CN106048741A - Method for preparing cellulose fibers by dry-wet spinning - Google Patents
Method for preparing cellulose fibers by dry-wet spinning Download PDFInfo
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- CN106048741A CN106048741A CN201610556038.6A CN201610556038A CN106048741A CN 106048741 A CN106048741 A CN 106048741A CN 201610556038 A CN201610556038 A CN 201610556038A CN 106048741 A CN106048741 A CN 106048741A
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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
- D01D11/00—Other features of manufacture
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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
- 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
- D01D5/12—Stretch-spinning methods
- D01D5/14—Stretch-spinning methods with flowing liquid or gaseous stretching media, e.g. solution-blowing
-
- 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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- Textile Engineering (AREA)
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for preparing cellulose fibers by dry-wet spinning. The method comprises the following steps: dissolving cellulose fibers in phosphoric acid/polyphosphoric acid compound solution and preparing the original liquid glue in the liquid crystal state by using a double-screw extruder; preheating the original liquid glue and then feeding to a metering pump; adjusting glue feeding quantity; spraying out the original liquid glue through a spinneret plate; allowing the original liquid glue to be subjected to air bath, first coagulating bath and second coagulating bath successively, wherein the air gap is 3-50mm and a solution comprising three components is used in each of the first coagulating bath and the second coagulating bath; carrying out water washing, neutralization, hot water washing, oil applying, drying, winding and the like to prepare the finished fire. The method is characterized in that filament spinning and forming time is short; filaments are formed quite uniformed; production efficiency is high, the fiber index is excellent and the like; no by-product is generated; the environment is less polluted; and cost is low.
Description
Technical field
The invention belongs to textile field, specifically, relate to a kind of method that dry-wet spinning prepares cellulose fibre.
Background technology
Cellulose is the natural polymer that reserves are the abundantest in the world, is widely present in the Nature.Trees,
The plant even secretions of some antibacterials such as Cotton Gossypii, wheat straw, rice straw, Semen Maydis, phragmites communis, bamboo, fiber crops, Cortex Mori, Folium et Cacumen Broussonetiae Kazinoki, Caulis Sacchari sinensis all contain
There is substantial amounts of cellulose.Along with the worsening shortages of petroleum resources, the utilization to cellulose increasingly comes into one's own, at energy shortage
Today, cellulose fibre has irreplaceable status.
Cellulose fibre has a good skin contact, snugness of fit, physiological security, hygroscopicity and easy arrangement property
And a series of synthetic fibers such as its easy biological decomposition of goods are cannoted the characteristic possessed completely, thus it is former with cellulose fibre
The non-weaving cloth of material has the purposes of uniqueness at medical treatment, nursing, hygienic article, cosmetic product and other industrial circle.In Europe
The developed country such as beautiful, Japanese, cellulose fibre, as a kind of important non-weaving cloth raw material, is widely used.
Cellulosic molecule degree of crystallinity is high, and strand rigidity is strong, and difficulty common solvent directly dissolves.At present, it has been found that have
Many solvents can dissolve cellulose, but also exists that course of dissolution is numerous and diverse, pollute environment and high in cost of production problem, such as the patent No.
The preparation technology of the spinning solution of cellulose fiber by solvent method disclosed in the Chinese patent of ZL02151225.6, uses N-methyl
Morpholine oxide (NMMO) aqueous solution is solvent, expensive, is unfavorable for industrialization promotion.
The spinning technique of cellulose fibre can use tradition spinning technique.The China of Application No. 201510263948.0 is specially
Profit discloses the wet spinning process of a kind of cellulose fiber by solvent method, is with cotton pulp, wood pulp or Populus deltoides slurry as raw material, and alkali/
Carbamide/water three component or alkali/urea/sulphur urea/water four component are solvent, are prepared as spinning solution, and warp through low temperature continuous-dissolution
Filtration, deaeration, then prepare through wet spinning.The method uses wet spinning, and technological process is complicated, and investment is big, spinning speed
Slowly, production efficiency is low, and cost is high.
