CN106048741B - A kind of method that dry-wet spinning prepares cellulose fibre - Google Patents
A kind of method that dry-wet spinning prepares cellulose fibre Download PDFInfo
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- CN106048741B CN106048741B CN201610556038.6A CN201610556038A CN106048741B CN 106048741 B CN106048741 B CN 106048741B CN 201610556038 A CN201610556038 A CN 201610556038A CN 106048741 B CN106048741 B CN 106048741B
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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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Abstract
The invention discloses a kind of method that dry-wet spinning prepares cellulose fibre, preparation step is as follows: by cellulose dissolution in phosphoric acid/polyphosphoric acids composite solution, the stoste glue of liquid crystal state is prepared by double screw extruder；The preheating of stoste glue is fed in metering pump, is adjusted into glue amount, is sprayed by spinneret；Then air bath and the first coagulating bath are passed sequentially through and the second gelation forms nascent strand, wherein the air gap is 3~50mm, and the first coagulating bath and the second gelation are three component solutions；Again by washing, neutralization, hot water wash, oil, the processes finished product fiber in turn such as dry, wind.The features such as this method has the spinning technique time short, shapes more evenly, high production efficiency, fiber index is superior, and no coupling product generates, environmental pollution is small, low in cost.
Description
Technical field
The invention belongs to textile fields, specifically, being related to a kind of method that dry-wet spinning prepares cellulose fibre.
Background technique
Cellulose is the most abundant natural polymer of reserves in the world, is widely present in the Nature.Trees,
All contain in the plants such as cotton, wheat straw, rice straw, corn, reed, bamboo, fiber crops, mulberry skin, paper mulberry skin, the sugarcane even secretion of some bacteriums
There is a large amount of cellulose.With the worsening shortages of petroleum resources, increasingly it is taken seriously to the utilization of cellulose, in energy shortage
Today, cellulose fibre have irreplaceable status.
Cellulose fibre have good skin contact, snugness of fit, physiological security, hygroscopicity and easily arrange property
And the characteristic that a series of synthetic fibers such as easy biological decomposition of its product can not have completely, thus with cellulose fibre be original
The non-woven cloth of material has unique purposes in medical treatment, nursing, amenities, cosmetic product and other industrial circles.In Europe
The developed countries such as beauty, Japan, cellulose fibre have been used as a kind of important non-woven cloth raw material, have been widely used.
Cellulosic molecule crystallinity is high, and molecule chain rigidity is strong, and hardly possible is directly dissolved with common solvent.At present, it has been found that have
Many solvents can dissolve cellulose, but that there is course of dissolution is many and diverse, pollution environment and it is at high cost the problems such as, such as patent No.
The preparation process of the spinning solution of cellulose fiber by solvent method disclosed in Chinese patent for ZL02151225.6, using N- methyl
Morpholine oxide (NMMO) aqueous solution is solvent, expensive, is unfavorable for industrialization promotion.
Traditional spinning technique can be used in the spinning technique of cellulose fibre.Application No. is 201510263948.0 China specially
Benefit discloses a kind of wet spinning process of cellulose fiber by solvent method, be using cotton pulp, wood pulp or Populus deltoides slurry as raw material, alkali/
Three component of urea/water or alkali/urea/sulphur urea/four groups of water are divided into solvent, are prepared into spinning solution through low temperature continuous-dissolution, and pass through
Filtering, deaeration, then be made through wet spinning.This method uses wet spinning, and process flow is complicated, and investment is big, spinning speed
Slowly, production efficiency is low, at high cost.
Application No. is the Chinese patents of CN201210238084.3 to disclose a kind of liquid crystal of regenerated bacterial cellulose fiber
Spinning process, comprising: (1) by bacteria cellulose dissolution in a solvent, be made into mass fraction be 5%~27%, temperature 35-
100 DEG C of bacterial cellulose solution, filtering, deaeration obtain spinning solution；(2) step (1) spinning solution is passed through into fiber spinning from crystalline state side
Method is solidified into strand；Then washing, stretching, dry, heat treatment, obtain regenerated bacterial cellulose fiber.This method uses dry and wet
Method spinning, but organic solvent and ion liquid solvent are used, equal environmental pollution is larger.
