WO2018161766A1 - 石墨烯/尼龙6纤维、织物及制备方法 - Google Patents

石墨烯/尼龙6纤维、织物及制备方法 Download PDF

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WO2018161766A1
WO2018161766A1 PCT/CN2018/075701 CN2018075701W WO2018161766A1 WO 2018161766 A1 WO2018161766 A1 WO 2018161766A1 CN 2018075701 W CN2018075701 W CN 2018075701W WO 2018161766 A1 WO2018161766 A1 WO 2018161766A1
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graphene
nylon
mass
fiber
fabric
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PCT/CN2018/075701
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English (en)
French (fr)
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高超
韩燚
陈琛
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杭州高烯科技有限公司
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Priority claimed from CN201710131351.XA external-priority patent/CN106906534B/zh
Priority claimed from CN201710134838.3A external-priority patent/CN106906535B/zh
Priority claimed from CN201710131531.8A external-priority patent/CN106884219B/zh
Application filed by 杭州高烯科技有限公司 filed Critical 杭州高烯科技有限公司
Priority to JP2019517948A priority Critical patent/JP6743296B2/ja
Priority to US16/465,574 priority patent/US11339505B2/en
Publication of WO2018161766A1 publication Critical patent/WO2018161766A1/zh

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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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/18—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from other substances
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • C08G69/14—Lactams
    • C08G69/16—Preparatory processes
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
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    • C08K7/00—Use of ingredients characterised by shape
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/04—Melting filament-forming substances
    • 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
    • D—TEXTILES; PAPER
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    • 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
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
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    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
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    • 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
    • D01F6/90—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 polyamides
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    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
    • C08J3/2056—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase the polymer being pre-melted
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    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/212—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase and solid additives
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    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods

Definitions

  • the invention relates to a high strength and high modulus graphene/nylon 6 fiber and a preparation method thereof, a graphene/nylon 6 fabric with permanent far infrared health care function, a preparation method thereof and a graphene with permanent ultraviolet protection property /Nylon 6 fabric and its preparation method belong to the field of functional fibers.
  • Polyamide fiber commonly known as nylon, is one of the world's first industrial synthetic fibers. It has excellent strength, wear resistance and elastic recovery. It is widely used in tire cords, industrial fabrics, cables, conveyor belts and fishing nets. And other industries. It can also be used as a parachute and other military fabrics in national defense. In these industrial yarn fields, high-strength and high-modulus properties of nylon 6 are particularly required. Pure nylon 6 cannot meet the industrial demand, and nylon 6 composite materials are often used in the industry to improve the strength and modulus of nylon 6. Early nylon 6 composites were mostly reinforced with glass fiber and nano-montmorillonite, with limited effect and limited spinning performance. In the invention, the nylon 6 is modified by a small amount of graphene, and the high-strength and high-modulus graphene/nylon 6 composite fiber is successfully prepared.
  • nylon 6/graphene composites can be industrially spun to prepare high-strength and high-modulus composite fibers faces the following two obstacles: 1.
  • Graphene has a two-dimensional sheet structure, and if graphene is added as a multilayer structure, it is easy. Uneven dispersion occurs and stacks, and the pores of the spinning nozzle are blocked.
  • single-layer graphene is a two-dimensional nanomaterial with a large specific surface area, so the viscosity-increasing effect of single-layer graphene on nylon 6 Obviously, if the viscosity of the composite melt is too large, on the one hand, the torque of the screw in the spinning equipment is increased, thereby increasing the energy consumption.
  • the present invention adopts industrial spinning equipment for high-speed melt spinning of nylon 6/graphene nanocomposites compounded by modified graphene, caprolactam and various auxiliaries, and successfully obtains graphene-modified flame retardant. And nylon 6 fiber with UV resistance.
  • the far-infrared is the part of the spectrum with a wavelength of 8-15 micrometers, which is an indispensable factor for biological survival, also known as "life light wave".
  • the far-infrared energy produces the most effective "resonance" with the water molecules of the cells in the living body, and at the same time has the permeability to effectively promote the growth of animals and plants.
  • the water molecules in the body can resonate, activate the water molecules, enhance the binding force between the molecules, and activate the biological macromolecules such as proteins, so that the living cells are at the highest vibration level.
  • the far-infrared heat energy can be transmitted to the deeper part of the human skin, and the deep temperature rises below, and the generated warm heat is emitted from the inside to the outside.
  • This kind of action intensity expands the capillaries, promotes blood circulation, strengthens the metabolism between tissues, increases the regenerative capacity of the tissues, and improves the immunity of the body, thereby playing a role in health care.
  • Ultraviolet light is generally a general term for partial radiation with a wavelength of 10 - 400 nm in the spectrum.
  • the sunlight contains a large amount of ultraviolet radiation, and the UVB (280-320 nm) which can reach the surface has a high energy, which can cause strong photodamage to human skin, causing symptoms such as dermal vasodilation, redness and blisters.
  • Long-term exposure to the skin can cause erythema, inflammation, skin aging, and even severe cases can cause skin cancer.
  • Ultraviolet rays in the UVA (315-340 nm) portion act on melanin in the epidermis, causing skin melanin to darken and darken the skin. Long-term accumulation is one of the causes of skin aging and serious damage.
  • ultraviolet light is also an important reason for the aging of many materials and equipment exposed to ultraviolet light.
  • Graphene is a nano-material with two-dimensional crystal structure. In addition to its high mechanical properties and electrical and thermal conductivity, it also has a large specific surface area, good far-infrared emission and UV absorption properties. UV protective material and far infrared functional material or filler. At present, some patents report that fabrics use the method of adding graphene to introduce far-infrared function. However, nylon 6 is one of the most consumed man-made fibers, and its far-infrared function of graphene composite fiber has not been reported. This is mainly because of the following three technical difficulties: 1. Nylon 6 is melt-spun, and graphene must be well dispersed in a polymer matrix in a single piece to perform high-speed spinning and weaving a nylon fabric suitable for wear.
  • the small lateral dimension of graphene is favorable for dispersion, but the far-infrared effect is not good; the large lateral dimension of graphene increases the difficulty of dispersion of graphene in nylon 6.
  • the carbon-oxygen ratio of graphene is small to help disperse, but the far-infrared effect of graphene with high oxygen content is poor; increasing the carbon-oxygen ratio of graphene also increases the difficulty of dispersing graphene in nylon 6.
  • the present invention provides a high-strength and high-modulus graphene/nylon 6 fiber and a preparation method thereof, a graphene/nylon 6 fabric with permanent far-infrared health care function, and a preparation method thereof, and a method for solving the problems in the prior art.
  • a high-strength high-modulus graphene/nylon 6 fiber composed of 100 parts by weight of graphene/nylon 6 nanometer composite material and 0-5 parts by weight of auxiliary agent.
  • the graphene/nylon 6 nano composite material is composed of nylon 6 and a single layer of graphene grafted with nylon 6, and the relative viscosity of the graphene/nylon 6 nano composite material is 3.2-3.6.
  • the lateral dimension of the single layer graphene grafted with nylon 6 is greater than 2 microns; the ratio of the mass of graphene to the total mass of nylon 6 is from 0.1 to 0.5:100.
  • a method for preparing high-strength and high-modulus graphene/nylon 6 fiber which comprises: mixing 100 parts by weight of graphene/nylon 6 nanometer composite material and 0-5 parts by weight of auxiliary agent, and melting at high speed By spinning, high strength and high modulus graphene/nylon 6 fibers can be obtained.
  • graphene/nylon 6 nano composite material is prepared by the following method:
  • modified graphene (1) 0.1-0.5 parts by mass of modified graphene, 0.05-0.3 parts by mass of a molecular weight modifier, and 1-10 parts by mass of deionized water are added to 100 parts by mass of caprolactam melt at a high speed (300 ⁇ at 80 ° C) 500rpm) stirring and mixing to form a dispersion;
  • the modified graphene is a single layer graphene having a carboxyl group and a hydroxyl group on the surface; a carbon to oxygen ratio of between 2.5 and 6;
  • the above dispersion is heated to 250-270 ° C in a polycondensation reactor, and reacted at 0.5-1 MPa for 3 hours; then reacted under vacuum for 4 hours to obtain a polymer melt; finally, polymerization is carried out.