The Chinese patent of Application No. CN201210238084.3 discloses the liquid crystal of a kind of regenerated bacterial cellulose fiber
Spinning process, including: (1) by Bacterial cellulose dissolve in a solvent, be made into mass fraction be 5%～27%, temperature be 35-
The bacterial cellulose solution of 100 DEG C, filters, deaeration, obtains spinning solution；(2) by step (1) spinning solution by fiber spinning from crystalline state side
Method is solidified into strand；Wash subsequently, stretch, be dried, heat treatment, obtain regenerated bacterial cellulose fiber.The method uses dry and wet
Method spinning, but use organic solvent and ion liquid solvent, equal environmental pollution is bigger.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, it is therefore intended that provide one to pass through dry and wet
The method of cellulose fibre is prepared in method spinning, and it is short that the method has the spinning technique time, shapes evenly, and production efficiency is high, fine
The features such as dimension indicator is superior, and use nontoxic solvent, with low cost, environmentally safe.
For solving above-mentioned technical problem, the present invention uses the basic conception of technical scheme to be:
A kind of dry-wet spinning prepares the method for cellulose fibre, it is characterised in that preparation process is as follows:
(1) cellulose is mixed with phosphoric acid/polyphosphoric acids composite solution, be prepared as by double screw extruder mesomorphic
Stock solution glue；
(2) the stock solution glue preheating described in step (1) is fed in dosing pump, adjusts into glue amount, spray through spinneret；
(3) passing sequentially through air bath, the first coagulating bath and the second gelation and form nascent strand, wherein the air gap is 3
～50mm, described first coagulating bath and the second gelation are three component solutions；
(4) again by washing, neutralization, hot water wash, oil, dry, operation and then the prepared finished fiber such as winding.
Owing to cellulose is difficult in direct solvent formation, there is the anisotropic solution of excellent mechanical property, need to select
Suitably solvent and technique can greatly improve the technique dissolving cellulose, and step of the present invention have employed cellulose in (1)
The phosphoric acid that solvability is strong/polyphosphoric acids composite solution system coordinates double screw extruder, can destroy fiber within a short period of time
The intramolecular of element and intermolecular hydrogen bonding so that cellulose can fully dissolve within a short period of time, when significantly shortening technique
Between, and form the anisotropic solution with excellent mechanical property, obtain liquid crystal state spinning virgin rubber, for obtaining high intensity, Gao Mo
Amount, the cellulose fibre of good combination property provide condition.
In wet-dry change, the length of air layer has considerable influence to the total draft multiple of fiber.When air layer length is excessive,
From the impact of tension force suffered by deadweight and solidification drawing-off of the thread of spinneret orifice ejection, fracture of wire phenomenon occurs, and air layer length is spent
Hour, coagulating bath easily produces siphon, makes spinning be difficult to normal table and carries out.By between air in wet-dry change step (2) of the present invention
Gap controls 3～50mm, makes the mesomorphic spinning solution glue of the present invention can carry out optimum after spinning head in air layer
Stretching, increase the degree of orientation.
Through two step coagulating baths in step of the present invention (3), the first step and second step coagulating bath component ratio and temperature are the most not
Identical.The present invention, through test of many times, has obtained optimal spinning curing condition, and cellulose fibre so can be made in the first step
The more complete spatial skeleton of very fast formation in coagulating bath, in second coagulating bath, the uncured shaped portion of fiber improves,
Thus be beneficial to improve the drafting multiple of fiber, and the fracture strength of fiber is greatly improved.
Wherein, three component solutions in described step (3) include that water, phosphoric acid and organic solvent, described organic solvent are third
One in ketone, ethanol, normal propyl alcohol, ethyl acetate, ethylene glycol.
In described first coagulating bath, the volume of organic solvent is the 10%～85% of three component solution volumes, preferably 30%～
80%, the temperature of the first coagulating bath is 5 DEG C～45 DEG C.
In described the second gelation, the volume of organic solvent is the 5%～50% of three component solution volumes, preferably 20%～
40%, the temperature of the second gelation is 10～40 DEG C.
In described step (1), the degree of polymerization of cellulose is 500～1000, and the water content of cellulose is 1%～10%.
The cellulose described in described step (1) mass percent in double solvents is 10～30%, controls fiber
Element content in material, plays the most crucial effect to solution property.
P in phosphoric acid/polyphosphoric acids composite solution in described step (1)2O5Weight/mass percentage composition be 72～80%.
Preferred 5mm～30mm in the air gap in described step (3).
Neutralization in described step (4) refers to that fiber is 0.1-5% sodium carbonate or sodium hydroxide solution by concentration, to go
Phosphoric acid except fiber surface.
