CN105525384A - Use of modified hollow cotton - Google Patents
Use of modified hollow cotton Download PDFInfo
- Publication number
- CN105525384A CN105525384A CN201610045894.5A CN201610045894A CN105525384A CN 105525384 A CN105525384 A CN 105525384A CN 201610045894 A CN201610045894 A CN 201610045894A CN 105525384 A CN105525384 A CN 105525384A
- Authority
- CN
- China
- Prior art keywords
- graphene
- hollow cotton
- cotton
- living beings
- modification hollow
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/02—Cotton wool; Wadding
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING 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
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-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
- D04H1/42—Non-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
- D04H1/4326—Condensation or reaction polymers
- D04H1/435—Polyesters
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to use of modified hollow cotton. The modified hollow cotton serves as filler of warm-keeping products and is doped with graphene. According to the use of the modified hollow cotton, the modified hollow cotton which is doped with the graphene serves as the filler of the warm-keeping products, so that the warm-keeping products with excellent warm-keeping property and air permeability are obtained; the heat insulation of the modified hollow cotton with the biomass graphene doped amount of 1.4% is equivalent to that of white duck down with the down content of 90%, whereas the air permeability is about 240mm/s and is far higher than that of duck down.
Description
Technical field
The invention belongs to terylene arts, be specifically related to a kind of purposes of modification hollow cotton.To be the applicant (Shengquan Group Co. Ltd., Jinan) submit to the denomination of invention of China national Department of Intellectual Property to be the continuation application of " a kind of modification hollow cotton and preparation method thereof " on January 21st, 2016 to the application.
Background technology
Terylene is an important kind in synthetic fiber, is the trade name of China's polyester fiber, and it is with polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), through the fiber that spinning and post processing are made.
Polyethylene terephthalate (PET) is for raw material is through esterification or ester exchange and polycondensation reaction and obtained fiber-forming polymer with poly terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG).Polybutylene terephthalate (PBT) is raw material through esterification or ester exchange and polycondensation reaction and obtained fiber-forming polymer with poly terephthalic acid (PTA) or dimethyl terephthalate (DMT) (DMT) and BDO.
Terylene is that in three large synthetic fiber, technique is the simplest a kind of, and price is also relatively cheap, and it has durable, good springiness, not yielding, corrosion-resistant, insulation, the feature such as well-pressed, quick-drying washable, by people are liked.
PET Hollow cotton is manufactured through special process by the dacron ultrafine fiber of different size, because matter is like eider down, is also referred to as silk floss or feather and down, is widely used in eider down cotton clothes, eider down cotton-padded trousers, ski-wear, insulated cold wear, feather and down quilt, the multiple warm-keeping product such as automobile cushion.The shortcoming of existing PET Hollow cotton is that warmth retention property is not high, not water-fastness, light not.
Graphene (Graphene) is the two dimensional crystal only having one deck atomic thickness being stripped out from graphite material, being made up of carbon atom, is the thinnest, intensity is maximum, electrical and thermal conductivity performance the is the strongest a kind of novel nano-material that find at present.Added by Graphene in the matrixes such as terylene, being expected to can the new performance of endowing terylene, and especially add and have antibacterial and living beings Graphene that is Low Temperature Far Infrared function, terylene is hopeful to have antibacterial and Low Temperature Far Infrared function.
But the solid state of Graphene is easily reunited, form larger particle agglomeration, when adding in the matrixes such as terylene, and be not easily uniformly dispersed, significantly reduce the processing fluidity of the matrix master batches such as terylene, thus cannot carry out spinning technique, Graphene cannot be applied in the matrix materials such as terylene.
Prior art is in order to disperse graphene uniform, normal interpolation dispersant, but dispersant has deterioration impact for material, how to find a kind of method of adding dispersant that do not need graphene uniform to be entrained in the base materials such as terylene, the performance (as heat-insulating property, Low Temperature Far Infrared and antibacterial performance) of abundant using mineral carbon alkene is one, this area problem demanding prompt solution.
Summary of the invention
For prior art, thering is provided a kind of is entrained in polyester material by Graphene, obtain the modification hollow cotton with excellent thermal insulation performance, Low Temperature Far Infrared performance and bacteriostasis property, the object of the invention is to utilize modification hollow cotton to be used as the purposes of the filler of warmth retention property product, doped with Graphene in described 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, eider down sleeveless jacket or down wadded trousers.
Quilt of the present invention, pillow, back cushion, clothes, sleeping bag, tent, and the preparation method of Insulation shirt, cold-proof underwear or down jackets is with reference to the preparation method of corresponding product in state of the art, the present invention is not specifically limited, and can be prepared even the technique of corresponding product with reference to this area by unmodified hollow cotton.
" modification hollow cotton " of the present invention is obtained by the form of doped graphene, and those skilled in the art also can be referred to as hollow cotton blend, hollow cotton compound, hollow cotton modifier, the hollow cotton containing Graphene or the modification hollow cotton containing Graphene.
Graphene adds in hollow cotton with the form that various those skilled in the art can expect by being meant to of " doping " of the present invention, typical but non-limiting can by being dispersed in the surface of hollow cotton, or by the base material of In-situ reaction modification hollow cotton, or with hollow cotton physical blending etc." doping " also can replace with by those skilled in the art to be contained, comprise, disperses, has.
Preferably, described Graphene is living beings Graphene.
Described living beings Graphene is prepared by living beings; The cellulose that preferred described living beings Graphene is obtained by living beings prepares.
The number of plies is more than 10 layers, and thickness is the cellular lamellar structure of the hexatomic ring of carbon within 100nm, is called graphene nano lamella; With living beings be the number of plies prepared of carbon source more than 10 layers, thickness is the cellular lamellar structure of the hexatomic ring of carbon within 100nm, is called living beings graphene nano lamella; The number of plies is the cellular lamellar structure of hexatomic ring of 1 ~ 10 layer of carbon, is called Graphene; The cellular lamellar structure of hexatomic ring of to take living beings as the number of plies prepared by carbon source be 1 ~ 10 layer of carbon, is called living beings Graphene.
Graphene of the present invention comprises graphene nano lamella and Graphene, comprises living beings graphene nano lamella and living beings Graphene further.
