CN106149083B - Functional graphene cellulose fiber prepared by melting method and preparation method thereof - Google Patents
Functional graphene cellulose fiber prepared by melting method and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title claims abstract description 77
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title abstract description 42
- 238000002844 melting Methods 0.000 title abstract description 13
- 230000008018 melting Effects 0.000 title abstract description 13
- 239000000835 fiber Substances 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 58
- 238000009987 spinning Methods 0.000 claims abstract description 46
- 229920002678 cellulose Polymers 0.000 claims abstract description 43
- 239000001913 cellulose Substances 0.000 claims abstract description 43
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 229920000297 Rayon Polymers 0.000 claims abstract description 9
- 230000006750 UV protection Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 54
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 238000001125 extrusion Methods 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 150000001450 anions Chemical class 0.000 claims description 16
- 150000001768 cations Chemical class 0.000 claims description 15
- 230000001112 coagulating effect Effects 0.000 claims description 15
- -1 alkyl imidazole Chemical compound 0.000 claims description 13
- 230000004927 fusion Effects 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000007500 overflow downdraw method Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000000354 decomposition reaction Methods 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 238000002074 melt spinning Methods 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 16
- 230000018044 dehydration Effects 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000004753 textile Substances 0.000 description 5
- 229920000433 Lyocell Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000004224 protection Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 3
- 235000017491 Bambusa tulda Nutrition 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 3
- 239000011425 bamboo Substances 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920000875 Dissolving pulp Polymers 0.000 description 2
- 235000014676 Phragmites communis Nutrition 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- Artificial Filaments (AREA)
Abstract
The invention discloses a functional graphene cellulose fiber prepared by a melting method, wherein the main components of the fiber comprise 0.5-10.0% of graphene and 90.0-99.5% of cellulose. The preparation method of the graphene cellulose fiber comprises the working procedures of graphene dispersion liquid preparation, cellulose/ionic liquid mixture preparation, mixing, pre-melting, spinning solution preparation and spinning. The far infrared normal emissivity of the prepared functional graphene cellulose fiber reaches 0.83-0.98, the ultraviolet protection coefficient reaches 62.78-560.32, the long-wave ultraviolet transmittance is less than 4.92%, and compared with the conventional viscose fiber, the thermal decomposition temperature is increased by 10-42 ℃. The method has short production flow, has little pollution to the environment, meets the requirement of sustainable development, and has great significance for realizing the high-temperature melt spinning route of functional cellulose.
Description
Technical field
The present invention relates to a kind of feature graphene fiber cellulose fiber and preparation method thereof, specifically, be related to it is a kind of with
Cellulose pulp and graphene are raw material, and ionic liquid is plasticizer, and feature graphite is prepared using high-temperature fusion plasticising technology
The method and fiber of alkene cellulose fibre, belong to textile technology field.
Background technology
Graphene is a kind of New Type of Carbon nanometer light material, has unique monoatomic layer two dimensional crystal structure, due to it
The characteristics such as intensity, electrical conductivity, thermal conductivity and the translucency of superelevation, are widely used, and as field of compound material
Research hotspot.
The Chinese patent of Application No. 201210005146.6 discloses a kind of system of graphene/polyimide composite fibers
Preparation Method；The Chinese patent of Application No. 201210319397.1 discloses a kind of in-situ suspension polymerization and prepares graphene-polychlorostyrene
The method of ethene nanocomposite；The Chinese patent of Application No. 201310332049.2 discloses a kind of graphene
The preparation method of composite fibre, the polymer used in this method include dissaving polymer and one kind in polyvinyl alcohol or two
Kind；The Chinese patent of Application No. 201410220720.9 discloses a kind of preparation method of graphene conductive composite fibre, should
Method is that the preparation of graphene composite fibre is carried out in the method for textile fabric face coat；Application No. 201310168803.3
Chinese patent disclose the preparation method of 6 fiber of graphene modification of nylon；Above-mentioned patent is essentially all with polymer, is such as gathered
Acid imide, polyvinyl alcohol etc. are matrix, using graphene oxide as added material, subsequently graphene oxide reduced again or
Graphene oxide is grafted onto in polymer molecular chain using the method for in-situ polymerization, obtains the composite material containing graphene,
The reduction of graphene oxide and in-situ polymerization in these methods, there are reduction rate is not high or the problem of the reaction time is long.
