A kind of graphene Jinlun-6 fireproof fiber and preparation method thereofTechnical field
The present invention relates to a kind of nylon fibre, particularly a kind of graphene Jinlun-6 fireproof fiber and preparation method thereof belongs toTextile technology field.
Background technology
Polyamide fibre, i.e. Fypro, it is most prominent the advantages of be wearability higher than other fibers, it is higher than cotton wearability by 10Times, some polyamide fibres are added in blended fabric, its wearability can be greatly improved.
Graphene is the two dimension crystalline substance of only one layer atomic thickness for being stripped out from graphite material, being made of carbon atomBody has the characteristics that intensity is big, electrical and thermal conductivity performance is strong, graphene is added in the matrix of polyamide fibre, it is desirable to it is new to assign polyamide fibrePerformance.
When preparing graphene nylon fibre, the graphene of addition can reduce the processing fluidity of chinlon master batch, increase moltenMelt the viscosity of chinlon master batch, limit the addition of graphene.
When preparing the graphene nylon fibre with excellent flame retardant performance, additional addition fire retardant is generally required, stillThe addition of fire retardant can influence the performances such as intensity, extensibility, elasticity modulus and the gas permeability of fiber.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of graphene Jinlun-6 fireproof fiber and preparation method thereof, with realityNow following goal of the invention：
（1）Overcome the influence of the addition of graphene to the viscosity and mobility of chinlon master batch, reduce the viscosity of melting chinlon master batch.
（2）Overcoming intensity of the addition on nylon fibre, extensibility, elasticity modulus and the gas permeability of fire retardant influences, and improvesIntensity, extensibility, elasticity modulus and the gas permeability of fiber.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is：
A kind of preparation method of graphene Jinlun-6 fireproof fiber,
（1）Prepare silica-graphene composite porous material
Include the following steps：
The 8-11% that the graphene that grain size is 400-600 nanometers is pressed to the dry silicic acid quality to production adds in a concentration of 35-40%'sIn sodium silicate aqueous solution, sodium bicarbonate is added in, 55-65 is being warming up to the speed of 1-1.5 DEG C/min after being sufficiently stirred 1-2 hoursDEG C heat preservation, be carried out at the same time ultrasonic echography 2-3 hours, while then stirring under 42-50 revs/min of rate, be slowly added toDilute sulfuric acid adjusts pH to 5-6, up to no flocculent deposit and bubble generate；Graphene silicic acid gel substance is obtained after filtering, is taken offAfter water, drying, for raising temperature to 155-165 DEG C, soaking time is powder after 4-5 hours to weight free of losses in 35-40 minutesIt is 1-1.5 microns that grain size is obtained after broken, and porosity is in 68-75%, silica-graphite of the aperture at 900 nanometers -1000 nanometersAlkene composite porous material.
The sodium bicarbonate, quality are the 1.7-1.8% of sodium metasilicate quality；
The dehydration is preferably dehydrated 30-40 minutes, and rotating speed is 500-800 revs/min.
The drying, preferably 100-106 DEG C 2-3 hours dry.
（2）Prepare graphene dispersion suspension
By grain size be 350-400 nanometers of graphene dispersion in NMP carriers, high-speed stirred 2-3 hours is made into graphene contentGraphene dispersion suspension for 24-28%.
（3）Prepare flame retarding function master batch
Silica-graphene composite porous material and graphene dispersion suspension, dried PET material, auxiliary agent addition is closeMixing in mill, the temperature of mixing is 130-135 DEG C, and the time is 10 minutes, then adds in fire retardant, and control mixing temperature is150-155 DEG C, 20MPa is boosted to the speed of 2MPa/min, is kept for 5 minutes, is then depressurized to often with the speed of 1MPa/minPressure then after single screw extrusion machine extruding pelletization and recycling design NMP, obtains flame retarding function master batch.
The temperature of the single screw extrusion machine is 270-275 DEG C, and screw speed is 80 ~ 100 revs/min, Screw Extrusion pressureFor 2.5-3Mpa；
The fire retardant is made of decabromodiphenyl oxide and melamine cyanurate, mass ratio 1:1.5-2；
The fire retardant, adding proportion are the 10-15% of common PET material dry weight；
The auxiliary agent, adding proportion are the 3-4% of common PET material dry weight；
The auxiliary agent, in parts by weight, including following components：
10 parts of ethylene bis stearic acid amide, 2 parts of calcium stearate, 3 parts of water calcium lotion, 4 parts of isopropanolamine, 1 part of hydroxyl magnesium silicate, fat2 parts of fat amine polyoxyethylene ether；
The water calcium lotion, model YZS-03D, solid content 45%, viscosity≤150mPa.s（25℃）；
The silica-graphene composite porous material expects the 28-32% of dry weight for PET；
Graphene powder in the graphene dispersion suspension expects the 13-16% of dry weight for PET.
