WO2017084622A1

WO2017084622A1 - Modified fiber and preparation method therefor

Info

Publication number: WO2017084622A1
Application number: PCT/CN2016/106435
Authority: WO
Inventors: 唐一林; 张金柱; 王双成; 马军强; 张安
Original assignee: 济南圣泉集团股份有限公司
Priority date: 2015-11-20
Filing date: 2016-11-18
Publication date: 2017-05-26
Also published as: EP3378978B1; KR20180085768A; EP3378978A1; EP3378978A4; CA3005917C; CA3005917A1

Abstract

Modified fiber and a preparation method therefor. By means of a physical method, uniform dispersion of graphite particles in a polyester base material and a polyamide base material is realized, the technology is simple, a dispersing agent is not needed, and industrial production is easy. By introducing graphene into hollow cotton or polyamide fiber, and particularly introducing biomass graphene into the hollow cotton or polyamide fiber, modified hollow cotton or polyamide fiber is enabled to have a low-temperature far infrared function, the far infrared normal emittance thereof being not less than 0.85; the antibacterial performance is greater than 90%; and the heat preservation performance and the air permeability are both remarkable, and when the content of the biomass graphene is 1.4%, the heat preservation rate is equal to that of white duck down and is about 90%, but the air permeability is about 240mm/s and is far higher than that of the duck down.

Description

Modified fiber and preparation method thereof

Technical field

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.

Background technique

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.

Polyethylene terephthalate (PET) is esterified or transesterified and polycondensed with polyterephthalic acid (PTA) or dimethyl terephthalate (DMT) and ethylene glycol (EG). And the resulting fiber-forming polymer. Polybutylene terephthalate (PBT) is esterified or transesterified and polycondensed with polyterephthalic acid (PTA) or dimethyl terephthalate (DMT) and 1,4-butanediol. A fiber-forming polymer produced by the reaction.

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.

The most outstanding advantage of nylon is that it 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.

However, 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.

Therefore, there is a need to develop a functional modified nylon fiber.

Graphene (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. Features.

However, 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.

In the prior art, in order to uniformly disperse graphene, a dispersant is often added, but the dispersant has a degrading effect on the material, how to find a method for uniformly doping the graphene in a substrate such as polyester or nylon without adding a dispersant. The full application of graphene properties (such as thermal insulation properties, low temperature far infrared and bacteriostatic properties) is an urgent problem to be solved in the field.

Summary of the invention

In view of the prior art, graphene can not be doped into fiber materials (including polyester materials and nylon materials) without using a dispersant, and a modified hollow having thermal insulation properties, low-temperature far-infrared properties or antibacterial properties can be obtained. Technical Problem of Cotton or Modified Nylon Fibers, an object of the present invention is to provide a modified hollow cotton which is doped with graphene.

The "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.

By "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.

Preferably, 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. However, it is difficult to achieve large-scale preparation of graphene in a strictly theoretical manner by any method. For example, in the graphene prepared by the prior art, 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.

Preferably, the biomass is selected from any one or a combination of at least two of agricultural forest waste and/or plants.

Preferably, the plant is any one or a combination of at least two of softwood or hardwood.

Preferably, 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.

Preferably, the agricultural and forestry waste is a corn cob.

In addition to the above enumeration of biomass, the 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:

Table a

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. Alternatively, 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.

It should be apparent to those skilled in the art that 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.

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≤10.0μm, pH 5.0-8.0, apparent density 0.2-0.4g/cm ³ .

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.

Preferably, 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.

Preferably, 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%.

In the carbon nanostructure-containing composite of the present invention, 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. 1 species Or a combination of at least two; preferably, the six-membered ring-shaped honeycomb sheet structure of carbon in the composite microscopically exhibits any one or a combination of at least two of a warp, curl, and folded conformation.

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. In fact, the internal structure of them (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 Defectively, 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.

Illustratively, 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):

(1) catalytically treating a biomass carbon source under the action of a catalyst to obtain a precursor;

(2) maintaining the precursor at 140 ° C to 180 ° C for 1.5 h to 2.5 h under protective gas conditions to obtain a first intermediate;

(3) heating the first intermediate to 350 ° C ~ 450 ° C for 3 h ~ 4 h under protective gas conditions to obtain a second intermediate;

(4) heating the second intermediate to a temperature of 1100 ° C to 1300 ° C for 2 h to 4 h under a protective gas condition to obtain a third intermediate;

(5) sequentially washing the third intermediate with alkali, pickling, and washing with water to obtain a composite;

The heating rate in the steps (3) and (4) is from 14 ° C / min to 18 ° C / min.

Preferably, the biomass carbon source is one or more of lignocellulose, cellulose and lignin.