Summary of the invention
The technical problem to be solved in the present invention is that overcome the deficiencies in the prior art is, and it is an object of the present invention to provide one kind passes through dry and wet
The method that method spinning prepares cellulose fibre, this method have the spinning technique time short, and more evenly, high production efficiency is fine for forming
The features such as index is superior is tieed up, and uses nontoxic solvent, low in cost, no pollution to the environment.
In order to solve the above technical problems, the present invention is using the basic conception of technical solution:
A kind of method that dry-wet spinning prepares cellulose fibre, which is characterized in that preparation step is as follows:
(1) cellulose is mixed with phosphoric acid/polyphosphoric acids composite solution, liquid crystal state is prepared by double screw extruder
Stoste glue；
(2) preheating of stoste glue described in step (1) is fed in metering pump, adjusts into glue amount, is sprayed by spinneret；
(3) air bath, the first coagulating bath and the second gelation are passed sequentially through and forms nascent strand, wherein the air gap is 3
~50mm, first coagulating bath and the second gelation are three component solutions；
(4) again by washing, neutralization, hot water wash, oil, the processes finished product fiber in turn such as dry, wind.
Since cellulose is difficult to form the anisotropic solution with excellent mechanical property in direct solvent, need to select
Suitable solvent and technique can greatly improve the technique of dissolution cellulose, use in step (1) of the present invention to cellulose
The strong phosphoric acid of solvability/polyphosphoric acids composite solution system cooperates double screw extruder, can destroy fiber within a short period of time
The intramolecular and intermolecular hydrogen bonding of element, enable cellulose sufficiently to dissolve within a short period of time, when significantly shortening technique
Between, and the anisotropic solution with excellent mechanical property is formed, liquid crystal state spinning virgin rubber is obtained, to obtain high-intensitive, Gao Mo
It measures, the cellulose fibre of good combination property provides condition.
The length of air layer has larger impact to the total draft multiple of fiber in wet-dry change.When air layer length is excessive,
There is fracture of wire phenomenon as being self-possessed and solidifying the influence of tension suffered by drawing-off in the thread sprayed from spinneret orifice, and air layer length is spent
Hour, coagulating bath is easy to produce siphon, and spinning is made to be difficult to normal table progress.It will be between air in wet-dry change step (2) of the present invention
Gap is controlled in 3~50mm, makes the spinning solution glue of liquid crystal state of the invention that can carry out optimum in air layer after spinning head
Stretching, increase the degree of orientation.
Pass through two step coagulating baths in step (3) of the present invention, the first step and the second step coagulating bath component ratio and temperature are not
It is identical.The present invention passes through test of many times, has obtained optimal spinning curing condition, cellulose fibre can have been made in the first step in this way
More complete spatial skeleton is comparatively fast formed in coagulating bath, the uncured shaped portion of fiber improves in second coagulating bath,
To be conducive to improve the drafting multiple of fiber, and the breaking strength of fiber greatly improves.
Wherein, three component solutions in the step (3) include water, phosphoric acid and organic solvent, and the organic solvent is third
One of ketone, ethyl alcohol, normal propyl alcohol, ethyl acetate, ethylene glycol.
In first coagulating bath volume of organic solvent be three component solution volumes 10%~85%, preferably 30%~
80%, the temperature of the first coagulating bath is 5 DEG C~45 DEG C.
In the second gelation volume of organic solvent be three component solution volumes 5%~50%, preferably 20%~
40%, the temperature of the second gelation is 10~40 DEG C.
The degree of polymerization of cellulose is 500~1000 in the step (1), and the water content of cellulose is 1%~10%.
Mass percent of the cellulose in double solvents described in the step (1) is 10~30%, controls fiber
Content of the element in material, very crucial effect is played to solution property.