Washing in described step (4) refers to that fiber passes through 15～50 DEG C of water-baths, removes the salt on fiber and solvent.
Whole preparation process, spinning speed is 20～400m/min
The fiber number of described finished fiber is 1.1～6.6dtex, and dry fracture strength is 3.2～9.4cN/dtex, extension at break
Rate is 4.0～11%；Regain is 5.0～13%, and drafting multiple is 1～20.
After using technique scheme, the present invention compared with prior art has the advantages that
(1) present invention employs the phosphoric acid/polyphosphoric acids composite solution system to cellulolytic capabilities is strong and coordinate pair spiral shell
Bar extruder, can destroy intramolecular and the intermolecular hydrogen bonding of cellulose within a short period of time so that cellulose can be when shorter
Interior fully dissolving, significantly shortens the process time.
(2) use the liquid crystal state cellulose dopes glue that the degree of polymerization is identical, make fiber can obtain under relatively low draw ratio
The higher degree of orientation, it is to avoid fiber, under high stretching ratio, produces internal stress and damage fiber, it is hereby achieved that high intensity,
High-modulus, the fiber of good combination property.
(3) present invention uses suitable the air gap and two step coagulating bath methods, makes the fibre forming time short and uniform, drawing-off
Multiple and dry fracture strength are greatly improved, and spinning speed is fast, and production efficiency is high.
(4) solvent that the present invention uses is phosphoric acid, water etc., and no coupling product generates, low in the pollution of the environment, with low cost.
Detailed description of the invention
By embodiment, technical scheme is further described below, it will help the technical side to the present invention
The advantage of case, effect have further to be understood, and embodiment does not limit protection scope of the present invention, protection scope of the present invention by
Claim determines.
Clearing point is that solution is transformed into the transition temperature of isotropic state by anisotropic states, and cellulose spinning is former
Liquid has good mechanical property when having anisotropy.Therefore research cellulose weight/mass percentage composition, P2O5Percent mass contains
The amount impact on spinning solution clearing point.
The reason of variable concentrations cellulose and the advantage of double screw extruder is used, test in order to the present invention is better described
Example 1～7 have employed the content of cellulose of variable concentrations, and comparative example 1～7 is being selected and test example 1～7 identical fibre cellulose content
In the case of employ kneader as spinning equipment, specific as follows:
Test example 1～7
Be separately added into the degree of polymerization be 700, moisture content be 7%, weight/mass percentage composition be 5%, 10%, 15%, 20%,
25%, the cellulose of 30%, 35%, P2O5The phosphoric acid that weight/mass percentage composition is 74%/polyphosphoric acids composite solution, twin screw
Extruder operating temperature is-10～35 DEG C, and the process time is 15 minutes, and step is with embodiment 1.
Comparative example 1
By P2O5The double solvents of phosphoric acid/polyphosphoric acids that weight/mass percentage composition is 74% join in kneader, pre-cooling
To 5 DEG C, be then mixed into the degree of polymerization be 700, aqueous be 1% cellulose, make cellulose percent mass in double solvents contain
Amount is 5%, mediates mixing 5 minutes, then heats to 35 DEG C, and mediate 10 minutes.
Comparative example 2～7
Be separately added into the degree of polymerization be 700, moisture content be 1%, weight/mass percentage composition be 10%, 15%, 20%, 25%,
30%, the cellulose of 35%, P2O5The phosphoric acid that weight/mass percentage composition is 74%/polyphosphoric acids composite solution, kneader work temperature
Degree is for-10～35 DEG C, and the process time is 15 minutes, and step is with comparative example 1.
Clearing point is that solution is transformed into the transition temperature of isotropic state by anisotropic states, and cellulose spinning is former
Liquid has good mechanical property when having anisotropy.Therefore research cellulose weight/mass percentage composition, P2O5Percent mass contains
The amount impact on spinning solution clearing point.
One, the research cellulose weight/mass percentage composition impact on clearing point,
By comparative example 1～7 and the clearing point of cellulose spin dope for preparing of test example 1～7 contrast, acquired results
As shown in table 1.