The Chinese patent of Application No. 201210549357.6 disclose a kind of graphene blending regeneration cellulose fiber and
Its preparation method.The patent is mixed using graphene oxide solution with regenerated cellulose solution, passes through viscose glue wet spinning technology
After shaping, then through reduction process prepare graphene blending regeneration cellulose fiber.This method utilizes viscose process technique, production process
Middle to use a large amount of chemical substances, production procedure is grown, and environment protection treating is costly.The Chinese patent of Application No. 201410670057.2
Disclose a kind of viscose rayon comprising graphene and preparation method thereof.Feelings of the patent present in there is also above-mentioned viscose process
Condition.
Seek that technique is simple, safely and effectively characteristics among new solvents of cellulose, be always numerous scientific workers' concerns with being engaged in
Important subject, represents the Lyocell fiber of solvent method industrialization kind as third generation regenerated celulose fibre, have compared with
Good prospect of production.The Korean Patent Publication of Patent No. KR10-2012-0082287A Lyocell/ graphene compound precursors
Body fiber and preparation method thereof.The patent uses Lyocell solvent method spinning techniques, and it is molten to add graphene oxide into cellulose
It is stirred in liquid, then produces the fiber as producing common Lyocell.Graphene oxide and stone used in this patent
Black alkene is compared, and surface of graphene oxide contains substantial amounts of functional group, is had superior dispersiveness, is readily dispersed in cellulose solution
In, and graphene is then not easy to disperse, it is necessary to reference to other dispersion technologies be disperseed.Meanwhile utilize graphene oxide and graphite
Fibre property and purposes difference prepared by two kinds of materials of alkene is larger.
Meanwhile melt spun fibre element and its derivative in process of production will not damage ecological environment, production procedure
It is short, efficient, there is molding melt-spun equipment to use for reference, raw material comes from regenerated resources, will not cause the imbalance of the ecological balance and plunder
The exploitation of taking by force property resource, has catered to sustainable development demand, environmentally friendly demand, is that the technology of the most long-range competitiveness of cellulose is created
New machining method.
Functional fibre plays important work in terms of protection, health care, material separation, biomedical and intelligent adjusting
With.With social progress, improvement of living standard, the mankind are not only satisfied with the general demand to fiber textile, and
The performance requirement such as health care, protection, comfortable is had also been proposed, the fiber product of simple function has been unable to meet the market demand, more
Function, it is high performance it is compound be the fields such as textile garment, fabrics for industrial use requirement.Science and technology develops into function composite fibre
Dimension exploitation provides advantage, and multifunctional all makes textile develop towards profound and high-grade direction.Feature stone
Black alkene cellulose fibre has the function of far infrared, uvioresistant, bacteriostasis and health-care etc., has catered to the direction of era development.
The content of the invention
The technical problem to be solved in the present invention is the deficiency for more than, there is provided feature graphene prepared by a kind of fusion method
Cellulose fibre and preparation method thereof.
The invention solves first technical problem be to provide a kind of feature graphene fiber cellulose fiber, the fiber
Main component includes the graphene of 0.5-10.0%, the cellulose of 90.0-99.5%.
The fiber far infrared normal emittance reaches 0.88-0.98；Ultraviolet UPF (UV protection factor) 172.62-
560.32, and UVA (long wave ultraviolet) transmitance is less than 3.89%；Thermal property is excellent, and heat decomposition temperature is improved than conventional fibre
10-42℃。
The invention solves another technical problem there is provided a kind of preparation of feature graphene fiber cellulose fiber
Method, using cellulose pulp and graphene as raw material, under the plasticization of ionic liquid, utilizes double screw extruder and single spiral shell
Make mixing, the melting of cellulose and graphene under the high shear force and high temperature action of the equipment such as bar extruder, improve cellulose
Fluidity of molten, effectively destroys in cellulosic molecule with intermolecular hydrogen bond, function is prepared using high-temperature fusion plasticising technology
Property graphene fiber cellulose fiber.Preparation method production procedure of the present invention is short, and environmental pollution is small, meets sustainable development
It is required that for realizing that the high temperature melt-spun route of functional fiber element is meaningful great.