P in phosphoric acid/polyphosphoric acids composite solution in the step (1)2O5Mass percentage be 72~80%.
Preferred 5mm~the 30mm in the air gap in the step (3).
It is 0.1-5% sodium carbonate or sodium hydroxide solution that neutralization in the step (4), which refers to that fiber passes through concentration, to go
Except the phosphoric acid of fiber surface.
Washing in the step (4) refers to that fiber by 15~50 DEG C of water-baths, removes salt and solvent on fiber.
Whole preparation process, spinning speed are 20~400m/min
The fiber number of the finished fiber is 1.1~6.6dtex, and doing breaking 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 adopting the above technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) present invention employs cooperate double spiral shells to the strong phosphoric acid of cellulolytic capabilities/polyphosphoric acids composite solution system
Bar extruder can destroy the intramolecular and intermolecular hydrogen bonding of cellulose within a short period of time, enable cellulose when shorter
Interior abundant dissolution, significantly shortens the process time.
(2) the identical liquid crystal state cellulose dopes glue of the degree of polymerization is used, obtains fiber under lower draw ratio
The higher degree of orientation avoids fiber under high stretching ratio, generates internal stress and damage fiber, it is hereby achieved that high-intensitive,
The fiber of high-modulus, good combination property.
(3) present invention keeps the fibre forming time short and uniform, drawing-off using suitable the air gap and two step coagulating bath methods
Multiple and dry breaking strength greatly improve, and spinning speed is fast, high production efficiency.
(4) solvent that the present invention uses is phosphoric acid, water etc., and no coupling product generates, low in the pollution of the environment, low in cost.
Specific embodiment
With embodiment, further description of the technical solution of the present invention below, it will help to technical side of the invention
, there are further understanding in the advantages of case, effect, and the scope of protection of the present invention is not limited for embodiment, protection scope of the present invention by
Claim determines.
Clearing point is the transition temperature that solution is transformed into isotropic state by anisotropic states, and cellulose spinning is former
Liquid possesses good mechanical property when with anisotropy.Therefore research cellulose mass percentage, P2O5Quality percentage contains
Measure the influence to spinning solution clearing point.
The advantage of the reason of using various concentration cellulose in order to better illustrate the present invention and double screw extruder, test
Example 1~7 uses the content of cellulose of various concentration, and comparative example 1~7 is being selected and 1~7 identical fibre cellulose content of test example
In the case of used kneader as spinning equipment, it is specific as follows:
Test example 1~7
Be separately added into the degree of polymerization be 700, moisture content 7%, mass percentage 5%, 10%, 15%, 20%,
25%, 30%, 35% cellulose, P2O5Mass percentage be 74% phosphoric acid/polyphosphoric acids composite solution, twin-screw
Extruder operating temperature is -10~35 DEG C, and the process time is 15 minutes, and step is the same as embodiment 1.
Comparative example 1
By P2O5Mass percentage be 74% phosphoric acid/polyphosphoric acids double solvents be added in kneader, be pre-chilled
To 5 DEG C, be then mixed into the degree of polymerization be 700, the aqueous cellulose for being 1%, contain quality percentage of the cellulose in double solvents
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 1%, mass percentage 10%, 15%, 20%, 25%,
30%, 35% cellulose, P2O5Mass percentage be 74% phosphoric acid/polyphosphoric acids composite solution, kneader work temperature
Degree is -10~35 DEG C, and the process time is 15 minutes, and step is the same as comparative example 1.
Clearing point is the transition temperature that solution is transformed into isotropic state by anisotropic states, and cellulose spinning is former
Liquid possesses good mechanical property when with anisotropy.Therefore research cellulose mass percentage, P2O5Quality percentage contains
Measure the influence to spinning solution clearing point.
One, influence of the research cellulose mass percentage to clearing point,
The clearing point of cellulose spin dope made from comparative example 1~7 and test example 1~7 is compared, acquired results
As shown in table 1.