  • the melt was water-cooled and granulated to obtain a graphene/nylon 6 nanocomposite.
  • the transverse dimension of the graphene is greater than 3 ⁇ m, and the transverse dimension of the graphene is 3-10 ⁇ m.
  • the molecular weight modifier may be one or more of formic acid, acetic acid, propionic acid, aqueous ammonia, methylamine, ethylamine, propylamine, ethylenediamine, or any combination.
  • the conditions for high-speed melt spinning are: a melt temperature of 250 to 320 ° C, a continuous spinning speed of 1000 to 4000 m / min, and a draw ratio of 4 to 6 times.
  • the auxiliary agent is composed of one or more of an antioxidant, an anti-aging agent, a heat stabilizer, and an antistatic agent in an arbitrary ratio.
  • a graphene/nylon 6 fabric with permanent far-infrared health care function which is obtained by fabricating graphene/nylon 6 composite fiber, and the amount of graphene/nylon 6 composite fiber is not less than 80g per square meter of fabric.
  • the graphene/nylon 6 composite fiber is obtained by high speed melt spinning of a graphene/nylon 6 nano composite material composed of nylon 6 and a single layer grafted with nylon 6.
  • Graphene composition the transverse dimension of the single-layer graphene grafted with nylon 6 is greater than 1 micrometer; the ratio of the mass of graphene to the total mass of nylon 6 is 0.01-0.5:100; auxiliary and graphene/nylon 6
  • the composite material mass ratio is 0-5:100.
  • the graphene/nylon 6 fabric has a far-infrared emissivity greater than 0.88.
  • a method for preparing a graphene/nylon 6 fabric having permanent far-infrared health care function which comprises: fabricating a graphene/nylon 6 composite fiber.
  • the amount of graphene/nylon 6 composite fiber is not less than 80 g per square meter of fabric.
  • graphene/nylon 6 composite fiber is prepared by the following method:
  • modified graphene is a single-layer graphene having a carboxyl group and a hydroxyl group on the surface; the carbon-oxygen ratio is between 3.0 and 6;
  • the above dispersion is heated to 250-270 ° C in a polycondensation reactor, and reacted at 0.5-1 MPa for 3 hours; then reacted under vacuum for 4 hours to obtain a polymer melt; finally, polymerization is carried out.
  • the melt is water-cooled and granulated to obtain a graphene/nylon 6 nano composite material;
  • the graphene has a lateral dimension greater than 1 ⁇ m.
  • the graphene has a carbon to oxygen ratio of between 4.5 and 6.
  • the auxiliary agent is composed of one or more of an antioxidant, an anti-aging agent, a heat stabilizer, an antistatic agent and the like in an arbitrary ratio.
  • the fabric is obtained by fabricating a graphene/nylon 6 composite fiber, and the amount of the graphene/nylon 6 composite fiber per square meter is not less than 150 g.
  • the graphene/nylon 6 composite fiber is obtained by high speed melt spinning of a graphene/nylon 6 nano composite material composed of nylon 6 and a single layer grafted with nylon 6.
  • Graphene composition the transverse dimension of the single-layer graphene grafted with nylon 6 is greater than 1 micrometer; the ratio of the mass of graphene to the total mass of nylon 6 is 0.01-0.5:100; auxiliary and graphene/nylon 6
  • the composite material mass ratio is 0-5:100.
  • the graphene/nylon 6 fabric has an ultraviolet protection factor of UPF>40 and an ultraviolet light transmittance T(UVA) ⁇ 5%.
  • a method for preparing a graphene/nylon 6 fabric having permanent ultraviolet protection properties by fabricating a graphene/nylon 6 composite fiber is not less than 150 g per square meter of fabric.
  • graphene/nylon 6 composite fiber is prepared by the following method:
  • modified graphene is a single-layer graphene having an oxygen-containing functional group such as a carboxyl group or a hydroxyl group on the surface; the carbon-oxygen ratio is between 2.5 and 6;
  • the above dispersion is heated to 250-270 ° C in a polycondensation reactor, and reacted at 0.5-1 MPa for 3 hours; then reacted under vacuum for 4 hours to obtain a polymer melt; finally, polymerization is carried out.
  • the melt was water-cooled and granulated to obtain a graphene/nylon 6 nanocomposite.
  • melt temperature is 250-320 ° C
  • continuous spinning speed is 600-6000 m / min
  • drafting The multiple is 1.5 ⁇ 4 times.
  • the obtained fiber has a diameter of 5 - 50 ⁇ m.
  • the graphene has a lateral dimension greater than 1 ⁇ m.
  • the graphene has a lateral dimension of 2 - 10 ⁇ m.
  • the auxiliary agent is composed of one or more of an antioxidant, an anti-aging agent, a heat stabilizer, an antistatic agent and the like in an arbitrary ratio.
  • the modified graphene was used to modify nylon 6 to obtain graphene/nylon 6 nanocomposites.
  • the modified graphene could be monolayer dispersed in the graphene/nylon 6 system, avoiding The spinning nozzle is clogged, and the combination of graphene and nylon 6 matrix is good, no broken yarn is formed, and the melt viscosity is controlled within an appropriate range, and continuous high-speed spinning, especially the production of coarse denier industrial yarn, can be performed.
  • the obtained graphene/nylon 6 nanometer composite fiber has excellent mechanical properties such as high strength and high modulus, tensile strength > 8.0 cN/dtex, initial modulus > 9 GPa, and can be used for tire cords, industrial fabrics, fishing nets, cables, etc. National defense and industrial fields.
  • the modified single-layer graphene has good compatibility with the nylon 6 matrix, and can be dispersed in the system in a single layer state, avoiding spinning.
  • the wire nozzle is clogged, no broken wire is formed, and industrial continuous high-speed spinning can be performed.
  • the obtained graphene/nylon 6 fabric not only has superior comprehensive performance than pure nylon 6 fabric, but also has a far infrared health care function.
  • graphene is uniformly dispersed inside the composite fiber constituting the fabric, the function is not degraded by an increase in the number of washings and wear of the surface of the fabric.
  • This functional graphene/nylon 6 fabric can be widely used in making close-fitting clothing, blankets, bedding, tents, and the like.
  • the preparation process is suitable for large-scale production and can be well adapted to traditional fabric manufacturing equipment.
  • the modified single-layer graphene has good compatibility with the nylon 6 matrix, and can be dispersed in the system in a single layer state, avoiding spinning.
  • the wire nozzle is clogged, no broken wire is formed, and industrial continuous high-speed spinning can be performed.
  • the obtained graphene/nylon 6 fabric not only has superior comprehensive properties than the pure nylon 6 fabric, but also makes the fabric have ultraviolet protection properties.
  • the graphene is uniformly dispersed inside the composite fiber constituting the woven fabric, the product stability is good, and there is no appearance of the ultraviolet absorbing agent or the shielding agent.
  • This functional graphene/nylon 6 fabric can be widely used to make protective masking products such as sun protection clothing, sun umbrellas, tents, curtains, and swimwear.
  • the preparation process is suitable for large-scale production and can be well adapted to traditional fabric manufacturing equipment.
  • 1 is a schematic view showing the partial structure of graphene/nylon 6 fibers, wherein 1 is a single-layer graphene sheet grafted with nylon 6, and 2 is a free nylon 6.
  • FIG. 2 is a digital photograph of a graphene/nylon 6 fabric having permanent far infrared health care function prepared in the present invention
  • Figure 3 is a graph showing the far-infrared emissivity of a graphene/nylon 6 fabric having a permanent far-infrared health care function as a function of the number of washings prepared in the present invention.
  • Fig. 5 is a quality inspection report of the ultraviolet protection performance of the graphene/nylon 6 fabric having permanent ultraviolet protection properties prepared by the Zhejiang Provincial Quality Inspection Institute.
  • 0.1 parts by mass of a single layer graphene having a carbon-oxygen ratio of 2.8, a lateral dimension of 3 ⁇ m, 0.07 parts by mass of a molecular weight modifier, and 10 parts by mass of deionized water are added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1,500 m/min, and a draw ratio of 5 times to obtain graphene/ Nylon 6 fiber.
  • the graphene/nylon 6 fiber was tested for mechanical properties in accordance with national standards. The experimental results are shown in Table 1.
