CN105525384B - A kind of purposes of modified hollow cotton - Google Patents

A kind of purposes of modified hollow cotton Download PDF

Info

Publication number
CN105525384B
CN105525384B CN201610045894.5A CN201610045894A CN105525384B CN 105525384 B CN105525384 B CN 105525384B CN 201610045894 A CN201610045894 A CN 201610045894A CN 105525384 B CN105525384 B CN 105525384B
Authority
CN
China
Prior art keywords
graphene
hollow cotton
purposes
terylene chips
modified hollow
Prior art date
Application number
CN201610045894.5A
Other languages
Chinese (zh)
Other versions
CN105525384A (en
Inventor
唐一林
张金柱
马军强
王双成
张安
Original Assignee
济南圣泉集团股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 济南圣泉集团股份有限公司 filed Critical 济南圣泉集团股份有限公司
Priority to CN201610045894.5A priority Critical patent/CN105525384B/en
Publication of CN105525384A publication Critical patent/CN105525384A/en
Priority claimed from CA3005917A external-priority patent/CA3005917C/en
Application granted granted Critical
Publication of CN105525384B publication Critical patent/CN105525384B/en

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/24Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/02Cotton wool; Wadding
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326Condensation or reaction polymers
    • D04H1/435Polyesters

Abstract

The present invention relates to a kind of purposes of modified hollow cotton, the modified hollow cotton is used as the filler of warmth retention property product;Doped with graphene in the modified hollow cotton.The present invention utilizes the filler for being used as warmth retention property product doped with the modification hollow cotton of graphene, obtain thermal property and warmth retention property product that permeability is excellent in, the heat preservation rate for the modification hollow cotton that biomass graphene doping is 1.4% is suitable in 90% white duck down with down content, but air penetrability is much higher than duck's down in 240mm/s or so.

Description

A kind of purposes of modified hollow cotton

Technical field

The invention belongs to terylene arts, and in particular to a kind of purposes of modified hollow cotton.The application is the applicant (Shengquan Group Co. Ltd., Jinan) submits the entitled of China State Intellectual Property Office on January 21st, 2016 The continuation application of " a kind of modified hollow cotton and preparation method thereof ".

Background technique

Terylene is an important species in synthetic fibers, is the product name of China's polyester fiber, it is with poly- to benzene Dioctyl phthalate second diester (PET) or polybutylene terephthalate (PBT) through spinning and post-process manufactured fiber.

Polyethylene terephthalate (PET) be with poly terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and Ethylene glycol (EG) is raw material through fiber-forming polymer prepared by esterification or transesterification and polycondensation reaction.Polybutylene terephthalate It (PBT) be using poly terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and 1,4- butanediol is raw material through esterification or ester Fiber-forming polymer prepared by exchange and polycondensation reaction.

Terylene is simplest one kind of technique in three big synthetic fibers, and price is also relatively cheap, and its with it is durable, Elasticity is good, be unlikely to deform, be corrosion-resistant, insulation, it is well-pressed, quick-drying washable the features such as, liked by people.

PET Hollow cotton is to be manufactured by the dacron ultrafine fiber of different size by special process, because matter is like natural feather, Also there are referred to as silk floss or feather and down, be widely used in natural feather cotton clothes, natural feather cotton-padded trousers, ski-wear, insulated cold wear, feather and down quilt, A variety of warm-keeping products such as automobile cushion.The shortcomings that existing PET Hollow cotton be warmth retention property it is not high, intolerant to washing, it is not light enough.

Graphene (Graphene) is the only one layer of atomic thickness for being stripped out from graphite material, being made of carbon atom Two dimensional crystal, be presently found most thin, maximum intensity, a kind of strongest novel nano-material of electrical and thermal conductivity performance.By stone Black alkene is added in the matrixes such as terylene, be expected to can the new performance of endowing terylene, particularly with the addition of with antibacterial and Low Temperature Far Infrared The biomass graphene of function, terylene are hopeful have the function of antibacterial and Low Temperature Far Infrared.

But the solid state of graphene is easy to reunite, and forms biggish particle agglomeration, when being added in the matrixes such as terylene, and It is not easy to be uniformly dispersed, and significantly reduces the processing fluidity of the matrixes master batch such as terylene, thus can not carry out spinning technique, nothing Method applies graphene in the basis materials such as terylene.

The prior art is in order to disperse graphene uniform, Chang Tianjia dispersing agent, but dispersing agent has material Deterioration influence, how to find it is a kind of do not need addition dispersing agent method graphene uniform is entrained in the substrates such as terylene, fill Divide the performance (such as thermal insulation property, Low Temperature Far Infrared and antibacterial performance) using graphene, is that this field one is urgently to be resolved Problem.

Summary of the invention

For the prior art, provide it is a kind of graphene is entrained in polyester material, obtaining has excellent thermal insulation performance, low The modification hollow cotton of warm far infrared performance and bacteriostasis property, it is an object of the invention to be produced using modified hollow cotton as warmth retention property The purposes of the filler of product, doped with graphene in the hollow cotton.

Warmth retention property product of the present invention is selected from quilt, pillow, back cushion, clothes, sleeping bag or tent.

Clothes of the present invention is selected from Insulation shirt, cold-proof underwear, down jackets, natural feather sleeveless jacket or down wadded trousers.

Quilt, pillow, back cushion, clothes, sleeping bag, tent and Insulation shirt of the present invention, cold-proof underwear or down jackets Preparation method with reference to the preparation method of corresponding product in state of the art, the present invention is not specifically limited, even may be used With the technique for preparing corresponding product by unmodified hollow cotton with reference to this field.

" modified hollow cotton " of the present invention is obtained by way of doped graphene, and those skilled in the art can also claim Be hollow cotton blend, hollow cotton compound, hollow cotton modifier, the hollow cotton containing graphene or changing containing graphene Property hollow cotton.

" doping " of the present invention mean graphene with various those skilled in the art it is conceivable that form add Enter in hollow cotton, it is typical but non-limiting can by being dispersed in the surface of hollow cotton, or by In-situ reaction it is modified in The substrate of empty cotton, or with hollow cotton physical blending etc..Those skilled in the art " doping " can also be replaced with containing, wrap It includes, disperse, have.

Preferably, the graphene is biomass graphene.

The biomass graphene is prepared by biomass;It is preferred that the fibre that the biomass graphene is obtained by biomass Dimension element is prepared.

The number of plies is more than 10 layers, the hexatomic ring honeycomb lamellar structure of thickness carbon within 100nm, referred to as graphene nanometer sheet Layer;The number of plies prepared using biomass as carbon source is more than 10 layers, the hexatomic ring honeycomb lamellar structure of thickness carbon within 100nm, Referred to as biomass graphene nano lamella;The number of plies is the hexatomic ring honeycomb lamellar structure of 1~10 layer of carbon, referred to as graphene;With Biomass is that the number of plies of carbon source preparation is the hexatomic ring honeycomb lamellar structure of 1~10 layer of carbon, referred to as biomass graphene.

