CN106435798B - A kind of back loading SiO2Prepare high-specific surface area continuous cellulose/SiO2The method of airsetting glue fiber - Google Patents
A kind of back loading SiO2Prepare high-specific surface area continuous cellulose/SiO2The method of airsetting glue fiber Download PDFInfo
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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
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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
- 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
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic System; Titanates; Zirconates; Stannates; Plumbates
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention discloses a kind of back loading SiO2Prepare high-specific surface area continuous cellulose/SiO2The method of airsetting glue fiber：Cellulose is configured to spinning solution；Acid solution, ethanol solution or acetone soln are added in coagulating basin as coagulating bath；Spinning solution is added in coagulating bath, wet spinning is carried out, obtains cellulose gel glue fiber；By the cellulose gel fiber roll of acquisition around, it immerses room temperature in aged solution and is aged 15min~1h, it is washed with deionized to neutrality, immerses in silicate or silanol colloidal sol, after taking-up, remove surface colloidal sol, it immerses room temperature in aged solution to be aged 2~10 days, is washed with deionized to neutrality, then carries out solvent displacement, it is dry to get.Continuous cellulose prepared by the present invention/SiO2 airsetting glue fibers have the specific surface area and relatively rich grade hole hole of superelevation, and fiber aperture and specific surface area are adjustable.
Description
Technical field
The invention belongs to the preparation field of airsetting glue fiber, more particularly to a kind of back loading SiO2Prepare high-specific surface area company
Continuous cellulose/SiO2The method of airsetting glue fiber.
Background technology
Aeroge (aerogel) is a kind of highly porous solid, is full of in the hole of solid matrix and network structure
Gas (being typically air).Because with high porosity, low-density, lower thermal conductivity, in a low voice speed, low-refraction and big specific surface
A series of excellent characteristics, the aeroges such as product are with a wide range of applications in many fields.Aeroge is divided into inorganic aerogels
And organic aerogel, compared to frangible inorganic aerogels, organic aerogel has mechanical property preferable, good excellent of flexibility
Point.But inorganic aerogels especially silica (SiO2) aeroge has compared to organic aerogel and very high compare table
Area (200~1000m2/ g), therefore combine the toughness of organic aerogel and the superhigh specific surface area of inorganic aerogels that can make gas
The performance of gel is larger promoted, and broader practice foreground is made it have.
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 be biodegradable.Highly porous cellulose aerogels can be used as fabricated in situ
The effective nano-reactor of nano-particle；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；
The current research in relation to cellulose aerogels nonloaded silica has focused largely on two dimension, three-dimensional fiber element aeroge
In the preparation of material (i.e. block and film), as Zhang Lina seminars of Wuhan University cellulose dissolution in low temperature alkali systems,
Cellulose aquagel film is obtained after regeneration, hydrogel thin film is immersed in TEOS (ethyl orthosilicate) precursor solution, is carried out molten
Gellation, the in-situ preparation SiO in cellulose skeleton2Nano particle, SiO2Load capacity is up to 60%, finally obtains specific surface
Product is up to 600m2Cellulose-the SiO of/g2Aerogel film；Jiao Jianbin seminars of university of the Chinese Academy of Sciences are blocky bacteria cellulose
It is freeze-dried after processing, obtained bacteria cellulose aeroge is immersed in TEOS colloidal sols, freezed after taking out aging
Dry SiO2Load capacity is up to 97%, and specific surface area is up to 734.1m2Cellulose-the SiO of/g2Block aeroge.After can pass through
Continue to immerse in MTMS (methyltriethoxysilane) colloidal sol and carries out hydrophobically modified for adsorbing grease in water.But it is one-dimensional at present
The fiber-loaded silica of cellulose aerogels but has not been reported.This is because compared to the aerogel material of other dimensions, it is fine
It is harsher to raw material and preparation condition requirement to tie up shape aerogel material.However, fibrous aerogel material is compared to two dimension, three
Dimension aerogel material has unique advantage.In terms of aeroge preparation, one dimension fibre material is more conducive to the diffusion of solvent, gas
It is transmitted with heat.Since many steps (such as ageing, cleaning, exchange of solvent, drying) prepared by aeroge are all passed by diffusion and heat
The control led, is prepared into one dimension fibre, can reduce the size of wet gel, to reduce time and the solvent needed for aeroge production
Dosage is conducive to the continuous production of aeroge and reduces cost.In application aspect, non-woven membrane prepared by airsetting glue fiber is compared
There is better gas permeability in the cellulose aerogels film directly prepared, be particularly suited for function clothes or wound dressing；Gas
Gelatinous fibre is applied to drop with lower filtering pressure compared to film and block aeroge in terms of absorption filtering material；For urging
It is more efficient when the fields such as change, absorption；Meanwhile organic and inorfil can be processed by means such as braiding, knotting, sewing
Two dimension or even three-dimensional flexible light-weight materials.Cellulose aerogels are prepared into continuous fiber shape, its performance will be made to obtain into one
Step improves, its application field is made to obtain the expansion of bigger.