Graphene of the present invention obtains by different preparation method, such as mechanical stripping method, epitaxial growth method, chemical vapor infiltration, graphite oxidation reducing process can also be by biomass resource hydrothermal carbonization method, and the Graphene that in prior art prepared by additive method.But, which kind of method is all difficult to realization and prepares the theoretic Graphene of stricti jurise on a large scale, such as, can there is some impurity element, other allotropes of carbon or the number of plies non-the individual layer even graphene-structured of multilayer (such as 3 layers, 5 layers, 10 layers, 20 layers etc.) in the Graphene that prior art prepares, the Graphene that the present invention utilizes also comprises the Graphene on above-mentioned non-critical theory of meaning.
Preferably, described living beings are selected from the combination of any a kind or at least 2 kinds in agriculture and forestry organic waste material and/or plant.
Preferably, described plant is the combination of any a kind or at least 2 kinds in needlebush or leaf wood.
Preferably, described agriculture and forestry organic waste material is the combination of any a kind or at least 2 kinds in cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk, shell and reed.
Preferably, described agriculture and forestry organic waste material is corncob.
Except above-mentioned to except the enumerating of living beings, living beings of the present invention can be any one biomass resources that those skilled in the art can be known, the present invention no longer continues to repeat.
Living beings Graphene of the present invention refers to living beings to be the Graphene that carbon source prepares, and process this area that carbon source that concrete with living beings is prepares Graphene has been reported, and typical but non-limitingly comprises CN104724699A, and the present invention repeats no more.
Preferably, in described modification hollow cotton, Graphene content is 0.2 ~ 10wt%, preferably 0.3 ~ 8wt%, further preferred 0.5 ~ 5wt%.
Exemplarily, in modification hollow cotton of the present invention, Graphene content is 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 modification hollow cotton of the present invention detects normal emittance and is greater than 0.85, such as 0.87,0.89,0.91,0.92,0.93 etc., is preferably greater than 0.88.
The warming effect of modification hollow cotton provided by the invention is: the warming effect of 1kg modification of the present invention hollow cotton is identical with the warming effect of 2.5 ~ 3kg common mesopore cotton, and while guarantee warming effect, good air permeability.
The preparation method of modification hollow cotton of the present invention, comprises the steps:
(1) pulverize blank terylene chips, obtain blank terylene chips particle;
(2) Graphene is mixed with blank terylene chips particle, Screw Extrusion, after drying, obtain the dacron master grain containing Graphene;
(3) dacron master grain containing Graphene is mixed with blank terylene chips;
(4) gained material is carried out melt spinning, then shredding obtains modification hollow cotton.
The present invention adopts in physics mode disperse solid Graphene and terylene base material, obtains the dispersed modification hollow cotton having Graphene.Particularly, first the terylene chips of blank shreds by the present invention, increases matsurface, increases specific area and the frictional force of its attachment Graphene, improves the dispersiveness of Graphene; Afterwards by solid-state graphene dispersion in the terylene chips particle of blank, Screw Extrusion obtains Graphene composite terylene master batch, and in Graphene composite terylene master batch, Graphene, as the carrier of Graphene, has been carried out preliminary dispersion by dacron master grain; Then load there is the dacron master grain of Graphene to carry out physical mixed by formula ratio and blank terylene chips, obtain the material treating spinning, treat that, in the material of spinning, Graphene achieves dispersed described; The preparation technology of last hollow cotton conveniently carries out melt spinning and can obtain the modification hollow cotton that Uniform Doped has Graphene, solve the technical problem that prior art graphene dispersion is uneven, obtain heat insulating ability, gas permeability, Low Temperature Far Infrared and antibiotic property and show excellent modification hollow cotton.
The master batch obtained, by being realized by the Graphene Granular composite of easily reuniting tentatively disperseing in blank terylene chips particle, mixes with blank terylene chips by the present invention afterwards again, obtains finely dispersedly to treat spinning material.
Blank terylene chips of the present invention refers to the terylene chips not adding functional particles Graphene.
Be uniformly distributed and refer to: the chance that measured value occurs everywhere in a certain scope is the same.For the application, described in be uniformly dispersed and refer to, in the scope for any cubic centimetre, the content of the Graphene of modification hollow cotton is more or less the same.
Preferably, the particle diameter≤3mm of described blank terylene chips particle, such as 0.1mm, 0.5mm, 0.9mm, 1.3mm, 1.8mm, 2.2mm, 2.5mm, 2.8mm etc.
Preferably, described step (1) and the blank terylene chips described in step (3) are PET (polyethylene terephthalate) and/or PBT (polybutylene terephthalate (PBT)) all independently of one another.
Preferably, the described blank terylene chips of step (1) is PET.
The selection of the present invention to the blank terylene chips described in step (1) and step (3) is not specifically limited, and those skilled in the art can select according to actual conditions.But PET fusing point is about 220 DEG C, PBT fusing point is about 270 DEG C, and from the Energy Angle of technological temperature, the present invention preferably the first blank terylene chips is PET, and the second blank terylene chips is PET.
Preferably, described is 1-20wt%, such as 2wt%, 4wt%, 6wt%, 8wt%, 12wt%, 15wt%, 17wt%, 19wt% etc. containing Graphene content in the dacron master grain of Graphene, preferred 5-15wt%, most preferably 6-10wt%.
Preferably, the melt 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, the moisture≤600ppm of the described dacron master grain containing Graphene, such as 50ppm, 80ppm, 130ppm, 180ppm, 230ppm, 280ppm, 350ppm, 390ppm, 420ppm, 450ppm, 480ppm etc., preferably≤300ppm.
Preferably, step (3) is described is 1:5 ~ 30, such as 1:6,1:7,1:9,1:13,1:16,1:22,1:26,1:29 etc. containing the dacron master grain of Graphene and the mass ratio of blank terylene chips; Preferred 1:15 ~ 20.
Preferably, inherent viscosity >=the 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.
Graphene of the present invention add the viscosity that membership reduces section, and viscosity is too low cannot carry out spinning process.
As optimal technical scheme, the described dacron master grain containing Graphene of step of the present invention (3) mixes with blank terylene chips and comprises the steps:
(3a) blank to the dacron master grain containing Graphene and part terylene chips is mixed;
(3b) continue in the mixture of step (3a), add the blank terylene chips of residue to mix.
2 step terylene chips are divided by dacron master grain containing Graphene to carry out dilution dispersion, the concentration of Graphene particle is made to reach preset requirement, can more even by graphene dispersion, the modification hollow cotton obtained shows more excellent in heat insulating ability, Low Temperature Far Infrared and antibiotic property.
