CN105970325B - A kind of continuous cellulose airsetting glue fiber and preparation method thereof - Google Patents

A kind of continuous cellulose airsetting glue fiber and preparation method thereof Download PDF

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CN105970325B
CN105970325B CN201610473161.1A CN201610473161A CN105970325B CN 105970325 B CN105970325 B CN 105970325B CN 201610473161 A CN201610473161 A CN 201610473161A CN 105970325 B CN105970325 B CN 105970325B
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cellulose
mass fraction
glue fiber
solution
fiber
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CN105970325A (en
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朱美芳
张君妍
陈文萍
孟思
江晓泽
王浩
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Donghua University
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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
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • 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

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  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)

Abstract

The present invention provides a kind of continuous cellulose airsetting glue fibers and preparation method thereof.The preparation method includes dispersing cellulose in dispersing agent, obtains spinning solution；Spinning solution is expressed into coagulating bath and carries out wet spinning, obtains cellulose gel glue fiber；After cellulose gel glue fiber is wound in coagulating bath, immerses in ageing liquid and be aged；It is dry by the cellulose gel fiber wash after ageing to neutrality, obtain continuous cellulose airsetting glue fiber.Method of the invention has the characteristics that raw material is cheap and easily-available, preparation process is simple and green non-pollution, good spinnability, solves the problems, such as that cellulose aerogels are difficult to be spun into fibre.Cellulose aerogels fibre diameter prepared by the present invention has high-specific surface area (>=88m less than 120 μm2/ g), high porosity (>=85%), low-density (≤0.2g/cm3) feature, while pulp freeness is adjustable, can be used for function clothes, sensing, catalyst load and adsorption filtration, cosmetics, the fields such as biologic medical.

Description

A kind of continuous cellulose airsetting glue fiber and preparation method thereof
Technical field
The present invention relates to airsetting glue fibers to research and develop field, and in particular to a kind of continuous cellulose airsetting glue fiber and its preparation Method.
Background technique
Aeroge is a kind of nanoporous solid material with three-dimensional net structure, in the hole and network of solid matrix Gassy (usually air) in structure.Because it is with big specific surface area, high porosity and low bulk density and leads The excellent characteristics such as hot coefficient, aeroge have huge latent in numerous areas such as heat-insulation and heat-preservation, catalysis, the energy, absorption, aerospaces It is applying.Aeroge is divided into inorganic aerogels and organic aerogel, and compared to frangible inorganic aerogels, organic aerogel has Mechanical property is preferable, the good advantage of flexibility.
Cellulose aerogels not only have good mechanical performance and flexibility as a kind of novel organic aerogel, but also Its raw material sources is most wide, rich reserves and can biodegrade.Highly porous cellulose aerogels can be used as fabricated in situ The effective nano-reactor of nanoparticle；A large amount of hydroxyl can provide a large amount of work for many chemical reactions on its strand Property site, functionalization of being more convenient for；Its low-density, lower thermal conductivity, in a low voice fast propagated, good biocompatibility, degradable simultaneously Feature, before it can be made to have wide application in fields such as sound-insulating and heat-insulating, catalysis load, adsorbing separation, cosmetics and biologic medicals Scape.The current research in relation to cellulose aerogels have focused largely on two-dimentional, three-dimensional fiber element aerogel material (i.e. block with it is thin Film) preparation on.And one-dimensional airsetting glue fiber has unique advantage compared to two dimension, three-dimensional aerogel material.In gas Gel preparation aspect, one dimension fibre material are more conducive to solvent, the diffusion of gas and heat transmitting.Due to many steps of aeroge preparation Suddenly (such as ageing, cleaning, exchange of solvent, drying) is prepared into one dimension fibre, can reduce wet all by the control of diffusion and heat transfer The size of gel, so that time and solvent usage needed for reducing aeroge production, are conducive to the continuous production and drop of aeroge Low cost.In application aspect, the non-woven membrane of airsetting glue fiber preparation is compared to the cellulose aerogels film tool directly prepared There is better gas permeability, is particularly suited for function clothes or wound dressing；Aeroge fiber applications are in terms of absorption filtering material It is dropped compared to film and block aeroge with lower filtering pressure；It is more efficient when for the fields such as being catalyzed, adsorbing；Meanwhile having Machine and inorfil can be processed into two dimension or even three-dimensional flexible light-weight materials by means such as braiding, knotting, sewing.
