pH to 5-6 until no flocculent precipitate or air bubbles are generated; filtering to obtain graphene silicic acid gel substance, dehydrating, drying, raising the temperature to 150-160 ℃ within 20-30 minutes, keeping the temperature for 4-5 hours until no weight loss exists, and crushing to obtain the silica-graphene composite porous material with the particle size of 3-3.5 micrometers, the porosity of 60-70% and the pore size of 600-1000 nanometers.
The mass of the sodium bicarbonate is 1.5-1.7% of that of the sodium silicate;
the filtration, preferably the filtration by a plate-and-frame filter, adopts an intermittent pressure pump to increase or reduce the pressure at the variable frequency rate of 0.16-0.20Mpa/10 seconds, and maintains the pressure at 0.5-0.8Mpa to obtain a silicic acid gel substance;
the dehydration is preferably performed for 30-40 minutes at a rotation speed of 500-800 rpm.
The drying is preferably carried out at the temperature of 100 ℃ and 106 ℃ for 2-3 hours;
and preparing the graphene dispersion turbid liquid, dispersing the graphene with the particle size of 200-400 nm in an NMP carrier, and stirring at a high speed for 2-3 hours to prepare the graphene dispersion turbid liquid with the graphene content of 20-25%.
Preparing the mixed functional master batch, namely adding the silicon dioxide-graphene composite porous material, the graphene dispersion turbid liquid, the dried PET material, the auxiliary agent ethylene bis stearamide and calcium stearate into an internal mixer for internal mixing, performing extrusion granulation, and recovering the solvent NMP to obtain the mixed functional master batch.
The auxiliary agent is ethylene bis stearamide and calcium stearate in a ratio of 3:2, and the addition ratio is 3-4% of the dry weight of the PET material;
the silicon dioxide-graphene composite porous material accounts for 30-35% of the dry weight of the PET material;
the graphene powder in the graphene dispersion suspension is 10-15% of the dry weight of the PET material.
The melt spinning comprises the steps of conveying the dried common PET material and the mixed functional master batch into a screw extruder for heating and melting, pressurizing the mixture in a molten state to 30-50MPa by a booster pump, then pumping the mixture into a super-high pressure kettle, pressurizing to 300-1300 MPa within 1-2 hours in the kettle, maintaining the pressure for 4-6 hours, slowly reducing the pressure to a normal pressure state within 2-3 hours, filtering by a spinning box and distributing by a metering pump, and then spraying filaments to form filament bundles, wherein the spinning speed is 1200-1300 m/min;
the dosage of the metering pump is preferably 1950-2050 g/min.
The mass fraction of the mixed functional master batch accounts for 15-25% of the sum of the dried common PET material and the mixed functional master batch.
And cooling and forming, namely cooling and forming the tows by circular blowing, wherein the circular blowing temperature is 16-19 ℃, and the circular blowing speed is 8.0-10.0 m/s.
The total draft multiple is 1.4-1.8 times; the speed of the first drafting machine is 50m/min-60m/min, the temperature of the drafting bath is 80-90 ℃, the speed of the second drafting machine is 135m/min-185m/min, the temperature of the heating box is 110-120 ℃, and the speed of the third drafting machine is 165m/min-195 m/min.
The spinning also comprises vacuum drum drying; the vacuum drum drying is carried out by drying common PET material for 6-7.5 h at 180-185 ℃ in a vacuum drum dryer, adding mixed functional master batch, wherein the final mass fraction of the mixed functional master batch is 15-25%, the total drying time is 16-18 h, and the water content is 80-90 ppm.
The spinning also comprises heat setting; and in the heat setting, after the drafted nascent fiber is curled and oiled, the fiber is subjected to heat setting by a heat setting machine, wherein the heat setting temperature is 180-185 ℃, and the heat setting time is 16-20 min.
Due to the adoption of the technical scheme, the invention achieves the technical effects that:
(1) the graphene polyester flame-retardant fiber prepared by the invention has the graphene content of 1.5-3.5%, the dry breaking strength of 6.1-6.5cN/dtex, the elongation at break of 6.0-7.3%, the stress corresponding to 3% elongation of not less than 4.8 cN/dtex, the dry heat shrinkage at 200 ℃ of less than 0.8-1.2% and the limiting oxygen index of 31-33%.
(2) The graphene terylene flame-retardant fiber prepared by the invention has low melt shrinkage rate when meeting high temperature, and the melt shrinkage rate is less than 2-3% within 20 minutes at the ignition point temperature of 500-600 ℃.