Preferably, the mass ratio of the blank terylene chips entirety that the blank terylene chips of step (3a) described part and step (3a) add is 1:2 ~ 10, such as 1:3,1:4,1:5,1:6,1:7,1:8,1:9 etc., preferred 1:4 ~ 8.
The blank terylene chips entirety that described step (3a) adds refers to a part of blank terylene chips and the blank terylene chips quality sum of residue.
Further preferably, setting steps (3 ') between step (3) with step (4): the material that step (3) mixes is carried out Screw Extrusion again;
Preferably, the melt temperature of 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.
Conventional terylene can cause the fracture of terylene polymer molecule through twice Screw Extrusion, reduces the intensity of its molecular chain length and terylene, finally in the process preparing hollow cotton, causes length of string inadequate; The present invention by adding Graphene particle in terylene base material, and improve the melt temperature of Screw Extrusion, even if carry out twice Screw Extrusion, the polyster fibre molecular chain length obtained also changes not quite, can prepare hollow cotton fiber.
As alternatives, the preparation method of hollow cotton of the present invention comprises the steps:
(1) pulverize the section of PET blank, obtain the blank chip granulate of PET;
(2) blank to Graphene and PET chip granulate is mixed, Screw Extrusion under the condition of 230 ~ 270 DEG C of melt temperatures, will extrude after product is dried to moisture≤600ppm, and obtain the PET dacron master grain containing Graphene;
(3) the PET dacron master grain containing Graphene is mixed with PET terylene chips, obtain the material of inherent viscosity >=0.60dL/g;
(4) by gained material melt spinning, then shredding obtains modification hollow cotton.
The another kind of preparation method of modification hollow cotton of the present invention, comprises the steps:
A Graphene mixes with blank terylene chips by (), Screw Extrusion, after drying, obtains the dacron master grain containing Graphene;
B blank to dacron master grain containing Graphene and part terylene chips mixes by (), mix afterwards with remaining blank terylene chips again;
C (), by gained material melt spinning, then shredding obtains modification hollow cotton.
The present invention adopts in physics mode disperse solid Graphene and terylene base material, obtains the dispersed modification hollow cotton having Graphene.Particularly, first the terylene chips of blank mixes with solid-state Graphene by the present invention, and Screw Extrusion obtains Graphene composite terylene master batch, and in Graphene composite terylene master batch, Graphene, as the carrier of Graphene, has been carried out preliminary dispersion by dacron master grain; Then load had the dacron master grain of Graphene to divide 2 steps to carry out physical mixed by formula ratio and blank terylene chips, obtain the material treating spinning, in described material, Graphene achieves dispersed; The preparation technology of last hollow cotton conveniently carries out spinning and can obtain the dispersed hollow cotton having Graphene, solve the technical problem that prior art graphene dispersion is uneven, obtain heat insulating ability, gas permeability, Low Temperature Far Infrared and antibiotic property and show excellent modification hollow cotton.
The present invention realizes preliminary dispersion by being first dispersed in by the Graphene particle of easily reuniting in blank terylene chips, the master batch obtained is divided 2 steps and blank terylene chips physical mixed afterwards, realize the dispersed of Graphene, obtain and finely dispersedly treat spinning material.
Preferably, described step (a) and the described blank terylene chips of step (b) are PET and/or PBT all independently of one another.
Preferably, the described blank terylene chips of step (a) is PET.
The selection of step (a) of the present invention and the described blank terylene chips of step (b) is not specifically limited, and those skilled in the art can select according to actual conditions.But PET fusing point is about 220 DEG C, PBT fusing point is about 270 DEG C, and from the Energy Angle of technological temperature, the preferred terylene chips of the present invention is PET.
Preferably, in the described dacron master grain containing Graphene, Graphene content is 1 ~ 20wt%, such as 2wt%, 4wt%, 6wt%, 8wt%, 12wt%, 15wt%, 17wt%, 19wt% etc., preferably 5 ~ 15wt%, further preferred 6 ~ 10wt%.
Preferably, the melt temperature of the described Screw Extrusion of step (a) 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, the moisture≤600ppm of the described dacron master grain containing Graphene, such as 50ppm, 80ppm, 130ppm, 180ppm, 230ppm, 280ppm, 350ppm, 390ppm, 420ppm, 450ppm, 480ppm etc., preferably≤300ppm.
Preferably, step (b) is described is 1:5 ~ 30, such as 1:6,1:7,1:9,1:13,1:16,1:22,1:26,1:29 etc. containing the dacron master grain of Graphene and the mass ratio of blank terylene chips; Preferred 1:15 ~ 20.
Preferably, in step (b), the ratio of the blank terylene chips entirety that the blank terylene chips of a described part and step (b) add is 1:2 ~ 10, such as 1:3,1:4,1:5,1:6,1:7,1:8,1:9 etc., preferred 1:4 ~ 8.
Described blank terylene chips b entirety refers to the quality sum of partial blank terylene chips b and remaining blank terylene chips b.
Preferably, inherent viscosity >=the 0.60dL/g of the raw material of the described melt spinning of step (c), 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.
Graphene of the present invention add the viscosity that membership reduces section, and viscosity is too low cannot carry out spinning process.
As optimal technical scheme, carry out step (a ') before step (a): pulverized by blank terylene chips as blank terylene chips particle, for mixing with the described Graphene of step (a);
Preferably, the particle diameter≤3mm of described blank terylene chips particle, such as 0.1mm, 0.5mm, 0.9mm, 1.3mm, 1.8mm, 2.2mm, 2.5mm, 2.8mm etc.
Step (a ') terylene chips of blank is shredded, increase matsurface, increase specific area and the frictional force of its attachment Graphene, the dispersiveness of Graphene can be improved further.
Further preferably, setting steps between step (b) with step (c) (b '): material step (b) mixed carries out Screw Extrusion again;
Preferably, the melt temperature of 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.
Conventional terylene can cause the fracture of terylene polymer molecule through twice Screw Extrusion, reduces the intensity of its molecular chain length and terylene, finally in the process preparing hollow cotton, causes length of string inadequate; The present invention by adding Graphene particle in terylene base material, and improve the melt temperature of Screw Extrusion, even if carry out twice Screw Extrusion, the polyster fibre molecular chain length obtained also changes not quite, can prepare hollow cotton fiber.