Table 1 cellulose weight/mass percentage composition affects result to spinning solution clearing point
| Scheme | Content of cellulose | Clearing point (DEG C) | Scheme | Content of cellulose | Clearing point (DEG C) |
| Test example 1 | 5% | 38.4 | Comparative example 1 | 5% | 23.8 |
| Test example 2 | 10% | 58.2 | Comparative example 2 | 10% | 41.8 |
| Test example 3 | 15% | 71.6 | Comparative example 3 | 15% | 58.6 |
| Test example 4 | 20% | 78.5 | Comparative example 4 | 20% | 67.4 |
| Test example 5 | 25% | 84.2 | Comparative example 5 | 25% | 73.1 |
| Test example 6 | 30% | 86.0 | Comparative example 6 | 30% | 75.2 |
| Test example 7 | 35% | 86.3 | Comparative example 7 | 35% | 75.9 |
As shown in Table 1, in the case of other experiment conditions are identical, along with the increase of cellulose percentage composition, spinning is former
The clearing point of liquid gradually rises, and cellulose weight/mass percentage composition is interval in 5～10% to be risen substantially, and ascendant trend 30～
Tending towards stability in 35% interval, therefore choosing 10～30% is optimum concentration range；Simultaneously from table 1, in cellulose concentration phase
In the case of Tong, the clearing point of embodiment is above the clearing point of comparative example, it can thus be appreciated that compare kneader, and double screw extruder
The cellulose spin dope made has more stable liquid crystal state, has more excellent mechanical property.
The reason of variable concentrations phosphoric acid/polyphosphoric acids composite solution and twin screw is used to squeeze in order to the present invention is better described
Going out the advantage of machine, test example 8～14 have employed the phosphoric acid/polyphosphoric acids composite solution of variable concentrations, and comparative example 8～14 is being selected
Kneader is employed as spinning equipment in the case of phosphoric acid identical with embodiment 11～17/polyphosphoric acids composite solution concentration,
Specific as follows:
Test example 8～14
It is separately added into P2O5The phosphoric acid that weight/mass percentage composition is 70%, 72%, 74%, 76%, 78%, 80%, 82%/
Polyphosphoric acids composite solution, the degree of polymerization is 700, moisture content is 10%, weight/mass percentage composition is the cellulose of 15%, and twin screw squeezes
Going out machine operating temperature and be-20～35 DEG C, the process time is 15 minutes, and step is with embodiment 1.
Comparative example 8～14
It is separately added into P2O5The phosphoric acid that weight/mass percentage composition is 70%, 72%, 74%, 76%, 78%, 80%, 82%/
Polyphosphoric acids composite solution, the degree of polymerization is 700, moisture content is 10%, weight/mass percentage composition is the cellulose of 15%, kneader work
Making temperature and be-20～35 DEG C, the process time is 15 minutes, and step is with comparative example 1.
Two, P2O5The weight/mass percentage composition impact on spinning solution clearing point
By comparative example 8～14 and the clearing point of cellulose spin dope for preparing of test example 8～14 contrast, gained is tied
Fruit is as shown in table 2.
Table 2 P2O5Weight/mass percentage composition affects result to spinning solution clearing point
| Scheme | P2O5Content | Clearing point (DEG C) | Scheme | P2O5Content | Clearing point (DEG C) |
| Test example 8 | 70% | 54.3 | Comparative example 8 | 70% | 52.1 |
| Test example 9 | 72% | 60.8 | Comparative example 9 | 72% | 58.8 |
| Test example 10 | 74% | 67.3 | Comparative example 10 | 74% | 63.7 |
| Test example 11 | 76% | 71.8 | Comparative example 11 | 76% | 66.9 |
| Test example 12 | 78% | 73.4 | Comparative example 12 | 78% | 68.9 |
| Test example 13 | 80% | 73.6 | Comparative example 13 | 80% | 69.1 |
| Test example 14 | 82% | 72.8 | Comparative example 14 | 82% | 67.8 |
As shown in Table 2, in the case of other experiment conditions are identical, along with P2O5The increase of weight/mass percentage composition, spinning is former
The clearing point of liquid gradually rises, P2O5Weight/mass percentage composition is obvious in the interval ascendant trend in 70～72%, and goes out when arriving 80%
Existing flex point, works as P2O5Weight/mass percentage composition is slow downward trend 80～82% time interval, traces it to its cause, is due to cellulose
Concentration raises and causes solution system viscosity to increase, and within the same process time, the decline of the solubility property of cellulose is caused,
Therefore choosing 72～80% is optimum concentration range；Simultaneously from table 2, at P2O5In the case of weight/mass percentage composition is identical, real
The clearing point executing example is above the clearing point of comparative example, it can thus be appreciated that compare kneader, and the cellulose that double screw extruder is made
Spinning solution has more stable liquid crystal state, has more excellent mechanical property.
