Classifications

• • 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
• • 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
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/08—Melt spinning methods
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—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
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—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
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
• • 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
  • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
  • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
  • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof

Definitions

• the invention belongs to the field of fiber preparation, and particularly relates to a modified fiber and a preparation method thereof, and the modified fiber comprises modified hollow cotton or modified nylon fiber.
• Polyester is an important variety in synthetic fiber. It is the trade name of polyester fiber in China. It is made of polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), which is spun and Post-processed fibers.
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PET Polyethylene terephthalate
• PTA polyterephthalic acid
• DMT dimethyl terephthalate
• EG ethylene glycol
• PBT polybutylene terephthalate
• PTA polyterephthalic acid
• DMT dimethyl terephthalate
• 1,4-butanediol 1,4-butanediol
• Polyester is the simplest one of the three synthetic fibers, and the price is relatively cheap, and it is characterized by its durability, elasticity, deformation, corrosion resistance, insulation, crispness, easy to wash and dry.
• Polyester hollow cotton is produced by special process of polyester microfiber of different specifications. Because it is like down, it is also called silk cotton or down cotton. It is widely used in down cotton clothes, down pants, ski shirts, winter clothes, down cotton. A variety of warm products such as car seat cushions. The disadvantages of the existing polyester hollow cotton are that the warmth is not high, the water is not washable, and it is not light enough.
• Polyamide known as polyamide fiber, commonly known as nylon (Nylon), English name Polyamide (referred to as PA), density of about 1.15g / cm 3 , is a generic term for thermoplastic resins containing repeating amide groups -NHCO- in the main chain of the molecule, including aliphatic PA, fat-aromatic PA and aromatic PA. Among them, aliphatic PA has many varieties, large yield and wide application, and its name is determined by the specific carbon number of the synthetic monomer.
• nylon has higher wear resistance than all other fibers, 10 times higher wear resistance than cotton, 20 times higher than wool, and some nylon is added to the blended fabric to greatly improve its abrasion resistance; When it reaches 3 to 6%, the elastic recovery rate can reach 100%; it can withstand tens of thousands of times without breaking.
• the strength of nylon fiber is 1 to 2 times higher than that of cotton and 4 to 5 times higher than that of wool, which is 3 times that of viscose fiber.
• nylon does not have thermal insulation properties. When it is used as a fabric such as socks and clothes, its heat preservation effect is not good, and it is particularly prone to cause joint pain and the like. For socks or close-fitting clothing, body dander can easily remain on it, breeding bacteria and causing odor.
• Graphene is a two-dimensional crystal with a thickness of one atom and is separated from the graphite material. It is the thinnest, strongest and most conductive nano-material.
• the addition of graphene to a matrix such as polyester or nylon is expected to impart new properties to polyester or nylon, especially to the addition of biomass graphene with bacteriostatic and low-temperature far-infrared functions. Polyester or nylon is promisingly bacteriostatic and low-temperature far-infrared.
• the solid state of graphene tends to agglomerate, forming a large particle agglomerate, and when it is added into a matrix such as polyester or nylon, it is not easily dispersed uniformly, which greatly reduces the processing fluidity of the base mother particles such as polyester or nylon, and thus cannot In the spinning process, graphene cannot be applied to a base material such as polyester or nylon.
• an object of the present invention is to provide a modified hollow cotton which is doped with graphene.
• modified hollow cotton of the present invention is obtained by doping graphene.
• the person skilled in the art can also be called hollow cotton blend, hollow cotton composite, hollow cotton modified, hollow containing graphene. Cotton or modified hollow cotton containing graphene.
• doping in the context of the present invention is meant that graphene is incorporated into hollow cotton in a variety of forms that can be envisioned by those skilled in the art, typically but not exclusively by dispersing on the surface of the hollow cotton or by in situ compounding The substrate of the modified hollow cotton, or physically blended with hollow cotton. Those skilled in the art can also replace “doping” with containing, including, dispersing, having, and the like.
• the so-called “hollow cotton” is a high-warm cotton wool product, and the fiber raw material is polyester.
• the graphene is biomass graphene.
• the biomass graphene is prepared from biomass; preferably, the biomass graphene is prepared from biomass-derived cellulose.
• a six-membered ring-shaped honeycomb sheet structure with a layer of more than 10 layers and a thickness of 100 nm or less is called a graphene nanosheet layer; a layer prepared by using biomass as a carbon source has more than 10 layers and a thickness of carbon within 100 nm.
• the six-membered ring-shaped honeycomb sheet structure is called a biomass graphene nanosheet layer; the six-membered loop honeycomb sheet layer structure with a layer number of 1 to 10 layers of carbon is called graphene; and the biomass is used as a carbon source.
• the six-membered ring-shaped honeycomb sheet structure having a layer of 1 to 10 layers of carbon is called biomass graphene.
• the graphene of the present invention includes a graphene nanosheet layer and graphene, and further includes a biomass graphene nanosheet layer and biomass graphene.
• the graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, chemical vapor deposition method, graphite redox method, hydrothermal carbonization method for biomass resources, and prior art.
• Graphene prepared by other methods it is difficult to achieve large-scale preparation of graphene in a strictly theoretical manner by any method.
• some impurity elements, other allotropes or layers of carbon elements may be present.
• Non-monolayer or even multi-layer graphene structures for example, 3 layers, 5 layers, 10 layers, 20 layers, etc.
• the graphene utilized in the present invention also includes the above-mentioned non-strict theoretical graphene.
• the biomass is selected from any one or a combination of at least two of agricultural forest waste and/or plants.
• the plant is any one or a combination of at least two of softwood or hardwood.
• the agricultural and forestry waste is any one or at least two of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalk, husk, and reed. The combination.
• the agricultural and forestry waste is a corn cob.
• biomass of the present invention may be any biomass resource known to those skilled in the art, and the present invention will not be further described.
• the biomass graphene of the present invention refers to a graphene prepared by using biomass as a carbon source, and a specific process for preparing graphene using biomass as a carbon source has been reported in the art, and typical but non-limiting includes CN104724699A, The present invention will not be described again.
• Typical, but not limiting, for the biomass graphene may be any one or a combination of at least two of substance 1, substance 2, substance 3 or substance 4 having the properties described in Table a:
• IG/ID is the peak height ratio of the G peak and the D peak in the Raman spectrum.
• the peak height ratio of the G peak and the D peak in the biomass graphene of the present invention is preferably ⁇ 2.0, further preferably ⁇ 3.0, particularly preferably ⁇ 5.0.
• the peak height ratio of the G peak and the D peak in the biomass graphene of the present invention is ⁇ 30, for example, 27, 25, 20, 18, 15, 12, 10, 8, 7, and the like.