  • 0.3 parts by mass of a single layer graphene having a carbon-oxygen ratio of 3.0, a lateral dimension of 3 ⁇ m, 0.1 part by mass of a molecular weight modifier, and 10 parts by mass of deionized water are added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 2000 m / min, and a draw ratio of 5 times to obtain graphene / Nylon 6 fiber.
  • the graphene/nylon 6 fiber was tested for mechanical properties in accordance with national standards. The experimental results are shown in Table 1.
  • 0.2 parts by mass of a single layer graphene having a carbon-oxygen ratio of 3.0, a lateral dimension of 7 ⁇ m, 0.08 parts by mass of a molecular weight modifier, and 10 parts by mass of deionized water are added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 2500 m / min, and a draw ratio of 5 times to obtain graphene / Nylon 6 fiber.
  • the graphene/nylon 6 fiber was tested for mechanical properties in accordance with national standards. The experimental results are shown in Table 1.
  • 0.2 parts by mass of a single layer graphene having a carbon-oxygen ratio of 4.2, a lateral dimension of 3 ⁇ m, 0.09 parts by mass of a molecular weight modifier, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 3000 m / min, and a draw ratio of 5 times to obtain graphene / Nylon 6 fiber.
  • the graphene/nylon 6 fiber was tested for mechanical properties in accordance with national standards. The experimental results are shown in Table 1.
  • 0.3 parts by mass of a single layer graphene having a carbon-oxygen ratio of 3.5, a lateral dimension of 5 ⁇ m, 0.01 parts by mass of a molecular weight modifier, and 10 parts by mass of deionized water are added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite. The obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, but was not stably spun in the spinning process due to excessive melt viscosity.
  • 0.6 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 3.5, a lateral dimension of 3 ⁇ m, 0.15 parts by mass of a molecular weight modifier, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and it was found that the graphene/nylon 6 composite material blocked the spinning nozzle, and the graphene/nylon 6 fiber could not be obtained.
  • 0.4 parts by mass of a single layer graphene having a carbon-oxygen ratio of 2.8, a lateral dimension of 1 ⁇ m, 0.1 part by mass of a molecular weight modifier, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 3000 m / min, and a draw ratio of 5.5 times to obtain graphene / Nylon 6 fiber.
  • the graphene/nylon 6 fiber was tested for mechanical properties in accordance with national standards. The experimental results are shown in Table 1.
  • 0.2 parts by mass of a single layer graphene having a carbon-oxygen ratio of 2.3, a lateral dimension of 5 ⁇ m, 0.09 parts by mass of a molecular weight modifier, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and a high speed at 80 ° C (400 rpm) stirred and mixed to form a dispersion; under nitrogen protection, the above dispersion was heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; The polymer melt was then subjected to water-cooling granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 3000 m / min, and a draw ratio of 5.5 times to obtain graphene / Nylon 6 fiber.
  • the graphene/nylon 6 fiber was tested for mechanical properties in accordance with national standards. The experimental results are shown in Table 1.
  • Table 1 shows the mechanical properties of pure nylon 6 and graphene/nylon 6 nanocomposites blended with various additives for high-speed melt spinning, and then graphene/nylon 6 fibers and pure nylon 6 fibers. Compare. In the examples 1, 2, 3, and 4, the amount of graphene added is within the scope of the present invention, and the mechanical properties of the fiber are obviously improved compared with the pure nylon 6, the tensile strength is > 8.0 cN / dtex, and the initial modulus is > 9 GPa; In Example 5, the amount of the molecular weight modifier was too small, and the melt viscosity was too large to cause stable spinning; in Example 6, when the amount of graphene added was 0.6%, the single-layer graphene was stacked, and the spray was generated at the time of high-speed spinning.
  • Example 7 the graphene was too small in size and had poor mechanical properties.
  • Example 8 the graphene has a carbon-oxygen ratio of less than 2.5, and the graphene contains a large number of defects, resulting in a small graphene conjugated region, resulting in poor mechanical properties of the graphene/nylon 6 fibers.
  • a large number of experimental data show that high-strength and high-modulus graphene/nylon 6 fibers can be obtained only by using graphene and a synthetic method whose technical parameters are within the scope of the present invention.
  • 0.1 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 4.9, a lateral dimension of 3 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / Nylon 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 120 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T130127 ⁇ 2013, and the test results are shown in Table 2.
  • the far-infrared emissivity of the product was tested as the number of washings was changed as shown in Fig. 3. It can be seen from the figure that the far-infrared emissivity of the fabric did not change significantly after 20 washings; thus, it can be seen that the present invention ensures spinnability. At the same time, the transition from the traditional physical bonding mode (coating method, blending method) to the chemical bonding mode between the far-infrared functional additive and the fiber matrix is realized, so that the graphene and the nylon 6 fiber matrix are relatively stable. The chemical combination greatly enhances the far infrared health care function of the fabric and extends the life of the fabric.
  • 0.2 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 5.4, a lateral dimension of 3 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of the antioxidant, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and the graphene/nylon 6 fiber used per square meter was 90 g, and the obtained fabric was tested according to GB/T130127-2013, and the test results are shown in Table 2.
  • 0.3 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 4.9, a lateral dimension of 5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nano composite material was uniformly dispersed with 0.5 part of the anti-aging agent, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and the graphene/nylon 6 fiber used per square meter was 90 g, and the obtained fabric was tested according to GB/T130127-2013, and the test results are shown in Table 2.
  • 0.05 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 4.9, a lateral dimension of 2 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of heat stabilizer, and then subjected to high speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and the graphene/nylon 6 fiber used per square meter was 180 g, and the obtained fabric was tested according to GB/T130127 ⁇ 2013, and the test results are shown in Table 2.
  • 0.1 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 4.9, a lateral dimension of 5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of heat stabilizer, and then subjected to high speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and the graphene/nylon 6 fiber used per square meter was 50 g, and the obtained fabric was tested according to GB/T130127-2013, and the test results are shown in Table 2.
  • 0.1 parts by mass of a single layer graphene having a carbon-oxygen ratio of 4.9, a lateral dimension of 0.5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C.
  • a high speed 400 rpm
  • the graphene/nylon 6 nanocomposite was obtained by water-cooling granulation.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of heat stabilizer, and then subjected to high speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 200 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T130127 ⁇ 2013, and the test results are shown in Table 2.
  • the obtained graphene/nylon 6 composite material and 1 part of various additives were uniformly dispersed and then subjected to high-speed melt spinning at 310 ° C. It was found that the graphene/nylon 6 nanometer composite material blocked the spinning nozzle, and the graphene/nylon 6 could not be obtained. fiber.
  • 0.1 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 2.8, a lateral dimension of 9 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of heat stabilizer, and then subjected to high speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 120 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T130127 ⁇ 2013, and the test results are shown in Table 2.
  • the caprolactam was melted and added to the polycondensation reaction vessel, and the temperature was raised to 255 ° C, and reacted at 0.75 MPa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; the polymer melt was further subjected to water-cooling granulation to obtain a nylon. 6.
  • the obtained nylon 6 and 1 part of the heat stabilizer were uniformly dispersed, and then subjected to high-speed melt spinning at 260 ° C, a spinning speed of 1,500 m / min, and a draw ratio of 2.3 times to obtain a nylon 6 fiber having a fiber diameter of 23 ⁇ m.
  • the obtained pure nylon 6 fiber was fabricated, and the obtained fabric was tested according to GB/T130127-2013, and the test results are shown in Table 2.
  • Table 2 shows the far-infrared of the fabric obtained by blending pure nylon 6 and graphene/nylon 6 nanocomposites with various additives for high-speed melt spinning and then fabricating graphene/nylon 6 fibers.
  • the emissivity is compared.
  • the amount of graphene added is within the scope of the present invention, and the far-infrared health care function is superior to that of the pure nylon 6.
  • the graphene/nylon 6 fibers are less per square meter of fabric.
  • the far-infrared emissivity is low, indicating that the graphene/nylon 6 fiber should not be less than 80g per square meter of fabric; in Example 6, the transverse dimension of graphene is 500nm, less than 1 ⁇ m, and the far-infrared emissivity is low, indicating that the graphene is lateral. Size is critical to far infrared emission performance. When the amount of graphene added in Example 7 was 0.6%, the single-layer graphene was stacked, and the spinhole was clogged at the time of high-speed spinning, and continuous fibers could not be obtained.