Currently reported airsetting glue fiber and preparation method thereof there are several types of.Superb seminar of Zhejiang University passes through Specific surface area 884m has been made using liquid nitrogen as coagulating bath in fiber spinning from crystalline state2/ g, tensile strength 188kNm/kg, modulus 3.3MPa Graphene aerogel fiber.Red seminar of the state of Qin of BJ University of Aeronautics & Astronautics is to help with PVP using butyl titanate as presoma Agent is spun, by electrostatic spinning, prepares composite cellulosic membrane, then through dry and high-temperature process, obtained TiO2Aeroge Nanowire Tie up film, specific surface area 241.6m2/g.German space center Materials Research Laboratories Lorenz Ratke study group uses cellulose It is dissolved in spinning when close to its gel point in zinc chloride hydrate or calcium thiocyanate hydrate melt, it is aged and overcritical CO2Dry method prepares the nanostructured fibers element airsetting glue fiber of high porosity, 150~220m of specific surface2/ g, but it is fine Diameter 0.5mm~1mm is tieed up, there is a problem of that fiber is thicker.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of continuous cellulose airsetting glue fibers and preparation method thereof, should Method has the characteristics that raw material is cheap and easily-available, preparation process is simple and green non-pollution, good spinnability, solves cellulose airsetting Glue is difficult to be spun into fine problem.
In order to solve the above-mentioned technical problems, the present invention provides a kind of preparation method of continuous cellulose airsetting glue fiber, It is characterised by comprising:
Step 1: dispersing cellulose in dispersing agent, obtain spinning solution；Cellulose material in the spinning solution Measuring score is 2%~7%, and the dispersing agent is the solution containing alkali metal hydroxide and urea and/or thiocarbamide；
Step 2: spinning solution being expressed into coagulating bath and carries out wet spinning, obtains cellulose gel glue fiber；Described Coagulating bath is acid solution, ethanol solution or acetone soln；
Step 3: after cellulose gel glue fiber is wound in coagulating bath, immerses in ageing liquid and be aged, the ageing liquid For mass fraction be 0.5%~1% dilute sulfuric acid, mass fraction be 0.5%~1% dilute acetic acid solution, ethyl alcohol or acetone；
Step 4: it is dry by the cellulose gel fiber wash after ageing to neutrality, it is fine to obtain continuous cellulose aeroge Dimension.
Preferably, the cellulose in the step 1 is plant cellulose or bacteria cellulose.
It is highly preferred that the plant cellulose is cotton pulp cellulose.
Preferably, the dispersing agent be containing mass fraction be 4.2% LiOH and mass fraction be 12% urea Solution, containing mass fraction be 7% NaOH and mass fraction be 12% urea solution, be containing mass fraction The solution for the thiocarbamide that 9.5% NaOH and mass fraction is 4.5%, or the NaOH containing mass fraction for 7%~8%, quality The solution for the thiocarbamide that the urea and mass fraction that score is 8% are 6.5%~10%.
Preferably, the coagulating bath is 3~5% for the sulfuric acid and mass fraction for being 2%~5% containing mass fraction The aqueous solution of sodium sulphate, the dilute acetic acid solution that mass fraction is 1%~3%, the ethyl alcohol that volume fraction is 10%~50% are water-soluble The aqueous acetone solution that liquid or volume fraction are 10%~30%.
Preferably, the extruded velocity of the spinning solution is 0.6m/min~6m/min.
Preferably, the condition of the wet spinning is normal temperature and pressure.