Illustratively, 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):

(1) mixing a biomass carbon source and a catalyst, stirring for catalytic treatment, and drying to obtain a precursor;

(2) 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;

(3) After washing the crude product, a composite containing carbon nanostructures is obtained.

In an alternative embodiment 2, the biomass carbon source and the catalyst mass ratio is 1: 0.1 ~ 10, preferably 1: 0.5 ~ 5, further preferably 1:1 ~ 3;

Preferably, 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; Preferably, 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. Any one or a combination of at least two of the salts; preferably, 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;

Preferably, 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;

Preferably, 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.

Illustratively, 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):

(1') 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;

(1) mixing the 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;

(2) In a protective atmosphere, 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;

(3) The crude product was acid-washed at a concentration of 5 wt% hydrochloric acid at 55 to 65 ° C, and then washed with water to obtain a composite containing carbon nanostructures.

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.

Preferably, 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.

Illustratively, 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%, 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.

Preferably, 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.

Illustratively, 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. %, 2.4 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.

Preferably, 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. .

Preferably, 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:

(A'-1) mixing graphene with blank polyester chips, extruding with a screw, and drying to obtain a polyester masterbatch containing graphene;

(A'-2) uniformly mixing the polyester masterbatch containing graphene with a portion of the blank polyester pellet, and then mixing with the remaining blank polyester pellet b;

(A'-3) melt-spinning the obtained material, and then opening to obtain a modified hollow cotton;

The invention adopts a physical method for dispersing solid graphene and a polyester substrate, and obtains a modified hollow cotton uniformly dispersed with graphene. Specifically, the present invention firstly mixes blank polyester chips with solid graphene, and extrudes the same into a graphene composite polyester masterbatch. In the 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.

Preferably, the blank polyester chips of the step (A'-1) and the step (A'-2) are each independently PET and/or PBT.

Preferably, the blank polyester sheet of step (A'-1) is PET.

The selection of the blank polyester chips of the step (A'-1) and the step (A'-2) of the present invention is not specifically limited, and those skilled in the art can select according to actual conditions. However, the melting point of PET is about 220 ° C, and the melting point of PBT is about 270 ° C. From the viewpoint of energy saving of process temperature, the polyester sheet is preferably PET.

Preferably, 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.

Preferably, 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.

Preferably, 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.

Preferably, 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.

Preferably, in the step (A'-2), 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.

Preferably, 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.

As a preferred technical solution, 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);

Preferably, 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.

In the step (a'), 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.

Further preferably, 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;

Preferably, 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.

Conventional polyester after two times of screw extrusion will cause the breakage of the polyester polymer molecules, reduce the molecular chain length and the strength of the polyester, and finally cause the drawing length to be insufficient in the process of preparing the hollow cotton; the invention is added to the polyester substrate by adding The graphene particles improve the melting temperature of the screw extrusion. Even if the screw extrusion is performed twice, the molecular length of the obtained polyester fiber does not change much, and hollow cotton fibers can be prepared.

As an alternative technical solution, the method for preparing hollow cotton according to the present invention comprises the following steps:

(A'-1') pulverizing the PET blank slice to obtain PET blank slice particles;

(A'-1) Mixing graphene with PET blank section granules, screw extrusion under the conditions of 230-270 ° C melting temperature, drying the extruded product to a moisture content ≤ 600 ppm, and obtaining PET polyester masterbatch containing graphene ;

(A'-2) mixing PET polyester masterbatch containing graphene with PET polyester chips to obtain a material having an intrinsic viscosity of ≥0.60 dL/g;

(A'-3) The obtained material was melt-spun, and then opened to obtain hollow cotton.

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:

(B'-1) mixing graphene with blank nylon chips, extruding with a screw, and drying to obtain a nylon masterbatch containing graphene;

(B'-2) mixing the nylon masterbatch containing graphene with a portion of the blank nylon pellet, and then mixing with the remaining blank nylon slice b;

(B'-3) The obtained material was melt-spun to obtain a modified nylon fiber.

The invention adopts physical dispersion of solid graphene and nylon substrate to obtain modified nylon fiber uniformly dispersed with graphene. Specifically, the present invention firstly mixes blank fiber sections with solid graphene, and extrudes the same into a graphene composite fiber masterbatch. In the 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. Technically, 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.

Preferably, 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 selection of the blank nylon chips in the step (B'-1) and the step (B'-2) of the present invention is not specifically limited, and those skilled in the art can select according to actual conditions.

Preferably, 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.

Preferably, 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.

Preferably, 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.

Preferably, 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.

Preferably, in the step (B'-2), 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.

Preferably, 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.

As a preferred technical solution, 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);

Preferably, 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.

Further preferably, 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;

Preferably, 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.