Graphene of the present invention includes graphene nano lamella and graphene, further comprises biomass graphene nano Lamella and biomass graphene.

Graphene of the present invention can be obtained by different preparation methods, such as mechanical stripping method, epitaxial growth method, change Vapor deposition method is learned, graphite oxidation reduction method can also be by biomass resource hydrothermal carbonization method, and in the prior art The graphene of other methods preparation.But no matter which kind of method large scale preparation all difficult to realize obtains stricti jurise theoretically Graphene, such as to have certain impurity elements, other homoatomics of carbon in the obtained graphene of prior art preparation different Body or the non-single layer of the number of plies even graphene-structured (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) of multilayer, what the present invention was utilized Graphene also includes the graphene on above-mentioned non-critical theory of meaning.

Preferably, any a kind or at least two kinds of of combination of the biomass in agriculture and forestry organic waste material and/or plant.

Preferably, the plant is any a kind or at least two kinds of of combination in needlebush or leaf wood.

Preferably, the agriculture and forestry organic waste material is cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose Any a kind or at least two kinds of of combination in slag, sawdust, cotton stalk, shell and reed.

Preferably, the agriculture and forestry organic waste material is corncob.

In addition to it is above-mentioned to the enumerating of biomass other than, biomass of the present invention can be those skilled in the art and can obtain Any biomass resource known, the present invention do not continue to repeat.

Biomass graphene of the present invention refers to the graphene being prepared using biomass as carbon source, specifically with biology Matter is that carbon source prepares process this field of graphene it has been reported that typical but non-limiting includes CN104724699A, this hair It is bright to repeat no more.

Preferably, in the modified hollow cotton graphene content be 0.2~10wt%, preferably 0.3~8wt%, further It is preferred that 0.5~5wt%.

Illustratively, in modified hollow cotton of the present invention graphene content be 0.3wt%, 0.6wt%, 0.9wt%, 1.1wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.1wt%, 2.4wt%, 2.5wt%, 2.8wt%, 3.0wt%, 3.4wt%, 3.6wt%, 3.9wt%, 4.2wt%, 4.5wt%, 4.9wt%, 5.2wt%, 5.8wt%, 6.3wt%, 6.5wt%, 6.6wt%, 6.9wt%, 7.3wt%, 7.5wt%, 7.9wt%, 8.2wt%, 8.8wt%, 9.3wt%, 9.9wt% etc..

Preferably, the far infrared of modified hollow cotton of the present invention detects normal emittance 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 modified hollow cotton provided by the invention are as follows: the warming effect of 1kg modified hollow cotton of the present invention Fruit is identical as the warming effect of the common mesoporous cotton of 2.5~3kg, and while guaranteeing warming effect, good air permeability.

The preparation method of modified hollow cotton of the present invention, includes the following steps:

(1) blank terylene chips are crushed, blank terylene chips particle is obtained;

(2) graphene is mixed, Screw Extrusion with blank terylene chips particle, after dry, obtains washing containing graphene Synthetic fibre master batch;

(3) dacron master grain containing graphene is uniformly mixed with blank terylene chips;

(4) resulting material is subjected to melt spinning, then shredding obtains modified hollow cotton.

The present invention evenly dispersed has graphene using obtaining in physics mode disperse solid graphene and terylene substrate Modified hollow cotton.Specifically, the present invention first shreds the terylene chips of blank, increases rough surface, increases it and adheres to graphene Specific surface area and frictional force, improve the dispersibility of graphene;Later by solid graphene dispersion in the terylene chips of blank In particle, Screw Extrusion obtains graphene composite terylene master batch, and in graphene composite terylene master batch, dacron master grain is as graphite Graphene has been carried out preliminary dispersion by the carrier of alkene;Then there is the dacron master grain of graphene by formula ratio and blank load Terylene chips carry out physical mixed, obtain the material to spinning, and in the material to spinning, graphene, which realizes, uniformly to be divided It dissipates;Uniform Doped finally, which can be obtained, according to the preparation process progress melt spinning of conventional hollow cotton has in the modification of graphene Empty cotton solves the non-uniform technical problem of prior art graphene dispersion, obtains heat insulating ability, gas permeability, Low Temperature Far Infrared The modification hollow cotton being excellent in antibiotic property.

The present invention realizes preliminary dispersion by the way that the graphene particles of easy reunion are dispersed in blank terylene chips particle, Obtained master batch is mixed with blank terylene chips again later, is obtained finely dispersed to spinning material.

Blank terylene chips of the present invention refer to the terylene chips for not adding functional particles graphene.

Be uniformly distributed and refer to: the chance that measured value occurs everywhere in a certain range is the same.For the application, the dispersion Uniformly refer to, in the range of any cubic centimetre, the content of the graphene of modified hollow cotton is not much different.

Preferably, partial size≤3mm of the blank terylene chips particle, for example, 0.1mm, 0.5mm, 0.9mm, 1.3mm, 1.8mm, 2.2mm, 2.5mm, 2.8mm etc..

Preferably, it is (poly- to benzene to be each independently PET for blank terylene chips described in the step (1) and step (3) Dioctyl phthalate second diester) and/or PBT (polybutylene terephthalate (PBT)).

Preferably, step (1) the blank terylene chips are PET.

The present invention is not specifically limited the selection of blank terylene chips described in step (1) and step (3), this field skill Art personnel can select according to the actual situation.But PET fusing point is 220 DEG C or so, and PBT fusing point is 270 DEG C or so, from technique The Energy Angle of temperature, the present invention preferably the first blank terylene chips are PET, and the second blank terylene chips are PET.

Preferably, in the dacron master grain containing graphene graphene content be 1-20wt%, such as 2wt%, 4wt%, 6wt%, 8wt%, 12wt%, 15wt%, 17wt%, 19wt% etc., preferably 5-15wt%, most preferably 6-10wt%.

Preferably, the melting temperature of step (2) described Screw Extrusion is 230~270 DEG C, such as 235 DEG C, 240 DEG C, 244 DEG C, 249 DEG C, 253 DEG C, 258 DEG C, 262 DEG C, 267 DEG C etc., preferably 240~260 DEG C.

Preferably, moisture content≤600ppm of the dacron master grain containing graphene, such as 50ppm, 80ppm, 130ppm, 180ppm, 230ppm, 280ppm, 350ppm, 390ppm, 420ppm, 450ppm, 480ppm etc., preferably≤ 300ppm。

Preferably, the mass ratio of the dacron master grain containing graphene and blank terylene chips described in step (3) be 1:5~ 30, such as 1:6,1:7,1:9,1:13,1:16,1:22,1:26,1:29 etc.;It is preferred that 1:15~20.