The dried common PET material, water content 70ppm-80ppm.
（4）Melt spinning
Dried common PET material and flame retarding function master batch are sent into screw extruder heating melting, the mixture of molten conditionBe pressurized to 40-45MPa by booster pump, after squeeze into Super-high pressure kettle, 350-410Mpa is pressurized to the rate of 3-5MPa/min, protectPressure 4-5 hour after, be slowly decompressed to normal pressure state at 2-3 hour, then through manifold filter with metering pump distribution, then spinneret intoTow；Spinning speed is 1300-1380m/min；
The screw extruder, the rotating speed of screw rod is 35-40r/min, and melting temperature is 280-290 DEG C；
The flame retarding function master batch account for it is dry after the mass fraction of the sum of common PET material and flame retarding function master batch be 30%-35%.
The dried common PET material, flame retarding function master batch, water content 70ppm-80ppm.
（5）It is cooled and shaped
Tow is molded by the cooling and shaping by ring wind quenching, and wind-warm syndrome is 17 DEG C -19 DEG C, and ring blowing speed is 1.4m/s-1.8m/s。
（6）It stretches, wind, thermal finalization
It stretched, wound and thermal finalization using three groups of godets, the temperature of first group of godet is 120-130 DEG C, and rotating speed is1000-1100m/min, the temperature of second group of godet is 185-190 DEG C, rotating speed 2900-2950m/min, third group seal wireThe temperature of roller is 165-170 DEG C, rotating speed 1500-1550m/min,
Total draw ratio is 2.0-2.5 times.
（7）Post processing
By conventional post processing, the graphene nylon fibre of the present invention is obtained.
By adopting the above-described technical solution, the present invention reach have the technical effect that：
（1）The present invention overcomes influence of the addition to the viscosity and mobility of chinlon master batch of graphene, and it is female to reduce melting polyamide fibreThe viscosity of grain improves the mobility of melting chinlon master batch.
（2）Graphene nylon fibre prepared by the present invention, graphene content are 3.5-4.5%, and it is 60- to do fracture strength65N/tex, elongation at break 18-24%, Young's modulus 2.3-2.8Gpa；Limit oxygen index is up to 35.5-36%, and air penetrability is240-242mm/s；The conductivity of fiber reaches 8.0-8.5 × 10-7S/cm, 260 DEG C of dry-hot shrinkages are less than 5.0%, in 390-400DEG C hot melt contracting is less than 9%.
The Young's modulus of common polyamide fibre is easily deformed in 1.4Gpa or so.
Specific embodiment
The following describes the present invention in detail with reference to examples.Following embodiment will be helpful to those skilled in the artThe present invention is further understood, but the invention is not limited in any way.It should be pointed out that those of ordinary skill in the artFor, without departing from the inventive concept of the premise, it can also make certain adjustments and improvements.These belong to the guarantor of the present inventionProtect range.
1 a kind of graphene Jinlun-6 fireproof fiber of embodiment and preparation method thereof
Include the following steps：
（1）Prepare silica-graphene composite porous material
Include the following steps：
The sodium metasilicate that the graphene that grain size is 400 nanometers is pressed to 8% addition a concentration of 35% of the dry silicic acid quality to production is water-solubleIn liquid, sodium bicarbonate is added in, 55 DEG C of heat preservations are being warming up to the speed of 1 DEG C/min after being sufficiently stirred 1 hour, are being carried out at the same time ultrasoundWave ultrasound 2 hours while then stirring under 42 revs/min of rate, is slowly added to dilute sulfuric acid, pH to 5 is adjusted, up to no waddingShape precipitates and bubble generates；Graphene silicic acid gel substance is obtained after filtering, after dehydration, drying, temperature was increased in 35 minutesTo 155 DEG C, soaking time is after 4 hours to weight free of losses, and it is 1 micron that grain size is obtained after crushing, and porosity is 68%, apertureIn 900 nanometers of silica-graphene composite porous material.
The sodium bicarbonate, quality are the 1.7% of sodium metasilicate quality；
The dehydration is preferably dehydrated 30 minutes, and rotating speed is 800 revs/min.
The drying, preferably 100 DEG C dryings 3 hours.
（2）Prepare graphene dispersion suspension
By grain size be 350 nanometers of graphene dispersion in NMP carriers, high-speed stirred 2 hours, it is 24% to be made into graphene contentGraphene dispersion suspension.