Conventional nylon after two times of screw extrusion will cause the breakage of the nylon polymer molecules, reduce the molecular chain length and the strength of the nylon, and finally cause the drawing length to be insufficient in the process of preparing the modified nylon fiber; the present invention passes to the nylon substrate The addition of graphene particles improves the melting temperature of the screw extrusion. Even if the screw extrusion is performed twice, the molecular length of the obtained nylon fiber does not change much, and the modified nylon fiber can be prepared.

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:

(A-1) pulverizing the blank polyester pellet to obtain blank polyester pellets;

(A-2) mixing graphene with blank polyester chip granules, extruding with a screw, and drying to obtain a polyester masterbatch containing graphene;

(A-3) uniformly mixing the polyester masterbatch containing graphene with the blank polyester pellet;

(A-4) The obtained material was melt-spun, and then opened to obtain a modified hollow cotton.

The invention adopts a physical method for dispersing solid graphene and a polyester substrate, and obtains a modified hollow cotton uniformly dispersed with graphene. Specifically, 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. In the granules, the graphene composite polyester masterbatch is obtained by screw extrusion. In the graphene composite polyester masterbatch, the polyester masterbatch is used as a carrier of graphene to preliminarily disperse graphene; then the graphene-loaded polyester masterbatch is loaded. Physically mixing with the blank polyester chips according to the formula amount to obtain the material to be spun, in the material to be spun, the graphene is uniformly dispersed; finally, the melt spinning is carried out according to the conventional hollow cotton preparation process. 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. For the purposes of the present application, the uniform dispersion means that the content of graphene of the modified hollow cotton differs little in the range of any cubic centimeter.

Preferably, 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).

Preferably, the blank polyester sheet of step (A-1) is PET.

The selection of the blank polyester chips described in the step (A-1) and the step (A-3) of the present invention is not specifically limited, and those skilled in the art can select according to actual conditions. However, the melting point of PET is about 220 ° C, and the melting point of PBT is about 270 ° C. From the viewpoint of energy saving of process temperature, in the present invention, it is preferred that the first blank polyester sheet is PET, and the second blank polyester sheet is PET.

Preferably, 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%.

Preferably, 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.

Preferably, 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.

Preferably, 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.

As a preferred technical solution, the graphene-containing polyester masterbatch of the step (A-3) of the present invention and the blank polyester pellet are mixed as follows:

(A-3a) mixing the polyester masterbatch containing graphene with a portion of the blank polyester pellet;

(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.

Preferably, 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.

Further preferably, 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;

Preferably, 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.

(A-1) pulverizing the PET blank slice to obtain PET blank slice particles;

(A-2) mixing graphene with PET blank section granules, screw extrusion under the conditions of 230-270 ° C melting temperature, drying the extruded product to a moisture content ≤ 600 ppm, and obtaining PET polyester masterbatch containing graphene;

(A-3) mixing PET polyester masterbatch containing graphene with PET polyester chips to obtain a material having an intrinsic viscosity of ≥0.60 dL/g;

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:

(B-1) pulverizing blank nylon chips to obtain blank nylon sliced granules;

(B-2) mixing graphene with blank nylon chip granules, extruding with a screw, and drying to obtain a nylon masterbatch containing graphene;

(B-3) mixing the nylon masterbatch containing graphene with the blank nylon slice;

(B-4) The obtained material was melt-spun to obtain a modified nylon fiber.

The invention adopts physical dispersion of solid graphene and nylon substrate to obtain modified nylon fiber uniformly dispersed with graphene. Specifically, 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 In the composite nylon masterbatch, 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. In the material 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. For the purposes of the present application, the uniform dispersion means that the content of graphene of the modified nylon fibers differs little in the range of any centimeter.

Preferably, 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 selection of the blank nylon chips described in the step (B-1) and the step (B-3) of the present invention is not specifically limited, and those skilled in the art can select according to actual conditions.

Preferably, 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.

Preferably, 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 addition of graphene will affect the melting temperature of nylon extruded plastic. If it is too high, the molecular chain of nylon will be broken, which will affect the strength of nylon fiber. If it is too low, the basis of nylon masterbatch cannot be completed.

Preferably, 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.

Preferably, the melt-spun raw material of the step (B-4) has an intrinsic viscosity of ≤ 3 dL/g, preferably ≤ 2.7 dL/g.

The addition of graphene of the present invention increases the viscosity of the nylon chips, while the viscosity is too high to affect the spinning step.

As a preferred technical solution, 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:

(B-3a) mixing the nylon masterbatch containing graphene with a portion of the blank nylon pellet;

(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.

Preferably, 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.

Further preferably, the 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;

Preferably, 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.