(3) The graphene polyester flame-retardant fiber prepared by the method has the fiber moisture regain of 12.5-13.5% and the electrical conductivity of the fiber of 8.2-8.7 × 10-7S/cm。
The fiber prepared by the invention is mainly used for carpets, fillers, decorative materials and the like.
Detailed Description
The present invention will be described in detail with reference to examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. All falling within the scope of the present invention.
Embodiment 1 graphene polyester flame-retardant fiber and preparation method thereof
The method comprises the following steps:
(1) preparation of silica-graphene composite porous material
1) Adding graphene with the particle size of 300-350 nm into 30% sodium silicate aqueous solution according to 6% of the mass of produced dry silicic acid, adding sodium bicarbonate, fully stirring for 2-2.5 hours, slowly heating to 50-52 ℃ within 50 minutes, preserving heat, ultrasonically treating for 2 hours, slowly adding dilute sulfuric acid while stirring at the speed of 30 revolutions per minute, and adjusting the pH to 5 until no flocculent precipitate or bubbles are generated.
The flocculent precipitate is silicic acid colloid, mainly mixture of silicic acid, ortho silicic acid and metasilicic acid.
The mass of the sodium bicarbonate is 1.5 percent of that of the sodium silicate.
2) Filtering with plate-and-frame filter with filter cloth structure of 5000 mesh flannelette, 6000 mesh stainless steel filter screen, 8000 mesh silk cloth and 9000 mesh flannelette (the arrangement of the filter cloth is from outside to inside), pressurizing with intermittent pressure pump at variable frequency rate of 0.16Mpa/10 s, maintaining at 0.5Mpa, dewatering for 30 min to obtain silicic acid gel substance, and rotating at 500 rpm.
3) And drying the dehydrated graphene-silica gel mixture at 100-102 ℃ for 2 hours, raising the temperature to 150 ℃ within 20 minutes, keeping the temperature for 4 hours until the weight is not lost, and crushing to obtain the silicon dioxide-graphene composite porous material A with the particle size of 3 micrometers, the porosity of 60 percent and the pore diameter of 600 nanometers.
(2) Preparation of graphene dispersion suspension
And dispersing the graphene with the particle size of 200 nanometers in an NMP carrier, and stirring at a high speed for 2-3 hours to prepare a graphene dispersion turbid liquid B with the graphene content of 20% and good dispersibility.
(3) Preparation of mixed functional master batch
Adding the silicon dioxide-graphene composite porous material A obtained in the step (1), the graphene dispersion suspension B, PET material obtained in the step (2), an auxiliary agent ethylene bis stearamide and calcium stearate into an internal mixer for internal mixing, extruding and granulating by a double screw, and recovering a solvent NMP to obtain the mixed functional master batch.
The auxiliary agent is ethylene bis stearamide and calcium stearate in a ratio of 3:2, and the addition ratio is 3% of the dry weight of the PET material.
The silicon dioxide-graphene composite porous material accounts for 30% of the dry weight of the PET material;
the graphene powder in the graphene dispersion turbid liquid accounts for 10% of the dry weight of the PET material;
(4) spinning
1) Drying by a vacuum drum: drying common PET materials for 6 hours at the drying temperature of 180 ℃ by using a vacuum drum dryer, and then adding mixed functional master batches, wherein the final mass fraction of the mixed functional master batches is 15%, the total drying time is 16 hours, and the water content is 80ppm, so that the drying is finished.
2) Melt spinning: feeding the dried common PET material and the master batch with the mixed function into a screw extruder for heating and melting, pressurizing the mixture in a molten state to 30MPa by a booster pump, then feeding the mixture into a super-high pressure kettle, pressurizing to 300MPa within 1 hour in the kettle, maintaining the pressure for 4 hours, slowly reducing the pressure to a normal pressure state within 2 hours, filtering by a spinning box and distributing by a metering pump, and then spinning into tows by a spinneret plate, wherein the temperatures of a screw of the screw extruder and a box body of the spinning box are 285 ℃, the aperture of the spinneret plate is 0.6mm, the number of holes is 6000, and the layout of the spinneret plate is 20 circles;
the supply of the metering pump is 1950g/min, and the spinning speed is 1200 m/min.
3) Cooling and forming
And cooling and forming the tows by circular blowing, wherein the temperature of the circular blowing is 16 ℃, and the speed of the circular blowing is 8.0 m/s.