Preferably, the winding speed of the cellulose gel glue fiber is 0.6~24m/min.
Preferably, the ageing carries out at normal temperature, and digestion time is 15min~1h.
Preferably, the washing is to be washed with deionized.
Preferably, the drying is freeze-drying or supercritical drying.
Preferably, before the drying, solvent displacement is first carried out.
It is highly preferred that the solvent displacement uses deionized water, ethyl alcohol or the tert-butyl alcohol.
Preferably, the temperature of the dispersing agent is -8~-12 DEG C.
The present invention also provides continuous celluloses prepared by the preparation method of above-mentioned continuous cellulose airsetting glue fiber Airsetting glue fiber.
The preparation method of continuous cellulose airsetting glue fiber is by fiber cheap and easy to get from a wealth of sources first in the present invention Element is configured to spinning solution, and using acid solution, ethanol solution or acetone soln as coagulating bath, spinning solution encounters in coagulating bath Acid, the active force that the double diffusion of fast solvent non-solvent destroys between solvent and cellulose occurs for ethyl alcohol or acetone solidifies cellulose Regeneration realizes quick liquid-solid phase transformation required by wet spinning, forms cellulose aerogels fiber；Make fiber in ageing process Element is further formed intermolecular and intramolecular hydrogen bond and gelation, finally obtains stable three-dimensional net structure, is formed more Hole.It is washed with deionized again to neutrality, then carries out solvent displacement, it is dry to get cellulose aerogels fiber.
Compared with prior art, the beneficial effects of the present invention are:
1, the present invention for the first time spinning solution in wet spinning in coagulating bath quick solidification regeneration principle and cellulose Directly dissolution regeneration preparation cellulose aerogels method combines, by changing concentration of dope, coagulating bath and ageing bath condition, And spinning solution extruded velocity and fiber winding speed, diameter is continuously prepared less than 120 μm, the cellulose with some strength Airsetting glue fiber.It is prepared into one dimension fibre, the size of wet gel can be reduced, thus time and molten needed for reducing aeroge production Agent dosage is conducive to the continuous production of aeroge and reduces cost.Cellulose aerogels fiber prepared by the present invention has high ratio Surface area (>=88m2/ g), high porosity (>=85%), low-density (≤0.2g/cm3) feature, while pulp freeness can It adjusts.
2, since one dimension fibre material is more conducive to the diffusion of liquid, gas, continuous cellulose airsetting prepared by the present invention Glue fiber all has advantage more outstanding in function clothes, sensing, catalysis load, filtering absorption, the fields such as biological medicine, There is very huge potential demand, there is practicability.
3, method of the invention has that raw material is cheap and easily-available, fiber manufacturing process green non-pollution, preparation process are simple, can The good feature of the property spun, solves the problems, such as that cellulose aerogels are difficult to be spun into fibre.
Detailed description of the invention
Fig. 1 is the knotting demonstration graph of cellulose aerogels fiber in embodiment 1；
Fig. 2 be embodiment 1 in cellulose aerogels fiber surface and Cross Section Morphology scanning electron microscope (SEM) photograph: (a), (b) be respectively The fiber surface photo of different amplification, (c), (d) be respectively different amplification fibre section photo；
Fig. 3 is cellulose aerogels fiber N in embodiment 12Adsorb De contamination isollaothermic chart；
Fig. 4 is cellulose aerogels fiber graph of pore diameter distribution in embodiment 1.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited Range.