As alternatives, the preparation method of hollow cotton of the present invention comprises the steps:
(a ') pulverize the section of PET blank, obtain the blank chip granulate of PET;
A blank to Graphene and PET chip granulate mixes by (), Screw Extrusion under the condition of 230 ~ 270 DEG C of melt temperatures, will extrude after product is dried to moisture≤600ppm, and obtain the PET dacron master grain containing Graphene;
B PET dacron master grain containing Graphene mixes with PET terylene chips by (), obtain the material of inherent viscosity >=0.60dL/g;
C (), by gained material melt spinning, then shredding obtains hollow cotton.
In the preparation method of hollow cotton of the present invention, step (4) or the spinning described in step (c) are the known technologies of this area.
Melt spinning method obtains doughnut by hollow spinneret plate, economical rationality, related process technologies comparative maturity, and process conditions all can control.
Melt spinning loads microbore catheter in hollow spinneret plate, the inflation doughnut that nitrogen or air obtain high degree of hollowness is filled with in fiber lumen, avoiding mechanism flattened fibers in production process causes degree of hollowness to decline, and make Conductivity of Fiber hot poorer than air, substantially increasing warmth retention property, is method well known in the art to the control of gas flow.Those skilled in the art can also by changing shape of spinneret, produce the doughnut of triangle, the multiple odd-shaped cross section such as quincunx, to improve the specific area of fiber, or the porous hollow fiber in 3 ~ 7 holes is obtained by special spinnerets, but its hollow rate may not be high, only within 30%.Those skilled in the art by design spinnerets shape and Reasonable adjustment spinning technique (ring blowing unsymmetrical excavation and then spin stretching control technology), can also obtain doughnut or three-dimensional static electric field by direct melt spinning.
Well known to a person skilled in the art, can adjust the process conditions of melt spinning and obtain desirable degree of hollowness, described process conditions are typical but non-limiting can be:
(1) spinneret design of melt-spun doughnut
The design of spinnerets comprises its shape and physical dimension two aspect, and the former is for different in nature cross-sectional hollow fiber, and its design is relevant with production requirement, and conventional hole shape has polygon, c shape, circular arc, multiple spot shape etc.; The feature dimension data such as slit length, two slit distance between two tips, equivalent diameter, sectional area, draw ratio that can comprise spinneret orifice is related to spinneret plate structure size;
Melt spinning spinning warmth retention property three-dimensional static electric field is typical but non-limiting is adopt triple-arc-shaped spinneret, and it can spin out the fiber that external diameter is comparatively thin, degree of hollowness is suitable easily.The good triple-arc-shaped spinneret of current effect mainly contains C shape and the porous hollow fiber spinnerets such as product shape spinnerets and circular arc combination, for spinning four holes, seven apertures in the human head and even tens hole doughnuts.When after melt extrusion spinnerets circular arc slit, circular arc melt is expanded, and end bonding forms cavity, after refinement, solidification, form doughnut.
Known in this fieldly, the size of spinnerets circular arc slit gap likely affects the formation of cavity: when excesssive gap, fiber hollow can not close, and can only spin open fiber; But when gap is too small, after melt extrusion spinneret orifice, very fast expanded bonding, cannot form cavity, and consider from mechanical strength, spinnerets gap is little, and intensity is low, fragile.Therefore for material of different nature, there is the size in different suitable spinnerets gaps, typical but non-limiting be the die swell of melt extrusion raw material than can the size in design spinnerets gap, and the ratio of gap center place width is slightly less than the die swell ratio of melt feed.
For spinneret orifice, slit width is large, and single hole extrusion capacity is large, and the sectional area of fiber spins greatly in institute, and the degree of hollowness of fiber is little; The width of slit is little, and extrusion capacity is little, to spin the degree of hollowness of fiber large; But slit is too little, to spin the wall of fiber too thin, hollow regularity is low, and hollow is yielding.For the spinnerets of C shape, gap center width is equivalent to 1.0 times of slit width; For product shape spinnerets, gap center place width is equivalent to 0.8 times of slit width.Those skilled in the art have the ability the difference according to product requirement and spinning material performance, the concrete size of setting spinnerets gap and slit.
Hollow-fibre membrane SPINNERETS FOR MELT SPINNING is except C shape and product shape, Crossed Circle and dicyclo sleeve-shaped spinnerets can also be had, the doughnut internal-and external diameter that latter two spinnerets spins is homogeneous, good concentricity, c shape and product shape are owing to there being the support of clearance material, can make multiple single hole at one block of spinnerets more simply, for spinning synnema, output is larger simultaneously.But Crossed Circle and dicyclo sleeve-shaped spinnerets are owing to being combined by multiple assembly, make porous spinnerets difficulty comparatively greatly, mostly only for spinning single hollow-fibre membrane.
(2) ring blowing unsymmetrical excavation
As well known to those skilled in the artly, affect the factor of melt-spun doughnut degree of hollowness except spinnerets size, also have the factor such as spinning temperature and cooling forming condition; Spinning temperature is high, and melt viscosity is little, and the expanded phenomenon after melt goes out spinneret orifice reduces greatly, and melt-forming resistance declines, and surface tension also declines thereupon, makes melt stream produce surperficial atrophy thus chamber portion is diminished, and institute's degree of hollowness that spins reduces.
Cooling forming comprises the conditions such as wind speed, wind-warm syndrome, blowing distance, to the rheological behavior spinning melt stream in journey, as the physical parameters such as elongational flow viscosity, tensile stress have a significant impact, directly decides the size of degree of hollowness.
Typically along with the increase of wind speed, cooling condition aggravates, the solidification rate of melt stream is accelerated, make to spin the doughnut internal cavity that journey is formed have little time atrophy and accelerate solidification, be conducive to the formation of doughnut cavity, the hollowness of fibre spun is high, but wind speed is excessive, strand can be caused to rock turbulence, and spinneret face temperature is declined, and wire vent is not smooth, easy generation hardhead silk, doubling and break end along with the reduction of wind-warm syndrome, cooling forming condition is strengthened, and improves the curing degree of melt stream, and it is high that hollowness of fibre spins in institute.But wind-warm syndrome is too low, the easy blast-cold of spinneret face, difficulty in spinning.For dicyclo sleeve-shaped spinnerets, the size passing into gas flow in sleeve pipe also likely can affect the degree of hollowness of fiber.Those skilled in the art have the ability by selecting gas with the pump of spinning slurry for the ratio measured, will prepare the hollow-fibre membrane with suitable degree of hollowness for the size of amount.