4) Drawing
Drawing the collected nascent fiber by a first drawing machine, a drawing bath, a second drawing machine, a heating box and a third drawing machine in sequence, wherein the total drawing multiple is 1.4 times;
the speed of the first drafting machine is 50m/min, the temperature of the drafting bath is 80 ℃, the speed of the second drafting machine is 135m/min, the temperature of the heating box is 110 ℃, and the speed of the third drafting machine is 165 m/min.
5) Heat setting
And (3) curling and oiling the drafted nascent fiber, and then performing heat setting by a heat setting machine, wherein the heat setting temperature is 180 ℃, and the heat setting time is 16 min.
6) Cutting off
And cutting to obtain the finished product of the graphene polyester staple fiber.
The graphene polyester flame-retardant fiber prepared in the embodiment 1 of the invention has the dry breaking strength of 6.1cN/dtex, the elongation at break of 6.0%, the stress corresponding to 3% elongation of not less than 4.8 cN/dtex, the dry heat shrinkage at 200 ℃ of less than 1.2% and the limiting oxygen index of up to 31%.
The graphene polyester flame-retardant fiber prepared in the embodiment 1 of the invention has low shrinkage rate in high temperature, and the shrinkage rate is less than 3% within 20 minutes at 500 ℃ ignition point temperature.
The graphene polyester flame-retardant fiber prepared in the embodiment 1 of the invention has the fiber moisture regain of 12.5% and the fiber conductivity of 8.2 × 10-7S/cm。
Embodiment 2 graphene polyester flame-retardant fiber and preparation method thereof
The method comprises the following steps:
(1) preparation of silica-graphene composite porous material
1) Graphene with the particle size of 370-4100 nm is added into 35% sodium silicate aqueous solution according to 8% of the mass of produced dry silicic acid, sodium bicarbonate is added, the mixture is fully stirred for 2.5 hours, then the temperature is slowly raised to 57 ℃ within 55-58 minutes, the temperature is kept, ultrasonic waves are used for 2.6 hours, dilute sulfuric acid is slowly added while stirring is carried out at the speed of 33-35 r/min, and the pH is adjusted to 5.4 until no flocculent precipitate and no air bubbles are generated.
The flocculent precipitate is silicic acid colloid, mainly mixture of silicic acid, ortho silicic acid and metasilicic acid.
The mass of the sodium bicarbonate is 1.6 percent of that of the sodium silicate.
2) Filtering with plate-and-frame filter with filter cloth structure of 5000 mesh flannelette, 6000 mesh stainless steel filter screen, 8000 mesh silk cloth and 9000 mesh flannelette (the arrangement of the filter cloth is from outside to inside), and pressurizing or depressurizing at a variable frequency rate of 0.17Mpa/10 seconds by using an intermittent pressure pump, maintaining at 0.7Mpa, dewatering for 30 min to obtain silicic acid gel substance, and rotating at 700 rpm.
3) And drying the dehydrated graphene-silica gel mixture at 105 ℃ for 2.5 hours, raising the temperature to 158 ℃ within 27 minutes, keeping the temperature for 4.5 hours until the weight is not lost, and crushing to obtain the silica-graphene composite porous material A with the particle size of 3.2 micrometers, the porosity of 68% and the pore diameter of 850 nanometers.
(2) Preparation of graphene dispersion suspension
And dispersing the graphene with the particle size of 280-290 nm in an NMP carrier, and stirring at a high speed for 2-3 hours to prepare a graphene dispersion suspension B with good dispersibility and the graphene content of 22%.
(3) Preparation of mixed functional master batch
Adding the silicon dioxide-graphene composite porous material A obtained in the step (1), the graphene dispersion suspension B, PET material obtained in the step (2), an auxiliary agent ethylene bis stearamide and calcium stearate into an internal mixer for internal mixing, extruding and granulating by a double screw, and recovering a solvent NMP to obtain the mixed functional master batch.
The auxiliary agent is ethylene bis stearamide and calcium stearate in a ratio of 3:2, and the addition ratio is 3.3% of the dry weight of the PET material.
The silicon dioxide-graphene composite porous material accounts for 32% of the dry weight of the PET material;
the graphene powder in the graphene dispersion turbid liquid accounts for 13% of the dry weight of the PET material.
(4) Spinning
1) Drying by a vacuum drum: drying common PET materials for 7 hours at the drying temperature of 180 ℃ by using a vacuum drum dryer, and then adding mixed functional master batches, wherein the final mass fraction of the mixed functional master batches is 20%, the total drying time is 16 hours, and the water content is 82ppm, so that the drying is finished.