To solve above technical problem, the technical solution adopted by the present invention is as follows：
Feature graphene fiber cellulose fiber prepared by a kind of fusion method, the main component of the fiber include 0.5-
10.0% graphene and the cellulose of 90.0-99.5%.
The far infrared normal emittance of the feature graphene fiber cellulose fiber reaches 0.83-0.98, ultraviolet protection
Coefficient reaches 62.78-560.32, and long wave ultraviolet transmitance is less than 4.92%, compared with conventional viscose rayon, thermal decomposition temperature
Degree improves 10-42 DEG C.
The preparation method of the feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and dispersant are added in deionized water, is disperseed using high-speed stirred, ball milling or ultrasonic wave disperses
Dispersing mode, is configured to the graphene dispersing solution of mass percent concentration 10%~30%；
（2）The preparation of cellulose/ion liquid mixture
By the cellulose pulp of 20-30%, the ionic liquid of 70-80% is pre-mixed using high speed disintegrator, makes fiber
Plain fully swelling, content is mass percent.
（3）Mixing
The graphene dispersing solution of above-mentioned preparation and cellulose/ion liquid mixture are fully mixed by a certain percentage
Close.
（4）Pre-fusion
Mixture is added to double screw extruder by charge door, adjust double screw extruder difference warm area temperature and
Screw speed etc., by the high temperature of continous way, high shear forces and vacuumizes mode, realize the dehydration of mixture, deaeration and
Heat pre-fusion.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, adjusts the temperature and screw speed of extruder difference warm area
Deng making mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene be prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret under certain Screw Extrusion pressure, in coagulating bath
Spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber.
Preferably, step（1）Described in dispersant by polyvinylpyrrolidone (PVP), neopelex
(SDBS), one or more of compositions in sodium carboxymethylcellulose (CMC), sodium alginate (SA), OP-10.
Preferably, step（1）Described in dispersant addition be graphene addition 4%~20%.
Preferably, step（2）Described in ionic liquid be alkyl imidazole type ionic liquid, cation is pi-allyl,
Ethyl, hydroxypropyl, the one or more of butyl；Anion is halogen, BF4 -、PF4 -、SCN-And CH3COO-In one kind or
It is a variety of.
Preferably, above-mentioned steps（2）Described in cellulose pulp use the degree of polymerization for 500~1200 cotton, wood, bamboo,
One or several kinds in reed, cotton stalk, stalk pulp.
Preferably, above-mentioned steps（3）Described in preparation graphene dispersing solution and cellulose/ion liquid mixture
Blending mass ratio be 1:10~1:200.
Preferably, above-mentioned steps（4）In used double screw extruder feeding section, melt zone, metering section and head section
Temperature is 80-115 DEG C, 90-125 DEG C, 105-135 DEG C and 115-150 DEG C respectively, and screw speed is 60 ~ 100 revs/min, vacuum
For -0.05 ~ -0.1MPa.
Preferably, above-mentioned steps（5）In used single screw extrusion machine feeding section, melt zone, metering section and head section
Temperature is 110-145 DEG C, 115-145 DEG C, 125-145 DEG C and 135-150 DEG C respectively, and screw speed is 80 ~ 100 revs/min, vacuum
Spend for -0.05 ~ -0.1MPa.
Preferably, the step（6）The Screw Extrusion pressure is 0.2-0.6 MPa during middle spinning.
Preferably, the step（6）Described in coagulating bath be that cation is pi-allyl, ethyl, hydroxypropyl, the one of butyl
Kind is a variety of, and anion is halogen, BF4 -、PF4 -、SCN-And CH3COO-Alkyl imidazole type ionic liquid it is one or several kinds of
The aqueous solution that manufactured temperature is 20~60 DEG C, concentration is≤32%.