• the performance index of the biomass graphene enumerated in Table a refers to the index of the powder of the biomass graphene. If the biomass graphene is a slurry, the above index is the preparation of the slurry. The index of the powder before the feed.
• the biomass graphene When the biomass graphene is a powder, the biomass graphene has the following properties in addition to the performance index described in Table a:
• Black powder uniform fineness, no obvious large particles, water content ⁇ 3.0%, particle size D90 ⁇ 10.0 ⁇ m, pH 5.0-8.0, apparent density 0.2-0.4g/cm 3 .
• the biomass graphene When the biomass graphene is a slurry, which is a product in which biomass graphene is dispersed in a solvent, the biomass graphene has the following properties in addition to the performance index described in Table a:
• the solid content is 1.0 to 10.0%, the particle size D50 is 0.7 um, the pH is 8.0 to 10.0, the zeta potential is ⁇ -10 mV, and the viscosity is 5.0 to 8.0 mPa ⁇ s.
• the biomass graphene belongs to a carbon-containing nanostructure composite containing graphene, amorphous carbon, and a non-carbon non-oxygen element; the non-carbon non-oxygen element includes Fe, Si, and Al elements.
• the non-carbon non-oxygen element content is from 0.5% by weight to 6% by weight of the composite.
• the carbon-containing nanostructure-containing composite has a carbon content of ⁇ 80 wt%, such as 82 wt%, 86 wt%, 89 wt%, 91 wt%, 94 wt%, 97 wt%, 99 wt%, etc., more preferably 85 wt% to 97 wt%. % is most preferably from 90% by weight to 95% by weight.
• the non-carbon non-oxygen element comprises from 0.3 wt% to 5 wt%, such as 0.7 wt%, 1.1 wt%, 1.3 wt%, 1.6 wt%, 2 wt%, 2.8 wt%, of the carbon nanostructure-containing composite, 3.5 wt%, 4.2 wt%, 5.3 wt% or 5.8 wt%, preferably 1.5 wt% to 5 wt%.
• the graphene structure is preferably a six-membered ring-shaped honeycomb sheet structure having carbon having a thickness of 100 nm or less, preferably a six-membered ring-shaped honeycomb sheet having carbon having a thickness of 20 nm or less.
• the structure is more preferably any one or a combination of at least two of the six-membered ring-shaped honeycomb sheet structures having a number of layers of 1 to 10 layers of carbon, and preferably any of a single layer, a double layer or a 3 to 10 layer structure.
• the carbon nanostructure-containing composite of the present invention preferably contains a graphene structure and amorphous carbon; the non-carbon non-oxygen non-hydrogen element is preferably a combination of any one or a combination of a simple substance, an oxide and a carbide.
• the form is adsorbed on the surface or inside of the carbon nanostructure.
• Amorphous carbon also contains two-dimensional graphite layer or three-dimensional graphite crystallites, and there are a large number of irregular bonds on the edge of the crystallite. In addition to containing a large amount of sp2 carbon, it also contains a lot of sp3 carbon.
• amorphous carbon is not a true amorphous body, but a crystal having the same structure as graphite, but the layered structure formed by the hexagonal annular plane of carbon atoms is disorderly and irregular, and crystal formation
• most of the amorphous carbon is a molecular layer of a graphite layer structure which is substantially parallel to each other and randomly stacked together, and may be simply referred to as a disordered layer structure. Interlayers or fragments are bonded by a diamond-structured tetrahedral bonding carbon atom.
• the biomass graphene can be prepared by the preparation method of the carbon nanostructure-containing composite, including the following steps (referred to as method 1):
• the heating rate in the steps (3) and (4) is from 14 ° C / min to 18 ° C / min.
• the biomass carbon source is one or more of lignocellulose, cellulose and lignin.
• the biomass graphene can be prepared by the preparation method of the carbon nanostructure-containing composite, including the following steps (referred to as method 2):
• the precursor In the protective atmosphere, the precursor is kept at 280-350 °C for 1.5-2.5 h, then the temperature is programmed to 950-1200 °C, and the heat is maintained for 3 ⁇ 4 h to obtain a crude product; the temperature rising rate of the programmed temperature is 15-20 °C. /min;
• the biomass carbon source and the catalyst mass ratio is 1: 0.1 ⁇ 10, preferably 1: 0.5 ⁇ 5, further preferably 1:1 ⁇ 3;
• the catalyst is selected from the group consisting of a manganese compound, an iron-containing compound, a cobalt-containing compound, and a nickel-containing compound. Any one or a combination of at least two of the compounds; preferably, the iron-containing compound is selected from the group consisting of a halogen compound of iron, a cyanide of iron, and a ferric acid salt, or a combination of at least two;
• the cobalt-containing compound is selected from any one or a combination of at least two of a halogen compound of cobalt and a cobalt-containing acid salt; preferably, the nickel-containing compound is selected from a nickel chloride salt and a nickel acid-containing compound.
• the catalyst is selected from the group consisting of iron chloride, ferrous chloride, iron nitrate, ferrous nitrate, iron sulfate, ferrous sulfate, potassium ferricyanide, and sub Any one or a combination of at least two of potassium ferricyanide, potassium trioxalate ferric acid, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate.
• the temperature at which the agitation is subjected to the catalytic treatment is 150 to 200 ° C, and the time is ⁇ 4 h, preferably 4 to 14 h; preferably, the moisture content in the precursor is 10 wt% or less; preferably, the precursor is heated to 280 ⁇
• the heating rate at 350 ° C is 3 to 5 ° C / min; preferably, the protective atmosphere is any one of nitrogen, helium, and argon, or a combination of at least two, preferably nitrogen; preferably, the crude product
• the washing is sequential pickling and water washing; the pickling preferably uses hydrochloric acid at a concentration of 3 to 6 wt%, further preferably hydrochloric acid at a concentration of 5 wt%; the water washing preferably uses deionized water and/or distilled water; preferably,
• the washing temperature is 55 to 65 ° C, preferably 60 ° C.
• the biomass carbon source is cellulose and/or lignin, preferably cellulose, further preferably porous cellulose;
• the porous cellulose is obtained by the following method:
• the biomass resource is subjected to acid hydrolysis to obtain lignocellulose, and then subjected to porous treatment to obtain porous cellulose; optionally, the porous cellulose is used after being bleached;
• the biomass resource is selected from any one or a combination of at least two of plant and/or agricultural and forestry waste; preferably any one or a combination of at least two of agricultural forest waste; preferably, said The agricultural and forestry waste is selected from the group consisting of corn cob, corn cob, sorghum, beet pulp, bagasse, furfural residue, xylose residue, wood chips, cotton stalks and reeds, or a combination of at least two, preferably corn cob.