Preferably, inherent viscosity >=0.60dL/g of the raw material of step (4) described melt spinning, such as 0.62dL/g, 0.66dL/g, 0.69dL/g, 0.72dL/g, 0.75dL/g, 0.78dL/g, 0.80dL/g, 0.85dL/g etc., preferably >= 0.65dL/g。

The addition of graphene of the present invention can reduce the viscosity of slice, and viscosity is too low can not carry out spinning process.

As optimal technical scheme, the dacron master grain containing graphene described in step (3) of the present invention and blank terylene chips Mixing includes the following steps:

Dacron master grain containing graphene is uniformly mixed by (3a) with a part of blank terylene chips;

(3b) continues the remaining blank terylene chips of the addition into the mixture of step (3a) and is uniformly mixed.

2 steps of dacron master grain containing graphene point are diluted dispersion with terylene chips, so that graphene particles is dense Degree reaches preset requirement, can be by the more uniform of graphene dispersion, and obtained modification hollow cotton is in heat insulating ability, Low Temperature Far Infrared It is more excellent with being showed in antibiotic property.

Preferably, the blank terylene chips that step (3a) a part of blank terylene chips and step (3a) are added are whole Mass ratio be 1:2~10, such as 1:3,1:4,1:5,1:6,1:7,1:8,1:9 etc., preferably 1:4~8.

The blank terylene chips that the step (3a) is added integrally refer to that a part of blank terylene chips are washed with remaining blank The sum of synthetic fibre chipping qualities.

It is further preferred that setting steps (3 ') between step (3) and step (4): the material that step (3) is uniformly mixed Screw Extrusion is carried out again;

Preferably, the melting temperature of the Screw Extrusion is 230~270 DEG C, such as 235 DEG C, 240 DEG C, 244 DEG C, 249 DEG C, 253 DEG C, 258 DEG C, 262 DEG C, 267 DEG C etc., preferably 240~260 DEG C.

Conventional terylene will cause the fracture of terylene polymer molecule by Screw Extrusion twice, reduce its molecular chain length With the intensity of terylene, finally cause length of string inadequate during preparing hollow cotton;The present invention passes through into terylene substrate Graphene particles are added, improve the melting temperature of Screw Extrusion, even if carrying out Screw Extrusion twice, obtained polyester fiber point Subchain length also changes less, can prepare hollow cotton fiber.

As optional technical solution, the preparation method of hollow cotton of the present invention includes the following steps:

(1) PET blank slice is crushed, PET blank chip granulate is obtained;

(2) graphene is mixed with PET blank chip granulate, Screw Extrusion under conditions of 230~270 DEG C of melting temperatures, After product drying to moisture content≤600ppm will be squeezed out, the PET dacron master grain containing graphene is obtained;

(3) the PET dacron master grain containing graphene is mixed with PET terylene chips, obtains inherent viscosity >=0.60dL/g Material;

(4) by resulting material melt spinning, then shredding obtains modified hollow cotton.

Another preparation method of modified hollow cotton of the present invention, includes the following steps:

(a) graphene is mixed, Screw Extrusion with blank terylene chips, after dry, it is female obtains the terylene containing graphene Grain;

(b) dacron master grain containing graphene is uniformly mixed with a part of blank terylene chips, later again with it is remaining The mixing of blank terylene chips;

(c) by resulting material melt spinning, then shredding obtains modified hollow cotton.

The present invention evenly dispersed has graphene using obtaining in physics mode disperse solid graphene and terylene substrate Modified hollow cotton.Specifically, the present invention first mixes the terylene chips of blank with solid graphene, and Screw Extrusion obtains stone Black alkene composite terylene master batch, in graphene composite terylene master batch, carrier of the dacron master grain as graphene carries out graphene Preliminary dispersion;Then the dacron master grain of graphene divides 2 steps to carry out physics by the terylene chips of formula ratio and blank load Mixing, obtains the material to spinning, in the material, graphene realizes evenly dispersed;Finally according to conventional hollow cotton Preparation process carry out spinning the evenly dispersed hollow cotton for having graphene can be obtained, solve prior art graphene dispersion not Uniform technical problem obtains the modification hollow cotton that heat insulating ability, gas permeability, Low Temperature Far Infrared and antibiotic property are excellent in.

The present invention realizes preliminary dispersion by being first dispersed in the graphene particles of easy reunion in the terylene chips of blank, Later by 2 steps of obtained master batch point and blank terylene chips physical mixed, realizes the evenly dispersed of graphene, be uniformly dispersed To spinning material.

Preferably, the step (a) and step (b) the blank terylene chips are each independently PET and/or PBT.

Preferably, step (a) the blank terylene chips are PET.

The selection of step (a) of the present invention and step (b) the blank terylene chips is not specifically limited, those skilled in the art Member can be selected according to the actual situation.But PET fusing point is 220 DEG C or so, and PBT fusing point is 270 DEG C or so, from technological temperature Energy Angle, the preferred terylene chips of the present invention be PET.

Preferably, in the dacron master grain containing graphene graphene content be 1~20wt%, such as 2wt%, 4wt%, 6wt%, 8wt%, 12wt%, 15wt%, 17wt%, 19wt% etc., preferably 5~15wt%, further preferred 6~ 10wt%.

Preferably, the melting temperature of step (a) Screw Extrusion is 230~270 DEG C, such as 235 DEG C, 240 DEG C, 244 DEG C, 249 DEG C, 253 DEG C, 258 DEG C, 262 DEG C, 267 DEG C etc., preferably 240~260 DEG C.

Preferably, moisture content≤600ppm of the dacron master grain containing graphene, such as 50ppm, 80ppm, 130ppm, 180ppm, 230ppm, 280ppm, 350ppm, 390ppm, 420ppm, 450ppm, 480ppm etc., preferably≤ 300ppm。

Preferably, the mass ratio of the dacron master grain containing graphene and blank terylene chips described in step (b) be 1:5~ 30, such as 1:6,1:7,1:9,1:13,1:16,1:22,1:26,1:29 etc.;It is preferred that 1:15~20.

Preferably, in step (b), a part of blank terylene chips and the blank terylene chips that step (b) is added are whole The ratio of body is 1:2~10, such as 1:3,1:4,1:5,1:6,1:7,1:8,1:9 etc., preferably 1:4~8.

The blank terylene chips b integrally refers to the matter of partial blank terylene chips b and remaining blank terylene chips b The sum of amount.

Preferably, inherent viscosity >=0.60dL/g of the raw material of step (c) melt spinning, such as 0.62dL/g, 0.66dL/g, 0.69dL/g, 0.72dL/g, 0.75dL/g, 0.78dL/g, 0.80dL/g, 0.85dL/g etc., preferably >= 0.65dL/g。

The addition of graphene of the present invention can reduce the viscosity of slice, and viscosity is too low can not carry out spinning process.