At present about back loading SiO2Prepare high-specific surface area continuous cellulose/SiO2The method of airsetting glue fiber yet there are no
Report.
Invention content
Technical problem to be solved by the invention is to provide a kind of back loading SiO2Prepare high-specific surface area continuous cellulose/
SiO2The method of airsetting glue fiber.
To solve the above-mentioned problems, the present invention provides a kind of back loading SiO2Prepare high-specific surface area continuous cellulose/
SiO2The method of airsetting glue fiber, which is characterized in that include the following steps：
Step 1)：Prepare cellulose dispersion liquid be used as spinning solution, in coagulating basin addition acid solution, ethanol solution or
Acetone soln is as coagulating bath；
Step 2)：Spinning solution prepared by step 1) is expressed into the coagulating bath of step 1), wet spinning is carried out, obtains
Cellulose gel glue fiber；
Step 3)：The cellulose gel glue fiber that step 2) obtains is wound in coagulating bath, the fiber after winding is immersed
Into aged solution, room temperature is aged 15min~1h, and the fiber after ageing is washed with deionized to neutrality, silicate is immersed
Removal surface colloidal sol is taken out or in silanol colloidal sol, after stirring, is immersed room temperature in aged solution and is aged 2~10 days, uses deionized water
Washing carries out solvent displacement to neutrality with deionized water, ethyl alcohol or the tert-butyl alcohol, dry, obtains continuous cellulose/SiO2Airsetting
Glue fiber.
Preferably, the cellulose that cellulose dispersion liquid uses in the step 1) for cotton pulp cellulose or bacteria cellulose,
Its mass concentration in cellulose dispersion liquid is 2%~7%.
Preferably, the dispersant that cellulose dispersion liquid uses in the step 1) is mass fraction 4.2%LiOH/12%
Urea, 7%NaOH/12% urea, 9.5%NaOH/4.5% thiocarbamides or 7%~8%NaOH/8% urea/6.5%~10%
Thiourea.
Preferably, acid solution uses mass fraction for 2%~5% sulfuric acid, 3~5% sodium sulphate water in the step 1)
Solution or 1%~3% dilute acetic acid solution；Ethanol solution use volume fraction for 10%~50% ethanol water；Acetone is molten
Liquid use volume fraction for 10%~30% aqueous acetone solution.
Preferably, the condition of wet spinning is normal temperature and pressure in the step 2).
Preferably, the extruded velocity of spinning solution is 0.6m/min~6m/min in the step 2).
Preferably, the speed wound in the step 2) is 0.6m/min~24m/min.
Preferably, in the step 3) aged solution be 0.5%~1% dilute sulfuric acid in terms of mass concentration, 0.5%~
1% dilute acetic acid solution, straight alcohol solution or pure acetone solution.