  • the graphene has a carbon-oxygen ratio of less than 3, graphene contains a large number of defects, and the graphene conjugated region is small, and the far-infrared emissivity of the fabric is not ideal.
  • the experimental data show that only graphene carbon-oxygen ratio can obtain graphene/nylon 6 fabric with higher far-infrared emissivity between 3 and 6.
  • the graphene carbon-oxygen ratio is the best between 4.5-6, graphene. The least amount is used.
  • a large number of experimental data show that only graphene with a technical parameter within the scope of the present invention can obtain a graphene/nylon 6 fabric with better far infrared health care function.
  • 0.1 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 3.2, a lateral dimension of 2 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of the antioxidant, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 208 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • the UV protection performance of the product varies with the number of washing times as shown in Fig. 4. It can be seen from the figure that the UV protection coefficient of the fabric does not change significantly after 20 washings; thus, it can be seen that the present invention ensures spinnability while ensuring spinnability.
  • the conversion between the UV protective agent and the fiber matrix from the traditional physical bonding method (coating method, blending method) to the chemical bonding mode is realized, so that the graphene and the nylon 6 fiber matrix have a fairly stable chemical combination. , greatly improving the UV protection of the fabric and extending the service life of the fabric.
  • 0.2 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 5.1, a lateral dimension of 7 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 part of the antioxidant, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 180 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • 0.3 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 3.2, a lateral dimension of 5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / Nylon 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 150 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • 0.05 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 3.2, a lateral dimension of 8 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nanocomposite material was uniformly dispersed with 0.5 parts of various auxiliaries, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / Nylon 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 180 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • 0.1 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 3.2, a lateral dimension of 5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nano composite material was uniformly dispersed with 0.5 part of the anti-aging agent, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 144 g of graphene/nylon 6 fiber per square meter was used, and the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • 0.1 parts by mass of a single layer graphene having a carbon-oxygen ratio of 3.5, a lateral dimension of 0.5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C.
  • the graphene/nylon 6 nanocomposite was obtained by water-cooling granulation.
  • the obtained graphene/nylon 6 nano composite material was uniformly dispersed with 0.5 part of the anti-aging agent, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 200 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • 0.6 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 3.2, a lateral dimension of 5 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 composite material and 1 part of the anti-aging agent were uniformly dispersed and then subjected to high-speed melt spinning at 310 ° C. It was found that the graphene/nylon 6 nanometer composite material blocked the spinning nozzle, and the graphene/nylon 6 fiber could not be obtained. .
  • 0.1 parts by mass of a single-layer graphene having a carbon-oxygen ratio of 2.1, a lateral dimension of 9 ⁇ m, and 10 parts by mass of deionized water were added to 100 parts by mass of a caprolactam melt, and stirred at a high speed (400 rpm) at 80 ° C to form a mixture.
  • Dispersing solution; under the protection of nitrogen, the above dispersion is heated to 250 ° C in a polycondensation reactor, reacted at 0.7 Mpa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; Water-cooled granulation to obtain a graphene/nylon 6 nanocomposite.
  • the obtained graphene/nylon 6 nano composite material was uniformly dispersed with 0.5 part of the anti-aging agent, and then subjected to high-speed melt spinning at 295 ° C, a spinning speed of 1000 m / min, and a draw ratio of 3 times to obtain graphene / nylon. 6 fiber.
  • the obtained graphene/nylon 6 fiber was fabricated, and 210 g of graphene/nylon 6 fiber per square meter was used.
  • the obtained fabric was tested according to GB/T18830 ⁇ 2009, and the test results are shown in Table 3.
  • the caprolactam was melted and added to the polycondensation reaction vessel, and the temperature was raised to 255 ° C, and reacted at 0.75 MPa for 3 hours, and then reacted under vacuum for 4 hours to obtain a polycondensate melt; the polymer melt was further subjected to water-cooling granulation to obtain a nylon. 6.
  • the obtained nylon 6 and 1 part of the anti-aging agent were uniformly dispersed, and then subjected to high-speed melt spinning at 260 ° C, a spinning speed of 1,500 m / min, and a draw ratio of 2.3 times to obtain a nylon 6 fiber having a fiber diameter of 23 ⁇ m.
  • the obtained pure nylon 6 fiber was fabricated, and the obtained fabric was tested according to GB/T18830-2009, and the test results are shown in Table 3.
  • Table 3 shows the UV protection of fabrics obtained by blending pure nylon 6 and graphene/nylon 6 nanocomposites with various additives for high-speed melt spinning and then fabricating graphene/nylon 6 fibers. Performance is compared.
  • Examples 1, 2, 3, and 4 are graphene addition amounts within the scope of the present invention, and the ultraviolet protection performance is superior to that of pure nylon 6; in Example 5, the graphene/nylon 6 fibers per square meter of fabric are less than 150g, the UV protection effect is poor, indicating that the graphene/nylon 6 fiber should not be less than 150g per square meter of fabric; in Example 6, the transverse dimension of graphene is 500nm, less than 1 ⁇ m, and the UV protection effect is poor, indicating that the transverse dimension of graphene is UV protection.
  • the performance is very critical, and a large number of experiments have proved that the lateral dimension of graphene is 2-10 ⁇ m, which is most beneficial to improve the UV protection of the fabric.
  • the amount of graphene added in Example 7 was 0.6%, the single-layer graphene was stacked, and the spinhole was clogged at the time of high-speed spinning, and continuous fibers could not be obtained.
  • the graphene has a carbon-oxygen ratio of less than 2.5, and the graphene contains a large number of defects, resulting in an unsatisfactory UV protection effect on the fabric.
  • a large number of experimental data show that only graphene with a technical parameter within the scope of the present invention can obtain a graphene/nylon 6 fabric having better ultraviolet protection properties.