（3）Prepare flame retarding function master batch
Silica-graphene composite porous material and graphene dispersion suspension, dried PET material, auxiliary agent addition is closeMixing in mill, the temperature of mixing is 130 DEG C, and the time is 10 minutes, then adds in fire retardant, and control mixing temperature is 150 DEG C,20MPa is boosted to the speed of 2MPa/min, is kept for 5 minutes, normal pressure is then depressurized to the speed of 1MPa/min, is then passed throughSingle screw extrusion machine extruding pelletization simultaneously after recycling design NMP, obtains flame retarding function master batch.
The temperature of the single screw extrusion machine is 270 DEG C, and screw speed is 80 revs/min, and Screw Extrusion pressure is 2.5Mpa；
The fire retardant is made of decabromodiphenyl oxide and melamine cyanurate, mass ratio 1:1.5；
The fire retardant, adding proportion are the 10% of common PET material dry weight；
The auxiliary agent, adding proportion are the 3% of common PET material dry weight；
The auxiliary agent, in parts by weight, including following components：
10 parts of ethylene bis stearic acid amide, 2 parts of calcium stearate, 3 parts of water calcium lotion, 4 parts of isopropanolamine, 1 part of hydroxyl magnesium silicate, fat2 parts of fat amine polyoxyethylene ether；
The water calcium lotion, model YZS-03D, solid content 45%, viscosity≤150mPa.s（25℃）；
The silica-graphene composite porous material expects the 28% of dry weight for PET；
Graphene powder in the graphene dispersion suspension expects the 13% of dry weight for PET.
The dried common PET material, water content 70ppm-80ppm.
（4）Melt spinning
Dried common PET material and flame retarding function master batch are sent into screw extruder heating melting, the mixture of molten conditionBe pressurized to 40MPa by booster pump, after squeeze into Super-high pressure kettle, 350Mpa, pressurize 4 hours are pressurized to the rate of 3MPa/minAfterwards, normal pressure state slowly was decompressed at 2 hours, is then distributed through manifold filtering and metering pump, then spinneret is into tow；Spinning speedIt spends for 1300m/min；
The screw extruder, the rotating speed of screw rod is 35r/min, and melting temperature is 280 DEG C；
The flame retarding function master batch account for it is dry after the mass fraction of the sum of common PET material and flame retarding function master batch be 30%%.
The dried common PET material, flame retarding function master batch, water content 70ppm-80ppm.
（5）It is cooled and shaped
Tow is molded by the cooling and shaping by ring wind quenching, and wind-warm syndrome is 17 DEG C, and ring blowing speed is 1.4m/s.
（6）It stretches, wind, thermal finalization
It stretched, wound and thermal finalization using three groups of godets, the temperature of first group of godet is 120 DEG C, and rotating speed is1000m/min, the temperature of second group of godet is 185 DEG C, rotating speed 2900m/min, and the temperature of third group godet is 165DEG C, rotating speed 1500m/min,
Total draw ratio is 2.0 times.
（7）Post processing
By conventional post processing, the graphene nylon fibre of the present invention is obtained.
Graphene nylon fibre prepared by the embodiment of the present invention 1, graphene content are 3.5%, and it is 61N/ to do fracture strengthTex, elongation at break 18%, Young's modulus are 2.3 Gpa, and limit oxygen index is up to 35.7%, air penetrability 241mm/s；FiberConductivity up to 8.2 × 10-7S/cm。
2 a kind of graphene Jinlun-6 fireproof fiber of embodiment and preparation method thereof
Include the following steps：
（1）Prepare silica-graphene composite porous material
Include the following steps：
The sodium metasilicate that the graphene that grain size is 500 nanometers is pressed to 10% addition a concentration of 38% of the dry silicic acid quality to production is water-solubleIn liquid, sodium bicarbonate is added in, 60 DEG C of heat preservations are being warming up to the speed of 1.3 DEG C/min after being sufficiently stirred 2 hours, are being carried out at the same time superSound wave ultrasound 3 hours while then stirring under 50 revs/min of rate, is slowly added to dilute sulfuric acid, adjusts pH to 6, until nothingFlocculent deposit and bubble generate；Graphene silicic acid gel substance is obtained after filtering, after dehydration, drying, temperature was increased in 38 minutesDegree is to 162 DEG C, and soaking time is after 4-5 hours to weight free of losses, and it is 1.3 microns that grain size is obtained after crushing, and porosity exists70%, silica-graphene composite porous material of the aperture at 970 nanometers.