Preferably, silicate is sodium silicate, nine water sodium metasilicate or potassium water glass in the step 3)；Silanol colloidal sol is just
Silester, phenyltrimethoxysila,e, methyltrimethoxysilane or methyltriethoxysilane hydrolytic sol.
Preferably, aged solution uses molar concentration for the oxalic acid of 0.005mol/L~0.01mol/L in the step 3).
Preferably, dry in the step 3) is specially freeze-drying or supercritical drying.
Back loading SiO prepared by the present invention2Prepare high-specific surface area continuous cellulose/SiO2The hole of airsetting glue fiber exists
Nanoscale range, and specific surface area size can be adjusted by changing preparation condition.
The present invention is in cellulose-binding aeroge fiber manufacturing process and SiO2The characteristics of aeroge preparation process, in fiber
In plain aeroge fiber manufacturing process, to be aged and remove the porous three-dimensional network structure of the cellulose gel glue fiber of residual solvent
For skeleton, carry out the collosol and gel in situ of silicate and silanol colloidal sol, then be dried, thus obtain high-specific surface area company
Continuous cellulose/SiO2Airsetting glue fiber.
The present invention utilizes the spinning solution principle of quick solidification regeneration and colloidal sol in situ in coagulating bath in wet spinning solidifying
Gelatinization principle realizes high-specific surface area continuous cellulose/SiO by wet spinning2Airsetting glue fiber has novelty.It is made
Standby high-specific surface area continuous cellulose/SiO2Airsetting glue fiber has more in the fields such as catalysis, absorption, filtering, heat preservation, dress ornament
Advantage outstanding has very huge potential demand, has practicability.
High-specific surface area continuous cellulose/SiO in the present invention2The preparation method of airsetting glue fiber is that will derive from a wealth of sources first
Cellulose cheap and easy to get is configured to spinning solution, using acid solution, ethanol solution or acetone soln as coagulating bath, by wet
Quick solventnonsolvent double diffusion makes cellulose solidification regeneration in method spinning coagulation bath, obtains cellulose gel glue fiber, will obtain
Cellulose gel fiber roll around, immerse aged solution in be aged, make cellulose gel glue fiber into one in ageing process
Gelation is walked, stable gel network structure is obtained, is washed with deionized to neutrality, then fiber is immersed into silicate or silanol
In colloidal sol, 30min is stirred, surface colloidal sol is removed after taking-up, room temperature in oxalic acid solution is immersed and is aged 2~10 days, by being aged
Journey makes in fiber silicate or silanol colloidal sol carry out collosol and gel, realizes from orthosilicic acid/silicate to SiO2The transformation of network,
It is formed simultaneously a large amount of holes.It is washed with deionized to neutrality, solvent displacement is carried out with deionized water, ethyl alcohol or the tert-butyl alcohol, do
It is dry, obtain continuous cellulose/SiO2Airsetting glue fiber.The method of the present invention is cheap and easily-available with raw material, preparation process is simple,
Good spinnability, environmentally protective feature, continuous cellulose/SiO prepared by the present invention2Airsetting glue fiber has the specific surface of superelevation
Product and relatively rich grade hole hole, fiber aperture and specific surface area are adjustable, and fiber has good flexibility.
The present invention has the characteristics that raw material is cheap and easily-available, preparation process is simple, good spinnability, environmentally protective, system of the present invention
Standby continuous cellulose/SiO2 airsetting glue fibers have superelevation specific surface area and relatively rich grade hole hole, fiber aperture and
Specific surface area is adjustable, and fiber has good flexibility, can be used for filtering absorption, catalyst carrier, sensing, cosmetics and doctor
Treat the fields such as health.
Description of the drawings
Fig. 1 is cellulose/SiO in embodiment 12The bending demonstration graph of airsetting glue fiber；
Fig. 2 is cellulose/SiO in embodiment 12Airsetting glue fiber N2Adsorb De contamination isollaothermic chart；
Fig. 3 is cellulose/SiO in embodiment 12Aeroge fiber graph of pore diameter distribution.