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Abstract

本发明涉及了一种高强高模量石墨烯/尼龙6纤维及制备方法，由改性石墨烯与己内酰胺原位聚合并经高速熔融纺丝得到；石墨烯/尼龙6纳米复合材料由改性石墨烯与己内酰胺和各种助剂复合得到。基于该复合纤维，本发明还提供了具有永久远红外保健功能的石墨烯/尼龙6织物和具有紫外防护性能的石墨烯/尼龙6织物，其远红外性能和紫外防护性能不会因织物水洗次数增加而产生衰减，具有极大的市场潜力。

Description

石墨烯/尼龙6纤维、织物及制备方法 技术领域
本发明涉及了一种高强高模量石墨烯/尼龙6纤维及制备方法，一种具有永久远红外保健功能的石墨烯/尼龙6织物及其制备方法以及一种具有永久紫外防护性能的石墨烯/尼龙6织物及其制备方法，属于功能纤维领域。
背景技术
聚酰胺纤维俗称锦纶，是一种世界上最早工业化的合成纤维，具有优良的强度、耐磨性、弹性回复率等优点，被广泛应用于轮胎帘子线、工业用布、线缆、传送带、渔网等行业。在国防上还可用作降落伞及其他军用织品。在这些工业丝领域尤其需要尼龙6的高强度高模量性能，纯尼龙6已无法满足工业需求，工业上多采用尼龙6复合材料来提高尼龙6的强度及模量。早期尼龙6复合材料多采用玻璃纤维和纳米蒙脱土进行增强，效果有限且纺丝性能受到限制。本发明则以少量石墨烯对尼龙6进行改性，成功制备了高强高模量石墨烯/尼龙6复合纤维。
但是尼龙6/石墨烯复合材料能否进行工业化纺丝制备高强高模量复合纤维面临以下两点障碍：1.石墨烯呈二维片层结构，若添加的石墨烯为多层结构，则易分散不均发生堆叠，堵塞极小的纺丝喷头孔；2.另一方面，单层石墨烯是一种比表面积极大的二维纳米材料，因此单层石墨烯对尼龙6的增粘效果非常明显，若复合材料熔体粘度过大，一方面增加纺丝设备中螺杆的扭矩从而增加了能耗，另一方面流动性变差导致不能纺出粗旦纤维而导致无法应用于工业丝领域。因此，即使单层石墨烯具有优异的增强作用，但是在高强高模工业丝领域尚未得到应用。基于此，本发明对由改性石墨烯、己内酰胺和各种助剂复合的尼龙6/石墨烯纳米复合材料采用工业化纺丝设备进行高速熔融纺丝，成功制得了石墨烯改性的具有阻燃和抗紫外性能的尼龙6纤维。
远红外是光谱中波长8‐15微米的部分，是生物生存必不可少的因素，也称为“生命光波”。远红外能与生物体内细胞的水分子产生最有效的“共振”，同时具备了渗透性能，有效地促进动物及植物的生长。远红外线被人体吸收后，可使体内水分子产生共振，使水分子活化，增强其分子间的结合力，从而活化蛋白质等生物大分子，使生物体细胞处于最高振动能级。由于生物细胞产生共振效应，可将远红外热能传递到人体皮下较深的部分，以下深层温度上升，产生的温热由内向外散发。这种作用强度，使毛细血管扩张，促进血液循环，强化各组织之间的新陈代谢，增加组织的再生能力，提高机体的免疫能力，从而起到医疗保健的作用。
紫外线通常是指是光谱中波长为10‐400nm部分辐射的总称。太阳光中含有大量的紫外线辐照，其中能够到达地表的UVB(280‐320nm)部分能量较高，能够对人的皮肤造成强烈的 光损伤，使其出现真皮血管扩张、红肿、水泡等症状。长久照射皮肤会出现红斑、炎症、皮肤老化，甚至严重者可引起皮肤癌。UVA(315‐340nm)部分的紫外线可对表皮部位的黑色素起作用，从而引起皮肤黑色素沉着，使皮肤变黑。长期积累是导致皮肤老化和严重损害的原因之一。近些年来，由于气候变暖和大气层臭氧层的破坏，紫外线对人体的伤害越来越引起广泛的重视。同时紫外线也是众多曝露在紫外线环境中的材料、设备老化的重要原因。
石墨烯是一种具有二维晶体结构的纳米材料，除了具有超高的机械性能和导电导热性能，还具有很大的比表面积和良好的远红外发射性能、紫外吸收性能，是一种理想的紫外防护材料和远红外功能材料或填料。目前，一些专利报道了织物采用添加石墨烯的方法来引入远红外功能。但是尼龙6作为消费量最大的几种人造纤维之一，其石墨烯复合纤维的远红外功能还未见报道。这主要是因为一下三个技术难点：1.尼龙6采用熔融纺丝，石墨烯必须呈单片形式很好地分散在聚合物基体中才能进行高速纺丝，织造出适合穿戴的尼龙织物。如果石墨烯分散效果不佳，会堵塞高速纺丝的喷丝头，导致纺丝失败。2.石墨烯横向尺寸小有利于分散，但是远红外效果不佳；石墨烯横向尺寸大则增加石墨烯在尼龙6里的分散的难度。3.石墨烯碳氧比小有助于分散，但是含氧量高的石墨烯远红外效果差；提高石墨烯碳氧比则同样增加了石墨烯在尼龙6里的分散难度。Carbon 95(2015)625‐633报道了通过织物表面涂覆的方法将石墨烯引入织物获得远红外功能，但这种方法存在远红外效果随洗涤次增加而衰退的风险，且会带来一定的环境污染问题。这一类远红外功能织物都会因洗涤和磨损导致使用寿命非常有限，不但降低了商品的性价比且失效后的产品因被淘汰而导致资源浪费和环境污染。因此开发出一种具有永久远红外保健功能的石墨烯/尼龙6织物是亟待解决的技术问题并具有极大的市场潜力。
。目前，许多织物采用涂覆紫外遮蔽剂的方法来提高织物的紫外防护性能。但这种方法中织物外层所涂敷的遮蔽剂会随着洗涤次数增加或使用时间增加而脱落导致紫外防护效果衰退甚至是环境污染问题。此外一些有机类遮蔽剂具有一定毒性，不适合与人体皮肤长时间接触。例如中国专利CN 103469555 B公开了一种利用石墨烯作为遮蔽剂的纺织面料的制备方法，虽然具有相当的紫外防护效果，但这种面料仍有随洗涤次数增加和织物表面磨损而导致紫外防护效果衰退的风险。市场上这一类紫外防护织物都会因洗涤和磨损导致使用寿命非常有限，不但降低了商品的性价比且失效后的产品因被淘汰而导致资源浪费和环境污染。因此开发出一种具有永久防紫外功能的石墨烯/尼龙6织物是亟待解决的技术问题并具有极大的市场潜力。
发明内容
本发明为解决现有技术存在的问题，提供了一种高强高模量石墨烯/尼龙6纤维及制备方法，一种具有永久远红外保健功能的石墨烯/尼龙6织物及其制备方法以及一种具有永久紫外防护性能的石墨烯/尼龙6织物及其制备方法。
本发明的目的是通过以下技术方案实现的：一种高强高模量石墨烯/尼龙6纤维，所述纤 维由100重量份的石墨烯/尼龙6纳米复合材料和0～5重量份的助剂经高速熔融纺丝得到，所述石墨烯/尼龙6纳米复合材料由尼龙6和接枝有尼龙6的单层石墨烯组成，所述石墨烯/尼龙6纳米复合材料相对粘度在3.2-3.6之间，所述接枝有尼龙6的单层石墨烯的横向尺寸大于2微米；石墨烯的质量与尼龙6的总质量之比为0.1-0.5:100。
一种高强高模量石墨烯/尼龙6纤维的制备方法，所述方法为：将100重量份的石墨烯/尼龙6纳米复合材料和0～5重量份的助剂混合均匀后，经高速熔融纺丝，即可得到高强度高模量石墨烯/尼龙6纤维。
进一步地，所述石墨烯/尼龙6纳米复合材料通过以下方法制备得到：
(1)将0.1-0.5质量份的改性石墨烯、0.05-0.3质量份分子量调节剂和1-10质量份去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(300～500rpm)搅拌混匀形成分散液；所述改性石墨烯为表面具有羧基、羟基的单层石墨烯；碳氧比为2.5到6之间；
(2)在氮气保护下，将上述分散液在缩聚反应釜中升温至250-270℃，在0.5-1MPa下反应3小时；然后在真空下反应4小时，得到聚合物熔体；最后将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。
进一步地，所述石墨烯的横向尺寸大于3μm，所述石墨烯的横向尺寸为3-10μm。
进一步地，所述的分子量调节剂可以是甲酸、乙酸、丙酸、氨水、甲胺、乙胺、丙胺、乙二胺中的一种或多种按照任意配比组成。
进一步地，高速熔融纺丝的条件为：熔体温度在250-320℃，连续纺丝速度为1000-4000米/分钟，牵伸倍数为4-6倍。
进一步地，所述助剂由抗氧化剂、抗老化剂、热稳定剂、抗静电剂中的一种或多种按照任意配比组成。
一种具有永久远红外保健功能的石墨烯/尼龙6织物，所述织物由石墨烯/尼龙6复合纤维经织物化得到，每平方米织物中，石墨烯/尼龙6复合纤维用量不少于80g。所述石墨烯/尼龙6复合纤维由石墨烯/尼龙6纳米复合材料和助剂经高速熔融纺丝得到，所述石墨烯/尼龙6纳米复合材料由尼龙6和接枝有尼龙6的单层石墨烯组成，所述接枝有尼龙6的单层石墨烯的横向尺寸大于1微米；石墨烯的质量与尼龙6的总质量之比为0.01‐0.5:100；助剂与石墨烯/尼龙6复合材料质量比为0‐5:100。
进一步地，所述石墨烯/尼龙6织物的远红外发射率大于0.88。
一种具有永久远红外保健功能的石墨烯/尼龙6织物的制备方法，该方法为：将石墨烯/尼龙6复合纤维进行织物化。每平方米织物中，石墨烯/尼龙6复合纤维用量不少于80g。
进一步地，所述石墨烯/尼龙6复合纤维通过以下方法制备得到：
(1)将0.01‐0.5质量份的改性石墨烯和1‐10质量份去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(300～500rpm)搅拌混匀形成分散液。所述改性石墨烯为表面具有 羧基、羟基的单层石墨烯；碳氧比为3.0到6之间；
(2)在氮气保护下，将上述分散液在缩聚反应釜中升温至250‐270℃，在0.5‐1MPa下反应3小时；然后在真空下反应4小时，得到聚合物熔体；最后将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料；
(3)将上述复合材料和助剂进行高速熔融纺丝，高速熔融纺丝的条件为：熔体温度在250‐320℃，连续纺丝速度为600‐6000米/分钟，牵伸倍数为1.5‐4倍，所得纤维直径5‐50μm。