As an alternative technical solution, the method for preparing the modified nylon fiber of the present invention comprises the following steps:

(B-1) pulverizing blank nylon chips to obtain blank nylon sliced granules;

(B-2) mixing graphene with blank nylon chip granules, screw extruding at a melt temperature of 210 to 240 ° C, and drying the extruded product to a moisture content of ≤ 600 ppm to obtain a nylon masterbatch containing graphene;

(B-3) mixing the nylon masterbatch containing graphene with the blank nylon chips to obtain a material having an intrinsic viscosity of ≤ 3 dL/g;

(B-4) The obtained material was melt-spun, and then opened to obtain a modified nylon fiber.

In the method for producing a modified fiber according to the present invention, the spinning described in the step (A'-3), the step (B'-3), the step (A-4), and the step (B-4) (step (A-4), step (V-4), step (A'-3) or step (B'-3)) 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. Moreover, 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. However, 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).

As is well known to those skilled in the art, the process conditions for melt spinning can be adjusted to achieve a desired degree of hollowness, which can be typically, but not limited to,:

(1) Spinning plate design of melt-spun hollow fiber

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. At present, 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. . When 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.

It is well known in the art that 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.

For the spinning hole, 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; However, 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. For a C-shaped spinneret, 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. Those skilled in the art have the ability to set the specific dimensions of the spinneret gap and slit depending on the product requirements and the properties of the spinning material.

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. However, since 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.

(2) ring blowing asymmetric cooling

It is well known to those skilled in the art that factors affecting the hollowness of the melt-spun hollow fiber, in addition to the size of the spinneret, are also factors such as spinning temperature and cooling forming conditions; high spinning temperature, low melt viscosity, and melt-spinning. The puffing phenomenon after the hole is greatly reduced, the melt deformation resistance is lowered, and the surface tension is also decreased, so that the surface of the melt flow is atrophied to make the cavity portion smaller, and the spinning hollowness is reduced.

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. .

Typically, as the wind speed increases, 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. However, the wind temperature is too low, the surface of the spinneret is easy to blow cold, and spinning is difficult. For a double-ring sleeve-shaped spinneret, 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.

Those skilled in the art can reduce the three-dimensional crimping of the hollow fibers obtained by direct melt spinning and the deterioration of the tensile properties of the post-spinning by controlling the asymmetric cooling of the ring blowing. 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. Field 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.

(3) After spinning

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. In the stretching, 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 mode, the stretching temperature and the stretching ratio are technical parameters in the post-spinning drawing, and those skilled in the art can select according to their own expertise. Typically, but not limited to, 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.

(4) Control technology of hollowness

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. In addition, those skilled in the art can also examine the slice moisture content required for conventional spinning (generally dehumidified by compressed air through a molecular sieve drying device), spinning temperature and speed, relaxation heat setting process, and silicon-containing products. Process conditions such as oil formulation and oiling method.

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:

A use of a modified hollow cotton according to one of the objects, the modified hollow cotton being used as a filler for a warm-keeping product;

Preferably, 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;

Preferably, 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.

A use of the 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.

Preferably, 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.

Preferably, the modified nylon fiber is used as a blending material with wool or other chemical fiber to form a clothing.

Preferably, 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.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The uniform dispersion of graphene in hollow cotton is realized by physical method, and the process is simple, no dispersing agent is needed, and industrial production is easy;

(2) The uniform dispersion of graphene in the nylon fiber is realized by a physical method, and the process is simple, no dispersing agent is needed, and industrial production is easy; and the spinning process of the modified nylon fiber of the present invention and the existing nylon fiber The spinning process is the same, no need to make any changes, and the spinning time and the spinning length can meet the spinning requirements of the existing unmodified nylon fiber;

(3) Introducing graphene into hollow cotton, especially introducing biomass graphene into hollow cotton, so that the obtained modified hollow cotton has low-temperature far-infrared function, and its far-infrared normal emissivity is above 0.85; The performance is more than 90%, and the thermal insulation performance and the gas permeability are excellent. When the biomass graphene content is 1.4%, the heat preservation rate is equivalent to that of the white duck down with 90% of the cashmere content, about 90%, but the air permeability is 240mm/s. Left and right, much higher than duck down;

(4) Introducing graphene into nylon fiber, especially introducing biomass graphene into nylon fiber, so that the obtained modified nylon fiber has low-temperature far-infrared function, and its far-infrared normal emissivity is above 0.85; Performance is greater than 90%.

detailed description

The technical solution of the present invention will be further described below by way of specific embodiments.

It should be understood by those skilled in the art that the present invention is not to be construed as limited.

Graphene Preparation Example 1 (Redox Graphene)

The method of the embodiment 1 of the patent publication CN105217621A is specifically:

(A) reacting 2 g of graphite powder with a mixture of 3 g of potassium dithionite, 3 g of phosphorus pentoxide and 12 mL of concentrated sulfuric acid in a reactor, stirring under a water bath condition of 80 ° C for 4 hours to form a dark blue solution, cooling, Pre-oxidized graphite obtained by suction filtration and drying;

(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;

(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;

(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;

(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.