Specific implementation mode
In order to make the present invention more obvious and understandable, hereby with preferred embodiment, and attached drawing is coordinated to be described in detail below.
Embodiment 1
It is 7% that bacteria cellulose (hundred million moral Food Co., Ltd of Hainan, particle compressed coconut), which is dispersed in mass fraction,
In the low-temperature solvent system of the thiocarbamide of NaOH/8% urea/10%, wherein bacteria cellulose mass fraction is 2% (all percentages
All include itself, similarly hereinafter), mechanical strong stirring 30min, carrying out deaeration processing 20min with centrifuge 10000r/min must spin
Spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure by silk stock solution, obtains cellulose gel glue fiber；It is described
Coagulating bath be ethanol water that volume fraction is 10%；The extruded velocity of the spinning solution is 0.6m/min；It will be fine
After the plain gelatinous fibre of dimension is wound in coagulating bath with the winding speed of 0.6m/min, immerse in ageing liquid ethyl alcohol in room temperature
Lower ageing 1h makes its complete gelation；After ageing, fiber is washed with deionized to neutrality, the cellulose gel that will be obtained
Fiber immerses in sodium silicate colloidal sol, stirs 30min, and surface colloidal sol is removed after taking-up, immerses in 0.005mol/L oxalic acid solutions
Room temperature is aged 10 days, is realized from orthosilicic acid/sodium metasilicate to SiO2The transformation of network is formed simultaneously a large amount of holes.It, will be fine after ageing
Dimension is washed with deionized to neutrality, then replaces deionized water with the tert-butyl alcohol, freeze-dried to get cellulose/SiO2Airsetting
Glue fiber.The successive silk of spinning process, cellulose/SiO obtained2Aeroge pulp freeness is 459m2/ g, most probable
Aperture is 5nm.Cellulose/SiO obtained2The bending demonstration graph of airsetting glue fiber is as shown in Figure 1；Cellulose/SiO obtained2Gas
Gelatinous fibre N2It is as shown in Figure 2 to adsorb De contamination thermoisopleth；Cellulose/the SiO obtained2The graph of pore diameter distribution of airsetting glue fiber such as Fig. 3
It is shown.
Embodiment 2
Low temperature the thiocarbamide of treated cotton pulp cellulose is dispersed in mass fraction is 8%NaOH/8% urea/6.5% is molten
In agent system, wherein cotton pulp cellulose mass fraction is 7%, and mechanical strong stirring 30min is carried out with centrifuge 10000r/min
Deaeration processing 20min obtains spinning solution, and spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure, obtains fibre
The plain gelatinous fibre of dimension；The coagulating bath is the ethanol water that volume fraction is 50%；The extrusion speed of the spinning solution
Degree is 3m/min；After cellulose gel glue fiber is wound in coagulating bath with the winding speed of 6m/min, ageing liquid is immersed
1h is aged in ethyl alcohol at normal temperatures, makes its complete gelation；After ageing, fiber is washed with deionized to neutrality, immerses nine
In water sodium metasilicate colloidal sol, 30min is stirred, surface colloidal sol is removed after taking-up, immerses room temperature ageing 7 in 0.01mol/L oxalic acid solutions
It, realizes from orthosilicic acid/sodium metasilicate to SiO2The transformation of network is formed simultaneously a large amount of holes.After ageing, by fiber deionization
Water washing is to neutrality, then with ethanol replacement deionized water, through supercritical drying to get cellulose aerogels fiber.Spinning process
Successive silk, cellulose/SiO obtained2Aeroge pulp freeness is 698m2/ g, most probable pore size 2nm.