As optimal technical scheme, step (a ') is carried out before step (a): blank terylene chips are crushed as blank terylene Chip granulate, for being mixed with step (a) graphene;

Preferably, partial size≤3mm of the blank terylene chips particle, for example, 0.1mm, 0.5mm, 0.9mm, 1.3mm, 1.8mm, 2.2mm, 2.5mm, 2.8mm etc..

Step (a ') shreds the terylene chips of blank, increases rough surface, increase its specific surface area for adhering to graphene and Frictional force can further increase the dispersibility of graphene.

It is further preferred that setting steps (b ') between step (b) and step (c): the material that step (b) is uniformly mixed Screw Extrusion is carried out again;

Preferably, the melting temperature of the Screw Extrusion is 230~270 DEG C, such as 235 DEG C, 240 DEG C, 244 DEG C, 249 DEG C, 253 DEG C, 258 DEG C, 262 DEG C, 267 DEG C etc., preferably 240~260 DEG C.

Conventional terylene will cause the fracture of terylene polymer molecule by Screw Extrusion twice, reduce its molecular chain length With the intensity of terylene, finally cause length of string inadequate during preparing hollow cotton;The present invention passes through into terylene substrate Graphene particles are added, improve the melting temperature of Screw Extrusion, even if carrying out Screw Extrusion twice, obtained polyester fiber point Subchain length also changes less, can prepare hollow cotton fiber.

As optional technical solution, the preparation method of hollow cotton of the present invention includes the following steps:

(a ') crushes PET blank slice, obtains PET blank chip granulate;

(a) graphene is mixed with PET blank chip granulate, Screw Extrusion under conditions of 230~270 DEG C of melting temperatures, After product drying to moisture content≤600ppm will be squeezed out, the PET dacron master grain containing graphene is obtained;

(b) the PET dacron master grain containing graphene is mixed with PET terylene chips, obtains inherent viscosity >=0.60dL/g Material;

(c) by resulting material melt spinning, then shredding obtains hollow cotton.

In the preparation method of hollow cotton of the present invention, spinning described in step (4) or step (c) is this field Well-known technique.

Melt spinning method is that doughnut, economical rationality are obtained by hollow spinneret plate, and related process technologies compare into Ripe, process conditions are controllable.

Melt spinning is that microbore catheter is packed into hollow spinneret plate, and nitrogen is filled in fiber lumen or air obtains height The inflation doughnut of degree of hollowness, avoiding mechanism flattened fibers in production process causes degree of hollowness to decline, and makes fibre It is more worse than air to tie up thermal conductivity, substantially increases warmth retention property, the control to gas flow is method well known in the art.This field Technical staff can also produce the doughnut of a variety of odd-shaped cross sections such as triangle, quincunx by change shape of spinneret, with The specific surface area of fiber is improved, or obtains the porous hollow fiber in 3~7 holes by special spinneret, but its hollow rate can Can be not high, only within 30%.Those skilled in the art can also be by designing spinneret plate shape and reasonably adjusting spinning work Skill (circular blow wind unsymmetrical excavation and rear spin stretch control technology), obtains doughnut or three-dimensional crimp by direct melt spinning Doughnut.

Well known to a person skilled in the art can could be adjusted to obtain ideal hollow to the process conditions of melt spinning Degree, the process conditions are typical but non-limiting to be may is that

(1) spinneret design of melt-spun doughnut

The design of spinneret includes two aspect of its shape and structure size, the former is used for anisotropic cross-sectional hollow fiber, sets Meter is related to production requirement, and common hole shape has polygon, c shape, arc-shaped, multiple spot shape etc.;Spinneret plate structure size is related to It and may include the characteristic sizes numbers such as the slit length of spinneret orifice, two slit distance between two tips, equivalent diameter, sectional area, draw ratio According to;

Typical but non-limiting melt spinning spinning warmth retention property three-dimensional static electric field is sprayed using circular arc slit Filament plate is convenient to spin out the fiber that outer diameter is relatively thin, degree of hollowness is suitable.The preferable triple-arc-shaped spinneret of effect at present Mainly there is the porous hollow fibers spinneret such as C-shaped and product shape spinneret and circular arc combination, for spinning four holes, seven apertures in the human head or even more than ten Hole doughnut.After melt extrusion spinneret circular arc slit, arc-shaped melt extruding, end bonds to form hollow cavity, through thin Change, form doughnut after solidification.

Known in this fieldly, the size of spinneret circular arc slit gap is possible to influence the formation of hollow cavity: when gap mistake When big, fiber is hollow to be closed, and can only spin open fiber;It is swollen quickly after melt extrusion spinneret orifice but when gap is too small Change bonding, hollow cavity can not be formed, and consider that spinneret sheet separation is small, and intensity is low, easy to damage from mechanical strength.Therefore it is directed to Material of different nature has the size of different suitable spinneret sheet separations, and typical but non-limiting is melt extrusion raw material Die swell is than can be with the size of design spinneret sheet separation, and the ratio between width is slightly less than the mould of melt feed at gap center Mouth extruding ratio.

For spinneret orifice, slit width is big, and single hole extrusion output is big, and the sectional area of spun fiber is big, and the degree of hollowness of fiber is small; The width of slit is small, and extrusion output is small, and the degree of hollowness of spun fiber is big;But slit is too small, and the wall of spun fiber is too thin, hollow regular Spend it is low, it is hollow easily-deformable.For the spinneret of C-shaped, gap center width is equivalent to 1.0 times of slit width;Product shape is sprayed Filament plate, width is equivalent to 0.8 times of slit width at gap center.Those skilled in the art have the ability according to product requirement and spinning The difference of silk materials performance sets the specific size of spinneret sheet separation and slit.

Hollow-fibre membrane in addition to C-shaped and product shape, can also there is Crossed Circle and bicyclic sleeve spinneret with SPINNERETS FOR MELT SPINNING, The doughnut internal-and external diameter that latter two spinneret is spun is uniform, good concentricity, c shape and product shape due to there is the support of clearance material, Multiple single holes relatively simply can be made simultaneously in one block of spinneret, for spinning synnema, yield is larger.But Crossed Circle and bicyclic For sleeve spinneret due to being composed of multiple components, it is larger to make porous spinneret difficulty, is served only for spinning mostly Single hollow-fibre membrane.

(2) circular blow wind unsymmetrical excavation

Well known to those skilled in the artly, the factor of melt-spun doughnut degree of hollowness is influenced in addition to spinneret board size, also The factors such as spinning temperature and cooling forming condition;Spinning temperature is high, and melt viscosity is small, and it is big that melt goes out the extruding phenomenon after spinneret orifice Big to reduce, melt-forming drop in resistance, surface tension also declines therewith, and melt stream is made to generate surface atrophy to make cavity portion Divide and become smaller, spun degree of hollowness is reduced.