The present invention uses the beneficial effect of above-mentioned technical proposal：
1st, the feature graphene fiber cellulose fiber containing graphene is prepared, the fiber of preparation not only has preferable thing
Mechanical performance is managed, and the fiber also has preferable far infrared, UV resistance and thermal property.
2nd, the cellulose fibre prepared does fracture strength >=2.80cN/dtex, wet breaking strength >=1.60cN/dtex, far
Infrared normal emittance reaches 0.88-0.98；UV protection factor reaches 172.62-560.32, and long wave ultraviolet passes through
Rate is less than 3.89%.
3rd, thermal property is excellent, compared with conventional viscose rayon, the heat point of the feature graphene fiber cellulose fiber of preparation
Solve temperature and improve 10-42 DEG C.
4th, it is used in combination using double screw extruder and single screw extrusion machine, improves the melting effect of cellulose, realize fibre
The melting of dimension element, dehydration, vacuum defoamation are completed in the lump, shorten the time.
5th, preparation method of the present invention, production procedure is short, efficient, and technique is simple, equips and passes through in existing melt-spun
Simple transformation can be achieved.Compared with viscose process technique, reduce the use of industrial chemicals, reduce the ring of fiber production process
Border is endangered, and the harm to operating personnel, and solvent can recycle use, is that the feature of regenerated cellulose fiber is developed
New method is provided.
With reference to embodiment, the present invention is described in detail.
Embodiment
The preferred embodiment of the present invention is illustrated below, it will be appreciated that preferred embodiment described herein is only used
In the description and interpretation present invention, it is not intended to limit the present invention.
Content percentage in embodiment is mass percent.
Embodiment 1：
A kind of preparation method of feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and polyvinylpyrrolidone (PVP) dispersant are added in deionized water, utilize high-speed stirred, ball milling point
Dissipate or ultrasonic wave such as disperses at the dispersing mode, be configured to the graphene dispersing solution of mass percent concentration 30%, the addition of dispersant
Measure as the 20% of graphene addition.
（2）The preparation of cellulose/ion liquid mixture
By the Cotton Pulp that 30% degree of polymerization is 562,70% alkyl imidazole type ionic liquid is carried out using high speed disintegrator
Premixing, makes cellulose fully be swollen, content is mass percent, and the ionic liquid cation is pi-allyl, and anion is
Cl-。
（3）Mixing
By step（1）The graphene dispersing solution and step of preparation（2）The cellulose/ion liquid mixture of preparation presses quality
Than for 1:10 ratio is sufficiently mixed.
（4）Pre-fusion
Mixture is added to double screw extruder, double screw extruder feeding section, melt zone, metering by charge door
Section and head section temperature are 81 DEG C, 91 DEG C, 105 DEG C and 112 DEG C respectively, and screw speed is 63 revs/min, and vacuum is -0.1
MPa, by the high temperature of continous way, high shear forces and vacuumizes mode, realizes the dehydration, deaeration and heating fritting of mixture
Melt.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, single screw extrusion machine feeding section, melt zone, metering section
And head section temperature is 110 DEG C, 118 DEG C, 127 DEG C and 139 DEG C respectively, screw speed is 80 revs/min, and vacuum is -0.1
MPa, makes mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene is prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret in the case where Screw Extrusion pressure is 0.2MPa, in coagulating bath
Middle spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber, wherein described
Coagulating bath cation is pi-allyl, anion be temperature made of the alkyl imidazole type ionic liquid of Cl- be 29 DEG C, concentration be
31.8% aqueous solution.