Embodiment 1
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It disperses bacteria cellulose (hundred million moral Food Co., Ltd of Hainan, particle compressed coconut) in -12 DEG C of dispersing agents, obtains To spinning solution, wherein the mass fraction of bacteria cellulose is 7%, mechanical strong stirring 30min, with centrifuge 10000r/min It carries out deaeration and handles 20min；The dispersing agent is the solution that NaOH and thiocarbamide are dissolved in water formation, wherein the quality of NaOH Score is 9.5%, and the mass fraction of thiocarbamide is 4.5%；Spinning solution is expressed into coagulating bath and carries out wet process under normal temperature and pressure Spinning obtains cellulose gel glue fiber；The coagulating bath is the aqueous acetone solution that volume fraction is 10%；The spinning is former The extruded velocity of liquid is 2.4m/min；Cellulose gel glue fiber is wound in coagulating bath with the winding speed of 6m/min Afterwards, it immerses in ageing liquid acetone and is aged 20min at normal temperature, make its complete gelation；By the cellulose gel glue fiber after ageing It is washed with deionized to neutrality, is freeze-dried through -60 DEG C, obtains continuous cellulose airsetting glue fiber.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 88m2/ g, most probable pore size For 9nm, porosity 85%, density 0.20g/cm3, diameter is 120 μm.The knotting demonstration obtained for tieing up plain airsetting glue fiber Figure is as shown in Figure 1；Cellulose aerogels fiber surface and cross-section morphology scanning electron microscope (SEM) photograph obtained are as shown in Figure 2；Fibre obtained Tie up plain airsetting glue fiber N2It is as shown in Figure 3 to adsorb De contamination isollaothermic chart；Cellulose aerogels fiber graph of pore diameter distribution obtained As shown in Figure 4.
Embodiment 2
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
Disperse bacteria cellulose (hundred million moral Food Co., Ltd of Hainan, particle compressed coconut are handled via homogenizer) in- In 8 DEG C of dispersing agents, obtain spinning solution, wherein the mass fraction of bacteria cellulose be 2%, mechanical strong stirring 30min, with from Scheming 10000r/min carries out deaeration and handles 20min；The dispersing agent be by NaOH, urea and thiocarbamide be dissolved in water formation it is molten Liquid, wherein the mass fraction of NaOH is 7%, and the mass fraction of urea is 8%, and the mass fraction of thiocarbamide is 10%；By spinning original Liquid, which is expressed into coagulating bath, carries out wet spinning under normal temperature and pressure, obtain cellulose gel glue fiber；The coagulating bath is volume The ethanol water that score is 10%；The extruded velocity of the spinning solution is 0.6m/min；Cellulose gel glue fiber is existed After winding speed in coagulating bath with 0.6m/min is wound, immerses in ageing liquid ethyl alcohol and be aged 1h at normal temperature, keep its complete Full gelation；Cellulose gel glue fiber after ageing is washed with deionized to neutrality, replaces deionized water with the tert-butyl alcohol, It is freeze-dried through -60 DEG C, obtains continuous cellulose airsetting glue fiber.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 178m2/ g, most probable pore size For 6nm, porosity 91%, density 0.13g/cm3, diameter is 110 μm.
Embodiment 3
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It will treated cotton pulp cellulose (Yanling County Di Lun Textile Co., Ltd., DP=550, processing method are as follows: cellulose Cotton Pulp is mechanically pulverized, 50 DEG C of drying in vacuum drying oven after repeatedly being washed with water and ethyl alcohol) it is scattered in -10 DEG C of dispersing agents, Spinning solution is obtained, wherein the mass fraction of cotton pulp cellulose is 7%, mechanical strong stirring 30min, with centrifuge 10000r/ Min carries out deaeration and handles 20min；The dispersing agent is the solution that NaOH, urea and thiocarbamide are dissolved in water formation, wherein The mass fraction of NaOH is 8%, and the mass fraction of urea is 8%, and the mass fraction of thiocarbamide is 6.5%；Spinning solution is squeezed out Wet spinning is carried out under normal temperature and pressure into coagulating bath, obtains cellulose gel glue fiber；The coagulating bath is that volume fraction is 50% ethanol water；The extruded velocity of the spinning solution is 3m/min；By cellulose gel glue fiber in coagulating bath After being wound with the winding speed of 6m/min, immerses in ageing liquid ethyl alcohol and be aged 1h at normal temperature, make its complete gelation；It will Cellulose gel glue fiber after ageing is washed with deionized to neutrality, with ethanol replacement deionized water, by resulting cellulose Alcogel fiber is put into drying kettle, and liquid CO is passed through at 4 DEG C, under the conditions of 5.3MPa2Ethyl alcohol 6h is replaced, after displacement completely, is led to It crosses thermostat and 40 DEG C is heated to system, reach critical pressure, and keep 0.5h at 10MPa, then keeping critical-temperature In the case where constant, CO is slowly discharged by bleed valve2To normal pressure, temperature is cooled to room temperature, and it is fine to obtain cellulose aerogels Dimension.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 410m2/ g, most probable pore size For 2nm, porosity 98%, density 0.08g/cm3, diameter is 80 μm.