• the biomass graphene can be prepared by the preparation method of the carbon nanostructure-containing composite, including the following steps (referred to as method 3):
• the corn cob is subjected to acid hydrolysis to obtain lignocellulose, and then subjected to porosification to obtain porous cellulose, and the porous cellulose is bleached and used;
• step (1') porous cellulose and the catalyst at a mass ratio of 1:0.5 to 1.5, stirring at 150 to 200 ° C for catalytic treatment for 4 hours or more, and drying to a precursor having a moisture content of less than 10% by weight to obtain a precursor body;
• the precursor is heated to 280-350 ° C at a rate of 3 to 5 ° C / min. 2h, after the temperature is programmed to 950 ⁇ 1050 ° C, heat preservation 3 ⁇ 4h to obtain a crude product; the temperature rising rate of the programmed temperature is 15 ⁇ 20 ° C / min;
• the carbon nanostructure-containing composite prepared by the above method is also a case containing biomass graphene.
• the biomass graphene of the present invention can also be prepared by the following preparation method of a carbon nanostructure-containing composite:
• Method 4 Using activated carbon resources to prepare activated carbon by existing processes, because the types and contents of trace elements in different plants are very different, so the content of non-carbon non-oxygen elements is controlled by later pickling, washing, etc. On the basis of this, graphene is introduced so that the non-carbon non-oxygen element accounts for 0.5% by weight to 6% by weight of the composite.
• Method 5 commercially available lignin, carbonized at a high temperature under an inert gas or subjected to incomplete graphitization reaction, and then added graphene, and later introduced nano-P, Si, Ca, Al, Na, Fe, Ni, Mn, A combination of any three or more of K, Mg, Cr, S or Co and the content thereof is controlled to be 0.5 wt% to 6 wt%.
• Method 6 For some organic wastes, such as phenolic resin foam sheets, after carbonization, graphene is introduced, and late introduction of nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or The combination of any three or more elements in Co and the content thereof is controlled to be 0.5 wt% to 6 wt%.
• Method 7 Adding activated carbon and graphene to the nano-graphite, and introducing any three or more elements of nano P, Si, Ca, Al, Na, Fe, Ni, Mn, K, Mg, Cr, S or Co later. Combine and control the content to be 0.5 wt% to 6 wt%.
• the biomass graphene of the present invention is not limited to the above production method.
• the biomass graphene prepared by the above method has far-infrared properties and antibacterial properties superior to the methods 4 to 7 obtained by the methods 1 to 3, but it is not necessary to activate the biomass graphene when preparing the downstream product or
• the modification treatment can be uniformly dispersed in the modified fiber, and has certain effects, especially the methods 1 to 3.
• the modified hollow cotton has a graphene content of 0.2 to 10% by weight, preferably 0.3 to 8% by weight, further preferably 0.5 to 5% by weight.
• the graphene content in the modified hollow cotton of the present invention is 0.3 wt%, 0.6 wt%, 0.9 wt%, 1.1 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2.1 wt%, 2.4.
• Wt% Wt%, 2.5 wt%, 2.8 wt%, 3.0 wt%, 3.4 wt%, 3.6 wt%, 3.9 wt%, 4.2 wt%, 4.5 wt%, 4.9 wt%, 5.2 wt%, 5.8 wt%, 6.3 wt% 6.5 wt%, 6.6 wt%, 6.9 wt%, 7.3 wt%, 7.5 wt%, 7.9 wt%, 8.2 wt%, 8.8 wt%, 9.3 wt%, 9.9 wt%, and the like.
• the doping amount of the graphene in the modified nylon fiber is 0.2 to 10% by weight, preferably 0.3 to 8% by weight, further preferably 0.5 to 5% by weight.
• the doping amount of graphene in the modified nylon fiber of the present invention is 0.3 wt%, 0.6 wt%, 0.9 wt%, 1.1 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, 2.1 wt.
• the far-infrared detection normal emissivity of the modified hollow cotton of the present invention is greater than 0.85, such as 0.87, 0.89, 0.91, 0.92, 0.93, etc., preferably greater than 0.88.
• the warming effect of the modified hollow cotton provided by the invention is: 1kg
• the warming effect of the modified hollow cotton according to the invention is the same as the warming effect of 2.5 ⁇ 3kg ordinary medium-hole cotton, and the air permeability is good while ensuring the warming effect. .
• the far-infrared detection normal emissivity of the modified nylon fibers of the present invention is greater than 0.85, such as 0.87, 0.89, 0.91, 0.92, 0.93, etc., preferably greater than 0.88.
• the modified nylon fiber provided by the invention has the far-infrared function, uses the same to make socks or clothes, has far-infrared emission, can protect human joints and avoid cold, and additionally, the modified nylon fiber added with graphene has antibacterial and antibacterial effect. It can be used to make fabrics, etc., and it will not produce odors for long-term use.
• Another object of the present invention is to provide an alternative method for preparing a modified hollow cotton according to one of the objects, comprising the steps of:
• the invention adopts a physical method for dispersing solid graphene and a polyester substrate, and obtains a modified hollow cotton uniformly dispersed with graphene.
• the present invention firstly mixes blank polyester chips with solid graphene, and extrudes the same into a graphene composite polyester masterbatch.
• the polyester masterbatch serves as a carrier of graphene and graphene.
• the preliminary dispersion is carried out; then the graphene-loaded polyester masterbatch is physically mixed with the blank polyester pellet in two steps according to the formula amount to obtain a material to be spun, in which the graphene is uniformly dispersed; Finally, according to the conventional hollow cotton preparation process, the hollow cotton uniformly dispersed with graphene can be obtained, which solves the problem that the prior art graphene is unevenly dispersed.
• Technical problems obtained modified hollow cotton with excellent heat retention, gas permeability, low temperature far infrared and antibacterial properties.
• the invention realizes preliminary dispersion by dispersing the easily agglomerated graphene particles in blank polyester chips, and then physically mixing the obtained master particles into blank polyester chips in two steps to achieve uniform dispersion of graphene, and obtaining uniform dispersion. Spinning material.
• the blank polyester chips of the step (A'-1) and the step (A'-2) are each independently PET and/or PBT.
• the blank polyester sheet of step (A'-1) is PET.
• the melting point of PET is about 220 ° C
• the melting point of PBT is about 270 ° C.
• the polyester sheet is preferably PET.
• the graphene-containing polyester masterbatch has a graphene content of 1 to 20 wt%, for example, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 12 wt%, 15 wt%, 17 wt%, 19 wt%, etc., preferably 5 ⁇ 15% by weight, further preferably 6 to 10% by weight.
• the melting temperature of the screw extrusion in the step (A'-1) is 230 to 270 ° C, for example, 235 ° C, 240 ° C, 244 ° C, 249 ° C, 253 ° C, 258 ° C, 262 ° C, 267 ° C, and the like. It is preferably 240 to 260 °C.