Embodiment 3
Bacteria cellulose is dispersed in the low-temperature solvent system that mass fraction is 9.5%NaOH/4.5% thiocarbamides, wherein
Bacteria cellulose mass fraction is 7%, mechanical strong stirring 30min, and carrying out deaeration with centrifuge 10000r/min handles 20min
Spinning solution is obtained, spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure, obtains cellulose gel glue fiber；
The coagulating bath is the aqueous acetone solution that volume fraction is 10%；The extruded velocity of the spinning solution is 2.4m/min；
After cellulose gel glue fiber is wound in coagulating bath with the winding speed of 6m/min, immerse in ageing liquid acetone normal
Temperature is lower to be aged 20min, makes its complete gelation；After ageing, potassium water glass is immersed after fiber is washed with deionized to neutrality
In colloidal sol, stir 30min, after taking-up remove surface colloidal sol, immerse 0.01mol/L oxalic acid solutions in room temperature be aged 7 days, realize by
Orthosilicic acid/potassium silicate is to SiO2The transformation of network is formed simultaneously a large amount of holes.After ageing, by fiber be washed with deionized to
Neutrality, it is freeze-dried to get cellulose/SiO2Airsetting glue fiber.The successive silk of spinning process, cellulose airsetting obtained
Glue fiber specific surface area is 379m2/ g, most probable pore size 7nm.
Embodiment 4
It is in the low-temperature solvent system of 4.2%LiOH/12% urea, wherein carefully bacteria cellulose dispersion quality score
Fungin mass fraction is 3%, mechanical strong stirring 30min, and carrying out deaeration processing 20min with centrifuge 10000r/min obtains
Spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure by spinning solution, obtains cellulose gel glue fiber；Institute
The coagulating bath stated is the aqueous acetone solution that volume fraction is 30%；The extruded velocity of the spinning solution is 1.8m/min；It will
After cellulose gel glue fiber is wound in coagulating bath with the winding speed of 6m/min, immerse in ageing liquid acetone at normal temperatures
It is aged 20min, makes its complete gelation；After ageing, fiber is washed with deionized to neutrality, ethyl orthosilicate colloidal sol is immersed
In, 30min is stirred, surface colloidal sol is removed after taking-up, room temperature in 0.01mol/L oxalic acid solutions is immersed and is aged 7 days, realize by former silicon
Acid is to SiO2The transformation of network is formed simultaneously a large amount of holes.After ageing, fiber is washed with deionized to neutrality, then uses uncle
Butanol replaces deionized water, freeze-dried to get cellulose aerogels fiber.The successive silk of spinning process, fibre obtained
Tie up element/SiO2Aeroge pulp freeness is 494m2/g, most probable pore size 5nm.
Embodiment 5
Treated, cotton pulp cellulose is dispersed in the low-temperature solvent system that mass fraction is 4.2%LiOH/12% urea
In, wherein cotton pulp cellulose mass fraction is 4%, and mechanical strong stirring 30min carries out deaeration with centrifuge 10000r/min
Processing 20min obtains spinning solution, and spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure, obtains cellulose
Gelatinous fibre；The coagulating bath be containing mass fraction be 5% sulfuric acid and mass fraction be 5% sodium sulphate it is water-soluble
Liquid；The extruded velocity of the spinning solution is 3m/min；By cellulose gel glue fiber with the volume of 18m/min in coagulating bath
After speed is wound, immerses in the dilute sulfuric acid that ageing liquid mass fraction is 0.5% and be aged 20min at normal temperatures, keep its complete
Full gelation；After ageing, fiber is washed with deionized to neutrality, is immersed in methyltriethoxysilane colloidal sol, stirring
30min, after taking-up remove surface colloidal sol, immerse 0.01mol/L oxalic acid solutions in room temperature be aged 7 days, realize from orthosilicic acid to
SiO2The transformation of network is formed simultaneously a large amount of holes.After ageing, fiber is washed with deionized to neutrality, then is set with ethyl alcohol
Deionized water is changed, through supercritical drying to get cellulose aerogels fiber.The successive silk of spinning process, cellulose obtained/
SiO2Aeroge pulp freeness is 653m2/ g, most probable pore size 2nm.