Cooling forming includes that the conditions such as wind speed, wind-warm syndrome, blowing distance such as draw the rheological behavior for spinning melt stream in journey It stretches the physical parameters such as kinematic viscosity, tensile stress to have a significant impact, directly decides the size of degree of hollowness.

Typically with the increase of wind speed, the solidification rate of cooling condition aggravation, melt stream is accelerated, so that spinning shape in journey At doughnut internal cavity have little time atrophy and accelerate to solidify, be conducive to the formation of doughnut cavity, in the fiber spun Reciprocal of duty cycle is high, but wind speed is excessive, will cause strand and rocks turbulence, declines spinneret face temperature, wire vent is unsmooth, is also easy to produce hardhead Silk and silk and the reduction breaked end with wind-warm syndrome, cooling forming condition are reinforced, improve the curing degree of melt stream, spun fiber Degree of hollowness is high.But wind-warm syndrome is too low, and spinneret face easily blows cold, difficulty in spinning.For bicyclic sleeve spinneret, it is passed through in casing The size of gas flow is also possible to will affect the degree of hollowness of fiber.Those skilled in the art have the ability through selection gas for amount Size will prepare the hollow-fibre membrane with suitable degree of hollowness with the pump of spinning slurry for the ratio of amount.

Those skilled in the art can be reduced by the control to circular blow wind unsymmetrical excavation passes through direct melt spinning system The doughnut taken forms three-dimensional crimp and spins the case where tensile property deteriorates after preventing.Circular blow wind unsymmetrical excavation technique includes This four aspects of cold air blast velocity, temperature and humidity and uniformity.Improve wind speed can with the dissymmetrical structure in reinforcing fibre section from And the better as-spun fibre of latent crimp is obtained, but wind speed is crossed may well cause that strand oscillation, wire vent is unsmooth, precursor preorientation Degree is big, tensile property deteriorates etc., therefore those skilled in the art can choose suitable wind speed to take into account the latent crimp of precursor And tensile property;Although reducing circular blow wind-warm syndrome cooling condition is aggravated, precursor preorientation increases, under tensile property simultaneously Drop, therefore those skilled in the art are also required to select suitable wind-warm syndrome;Circular blow wind can also have certain humidity to reduce and spin Electrostatic phenomenon and strand disturbance during silk, control cooling condition;The uniformity for improving circular blow wind simultaneously guarantees that spinning is stablized With rear spinning tensile property.

(3) it spins and stretches afterwards

The purpose of three-dimensional static electric field stretching does not simultaneously lie in the mechanical property for improving fiber, but makes in as-spun fibre The stress difference in portion and latent crimp emerge from, and should pull open the stress difference in every cross section of single fiber in stretching as much as possible, This species diversity between single fiber is set to be maintained at same level again, therefore doughnut generally uses one-off drawing technique.

Stretching mode, draft temperature and stretching ratio spin the technical parameter in stretching after being, those skilled in the art can be with The professional knowledge grasped according to oneself is selected.It is typical but without limitation, there are steam stretching and water-bath to draw by drawing medium Point stretched: water-bath is stretched using the grease heated as medium, and fiber generates secondary orientation in stretching, causes fiber immanent structure poor Different reduction, curling and the decline of fluffy performance;Steam stretching is that insulation stretches, orientation is primary complete then using saturated vapor as medium At comparatively speaking the crystalline texture of fiber is more obvious after steam stretching and stablizes.The selection of stretching ratio and temperature will be same When take into account the tensile property of as-spun fibre and the release of curling.

(4) control technology of degree of hollowness

The hollow control of degree of hollowness is through during entire melt spinning, all from spinneret pore size to rear spinning drawing process In the presence of the control to degree of hollowness.The size of the width of typical but non-limiting spinneret orifice slit and two slit distance between two tips is to spin Knit the suitable precondition of round doughnut degree of hollowness;And spinning temperature and cooling forming condition are to control the main work of degree of hollowness Skill factor, spinning temperature is low, melt viscosity is big, melt-forming resistance and surface tension are conducive to greatly hollow formation, but too low general Phenomena such as causing hard silk;And it is improved with draw ratio, weakened fiber walls are so as to cause degree of hollowness raising.In addition to this, ability It is (generally dry through molecular sieve by compressed air that field technique personnel can also investigate the slice moisture content controlled needed for conventional spinning Device dries), the techniques such as spinning temperature and speed, the oil formula of relaxation heat setting technique and siliceous product and oiling method Condition.

It is techniques known for melt-spinning technology, those skilled in the art can grasp special according to oneself Industry knowledge consults the specific melt-spinning technology condition of background technique acquisition, typical but non-limiting melt-spinning technology item Part can be with are as follows:

Compared with prior art, the invention has the following advantages:

The present invention utilizes the filler for being used as warmth retention property product doped with the modification hollow cotton of graphene, obtains warmth retention property The warmth retention property product that can be excellent in permeability, the guarantor for the modification hollow cotton that biomass graphene doping is 1.4% Warm rate is suitable in 90% white duck down with down content, but air penetrability is much higher than duck's down in 240mm/s or so.

Specific embodiment

The technical scheme of the invention is further explained by means of specific implementation.

Those skilled in the art are not construed as to this hair it will be clearly understood that the described embodiments are merely helpful in understanding the present invention Bright concrete restriction.

Graphene preparation example 1 (redox graphene)

Using the method for embodiment 1 in the patent of Publication No. CN105217621A, specifically:

(A) by the mixing of 2g graphite powder and 3g potassium dithionate, 3g phosphorus pentoxide and the 12mL concentrated sulfuric acid in reactor It reacts in system, is stirred 4 hours under 80 DEG C of water bath conditions, until forming dark blue solution, obtain pre- oxygen after cooling, suction filtration, drying The graphite of change;

(B) take graphite oxide 2g obtained by step (A) in three-neck flask, it is dense with 150mL under conditions of ice-water bath Sulfuric acid solution is gradually added into the potassium permanganate of 25g, stirs 2 hours;

(C) three-neck flask of above-mentioned steps (B) is transferred to oil bath, is warming up to 35 DEG C, stirred 2 hours, continue stirring and by The mixed solution of 30wt% hydrogen peroxide and deionized water is added according to the amount that volume ratio is 1:15;It filters, respectively with 4mL mass point Number cleans 1 time for 10% dilute hydrochloric acid and deionized water, and centrifugation obtains the graphene oxide aoxidized for the first time after dry;

(D) the graphene oxide 2g prepared in step (C) is molten with the concentrated sulfuric acid of 50mL under conditions of ice-water bath again Liquid is mixed in three-neck flask, is gradually added into the KMnO of 8g4, stir 1 hour;

(E) three-neck flask of above-mentioned steps (D) is transferred to oil bath, is warming up to 40 DEG C, stirred 1 hour, then proceed to heat up To 90 DEG C, after stirring 1 hour, continues stirring and 30wt% hydrogen peroxide and deionized water is added according to the amount that volume ratio is 1:7 Mixed solution, it is cooling after continuing stirring 6 hours, filter, respectively with 4mL mass fraction be 10% dilute hydrochloric acid and deionized water Cleaning 2 times, centrifugation obtain the graphene oxide of size uniformity after dry.