• the graphene-containing polyester masterbatch has a moisture content of ⁇ 600 ppm, such as 50 ppm, 80 ppm, 130 ppm, 180 ppm, 230 ppm, 280 ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc., preferably ⁇ 300 ppm.
• the mass ratio of the graphene-containing polyester masterbatch to the blank polyester pellet of the step (A'-2) is 1:5 to 30, for example, 1:6, 1:7, 1:9, 1:13, 1:16, 1:22, 1:26, 1:29, etc.; preferably 1:15-20.
• the ratio of the part of the blank polyester slice to the blank polyester slice added in the step (b) is 1:2 to 10, for example, 1:3, 1:4, 1:5. , 1:6, 1:7, 1:8, 1:9, etc., preferably 1:4-8.
• the blank polyester sheet b as a whole refers to the sum of the masses of the partially blank polyester sheets b and the remaining blank polyester sheets b.
• the melt-spun raw material of the step (A'-3) has an intrinsic viscosity of ⁇ 0.60 dL/g, for example, 0.62 dL/g, 0.66 dL/g, 0.69 dL/g, 0.72 dL/g, 0.75 dL/ g, 0.78 dL/g, 0.80 dL/g, 0.85 dL/g, etc., preferably ⁇ 0.65 dL/g.
• the addition of the graphene of the present invention reduces the viscosity of the slice, while the viscosity is too low to perform the spinning step.
• the step (A'-1') is performed before the step (A'-1): the blank polyester slice is pulverized into blank polyester chip particles for mixing with the graphene described in the step (A'-1);
• the blank polyester chip particles have a particle size of ⁇ 3 mm, such as 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, and the like.
• the blank polyester sheet is chopped to increase the rough surface, and the specific surface area and frictional force of the attached graphene are increased, whereby the dispersibility of the graphene can be further improved.
• a step (A'-2') is provided between the step (A'-2) and the step (A'-3): the step (A'-2) is mixed with a uniform material and subjected to screw extrusion again;
• the molten hollow of the modified hollow cotton has a melting temperature of 230 to 270 ° C, for example, 235 ° C, 240 ° C, 244 ° C, 249 ° C, 253 ° C, 258 ° C, 262 ° C, 267 ° C, etc., preferably 240 ° 260 ° C.
• the method for preparing hollow cotton according to the present invention comprises the following steps:
• a third object of the present invention is to provide another method for preparing a modified nylon fiber according to one of the objects, comprising the steps of:
• the invention adopts physical dispersion of solid graphene and nylon substrate to obtain modified nylon fiber uniformly dispersed with graphene.
• the present invention firstly mixes blank fiber sections with solid graphene, and extrudes the same into a graphene composite fiber masterbatch.
• the fiber masterbatch serves as a carrier of graphene, and graphene is used.
• the preliminary dispersion is carried out; then the fiber masterbatch loaded with graphene is physically mixed with the blank fiber slice in two steps to obtain the material to be spun, Among the materials, graphene achieves uniform dispersion; finally, according to the conventional nylon spinning preparation process, the modified nylon fiber uniformly dispersed with graphene can be obtained, which solves the problem that the prior art graphene is unevenly dispersed.
• a modified nylon fiber having excellent low-temperature far-infrared and antibacterial properties was obtained.
• the invention realizes preliminary dispersion by dispersing the easily agglomerated graphene particles in a blank nylon slice, and then physically mixing the obtained masterbatch in two steps with the blank nylon slice to achieve uniform dispersion of the graphene, and obtaining a uniform dispersion. Spinning material.
• the blank nylon chips of the step (B'-1) and the step (B'-2) are each independently any of PA-6, PA-66, PA-610, PA-1010, MCPA. 1 species.
• the graphene-containing nylon masterbatch has a graphene content of from 3 to 10% by weight, such as 4% by weight, 6% by weight, 8% by weight, 9% by weight, and the like, preferably from 5 to 8% by weight.
• the melting temperature of the screw extrusion in the step (B'-1) is 210 to 240 ° C, for example, 215 ° C, 217 ° C, 221 ° C, 225 ° C, 228 ° C, 231 ° C, 234 ° C, 238 ° C, etc. It is preferably 240 to 260 °C.
• the graphene-containing nylon masterbatch has a moisture content of ⁇ 600 ppm, such as 50 ppm, 80 ppm, 130 ppm, 180 ppm, 230 ppm, 280 ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc., preferably ⁇ 300 ppm.
• the mass ratio of the graphene-containing nylon masterbatch to the blank nylon slice in step (B'-2) is 1:5 to 30, for example, 1:6, 1:7, 1:9, 1:13, 1:16, 1:22, 1:26, 1:29, etc.; preferably 1:15-20.
• the ratio of the part of the blank nylon slice to the blank of the blank nylon slice added in the step (B'-2) is 1:2 to 10, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, etc., preferably 1:4-8.
• the blank nylon slice as a whole refers to the sum of the mass of a portion of the blank nylon slice and the remaining blank nylon slice.
• the melt-spun raw material of the step (B'-3) has an intrinsic viscosity ⁇ 3 dL/g, preferably ⁇ 2.7 dL/g.
• the addition of the graphene of the present invention increases the viscosity of the slice, while the viscosity is too high to perform the spinning step.
• the step (B'-1') is carried out before the step (B'-1): the blank nylon slice is pulverized into blank nylon chip particles for mixing with the graphene of the step (B'-1);
• the blank nylon chip particles have a particle size of ⁇ 3 mm, such as 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, and the like.
• the step (B'-1') shreds the blank nylon sheet to increase the rough surface, increases the specific surface area and frictional force of the attached graphene, and further improves the dispersibility of the graphene.
• a step (B'-2') is provided between the step (B'-2) and the step (B'-3): the step (B'-2) of the uniformly mixed material is again subjected to screw extrusion;
• the method for preparing the modified nylon fiber has a melting temperature of 210 to 240 ° C, for example, 215 ° C, 217 ° C, 221 ° C, 225 ° C, 228 ° C, 231 ° C, 234 ° C, 238 ° C, etc., preferably 240 ⁇ 260 ° C.
• a third object of the present invention is to provide a method for preparing a modified hollow cotton according to one of the objects, comprising the steps of:
• the invention adopts a physical method for dispersing solid graphene and a polyester substrate, and obtains a modified hollow cotton uniformly dispersed with graphene.
• the present invention first shreds blank polyester chips, increases the rough surface, increases the specific surface area and friction of the attached graphene, and improves the dispersibility of the graphene; then disperses the solid graphene in the blank polyester sheet.
• the graphene composite polyester masterbatch is obtained by screw extrusion.
• the polyester masterbatch is used as a carrier of graphene to preliminarily disperse graphene; then the graphene-loaded polyester masterbatch is loaded.