2) Melt spinning: feeding the dried common PET material and the master batch with the mixed function into a screw extruder for heating and melting, pressurizing the mixture in a molten state to 45MPa by a booster pump, then feeding the mixture into a super-high pressure kettle, pressurizing to 450MPa within 1.7 hours in the kettle, maintaining the pressure for 5 hours, slowly reducing the pressure to a normal pressure state within 2-3 hours, then filtering by a spinning box and distributing by a metering pump, and spinning into tows by a spinneret plate, wherein the temperatures of a screw and a box body of the spinning box of the screw extruder are 292 ℃, the aperture of the spinneret plate is 0.6mm, the number of holes is 6000, and the layout of the spinneret plate is 20 circles;
the supply amount of the metering pump is 1985g/min, and the spinning speed is 1245-1250 m/min.
3) Cooling and forming
And cooling and forming the tows by circular blowing, wherein the temperature of the circular blowing is 18 ℃, and the speed of the circular blowing is 8.5 m/s.
4) Drawing
Drawing the collected nascent fiber by a first drawing machine, a drawing bath, a second drawing machine, a heating box and a third drawing machine in sequence, wherein the total drawing multiple is 1.7 times;
the speed of the first drafting machine is 28m/min, the temperature of the drafting bath is 85 ℃, the speed of the second drafting machine is 170m/min, the temperature of the heating box is 114 ℃, and the speed of the third drafting machine is 182 m/min.
5) Heat setting
And (3) curling and oiling the drafted nascent fiber, and then performing heat setting by a heat setting machine, wherein the heat setting temperature is 185 ℃, and the heat setting time is 17 min.
6) Cutting off
And cutting to obtain the finished product of the graphene polyester staple fiber.
The graphene polyester flame-retardant fiber prepared in the embodiment 2 of the invention has the dry breaking strength of 6.5cN/dtex, the elongation at break of 7.3%, the stress corresponding to 3% elongation of not less than 4.8 cN/dtex, the dry heat shrinkage at 200 ℃ of less than 0.8%, and the limiting oxygen index of 33%.
The graphene polyester flame-retardant fiber prepared in the embodiment 2 of the invention has low shrinkage rate in high temperature, and the shrinkage rate is less than 2% within 20 minutes at the ignition temperature of 600 ℃.
The graphene polyester flame-retardant fiber prepared in the embodiment 2 of the invention has the fiber moisture regain of 13.5% and the fiber conductivity of 8.7 × 10-7S/cm。
Embodiment 3 graphene polyester flame-retardant fiber and preparation method thereof
The method comprises the following steps:
(1) preparation of silica-graphene composite porous material
1) Adding graphene with the particle size of 500 nanometers into 40% sodium silicate aqueous solution according to the mass of 10% of that of produced dry silicic acid, adding sodium bicarbonate, fully stirring for 2-3 hours, slowly heating to 60 ℃ within 70 minutes, preserving heat, ultrasonically treating for 2-3 hours, slowly adding dilute sulfuric acid while stirring at the speed of 40 revolutions per minute, and adjusting the pH value to 6 until no flocculent precipitate or bubbles are generated.
The flocculent precipitate is silicic acid colloid, mainly mixture of silicic acid, ortho silicic acid and metasilicic acid.
The mass of the sodium bicarbonate is 1.7 percent of that of the sodium silicate.
2) Filtering with plate-and-frame filter with filter cloth structure of 5000 mesh flannelette, 6000 mesh stainless steel filter screen, 8000 mesh silk cloth and 9000 mesh flannelette (the arrangement of the filter cloth is from outside to inside), and pressurizing or depressurizing at a variable frequency rate of 0.20Mpa/10 seconds by using an intermittent pressure pump, maintaining at 0.8Mpa, dewatering for 40 min to obtain silicic acid gel substance, and rotating at 800 rpm.
3) And drying the dehydrated graphene-silica gel mixture at 100 ℃ for 3 hours, raising the temperature to 160 ℃ within 30 minutes, keeping the temperature for 5 hours until the weight is not lost, and crushing to obtain the silicon dioxide-graphene composite porous material A with the particle size of 3.5 micrometers, the porosity of 70 percent and the pore diameter of 1000 nanometers.