Embodiment 6
Low temperature the thiocarbamide of treated cotton pulp cellulose is dispersed in mass fraction is 8%NaOH/8% urea/6.5% is molten
In agent system, wherein cotton pulp cellulose mass fraction is 6%, and mechanical strong stirring 30min is carried out with centrifuge 10000r/min
Deaeration processing 20min obtains spinning solution, and spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure, obtains fibre
The plain gelatinous fibre of dimension；The coagulating bath is the dilute acetic acid solution that mass fraction is 3%；The extruded velocity of the spinning solution
For 6m/min；After cellulose gel glue fiber is wound in coagulating bath with the winding speed of 24m/min, ageing liquid matter is immersed
It is aged 20min at normal temperatures in the spirit of vinegar that amount score is 0.5%, makes its complete gelation；After ageing, by fiber deionization
Water washing is immersed to neutrality in methyltrimethoxysilane colloidal sol, stirs 30min, and surface colloidal sol is removed after taking-up, is immersed
Room temperature is aged 7 days in 0.01mol/L oxalic acid solutions, is realized from orthosilicic acid to SiO2The transformation of network is formed simultaneously a large amount of holes.
After ageing, fiber is washed with deionized to neutrality, it is freeze-dried to get cellulose aerogels fiber.Spinning process connects
Continuous not fracture of wire, cellulose/SiO obtained2Aeroge pulp freeness is 325m2/ g, most probable pore size 7nm.
Embodiment 7
Treated, cotton pulp cellulose is dispersed in the low-temperature solvent system that mass fraction is 7%NaOH/12% urea,
Wherein cotton pulp cellulose mass fraction is 2%, and mechanical strong stirring 30min carries out deaeration processing with centrifuge 10000r/min
20min obtains spinning solution, and spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure, obtains cellulose gel
Fiber；The coagulating bath be containing mass fraction be 2% sulfuric acid and mass fraction be 3% sodium sulphate aqueous solution；Institute
The extruded velocity for the spinning solution stated is 3m/min；By cellulose gel glue fiber with the winding speed of 12m/min in coagulating bath
After being wound, immerses in the dilute sulfuric acid that ageing liquid mass fraction is 1% and be aged 15min at normal temperatures, make its complete gelation；
Fiber is washed with deionized to neutrality, is immersed in phenyltrimethoxysila,e colloidal sol, 30min is stirred, table is removed after taking-up
Face colloidal sol immerses room temperature in 0.01mol/L oxalic acid solutions and is aged 7 days, realizes from orthosilicic acid to SiO2The transformation of network, while shape
At a large amount of holes.After ageing, fiber is washed with deionized to neutrality, it is freeze-dried to get cellulose aerogels fiber.
The successive silk of spinning process, cellulose/SiO obtained2Aeroge pulp freeness is 310m2/ g, most probable pore size are
7nm。
Embodiment 8
Low temperature the thiocarbamide of treated cotton pulp cellulose is dispersed in mass fraction is 8%NaOH/8% urea/6.5% is molten
In agent system, wherein cotton pulp cellulose mass fraction is 7%, and mechanical strong stirring 30min is carried out with centrifuge 10000r/min
Deaeration processing 20min obtains spinning solution, and spinning solution is expressed into coagulating bath and carries out wet spinning under normal temperature and pressure, obtains fibre
The plain gelatinous fibre of dimension；The coagulating bath is that mass fraction is 1% dilute acetic acid solution；The extruded velocity of the spinning solution is
4.8m/min；After cellulose gel glue fiber is wound in coagulating bath with the winding speed of 18m/min, ageing liquid matter is immersed
It is aged 15min at normal temperatures in the spirit of vinegar that amount score is 1%, makes its complete gelation；After ageing, by fiber deionized water
Washing immerses obtained cellulose gel glue fiber in sodium silicate colloidal sol to neutrality, stirs 30min, surface is removed after taking-up
Colloidal sol immerses room temperature in 0.1mol/L oxalic acid solutions and is aged 2 days, realizes from orthosilicic acid/sodium metasilicate to SiO2The transformation of network, together
When form a large amount of holes.After ageing, fiber is washed with deionized to neutrality, it is freeze-dried to get cellulose aerogels
Fiber.The successive silk of spinning process, cellulose/SiO obtained2Aeroge pulp freeness is 397m2/ g, most probable hole
Diameter is 7nm.