• the modified hollow cotton uniformly doped with graphene can be obtained, which solves the technical problem of uneven dispersion of graphene in the prior art, and obtains modified hollow cotton with excellent heat preservation, gas permeability, low temperature far infrared and antibacterial performance.
• the present invention realizes preliminary dispersion by dispersing the easily agglomerated graphene particles in the blank polyester chip particles, and then mixing the obtained master particles with the blank polyester chips to obtain a uniformly dispersed material to be spun.
• the blank polyester slice of the present invention refers to a polyester slice without the addition of functional particulate graphene.
• Uniform distribution means that the measured value has the same chance of appearing everywhere in a certain range.
• the uniform dispersion means that the content of graphene of the modified hollow cotton differs little in the range of any cubic centimeter.
• the blank polyester chip particles have a particle size of ⁇ 3 mm, such as 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, and the like.
• the blank polyester chips described in the step (A-1) and the step (A-3) are each independently PET (polyethylene terephthalate) and/or PBT (polyterephthalic acid). Butylene glycol ester).
• the blank polyester sheet of step (A-1) is PET.
• the melting point of PET is about 220 ° C
• the melting point of PBT is about 270 ° C.
• the first blank polyester sheet is PET
• the second blank polyester sheet is PET.
• the graphene-containing polyester masterbatch has a graphene content of 1 to 20 wt%, for example, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 12 wt%, 15 wt%, 17 wt%, 19 wt%, etc., preferably 5 -15 wt%, most preferably 6-10 wt%.
• the melting temperature of the screw extrusion in the step (A-2) is 230 to 270 ° C, for example, 235 ° C, 240 ° C, 244 ° C, 249 ° C, 253 ° C, 258 ° C, 262 ° C, 267 ° C, etc., preferably 240 ⁇ 260 ° C.
• the graphene-containing polyester masterbatch has a moisture content of ⁇ 600 ppm, such as 50 ppm, 80 ppm, 130 ppm, 180 ppm, 230 ppm, 280 ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc., preferably ⁇ 300 ppm.
• the mass ratio of the graphene-containing polyester masterbatch to the blank polyester pellet of the step (A-3) is 1:5 to 30, for example, 1:6, 1:7, 1:9, 1:13, 1 : 16, 1:22, 1:26, 1:29, etc.; preferably 1:15-20.
• the melt-spun raw material of the step (A-4) has an intrinsic viscosity of ⁇ 0.60 dL/g, for example, 0.62 dL/g, 0.66 dL/g, 0.69 dL/g, 0.72 dL/g, 0.75 dL/g. 0.78 dL/g, 0.80 dL/g, 0.85 dL/g, etc., preferably ⁇ 0.65 dL/g.
• the addition of the graphene of the present invention reduces the viscosity of the slice, while the viscosity is too low to perform the spinning step.
• the graphene-containing polyester masterbatch of the step (A-3) of the present invention and the blank polyester pellet are mixed as follows:
• step (A-3b) Continue to add the remaining blank polyester chips to the mixture of step (A-3a) and mix well.
• the polyester masterbatch containing graphene is diluted and dispersed in two steps with polyester chips to make graphene particles.
• the concentration of the particles reaches a predetermined requirement, and the graphene can be more uniformly dispersed, and the obtained modified hollow cotton is more excellent in heat retention, low temperature far infrared and antibacterial properties.
• the mass ratio of the portion of the blank polyester sheet of the step (A-3a) to the blank polyester sheet added by the step (A-3a) is 1:2 to 10, for example, 1:3, 1:4, 1:5. , 1:6, 1:7, 1:8, 1:9, etc., preferably 1:4-8.
• the blank polyester sheet added by the step (A-3a) as a whole refers to the sum of the quality of a part of the blank polyester sheet and the remaining blank polyester sheet.
• step (A-3') is provided between step (A-3) and step (A-4): the uniformly mixed material of step (A-3) is again subjected to screw extrusion;
• the screw extrusion has a melting temperature of 230 to 270 ° C, for example, 235 ° C, 240 ° C, 244 ° C, 249 ° C, 253 ° C, 258 ° C, 262 ° C, 267 ° C, etc., preferably 240 to 260 ° C.
• the method for preparing hollow cotton according to the present invention comprises the following steps:
• a second object of the present invention is to provide a method for preparing a modified nylon fiber according to one of the objectives, comprising the steps of:
• the invention adopts physical dispersion of solid graphene and nylon substrate to obtain modified nylon fiber uniformly dispersed with graphene.
• the present invention first shreds blank nylon slices to increase roughness Surface, increase the specific surface area and friction of the attached graphene, improve the dispersibility of graphene; then disperse the solid graphene in the blank nylon chip particles, and screw out the graphene composite nylon masterbatch in the graphene
• the nylon masterbatch is used as the carrier of graphene to preliminarily disperse the graphene; then the nylon masterbatch loaded with graphene is physically mixed with the blank nylon chips according to the formula amount to obtain the spun yarn to be spun.
• the graphene is uniformly dispersed; finally, the modified nylon fiber uniformly doped with graphene can be obtained by melt spinning according to a conventional spinning process for preparing a nylon fiber.
• the technical problem of uneven dispersion of graphene in the prior art is obtained, and the modified nylon fiber excellent in heat retention, gas permeability, low temperature far infrared and antibacterial property is obtained.
• the present invention achieves preliminary dispersion by dispersing easily agglomerated graphene particles in blank nylon chip particles, and then the obtained master particles are again mixed with blank nylon chips to obtain a uniformly dispersed to-be-spun material.
• the blank nylon slice of the present invention refers to a nylon slice without the addition of functional particulate graphene.
• Uniform distribution means that the measured value has the same chance of appearing everywhere in a certain range.
• the uniform dispersion means that the content of graphene of the modified nylon fibers differs little in the range of any centimeter.
• the blank nylon chip particles have a particle size of ⁇ 3 mm, such as 0.1 mm, 0.5 mm, 0.9 mm, 1.3 mm, 1.8 mm, 2.2 mm, 2.5 mm, 2.8 mm, and the like.
• the blank nylon chips described in the step (1) and the step (3) are each independently one of PA-6, PA-66, PA-610, PA-1010, and MCPA.
• the graphene-containing nylon masterbatch has a graphene content of from 3 to 10% by weight, such as 4% by weight, 6% by weight, 8% by weight, 9% by weight, and most preferably from 5 to 8% by weight.
• the melting temperature of the screw extrusion in the step (B-2) is 210 to 240 ° C, for example, 215 ° C, 217 ° C, 221 ° C, 225 ° C, 228 ° C, 233 ° C, 236 ° C, 238 ° C, etc., preferably 220 ⁇ 230 ° C.