Embodiment 4
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It disperses bacteria cellulose (hundred million moral Food Co., Ltd of Hainan, particle compressed coconut) in -12 DEG C of dispersing agents, obtains To spinning solution, wherein the mass fraction of bacteria cellulose is 2%, mechanical strong stirring 30min, with centrifuge 10000r/min It carries out deaeration and handles 20min；The dispersing agent is the solution that LiOH and urea are dissolved in water formation, wherein the quality of LiOH Score is 4.2%, and the mass fraction of urea is 12%；Spinning solution is expressed into coagulating bath and carries out Wet-spinning under normal temperature and pressure Silk, obtains cellulose gel glue fiber；The coagulating bath is the aqueous acetone solution that volume fraction is 30%；The spinning solution Extruded velocity be 1.8m/min；After winding speed of the cellulose gel glue fiber in coagulating bath with 6m/min is wound, It immerses in ageing liquid acetone and is aged 20min at normal temperature, make its complete gelation；Cellulose gel glue fiber after ageing is spent Ion water washing is replaced deionized water with the tert-butyl alcohol, is freeze-dried through -60 DEG C, it is fine to obtain continuous cellulose aeroge to neutrality Dimension.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 134m2/ g, most probable pore size For 6nm, porosity 90%, density 0.11g/cm3, diameter is 120 μm.
Embodiment 5
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It will treated cotton pulp cellulose (Yanling County Di Lun Textile Co., Ltd., DP=550, processing method are as follows: cellulose Cotton Pulp is mechanically pulverized, 50 DEG C of drying in vacuum drying oven after repeatedly being washed with water and ethyl alcohol) it is scattered in -10 DEG C of dispersing agents, Spinning solution is obtained, wherein the mass fraction of cotton pulp cellulose is 4%, mechanical strong stirring 30min, with centrifuge 10000r/ Min carries out deaeration and handles 20min；The dispersing agent is the solution that LiOH and urea are dissolved in water formation, wherein the matter of LiOH Measuring score is 4.2%, and the mass fraction of urea is 12%；Spinning solution is expressed into coagulating bath and carries out wet process under normal temperature and pressure Spinning obtains cellulose gel glue fiber；The coagulating bath is 5% for the sulfuric acid and mass fraction for being 5% containing mass fraction Sodium sulphate aqueous solution；The extruded velocity of the spinning solution is 3m/min；By cellulose gel glue fiber in coagulating bath After being wound with the winding speed of 18m/min, immerses in the dilute sulfuric acid that ageing liquid mass fraction is 0.5% and be aged at normal temperature 20min makes its complete gelation；Cellulose gel glue fiber after ageing is washed with deionized to neutrality, ethanol replacement is used Cellulose alcogel fiber is put into drying kettle, liquid CO is passed through at 4 DEG C, under the conditions of 5.3MPa by deionized water2Replace ethyl alcohol 6h is heated to 40 DEG C to system by thermostat, reaches critical pressure, and keep 0.5h at 10MPa, so after displacement completely Afterwards in the case where keeping critical-temperature constant, CO is slowly discharged by bleed valve2To normal pressure, temperature is cooled to room temperature, and is obtained Obtain cellulose aerogels fiber.Obtain continuous cellulose airsetting glue fiber.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 350m2/ g, most probable pore size For 2nm, porosity 95%, density 0.10g/cm3, diameter is 80 μm.