Graphene preparation example 2 (biomass graphene)

Using the method for embodiment 10 in the patent of Publication No. CN104724696A, specifically:

Stalk is collected, small pieces is shredded into after processing is clean, is immersed in ethanol solution, is at the uniform velocity stirred with the revolving speed of 100r/min It mixes 5 hours;Then solution is transferred in supercentrifuge, revolving speed is set as 3000r/min, and centrifugation time is 20 minutes, knot The broken sample of Shu Houqu lower layer.Under normal temperature and pressure, broken sample is fitted into the Tissue Culture Dish that diameter is 15cm, is placed in air inlet, adjusted Amount of restriction parameter, setting wind speed are 6m/s, air quantity 1400m3/h, are kept for ventilation state 12 hours;Tube furnace is warming up to 1300 DEG C, it is passed through inert gas shielding, is kept for 30 minutes;Broken sample after drying is placed in tube furnace, heats 5 hours, is cooled to After room temperature, the obvious graphene of overburden ratio is obtained.

Graphene preparation example 3 (the biomass graphene in special source)

The preparation method of conventional fibre element, specifically:

(1) dense for the formic acid of 80wt% and the organic acid solution pair of acetic acid using total acid by after wheat straw comminution pretreatment Treated, and wheat straw carries out boiling, and the mass ratio of acetic acid and formic acid is 1:12 in the organic acid solution of the present embodiment, and is being added The hydrogen peroxide (H2O2) for accounting for wheat straw raw material 1wt% is added as catalyst before entering raw material, controls 120 DEG C of reaction temperature, 30min, solid-liquid mass ratio 1:10 are reacted, and obtained reaction solution is subjected to first time separation of solid and liquid;

(2) being separated by solid-liquid separation obtained solid for the first time, that total acid is added is dense for the formic acid of 75wt% and the organic acid solution of acetic acid Acid elution is carried out, wherein joined the peroxide for accounting for wheat straw raw material 8wt% in the dense organic acid solution for 75wt% of above-mentioned total acid Changing hydrogen (H2O2) as the mass ratio of catalyst and acetic acid and formic acid is 1:12, controlled at 90 DEG C, wash time 1h, solid-liquid Mass ratio is 1:9, and reaction solution is carried out second and is separated by solid-liquid separation;

(3) it collects for the first time and is separated by solid-liquid separation obtained liquid for the second time, high temperature and pressure is carried out under 120 DEG C, 301kPa Obtained formic acid and acetic acid vapor are condensed back into the reaction kettle of step (1) as cooking liquor, use until being evaporated by evaporation Boiling in step (1);

(4) it collects and is separated by solid-liquid separation obtained solid for the second time, and washed, control washing temperature is 80 DEG C, washing slurry Dense is 6wt%, and obtained washing slurry is carried out third time separation of solid and liquid;

(5) it collects and is separated by solid-liquid separation obtained liquid for the third time, carry out water, sour rectifying, obtained mix acid liquor is back to step Suddenly the boiling of step (1) is used in the reaction kettle of (1) as cooking liquor, obtained water to be back to step (5) and water is washed with water;

(6) it collects and is separated by solid-liquid separation obtained solid for the third time and is screened to obtain required screened stock cellulose.

Biomass graphene is prepared by raw material of cellulose:

(1) 1:1 cellulose mixture and frerrous chloride in mass ratio, stirring carries out catalytic treatment 4h at 150 DEG C, it is dry extremely Presoma moisture content 10wt%, obtains presoma;

(2) in N2 atmosphere, presoma is warming up to 170 DEG C with 3 DEG C/min rate, keeps the temperature 2h, temperature programming later to 400 DEG C, 3h is kept the temperature, is warming up to 1200 DEG C later, obtains crude product after keeping the temperature 3h;The heating rate of described program heating is 15 DEG C/min;

At (3) 55~65 DEG C, by crude product through over-richness be 10% sodium hydroxide solution, 4wt% chlorohydric acid pickling after, water It washes to obtain biomass graphene.

Lower mask body is by taking PET is the modified hollow cotton products of raw material preparation as an example:

Embodiment 1

A kind of modified hollow cotton, is prepared via a method which to obtain:

(1) PET blank terylene chips are crushed to average grain diameter 1mm, obtain PET blank terylene chips particle;

(2) 1kg graphene powder (graphene powder that graphene preparation example 3 obtains) and 9kg PET blank terylene are mixed Chip granulate, 250 DEG C of Screw Extrusions of melting temperature are dried to moisture < 300ppm in a vacuum drying oven, are obtained containing stone The dacron master grain of black alkene;

(3) after mixing by the 1kg dacron master grain for containing graphene and 1kgPET blank terylene chips, it continuously adds 5kgPET blank terylene chips are uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 1.4wt%.

Use the modification hollow cotton that is prepared as 2 × 2m2The filler of quilt, the quilt inside are filled with 1.5kg Modification hollow cotton.

Embodiment 2

A kind of modified hollow cotton, the difference from embodiment 1 is that:

(3) after mixing by the 1kg dacron master grain for containing graphene and 1kg PET blank terylene chips, it continuously adds 3kg PET blank terylene chips are uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 2wt%.

Use the modification hollow cotton that is prepared as 2 × 2m2The filler of quilt, the quilt inside are filled with 1.5kg Modification hollow cotton.

Embodiment 3

A kind of modified hollow cotton, the difference from embodiment 1 is that:

(3) after mixing by the 1kg dacron master grain for containing graphene and 1kg PET blank terylene chips, it continuously adds 8kg PET blank terylene chips are uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 1wt%.

Use the modification hollow cotton that is prepared as cold-proof underwear filler.

Embodiment 4

A kind of modified hollow cotton, the difference from embodiment 1 is that:

(3) after mixing by the 1kg dacron master grain for containing graphene and 4.5kg PET blank terylene chips, continue to add Enter 45kg PET blank terylene chips to be uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 0.2wt%.

Use the modification hollow cotton that is prepared as tent filler.

Embodiment 5

A kind of modified hollow cotton, the difference from embodiment 1 is that:

Carry out step (3 ') after step (3): the material that step (3) is obtained is in 250 DEG C of Screw Extrusions.

Use the modification hollow cotton that is prepared as down-coat packing.