进一步地，所述石墨烯的横向尺寸大于1μm。所述石墨烯的碳氧比为4.5到6之间。
进一步地，所述助剂由抗氧化剂、抗老化剂、热稳定剂、抗静电剂等中的一种或多种按照任意配比组成。
进一步地，所述织物由石墨烯/尼龙6复合纤维经织物化得到，每平方米石墨烯/尼龙6复合纤维用量不少于150g。所述石墨烯/尼龙6复合纤维由石墨烯/尼龙6纳米复合材料和助剂经高速熔融纺丝得到，所述石墨烯/尼龙6纳米复合材料由尼龙6和接枝有尼龙6的单层石墨烯组成，所述接枝有尼龙6的单层石墨烯的横向尺寸大于1微米；石墨烯的质量与尼龙6的总质量之比为0.01‐0.5:100；助剂与石墨烯/尼龙6复合材料质量比为0‐5:100。
进一步地，所述石墨烯/尼龙6织物的紫外防护系数UPF>40，紫外光透过率T(UVA)<5％。
一种具有永久紫外防护性能的石墨烯/尼龙6织物的制备方法，该方法为：将石墨烯/尼龙6复合纤维进行织物化。每平方米织物中，石墨烯/尼龙6复合纤维用量不少于150g。
进一步地，所述石墨烯/尼龙6复合纤维通过以下方法制备得到：
(1)将0.01‐0.5质量份的改性石墨烯和1‐10质量份去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(300～500rpm)搅拌混匀形成分散液。所述改性石墨烯为表面具有羧基、羟基等含氧官能团的单层石墨烯；碳氧比为2.5到6之间；
(2)在氮气保护下，将上述分散液在缩聚反应釜中升温至250‐270℃，在0.5‐1MPa下反应3小时；然后在真空下反应4小时，得到聚合物熔体；最后将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。
(3)将上述复合材料和助剂混合后，进行高速熔融纺丝，高速熔融纺丝的条件为：熔体温度在250‐320℃，连续纺丝速度为600‐6000米/分钟，牵伸倍数为1.5‐4倍。所得纤维直径5‐50μm。
进一步地，所述石墨烯的横向尺寸大于1μm。所述石墨烯的横向尺寸为2‐10μm。
进一步地，所述助剂由抗氧化剂、抗老化剂、热稳定剂、抗静电剂等中的一种或多种按照任意配比组成。
本发明的有益效果在于：
(1)采用改性石墨烯对尼龙6进行改性，制得石墨烯/尼龙6纳米复合材料，一定质量范围内，改性石墨烯能够单层分散于石墨烯/尼龙6体系中，避免了纺丝喷头堵塞，且石墨烯 与尼龙6基体结合性好，不会形成断头丝，同时控制熔体粘度在恰当范围内，可进行连续高速纺丝，尤其是粗旦工业丝的生产。所得石墨烯/尼龙6纳米复合纤维具有高强度高模量等优异的力学性能，拉伸强度>8.0cN/dtex，初始模量>9GPa，可用于轮胎帘子线、工业用布、渔网以及缆绳等国防、工业领域。
(2)采用原位聚合的方法将极少量石墨烯添加在尼龙6基体中，改性的单层石墨烯与尼龙6基体相容性好，能够呈单层状态分散在体系中，避免了纺丝喷头堵塞，不会形成断头丝，可进行工业化连续高速纺丝。所得石墨烯/尼龙6织物不但比纯尼龙6织物具有更优异的的综合性能，还使其具有了远红外保健功能。而且，由于石墨烯是均匀分散在构成织物的复合纤维内部，因此该功能不会因洗涤次数增加和织物表面磨损而衰退。这种功能性石墨烯/尼龙6织物可以广泛用于制作贴身衣物、毛毯、床上用品、帐篷等。制备过程适合规模化生产，能够很好的适应传统的织物制造生产设备。
(3)采用原位聚合的方法将极少量石墨烯添加在尼龙6基体中，改性的单层石墨烯与尼龙6基体相容性好，能够呈单层状态分散在体系中，避免了纺丝喷头堵塞，不会形成断头丝，可进行工业化连续高速纺丝。所得石墨烯/尼龙6织物不但比纯尼龙6织物具有更优异的的综合性能，还使得织物具有了紫外防护性能。而且，由于石墨烯是均匀分散在构成织物的复合纤维内部，产品稳定性好，不会存在紫外吸收剂、屏蔽剂析出现象。因此紫外防护功能不会因洗涤次数增加和织物表面磨损而衰退。这种功能性石墨烯/尼龙6织物可以广泛用于制作防晒衣、太阳伞、帐篷、窗帘、泳衣等防护遮蔽产品。制备过程适合规模化生产，能够很好的适应传统的织物制造生产设备。
附图说明
图1为石墨烯/尼龙6纤维的局部结构示意图，其中1为接枝有尼龙6的单层石墨烯片，2为游离的尼龙6。
图2是本发明中制备的具有永久远红外保健功能的石墨烯/尼龙6织物的数码相片；
图3是本发明中制备的具有永久远红外保健功能的石墨烯/尼龙6织物远红外发射率随洗涤次数变化图。
图4是本发明中制备的具有永久紫外防护性能的石墨烯/尼龙6织物紫外防护系数UPF值随洗涤次数变化图；
图5是浙江省质检院对本发明中制备的具有永久紫外防护性能的石墨烯/尼龙6织物紫外防护性能的质检报告。
具体实施方式
下面通过实施例对本发明进行具体描述，本实施例只用于对本发明做进一步的说明，不 能理解为对本发明保护范围的限制，本领域的技术人员根据上述发明的内容做出一些非本质的改变和调整均属本发明的保护范围。
实施例1-1
将0.1质量份的碳氧比为2.8、横向尺寸为3μm的单层石墨烯、0.07质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度1500米/分钟，牵伸倍数5倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。对石墨烯/尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
实施例1-2
将0.3质量份的碳氧比为3.0、横向尺寸为3μm的单层石墨烯、0.1质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度2000米/分钟，牵伸倍数5倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。对石墨烯/尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
实施例1-3
将0.2质量份的碳氧比为3.0、横向尺寸为7μm的单层石墨烯、0.08质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度2500米/分钟，牵伸倍数5倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。对石墨烯/尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
实施例1-4
将0.2质量份的碳氧比为4.2、横向尺寸为3μm的单层石墨烯、0.09质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在 295℃，纺丝速度3000米/分钟，牵伸倍数5倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。对石墨烯/尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
实施例1-5
将0.3质量份的碳氧比为3.5、横向尺寸为5μm的单层石墨烯、0.01质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀，但在纺丝过程由于熔体粘度过大，并不能稳定纺丝。
实施例1-6
将0.6质量份的碳氧比为3.5、横向尺寸为3μm的单层石墨烯、0.15质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后发现石墨烯/尼龙6复合材料堵塞了纺丝喷头，不能得到石墨烯/尼龙6纤维。
实施例1-7
将0.4质量份的碳氧比为2.8、横向尺寸为1μm的单层石墨烯、0.1质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度3000米/分钟，牵伸倍数5.5倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。对石墨烯/尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
实施例1-8
将0.2质量份的碳氧比为2.3、横向尺寸为5μm的单层石墨烯、0.09质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度3000米/分钟，牵伸倍数5.5倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。对石墨烯/尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
对比例1-1：
将0.09质量份分子量调节剂以及10质量份的去离子水加入100质量份的己内酰胺熔体中并加入至缩聚反应釜内，升温至255℃，在0.75Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到尼龙6。得到的尼龙6与1份各种助剂分散均匀后在260℃，纺丝速度3500米/分钟，牵伸倍数5.5倍的条件下进行高速熔融纺丝，得到尼龙6纤维。对尼龙6纤维按照国家标准进行力学性能测试，实验结果见附表1。
附表1中给出了由纯尼龙6和石墨烯/尼龙6纳米复合材料与各种助剂共混后进行高速熔融纺丝，再将石墨烯/尼龙6纤维与纯尼龙6纤维的力学性能进行比对。其中实施例1、2、3、4为石墨烯添加量在本发明范围内，与纯尼龙6相比，纤维力学性能明显提升，拉伸强度均>8.0cN/dtex，初始模量>9GPa；实施例5中，分子量调节剂用量太少，熔体粘度过大导致不能稳定纺丝；实施例6中，石墨烯添加量为0.6％时，单层石墨烯发生堆叠，高速纺丝时发生喷丝孔堵塞，不能得到连续纤维。实施例7中，石墨烯尺寸太小，力学性能欠佳。实施例8中，石墨烯碳氧比小于2.5，石墨烯含有大量缺陷导致石墨烯共轭区域较小，导致石墨烯/尼龙6纤维力学性能欠佳。大量实验数据表明，只有采用技术参数在本发明所指范围内的石墨烯以及合成方法，才能得到高强度高模量的石墨烯/尼龙6纤维。