• the graphene-containing nylon masterbatch has a moisture content of ⁇ 600 ppm, such as 50 ppm, 80 ppm, 130 ppm, 180 ppm, 230 ppm, 280 ppm, 350 ppm, 390 ppm, 420 ppm, 450 ppm, 480 ppm, etc., preferably ⁇ 300 ppm.
• the mass ratio of the graphene-containing nylon masterbatch to the blank nylon slice in the step (B-3) is 1:5 to 30, for example, 1:6, 1:7, 1:9, 1:13, 1 : 16, 1:22, 1:26, 1:29, etc.; preferably 1:15-20.
• the melt-spun raw material of the step (B-4) has an intrinsic viscosity of ⁇ 3 dL/g, preferably ⁇ 2.7 dL/g.
• graphene of the present invention increases the viscosity of the nylon chips, while the viscosity is too high to affect the spinning step.
• the mixture of the graphene-containing nylon masterbatch and the blank nylon slice of the step (B-3) of the present invention comprises the following steps:
• step (B-3b) Continue to add the remaining blank nylon chips to the mixture of step (B-3a) and mix well.
• the nylon masterbatch containing graphene is diluted and dispersed in two steps with nylon chips, so that the concentration of graphene particles reaches a predetermined requirement, and the graphene can be dispersed more uniformly, and the melt spinning process conditions are not too harsh, and
• the obtained modified nylon fiber is excellent in low-temperature far-infrared and antibacterial properties while maintaining good strength.
• the mass ratio of the part of the blank nylon piece of the step (B-3a) to the blank nylon piece added by the step (B-3a) is 1:2 to 10, for example, 1:3, 1:4, 1:5. , 1:6, 1:7, 1:8, 1:9, etc., preferably 1:4-8.
• the blank nylon slice added in the step (B-3a) as a whole refers to the sum of the quality of a part of the blank nylon slice and the remaining blank nylon slice.
• step (B-3') is provided between the step (B-3) and the step (B-4): the uniformly mixed material of the step (B-3) is again subjected to screw extrusion;
• the screw has a melting temperature of 210 to 240 ° C, for example, 215 ° C, 217 ° C, 219 ° C, 224 ° C, 227 ° C, 228 ° C, etc., preferably 240 to 260 ° C.
• the method for preparing the modified nylon fiber of the present invention comprises the following steps:
• step (A'-3), the step (B'-3), the step (A-4), and the step (B-4) are well known in the art.
• the melt spinning method is to obtain hollow fibers through a hollow spinneret, which is economical and reasonable, and the related process technology is relatively mature, and the process conditions can be controlled.
• the melt spinning is to insert a microporous conduit into the hollow spinneret, and to fill the fiber cavity with nitrogen or air to obtain a hollow hollow hollow fiber with high hollowness, thereby avoiding the mechanical decrease of the hollow fiber caused by the mechanical action during the production process.
• the thermal conductivity of the fiber is made worse than that of air, which greatly improves the warmth retention, and the control of the gas flow rate is a well-known method in the art.
• Those skilled in the art can also produce hollow fiber with various cross-sections such as triangles and plum blossoms by changing the shape of the spinneret holes to increase the specific surface area of the fibers, or obtain porous hollow fibers of 3 to 7 holes through a special spinneret.
• the airspeed may not be high, only within 30%.
• Those skilled in the art can also obtain hollow fiber or three-dimensionally crimped hollow fiber by direct melt spinning by designing the shape of the spinneret and rationally adjusting the spinning process (ring blowing asymmetric cooling and post-spinning stretching control technology).
• melt spinning can be adjusted to achieve a desired degree of hollowness, which can be typically, but not limited to,:
• the design of the spinneret includes its shape and structural dimensions.
• the former is used for the hollow fiber of the opposite cross section. Its design and production requirements are related.
• the commonly used hole shape has polygon, c shape, circular arc shape, multi-point shape, etc.
• the size of the silk plate structure may include the slit length of the spinning hole, the distance between the two slit tips, the equivalent diameter, the cross-sectional area, the aspect ratio data, and the like;
• the melt-spun spinning warm three-dimensionally crimped hollow fiber is typically, but not exclusively, a circular slit-type spinneret that can be easily spun into fibers having a relatively small outer diameter and a suitable hollowness.
• the arc slit type spinneret with better effect mainly has porous hollow fiber spinneret such as C-shaped and shape-shaped spinneret and arc combination, and is used for spinning hollow fiber of four holes, seven holes or even ten holes. .
• the melt is extruded into the arc slit of the spinneret, the arc-shaped melt is expanded, and the ends are bonded to form a hollow cavity, which is refined and solidified to form hollow fibers.
• the size of the arc slit gap of the spinneret may affect the formation of the hollow cavity: when the gap is too large, the fiber hollow cannot be closed, and only the open fiber can be spun; but when the gap is too small, the melt is squeezed. After the spinneret hole is quickly expanded and bonded, the hollow cavity cannot be formed, and from the viewpoint of mechanical strength, the spinneret gap is small, the strength is low, and the damage is easy. Therefore, for different materials, there are different sizes of suitable spinneret gaps. Typical but non-limiting examples are the extrusion ratio of the extruded melt raw material, which can guide the design of the gap of the spinneret and the width at the center of the gap. The ratio is slightly less than the die expansion ratio of the melt raw material.
• the slit width is large, the single hole extrusion amount is large, the cross-sectional area of the spun fiber is large, and the hollowness of the fiber is small; the width of the slit is small, the extrusion amount is small, and the hollowness of the spun fiber is large;
• the slit is too small, the wall of the spun fiber is too thin, the hollow gauge is low, and the hollow is easily deformed.
• the center width of the gap corresponds to 1.0 times the width of the slit; for a spinneret of the shape, the width at the center of the gap corresponds to 0.8 times the width of the slit.
• the hollow fiber membrane uses a melt-spinning spinneret in addition to the C-shape and the shape, and may also have a double-ring and a double-ring sleeve-shaped spinneret.
• the inner and outer diameters of the hollow fiber spun from the latter two spinnerets are uniform, and the concentricity is good. Due to the support of the gap material, the c-shape and the shape can be used to make a plurality of single holes at the same time in a single spinneret for spinning the bundle wire, and the output is large.
• the double-ring and double-ring sleeve-shaped spinnerets are composed of a plurality of components, it is difficult to make a porous spinneret, and most of them are only used for spinning a single hollow fiber membrane.
• Cooling forming includes conditions such as wind speed, wind temperature, and blowing distance. It has a great influence on the rheological properties of the melt flow on the spinning process, such as tensile flow viscosity and tensile stress, and directly determines the size of the hollowness. .
• the cooling conditions increase, and the solidification rate of the melt stream is accelerated, so that the hollow fiber cavity formed on the spinning process can not be atrophied and accelerates to solidify, which is beneficial to the formation of the hollow fiber cavity.