The doughnut that those skilled in the art can produce by being decreased through direct melt spinning to the control of ring blowing unsymmetrical excavation forms three-dimensional crimp and spins the situation of tensile property deterioration after preventing.Ring blowing unsymmetrical excavation technique comprises these four aspects of cold air blast velocity, temperature and humidity and uniformity.Improve wind speed can reinforcing fibre cross section dissymmetrical structure thus obtain latent crimp better as-spun fibre, but wind speed is crossed may well cause that strand vibrates, wire vent is smooth, precursor pre-orientation degree large, tensile property deterioration etc., and therefore those skilled in the art can choose suitable wind speed to take into account latent crimp and the tensile property of precursor; Although reduce ring blowing temperature, cooling condition is aggravated, precursor preorientation increase simultaneously, tensile property decline, and therefore those skilled in the art also need to select suitable wind-warm syndrome; Ring blowing can also have certain humidity to reduce electrostatic phenomenon in spinning process and strand disturbance, controlled cooling model condition; The uniformity simultaneously improving ring blowing ensure spinning stable and after spin tensile property.
(3) stretching is spun after
The object that three-dimensional static electric field stretches also does not lie in the mechanical property improving fiber, but the stress difference of as-spun fibre inside and latent crimp are embodied, the stress difference on every root filament cross section should be pulled open as much as possible in stretching, make this species diversity between filament remain on same level again, therefore doughnut generally adopts one-off drawing technique.
Stretching mode, draft temperature and stretching ratio spin the technical parameter in stretching after being, the professional knowledge that those skilled in the art can grasp according to oneself is selected.Typical case but without limitation, by drawing medium have steam stretching and water-bath stretchings point: water-bath stretches with the profit heated for medium, and fiber produces secondary orientation in stretching, causes fiber immanent structure difference to reduce, curling and fluffy hydraulic performance decline; Steam stretching is then medium with saturated vapor, and be adiabatic stretching, orientation once completes, and comparatively speaking after steam stretching, the crystalline texture of fiber is more obviously and stable.The selection of stretching ratio and temperature all will take into account the tensile property of as-spun fibre and curling release simultaneously.
(4) control technology of degree of hollowness
The hollow of degree of hollowness controls through in whole melt spinning process, from spinneret orifice size to after spin drawing process and all there is control to degree of hollowness.The width of typical but non-limiting spinneret orifice slit and the size of two slit distance between two tips are preconditions that weaving circle doughnut degree of hollowness is suitable for; And spinning temperature and cooling forming condition control the main process factor of degree of hollowness, the formation that spinning temperature is low, melt viscosity is large, melt-forming resistance and surface tension are beneficial to greatly hollow, but the too low phenomenons such as hard silk that will cause; And improve with draw ratio, weakened fiber walls thus cause degree of hollowness to improve.In addition, those skilled in the art can also investigate the process conditions such as required section moisture content (generally being dried through molecular sieve drying device by compressed air), the oil formula of spinning temperature and speed, relaxation heat setting technique and siliceous product and the oiling method controlled of conventional spinning.
For the known technology that melt-spinning technology is this area, the professional knowledge that those skilled in the art can grasp according to oneself, consult background technology and obtain concrete melt-spinning technology condition, typical but non-limiting melt-spinning technology condition can be:
Compared with prior art, the present invention has following beneficial effect:
The present invention utilizes the modification hollow cotton doped with Graphene to be used as the filler of warmth retention property product, obtain thermal property and permeability and all show excellent warmth retention property product, living beings Graphene doping is that the insulation rate of the modification hollow cotton of 1.4% is suitable at the white duck down of 90% with down content, but air penetrability is at about 240mm/s, far above duck's down.
Detailed description of the invention
Technical scheme of the present invention is further illustrated below by detailed description of the invention.
Those skilled in the art should understand, described embodiment is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Graphene preparation example 1 (redox Graphene)
Employing publication number is the method for embodiment 1 in the patent of CN105217621A, is specially:
(A) react in the mixed system of 2g graphite powder and 3g potassium dithionate, 3g phosphorus pentoxide and the 12mL concentrated sulfuric acid in reactor, stir 4 hours under 80 DEG C of water bath condition, to forming dark blue solution, after cooling, suction filtration, drying, obtain the graphite of pre-oxidation;
(B) get graphite oxide 2g obtained by step (A) in three-neck flask, with 150mL concentrated sulfuric acid solution under the condition of ice-water bath, add the potassium permanganate of 25g gradually, stir 2 hours;
(C) three-neck flask of above-mentioned steps (B) is proceeded to oil bath, be warming up to 35 DEG C, stir 2 hours, continuation is stirred and is added the mixed solution of 30wt% hydrogen peroxide and deionized water according to the amount that volume ratio is 1:15; Suction filtration is watery hydrochloric acid and the washed with de-ionized water 1 time of 10% respectively with 4mL mass fraction, centrifugal, obtains the graphene oxide of first time oxidation after drying;
(D) the graphene oxide 2g of preparation in step (C) is mixed in three-neck flask with the concentrated sulfuric acid solution of 50mL again under the condition of ice-water bath, adds the KMnO of 8g gradually
4, stir 1 hour;
(E) three-neck flask of above-mentioned steps (D) is proceeded to oil bath, be warming up to 40 DEG C, stir 1 hour, then continue to be warming up to 90 DEG C, stir after 1 hour, continuation is stirred and is added the mixed solution of 30wt% hydrogen peroxide and deionized water according to the amount that volume ratio is 1:7, continuing stirring to cool after 6 hours, suction filtration, is watery hydrochloric acid and the washed with de-ionized water 2 times of 10% respectively with 4mL mass fraction, centrifugal, obtain the graphene oxide of size uniformity after drying.