The feature graphene fiber cellulose fiber containing graphene prepared by embodiment 1 do fracture strength >=
2.81cN/dtex, wet breaking strength >=1.62cN/dtex, far infrared normal emittance reach 0.98, ultraviolet UPF (ultraviolets
Protecting factor) it is that 560.32 and UVA (long wave ultraviolet) transmitance is 0.31%, thermal property is excellent, and heat decomposition temperature improves 42
℃。
Embodiment 2：
A kind of preparation method of feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and sodium alginate (SA) dispersant are added in deionized water, disperseed using high-speed stirred, ball milling or
Ultrasonic wave disperses to wait dispersing mode, is configured to the graphene dispersing solution of mass percent concentration 25%, the addition of dispersant is stone
The 16% of black alkene addition.；
（2）The preparation of cellulose/ion liquid mixture
By the wood pulps that 26% degree of polymerization is 637,74% cation is ethyl, anion SCN-Alkyl imidazole type
Ionic liquid is pre-mixed using high speed disintegrator, cellulose is fully swollen, and content is mass percent.
（3）Mixing
By above-mentioned steps（1）The graphene dispersing solution and step of preparation（2）The cellulose/ion liquid mixture of preparation is pressed
Mass ratio is 1:35 ratio is sufficiently mixed.
（4）Pre-fusion
Mixture is added to double screw extruder, double screw extruder feeding section, melt zone, metering by charge door
Section and head section temperature be 92 DEG C, 103 DEG C, 116 DEG C and 124 DEG C respectively, screw speed be 75 revs/min, vacuum for-
0.08MPa, by the high temperature of continous way, high shear forces and vacuumizes mode, realizes the dehydration, deaeration and heating of mixture
Pre-fusion.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, single screw extrusion machine feeding section, melt zone, metering section
And head section temperature is 125 DEG C, 132 DEG C, 138 DEG C and 145 DEG C respectively, screw speed is 88 revs/min, and vacuum is -0.08
MPa, makes mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene is prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret in the case where Screw Extrusion pressure is 0.26MPa, in coagulating bath
Middle spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber, wherein described
Coagulating bath cation is ethyl, anion SCN-Alkyl imidazole type ionic liquid made of temperature be 38 DEG C, concentration be
25.6% aqueous solution.
The feature graphene fiber cellulose fiber containing graphene prepared by embodiment 2 do fracture strength >=
2.93cN/dtex, wet breaking strength >=1.75cN/dtex, far infrared normal emittance reach 0.95, ultraviolet UPF (ultraviolets
Protecting factor) it is that 420.59 and UVA (long wave ultraviolet) transmitance is 1.32 %, thermal property is excellent, and heat decomposition temperature improves
31℃。
Embodiment 3：
A kind of preparation method of feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and sodium carboxymethylcellulose (CMC) dispersant are added in deionized water, utilize high-speed stirred, ball milling point
Dissipate or ultrasonic wave such as disperses at the dispersing mode, be configured to the graphene dispersing solution of mass percent concentration 22%, the addition of dispersant
Measure as the 12% of graphene addition.
（2）The preparation of cellulose/ion liquid mixture
By the stalk pulp that 19% degree of polymerization is 769,81% cation is hydroxypropyl, anion PF4 -Alkyl miaow
Azoles type ionic liquid is pre-mixed using high speed disintegrator, cellulose is fully swollen, and content is mass percent.
（3）Mixing
By above-mentioned steps（1）The graphene dispersing solution and step of preparation（2）The cellulose/ion liquid mixture of preparation is pressed
Mass ratio is 1:63 ratio is sufficiently mixed.
（4）Pre-fusion
Mixture is added to double screw extruder, double screw extruder feeding section, melt zone, metering by charge door
Section and head section temperature be 103 DEG C, 116 DEG C, 128 DEG C and 136 DEG C respectively, screw speed be 86 revs/min, vacuum for-
0.07MPa, by the high temperature of continous way, high shear forces and vacuumizes mode, realizes the dehydration, deaeration and heating of mixture
Pre-fusion.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, single screw extrusion machine feeding section, melt zone, metering section
And head section temperature is 129 DEG C, 136 DEG C, 145 DEG C and 149 DEG C respectively, screw speed is 90 revs/min, and vacuum is -0.07
MPa, makes mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene is prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret in the case where Screw Extrusion pressure is 0.35MPa, in coagulating bath
Middle spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber, wherein described
Coagulating bath cation is hydroxypropyl, anion PF4 -Alkyl imidazole type ionic liquid made of temperature be 46 DEG C, concentration be
19.6% aqueous solution.