Embodiment 6
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It will treated cotton pulp cellulose (Yanling County Di Lun Textile Co., Ltd., DP=550, processing method are as follows: cellulose Cotton Pulp is mechanically pulverized, 50 DEG C of drying in vacuum drying oven after repeatedly being washed with water and ethyl alcohol) it is scattered in -10 DEG C of dispersing agents, Spinning solution is obtained, wherein the mass fraction of cotton pulp cellulose is 7%, mechanical strong stirring 30min, with centrifuge 10000r/ Min carries out deaeration and handles 20min；The dispersing agent is the solution that NaOH, urea and thiocarbamide are dissolved in water formation, wherein The mass fraction of NaOH is 8%, and the mass fraction of urea is 8%, and the mass fraction of thiocarbamide is 6.5%；Spinning solution is squeezed out Wet spinning is carried out under normal temperature and pressure into coagulating bath, obtains cellulose gel glue fiber；The coagulating bath is that mass fraction is 3% dilute acetic acid solution；The extruded velocity of the spinning solution is 6m/min；By cellulose gel glue fiber in coagulating bath with After the winding speed of 24m/min is wound, immerses in the spirit of vinegar that ageing liquid mass fraction is 0.5% and be aged at normal temperature 20min makes its complete gelation；Cellulose gel glue fiber after ageing is washed with deionized to neutrality, is freezed through -60 DEG C It is dry, obtain continuous cellulose airsetting glue fiber.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 110m2/ g, most probable pore size For 9nm, porosity 87%, density 0.19g/cm3, diameter is 120 μm.
Embodiment 7
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It will treated cotton pulp cellulose (Yanling County Di Lun Textile Co., Ltd., DP=550, processing method are as follows: cellulose Cotton Pulp is mechanically pulverized, 50 DEG C of drying in vacuum drying oven after repeatedly being washed with water and ethyl alcohol) it is scattered in -12 DEG C of dispersing agents, Spinning solution is obtained, wherein the mass fraction of cotton pulp cellulose is 2%, mechanical strong stirring 30min, with centrifuge 10000r/ Min carries out deaeration and handles 20min；The dispersing agent is the solution that NaOH, urea are dissolved in water formation, wherein the matter of NaOH Measuring score is 7%, and the mass fraction of urea is 12%；Spinning solution is expressed into coagulating bath and carries out Wet-spinning under normal temperature and pressure Silk, obtains cellulose gel glue fiber；The coagulating bath is 3% for the sulfuric acid and mass fraction for being 2% containing mass fraction The aqueous solution of sodium sulphate；The extruded velocity of the spinning solution is 3m/min；By cellulose gel glue fiber in coagulating bath with After the winding speed of 12m/min is wound, immerses in the dilute sulfuric acid that ageing liquid mass fraction is 1% and be aged at normal temperature 15min makes its complete gelation；Cellulose gel glue fiber after ageing is washed with deionized to neutrality, then uses the tert-butyl alcohol Deionized water is replaced, is freeze-dried through -60 DEG C, obtains continuous cellulose airsetting glue fiber.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 271m2/ g, most probable pore size For 6nm, porosity 91%, density 0.12g/cm3, diameter is 110 μm.