Embodiment 1
(1) being 1% by water content, the degree of polymerization is that the cellulose dissolution of 500 is at P2O5The phosphorus that weight/mass percentage composition is 72%
In acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 10%, is prepared as mesomorphic former by double screw extruder
Sol；
(2) the cellulose dopes glue that has being preheated to 50 DEG C is fed in dosing pump, sets and spin speed 20m/min, pass through
Adjusting to set and necessarily enter glue amount, spray through spinneret, by air bath, wherein the air gap is 5mm, then through the first solidification
Bath and the second gelation form nascent strand.Wherein, in the first coagulating bath, the volume of ethanol is the 85% of three component solution volumes,
Temperature is 20 DEG C, and in the second gelation, the volume of ethanol is the 50% of three component solution volumes, and temperature is 10 DEG C；
(3) again by 15 DEG C of washings, 5% sodium hydroxide solution neutralization, 70 DEG C of hot water wash, oil, dry, the operation such as winding
And then prepared finished product.
The fibrous finished product fiber number finally given is 2.87dtex, and dry fracture strength is 8.31cN/dtex, and elongation at break is
11%；Elastic modelling quantity is 4.18cN/dtex；Regain is 13%, and drafting multiple is 12.6.
Embodiment 2
(1) being 10% by water content, the degree of polymerization is that the cellulose dissolution of 800 is at P2O5Weight/mass percentage composition be 80%
In phosphoric acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 20%, is prepared as mesomorphic by double screw extruder
Stock solution glue；
(2) the cellulose dopes glue that has being preheated to 45 DEG C is fed in dosing pump, sets and spin speed 150m/min, pass through
Adjusting to set and necessarily enter glue amount, spray through spinneret, by air bath, wherein the air gap is 50mm, then coagulates through first
Gu bath and the second gelation form nascent strand.Wherein, in the first coagulating bath, the volume of ethylene glycol is three component solution volumes
30%, temperature is 45 DEG C, and in the second gelation, the volume of ethylene glycol is the 30% of three component solution volumes, and temperature is 40 DEG C；
(3) again by 30 DEG C of washings, 2% sodium hydroxide solution neutralization, 80 DEG C of hot water wash, oil, dry, the operation such as winding
And then prepared finished product.
The fibrous finished product fiber number finally given is 5.86dtex, and dry fracture strength is 6.98cN/dtex, and elongation at break is
5.8%；Elastic modelling quantity is 2.21cN/dtex；Regain is 8.6%, and drafting multiple is 6.3.
Embodiment 3
(1) being 5% by water content, the degree of polymerization is that the cellulose dissolution of 1000 is at P2O5Weight/mass percentage composition be 78%
In phosphoric acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 30%, is prepared as mesomorphic by double screw extruder
Stock solution glue；
(2) the cellulose dopes glue that has being preheated to 70 DEG C is fed in dosing pump, sets and spin speed 250m/min, pass through
Adjusting to set and necessarily enter glue amount, spray through spinneret, by air bath, wherein the air gap is 30mm, then coagulates through first
Gu bath and the second gelation form nascent strand.Wherein, in the first coagulating bath, the volume of acetone is three component solution volumes
10%, temperature is 5 DEG C, and in the second gelation, the volume of acetone is the 5% of three component solution volumes, and temperature is 10 DEG C；
(3) again by 20 DEG C of washings, 2% sodium hydroxide solution neutralization, 90 DEG C of hot water wash, oil, dry, the operation such as winding
And then prepared finished product.
The fibrous finished product fiber number finally given is 1.1dtex, and dry fracture strength is 9.4cN/dtex, and elongation at break is
5.3%；Elastic modelling quantity is 4.75cN/dtex；Regain is 8.9%, and drafting multiple is 20.