The feature graphene fiber cellulose fiber containing graphene prepared by embodiment 3 do fracture strength >=
2.98cN/dtex, wet breaking strength >=1.83cN/dtex, far infrared normal emittance reach 0.92, ultraviolet UPF (ultraviolets
Protecting factor) it is that 332.13 and UVA (long wave ultraviolet) transmitance is 2.56 %, thermal property is excellent, and heat decomposition temperature improves
25℃。
Embodiment 4：
A kind of preparation method of feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and neopelex (SDBS) dispersant are added in deionized water, utilize high-speed stirred, ball
The dispersing modes such as mill is scattered or ultrasonic wave disperses, are configured to the graphene dispersing solution of mass percent concentration 18%, dispersant
Addition is the 6% of graphene addition.
（2）The preparation of cellulose/ion liquid mixture
The reed pulp that the stalk pulp and the degree of polymerization that the degree of polymerization by 15% is 963 are 972,85% cation is fourth
Base, anion CH3COO-Alkyl imidazole type ionic liquid be pre-mixed using high speed disintegrator, make cellulose fully molten
Swollen, content is mass percent.
（3）Mixing
By above-mentioned steps（1）The graphene dispersing solution and step of preparation（2）The cellulose/ion liquid mixture of preparation is pressed
Mass ratio is 1:105 ratio is sufficiently mixed.
（4）Pre-fusion
Mixture is added to double screw extruder, double screw extruder feeding section, melt zone, metering by charge door
Section and head section temperature be 115 DEG C, 123 DEG C, 134 DEG C and 145 DEG C respectively, screw speed be 92 revs/min, vacuum for-
0.09MPa, by the high temperature of continous way, high shear forces and vacuumizes mode, realizes the dehydration, deaeration and heating of mixture
Pre-fusion.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, single screw extrusion machine feeding section, melt zone, metering section
And head section temperature is 142 DEG C, 143 DEG C, 145 DEG C and 150 DEG C respectively, screw speed be 92 revs/min, vacuum for-
0.09MPa, makes mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene is prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret in the case where Screw Extrusion pressure is 0.43MPa, in coagulating bath
Middle spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber, wherein described
Coagulating bath cation is butyl, anion CH3COO-Alkyl imidazole type ionic liquid made of temperature be 52 DEG C, concentration be
13.1% aqueous solution.
The feature graphene fiber cellulose fiber containing graphene prepared by embodiment 4 do fracture strength >=
3.02cN/dtex, wet breaking strength >=1.91cN/dtex, far infrared normal emittance reach 0.90, ultraviolet UPF (ultraviolets
Protecting factor) it is that 256.78 and UVA (long wave ultraviolet) transmitance is 2.89 %, thermal property is excellent, and heat decomposition temperature improves
19℃。
Embodiment 5：
A kind of preparation method of feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and OP-10 dispersants are added in deionized water, disperseed using high-speed stirred, ball milling or ultrasonic wavelength-division
Dissipate and wait dispersing mode, be configured to the graphene dispersing solution of mass percent concentration 15%, the addition of dispersant adds for graphene
The 4% of amount.
（2）The preparation of cellulose/ion liquid mixture
The cotton stalk dissolving pulp that the bamboo pulp and the degree of polymerization that the degree of polymerization by 10% is 1000 are 1120,90% cation is hydroxypropyl
Base, anion BF4 -Alkyl imidazole type ionic liquid be pre-mixed using high speed disintegrator, cellulose is fully swollen,
Content is mass percent.
（3）Mixing
By above-mentioned steps（1）The graphene dispersing solution and step of preparation（2）The cellulose/ion liquid mixture of preparation is pressed
Mass ratio is 1:195 ratio is sufficiently mixed.