Graphene preparation example 2 (living beings Graphene)
Employing publication number is the method for embodiment 10 in the patent of CN104724696A, is specially:
Collect stalk, cut crumble into fractions after process is clean, be immersed in ethanolic solution, at the uniform velocity stir 5 hours with the rotating speed of 100r/min; Then be transferred in supercentrifuge by solution, rotating speed is set to 3000r/min, and centrifugation time is 20 minutes, takes off the broken sample of layer after terminating.Under normal temperature and pressure, it is in the Tissue Culture Dish of 15cm that broken sample is loaded diameter, and be placed in air inlet, adjust flux parameter, arranging wind speed is 6m/s, and air quantity is 1400m3/h, keeps ventilation state 12 hours; Tube furnace is warmed up to 1300 DEG C, passes into inert gas shielding, keeps 30 minutes; Dried broken sample is positioned in tube furnace, heats 5 hours, after cool to room temperature, obtain the obvious Graphene of overburden ratio.
Graphene preparation example 3 (the living beings Graphene in special source)
The preparation method of conventional fibre element, is specially:
(1) by after wheat straw comminution pretreatment, use total acid dense for the formic acid of 80wt% and the organic acid solution of acetic acid carry out boiling to the wheat straw after process, in the organic acid solution of the present embodiment, the mass ratio of acetic acid and formic acid is 1:12, and add before adding raw material account for wheat straw raw material 1wt% hydrogen peroxide (H2O2) as catalyst, control reaction temperature 120 DEG C, reaction 30min, solid-liquid mass ratio is 1:10, and the reactant liquor obtained is carried out first time Separation of Solid and Liquid;
(2) solid that first time Separation of Solid and Liquid obtains is added total acid is dense carries out acid elution for the formic acid of 75wt% and the organic acid solution of acetic acid, wherein add in the dense organic acid solution for 75wt% of above-mentioned total acid account for wheat straw raw material 8wt% hydrogen peroxide (H2O2) as catalyst and the mass ratio of acetic acid and formic acid is 1:12, control temperature is 90 DEG C, wash time 1h, solid-liquid mass ratio is 1:9, and reactant liquor is carried out second time Separation of Solid and Liquid;
(3) liquid obtained with second time Separation of Solid and Liquid is for the first time collected, in 120 DEG C, High Temperature High Pressure evaporation is carried out under 301kPa, until evaporate to dryness, using in the formic acid that obtains and acetic acid vapor condensing reflux to the reactor of step (1) as cooking liquor, for the boiling of step (1);
(4) collect the solid that second time Separation of Solid and Liquid obtains, and wash, controlling washing temperature is 80 DEG C, and washing slurry is dense is 6wt%, and the washing slurry obtained is carried out third time Separation of Solid and Liquid;
(5) liquid that Separation of Solid and Liquid for the third time obtains is collected, carry out water, sour rectifying, the mix acid liquor obtained is back to the boiling being used for step (1) in the reactor of step (1) as cooking liquor, and the Water circulation obtained washes water with water in step (5);
(6) collect the third time solid that obtains of Separation of Solid and Liquid row filter of going forward side by side and obtain required screened stock cellulose.
Be that living beings Graphene prepared by raw material with cellulose:
(1) 1:1 cellulose mixture and frerrous chloride in mass ratio, stirs and carries out catalytic treatment 4h, be dried to presoma moisture 10wt%, obtain presoma at 150 DEG C;
(2) in N2 atmosphere, with 3 DEG C/min speed, presoma is warming up to 170 DEG C, insulation 2h, temperature programming to 400 afterwards DEG C, insulation 3h, is warming up to 1200 DEG C afterwards, obtains crude product after insulation 3h; The heating rate of described temperature programming 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, washing obtain living beings Graphene.
Lower mask body is that to prepare modification hollow cotton goods be example to raw material with PET:
Embodiment 1
A kind of modification hollow cotton, prepares by the following method:
(1) pulverize the blank terylene chips of PET to average grain diameter 1mm, obtain the blank terylene chips particle of PET;
(2) the blank terylene chips particle of 1kg graphene powder (graphene powder that Graphene preparation example 3 obtains) and 9kgPET is mixed, melt temperature 250 DEG C of Screw Extrusions, be dried to moisture < 300ppm in vacuum drying chamber after, obtain the dacron master grain containing Graphene;
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 1kgPET, continue to add the blank terylene chips of 5kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 1.4wt%.
With the modification hollow cotton prepared as 2 × 2m
2the filler of quilt, described quilt inside is filled with the modification hollow cotton of 1.5kg.
Embodiment 2
A kind of modification hollow cotton, is with the difference of embodiment 1:
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 1kgPET, continue to add the blank terylene chips of 3kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 2wt%.
With the modification hollow cotton prepared as 2 × 2m
2the filler of quilt, described quilt inside is filled with the modification hollow cotton of 1.5kg.
Embodiment 3
A kind of modification hollow cotton, is with the difference of embodiment 1:
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 1kgPET, continue to add the blank terylene chips of 8kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 1wt%.
With the modification hollow cotton prepared as cold-proof underwear filler.
Embodiment 4
A kind of modification hollow cotton, is with the difference of embodiment 1:
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 4.5kgPET, continue to add the blank terylene chips of 45kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 0.2wt%.
With the modification hollow cotton prepared as tent filler.
Embodiment 5
A kind of modification hollow cotton, is with the difference of embodiment 1:
Step (3 ') is carried out: material step (3) obtained is at 250 DEG C of Screw Extrusions after step (3).
With the modification hollow cotton prepared as down-coat packing.
Embodiment 6
A kind of modification hollow cotton, prepares by the following method:
(1) pulverize the blank terylene chips of PET to average grain diameter 1mm, obtain the blank terylene chips particle of PET;
(2) the blank terylene chips particle of 1kg graphene powder (graphene powder that Graphene preparation example 3 obtains) and 4kgPET is mixed, melt temperature 250 DEG C of Screw Extrusions, be dried to moisture < 300ppm in vacuum drying chamber after, obtain the dacron master grain containing Graphene;
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 1kgPET, continue to add the blank terylene chips of 4.7kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 3wt%.
With the modification hollow cotton prepared as tent filler.
Embodiment 7
A kind of modification hollow cotton, is with the difference of embodiment 6:
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 1kgPET, continue to add the blank terylene chips of 2kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 5wt%.
With the modification hollow cotton prepared as cold-proof underwear filler.
Embodiment 8
A kind of modification hollow cotton, is with the difference of embodiment 6:
(3), after dacron master grain 1kg being contained Graphene mixes with the blank terylene chips of 0.5kgPET, continue to add the blank terylene chips of 0.5kgPET and mix;
(4) by the material melts that step (3) obtains, then carry out spinning, after spun after carry out shredding and obtain modified dacron hollow cotton, Graphene content is 10wt%.