Embodiment 4
(1) being 7% by water content, the degree of polymerization is that the cellulose dissolution of 700 is at P2O5The phosphorus that weight/mass percentage composition is 75%
In acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 20%, is prepared as mesomorphic former by double screw extruder
Sol；
(2) the cellulose dopes glue that has being preheated to 20 DEG C is fed in dosing pump, sets and spin speed 400m/min, pass through
Adjusting to set and necessarily enter glue amount, spray through spinneret, by air bath, wherein the air gap is 3mm, then through the first solidification
Bath and the second gelation form nascent strand.Wherein, in the first coagulating bath, the volume of acetone is the 80% of three component solution volumes,
Temperature is 15 DEG C, and in the second gelation, the volume of acetone is the 20% of three component solution volumes, and temperature is 20 DEG C；
(3) again by 15 DEG C of washings, the neutralization of 0.1%T sodium carbonate liquor, 85 DEG C of hot water wash, oil, dry, the work such as winding
Sequence and then prepared finished product.
The fibrous finished product fiber number finally given is 6.6dtex, and dry fracture strength is 3.2cN/dtex, and elongation at break is
4.0%；Elastic modelling quantity is 1.15cN/dtex；Regain is 5.0%, and drafting multiple is 1.
Test example 15
(1) being 5% by water content, the degree of polymerization is that the cellulose dissolution of 1000 is at P2O5Weight/mass percentage composition be 75%
In phosphoric acid/polyphosphoric acids composite solution, being prepared as mesomorphic stock solution glue by double screw extruder, in stock solution glue, cellulose contains
Amount is 20%；
(2) the cellulose dopes glue that has being preheated to 70 DEG C is fed in dosing pump, sets and spin speed 250m/min, pass through
Adjust to set and necessarily enter glue amount, spray through spinneret, bathed by air bath and two step normal propyl alcohols and form nascent strand, its hollow
Gas gap is 1mm, and in first step coagulating bath, the volume of normal propyl alcohol is the 55% of three component solution volumes, and temperature is 15 DEG C, second
In step coagulating bath, the volume of ethylene glycol is the 35% of three component solution volumes, and temperature is 10 DEG C.
(3) again by 25 DEG C of washings, 2% sodium hydroxide solution neutralization, 90 DEG C of hot water wash, oil, dry, the operation such as winding
And then prepared finished product.
Test example 16-test example 24
Test example 16-test example 24 respectively spinning air bath the air gap is respectively set to 3mm, 5mm, 10mm, 20mm,
30mm, 40mm, 50mm, 60mm and 80mm, other parameter is identical with test example 1 with preparation method.
Table 3 gained cellulose fibre performance parameter
As shown in Table 3, air layer length has certain impact to drawing of fiber multiple and fibre property.When air layer length is spent
Little or excessive time, spinning all cannot be normally carried out, such as test example 16 and test example 25.The drawing-off of test example 18-test example 21 times
Number and fibrous fracture intensity are better than test example 17-test example 23, and therefore selecting the air gap is 3mm～50mm, preferably 5～
30mm。
Test example 25-test example 32
Spinning process is identical with test example 15, and the air gap is 30mm, and other condition is shown in Table 4.
Table 4 first coagulation bath condition and fibre property
As shown in Table 4, test example 25-test example 30 fibre property is substantially better than test example 31-32, therefore selects first to coagulate
Gu in Yu, the volumetric concentration of normal propyl alcohol is 10%～85%, preferably 30%～80%, temperature is 5～45 DEG C.
Other organic solvents such as acetone, ethanol, ethyl acetate, ethylene glycol, the result obtained is used in the first coagulating bath
Similar to the above results.
Comparative example 15
(1) being 5% by water content, the degree of polymerization is that the cellulose dissolution of 1000 is at P2O5Weight/mass percentage composition be 75%
In phosphoric acid/polyphosphoric acids composite solution, being prepared as mesomorphic stock solution glue by double screw extruder, in stock solution glue, cellulose contains
Amount is 20%；
(2) the cellulose dopes glue that has being preheated to 70 DEG C is fed in dosing pump, sets and spin speed 250m/min, pass through
Adjust to set and necessarily enter glue amount, spray through spinneret, bathed by air bath and a step normal propyl alcohol and form nascent strand, its hollow
Gas gap is 30mm, and the volume of normal propyl alcohol is the 55% of three component solution volumes, and temperature is 10 DEG C.
(3) again by 25 DEG C of washings, 30% sodium hydroxide solution neutralization, 90 DEG C of hot water wash, oil, dry, the work such as winding
Sequence and then prepared finished product.