附表1
Figure PCTCN2018075701-appb-000001
实施例2‐1
将0.1质量份的碳氧比为4.9、横向尺寸为3μm的单层石墨烯和10质量份的去离子水加 入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维120g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
该产物的远红外发射率随洗涤次数变化测试如图3所示，从图中可以看出织物的远红外发射率在20次洗涤后没有明显变化；由此可见，本发明在保证可纺性的同时，实现了远红外功能添加剂与纤维基体之间从传统的物理结合的方式(涂覆方法、共混方式)向化学结合方式的转变，使得石墨烯与尼龙6纤维基体之间具有相当稳定的化学结合，大大提升了织物的远红外保健功能并延长了织物的使用寿命。
实施例2‐2
将0.2质量份的碳氧比为5.4、横向尺寸为3μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗氧化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维90g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
实施例2‐3
将0.3质量份的碳氧比为4.9、横向尺寸为5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗老化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维90g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
实施例2‐4
将0.05质量份的碳氧比为4.9、横向尺寸为2μm的单层石墨烯和10质量份的去离子水 加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份热稳定剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维180g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
实施例2‐5
将0.1质量份的碳氧比为4.9、横向尺寸为5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份热稳定剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维50g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
实施例2‐6
将0.1质量份的碳氧比为4.9、横向尺寸为0.5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份热稳定剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维200g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
实施例2‐7
将0.6质量份的碳氧比为4.9、横向尺寸为5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6复合材料与1份各种助剂分散均匀后在310℃进行高速熔融纺丝，发现石墨烯/尼龙6纳米复合材料堵塞了纺丝喷头，不能得到石墨烯/尼龙6纤维。
实施例2‐8
将0.1质量份的碳氧比为2.8、横向尺寸为9μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份热稳定剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维120g，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
对比例2‐1：
将己内酰胺熔融加入至缩聚反应釜内，并升温至255℃，在0.75Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到尼龙6。得到的尼龙6与1份热稳定剂分散均匀后在260℃，纺丝速度1500米/分钟，牵伸倍数2.3倍的条件下进行高速熔融纺丝，得到尼龙6纤维，纤维直径23μm。将所得纯尼龙6纤维织物化，所得织物根据GB/T130127‐2013进行测试，测试结果见附表2。
附表2中给出了由纯尼龙6和石墨烯/尼龙6纳米复合材料与各种助剂共混后进行高速熔融纺丝，再将石墨烯/尼龙6纤维织物化后所得织物的远红外发射率进行对比。其中实施例1、2、3、4为石墨烯添加量在本发明范围内，与纯尼龙6相比，远红外保健功能优越；实施例5中，每平米织物中石墨烯/尼龙6纤维少于80g，远红外发射率较低，说明每平米织物中石墨烯/尼龙6纤维不能少于80g；实施例6中，石墨烯横向尺寸500nm，小于1μm，远红外发射率低，说明石墨烯横向尺寸对远红外发射性能关键。实施例7中石墨烯添加量为0.6％时，单层石墨烯发生堆叠，高速纺丝时发生喷丝孔堵塞，不能得到连续纤维。实施例8中，石墨烯碳氧比小于3，石墨烯含有大量缺陷导致石墨烯共轭区域较小，织物远红外发射率不理想。实验数据表明，只有石墨烯碳氧比在3‐6之间可以获得远红外发射率较高的石墨烯/尼龙6织物；其中石墨烯碳氧比在4.5‐6之间效果最佳，石墨烯用量最少。大量实验数据表明，只有采用技术参数在本发明所指范围内的石墨烯，才能得到具较好远红外保健功能的石墨烯/尼龙6织物。
附表2
Figure PCTCN2018075701-appb-000002
Figure PCTCN2018075701-appb-000003
实施例3‐1
将0.1质量份的碳氧比为3.2、横向尺寸为2μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗氧化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维208g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
该产物的紫外防护性能随洗涤次数变化测试如图4所示，从图中可以看出织物的紫外防护系数在20次洗涤后没有明显变化；由此可见，本发明在保证可纺性的同时，实现了紫外防护剂与纤维基体之间从传统的物理结合的方式(涂覆方法、共混方式)向化学结合方式的转变，使得石墨烯与尼龙6纤维基体之间具有相当稳定的化学结合，大大提升了织物的紫外防护效果并延长了织物的使用寿命。
实施例3‐2
将0.2质量份的碳氧比为5.1、横向尺寸为7μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗氧化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维180g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
实施例3‐3
将0.3质量份的碳氧比为3.2、横向尺寸为5μm的单层石墨烯和10质量份的去离子水加 入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维150g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
实施例3‐4
将0.05质量份的碳氧比为3.2、横向尺寸为8μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份各种助剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维180g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
实施例3‐5
将0.1质量份的碳氧比为3.2、横向尺寸为5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗老化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维144g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
实施例3‐6
将0.1质量份的碳氧比为3.5、横向尺寸为0.5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗老化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/ 尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维200g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
实施例3‐7