With the modification hollow cotton prepared as sleeping bag filler.
Embodiment 9
A kind of modification hollow cotton, be with the difference of embodiment 1: the pulverising step not carrying out step (1), in step (2) directly by 1kg graphene powder (graphene powder that Graphene preparation example 3 obtains) and the blank terylene chips mixing of 9kgPET.
With the modification hollow cotton prepared as pillow filler.
Embodiment 10
A kind of modification hollow cotton, is with the difference of embodiment 1: the dacron master grain that 1kg is directly contained Graphene by step (3) mixes with the blank terylene chips of 6kgPET; Carry out step (4) afterwards.
With the modification hollow cotton prepared as back cushion filler.
Embodiment 11
A kind of modification hollow cotton, is with the difference of embodiment 1: the graphene powder adopting Graphene preparation example 1 to obtain in step (2) replaces the graphene powder that Graphene preparation example 3 obtains.
With the modification hollow cotton prepared as 2 × 2m
2the filler of quilt, described quilt inside is filled with the modification hollow cotton of 1.5kg.
Embodiment 12
A kind of modification hollow cotton, is with the difference of embodiment 1: the graphene powder adopting Graphene preparation example 2 to obtain in step (2) replaces the graphene powder that Graphene preparation example 3 obtains.
With the modification hollow cotton prepared as 2 × 2m
2the filler of quilt, described quilt inside is filled with the modification hollow cotton of 1.5kg.
Comparative example 1 provides a kind of 2 × 2m
2quilt, described quilt inside is filled with the white duck down of 2.3kg down content 90%.
Comparative example 2 provides a kind of 2 × 2m
2quilt, described quilt inside is filled with the unmodified hollow cotton of 3kg;
Described unmodified hollow cotton prepares by the following method:
(1) pulverize the blank terylene chips of PET to average grain diameter 1mm, obtain the blank terylene chips particle of PET;
(2) by the material melts that step (1) obtains, then carry out spinning, after spun after carry out shredding and obtain unmodified hollow cotton.
Performance test:
Modification hollow cotton goods embodiment and comparative example prepared are tested as follows:
(1) warming rate: method of testing is the mensuration of thermal resistance and dampness under GBT11048-2008 textiles physiological comfort limit;
(2) air penetrability: method of testing is that GBT5453-1997 textiles gas permeability detects;
(3) far infrared normal emittance: through national textile fabrics Quality Supervision and Inspection Center, test according to the FZ/T64010-2000 method of inspection;
(4) antibacterial inspection: through national textile fabrics Quality Supervision and Inspection Center, according to the GB/T20944.3-2008 method of inspection, for staphylococcus aureus;
Test result is in table 1:
The performance test results of table 1 embodiment 1,2,11,12 and comparative example
Applicant states, the present invention illustrates product of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned limited range, does not namely mean that the present invention must rely on above-mentioned restriction and could implement.Person of ordinary skill in the field should understand; any improvement in the present invention; to equivalence replacement and the interpolation of auxiliary element, the concrete way choice etc. of raw material selected by the present invention or already known processes, all drop within protection scope of the present invention and open scope.
Claims (7)
1. a purposes for modification hollow cotton, is characterized in that, described modification hollow cotton is used as the filler of warmth retention property product;
Doped with Graphene in described modification hollow cotton.
2. purposes as claimed in claim 1, it is characterized in that, described warmth retention property product is selected from quilt, pillow, back cushion, clothes, sleeping bag or tent.
3. purposes as claimed in claim 2, it is characterized in that, described clothes is selected from Insulation shirt, cold-proof underwear, down jackets, eider down sleeveless jacket or down wadded trousers.
4. the purposes as described in one of claims 1 to 3, is characterized in that, described Graphene is living beings Graphene.
5. purposes as claimed in claim 4, it is characterized in that, described living beings Graphene is prepared by living beings, and the cellulose that preferred described living beings Graphene is obtained by living beings prepares;
Preferably, described living beings are selected from the combination of any a kind or at least 2 kinds in agriculture and forestry organic waste material and/or plant;
Preferably, described plant is the combination of any a kind or at least 2 kinds in needlebush or leaf wood;
Preferably, described agriculture and forestry organic waste material is selected from the combination of any a kind or at least 2 kinds in cornstalk, corncob, kaoliang stalk, megasse, bagasse, furfural dregs, xylose residue, wood chip, cotton stalk, shell and reed;
Preferably, described agriculture and forestry organic waste material is corncob.
6. the purposes as described in one of Claims 1 to 5, is characterized in that, in described modification hollow cotton, the doping of Graphene is 0.2 ~ 10wt%, preferably 0.3 ~ 8wt%, further preferred 0.5 ~ 5wt%.
7. the modification hollow cotton as described in one of claim 1 ~ 6, is characterized in that, the far infrared of described modification hollow cotton detects normal emittance and is greater than 0.85, is preferably greater than 0.88.