Claims (11)
1. a kind of back loading SiO2Prepare high-specific surface area continuous cellulose/SiO2The method of airsetting glue fiber, which is characterized in that
Include the following steps：
Step 1)：Cellulose dispersion liquid is prepared as spinning solution, acid solution, ethanol solution or acetone are added in coagulating basin
Solution is as coagulating bath；
Step 2)：Spinning solution prepared by step 1) is expressed into the coagulating bath of step 1), wet spinning is carried out, obtains fiber
Plain gelatinous fibre；
Step 3)：The cellulose gel glue fiber that step 2) obtains is wound in coagulating bath, the fiber after winding is immersed in old
Change in solution, room temperature is aged 15min~1h, and the fiber after ageing is washed with deionized to neutrality, silicate or silicon are immersed
Removal surface colloidal sol is taken out in alcosol, after stirring, is immersed room temperature in aged solution and is aged 2~10 days, is washed with deionized
To neutrality, solvent displacement is carried out with deionized water, ethyl alcohol or the tert-butyl alcohol, it is dry, obtain continuous cellulose/SiO2Aeroge is fine
Dimension.
2. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that the cellulose that cellulose dispersion liquid uses in the step 1) for cotton pulp cellulose or bacteria cellulose,
Mass concentration in cellulose dispersion liquid is 2%~7%.
3. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that the dispersant that cellulose dispersion liquid uses in the step 1) is urinated for mass fraction 4.2%LiOH/12%
Element, the thiocarbamide of 7%NaOH/12% urea, 9.5%NaOH/4.5% thiocarbamides or 7%~8%NaOH/8% urea/6.5%~10%
System.
4. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that acid solution uses mass fraction for 2%~5% sulfuric acid, 3~5% aqueous sodium sulfates in the step 1)
Liquid or 1%~3% dilute acetic acid solution；Ethanol solution use volume fraction for 10%~50% ethanol water；Acetone soln
Use volume fraction for 10%~30% aqueous acetone solution.
5. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that the condition of wet spinning is normal temperature and pressure in the step 2).
6. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that the extruded velocity of spinning solution is 0.6m/min~6m/min in the step 2).
7. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that the speed wound in the step 2) is 0.6m/min~24m/min.
8. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that aged solution is 0.5%~1% dilute sulfuric acid in terms of mass concentration, 0.5%~1% in the step 3)
Dilute acetic acid solution, straight alcohol solution or pure acetone solution.
9. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that silicate is sodium silicate, nine water sodium metasilicate or potassium water glass in the step 3)；Silanol colloidal sol is just
Silester, phenyltrimethoxysila,e, methyltrimethoxysilane or methyltriethoxysilane hydrolytic sol.
10. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that aged solution uses molar concentration for the oxalic acid of 0.005mol/L~0.01mol/L in the step 3).
11. back loading SiO as described in claim 12Prepare high-specific surface area continuous cellulose/SiO2The side of airsetting glue fiber
Method, which is characterized in that dry in the step 3) is specially freeze-drying or supercritical drying.
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| CN109487537B (en) * | 2018-10-22 | 2021-01-26 | 内蒙古科技大学 | High-strength cellulose/SiO2Preparation method of composite aerogel long fiber |
| CN114855291A (en) * | 2021-02-03 | 2022-08-05 | 河南爱彼爱和新材料有限公司 | cellulose/SiO 2 Hybrid aerogel fibers and methods of making the same |
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