Graphene Preparation Example 2 (Biomass Graphene)

The method of embodiment 10 of the patent publication CN104724696A is specifically:

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.

Graphene Preparation Example 3 (Special Source Biomass Graphene)

The preparation method of conventional cellulose is specifically:

(1) After pulverizing and pretreating the wheat straw, 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;

(2) 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. 8wt% hydrogen peroxide (H2O2) as a catalyst and a mass ratio of acetic acid to formic acid of 1:12, a control temperature of 90 ° C, a washing time of 1 h, a solid-liquid mass ratio of 1:9, and the reaction liquid was subjected to the first Secondary solid-liquid separation;

(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);

(4) collecting the solid obtained by the second solid-liquid separation, and washing with water, controlling the water washing temperature to be 80 ° C, the water washing slurry is concentrated to 6 wt%, and the obtained water washing slurry is subjected to a third solid-liquid separation;

(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;

(6) Collecting the solid obtained by the third solid-liquid separation and screening to obtain the desired fine pulp cellulose.

Preparation of biomass graphene from cellulose:

(1) mixing cellulose and ferrous chloride in a mass ratio of 1:1, stirring at 150 ° C for catalytic treatment for 4 h, drying to a precursor moisture content of 10 wt%, to obtain a precursor;

(2) In a N2 atmosphere, 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;

(3) The crude product was acid-washed at a concentration of 10% sodium hydroxide solution and 4 wt% hydrochloric acid at 55 to 65 ° C, and then washed with water to obtain biomass graphene.

The following specifically takes PET as a raw material to prepare hollow cotton as an example:

Example A1

A hollow cotton prepared by the following method:

(1) pulverizing PET blank polyester chips to an average particle diameter of 1 mm to obtain PET blank polyester chip particles;

(2) mixing 1 kg of graphene powder (graphene powder obtained in graphene preparation example 3) and 9 kg of PET blank polyester pellets, screw-squeezed at a melt temperature of 250 ° C, and dried in a vacuum oven to a moisture content of <300 ppm, and then obtained. Graphene polyester masterbatch;

(3) After mixing 1kg of graphene-containing polyester masterbatch with 1kg PET blank polyester pellet, continue to add 5kg PET blank polyester pellets to mix evenly;

(4) The material obtained in the step (3) was melted, and then spun, and after the completion of the spinning, the polyester hollow cotton was obtained to obtain a graphene content of 1.4% by weight.

Example A2

A hollow cotton, which differs from Embodiment 1 in that:

(3) After mixing 1kg of graphene-containing polyester masterbatch with 1kg PET blank polyester pellet, continue to add 3kg PET blank polyester pellets and mix evenly;

(4) The material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the polyester hollow cotton is obtained to obtain a graphene content of 2% by weight.

Example A3

A hollow cotton, which differs from Embodiment 1 in that:

(3) After mixing 1kg of graphene-containing polyester masterbatch with 1kg PET blank polyester pellet, continue to add 8kg PET blank polyester pellets to mix evenly;

(4) The material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the polyester hollow cotton is obtained to obtain a graphene content of 1% by weight.

Example A4

A hollow cotton, which differs from Embodiment 1 in that:

(3) After mixing 1kg of graphene-containing polyester masterbatch with 4.5kg PET blank polyester pellets, continue to add 45kg PET blank polyester chips and mix evenly;

(4) The material obtained in the step (3) was melted, and then spun, and after the completion of the spinning, the polyester hollow cotton was obtained to obtain a graphene content of 0.2% by weight.

Example A5

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.

Example A6

A hollow cotton prepared by the following method:

(2) mixing 1 kg of graphene powder (graphene powder obtained in graphene preparation example 3) and 4 kg of PET blank polyester pellets, screw-extruding at a melt temperature of 250 ° C, and drying in a vacuum drying oven to a moisture content of <300 ppm, and obtaining Graphene polyester masterbatch;

(3) After mixing 1kg of graphene-containing polyester masterbatch with 1kg PET blank polyester pellet, continue to add 4.7kg PET blank polyester pellets and mix evenly;

(4) The material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the polyester hollow cotton is obtained, and the graphene content is 3 wt%.

Example A7

A hollow cotton, which differs from Embodiment 6 in that:

(3) After mixing 1kg of graphene-containing polyester masterbatch with 1kg PET blank polyester pellet, continue to add 2kg PET blank polyester pellets to mix evenly;

(4) The material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the polyester hollow cotton is obtained to obtain a graphene content of 5 wt%.

Example A8

A hollow cotton, which differs from Embodiment 6 in that:

(3) After mixing 1kg of graphene-containing polyester masterbatch with 0.5kg PET blank polyester pellet, continue to add 0.5kg PET blank polyester pellet to mix evenly;

(4) The material obtained in the step (3) is melted, and then spun, and after the completion of the spinning, the polyester hollow cotton is obtained to obtain a graphene content of 10% by weight.

