CN106149083A - 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 134
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 64
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title abstract description 34
- 238000002844 melting Methods 0.000 title abstract description 10
- 230000008018 melting Effects 0.000 title abstract description 10
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- 229920002678 cellulose Polymers 0.000 claims abstract description 46
- 239000001913 cellulose Substances 0.000 claims abstract description 46
- 238000009987 spinning Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 239000002608 ionic liquid Substances 0.000 claims abstract description 23
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- 238000001125 extrusion Methods 0.000 claims description 26
- 230000004927 fusion Effects 0.000 claims description 25
- -1 alkyl imidazole Chemical compound 0.000 claims description 19
- 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 16
- 230000001112 coagulating effect Effects 0.000 claims description 15
- 238000007500 overflow downdraw method Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000000354 decomposition reaction Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 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
- 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
- CGKQZIULZRXRRJ-UHFFFAOYSA-N Butylone Chemical compound CCC(NC)C(=O)C1=CC=C2OCOC2=C1 CGKQZIULZRXRRJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- IVKNZCBNXPYYKL-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO)C=C1 IVKNZCBNXPYYKL-UHFFFAOYSA-N 0.000 claims description 3
- 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
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 17
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- 238000004519 manufacturing process Methods 0.000 abstract description 8
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- 239000004642 Polyimide Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
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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 functional graphene fiber cellulose fiber and preparation method thereof, specifically, relate to a kind of with cellulose pulp and Graphene as raw material, ionic liquid is plasticizer, use high-temperature fusion molding technology to prepare method and the fiber of functional graphene fiber cellulose fiber, belong to textile technology field.
Background technology
Graphene is a kind of New Type of Carbon nanometer light material, has the monoatomic layer two dimensional crystal structure of uniqueness, due to the characteristic such as intensity, electrical conductivity, thermal conductivity and light transmission of its superelevation, is widely used, and becomes the study hotspot of field of compound material.
The Chinese patent of Application No. 201210005146.6 discloses the preparation method of a kind of graphene/polyimide composite fibers；The Chinese patent of Application No. 201210319397.1 discloses a kind of method that in-situ suspension polymerization prepares Graphene-polyvinyl chloride nano composite resin；The Chinese patent of Application No. 201310332049.2 discloses the preparation method of a kind of electric graphene composite fiber, and the polymer used by the method includes one or both in dissaving polymer and polyvinyl alcohol；The Chinese patent of Application No. 201410220720.9 discloses the preparation method of a kind of graphene conductive composite fibre, and the method is to carry out the preparation of Graphene composite fibre with the method for textile fabric face coat；The Chinese patent of Application No. 201310168803.3 discloses the preparation method of Graphene modification of nylon 6 fiber；Above-mentioned patent is essentially all with polymer, if polyimides, polyvinyl alcohol etc. are matrix, with graphene oxide for adding material, follow-up again graphene oxide carried out the method reducing or utilizing in-situ polymerization graphene oxide is grafted onto in polymer molecular chain, obtain the composite containing Graphene, in these methods, there is the problem that percent reduction is the highest or the response time is long in the reduction of graphene oxide and in-situ polymerization.
The Chinese patent of Application No. 201210549357.6 discloses a kind of Graphene blending regeneration cellulose fiber and preparation method thereof.This patent utilization graphene oxide solution mixes with regenerated fiber cellulose solution, after viscose glue wet spinning technology molding, then prepares Graphene blending regeneration cellulose fiber through reduction process.The method utilizes viscose process technique, uses a large amount of chemical substance in production process, and production procedure is long, and environment protection treating is costly.The Chinese patent of Application No. 201410670057.2 discloses a kind of viscose rayon comprising Graphene and preparation method thereof.This patent there is also the situation existing for above-mentioned viscose process.
Seek technique simply, safely and effectively characteristics among new solvents of cellulose, the most numerous scientists pay close attention to and the important subject being engaged in, and represent the Lyocell fiber of solvent method industrialization kind as third generation regenerated celulose fibre, have preferable prospect of production.The Korean Patent Publication of Patent No. KR10-2012-0082287A Lyocell/ Graphene composite precursor fiber and preparation method thereof.This patent uses Lyocell solvent method spinning technique, adds graphene oxide into stirring mixing in cellulose solution, then produces this fiber as producing common Lyocell.Graphene oxide used by this patent is compared with Graphene, and surface of graphene oxide contains substantial amounts of functional group, has superior dispersibility, it is easy to be scattered in cellulose solution, and Graphene is then difficult to dispersion, needs to combine other dispersion technologies and disperses.Meanwhile, utilize fibre property prepared by graphene oxide and two kinds of materials of Graphene and purposes difference bigger.
Simultaneously, ecological environment will not be worked the mischief by melt spun fibre element and derivant in process of production thereof, production procedure is short, efficiency is high, the melt-spun equipment having molding can be used for reference, raw material, from regenerated resources, does not results in imbalance and the exploitation of predatory resource of ecological balance, has catered to sustainable development demand, the demand of environmental protection, is the technological innovation processing method of the most long-range competitiveness of cellulose.
Functional fibre plays an important role in terms of protection, health care, material separation, biomedicine and Intelligent adjustment.Progress, growth in the living standard along with society, the mankind are not only satisfied with the general demand to fiber textile, and also been proposed health care, protection, the performance requirement such as comfortable, the fiber product of simple function can not meet the market demand, multi-functional, high performance compound be the requirement in the field such as textile garment, fabrics for industrial use.The function composite fiber development that develops into of science and technology provides advantage, and multifunctional all makes textile develop towards profound and high-grade direction.Functional graphene fiber cellulose fiber has the functions such as far infrared, uvioresistant, bacteriostasis and health-care, has catered to the direction of era development.
Summary of the invention
The technical problem to be solved in the present invention is for above not enough, it is provided that functional graphene fiber cellulose fiber prepared by a kind of fusion method and preparation method thereof.
First technical problem that the invention solves the problems that is to provide a kind of functional graphene fiber cellulose fiber, and the main component of this fiber includes the Graphene of 0.5-10.0%, the cellulose of 90.0-99.5%.
This fiber far infrared normal emittance reaches 0.88-0.98；Ultraviolet UPF (UPF) 172.62-560.32, and UVA (long wave ultraviolet) transmitance is less than 3.89%；Thermal property is excellent, and heat decomposition temperature improves 10-42 DEG C than conventional fibre.
Another technical problem that the invention solves the problems that there is provided the preparation method of a kind of functional graphene fiber cellulose fiber, with cellulose pulp and Graphene as raw material, under the plasticization of ionic liquid, utilize and under the high shear force of the equipment such as double screw extruder and single screw extrusion machine and high temperature action, make cellulose and the mixing of Graphene, melted, improve the fluidity of molten of cellulose, functional graphene fiber cellulose fiber is prepared with intermolecular hydrogen bond, employing high-temperature fusion molding technology in effectively destroying cellulosic molecule.Preparation method production procedure of the present invention is short, and environmental pollution is little, meets the requirement of sustainable development, has significant for realizing the high temperature melt-spun route of functional fiber element.
For solving above technical problem, the technical solution used in the present invention is as follows:
Functional graphene fiber cellulose fiber prepared by a kind of fusion method, the main component of described fiber includes the Graphene of 0.5-10.0% and the cellulose of 90.0-99.5%.
The far infrared normal emittance of described functional graphene fiber cellulose fiber reaches 0.83-0.98, and UPF reaches 62.78-560.32, and long wave ultraviolet transmitance is less than 4.92%, and compared with conventional viscose rayon, heat decomposition temperature improves 10-42 DEG C.
The preparation method of described functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and dispersant are added in deionized water, utilizes the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, be configured to the graphene dispersing solution of percent mass Particle density 10%～30%；
(2) preparation of cellulose/ion liquid mixture
By the cellulose pulp of 20-30%, the ionic liquid of 70-80% uses high speed disintegrator to carry out premixing, makes cellulose the most swelling, and content is mass percent.
(3) mixing
Graphene dispersing solution and the cellulose/ion liquid mixture of above-mentioned preparation are sufficiently mixed by a certain percentage.
(4) pre-fusion
Compound is joined double screw extruder by charge door, adjusts temperature and the screw speed etc. of double screw extruder difference warm area, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
The blend composition of pre-fusion is placed in single screw extrusion machine, adjusts the temperature of extruder difference warm area and screw speed etc., make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under certain Screw Extrusion pressure through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber.
As preferably, the dispersant described in step (1) is made up of one or more in polyvinylpyrrolidone (PVP), dodecylbenzene sodium sulfonate (SDBS), sodium carboxymethyl cellulose (CMC), sodium alginate (SA), OP-10.
As preferably, addition is Graphene addition 4%～20% of dispersant described in step (1).
As preferably, the ionic liquid described in step (2) is alkyl imidazole type ionic liquid, cation be pi-allyl, ethyl, hydroxypropyl, butyl one or more；Anion is halogen, BF4 -、PF4 -、SCN-And CH3COO-In one or more.
As preferably, one or several in cotton that cellulose pulp described in above-mentioned steps (2) uses the degree of polymerization to be 500～1200, wood, bamboo, phragmites communis, cotton stalk, straw pulp.
As preferably, the graphene dispersing solution of the preparation described in above-mentioned steps (3) and the blended mass ratio of cellulose/ion liquid mixture are 1:10 ~ 1:200.
As preferably, double screw extruder feeding section, melt zone, metering section and head section temperature used in above-mentioned steps (4) are 80-115 DEG C, 90-125 DEG C, 105-135 DEG C and 115-150 DEG C respectively, screw speed is 60 ~ 100 revs/min, and vacuum is-0.05 ~-0.1MPa.
As preferably, single screw extrusion machine feeding section, melt zone, metering section and head section temperature used in above-mentioned steps (5) are 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, and vacuum is-0.05 ~-0.1MPa.
As preferably, in described step (6), during spinning, described Screw Extrusion pressure is 0.2-0.6 MPa.
As preferably, coagulating bath described in described step (6) be cation be pi-allyl, ethyl, hydroxypropyl, butyl one or more, anion is halogen, BF4 -、PF4 -、SCN-And CH3COO-One or several temperature made of alkyl imidazole type ionic liquid be 20～60 DEG C, concentration be the aqueous solution of≤32%.
The present invention uses the beneficial effect of technique scheme:
1, preparing the functional graphene fiber cellulose fiber containing Graphene, the fiber of preparation not only has preferable physical and mechanical properties, and this fiber also has preferable far infrared, UV resistance and thermal property.
2, the cellulose fibre of preparation does fracture strength >=2.80cN/dtex, wet breaking strength >=1.60cN/dtex, and far infrared normal emittance reaches 0.88-0.98；UPF reaches 172.62-560.32, and long wave ultraviolet transmitance is less than 3.89%.
3, thermal property is excellent, and compared with conventional viscose rayon, the heat decomposition temperature of the functional graphene fiber cellulose fiber of preparation improves 10-42 DEG C.
4, use double screw extruder and single screw extrusion machine use, improve the melted effect of cellulose, it is achieved that cellulose is melted, be dehydrated, vacuum defoamation completes in the lump, shortens the time.
5, preparation method of the present invention, production procedure is short, efficiency is high, and technique is simple, can realize through simple transformation at existing melt-spun equipment.Compared with viscose process technique, decrease the use of industrial chemicals, reduce the environmental hazard of fiber production process, and the harm to operator, and solvent can reclaim use, for the method that the functional exploitation offer of regenerated cellulose fibrid is new.
Below in conjunction with embodiment, the present invention is described in detail.
Detailed description of the invention
Hereinafter the preferred embodiments of the present invention are illustrated, it will be appreciated that preferred embodiment described herein is merely to illustrate and explains the present invention, is not intended to limit the present invention.
Content percent in embodiment is mass percent.
Embodiment
1
:
The preparation method of a kind of functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and polyvinylpyrrolidone (PVP) dispersant are added in deionized water, utilize the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, being configured to the graphene dispersing solution of percent mass Particle density 30%, the addition of dispersant is the 20% of Graphene addition.
(2) preparation of cellulose/ion liquid mixture
The degree of polymerization by 30% is the Cotton Pulp of 562, and the alkyl imidazole type ionic liquid of 70% uses high speed disintegrator to carry out premixing, makes cellulose the most swelling, and content is mass percent, and described ionic liquid cation is pi-allyl, and anion is Cl-。
(3) mixing
Cellulose/ion liquid mixture prepared by graphene dispersing solution step (1) prepared and step (2) is that the ratio of 1:10 is sufficiently mixed in mass ratio.
(4) pre-fusion
Compound is joined double screw extruder by charge door, double screw extruder feeding section, melt zone, metering section and head section temperature are 81 DEG C, 91 DEG C, 105 DEG C and 112 DEG C respectively, screw speed is 63 revs/min, vacuum is-0.1 MPa, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
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 are 110 DEG C, 118 DEG C, 127 DEG C and 139 DEG C respectively, screw speed is 80 revs/min, vacuum is-0.1 MPa, make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under Screw Extrusion pressure is 0.2MPa through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber, wherein said coagulating bath cation be pi-allyl, anion be the temperature that the alkyl imidazole type ionic liquid of Cl-is made be 29 DEG C, concentration be the aqueous solution of 31.8%.
The functional graphene fiber cellulose fiber containing Graphene prepared by embodiment 1 does fracture strength >=2.81cN/dtex, wet breaking strength >=1.62cN/dtex, far infrared normal emittance reaches 0.98, ultraviolet UPF (UPF) be 560.32 and UVA (long wave ultraviolet) transmitance be 0.31%, thermal property is excellent, and heat decomposition temperature improves 42 DEG C.
Embodiment
2
:
The preparation method of a kind of functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and sodium alginate (SA) dispersant are added in deionized water, utilize the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, being configured to the graphene dispersing solution of percent mass Particle density 25%, the addition of dispersant is the 16% of Graphene addition.；
(2) preparation of cellulose/ion liquid mixture
The degree of polymerization by 26% is the wood pulps of 637, the cation of 74% be ethyl, anion be SCN-Alkyl imidazole type ionic liquid use high speed disintegrator carry out premixing, make cellulose the most swelling, content is mass percent.
(3) mixing
Cellulose/ion liquid mixture prepared by graphene dispersing solution above-mentioned steps (1) prepared and step (2) is that the ratio of 1:35 is sufficiently mixed in mass ratio.
(4) pre-fusion
Compound is joined double screw extruder by charge door, double screw extruder feeding section, melt zone, metering section and head section temperature are 92 DEG C, 103 DEG C, 116 DEG C and 124 DEG C respectively, screw speed is 75 revs/min, vacuum is-0.08MPa, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
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 are 125 DEG C, 132 DEG C, 138 DEG C and 145 DEG C respectively, screw speed is 88 revs/min, vacuum is-0.08 MPa, make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under Screw Extrusion pressure is 0.26MPa through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber, wherein said coagulating bath cation be ethyl, anion be SCN-The temperature made of alkyl imidazole type ionic liquid be 38 DEG C, concentration be the aqueous solution of 25.6%.
The functional graphene fiber cellulose fiber containing Graphene prepared by embodiment 2 does fracture strength >=2.93cN/dtex, wet breaking strength >=1.75cN/dtex, far infrared normal emittance reaches 0.95, ultraviolet UPF (UPF) be 420.59 and UVA (long wave ultraviolet) transmitance be 1.32 %, thermal property is excellent, and heat decomposition temperature improves 31 DEG C.
Embodiment
3
:
The preparation method of a kind of functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and sodium carboxymethyl cellulose (CMC) dispersant are added in deionized water, utilize the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, being configured to the graphene dispersing solution of percent mass Particle density 22%, the addition of dispersant is the 12% of Graphene addition.
(2) preparation of cellulose/ion liquid mixture
The degree of polymerization by 19% is the straw pulp of 769, the cation of 81% be hydroxypropyl, anion be PF4 -Alkyl imidazole type ionic liquid use high speed disintegrator carry out premixing, make cellulose the most swelling, content is mass percent.
(3) mixing
Cellulose/ion liquid mixture prepared by graphene dispersing solution above-mentioned steps (1) prepared and step (2) is that the ratio of 1:63 is sufficiently mixed in mass ratio.
(4) pre-fusion
Compound is joined double screw extruder by charge door, double screw extruder feeding section, melt zone, metering section and head section temperature are 103 DEG C, 116 DEG C, 128 DEG C and 136 DEG C respectively, screw speed is 86 revs/min, vacuum is-0.07MPa, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
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 are 129 DEG C, 136 DEG C, 145 DEG C and 149 DEG C respectively, screw speed is 90 revs/min, vacuum is-0.07 MPa, make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under Screw Extrusion pressure is 0.35MPa through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber, wherein said coagulating bath cation be hydroxypropyl, anion be PF4 -The temperature made of alkyl imidazole type ionic liquid be 46 DEG C, concentration be the aqueous solution of 19.6%.
The functional graphene fiber cellulose fiber containing Graphene prepared by embodiment 3 does fracture strength >=2.98cN/dtex, wet breaking strength >=1.83cN/dtex, far infrared normal emittance reaches 0.92, ultraviolet UPF (UPF) be 332.13 and UVA (long wave ultraviolet) transmitance be 2.56 %, thermal property is excellent, and heat decomposition temperature improves 25 DEG C.
Embodiment
4
:
The preparation method of a kind of functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and dodecylbenzene sodium sulfonate (SDBS) dispersant are added in deionized water, utilize the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, being configured to the graphene dispersing solution of percent mass Particle density 18%, the addition of dispersant is the 6% of Graphene addition.
(2) preparation of cellulose/ion liquid mixture
The degree of polymerization by 15% is the straw pulp of 963 and phragmites communis pulp that the degree of polymerization is 972, the cation of 85% be butyl, anion be CH3COO-Alkyl imidazole type ionic liquid use high speed disintegrator carry out premixing, make cellulose the most swelling, content is mass percent.
(3) mixing
Cellulose/ion liquid mixture prepared by graphene dispersing solution above-mentioned steps (1) prepared and step (2) is that the ratio of 1:105 is sufficiently mixed in mass ratio.
(4) pre-fusion
Compound is joined double screw extruder by charge door, double screw extruder feeding section, melt zone, metering section and head section temperature are 115 DEG C, 123 DEG C, 134 DEG C and 145 DEG C respectively, screw speed is 92 revs/min, vacuum is-0.09MPa, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
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 are 142 DEG C, 143 DEG C, 145 DEG C and 150 DEG C respectively, screw speed is 92 revs/min, vacuum is-0.09MPa, make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under Screw Extrusion pressure is 0.43MPa through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber, wherein said coagulating bath cation be butyl, anion be CH3COO-The temperature made of alkyl imidazole type ionic liquid be 52 DEG C, concentration be the aqueous solution of 13.1%.
The functional graphene fiber cellulose fiber containing Graphene prepared by embodiment 4 does fracture strength >=3.02cN/dtex, wet breaking strength >=1.91cN/dtex, far infrared normal emittance reaches 0.90, ultraviolet UPF (UPF) be 256.78 and UVA (long wave ultraviolet) transmitance be 2.89 %, thermal property is excellent, and heat decomposition temperature improves 19 DEG C.
Embodiment
5
:
The preparation method of a kind of functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and OP-10 dispersant being added in deionized water, utilize the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, be configured to the graphene dispersing solution of percent mass Particle density 15%, the addition of dispersant is the 4% of Graphene addition.
(2) preparation of cellulose/ion liquid mixture
The degree of polymerization by 10% be 1000 bamboo pulp and the degree of polymerization be the cotton stalk dissolving pulp of 1120, the cation of 90% be hydroxypropyl, anion be BF4 -Alkyl imidazole type ionic liquid use high speed disintegrator carry out premixing, make cellulose the most swelling, content is mass percent.
(3) mixing
Cellulose/ion liquid mixture prepared by graphene dispersing solution above-mentioned steps (1) prepared and step (2) is that the ratio of 1:195 is sufficiently mixed in mass ratio.
(4) pre-fusion
Compound is joined double screw extruder by charge door, double screw extruder feeding section, melt zone, metering section and head section temperature are 112 DEG C, 127 DEG C, 134 DEG C and 143 DEG C respectively, screw speed is 72 revs/min, vacuum is-0.06MPa, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
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 are 118 DEG C, 127 DEG C, 135 DEG C and 144 DEG C respectively, screw speed is 92 revs/min, vacuum is-0.06MPa, make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under Screw Extrusion pressure is 0.31MPa through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber, wherein said coagulating bath cation be hydroxypropyl, anion be BF4 -The temperature made of alkyl imidazole type ionic liquid be 46 DEG C, concentration be the aqueous solution of 7.9%.
The functional graphene fiber cellulose fiber containing Graphene prepared by embodiment 5 does fracture strength >=2.92cN/dtex, wet breaking strength >=1.83cN/dtex, far infrared normal emittance reaches 0.88, ultraviolet UPF (UPF) be 172.62 and UVA (long wave ultraviolet) transmitance be 3.89 %, thermal property is excellent, and heat decomposition temperature improves 15 DEG C.
Embodiment
6
:
The preparation method of a kind of functional graphene fiber cellulose fiber, comprises the following steps:
(1) preparation of graphene dispersing solution
Graphene and polyvinylpyrrolidone (PVP) dispersant are added in deionized water, utilize the dispersing modes such as the dispersion of high-speed stirred, ball milling or ultrasound wave dispersion, being configured to the graphene dispersing solution of percent mass Particle density 10%, the addition of dispersant is the 7% of Graphene addition.
(2) preparation of cellulose/ion liquid mixture
The degree of polymerization by 10% be 856 bamboo pulp and the degree of polymerization be the cotton stalk dissolving pulp of 918, the cation of 90% be pi-allyl, anion be SCN-Alkyl imidazole type ionic liquid use high speed disintegrator carry out premixing, make cellulose the most swelling, content is mass percent.
(3) mixing
Cellulose/ion liquid mixture prepared by graphene dispersing solution above-mentioned steps (1) prepared and step (2) is that the ratio of 1:200 is sufficiently mixed in mass ratio.
(4) pre-fusion
Compound is joined double screw extruder by charge door, double screw extruder feeding section, melt zone, metering section and head section temperature are 95 DEG C, 112 DEG C, 128 DEG C and 150 DEG C respectively, screw speed is 82 revs/min, vacuum is-0.08MPa, by the high temperature of continuous way, high shear forces and evacuation mode, it is achieved the dehydration of compound, deaeration and heating pre-fusion.
(5) spinning solution is prepared
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 are 118 DEG C, 125 DEG C, 135 DEG C and 145 DEG C respectively, screw speed is 76 revs/min, vacuum is-0.08MPa, make compound be dehydrated further, deaeration and mixed melting, prepare the spinning solution containing Graphene.
(6) spinning process
The spinning solution of above-mentioned preparation under Screw Extrusion pressure is 0.43MPa through dosing pump, spinneret, spinning moulding in coagulating bath, through drafting process, operation of washing and oil, prepare finished product functional graphene fiber cellulose fiber, wherein said coagulating bath cation be pi-allyl, anion be SCN-The temperature made of alkyl imidazole type ionic liquid be 52 DEG C, concentration be the aqueous solution of 18.2%.
The functional graphene fiber cellulose fiber containing Graphene prepared by embodiment 6 does fracture strength >=3.12cN/dtex, wet breaking strength >=1.98cN/dtex, far infrared normal emittance reaches 0.88, ultraviolet UPF (UPF) be 62.78 and UVA (long wave ultraviolet) transmitance be 4.92%, thermal property is excellent, and heat decomposition temperature improves 10 DEG C.
Last it is noted that the foregoing is only the preferred embodiments of the present invention; it is not limited to the present invention; although the present invention being described in detail with reference to previous embodiment; for a person skilled in the art; technical scheme described in foregoing embodiments still can be modified by it; all within the spirit and principles in the present invention, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.
Claims (10)
1. the functional graphene fiber cellulose fiber that prepared by a fusion method, it is characterised in that: the main component of described fiber includes the Graphene of 0.5-10.0% and the cellulose of 90.0-99.5%.
Functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 1, it is characterized in that: the far infrared normal emittance of prepared functional graphene fiber cellulose fiber reaches 0.83-0.98, UPF reaches 62.78-560.32, and long wave ultraviolet transmitance is less than 4.92%, compared with conventional viscose rayon, heat decomposition temperature improves 10-42 DEG C.
3. the preparation method of functional graphene fiber cellulose fiber prepared by a fusion method, it is characterised in that: include that prepared by graphene dispersing solution, prepared by cellulose/ion liquid mixture, mix, pre-fusion, prepare spinning solution, spinning process.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is characterized in that: described pre-fusion step, double screw extruder feeding section, melt zone, metering section and head section temperature used are 80-115 DEG C, 90-125 DEG C, 105-135 DEG C and 115-150 DEG C respectively, screw speed is 60 ~ 100 revs/min, and vacuum is-0.05 ~-0.1MPa.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is wherein said that to prepare in spinning solution step single screw extrusion machine feeding section, melt zone, metering section and head section temperature used be 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, and vacuum is-0.05 ~-0.1MPa.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is characterized in that: described graphene dispersing solution preparation process, dispersant is made up of one or more in polyvinylpyrrolidone, dodecylbenzene sodium sulfonate, sodium carboxymethyl cellulose, sodium alginate, OP-10.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is characterised in that: described graphene dispersing solution preparation process, the addition of dispersant is the 4%～20% of Graphene addition.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is characterized in that: described cellulose/ion liquid mixture preparation process, ionic liquid is alkyl imidazole type ionic liquid, cation be pi-allyl, ethyl, hydroxypropyl, butyl one or more；Anion is halogen, BF4 -、PF4 -、SCN-And CH3COO-In one or more.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is characterised in that: the blended mass ratio of described blend step, graphene dispersing solution and cellulose/ion liquid mixture is 1:10 ~ 1:200.
The preparation method of functional graphene fiber cellulose fiber prepared by a kind of fusion method the most according to claim 3, it is characterised in that: described spinning process, during spinning, Screw Extrusion pressure is 0.2-0.6 MPa；
Described spinning process, coagulating bath be cation be pi-allyl, ethyl, hydroxypropyl, butyl one or more, anion is halogen, BF4 -、PF4 -、SCN-And CH3COO-One or several temperature made of alkyl imidazole type ionic liquid be 20～60 DEG C, concentration be the aqueous solution of≤32%；
Described cellulose/ion liquid mixture preparation process, the cellulose pulp degree of polymerization of use is 500～1200.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757511A (en) * | 2017-01-11 | 2017-05-31 | 珠海泓利服饰股份有限公司 | The modified nylon fiber and its preparation technology of a kind of platelet of Graphene containing polymolecularity and liquid phase surface conductance film |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838861A (en) * | 2010-05-07 | 2010-09-22 | 天津工业大学 | Method for preparing cellulose fiber |
| CN102154720A (en) * | 2010-12-21 | 2011-08-17 | 天津工业大学 | Preparation method of cellulose fibres |
| CN103046151A (en) * | 2012-12-18 | 2013-04-17 | 青岛大学 | Graphene blend regenerated cellulose fiber and preparation method thereof |
| CN103160945A (en) * | 2013-03-11 | 2013-06-19 | 青岛大学 | Functional nano-graphite/regenerated cellulose blend fiber and preparation method thereof |
| CN103173932A (en) * | 2013-03-20 | 2013-06-26 | 天津工业大学 | Preparation method of antiflaming cellulose non-woven cloth |
| CN103966691A (en) * | 2014-04-29 | 2014-08-06 | 中原工学院 | Preparation method for nanometer ATO/ cellulose diacetate composite electro-conductive fiber |
| 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 |
-
2015
- 2015-04-02 CN CN201510152558.6A patent/CN106149083B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838861A (en) * | 2010-05-07 | 2010-09-22 | 天津工业大学 | Method for preparing cellulose fiber |
| CN102154720A (en) * | 2010-12-21 | 2011-08-17 | 天津工业大学 | Preparation method of cellulose fibres |
| CN103046151A (en) * | 2012-12-18 | 2013-04-17 | 青岛大学 | Graphene blend regenerated cellulose fiber and preparation method thereof |
| CN103160945A (en) * | 2013-03-11 | 2013-06-19 | 青岛大学 | Functional nano-graphite/regenerated cellulose blend fiber and preparation method thereof |
| CN103173932A (en) * | 2013-03-20 | 2013-06-26 | 天津工业大学 | Preparation method of antiflaming cellulose non-woven cloth |
| CN103966691A (en) * | 2014-04-29 | 2014-08-06 | 中原工学院 | Preparation method for nanometer ATO/ cellulose diacetate composite electro-conductive fiber |
| 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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106757511A (en) * | 2017-01-11 | 2017-05-31 | 珠海泓利服饰股份有限公司 | The modified nylon fiber and its preparation technology of a kind of platelet of Graphene containing polymolecularity and liquid phase surface conductance film |
| CN107311102A (en) * | 2017-06-05 | 2017-11-03 | 何竞钟 | A kind of filler of bedding |
| CN107501614A (en) * | 2017-06-13 | 2017-12-22 | 绍兴标点纺织科技有限公司 | A kind of compound VF fibers of graphene and preparation method |
| WO2019061817A1 (en) * | 2017-09-26 | 2019-04-04 | 南通强生石墨烯科技有限公司 | Modified graphene oxide regenerated cellulose composite fiber and preparation method therefor |
| CN107653519A (en) * | 2017-10-23 | 2018-02-02 | 南京旭羽睿材料科技有限公司 | A kind of preparation method of graphene fiber |
| CN107604480A (en) * | 2017-10-26 | 2018-01-19 | 青岛大学 | A kind of lignin-base activated carbon fiber preparation method for electrode of super capacitor |
| CN107955984A (en) * | 2017-12-01 | 2018-04-24 | 山东英利实业有限公司 | A kind of graphene polysaccharide graft Lyocell fiber and preparation method thereof |
| CN108842224A (en) * | 2018-06-13 | 2018-11-20 | 东华大学 | A kind of core-skin type graphene/alginic acid electrically conductive composite fibre and preparation method thereof |
| CN110373764A (en) * | 2019-06-26 | 2019-10-25 | 圣华盾防护科技股份有限公司 | A kind of antibacterial antistatic graphene viscose yarn and preparation method thereof |
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