• the hollowness of the fiber is high, but the wind speed is too large, which will cause the yarn to shake and sway, so that the temperature of the surface of the spinneret is lowered, the wire is not smooth, and the hard wire is easily generated, and the broken wire is broken with the wind temperature.
• the cooling forming conditions are strengthened, the solidification rate of the melt flow is improved, and the hollow fiber is high in hollowness.
• the wind temperature is too low, the surface of the spinneret is easy to blow cold, and spinning is difficult.
• the amount of gas flow into the casing may also affect the hollowness of the fiber.
• Those skilled in the art have the ability to prepare hollow fiber membranes having suitable hollowness by selecting the ratio of the amount of gas supplied to the pumping amount of the spinning slurry.
• the ring blowing asymmetric cooling process includes four aspects: blowing speed, temperature and humidity, and uniformity. Increasing the wind speed can enhance the asymmetric structure of the fiber cross section to obtain a virgin fiber with better potential curl, but excessive wind speed may cause the yarn to oscillate, the yarn is not smooth, the pre-oriented degree of the original yarn is large, and the tensile property is deteriorated.
• the skilled person can select a suitable wind speed to balance the potential curling and tensile properties of the strand; although reducing the ring blowing temperature causes the cooling condition to be aggravated, at the same time the pre-orientation of the strand is increased and the tensile properties are degraded, so those skilled in the art also need to select Suitable air temperature; the ring blower can also have a certain humidity to reduce the electrostatic phenomenon and the wire rod disturbance during the spinning process, control the cooling condition; at the same time, improve the uniformity of the ring blowing to ensure the spinning stability and the post-spinning tensile performance.
• the purpose of stretching the three-dimensional crimped hollow fiber is not to improve the mechanical properties of the fiber, but to reflect the stress difference and potential curl inside the nascent fiber.
• the stress on each single fiber cross section should be pulled as much as possible. Poor, and this difference between the single fibers is kept at the same level, so the hollow fiber generally adopts a one-time stretching process.
• the stretching medium has a steam stretching and a water bath stretching: the water bath is stretched with heated oil water as a medium, and the fibers are subjected to secondary orientation during stretching, resulting in a decrease in fiber internal structural difference.
• the curling and fluffing performance is degraded; the steam drawing is saturated with water vapor as the medium, and the adiabatic stretching is performed once, and the crystal structure of the fiber is more obvious and stable after the steam drawing.
• the draw ratio and temperature are selected to take into account both the tensile properties of the nascent fibers and the release of the curl.
• the hollow control of the hollowness runs through the entire melt spinning process, and there is control of the hollowness from the size of the orifice to the post-spinning process.
• the typical but non-limiting width of the slit of the spinneret and the distance between the tips of the two slits are suitable preconditions for the hollowness of the hollow fiber hollow fiber; and the spinning temperature and the cooling forming condition are the main process factors for controlling the hollowness.
• Low spinning temperature, high melt viscosity, melt deformation resistance and surface tension are advantageous for hollow formation, but too low will cause hard filaments and the like; and as the draw ratio is increased, the fiber walls become thinner and the hollowness is increased.
• melt spinning process conditions For the melt spinning process, which is well known in the art, those skilled in the art can obtain specific melt spinning process conditions according to their own professional knowledge and background technology. Typical but non-limiting melt spinning process conditions can be:
• the warmth-protecting product is selected from the group consisting of a quilt, a pillow, a cushion, a clothes, a sleeping bag or a tent;
• the garment is selected from the group consisting of a warm shirt, a thermal underwear, a down jacket, a down vest or a down pants.
• the preparation method of the quilt, the pillow, the cushion, the clothes, the sleeping bag, the tent, and the warm shirt, the thermal underwear or the down jacket of the present invention refers to the preparation method of the corresponding product in the prior art in the prior art, and the invention is not specifically limited, and even Reference is made to the art for preparing a corresponding product by unmodified hollow cotton.
• modified nylon fiber according to any one of the objects, wherein the modified nylon fiber is used as any one of a knitwear, a medical article, and an outdoor article.
• the modified nylon fiber is used as a nylon stocking, a nylon shawl, a mosquito net, a nylon lace, a stretch nylon outer cover, a nylon silk or an interwoven silk product.
• the modified nylon fiber is used as a blending material with wool or other chemical fiber to form a clothing.
• the modified nylon fiber is used as a cord, industrial cloth, cable, conveyor belt, tent, fishing net or fishing line.
• a nylon fabric which is woven or blended from a modified nylon fiber as described in one of the objects.
• a nylon stocking which is woven or blended from a modified nylon fiber as described in one of the objects.
• the present invention has the following beneficial effects:
• step (B) taking 2 g of the graphite oxide obtained in the step (A) in a three-necked flask, and gradually adding 25 g of potassium permanganate in an ice water bath with 150 mL of a concentrated sulfuric acid solution, and stirring for 2 hours;
• step (C) The three-necked flask of the above step (B) was transferred to an oil bath, heated to 35 ° C, stirred for 2 hours, stirring was continued, and a mixed solution of 30 wt% of hydrogen peroxide and deionized water was added in an amount of 1:15 by volume. Filtration, respectively, using 4 mL of 10% dilute hydrochloric acid and deionized water for 1 wash, centrifugation, and drying to obtain the first oxidized graphene oxide;
• step (D) 2 g of graphene oxide prepared in step (C) was again mixed with 50 mL of concentrated sulfuric acid solution in a three-necked flask under ice water bath, gradually adding 8 g of KMnO 4 and stirring for 1 hour;
• step (E) The three-necked flask of the above step (D) was transferred to an oil bath, heated to 40 ° C, stirred for 1 hour, and then further heated to 90 ° C. After stirring for 1 hour, stirring was continued and the volume ratio was 1:7. Add 30wt% mixed solution of hydrogen peroxide and deionized water, continue stirring for 6 hours, then cool, suction filtration, wash with 2mL of 10% dilute hydrochloric acid and deionized water twice, centrifuge, and dry to obtain uniform size. Graphene oxide.
• the straw was collected, cleaned, cut into small pieces, immersed in an ethanol solution, and stirred at a constant speed of 100 r/min for 5 hours; then the solution was transferred to a high-speed centrifuge at a speed of 3000 r/min and a centrifugation time of 20 minutes. After the end, take the next layer of the sample. Under normal temperature and pressure, the sample was placed in a cell culture dish with a diameter of 15 cm, placed at the air inlet, and the flow parameters were adjusted. The wind speed was set to 6 m/s, the air volume was 1400 m3/h, and the ventilation state was maintained for 12 hours; The furnace was heated to 1300 ° C, and was purged with inert gas for 30 minutes. The dried sample was placed in a tube furnace and heated for 5 hours. After cooling to room temperature, graphene with relatively obvious peeling was obtained.