Embodiment 6

A kind of modified hollow cotton, is prepared via a method which to obtain:

(1) PET blank terylene chips are crushed to average grain diameter 1mm, obtain PET blank terylene chips particle;

(2) 1kg graphene powder (graphene powder that graphene preparation example 3 obtains) and 4kg PET blank terylene are mixed Chip granulate, 250 DEG C of Screw Extrusions of melting temperature are dried to moisture < 300ppm in a vacuum drying oven, are obtained containing stone The dacron master grain of black alkene;

(3) after mixing by the 1kg dacron master grain for containing graphene and 1kgPET blank terylene chips, it continuously adds 4.7kgPET blank terylene chips are uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 3wt%.

Use the modification hollow cotton that is prepared as tent filler.

Embodiment 7

A kind of modified hollow cotton, the difference with embodiment 6 are:

(3) after mixing by the 1kg dacron master grain for containing graphene and 1kg PET blank terylene chips, it continuously adds 2kg PET blank terylene chips are uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 5wt%.

Use the modification hollow cotton that is prepared as cold-proof underwear filler.

Embodiment 8

A kind of modified hollow cotton, the difference with embodiment 6 are:

(3) after mixing by the 1kg dacron master grain for containing graphene and 0.5kg PET blank terylene chips, continue to add Enter 0.5kg PET blank terylene chips to be uniformly mixed;

(4) material melts for obtaining step (3), then carry out spinning, carry out shredding after the completion of rear spinning and obtain Modified Polyester Synthetic fibre hollow cotton, graphene content are 10wt%.

Use the modification hollow cotton that is prepared as sleeping bag filler.

Embodiment 9

A kind of modified hollow cotton, the difference from embodiment 1 is that: without the pulverising step of step (1), in step (2) Directly 1kg graphene powder (graphene powder that graphene preparation example 3 obtains) and 9kg PET blank terylene chips are mixed.

Use the modification hollow cotton that is prepared as pillow fillers.

Embodiment 10

A kind of modified hollow cotton, the difference from embodiment 1 is that: the terylene that 1kg is directly contained graphene by step (3) is female Grain is uniformly mixed with 6kgPET blank terylene chips;Carry out step (4) later.

Use the modification hollow cotton that is prepared as back cushion filler.

Embodiment 11

A kind of modified hollow cotton, the difference from embodiment 1 is that: the stone obtained in step (2) using graphene preparation example 1 The graphene powder that black alkene powder replacement graphene preparation example 3 obtains.

Use the modification hollow cotton that is prepared as 2 × 2m2The filler of quilt, the quilt inside are filled with 1.5kg Modification hollow cotton.

Embodiment 12

A kind of modified hollow cotton, the difference from embodiment 1 is that: the stone obtained in step (2) using graphene preparation example 2 The graphene powder that black alkene powder replacement graphene preparation example 3 obtains.

Use the modification hollow cotton that is prepared as 2 × 2m2The filler of quilt, the quilt inside are filled with 1.5kg Modification hollow cotton.

Comparative example 1 provides 2 × 2m of one kind2Quilt, the white duck of 2.3kg down content 90% is filled with inside the quilt Suede.

Comparative example 2 provides 2 × 2m of one kind2Quilt, be filled with the unmodified hollow cotton of 3kg inside the quilt;

The unmodified hollow cotton is prepared via a method which to obtain:

(1) PET blank terylene chips are crushed to average grain diameter 1mm, obtain PET blank terylene chips particle;

(2) material melts for obtaining step (1), then carry out spinning, and progress shredding obtains unmodified after the completion of rear spinning Hollow cotton.

Performance test:

The hollow cotton products of modification that embodiment and comparative example is prepared are tested as follows:

(1) keep warm rate: test method is thermal resistance and dampness under GBT11048-2008 textile physiological comfort limit Measurement;

(2) air penetrability: test method is the detection of GBT5453-1997 textile fabric gas permeability;

(3) far infrared normal emittance: through national textile fabrics Quality Supervision and Inspection Center, according to FZ/T64010-2000 The method of inspection is tested;

(4) antibacterial inspection: through national textile fabrics Quality Supervision and Inspection Center, according to GB/T20944.3-2008 inspection party Method, by taking staphylococcus aureus as an example;

Test result is shown in Table 1:

The performance test results of table 1 embodiment 1,2,11,12 and comparative example

The Applicant declares that the present invention is explained by the above embodiments product of the invention, but the invention is not limited to Above-mentioned restriction range does not mean that the present invention must rely on above-mentioned restriction and could implement.Person of ordinary skill in the field It will be clearly understood that any improvement in the present invention, to the equivalence replacement and auxiliary element of raw material selected by the present invention or already known processes Addition, the selection of concrete mode etc., all of which fall within the scope of protection and disclosure of the present invention.

Claims (14)

1. a kind of purposes of modified dacron hollow cotton, which is characterized in that the modified hollow cotton is used as the filling of warmth retention property product Object;
Doped with graphene in the modified hollow cotton;
The preparation method of the modified hollow cotton includes the following steps:
(1) blank terylene chips are crushed, blank terylene chips particle is obtained;
(2) graphene is mixed, Screw Extrusion with blank terylene chips particle, after dry, it is female obtains the terylene containing graphene Grain;
(3) dacron master grain containing graphene is uniformly mixed with blank terylene chips;
(4) resulting material is subjected to melt spinning, then shredding obtains modified hollow cotton;
Alternatively, preparation method includes the following steps:
(a) graphene is mixed, Screw Extrusion with blank terylene chips, after dry, obtains the dacron master grain containing graphene;
(b) dacron master grain containing graphene is uniformly mixed with a part of blank terylene chips, later again with remaining blank Terylene chips mixing;
(c) by resulting material melt spinning, then shredding obtains hollow cotton;
The graphene is biomass graphene.
2. purposes as described in claim 1, which is characterized in that the warmth retention property product be selected from quilt, pillow, back cushion, clothes, Sleeping bag or tent.
3. purposes as claimed in claim 2, which is characterized in that the clothes is selected from Insulation shirt, cold-proof underwear or down jackets.
4. purposes as described in claim 1, which is characterized in that the biomass graphene is prepared by biomass.
5. purposes as described in claim 1, which is characterized in that the cellulose system that the biomass graphene is obtained by biomass It is standby to obtain.
6. purposes as described in claim 1, which is characterized in that the biomass is in agriculture and forestry organic waste material and/or plant Any a kind or at least two kinds of of combination.
7. purposes as claimed in claim 6, which is characterized in that the plant be any a kind in needlebush or leaf wood or At least two kinds of combinations.
8. purposes as claimed in claim 6, which is characterized in that the agriculture and forestry organic waste material is selected from cornstalk, corncob, sorghum Any a kind or at least two kinds of of group in bar, megasse, bagasse, furfural dregs, xylose residue, sawdust, cotton stalk, shell and reed It closes.
9. purposes as claimed in claim 6, which is characterized in that the agriculture and forestry organic waste material is corncob.
10. purposes as described in claim 1, which is characterized in that in the modified hollow cotton doping of graphene be 0.2~ 10wt%.
11. purposes as described in claim 1, which is characterized in that in the modified hollow cotton doping of graphene be 0.3~ 8wt%.
12. purposes as described in claim 1, which is characterized in that in the modified hollow cotton doping of graphene be 0.5~ 5wt%.
13. purposes as described in claim 1, which is characterized in that the far infrared of the modified hollow cotton detects normal emittance Greater than 0.85.
14. purposes as described in claim 1, which is characterized in that the far infrared of the modified hollow cotton detects normal emittance Greater than 0.88.
CN201610045894.5A 2016-01-22 2016-01-22 A kind of purposes of modified hollow cotton CN105525384B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610045894.5A CN105525384B (en) 2016-01-22 2016-01-22 A kind of purposes of modified hollow cotton