Test example 33-test example 40
Test example 33-test example 40 spinning process is identical with comparative example 15, but through the second gelation normal propyl alcohol, second coagulates
Admittedly bath condition is shown in Table 5.
Table 5 Second Gelation Condition and fibre property
As shown in Table 5, with compared with the comparative example 15 of the second gelation, test example 33-test example 40 fiber is dry disconnected
Resistance to spalling and elongation at break are considerably higher, have remarkable result hence with two step coagulating bath spinning for fibre property raising,
And when the second gelation concentration is 5%～50%, and preferably 20%～40%, when temperature is 10～40 DEG C, fibre property is best.
Other organic solvents such as acetone, ethanol, ethyl acetate, ethylene glycol, the result obtained is used in the second gelation
Similar to the above results.
The above is only presently preferred embodiments of the present invention, and the present invention not makees any pro forma restriction, though
So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any technology people being familiar with this patent
Member is in the range of without departing from technical solution of the present invention, when the technology contents of available above-mentioned prompting is made a little change or is modified to
The Equivalent embodiments of equivalent variations, as long as being the content without departing from technical solution of the present invention, according to the technical spirit pair of the present invention
Any simple modification, equivalent variations and the modification that above example is made, all still falls within the range of the present invention program.
Claims (10)
1. the method that a dry-wet spinning prepares cellulose fibre, it is characterised in that preparation process is as follows:
(1) cellulose is mixed with phosphoric acid/polyphosphoric acids composite solution, be prepared as mesomorphic stock solution by double screw extruder
Glue；
(2) the stock solution glue preheating described in step (1) is fed in dosing pump, adjusts into glue amount, spray through spinneret；
(3) pass sequentially through air bath, the first coagulating bath and the second gelation and form nascent strand, wherein the air gap be 3～
50mm, described first coagulating bath and the second gelation are three component solutions；
(4) pass through washing, neutralization, hot water wash again, oil, drying, rolling step and then prepared finished fiber.
The method that a kind of dry-wet spinning the most according to claim 1 prepares cellulose fibre, it is characterised in that step
(3) three component mixed liquors described in include that water, phosphoric acid and organic solvent, described organic solvent are acetone, ethanol, normal propyl alcohol, second
One in acetoacetic ester or ethylene glycol.
The method that a kind of dry-wet spinning the most according to claim 2 prepares cellulose fibre, it is characterised in that described
In one coagulating bath, the volume of organic solvent is the 10%～85% of three component solution volumes, preferably 30%～80%, the first solidification
The temperature of bath is 5 DEG C～45 DEG C.
The method that a kind of dry-wet spinning the most according to claim 2 prepares cellulose fibre, it is characterised in that described
In two coagulating baths, the volume of organic solvent is the 5%～50% of three component solution volumes, preferably 20%～40%, the second gelation
Temperature be 10～40 DEG C.
The method that a kind of dry-wet spinning the most according to claim 1 prepares cellulose fibre, it is characterised in that described step
Suddenly in (1), the degree of polymerization of cellulose is 500～1000, and the water content of cellulose is 1%～10%.
The method that a kind of dry-wet spinning the most according to claim 1 prepares cellulose fibre, it is characterised in that described step
Suddenly the mass fraction in double solvents of the cellulose described in (1) is 10～30%.
The method that a kind of dry-wet spinning the most according to claim 1 prepares cellulose fibre, it is characterised in that described step
Suddenly P in phosphoric acid/polyphosphoric acids composite solution in (1)2O5Weight/mass percentage composition be 72～80%.
The method that a kind of dry-wet spinning the most according to claim 1 prepares cellulose fibre, it is characterised in that described step
Suddenly the air gap in (3) is 5mm～30mm.
The method preparing cellulose fibre by dry-wet spinning the most according to claim 1, it is characterised in that described step
Suddenly the neutralization in (4) refers to that fiber is by sodium carbonate that concentration is 0.1-5% or sodium hydrate aqueous solution.
The method that a kind of dry-wet spinning the most according to claim 1 prepares cellulose fibre, it is characterised in that described
The fiber number of finished fiber is 1.1～6.6dtex, and dry fracture strength is 3.2～9.4cN/dtex, elongation at break be 4.0～
11%；Regain is 5.0～13%, and drafting multiple is 1～20.
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