• the preparation method of conventional cellulose is specifically:
• the treated wheat straw is cooked using an organic acid solution of formic acid and acetic acid having a total acid concentration of 80% by weight, and the quality of acetic acid and formic acid in the organic acid solution of the present embodiment
• the ratio is 1:12, and 1 wt% of hydrogen peroxide (H2O2), which is the raw material of wheat straw, is added as a catalyst before the feedstock is added.
• the reaction temperature is controlled at 120 ° C, the reaction is carried out for 30 min, and the solid-liquid mass ratio is 1:10.
• the reaction solution is subjected to a first solid-liquid separation;
• the solid obtained by the first solid-liquid separation is added to an organic acid solution having a total acid concentration of 75 wt% of formic acid and acetic acid for acid washing, wherein the total acid concentration of 75 wt% of the organic acid solution is added to the wheat straw.
• step (3) collecting the liquid obtained by the first and second solid-liquid separation, performing high-temperature and high-pressure evaporation at 120 ° C, 301 kPa until evaporation to dryness, and condensing the obtained formic acid and acetic acid vapor back to the reaction kettle of the step (1). Used as a cooking liquor for the cooking of step (1);
• step (5) collecting the liquid obtained by the third solid-liquid separation, performing water and acid distillation, and returning the obtained mixed acid solution to the reaction vessel of the step (1) for use as a cooking liquid for the cooking of the step (1).
• Water is used in step (5) to act as water for washing;
• the precursor is heated to 170 ° C at a rate of 3 ° C / min, and kept for 2 h, after which The temperature is programmed to 400 ° C, heat for 3 h, then warmed to 1200 ° C, after 3 h of heat to obtain a crude product; the temperature rising rate of the programmed temperature is 15 ° C / min;
• a hollow cotton which differs from Embodiment 1 in that:
• a hollow cotton which differs from Embodiment 1 in that:
• a hollow cotton which differs from Embodiment 1 in that:
• a hollow cotton which differs from Embodiment 1 in that:
• Step (3') is carried out after the step (3): the material obtained in the step (3) is screw extruded at 250 °C.
• a hollow cotton which differs from Embodiment 6 in that:
• a hollow cotton which differs from Embodiment 6 in that:
• a hollow cotton differs from Example 1 in that the pulverization step of the step (1) is not carried out, and 1 kg of graphene powder (graphene powder obtained in the graphene preparation example 3) and 9 kg of PET are directly directly introduced in the step (2). Blank polyester slice mix.
• a hollow cotton differs from Example 1 in that step (3) directly mixes 1 kg of graphene-containing polyester masterbatch with 6 kg of PET blank polyester pellets; and then proceeds to step (4).
• a hollow cotton differs from the first embodiment in that the graphene powder obtained in the graphene preparation example 3 is replaced with the graphene powder obtained in the graphene preparation example in the step (2).
• a hollow cotton differs from the first embodiment in that the graphene powder obtained in the graphene preparation example 3 is replaced with the graphene powder obtained in the graphene preparation example 2 in the step (2).
• Example 1 The difference from Example 1 is that the pulverization step of the step (1) is not carried out, and 1 kg of graphene powder and 9 kg of PET blank polyester chips are directly mixed in the step (2); and the step (3) directly applies 1 kg of graphene-containing polyester.
• the masterbatch was uniformly mixed with 6 kg of PET blank polyester chips; then step (4) was carried out.
• a white duck down with a cashmere content of 90% was used as a comparative example 2.
• step (2) The material obtained in the step (1) is melted, and then spun, and after the completion of the spinning, the polyester hollow cotton is obtained by opening.
• polyester hollow cotton prepared in the examples and the comparative examples was tested as follows:
• Warming rate the test method is GBT11048-2008 Determination of thermal resistance and moisture resistance under steady state conditions of textile physiological comfort
• Air permeability the test method is GBT5453-1997 textile material permeability test
• PA-6 and PA-66 as raw materials to prepare modified nylon fiber as an example:
• a modified nylon fiber is prepared by the following method:
• a modified nylon fiber differs from Example 1 in that:
• the material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the modified PA-6 fiber is obtained, and the graphene content is 2% by weight, and the spinning can be performed normally for 8 hours.
• a modified nylon fiber differs from Example 1 in that:
• the material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the modified PA-6 fiber is obtained, and the graphene content is 1% by weight, and the spinning can be performed normally for 8 hours.
• a modified nylon fiber differs from Example 1 in that:
• a modified nylon fiber differs from Example 1 in that:
• Step (3') is carried out after the step (3): the material obtained in the step (3) is screw extruded at 210 °C.
• a modified nylon fiber is prepared by the following method:
• the material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the modified PA-66 fiber is obtained, and the graphene content is 3 wt%, and the spinning can be performed normally for 8 hours.
• a modified nylon fiber differs from Example 6 in that:
• a modified nylon fiber differs from Example 6 in that:
• the material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the modified PA-66 fiber is obtained, and the graphene content is 10% by weight, and the spinning can be performed normally for 8 hours.
• a modified nylon fiber differs from Example 1 in that the pulverization step of the step (1) is not carried out, and 1 kg of graphene powder (graphene powder obtained in the graphene preparation example 3) and 9 kg are directly directly introduced in the step (2).
• the blank PA-66 slices were mixed and able to be spun normally for 8 hours.
• a modified nylon fiber differs from Example 1 in that step (3) directly mixes 1 kg of graphene-containing PA-66 masterbatch with 6 kg of blank PA-66 slice uniformly; and then proceeds to step (4).
• a modified nylon fiber differs from Example 1 in that the graphene powder obtained in the graphene preparation example 1 is replaced with the graphene powder obtained in the graphene preparation example 3 in the step (2).
• a modified nylon fiber differs from Example 1 in that the graphene powder obtained in the graphene preparation example 2 was replaced with the graphene powder obtained in the graphene preparation example 2 in the step (2).
• Example 1 The difference from Example 1 is that the pulverization step of the step (1) is not carried out, and 1 kg of graphene powder and 9 kg of blank PA-6 chips are directly mixed in the step (2); and the step (3) directly applies 1 kg of graphene-containing The PA-6 masterbatch was uniformly mixed with 6 kg of blank PA-6 chips; then step (4) was carried out.
• breaking strength and elongation at break the test method is GB/T 3923.1-1997 fabric breaking strength and elongation at break;
• Air permeability the test method is GBT5453-1997 textile material permeability test
• the present invention illustrates the process of the present invention by the above-described embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of the materials selected for the present invention, and the addition of the auxiliary ingredients, the selection of the specific means, etc., are all within the scope of the present invention.

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• 2016
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