Priority Applications (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 |
| KR1020187017543A KR20180085768A (en) | 2015-11-20 | 2016-11-18 | Modified fiber and method for manufacturing the same |
| EP16865799.7A EP3378978B1 (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 |
| CA3005917A CA3005917C (en) | 2015-11-20 | 2016-11-18 | Modified fiber and preparation method therefor |
Applications Claiming Priority (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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105525384A true CN105525384A (en) | 2016-04-27 |
| CN105525384B CN105525384B (en) | 2019-05-10 |
Family
ID=55767895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610045894.5A Active CN105525384B (en) | 2015-11-20 | 2016-01-22 | A kind of purposes of modified hollow cotton |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105525384B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN108277650A (en) * | 2018-02-24 | 2018-07-13 | 璧典附 | A kind of graphene/feather composite material and preparation method |
| 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 |
| CN110499554A (en) * | 2019-09-23 | 2019-11-26 | 济南圣泉集团股份有限公司 | A kind of natural feather composite material and preparation method and application |
| US10494263B2 (en) | 2015-03-04 | 2019-12-03 | Heilongjiang University | Method for preparing biomass graphene by using cellulose as raw material |
| 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 |
| US10836640B2 (en) | 2015-10-15 | 2020-11-17 | Jinan Shengquan Group Holding Co. Ltd. | Composite containing carbon nanostructure, high molecular material using same and preparation method |
| US10941273B2 (en) | 2015-11-20 | 2021-03-09 | Jinan Shengquan Group Share Holding Co., Ltd. | Graphene-containing modified latex as well as preparation method therefor and application thereof |
| CN112680819A (en) * | 2020-12-24 | 2021-04-20 | 高意匠新材料科技(苏州)有限公司 | Heating hollow cotton containing feldspar minerals and application thereof |
| US11306416B2 (en) | 2015-11-26 | 2022-04-19 | Jinan Shengquan Group Share Holding Co., Ltd. | Functional regenerated viscose fiber |
| CN115012049A (en) * | 2022-05-19 | 2022-09-06 | 张家港江苏科技大学产业技术研究院 | Hollow fiber and processing equipment and processing method thereof |
| CN115381627A (en) * | 2022-08-16 | 2022-11-25 | 山东希瑞新材料有限公司 | Composite multilayer high-water-absorptivity sanitary dressing and preparation method thereof |
Citations (6)
| 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 |
| 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 |
| CN104328523A (en) * | 2014-11-20 | 2015-02-04 | 济南圣泉集团股份有限公司 | Grapheme-containing viscose fiber and preparation method thereof |
| 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 |
-
2016
- 2016-01-22 CN CN201610045894.5A patent/CN105525384B/en active Active
Patent Citations (6)
| 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 |
| CN103044865A (en) * | 2012-12-18 | 2013-04-17 | 南京大学 | Preparation method for amino graphene modified polyethylene terephthalate (PET) material |
| 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 |
| CN104328523A (en) * | 2014-11-20 | 2015-02-04 | 济南圣泉集团股份有限公司 | Grapheme-containing viscose fiber and preparation method thereof |
| 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 (3)
| Title |
|---|
| 刘锋: "《服装工艺第2版》", 31 March 2002, 中国纺织出版社 * |
| 新华网: "《圣泉集团：生物源石墨烯内暖智能纤维》", 《HTTP://NEWS.XINHUANET.COM/TECH/2015-04/29/C_127747148.HTM》 * |
| 通讯员 郑宁来: "《圣泉基团推出石墨烯内暖纤维》", 《合成纤维工业》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10494263B2 (en) | 2015-03-04 | 2019-12-03 | Heilongjiang University | Method for preparing biomass graphene by using cellulose as raw material |
| US10836640B2 (en) | 2015-10-15 | 2020-11-17 | Jinan Shengquan Group Holding Co. Ltd. | Composite containing carbon nanostructure, high molecular material using same and preparation method |
| US10941273B2 (en) | 2015-11-20 | 2021-03-09 | Jinan Shengquan Group Share Holding Co., Ltd. | Graphene-containing modified latex as well as preparation method therefor and application thereof |
| 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 |
| US11306416B2 (en) | 2015-11-26 | 2022-04-19 | Jinan Shengquan Group Share Holding Co., Ltd. | Functional regenerated viscose fiber |
| 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 |
| CN108277650A (en) * | 2018-02-24 | 2018-07-13 | 璧典附 | A kind of graphene/feather composite material and preparation method |
| 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 |
| CN110499554A (en) * | 2019-09-23 | 2019-11-26 | 济南圣泉集团股份有限公司 | A kind of natural feather composite material and preparation method and application |
| CN112680819A (en) * | 2020-12-24 | 2021-04-20 | 高意匠新材料科技(苏州)有限公司 | Heating hollow cotton containing feldspar minerals and application thereof |
| CN115012049A (en) * | 2022-05-19 | 2022-09-06 | 张家港江苏科技大学产业技术研究院 | Hollow fiber and processing equipment and processing method thereof |
| CN115381627A (en) * | 2022-08-16 | 2022-11-25 | 山东希瑞新材料有限公司 | Composite multilayer high-water-absorptivity sanitary dressing and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105525384B (en) | 2019-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105525384A (en) | Use of modified hollow cotton | |
| CN105603568B (en) | A kind of modified hollow cotton and preparation method thereof | |
| CN105586658B (en) | A kind of modified nylon fiber, Preparation method and use | |
| EP3378978B1 (en) | Modified fiber and preparation method therefor | |
| CN106367836B (en) | A kind of manufacturing method of hollow biomass graphene polyester fiber | |
| CN105002595B (en) | Polymer composite function fibers containing partial graphene, and preparation method thereof | |
| CN103046151A (en) | Graphene blend regenerated cellulose fiber and preparation method thereof | |
| EP3202848B1 (en) | Composite polyester material, composite polyester fibre, preparation method therefor and use thereof | |
| CN110565184A (en) | Preparation method of high-self-crimpability PET/PTT parallel composite filament | |
| CN102002772B (en) | Method for preparing polyacrylonitrile bamboo charcoal composite fiber by in-situ polymerization | |
| JPH01213409A (en) | Production of organic short fiber containing microfiber | |
| CN107460559A (en) | A kind of preparation method of graphene polyester fiber | |
| CN106222789A (en) | A kind of manufacture method of biomass Graphene fire-retardant polyester fibre | |
| JP2018504531A (en) | Thermal storage heat retention fleece and manufacturing method thereof | |
| CN103993382B (en) | A kind of method improving polyacrylonitrile fibre pre-oxidation speed by physical blending | |
| CN109137128A (en) | A kind of anion terylene fiber and preparation method thereof | |
| CN1381619A (en) | Antibacterial antistatic dyeable fine-denier polypropylkene filament | |
| CN114351279A (en) | Preparation method of aerogel-containing special-shaped polyester staple fibers | |
| CN103184582A (en) | Preparation method of PVA composite high-strength high-modulus cellulose fiber | |
| CN109706545B (en) | Microporous hollow graphene sea-island fiber and manufacturing method thereof | |
| CN116262990B (en) | Light-absorbing, heating and warm-keeping polyester fiber and preparation method thereof | |
| KR101213899B1 (en) | Method for Manufacturing Multi-Function Nylon Fiber and Multi-Function Nylon Fiber Made Thereof | |
| CN108948694A (en) | A kind of PLA/PBS conductive material and preparation method thereof | |
| KR100650885B1 (en) | Polyester conjugated fiber with excellent stretchability and anti-microbial property and process of making | |
| WO2021208191A1 (en) | Production process of fast biodegradable porous polyester fiber |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |