CN109183170A - A kind of preparation method of the compound short fibre of cellulose graphene - Google Patents
A kind of preparation method of the compound short fibre of cellulose graphene Download PDFInfo
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- CN109183170A CN109183170A CN201811013278.7A CN201811013278A CN109183170A CN 109183170 A CN109183170 A CN 109183170A CN 201811013278 A CN201811013278 A CN 201811013278A CN 109183170 A CN109183170 A CN 109183170A
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- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- 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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- 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
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
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- 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
- D01F1/103—Agents inhibiting growth of microorganisms
Abstract
The invention discloses a kind of preparation methods of the compound short fibre of cellulose graphene, include the following steps: to be dissolved in ionic liquid aqueous solution after a) mixing dispersing agent, graphene oxide and cellulose, wherein, the additive amount of graphene oxide is 0.1~0.3wt% of cellulose, and blend spinning stoste is made；B) gained blend spinning stoste through filtering, spinning, solidification, stretching, washing, bleach, oil, cut off, dry to get the compound short fibre of the cellulose graphene；The ionic liquid is mixed to get by 1- butyl -3- methylimidazole villaumite and connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl and connection two perchlorate of 1,4- bis- [1- (3- methylimidazole)] butyl.Experiment shows: the compound short fibre of cellulose graphene produced by the present invention has excellent mechanical performance, antistatic property, stability, and preparation process is simple, low in cost, environmental-friendly pollution-free.
Description
Technical field
The present invention relates to a kind of preparation methods of the compound short fibre of cellulose graphene, belong to functional cellulose fibre technology neck
Domain.
Background technique
Cellulose is that a kind of most wide, content is most polysaccharide is distributed in nature, accounts for 50% or more of plant kingdom's carbon content,
It is one of the most abundant natural organic matter of nature.Cellulose is mainly derived from plant, such as cotton, timber, cotton linter, wheat
Grass, straw, reed, fiber crops, mulberry skin etc., wherein the content of cellulose of cotton is natural most pure cellulose source close to 100%,
And in general timber, cellulose accounts for 40~50%, and there are also 10~30% hemicellulose and 20~30% lignin.As one
Kind degradable Green biological material, the superior property such as natural fiber is light with its, degradable, inexpensive, high-modulus, high intensity
Can, gradually play an increasingly important role.Therefore, regenerated fiber is made after obtaining native cellulose dissolution in plant, it is real
The regeneration and functionalization of existing cellulose are an important channels for efficiently using cellulose.
Graphene is a kind of novel carbon two-dimension nano materials, has excellent high intensity, electric conductivity, thermal conductivity, light transmission
The features such as property, flexibility, at present solar battery, sensor, nanoelectronics, high-performance nanometer electronic device, composite material,
The fields such as field emmision material, gas sensor and energy stores all have broad application prospect.Graphene is added to and is taken
In fiber, fabric can be made to have the function of stronger electric conductivity, thermal conductivity, antibiotic property, antistatic property etc., therefore, by graphene
It is current research hotspot with fiber composite preparation functional composite fiber.
Have at present by cellulose fibre and the compound relevant report for preparing composite fibre of graphene.Fiber flat band at present
The preparation of black alkene composite fibre, mainly uses finishing method, i.e., using impregnate, pad, the methods of coating or spraying are by graphite
Alkene is arranged onto fiber, obtained composite fibre, but the inert state of graphene surface, the interaction pole with other media
It is weak, easily reunite, be difficult it is evenly dispersed in polymer or its solution, therefore there are graphene fiber surface be distributed not
, the graphene problem low with fiber combination fastness.
For graphene problem easy to reunite, presently mainly graphene and fiber is replaced to be answered using graphene oxide
It closes, i.e., first prepares graphene oxide dispersion, then impregnate, pad, the methods of coating or spraying are by graphene oxide dispersion
It arranges fiber surface and forms graphite oxide ene coatings, weaker, the fiber baking but the binding force of graphene oxide and fiber remains unchanged
The graphite oxide ene coatings of dry rear surface are easy to appear cracking and peeling phenomenon, also, in the preparation process of composite fibre usually
It needs to carry out reduction treatment to the graphene oxide of fiber surface, graphene oxide is reduced to graphene, reduction treatment process
In inevitably use the high toxicities go back original reagent such as hydrazine hydrate, all there is great harm, and reducing agent to environmental and human health impacts
It is difficult to remove in post-processing, adverse effect will cause to fibre property.Although having at present using otherwise to graphite oxide
Alkene carries out the relevant report of reduction treatment, but still there are some defects, such as: in Chinese patent CN201310616126.7
Graphene oxide dispersion is coated on cellulosic fabric surface, graphene oxide coated fiber cellulose fabric is formed, then makes fibre
The graphene oxide on dimension cellulose fabric surface restores completely, and conductive fiber cellulose fabric is made, although not toxic using hydrazine hydrate etc.
Reagent, but coating, drying, ultraviolet light are repeated in preparation process, complicated operation, is unfavorable for industrial metaplasia
It produces.
In addition to the preparation method of finishing method, cellulose graphene composite fibre more commonly used at present is blend spinning
Method, i.e., progress spinning prepares composite fibre after graphene and cellulose solution being directly mixed into spinning solution.Such as: China is specially
Respectively by graphene aqueous solution and wood in sharp CN201510682674.9, CN201510682733.2, CN201510682720.5
Mixed dissolution is starched in methyl morpholine oxide, forms spinning mucus after removing pigment, then in a manner of spunbond, dry spray-wet type spinning
Composite fibre is made in silk method or melt-blown mode.This preparation method is compared to finishing method, although firmness is promoted, but still
Inevitably there is graphene agglomeration, seriously affects the performance of composite fibre.
It is similar to finishing method for graphene agglomeration traits, graphene, example are mainly replaced using graphene oxide at present
Such as: spinning after mixing graphene oxide solution with cellulose solution in Chinese patent CN201210549357.6, then through also
Original place reason, is made composite fibre；By graphene oxide and nano-cellulose dispersion liquid in Chinese patent CN201410363321.8
It is mixed to prepare spinning after spinning solution, then through reduction treatment, composite fibre is made.Although although this method avoids graphite
Alkene agglomeration traits, but reducing agent is used to carry out reduction treatment to graphene oxide, not only treatment effeciency is low, and the reduction used
Agent (such as: hydrazine hydrate, hydroiodic acid etc.) inevitably all there is to environmental and human health impacts great harm, and reducing agent is post-processing
In be difficult to remove, adverse effect will cause to fibre property.
For reducing agent problem, have at present and processing is modified to graphene oxide, by modified graphene oxide and fiber
Element is compound to prepare composite fibre, to avoid the report for using reducing agent, such as: Chinese patent CN201710884919.5 microcapsules
Technical treatment modified graphene oxide solution improves modified graphene oxide dispersibility, then uses regenerated cellulose spinning work
Skill prepares composite fibre.But the modification of microcapsules inevitably makes the preparation process of composite fibre complex, production cost
It is higher, and a large amount of modifying agent box alkaline reagent is used in modifying process, certain pollution is caused to environment, is unsuitable for work
Industry metaplasia produces.
In addition, the characteristics of cellulose is due to self assemble state structure, i.e. intramolecular, it is intermolecular there is a large amount of hydrogen bond,
Crystallinity with higher again simultaneously so that cellulose be difficult in conventional solvent (such as water and most of organic solvents) it is molten
Solution, graphene is also not readily dissolved in water in addition, this results in cellulose and graphene to be difficult to be directly dissolved in conventional solvent.This
It results in, either finishing method or blend spinning method prepare composite fibre, highly basic, N are all inevitably used in preparation process,
N- dimethyl acetamide/lithium chloride (DMAc/LiCl), N,N-dimethylformamide/dinitrogen tetroxide (DMF/N2O4), N- first
Base-N- oxygen morpholine (NMMO), dimethyl sulfoxide/tetrabutyl ammonium fluoride (DMSO/TBAF), fused salt hydrate (such as LiClO4
3H2O, LiSCN2H2O) and pollution organic solvent equal solvent system, such as: CN201510682674.9,
Methyl morpholine oxide dissolution graphene and wood pulp are used in CN201510682733.2, CN201510682720.5；
Regenerated cellulose pulp is dissolved using sodium hydroxide in CN201710884919.5；Hydroxide is used in CN201810051706.9
The mixed liquor dissolution cellulose and graphene of sodium, urea and water；It can be seen that at present used in the preparation method of composite fibre
There is strong toxicity in dicyandiamide solution, at high cost, solvent is difficult to recycle and use process in it is unstable the disadvantages of, be unsuitable for work
Industry metaplasia produces.
Ionic liquid is a kind of salt existing for room temperature or nearly liquid at room temperature, it has both the mobility and salt of liquid
Chemical activity, and have many unique properties, as structure can design, liquid journey range is wide, close to zero vapour pressure, can not
It fires, with high thermal stability and chemical stability etc..Ionic liquid is at present in separation process, catalysis, organic synthesis, electrochemistry
Etc. research obtained many progress, and be considered as that there is broad prospect of application in a kind of green syt and clean manufacturing
The green medium of novel environmental close friend.
The study found that ionic liquid can directly dissolve cellulose, Chinese patent CN 200610078784.5,
Ionic liquid is all individually disclosed in the patents such as CN200680012598.X, CN200710085298.0, CN201310158819.6
The method that body dissolves cellulose also has prepare functionality again using ion liquid dissolving cellulose and other functional materials at present
The relevant report of condensating fiber, such as Chinese patent CN200510077288.3 are disclosed and are moved by solvent mixed dissolution of ionic liquid
The method that object hair and cellulosic material prepare bioprotein hair fibre；Chinese patent CN201510313099.5 is disclosed with ionic liquid
Body is the method that solvent dissolves that keratin and cellulose prepare composite kerating fiber；Chinese patent CN201410186603.5 is public
It has opened and has dissolved the method that cellulose and retardant polymer prepare fire resistance fibre by solvent of ionic liquid；Chinese patent CN
201510152558.6 disclose using ionic liquid as solvent dissolution cellulose and the functional graphene fiber element of graphene preparation
The method of fiber.But at present in the preparation process of functional fiber using ionic liquid (alkyl quaternary ammonium salts, alkyl imidazole salt,
Alkyl pyrroles's salt etc.) dissolution cellulose and when functional materials, it is all made of pure ion liquid dissolving, so that spinning obtained is former
Fluid viscosity is larger, and spinnability is poor, all has a great impact in subsequent spinning process for the resistance to pressure of spinneret and drawing-off,
It is unfavorable for subsequent spinning；In addition, ionic liquid is when dissolving cellulose, dissolution time is longer, usually at 2~48 hours, even
Up to 120 hours；And solution temperature is higher, and usually at 100 DEG C or so, even as high as 150 DEG C, energy consumption is higher；Just so,
It causes to prepare functional fiber currently with ionic liquid and is still in laboratory stage, also cannot achieve industrialized scale, sternly
The application and development of functional fiber (including cellulose graphene composite fibre) are limited again.
Summary of the invention
In view of the above-mentioned problems existing in the prior art, the object of the present invention is to provide a kind of compound short fibres of cellulose graphene
Preparation method, to promote the industrialized production of cellulose graphene composite fibre.
For achieving the above object, The technical solution adopted by the invention is as follows:
A kind of preparation method of the compound short fibre of cellulose graphene, includes the following steps:
A) it is dissolved in ionic liquid aqueous solution after mixing dispersing agent, graphene oxide and cellulose, wherein oxidation stone
The additive amount of black alkene is 0.1~0.3wt% of cellulose, and blend spinning stoste is made；
B) gained blend spinning stoste through filtering, spinning, solidification, stretching, washing, bleach, oil, cut off, dry to get
The compound short fibre of cellulose graphene；
Wherein, ionic liquid used is by following components:
1- butyl -3- methylimidazole villaumite: 100 mass parts；
Join two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl: 5~10 mass parts；
Join two perchlorate of 1,4- bis- [1- (3- methylimidazole)] butyl: 10~20 mass parts；
It is mixed to get；Wherein:
Join the chemical structural formula of two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl are as follows:
Join the chemical structural formula of two perchlorate of 1,4- bis- [1- (3- methylimidazole)] butyl are as follows:
Preferably, the mass fraction of the ionic liquid aqueous solution be 30~95%, further preferred 60~
95%.
Preferably, the solution temperature in step a) is 50~110 DEG C (preferably 60~80 DEG C), dissolution time 10
~45 minutes (preferably 15~30 minutes).
Preferably, the preparation of the ionic liquid includes the following steps:
First make 1- butyl -3- methylimidazole villaumite and connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl and connection 1,4-
Two [1- (3- methylimidazole)] butyl, two perchlorate is measured according to the ratio to be uniformly mixed, and is then stirred to react 5 at 110~130 DEG C
~25 hours.
Preferably, the preparation of two villaumite of the connection Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl includes following step
It is rapid: under 65~85 DEG C, inert gas shielding, N- methylimidazole being added dropwise in Isosorbide-5-Nitrae-dichloroetane, is then refluxed for reaction 12
~72 hours.
As further preferred scheme, the molar ratio of Isosorbide-5-Nitrae-dichloroetane and N- methylimidazole is 1:1~1:1.5.
As further preferred scheme, the inert gas is nitrogen or argon gas.
Preferably, the preparation of two perchlorate of the connection Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl includes such as
Lower step:
To first two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl be joined and lithium perchlorate is soluble in water, then 75~85
It is stirred to react at DEG C 12~48 hours, is cooled to room temperature, continue stirring at room temperature 5~15 hours.
As further preferred scheme, join mole of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl two villaumite and lithium perchlorate
Than for 1:1~1:1.5.
Preferably, the cellulose be selected from wood pulps, Cotton Pulp, bamboo pulp, the mulberry root bark pulp dregs of rice, straw pulp,
Any one in the reed pulp dregs of rice, the multitudinous slurry dregs of rice or hemp dissolving pulp, content of cellulose >=90wt%, the degree of polymerization >=500 (preferably 500~
700)。
Preferably, the mass ratio of the total amount and ionic liquid aqueous solution of cellulose and graphene oxide be 1:5~
1:25。
Preferably, the dispersing agent is silica, and additive amount is 0.3~1wt% of ionic liquid aqueous solution.
Preferably, in step b), spinning is carried out using dry-jet wet-spinning spinning technique, the temperature of spinning solution is 50
~110 DEG C (preferably 60~80 DEG C), spinning speed is 60~150 ms/min.
The dry-jet wet-spinning spinning technique refers to spinning solution by forming dynamic analysis of spinning after spinning head extrusion, wet
First one-step forming in cold air.Clammy air refers to that temperature is 5~25 DEG C, the air that relative humidity is 60~95%.
Preferably, in step b), the coagulating bath that when solidification uses is made of ionic liquid and water, coagulation bath temperature
For 0~20 DEG C (preferably 5~15 DEG C), wherein the mass percent of ionic liquid is 5~25%.
Preferably, in step b), shearing length is 35~105mm.
Compared with prior art, the present invention have following conspicuousness the utility model has the advantages that
1) present invention by 1- butyl -3- methylimidazole villaumite, connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl and
Connection two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl, which compound, is made a kind of novel ionic liquid, then will divide
Spinning solution is made in the ionic liquid aqueous solution in powder, graphene oxide and cellulose co-dissolve, then filtered,
Spinning, stretching, washing, is bleached, is oiled, cutting off, drying at solidification, and the compound short fibre of cellulose graphene, prepared fiber is made
The specific resistance of the plain compound short fibre of graphene is 1.1~7.3*105Ω m has excellent antistatic property, while also having excellent
Different anti-microbial property, far infrared performance, excellent combination property；
2) present invention realizes the molten symbiosis altogether of graphene oxide and cellulose, and graphene oxide disperses in spinning solution
Uniformly, soilless sticking phenomenon after washing several times, prints so that combination fastness is good between graphene oxide and fiber in composite fibre
After dye, properties do not change substantially, excellent in stability, especially, in preparation process, without carrying out to graphene oxide
Reduction treatment, easy to operate, clean and environmental protection；
3) spinning solution, spinning obtained is made using ionic liquid aqueous solution dissolution cellulose and graphene oxide in the present invention
Silk stock solution viscosity is lower, and be conducive to spinning makes to be made but also will not cause damages to the fibrous characteristic of raw material in subsequent technique
Cellulose graphene it is compound short fine when filament number is 1.5dtex, breaking strength can achieve as 3.4~3.8cN/
Dtex has excellent mechanical performance, is also conducive to scale spinning, when spinning spinneret hole count by the traditional experiment room stage 60~
100 holes are promoted to 14000~30000 holes, realize industrialized production；
4) when the present invention realizes cellulose and graphene oxide molten altogether, solution temperature is significantly reduced, and dissolution time significantly contracts
It is short, it saved cost, improved production efficiency, it is easy to accomplish industrialized production；
5) need not move through deaeration step in preparation process of the invention, and graphene oxide and cellulose co-dissolve in
Economical and practical in ionic liquid, preparation process is simple, low in cost, without using any organic solvent, environmental-friendly no dirt
Dye is not necessarily to special installation and harsh conditions, it is easy to accomplish industrialized production has extremely strong practical value.
Specific embodiment
Technical solution of the present invention is described in further detail and completely below with reference to embodiment, application examples and comparative example.
Embodiment 1
One, join the preparation of two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl:
At nitrogen protection, 80 DEG C, 1.2mol N- methylimidazole is slowly added dropwise in 1mol Isosorbide-5-Nitrae-dichloroetane, is dripped
After adding, back flow reaction 72 hours, reaction was completed, and reaction solution is cooled to room temperature, and products therefrom is washed with ether to remove not
The raw material of reaction obtains white solid matter, and as (HPLC purity is connection two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl
98.8%, yield 88%).
Two, join the preparation of two perchlorate of 1,4- bis- [1- (3- methylimidazole)] butyl:
1mol is joined into two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl and 1.2mol lithium perchlorate is dissolved in 1L water, so
It is stirred to react 36 hours, is cooled to room temperature at 80 DEG C afterwards, continue stirring 12 hours at room temperature, reaction solution is dispersed in equal volume
Chloroform in, separation, chloroform mutually washes with water, until water phase, without chloride ion, chloroform is mutually concentrated under reduced pressure, and obtains colorless and transparent liquid
Body, as connection two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl (HPLC purity is 98.9%, yield 78%).
Three, the preparation of ionic liquid:
By 100g 1- butyl -3- methylimidazole villaumite, 8g connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl and
15g joins two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl after mixing, is stirred to react at 125 DEG C 11 hours,
Reaction was completed, is cooled to room temperature to get the ionic liquid.
Four, the preparation of the compound short fibre of cellulose graphene:
A) by ion liquid dissolving in deionized water, configuration obtains the ionic liquid aqueous solution of 85wt%；By 0.5 mass
(content of cellulose is for part silica (partial size is about 100nm), 0.01 mass parts graphene oxide and 9.49 mass parts Cotton Pulps
99%, the degree of polymerization 600) be added after mixing 100 mass parts, 85wt% ionic liquid aqueous solution in, stirred at 75 DEG C
It mixes 20 minutes, obtains the blend spinning stoste of stable uniform；
B) gained blend spinning stoste is filtered that (traditional preparation method spinning solution will could be by filtering, deaeration
Row spinning, processing step are complex), porous spinneret spinning (spinneret hole number be 20000 holes, spinning solution temperature be 75
DEG C, spinning speed is 100 ms/min) afterwards, be immersed in the coagulating bath of the ionic liquid containing 15wt% and solidify, coagulation bath temperature is
15 DEG C, through 3.5 times stretch after, then through washing, bleach, oil, cut off (50nm), dry it is compound short to get cellulose graphene
It is fine.
After tested, the cellulose graphene that the present embodiment is prepared is compound short fine in the feelings that filament number is 1.5dtex
Under condition, breaking strength is 3.4cN/dtex or so；And test and show: under equal conditions, using the 1- butyl -3- of 85wt%
Methylimidazole villaumite, connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl or 1,4- bis- [1- (3- methylimidazole)] butyl two
When the single ionic liquid aqueous solution dissolution graphene oxide and Cotton Pulp of perchlorate, need to stir 3 at 110~130 DEG C
The spinning solution of stable uniform can be just obtained within~5 hours, and in the case where filament number is all 1.5dtex, it is obtained right
The breaking strength of short fibre more compound than cellulose graphene is only 2.7cN/dtex or so, illustrates the preparation work using the present embodiment
Skill not only realizes the molten altogether of cellulose and graphene oxide, and the mechanicalness of the compound short fibre of cellulose graphene prepared
It can be preferably；
In addition, the specific resistance of the compound short fibre of cellulose graphene manufactured in the present embodiment is 7.3*105Ω m or so, and
The specific resistance that its specific resistance does not change substantially, and compares the compound short fibre of cellulose graphene after washing, printing and dyeing is 1.1*106
Ω m or so, it can be seen that, using the preparation process of the present embodiment, cellulose graphene obtained is compound short fine with excellent
Antistatic property and stability, while also have excellent anti-microbial property, far infrared performance.
In addition, the present embodiment, which by using the ionic liquid, is realized, removes dissolution stone using ionic liquid aqueous solution
Black alkene and cellulose, and in fact graphene and cellulose are all not readily dissolved in water, the water of addition is actually to be unfavorable for cellulose
(this is also that organic solvent, such as DMSO are added in traditional ionic liquid to promote cellulose dissolution for dissolution with graphene
Reason)；In addition, the application can also reduce the viscosity of spinning solution simultaneously, be advantageously implemented height by the way that water is added in dissolution system
Hole spinneret；Also, solution temperature is significantly reduced, and dissolution time significantly shortens.
Due to the better mechanical property for the compound short fibre of cellulose graphene that the present embodiment is prepared, the viscosity of spinning solution
Lower, so that spinneret hole number when the present embodiment spinning can achieve 20000 holes, spinning speed can be 100 ms/min
Clock realizes industrialized production.
The mass fraction of the present embodiment step a) intermediate ion liquid aqueous solution can be 30~95%, remaining condition is constant.
Solution temperature can be 50~110 DEG C in the present embodiment step a), and dissolution time can be 10~45 minutes, remaining
Condition is constant.
Cotton Pulp can be wood pulps, bamboo pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, multitudinous in the present embodiment step a)
The slurry dregs of rice or hemp dissolving pulp, remaining condition are constant.
The additional amount of silica can be 0.3~1wt% of ionic liquid aqueous solution in the present embodiment step a), remaining
Part is constant.
Spinning hole count can be 14000~30000 holes in the present embodiment step b), remaining condition is constant, spinning solution temperature
Degree can be 50~110 DEG C, and spinning speed can be 60~150 ms/min, remaining condition is constant.
Coagulating bath can be the ionic liquid aqueous solution of 5~25wt% in the present embodiment step b), and solidification bath temperature can be 0
~20 DEG C, remaining condition is constant.
Stretching in the present embodiment step b) can be 1.5~4 times of stretchings, remaining condition is constant.
Shearing length can be 35~105mm in the present embodiment step b), remaining condition is constant.
Embodiment 2
The present embodiment be different from that of the embodiment 1 only in the following aspects: by 0.5 mass parts silica (partial size is about 100nm),
0.015 mass parts graphene oxide and 9.485 mass parts Cotton Pulps (content of cellulose 99%, the degree of polymerization 600) mixing are equal
It is even after be added 100 mass parts, 85wt% ionic liquid aqueous solution in, remaining content is identical as described in embodiment 1.
After tested, the cellulose graphene that the present embodiment is prepared is compound short fine in the feelings that filament number is 1.5dtex
Under condition, breaking strength is 3.6cN/dtex or so；And test and show: under equal conditions, using the 1- butyl -3- of 85wt%
Methylimidazole villaumite, connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl or 1,4- bis- [1- (3- methylimidazole)] butyl two
When the single ionic liquid aqueous solution dissolution graphene oxide and Cotton Pulp of perchlorate, need to stir 3 at 110~130 DEG C
The spinning solution of stable uniform can be just obtained within~5 hours, and in the case where filament number is all 1.5dtex, it is obtained right
The breaking strength of short fibre more compound than cellulose graphene is only 2.9cN/dtex or so；
In addition, the specific resistance of the compound short fibre of cellulose graphene manufactured in the present embodiment is 4.1*105Ω m or so, and
The specific resistance that its specific resistance does not change substantially, and compares the compound short fibre of cellulose graphene after washing, printing and dyeing is 7.5*105
Ω m or so.
Embodiment 3
The present embodiment be different from that of the embodiment 1 only in the following aspects: by 0.5 mass parts silica (partial size is about 100nm),
0.025 mass parts graphene and 9.475 mass parts Cotton Pulps (content of cellulose 99%, the degree of polymerization 600) are after mixing
Be added 100 mass parts, 85wt% ionic liquid aqueous solution in, remaining content is identical as described in embodiment 1.
After tested, the cellulose graphene that the present embodiment is prepared is compound short fine in the feelings that filament number is 1.5dtex
Under condition, breaking strength is 3.8cN/dtex or so；And test and show: under equal conditions, using the 1- butyl -3- of 85wt%
Methylimidazole villaumite, connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl or 1,4- bis- [1- (3- methylimidazole)] butyl two
When the single ionic liquid aqueous solution dissolution Cotton Pulp and graphene and Cotton Pulp of perchlorate, need to stir at 110~130 DEG C
3~5 hours spinning solutions that can just obtain stable uniform are mixed, and in the case where filament number is all 1.5dtex, it is obtained
The breaking strength for comparing the compound short fibre of cellulose graphene is only 3.0cN/dtex or so；
In addition, the specific resistance of the compound short fibre of cellulose graphene manufactured in the present embodiment is 1.1*105Ω m or so, and
The specific resistance that specific resistance after washing, printing and dyeing does not change substantially, and compares the compound short fibre of cellulose graphene is 3.5*105
Ω m or so.
By embodiment 1 to embodiment 3 as it can be seen that using preparation process of the invention, in particular by it is of the invention it is compound from
Sub- liquid dissolves cellulose and graphene oxide, and the compound short fibre of the cellulose graphene being prepared is in identical monofilament
Under fiber number, the breaking strength for the compound short fibre of cellulose graphene being prepared using compound ion liquid of the invention is than comparison
The breaking strength of the compound short fibre of cellulose graphene improves 20% or more, illustrates the fiber prepared using preparation process of the invention
The mechanical performance of the plain compound short fibre of graphene is more preferable, especially, the ratio electricity of the compound short fibre of cellulose graphene prepared by the present invention
Resistance can achieve 1.1*105Ω m, and its specific resistance does not change substantially after washing, printing and dyeing, and benefit can be repeated several times
With antistatic property is good, and stability is good.
In summary: the present invention by 1- butyl -3- methylimidazole villaumite, connection 1,4- bis- [1- (3- methylimidazole)] butyl two
Villaumite and connection two perchlorate of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl, which compound, is made a kind of novel ionic liquid, obtains
To ionic liquid be used to prepare the compound short fibre of cellulose graphene, cellulose graphene obtained it is compound it is short it is fine have it is excellent
Mechanical performance and stability, and during the preparation process, without the use of pure ionic liquid, cellulose and oxidation stone can be realized
The dissolution of black alkene, effectively reduces solution temperature, shortens dissolution time, improves dissolved efficiency, while avoiding graphene
Reunion, and for the use of ionic liquid aqueous solution is compared to pure ionic liquid, obtained dope viscosity is lower, and can
To adjust the concentration of ionic liquid aqueous solution, and then flexible modulation dope viscosity as needed, so that spinning solution is easy to
Spinning, spinneret hole count can achieve 14000~30000 holes when spinning, and spinning speed can be 60~150 ms/min, realize
Industrialized production；In addition, needing not move through deaeration step in preparation process of the invention, and graphene oxide can be total to cellulose
With being dissolved in ionic liquid, economical and practical, preparation process is simple, low in cost, without using any organic solvent, environment friend
It is good pollution-free, it is not necessarily to special installation and harsh conditions, it is easy to accomplish and industrialized production has extremely strong practical value, relative to
For the prior art, conspicuousness progress and unexpected effect are achieved.
Finally need indicated herein be: the above is only part preferred embodiments of the invention, should not be understood as to this hair
The limitation of bright protection scope, those skilled in the art's above content according to the present invention make it is some it is nonessential improvement and
Adjustment all belongs to the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of the compound short fibre of cellulose graphene, which comprises the steps of:
A) it is dissolved in ionic liquid aqueous solution after mixing dispersing agent, graphene oxide and cellulose, wherein graphene oxide
Additive amount be cellulose 0.1~0.3wt%, be made blend spinning stoste；
B) gained blend spinning stoste through filtering, spinning, solidification, stretching, washing, bleach, oil, cut off, dry to get described
The compound short fibre of cellulose graphene；
Wherein, ionic liquid used is by following components:
100 mass parts of 1- butyl -3- methylimidazole villaumite；
Join 5~10 mass parts of 1,4- bis- [1- (3- methylimidazole)] two villaumite of butyl；
Join 10~20 mass parts of 1,4- bis- [1- (3- methylimidazole)] two perchlorate of butyl；
It is mixed to get；Wherein:
Join the chemical structural formula of two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl are as follows:
Join the chemical structural formula of two perchlorate of 1,4- bis- [1- (3- methylimidazole)] butyl are as follows:
2. preparation method according to claim 1, it is characterised in that: the mass fraction of the ionic liquid aqueous solution is 30
~95%.
3. preparation method according to claim 1, it is characterised in that: the solution temperature in step a) is 50~110 DEG C, molten
Solving the time is 10~45 minutes.
4. preparation method according to claim 1, which is characterized in that the preparation of the ionic liquid includes the following steps:
First make 1- butyl -3- methylimidazole villaumite and connection two villaumite of 1,4- bis- [1- (3- methylimidazole)] butyl and connection 1,4- bis-
Two perchlorate of [1- (3- methylimidazole)] butyl is measured according to the ratio to be uniformly mixed, then it is stirred to react 5 at 110~130 DEG C~
25 hours.
5. the preparation method according to claim 4, which is characterized in that described connection Isosorbide-5-Nitrae-two [1- (3- the methylimidazole)] fourth
The preparation of two villaumite of base includes the following steps: under 65~85 DEG C, inert gas shielding, and N- methylimidazole is added dropwise to Isosorbide-5-Nitrae-two
In chlorobutane, it is then refluxed for reaction 12~72 hours.
6. the preparation method according to claim 4, which is characterized in that described connection Isosorbide-5-Nitrae-two [1- (3- the methylimidazole)] fourth
The preparation of two perchlorate of base includes the following steps:
To first two villaumite of Isosorbide-5-Nitrae-two [1- (3- methylimidazole)] butyl be joined and lithium perchlorate is soluble in water, then at 75~85 DEG C
It is stirred to react 12~48 hours, is cooled to room temperature, continue stirring at room temperature 5~15 hours.
7. preparation method according to claim 1, it is characterised in that: the cellulose is selected from wood pulps, Cotton Pulp, bamboo
Any one in pulp, the mulberry root bark pulp dregs of rice, straw pulp, the reed pulp dregs of rice, the multitudinous slurry dregs of rice or hemp dissolving pulp, content of cellulose >=
90wt%, the degree of polymerization >=500.
8. preparation method according to claim 1, it is characterised in that: the dispersing agent is silica, and additive amount is ion
0.3~1wt% of liquid aqueous solution.
9. preparation method according to claim 1, it is characterised in that: in step b), shearing length is 35~105mm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109763210A (en) * | 2019-01-15 | 2019-05-17 | 中国科学院过程工程研究所 | The method that ionic liquid prepares cellulose base carbon fiber or carbon film |
| CN111235659A (en) * | 2020-03-19 | 2020-06-05 | 当阳市鸿阳新材料科技有限公司 | Lyocell fiber with heat storage and insulation functions and preparation method thereof |
| CN113802200A (en) * | 2021-08-30 | 2021-12-17 | 兰州大学 | Functionalized graphene oxide/bacterial cellulose composite fiber and preparation method and application thereof |
| CN115559011A (en) * | 2022-09-29 | 2023-01-03 | 武汉纺织大学 | Anisotropic organic-inorganic hybrid ionic liquid gel fiber and preparation method thereof |
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| CN104878454A (en) * | 2014-02-28 | 2015-09-02 | 恒天海龙股份有限公司 | High-water-content ionic liquid/cellulose spinning solution preparation method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763210A (en) * | 2019-01-15 | 2019-05-17 | 中国科学院过程工程研究所 | The method that ionic liquid prepares cellulose base carbon fiber or carbon film |
| CN111235659A (en) * | 2020-03-19 | 2020-06-05 | 当阳市鸿阳新材料科技有限公司 | Lyocell fiber with heat storage and insulation functions and preparation method thereof |
| CN113802200A (en) * | 2021-08-30 | 2021-12-17 | 兰州大学 | Functionalized graphene oxide/bacterial cellulose composite fiber and preparation method and application thereof |
| CN115559011A (en) * | 2022-09-29 | 2023-01-03 | 武汉纺织大学 | Anisotropic organic-inorganic hybrid ionic liquid gel fiber and preparation method thereof |
| CN115559011B (en) * | 2022-09-29 | 2024-01-26 | 武汉纺织大学 | Anisotropic organic-inorganic hybrid ionic liquid gel fiber and preparation method thereof |
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