（4）Pre-fusion
Mixture is added to double screw extruder, double screw extruder feeding section, melt zone, metering by charge door
Section and head section temperature be 112 DEG C, 127 DEG C, 134 DEG C and 143 DEG C respectively, screw speed be 72 revs/min, vacuum for-
0.06MPa, by the high temperature of continous way, high shear forces and vacuumizes mode, realizes the dehydration, deaeration and heating of mixture
Pre-fusion.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, single screw extrusion machine feeding section, melt zone, metering section
And head section temperature is 118 DEG C, 127 DEG C, 135 DEG C and 144 DEG C respectively, screw speed be 92 revs/min, vacuum for-
0.06MPa, makes mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene is prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret in the case where Screw Extrusion pressure is 0.31MPa, in coagulating bath
Middle spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber, wherein described
Coagulating bath cation is hydroxypropyl, anion BF4 -Alkyl imidazole type ionic liquid made of temperature be 46 DEG C, concentration be
7.9% aqueous solution.
The feature graphene fiber cellulose fiber containing graphene prepared by embodiment 5 do fracture strength >=
2.92cN/dtex, wet breaking strength >=1.83cN/dtex, far infrared normal emittance reach 0.88, ultraviolet UPF (ultraviolets
Protecting factor) it is that 172.62 and UVA (long wave ultraviolet) transmitance is 3.89 %, thermal property is excellent, and heat decomposition temperature improves
15℃。
Embodiment 6：
A kind of preparation method of feature graphene fiber cellulose fiber, comprises the following steps：
（1）The preparation of graphene dispersing solution
Graphene and polyvinylpyrrolidone (PVP) dispersant are added in deionized water, utilize high-speed stirred, ball milling point
Dissipate or ultrasonic wave such as disperses at the dispersing mode, be configured to the graphene dispersing solution of mass percent concentration 10%, the addition of dispersant
Measure as the 7% of graphene addition.
（2）The preparation of cellulose/ion liquid mixture
The cotton stalk dissolving pulp that the bamboo pulp and the degree of polymerization that the degree of polymerization by 10% is 856 are 918,90% cation is allyl
Base, anion SCN-Alkyl imidazole type ionic liquid be pre-mixed using high speed disintegrator, cellulose is fully swollen,
Content is mass percent.
（3）Mixing
By above-mentioned steps（1）The graphene dispersing solution and step of preparation（2）The cellulose/ion liquid mixture of preparation is pressed
Mass ratio is 1:200 ratio is sufficiently mixed.
（4）Pre-fusion
Mixture is added to double screw extruder, double screw extruder feeding section, melt zone, metering by charge door
Section and head section temperature be 95 DEG C, 112 DEG C, 128 DEG C and 150 DEG C respectively, screw speed be 82 revs/min, vacuum for-
0.08MPa, by the high temperature of continous way, high shear forces and vacuumizes mode, realizes the dehydration, deaeration and heating of mixture
Pre-fusion.
（5）Prepare spinning solution
The blend composition of pre-fusion is placed in single screw extrusion machine, single screw extrusion machine feeding section, melt zone, metering section
And head section temperature is 118 DEG C, 125 DEG C, 135 DEG C and 145 DEG C respectively, screw speed be 76 revs/min, vacuum for-
0.08MPa, makes mixture further be dehydrated, deaeration and mixed melting, the spinning solution containing graphene is prepared.
（6）Spinning process
The spinning solution of above-mentioned preparation passes through metering pump, spinneret in the case where Screw Extrusion pressure is 0.43MPa, in coagulating bath
Middle spinning moulding, through drafting process, is washed and the process that oils, finished product feature graphene fiber cellulose fiber, wherein described
Coagulating bath cation is pi-allyl, anion SCN-Alkyl imidazole type ionic liquid made of temperature be 52 DEG C, concentration be
18.2% aqueous solution.