Example A9

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.

Example A10

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).

Example A11

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).

Example A12

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).

Comparative example A1

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.

Comparative example A2

A white duck down with a cashmere content of 90% was used as a comparative example 2.

Comparative example A3

A hollow cotton prepared by the following method:

(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.

Performance Testing:

The polyester hollow cotton prepared in the examples and the comparative examples was tested as follows:

(1) Warming rate: the test method is GBT11048-2008 Determination of thermal resistance and moisture resistance under steady state conditions of textile physiological comfort;

(2) Air permeability: the test method is GBT5453-1997 textile material permeability test;

(3) Far-infrared normal emissivity: by the National Textile Products Quality Supervision and Inspection Center, in accordance with the FZ/T64010-2000 test method;

(4) Antibacterial test: by the National Textile Products Quality Supervision and Inspection Center, according to the test method of GB/T20944.3-2008, taking Staphylococcus aureus as an example;

The test results are shown in Table 1:

Table 1-1 Performance test results of the examples A1 to A9

Table 1-2 Examples 10 to 12 and comparative performance test results

The following specifically takes PA-6 and PA-66 as raw materials to prepare modified nylon fiber as an example:

Example B1

A modified nylon fiber is prepared by the following method:

(1) pulverizing the blank PA-6 slice to an average particle diameter of 1 mm to obtain blank PA-6 slice particles;

(2) 1 kg of graphene powder (graphene powder obtained in graphene preparation example 3) and 9 kg of blank PA-6 chip pellets were mixed, screw-extruded at a melt temperature of 220 ° C, and dried in a vacuum oven to a moisture content of <300 ppm. Graphene-containing PA-6 masterbatch;

(3) After mixing 1 kg of graphene-containing PA-6 masterbatch with 1 kg of blank PA-6 chips, continue to add 5 kg of blank PA-6 slices and mix well;

(4) 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 1.4 wt%, which can be normally spun for 8 hours.

Example B2

A modified nylon fiber differs from Example 1 in that:

(3) After mixing 1 kg of graphene-containing PA-6 masterbatch with 1 kg of blank PA-6 chips, continue to add 3 kg of blank PA-6 slices and mix well;

(4) 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.

Example B3

A modified nylon fiber differs from Example 1 in that:

(3) After mixing 1 kg of graphene-containing PA-6 masterbatch with 1 kg of blank PA-6 chips, continue to add 8 kg of blank PA-6 slices and mix well;

(4) 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.

Example B4

A modified nylon fiber differs from Example 1 in that:

(3) After mixing 1 kg of graphene-containing PA-6 masterbatch with 4.5 kg of blank PA-6 chips, continue to add 45 kg of blank PA-6 slices and mix well;

(4) 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 0.2 wt%, which can be normally spun for 8 hours.

Example B5

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.

Example B6

A modified nylon fiber is prepared by the following method:

(1) pulverizing the blank PA-66 slice to an average particle diameter of 1 mm to obtain blank PA-66 slice particles;

(2) 1 kg of graphene powder (graphene powder obtained in the graphene preparation example 3) and 4 kg of blank PA-66 pellets were mixed, screw-extruded at a melt temperature of 240 ° C, and dried in a vacuum oven to a moisture content of <300 ppm. Graphene-containing PA-66 masterbatch;

(3) After mixing 1 kg of graphene-containing PA-66 masterbatch with 1 kg of blank PA-66 slices, continue to add 4.7 kg of blank PA-66 slices and mix well;

(4) 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.

Example B7

A modified nylon fiber differs from Example 6 in that:

(3) After mixing 1 kg of graphene-containing PA-66 masterbatch with 1 kg of blank PA-66 slices, continue to add 2 kg of blank PA-66 slices and mix well;

(4) 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 5 wt%, which can be normally spun for 8 hours.

Example B8

A modified nylon fiber differs from Example 6 in that:

(3) After mixing 1 kg of graphene-containing PA-66 masterbatch with 0.5 kg of blank PA-66 slices, continue to add 0.5 kg of blank PA-66 slices and mix well;

(4) 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.

Example B9

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.

Example B10

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).

Example B11

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).

Example B12

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).

Comparative example B1

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.

Comparative example B2

A nylon fiber prepared by the following method:

(2) The material obtained in the step (1) is melted, and then spun, and after the completion of the spinning, the PA-6 fiber is obtained.

Performance Testing:

The modified nylon fibers and nylon fibers prepared in the examples and the comparative examples were tested as follows:

(1) breaking strength and elongation at break: the test method is GB/T 3923.1-1997 fabric breaking strength and elongation at break;

The test results are shown in Table 2:

Table 2-1 Performance test results of Embodiments 1 to 9

Table 2-2 Examples 10 to 12 and Comparative Performance Test Results

The Applicant declares that 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.