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
CN201610045894.5A CN105525384B (en) 2016-01-22 2016-01-22 A kind of purposes of modified hollow cotton
CA3005917A CA3005917C (en) 2015-11-20 2016-11-18 Modified fiber and preparation method therefor
EP16865799.7A EP3378978A4 (en) 2015-11-20 2016-11-18 Modified fiber and preparation method therefor
PCT/CN2016/106435 WO2017084622A1 (en) 2015-11-20 2016-11-18 Modified fiber and preparation method therefor
KR1020187017543A KR20180085768A (en) 2015-11-20 2016-11-18 Modified fiber and method for manufacturing the same

Publications (2)

Publication Number Publication Date
CN105525384A CN105525384A (en) 2016-04-27
CN105525384B true CN105525384B (en) 2019-05-10

Family

ID=55767895

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610045894.5A CN105525384B (en) 2016-01-22 2016-01-22 A kind of purposes of modified hollow cotton

Country Status (1)

Country Link
CN (1) CN105525384B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104724699B (en) 2015-03-04 2017-04-26 黑龙江大学 Method for preparing biomass graphene employing cellulose as raw material
WO2017084622A1 (en) * 2015-11-20 2017-05-26 济南圣泉集团股份有限公司 Modified fiber and preparation method therefor
CN108277650A (en) * 2018-02-24 2018-07-13 璧典附 A kind of graphene/feather composite material and preparation method
CN108085993A (en) * 2018-02-24 2018-05-29 璧典附 A kind of nano silver/feather composite material of graphene package and preparation method thereof
CN109430957A (en) * 2018-11-30 2019-03-08 海南中美达纳米技术股份有限公司 A kind of nanofiber ecological heat preservation underwear
CN110575034A (en) * 2019-07-30 2019-12-17 江苏缔凡蚕丝科技创意园有限公司 silk graphene quilt

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103814080A (en) * 2011-05-03 2014-05-21 俄克拉荷马州大学评议会 Polyethylene terephthalate-graphene nanocomposites
CN104016341A (en) * 2014-07-01 2014-09-03 济南圣泉集团股份有限公司 Preparation method of porous graphene
CN104386684A (en) * 2014-12-16 2015-03-04 中国科学院宁波材料技术与工程研究所 Preparation method of graphene and graphene
CN104724699A (en) * 2015-03-04 2015-06-24 黑龙江大学 Method for preparing biomass graphene employing cellulose as raw material

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103044865A (en) * 2012-12-18 2013-04-17 南京大学 Preparation method for amino graphene modified polyethylene terephthalate (PET) material
CN104328523B (en) * 2014-11-20 2016-01-20 济南圣泉集团股份有限公司 Viscose comprising Graphene and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103814080A (en) * 2011-05-03 2014-05-21 俄克拉荷马州大学评议会 Polyethylene terephthalate-graphene nanocomposites
CN104016341A (en) * 2014-07-01 2014-09-03 济南圣泉集团股份有限公司 Preparation method of porous graphene
CN104386684A (en) * 2014-12-16 2015-03-04 中国科学院宁波材料技术与工程研究所 Preparation method of graphene and graphene
CN104724699A (en) * 2015-03-04 2015-06-24 黑龙江大学 Method for preparing biomass graphene employing cellulose as raw material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《圣泉基团推出石墨烯内暖纤维》;通讯员 郑宁来;《合成纤维工业》;20151015;第38卷(第5期);第46页
《圣泉集团:生物源石墨烯内暖智能纤维》;新华网;《http://news.xinhuanet.com/tech/2015-04/29/c_127747148.htm》;20150429;第1-2页

Also Published As

Publication number Publication date
CN105525384A (en) 2016-04-27

Similar Documents

Publication Publication Date Title
JP4355945B2 (en) Near-infrared absorbing fiber and fiber product using the same
CN103046151B (en) Graphene blend regenerated cellulose fiber and preparation method thereof
CN104818543B (en) A kind of modified polylactic acid fiber haveing excellent performance
CN105525381B (en) A kind of composite polyester fiber containing graphene, preparation method and use
CN100400579C (en) Method for preparing functional material of regenerated cellulose
CN105200547B (en) A kind of preparation method of graphene-terylene nanometer composite fibre
US4420534A (en) Conductive composite filaments and methods for producing said composite filaments
CN101705527B (en) Antibiosis antistatic multifunctional nylon 6 fiber, preparation and application thereof
CN102877156B (en) Preparation method of anti-flaming recyle polyester staple fiber
CN101481830B (en) Engaging double-screw rod spinning pearl functional fibre and manufacturing process thereof
CN105420835A (en) Manufacturing method of antibacterial and far infrared health polyester fibers
CN102864507B (en) Preparation method and product of melt direct spinning superfine porous differential polyester fiber
CN103147151B (en) Processing method of composite filament for netting gear manufacture
CN103526372B (en) A kind of NEW TYPE OF COMPOSITE high strength textile material and manufacture method
CN104846536B (en) A kind of preparation method of the screen cloth based on warp JIA card Jacquard Technique
CN104073908B (en) A kind of preparation method of multi-functional super imitative cotton biomass polyester short fiber dimension
CN105002592B (en) A kind of vinegar nitrile fiber and preparation method thereof
CN101805941B (en) Preparation method of polylactic acid fiber with high melting point
CN104846466B (en) A kind of high heat conduction polyacrylonitrile fibre and preparation method thereof
CN103526415B (en) Far infrared heat-generating home textile fabric
CN105504700B (en) A kind of composite polyester material containing graphene, preparation method and purposes
CN106149083A (en) Functional graphene fiber cellulose fiber prepared by a kind of fusion method and preparation method thereof
CN105504341B (en) A kind of compound and preparation method thereof and a kind of macromolecular material and preparation method thereof
CN102978744B (en) Method for manufacturing conductive polyester fibers
CN102505182A (en) Method for preparing functional ultraviolet-resistant polyester staple fiber from waste renewable polyester bottle chips

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
GR01 Patent grant