将0.6质量份的碳氧比为3.2、横向尺寸为5μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6复合材料与1份抗老化剂分散均匀后在310℃进行高速熔融纺丝，发现石墨烯/尼龙6纳米复合材料堵塞了纺丝喷头，不能得到石墨烯/尼龙6纤维。
实施例3‐8
将0.1质量份的碳氧比为2.1、横向尺寸为9μm的单层石墨烯和10质量份的去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(400rpm)搅拌混匀形成分散液；氮气保护下，将上述分散液在缩聚反应釜中升温至250℃，在0.7Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。得到的石墨烯/尼龙6纳米复合材料与0.5份抗老化剂分散均匀后在295℃，纺丝速度1000米/分钟，牵伸倍数3倍的条件下进行高速熔融纺丝，得到石墨烯/尼龙6纤维。将所得石墨烯/尼龙6纤维织物化，每平米所用石墨烯/尼龙6纤维210g，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
对比例3‐1：
将己内酰胺熔融加入至缩聚反应釜内，并升温至255℃，在0.75Mpa下反应3小时，然后在真空下反应4小时，得到缩聚物熔体；再将聚合物熔体经水冷造粒得到尼龙6。得到的尼龙6与1份抗老化剂分散均匀后在260℃，纺丝速度1500米/分钟，牵伸倍数2.3倍的条件下进行高速熔融纺丝，得到尼龙6纤维，纤维直径23μm。将所得纯尼龙6纤维织物化，所得织物根据GB/T18830‐2009进行测试，测试结果见附表3。
附表3中给出了由纯尼龙6和石墨烯/尼龙6纳米复合材料与各种助剂共混后进行高速熔融纺丝，再将石墨烯/尼龙6纤维织物化后所得织物的紫外防护性能进行对比。其中实施例1、2、3、4为石墨烯添加量在本发明范围内，与纯尼龙6相比，紫外防护性能优越；实施例5中，每平米织物中石墨烯/尼龙6纤维少于150g，紫外防护效果差，说明每平米织物中石墨烯/尼龙6纤维不能少于150g；实施例6中，石墨烯横向尺寸500nm，小于1μm，紫外防护效果差，说明石墨烯横向尺寸对紫外防护性能非常关键，大量实验证明在石墨烯横向尺寸在2‐10μm最有利于提高织物的紫外防护性能。实施例7中石墨烯添加量为0.6％时，单层石墨 烯发生堆叠，高速纺丝时发生喷丝孔堵塞，不能得到连续纤维。实施例8中，石墨烯碳氧比小于2.5，石墨烯含有大量缺陷导致织物紫外防护效果并不理想。大量实验数据表明，只有采用技术参数在本发明所指范围内的石墨烯，才能得到具较好紫外防护性能的石墨烯/尼龙6织物。
附表3
Figure PCTCN2018075701-appb-000004

Claims (22)

  1. 一种高强高模量石墨烯/尼龙6纤维，其特征在于，所述纤维由100重量份的石墨烯/尼龙6纳米复合材料和0～5重量份的助剂经高速熔融纺丝得到，所述石墨烯/尼龙6纳米复合材料由尼龙6和接枝有尼龙6的单层石墨烯组成，所述石墨烯/尼龙6纳米复合材料相对粘度在3.2-3.6之间，所述接枝有尼龙6的单层石墨烯的横向尺寸大于2微米；石墨烯的质量与尼龙6的总质量之比为0.1-0.5:100。
  2. 一种高强高模量石墨烯/尼龙6纤维的制备方法，其特征在于，所述方法为：将100重量份的石墨烯/尼龙6纳米复合材料和0～5重量份的助剂混合均匀后，经高速熔融纺丝，即可得到高强度高模量石墨烯/尼龙6纤维。
  3. 根据权利要求1或2所述的石墨烯/尼龙6纤维，其特征在于，所述石墨烯/尼龙6纳米复合材料通过以下方法制备得到：
    (1)将0.1-0.5质量份的改性石墨烯、0.05-0.3质量份分子量调节剂和1-10质量份去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(300～500rpm)搅拌混匀形成分散液；所述改性石墨烯为表面具有羧基、羟基的单层石墨烯；碳氧比为2.5到6之间；
    (2)在氮气保护下，将上述分散液在缩聚反应釜中升温至250-270℃，在0.5-1MPa下反应3小时；然后在真空下反应4小时，得到聚合物熔体；最后将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。
  4. 根据权利要求3所述的石墨烯/尼龙6纤维，其特征在于，所述石墨烯的横向尺寸大于3μm。
  5. 根据权利要求4所述的石墨烯/尼龙6纤维，其特征在于，所述石墨烯的横向尺寸为3-10μm。
  6. 根据权利要求3所述的石墨烯/尼龙6纤维，其特征在于，所述的分子量调节剂可以是甲酸、乙酸、丙酸、氨水、甲胺、乙胺、丙胺、乙二胺中的一种或多种按照任意配比组成。
  7. 根据权利要求1或2所述的石墨烯/尼龙6纤维，其特征在于，高速熔融纺丝的条件为：熔体温度在250-320℃，连续纺丝速度为1000-4000米/分钟，牵伸倍数为4-6倍。
  8. 根据权利要求1或2所述的石墨烯/尼龙6纤维，其特征在于，所述助剂由抗氧化剂、抗老化剂、热稳定剂、抗静电剂中的一种或多种按照任意配比组成。
  9. 一种具有永久远红外保健功能的石墨烯/尼龙6织物，其特征在于，所述织物由石墨烯/尼龙6复合纤维经织物化得到，每平方米织物中，石墨烯/尼龙6复合纤维用量不少于80g。所述石墨烯/尼龙6复合纤维由石墨烯/尼龙6纳米复合材料和助剂经高速熔融纺丝得到，所述石墨烯/尼龙6纳米复合材料由尼龙6和接枝有尼龙6的单层石墨烯组成，所述接枝有尼龙6的单层石墨烯的横向尺寸大于1微米；石墨烯的质量与尼龙6的总质量之比为0.01‐0.5:100；助剂与石墨烯/尼龙6复合材料质量比为0‐5:100。
  10. 根据权利要求9所述的石墨烯/尼龙6织物，其特征在于，所述石墨烯/尼龙6织物的远红外发射率大于0.88。
  11. 一种具有永久远红外保健功能的石墨烯/尼龙6织物的制备方法，其特征在于，该方法为：将石墨烯/尼龙6复合纤维进行织物化。每平方米织物中，石墨烯/尼龙6复合纤维用量不少于80g。
  12. 根据权利要求11所述的方法，其特征在于，所述石墨烯/尼龙6复合纤维通过以下方法制备得到：
    (1)将0.01‐0.5质量份的改性石墨烯和1‐10质量份去离子水加入100质量份的己内酰胺熔体中，在80℃下高速(300～500rpm)搅拌混匀形成分散液。所述改性石墨烯为表面具有羧基、羟基的单层石墨烯；碳氧比为3.0到6之间；
    (2)在氮气保护下，将上述分散液在缩聚反应釜中升温至250‐270℃，在0.5‐1MPa下反应3小时；然后在真空下反应4小时，得到聚合物熔体；最后将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料；
    (3)将上述复合材料和助剂进行高速熔融纺丝，高速熔融纺丝的条件为：熔体温度在250‐320℃，连续纺丝速度为600‐6000米/分钟，牵伸倍数为1.5‐4倍，所得纤维直径5‐50μm。
  13. 根据权利要求12所述的方法，其特征在于，所述石墨烯的横向尺寸大于1μm。
  14. 根据权利要求12所述的方法，其特征在于，所述石墨烯的碳氧比为4.5到6之间。
  15. 根据权利要求9所述的石墨烯/尼龙6织物，其特征在于，所述助剂由抗氧化剂、抗老化剂、热稳定剂、抗静电剂等中的一种或多种按照任意配比组成。
  16. 一种具有永久紫外防护性能的石墨烯/尼龙6织物，其特征在于，所述织物由石墨烯/尼龙6复合纤维经织物化得到，每平方米石墨烯/尼龙6复合纤维用量不少于150g。所述石墨烯/尼龙6复合纤维由石墨烯/尼龙6纳米复合材料和助剂经高速熔融纺丝得到，所述石墨烯/尼龙6纳米复合材料由尼龙6和接枝有尼龙6的单层石墨烯组成，所述接枝有尼龙6的单层石墨烯的横向尺寸大于1微米；石墨烯的质量与尼龙6的总质量之比为0.01‐0.5:100；助剂与石墨烯/尼龙6复合材料质量比为0‐5:100。
  17. 根据权利要求16所述的石墨烯/尼龙6织物，其特征在于，所述石墨烯/尼龙6织物的紫外防护系数UPF>40，紫外光透过率T(UVA)<5％。
  18. 一种具有永久紫外防护性能的石墨烯/尼龙6织物的制备方法，其特征在于，该方法为：将石墨烯/尼龙6复合纤维进行织物化。每平方米织物中，石墨烯/尼龙6复合纤维用量不少于150g。
  19. 根据权利要求18所述的方法，其特征在于，所述石墨烯/尼龙6复合纤维通过以下方法制备得到：
    (1)将0.01‐0.5质量份的改性石墨烯和1‐10质量份去离子水加入100质量份的己内酰 胺熔体中，在80℃下高速(300～500rpm)搅拌混匀形成分散液。所述改性石墨烯为表面具有羧基、羟基等含氧官能团的单层石墨烯；碳氧比为2.5到6之间；
    (2)在氮气保护下，将上述分散液在缩聚反应釜中升温至250‐270℃，在0.5‐1MPa下反应3小时；然后在真空下反应4小时，得到聚合物熔体；最后将聚合物熔体经水冷造粒得到石墨烯/尼龙6纳米复合材料。
    (3)将上述复合材料和助剂混合后，进行高速熔融纺丝，高速熔融纺丝的条件为：熔体温度在250‐320℃，连续纺丝速度为600‐6000米/分钟，牵伸倍数为1.5‐4倍。所得纤维直径5‐50μm。
  20. 根据权利要求18所述的方法，其特征在于，所述石墨烯的横向尺寸大于1μm。
  21. 根据权利要求20所述的方法，其特征在于，所述石墨烯的横向尺寸为2‐10μm。
  22. 根据权利要求16所述的石墨烯/尼龙6纤维，其特征在于，所述助剂由抗氧化剂、抗老化剂、热稳定剂、抗静电剂等中的一种或多种按照任意配比组成。
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