Claims

a modified fiber characterized in that the modified fiber is doped with graphene;

The modified fiber includes any one of a modified hollow cotton and a modified nylon fiber.
The modified fiber according to claim 1, wherein the graphene is biomass graphene.
The modified fiber according to claim 2, wherein the biomass graphene is prepared from biomass, and preferably the biomass graphene is prepared from biomass-derived cellulose.
The modified fiber according to claim 2, wherein the biomass is selected from any one or a combination of at least two of agricultural forest waste and/or plants;

Preferably, the plant is any one or a combination of at least two of softwood or hardwood;

Preferably, 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 stalk, husk and reed, or at least 2 species. The combination;

Preferably, the agricultural and forestry waste is a corn cob.
The modified fiber according to any one of claims 1 to 3, wherein the amount of graphene in the modified hollow cotton is 0.2 to 10% by weight, preferably 0.3 to 8% by weight, further preferably 0.5 to 5% by weight. ;

Preferably, the doping amount of 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 3% by weight.
The modified fiber according to any one of claims 1 to 5, wherein the modified hollow cotton has a far-infrared detection normal emissivity of more than 0.85, preferably more than 0.88;

Preferably, the far-infrared detection normal emissivity of the modified nylon fiber is greater than 0.85, preferably greater than 0.88.
The method for preparing a modified fiber according to any one of claims 1 to 6, wherein the method for preparing the modified hollow cotton comprises the following steps:

(A'-1) mixing graphene with blank polyester chips, extruding with a screw, and drying to obtain a polyester masterbatch containing graphene;

(A'-2) uniformly mixing the polyester masterbatch containing graphene with a portion of the blank polyester pellet, and then mixing with the remaining blank polyester pellet b;

(A'-3) melt-spinning the obtained material, and then opening to obtain a modified hollow cotton;

The preparation method of the modified nylon fiber comprises the following steps:

(B'-1) mixing graphene with blank nylon chips, extruding with a screw, and drying to obtain a nylon masterbatch containing graphene;

(B'-2) mixing the nylon masterbatch containing graphene with a portion of the blank nylon pellet, and then mixing with the remaining blank nylon slice b;

(B'-3) The obtained material was melt-spun to obtain a modified nylon fiber.
The preparation method according to claim 7, wherein the blank polyester chips of the step (A'-1) and the step (A'-2) are PET and/or PBT;

Preferably, the blank polyester slice of step (A'-1) is PET;

Preferably, the graphene-containing polyester masterbatch has a graphene content of 1 to 20% by weight, preferably 5 to 15% by weight, further preferably 6 to 10% by weight;

Preferably, the screw extrusion of the step (A'-1) has a melting temperature of 230 to 270 ° C, preferably 240 to 260 ° C;

Preferably, the graphene-containing polyester masterbatch has a moisture content of ≤600 ppm, preferably ≤300 ppm;

The blank nylon slice of the step (B'-1) and the step (B'-2) is any one of PA-6, PA-66, PA-610, PA-1010, and MCPA;

Preferably, the graphene-containing nylon masterbatch has a graphene content of 3 to 10% by weight, preferably 5 to 8% by weight;

Preferably, the screw extrusion of the step (B'-1) has a melting temperature of 210 to 240 ° C, preferably 220 to 230 ° C;

Preferably, the graphene-containing nylon masterbatch has a moisture content of ≤600 ppm, preferably ≤300 ppm.
The preparation method according to claim 7 or 8, wherein the mass ratio of the graphene-containing polyester masterbatch to the blank polyester pellet of the step (A'-2) is 1:5 to 30; preferably 1:15. ～20;

Preferably, in step (A'-2), the ratio of the portion of the blank polyester sheet to the blank polyester sheet added in the step (A'-2) is 1:2 to 10, preferably 1:4 to 8;

Preferably, the mass ratio of the graphene-containing nylon masterbatch to the blank nylon slice in step (B'-2) is 1:5-30; preferably 1:15-20;

Preferably, in the step (B'-2), the ratio of the part of the blank nylon piece to the blank of the blank nylon piece added in the step (B'-2) is 1:2 to 10, preferably 1:4 to 8.
The preparation method according to any one of claims 7 to 9, wherein the melt-spun raw material of step (A'-3) has an intrinsic viscosity ≥ 0.60 dL / g, preferably ≥ 0.65 dL / g;

Preferably, the melt-spun raw material of the step (B'-3) has an intrinsic viscosity ≤ 3 dL/g, preferably ≤ 2.7 dL/g.
The preparation method according to any one of claims 7 to 10, characterized in that the step (A'-2') is set between the step (A'-4) and the step (A'-3): the step (A' -2) mixing the homogeneous material again for screw extrusion;