The sodium bicarbonate, quality are the 1.8% of sodium metasilicate quality；
The dehydration is preferably dehydrated 40 minutes, and rotating speed is 800 revs/min.
The drying, preferably 106 DEG C dryings 2 hours.
（2）Prepare graphene dispersion suspension
By grain size be 400 nanometers of graphene dispersion in NMP carriers, high-speed stirred 2.5 hours, being made into graphene content is25% graphene dispersion suspension.
（3）Prepare flame retarding function master batch
Silica-graphene composite porous material and graphene dispersion suspension, dried PET material, auxiliary agent addition is closeMixing in mill, the temperature of mixing is 132 DEG C, and the time is 10 minutes, then adds in fire retardant, and control mixing temperature is 153 DEG C,20MPa is boosted to the speed of 2MPa/min, is kept for 5 minutes, normal pressure is then depressurized to the speed of 1MPa/min, is then passed throughSingle screw extrusion machine extruding pelletization simultaneously after recycling design NMP, obtains flame retarding function master batch.
The temperature of the single screw extrusion machine is 272 DEG C, and screw speed is 95 revs/min, and Screw Extrusion pressure is 2.8Mpa；
The fire retardant is made of decabromodiphenyl oxide and melamine cyanurate, mass ratio 1:1.7；
The fire retardant, adding proportion are the 12% of common PET material dry weight；
The auxiliary agent, adding proportion are the 3.3% of common PET material dry weight；
The auxiliary agent, in parts by weight, including following components：
10 parts of ethylene bis stearic acid amide, 2 parts of calcium stearate, 3 parts of water calcium lotion, 4 parts of isopropanolamine, 1 part of hydroxyl magnesium silicate, fat2 parts of fat amine polyoxyethylene ether；
The water calcium lotion, model YZS-03D, solid content 45%, viscosity≤150mPa.s（25℃）；
The silica-graphene composite porous material expects the 30% of dry weight for PET；
Graphene powder in the graphene dispersion suspension expects the 15% of dry weight for PET.
The dried common PET material, water content 70ppm-80ppm.
（4）Melt spinning
Dried common PET material and flame retarding function master batch are sent into screw extruder heating melting, the mixture of molten conditionBe pressurized to 45MPa by booster pump, after squeeze into Super-high pressure kettle, 400Mpa, pressurize 4 hours are pressurized to the rate of 4MPa/minAfterwards, normal pressure state slowly was decompressed at 2 hours, is then distributed through manifold filtering and metering pump, then spinneret is into tow；Spinning speedIt spends for 1380m/min；
The screw extruder, the rotating speed of screw rod is 40r/min, and melting temperature is 285 DEG C；
The flame retarding function master batch account for it is dry after the mass fraction of the sum of common PET material and flame retarding function master batch be 32%.
The dried common PET material, flame retarding function master batch, water content 70ppm-80ppm.
（5）It is cooled and shaped
Tow is molded by the cooling and shaping by ring wind quenching, and wind-warm syndrome is 18 DEG C, and ring blowing speed is 1.5m/s.
（6）It stretches, wind, thermal finalization
It stretched, wound and thermal finalization using three groups of godets, the temperature of first group of godet is 128 DEG C, and rotating speed is1080m/min, the temperature of second group of godet is 190 DEG C, rotating speed 2900m/min, and the temperature of third group godet is 170DEG C, rotating speed 1550m/min,
Total draw ratio is 2.4 times.
（7）Post processing
By conventional post processing, the graphene nylon fibre of the present invention is obtained.
Graphene nylon fibre prepared by the embodiment of the present invention 2, graphene content are 4.0%, and it is 65N/ to do fracture strengthTex, elongation at break 24%, Young's modulus 2.8Gpa, limit oxygen index are up to 36%, air penetrability 242mm/s；The electricity of fiberConductance is up to 8.5 × 10-7S/cm。
3 a kind of graphene Jinlun-6 fireproof fiber of embodiment and preparation method thereof
Include the following steps：
（1）Prepare silica-graphene composite porous material
Include the following steps：
The sodium metasilicate that the graphene that grain size is 600 nanometers is pressed to 11% addition a concentration of 40% of the dry silicic acid quality to production is water-solubleIn liquid, sodium bicarbonate is added in, 65 DEG C of heat preservations are being warming up to the speed of 1.5 DEG C/min after being sufficiently stirred 1-2 hours, are being carried out at the same timeUltrasonic echography 3 hours while then stirring under 50 revs/min of rate, is slowly added to dilute sulfuric acid, adjusts pH to 5, untilNo flocculent deposit and bubble generate；Graphene silicic acid gel substance is obtained after filtering, after dehydration, drying, was increased in 40 minutesTemperature is to 165 DEG C, and soaking time is after 5 hours to weight free of losses, and it is 1.5 microns that grain size is obtained after crushing, and porosity exists75%, silica-graphene composite porous material of the aperture at 1000 nanometers.