(2) Preparation of graphene dispersion suspension
And dispersing the graphene with the particle size of 400 nanometers in an NMP carrier, and stirring at a high speed for 3 hours to prepare a graphene dispersion turbid liquid B with the graphene content of 25% and good dispersibility.
(3) Preparation of mixed functional master batch
Adding the silicon dioxide-graphene composite porous material A obtained in the step (1), the graphene dispersion suspension B, PET material obtained in the step (2), an auxiliary agent ethylene bis stearamide and calcium stearate into an internal mixer for internal mixing, extruding and granulating by a double screw, and recovering a solvent NMP to obtain the mixed functional master batch.
The auxiliary agent is ethylene bis stearamide and calcium stearate in a ratio of 3:2, and the addition ratio is 4% of the dry weight of the PET material.
The silicon dioxide-graphene composite porous material accounts for 35% of the dry weight of the PET material;
the graphene powder in the graphene dispersion turbid liquid accounts for 15% of the dry weight of the PET material.
(4) Spinning
1) Drying by a vacuum drum: drying common PET materials for 7.5h by using a vacuum drum dryer at the drying temperature of 185 ℃, then adding mixed functional master batches, wherein the final mass fraction of the mixed functional master batches is 25%, the total drying time is 18h, and the drying is finished when the water content is 90 ppm.
2) Melt spinning: feeding the dried common PET material and the master batch with mixed functions into a screw extruder for heating and melting, pressurizing the mixture in a molten state to 50MPa by a booster pump, then feeding the mixture into a super-high pressure kettle, pressurizing to 500MPa within 1-2 hours in the kettle, maintaining the pressure for 6 hours, slowly reducing the pressure to a normal pressure state within 2-3 hours, then filtering by a spinning box and distributing by a metering pump, and spinning into tows by a spinneret plate, wherein the temperatures of a screw rod and a box body of the spinning box of the screw extruder are 295 ℃, the aperture of the spinneret plate is 0.6mm, the number of holes is 6000, the layout of the spinneret plate is 20 circles,
the supply of the metering pump is 2000g/min, and the spinning speed is 1280 m/min.
3) Cooling and forming
And cooling and forming the tows by circular blowing, wherein the temperature of the circular blowing is 18 ℃, and the speed of the circular blowing is 10.0 m/s.
4) Drawing
Drawing the collected nascent fiber by a first drawing machine, a drawing bath, a second drawing machine, a heating box and a third drawing machine in sequence, wherein the total drawing multiple is 1.8 times;
the speed of the first drafting machine is 60m/min, the temperature of the drafting bath is 90 ℃, the speed of the second drafting machine is 180m/min, the temperature of the heating box is 118 ℃, and the speed of the third drafting machine is 195 m/min.
5) Heat setting
And (3) curling and oiling the drafted nascent fiber, and then performing heat setting by a heat setting machine, wherein the heat setting temperature is 185 ℃, and the heat setting time is 20 min.
6) Cutting off
And cutting to obtain the finished product of the graphene polyester staple fiber.
The graphene polyester flame-retardant fiber prepared in the embodiment 3 of the invention has the dry breaking strength of 6.2cN/dtex, the elongation at break of 6.5%, the stress corresponding to 3% elongation of not less than 4.8 cN/dtex, the dry heat shrinkage at 200 ℃ of less than 1.1% and the limiting oxygen index of up to 32%.
The graphene polyester flame-retardant fiber prepared in the embodiment 3 of the invention has low shrinkage rate in high temperature, and the shrinkage rate is less than 3% within 20 minutes at 500 ℃ ignition point temperature.
The graphene polyester flame-retardant fiber prepared in the embodiment 3 of the invention has the fiber moisture regain of 12.6 percent and the electrical conductivity of the fiber of 8.3 × 10-7S/cm。
The fiber prepared by the invention is mainly used for carpets, fillers, decorative materials and the like.