Preferably, the melting temperature of the screw extrusion in step (A'-2') is 230 to 270 ° C, preferably 240 to 260 ° C;

Preferably, step (B'-2') is provided between step (B'-2) and step (B'-3): the step (B'-2) is mixed and the material is again subjected to screw extrusion;

Preferably, the screw extrusion of the step (B'-2') has a melting temperature of 210 to 240 ° C, preferably 220 to 230 ° C. .
The preparation method according to any one of claims 7 to 11, wherein the step (A'-1') is carried out before the step (A'-1): the blank polyester sheet is pulverized into blank polyester chip particles for use in Step (A'-1) of the graphene mixture;

Preferably, the step (A'-1') of the blank polyester chip particles has a particle size of ≤ 3 mm;

Preferably, step (B'-1') is carried out before step (B'-1): the blank nylon slice is pulverized into blank nylon chip particles for mixing with the graphene of step (B'-1);

Preferably, the step (B'-1') of the blank nylon chip particles has a particle size of ≤ 3 mm.
The method for preparing a modified fiber according to any one of claims 1 to 6, wherein the method for preparing the modified hollow cotton comprises the following steps:

(A-1) pulverizing the blank polyester pellet to obtain blank polyester pellets;

(A-2) mixing graphene with blank polyester chip granules, extruding with a screw, and drying to obtain a polyester masterbatch containing graphene;

(A-3) uniformly mixing the polyester masterbatch containing graphene with the blank polyester pellet;

(A-4) the obtained material is melt-spun, and then opened to obtain a modified hollow cotton;

The preparation method of the modified nylon fiber comprises the following steps:

(B-1) pulverizing blank nylon chips to obtain blank nylon sliced granules;

(B-2) mixing graphene with blank nylon chip granules, extruding with a screw, and drying to obtain a nylon masterbatch containing graphene;

(B-3) mixing the nylon masterbatch containing graphene with the blank nylon slice;

(B-4) The obtained material was melt-spun to obtain a modified nylon fiber.
The preparation method according to claim 13, wherein the blank polyester chip particles and the blank nylon chip particles have a particle size of ≤ 3 mm;

Preferably, the blank polyester chips described in the step (A-1) and the step (A-3) are PET and/or PBT;

Preferably, the blank polyester slice of step (A-1) is PET;

Preferably, the blank nylon chips described in the step (B-1) and the step (B-3) are any one of PA-6, PA-66, PA-610, PA-1010, and MCPA.
The method according to claim 13 or 14, wherein the graphene-containing polyester masterbatch has a graphene content of 1 to 20% by weight, preferably 5 to 15% by weight, most preferably 6 to 10% by weight;

Preferably, the graphene-containing nylon masterbatch has a graphene content of 3 to 10% by weight, preferably 5 to 8% by weight;

Preferably, the screw extrusion of the step (A-2) has a melting temperature of 230 to 270 ° C, preferably 240 to 260 ° C;

Preferably, the screw extrusion of the step (B-2) has a melting temperature of 210 to 240 ° C, preferably 220 to 230 ° C;

Preferably, the graphene-containing polyester masterbatch has a moisture content of ≤600 ppm, preferably ≤300 ppm;

Preferably, the graphene-containing nylon masterbatch has a moisture content of ≤600 ppm, preferably ≤300 ppm.
The preparation method according to any one of claims 13 to 15, wherein the mass ratio of the graphene-containing polyester masterbatch to the blank polyester pellet of the step (A-3) is 1:5 to 30; preferably 1: 15~20;

Preferably, the mass ratio of the graphene-containing nylon masterbatch to the blank nylon slice in the step (B-3) is 1:5 to 30; preferably 1:15 to 20.
The preparation method according to any one of claims 13 to 16, wherein the melt-spun raw material of step (A-4) has an intrinsic viscosity ≥ 0.60 dL / g, preferably ≥ 0.65 dL / g;

Preferably, the melt-spun raw material of the step (B-4) has an intrinsic viscosity of ≤ 3 dL/g, preferably ≤ 2.7 dL/g.
Use of the modified hollow cotton according to any one of claims 1 to 6, characterized in that the modified hollow cotton is used as a filling for a warm-keeping product;

Preferably, 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;

Preferably, 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 use of the modified nylon fiber according to any one of claims 1 to 6, wherein the modified nylon fiber is used as any one of knitwear, medical articles, and outdoor articles;

Preferably, 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;

Preferably, the modified nylon fiber is used as a wool-type product blended with wool or other chemical fibers to form a clothing;

Preferably, the modified nylon fiber is used as a cord, industrial cloth, cable, conveyor belt, tent, fishing net or fishing line.