The feature graphene fiber cellulose fiber containing graphene prepared by embodiment 6 do fracture strength >=
3.12cN/dtex, wet breaking strength >=1.98cN/dtex, far infrared normal emittance reach 0.88, ultraviolet UPF (ultraviolets
Protecting factor) it is that 62.78 and UVA (long wave ultraviolet) transmitance is 4.92%, thermal property is excellent, and heat decomposition temperature improves 10
℃。
Finally it should be noted that：The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To modify to the technical solution described in foregoing embodiments, within the spirit and principles of the invention, that is made appoints
What modification, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (7)
- A kind of 1. feature graphene fiber cellulose fiber prepared by fusion method, it is characterised in that：The main component bag of the fiber Include the graphene of 0.5-10.0% and the cellulose of 90.0-99.5%；The far infrared normal emittance of prepared feature graphene fiber cellulose fiber reaches 0.83-0.98, ultraviolet protection system Number reaches 62.78-560.32, and long wave ultraviolet transmitance is less than 4.92%, compared with conventional viscose rayon, heat decomposition temperature Improve 10-42 DEG C；The preparation method of the fiber, including pre-fusion, prepare spinning solution；The pre-fusion step, twin-screw used squeeze It is 80-115 DEG C, 90-125 DEG C, 105-135 DEG C and 115- respectively to go out machine feeding section, melt zone, metering section and head section temperature 150 DEG C, screw speed is 60 ~ 100 revs/min, and vacuum is -0.05 ~ -0.1MPa；It is described to prepare single screw extrusion machine feeding section, melt zone, metering section and head section temperature used in spinning solution step It is 110-145 DEG C, 115-145 DEG C, 125-145 DEG C and 135-150 DEG C respectively, screw speed is 80 ~ 100 revs/min, vacuum For -0.05 ~ -0.1MPa.
- 2. the preparation method of feature graphene fiber cellulose fiber prepared by a kind of fusion method according to claim 1, its It is characterized in that：Including graphene dispersing solution preparation, the preparation of cellulose/ion liquid mixture, mixing, pre-fusion, preparation spinning Stoste, spinning process.
- 3. the preparation method of feature graphene fiber cellulose fiber prepared by a kind of fusion method according to claim 2, its It is characterized in that：The graphene dispersing solution preparation process, dispersant is by polyvinylpyrrolidone, neopelex, carboxylic One or more of compositions in sodium carboxymethylcellulose pyce, sodium alginate, OP-10.
- 4. the preparation method of feature graphene fiber cellulose fiber prepared by a kind of fusion method according to claim 2, its It is characterized in that：The graphene dispersing solution preparation process, the addition of dispersant are the 4%~20% of graphene addition.
- 5. the preparation method of feature graphene fiber cellulose fiber prepared by a kind of fusion method according to claim 2, its It is characterized in that：The cellulose/ion liquid mixture preparation process, ionic liquid are alkyl imidazole type ionic liquid, sun from Son is pi-allyl, ethyl, hydroxypropyl, the one or more of butyl；Anion is halogen, BF4 -、PF4 -、SCN-And CH3COO- In one or more.
- 6. the preparation method of feature graphene fiber cellulose fiber prepared by a kind of fusion method according to claim 2, its It is characterized in that：The blending mass ratio of the blend step, graphene dispersing solution and cellulose/ion liquid mixture is 1:10~ 1:200。
- 7. the preparation method of feature graphene fiber cellulose fiber prepared by a kind of fusion method according to claim 2, its It is characterized in that：The spinning process, Screw Extrusion pressure is 0.2-0.6 MPa during spinning；The spinning process, coagulating bath are the one or more that cation is pi-allyl, ethyl, hydroxypropyl, butyl, anion For halogen, BF4 -、PF4 -、SCN-And CH3COO-Alkyl imidazole type ionic liquid one or several kinds made of temperature for 20~ 60 DEG C, the aqueous solution that concentration is≤32%；The cellulose/ion liquid mixture preparation process, the cellulose pulp degree of polymerization used are 500~1200.
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| CN108842224B (en) * | 2018-06-13 | 2020-12-04 | 东华大学 | Sheath-core graphene/alginic acid conductive composite fiber and preparation method thereof |
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