Unless otherwise stated, the percentages used in the present invention are percentages by weight, and the proportions described in the present invention are proportions by mass.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A graphene polyester flame-retardant fiber is characterized in that: the content of graphene in the fiber is 1.5-3.5%, the dry breaking strength is 6.1-6.5cN/dtex, and the limiting oxygen index is 31-33%;
the preparation method of the fiber comprises the steps of preparing mixed functional master batches and melt spinning;
preparing a mixed functional master batch, namely adding a silicon dioxide-graphene composite porous material, a graphene dispersion suspension, a dried PET material, an auxiliary agent ethylene bis stearamide and calcium stearate into an internal mixer for internal mixing, performing extrusion granulation, and recovering a solvent NMP to obtain the mixed functional master batch;
the auxiliary agent is ethylene bis stearamide and calcium stearate in a ratio of 3:2, and the addition ratio is 3-4% of the dry weight of the PET material;
the silicon dioxide-graphene composite porous material has the particle size of 3-3.5 micrometers, the porosity of 60-70%, the pore diameter of 600-1000 nanometers, and the mass percentage of graphene relative to dry silicic acid of 6-10%;
the graphene dispersion suspension liquid contains 20-25% of graphene, and the particle size of the graphene is 200-400 nm;
the silicon dioxide-graphene composite porous material accounts for 30-35% of the dry weight of the PET material;
the graphene powder in the graphene dispersion turbid liquid accounts for 10-15% of the dry weight of the PET material;
the melt spinning comprises the steps of conveying the dried common PET material and the mixed functional master batch into a screw extruder for heating and melting, pressurizing the mixture in a molten state to 30-50MPa by a booster pump, then pumping the mixture into a super-high pressure kettle, pressurizing to 300-500MP a within 1-2 hours in the kettle, maintaining the pressure for 4-6 hours, slowly reducing the pressure to a normal pressure state within 2-3 hours, then filtering by a spinning box and distributing by a metering pump, and then spraying silk to form silk bundles, wherein the spinning speed is 1200-1300-
m/min; the mass fraction of the mixed functional master batch accounts for 15-25% of the sum of the dried common PET material and the mixed functional master batch.
2. The graphene polyester flame-retardant fiber according to claim 1, characterized in that: the fiber has a melt shrinkage rate of less than 2-3% within 20 minutes at an ignition point temperature of 500-600 ℃.
3. The preparation method of the graphene polyester flame-retardant fiber according to claim 1, which is characterized by comprising the following steps: the preparation method comprises the steps of preparing the silicon dioxide-graphene composite porous material, preparing the graphene dispersion turbid liquid, preparing the mixed functional master batch, carrying out melt spinning, cooling and forming, and drawing.
4. The preparation method of the graphene polyester flame-retardant fiber according to claim 3, which is characterized by comprising the following steps: the preparation method of the silicon dioxide-graphene composite porous material comprises the following steps:
adding graphene with the particle size of 300-500 nm into 30-40% sodium silicate aqueous solution according to the mass of 6-10% of that of produced dry silicic acid, adding sodium bicarbonate, fully stirring for 2-3 hours, slowly heating to 50-60 ℃ within 50-70 minutes, preserving heat, ultrasonically treating for 2-3 hours by ultrasonic waves, slowly adding dilute sulfuric acid while stirring at the speed of 30-40 rpm, and adjusting the pH to 5-6 until no flocculent precipitate or air bubbles are generated; filtering to obtain graphene silicic acid gel substance, dehydrating, drying, raising the temperature to 150-160 ℃ within 20-30 minutes, keeping the temperature for 4-5 hours until no weight loss exists, and crushing to obtain the silica-graphene composite porous material with the particle size of 3-3.5 micrometers, the porosity of 60-70% and the pore size of 600-1000 nanometers.
5. The preparation method of the graphene polyester flame-retardant fiber according to claim 3, which is characterized by comprising the following steps:
and preparing the graphene dispersion turbid liquid, dispersing the graphene with the particle size of 200-400 nm in an NMP carrier, and stirring at a high speed for 2-3 hours to prepare the graphene dispersion turbid liquid with the graphene content of 20-25%.
6. The preparation method of the graphene polyester flame-retardant fiber according to claim 3, which is characterized by comprising the following steps:
and cooling and forming, namely cooling and forming the tows by circular blowing, wherein the circular blowing temperature is 16-19 ℃, and the circular blowing speed is 8.0-10.0 m/s.
7. The preparation method of the graphene polyester flame-retardant fiber according to claim 3, which is characterized by comprising the following steps:
the total draft multiple is 1.4-1.8 times; the speed of the first drafting machine is 50m/min-60m/min, the temperature of the drafting bath is 80-90 ℃, the speed of the second drafting machine is 135m/min-185m/min, the temperature of the heating box is 110-120 ℃, and the speed of the third drafting machine is 165m/min-195 m/min.
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| CN110565200B (en) * | 2019-09-16 | 2022-03-25 | 浙江尤夫科技工业有限公司 | Flame-retardant polyester industrial yarn and preparation method thereof |
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