The sodium bicarbonate, quality are the 1.8% of sodium metasilicate quality；
The dehydration is preferably dehydrated 40 minutes, and rotating speed is 500 revs/min.
The drying, preferably 100 DEG C dryings 2.5 hours.
（2）Prepare graphene dispersion suspension
By grain size be 400 nanometers of graphene dispersion in NMP carriers, high-speed stirred 3 hours, it is 28% to be made into graphene contentGraphene dispersion suspension.
（3）Prepare flame retarding function master batch
Silica-graphene composite porous material and graphene dispersion suspension, dried PET material, auxiliary agent addition is closeMixing in mill, the temperature of mixing is 135 DEG C, and the time is 10 minutes, then adds in fire retardant, and control mixing temperature is 155 DEG C,20MPa is boosted to the speed of 2MPa/min, is kept for 5 minutes, normal pressure is then depressurized to the speed of 1MPa/min, is then passed throughSingle screw extrusion machine extruding pelletization simultaneously after recycling design NMP, obtains flame retarding function master batch.
The temperature of the single screw extrusion machine is 275 DEG C, and screw speed is 100 revs/min, and Screw Extrusion pressure is 3Mpa；
The fire retardant is made of decabromodiphenyl oxide and melamine cyanurate, mass ratio 1:2；
The fire retardant, adding proportion are the 15% of common PET material dry weight；
The auxiliary agent, adding proportion are the 4% of common PET material dry weight；
The auxiliary agent, in parts by weight, including following components：
10 parts of ethylene bis stearic acid amide, 2 parts of calcium stearate, 3 parts of water calcium lotion, 4 parts of isopropanolamine, 1 part of hydroxyl magnesium silicate, fat2 parts of fat amine polyoxyethylene ether；
The water calcium lotion, model YZS-03D, solid content 45%, viscosity≤150mPa.s（25℃）；
The silica-graphene composite porous material expects the 32% of dry weight for PET；
Graphene powder in the graphene dispersion suspension expects the 16% of dry weight for PET.
The dried common PET material, water content 70ppm-80ppm.
（4）Melt spinning
Dried common PET material and flame retarding function master batch are sent into screw extruder heating melting, the mixture of molten conditionBe pressurized to 45MPa by booster pump, after squeeze into Super-high pressure kettle, 410Mpa, pressurize 4 hours are pressurized to the rate of 5MPa/minAfterwards, normal pressure state slowly was decompressed at 2 hours, is then distributed through manifold filtering and metering pump, then spinneret is into tow；Spinning speedIt spends for 1380m/min；
The screw extruder, the rotating speed of screw rod is 40r/min, and melting temperature is 290 DEG C；
The flame retarding function master batch account for it is dry after the mass fraction of the sum of common PET material and flame retarding function master batch be 35%.
The dried common PET material, flame retarding function master batch, water content 70ppm-80ppm.
（5）It is cooled and shaped
Tow is molded by the cooling and shaping by ring wind quenching, 19 DEG C of wind-warm syndrome, and ring blowing speed is 1.8m/s.
（6）It stretches, wind, thermal finalization
It stretched, wound and thermal finalization using three groups of godets, the temperature of first group of godet is 130 DEG C, and rotating speed is1100m/min, the temperature of second group of godet is 190 DEG C, rotating speed 2900m/min, and the temperature of third group godet is 170DEG C, rotating speed 1550m/min,
Total draw ratio is 2.5 times.
（7）Post processing
By conventional post processing, the graphene nylon fibre of the present invention is obtained.
Graphene nylon fibre prepared by the embodiment of the present invention 3, graphene content are 4.5%, and it is 60N/ to do fracture strengthTex, elongation at break 20%, Young's modulus 2.5Gpa, limit oxygen index are up to 35.6%, air penetrability 240mm/s；FiberConductivity is up to 8.0 × 10-7S/cm。
The test method of air penetrability of the present invention is detected for GBT5453-1997 textile fabrics gas permeability.
Unless otherwise indicated, the percentage employed in the present invention is weight percent, ratio of the present invention,For mass ratio.
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention,Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still may be usedTo modify to the technical solution recorded in foregoing embodiments or carry out equivalent replacement to which part technical characteristic.All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in the present invention'sWithin protection domain.