Embodiment 8
A kind of preparation method of continuous cellulose airsetting glue fiber, specific steps are as follows:
It will treated cotton pulp cellulose (Yanling County Di Lun Textile Co., Ltd., DP=550, processing method are as follows: cellulose Cotton Pulp is mechanically pulverized, 50 DEG C of drying in vacuum drying oven after repeatedly being washed with water and ethyl alcohol) it is scattered in -8 DEG C of dispersing agents, it obtains To spinning solution, wherein the mass fraction of cotton pulp cellulose is 5%, mechanical strong stirring 30min, with centrifuge 10000r/min It carries out deaeration and handles 20min；The dispersing agent is the solution that NaOH, urea and thiocarbamide are dissolved in water formation, wherein NaOH's Mass fraction is 8%, and the mass fraction of urea is 8%, and the mass fraction of thiocarbamide is 6.5%；Spinning solution is expressed into solidification Wet spinning is carried out in bath under normal temperature and pressure, obtains cellulose gel glue fiber；The coagulating bath is that mass fraction is 1% dilute vinegar Acid solution；The extruded velocity of the spinning solution is 4.8m/min；By cellulose gel glue fiber with 18m/min in coagulating bath Winding speed be wound after, immerse ageing liquid mass fraction be 1% spirit of vinegar in be aged 15min at normal temperature, make it Complete gelation；Cellulose gel glue fiber after ageing is washed with deionized to neutrality, is freeze-dried, obtains through -60 DEG C Continuous cellulose airsetting glue fiber.
The successive silk of spinning process, cellulose aerogels pulp freeness obtained are 103m2/ g, most probable pore size For 9nm, porosity 86%, density 0.20g/cm3, diameter is 115 μm.

Claims (7)

1. a kind of preparation method of continuous cellulose airsetting glue fiber characterized by comprising
Step 1: dispersing cellulose in dispersing agent, obtain spinning solution；Cellulose quality point in the spinning solution Number is 2% ~ 7%, and the dispersing agent is the solution containing alkali metal hydroxide and urea and/or thiocarbamide；
Step 2: spinning solution being expressed into coagulating bath and carries out wet spinning, obtains cellulose gel glue fiber, the spinning The extruded velocity of stoste is 0.6m/min ~ 6m/min；The coagulating bath is acid solution, ethanol solution or acetone soln；
Step 3: after cellulose gel glue fiber is wound in coagulating bath, the winding speed of the cellulose gel glue fiber is 0.6 ~ 24m/min, the coagulating bath be containing mass fraction be 2% ~ 5% sulfuric acid and mass fraction be 3 ~ 5% sodium sulphate Aqueous solution, the dilute acetic acid solution that mass fraction is 1% ~ 3%, the ethanol water or volume fraction that volume fraction is 10% ~ 50% are 10% ~ 30% aqueous acetone solution, immerse ageing liquid in be aged, the ageing liquid be mass fraction be 0.5% ~ 1% dilute sulfuric acid, The dilute acetic acid solution that mass fraction is 0.5% ~ 1%, ethyl alcohol or acetone；
Step 4: it is dry by the cellulose gel fiber wash after ageing to neutrality, obtain continuous cellulose airsetting glue fiber.
2. the preparation method of continuous cellulose airsetting glue fiber as described in claim 1, which is characterized in that in the step 1 Cellulose be plant cellulose or bacteria cellulose.
3. the preparation method of continuous cellulose airsetting glue fiber as described in claim 1, which is characterized in that the dispersing agent For the solution of the LiOH and mass fraction that are 4.2% containing the mass fraction urea for being 12%, the NaOH for being 7% containing mass fraction With mass fraction be 12% urea solution, containing mass fraction be 9.5% NaOH and mass fraction be 4.5% thiocarbamide Solution, or containing mass fraction be 7% ~ 8% NaOH, mass fraction be 8% urea and mass fraction be 6.5% ~ 10% thiocarbamide Solution.
4. the preparation method of continuous cellulose airsetting glue fiber as described in claim 1, which is characterized in that the Wet-spinning The condition of silk is normal temperature and pressure.
5. the preparation method of continuous cellulose airsetting glue fiber as described in claim 1, which is characterized in that the ageing exists It is carried out under room temperature, digestion time is 15min ~ 1h.
6. the preparation method of continuous cellulose airsetting glue fiber as described in claim 1, which is characterized in that the drying is Freeze-drying or supercritical drying.
7. continuous fiber prepared by the preparation method of continuous cellulose airsetting glue fiber of any of claims 1-6 Plain airsetting glue fiber.
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