Influence result of the 1 cellulose mass percentage of table 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 identical situation of other experiment conditions, with the increase of cellulose percentage composition, spinning is former
The clearing point of liquid gradually rises, cellulose mass percentage rise in 5~10% sections it is obvious, and ascendant trend 30~
35% section is tended towards stability, therefore choosing 10~30% is optimum concentration range；Simultaneously seen from table 1, in cellulose concentration phase
With in the case where, the clearing point of embodiment is above the clearing point of comparative example, it can thus be appreciated that comparing kneader, double screw extruder
Manufactured cellulose spin dope possesses more stable liquid crystal state, has more excellent mechanical property.
The reason of using various concentration phosphoric acid/polyphosphoric acids composite solution in order to better illustrate the present invention and twin-screw squeeze
The advantage of machine out, test example 8~14 use phosphoric acid/polyphosphoric acids composite solution of various concentration, and comparative example 8~14 is being selected
Use kneader as spinning equipment in the case where phosphoric acid identical as embodiment 11~17/polyphosphoric acids composite solution concentration,
It is specific as follows:
Test example 8~14
It is separately added into P2O5Mass percentage be 70%, 72%, 74%, 76%, 78%, 80%, 82% phosphoric acid/
Polyphosphoric acids composite solution, the cellulose that the degree of polymerization 700, moisture content 10%, mass percentage are 15%, twin-screw squeeze
Machine operating temperature is -20~35 DEG C out, and the process time is 15 minutes, and step is the same as embodiment 1.
Comparative example 8~14
It is separately added into P2O5Mass percentage be 70%, 72%, 74%, 76%, 78%, 80%, 82% phosphoric acid/
Polyphosphoric acids composite solution, the cellulose that the degree of polymerization 700, moisture content 10%, mass percentage are 15%, kneader work
Making temperature is -20~35 DEG C, and the process time is 15 minutes, and step is the same as comparative example 1.
Two, P2O5Influence of the mass percentage to spinning solution clearing point
The clearing point of cellulose spin dope made from comparative example 8~14 and test example 8~14 is compared, gained knot
Fruit is as shown in table 2.
2 P of table2O5Influence result of the mass percentage 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 identical situation of other experiment conditions, with P2O5The increase of mass percentage, spinning are former
The clearing point of liquid gradually rises, P2O5Mass percentage is obvious in 70~72% section ascendant trends, and goes out when reaching 80%
Existing inflection point, works as P2O5Mass percentage is in slow downward trend at 80~82% section, to find out its cause, being due to cellulose
Concentration raising causes solution system viscosity to increase, and caused by the solubility property decline within the same process time to cellulose,
Therefore choosing 72~80% is optimum concentration range；Simultaneously as can be seen from Table 2, in P2O5It is real in the identical situation of mass percentage
The clearing point for applying example is above the clearing point of comparative example, it can thus be appreciated that kneader is compared, cellulose made of double screw extruder
Spinning solution possesses more stable liquid crystal state, has more excellent mechanical property.
Embodiment 1
It (1) is 1% by water content, the cellulose dissolution that the degree of polymerization is 500 is in P2O5Mass percentage be 72% phosphorus
In acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 10%, and the original of liquid crystal state is prepared by double screw extruder
Liquid glue；
(2) by be preheated to 50 DEG C have cellulose dopes glue be fed in metering pump, setting spin speed 20m/min, pass through
Adjustment setting sprays centainly into glue amount by spinneret, and by air bath, wherein the air gap is 5mm, using the first solidification
Bath and the second gelation form nascent strand.Wherein, the volume of ethyl alcohol is the 85% of three component solution volumes in the first coagulating bath,
Temperature is 20 DEG C, and the volume of ethyl alcohol is the 50% of three component solution volumes in the second gelation, and temperature is 10 DEG C；
(3) it neutralized, 70 DEG C of hot water wash, oiled by 15 DEG C of washings, 5% sodium hydroxide solution again, the processes such as dry, wind
And then finished product.
Finally obtained fibrous finished product fiber number is 2.87dtex, and doing breaking strength is 8.31cN/dtex, and elongation at break is
11%；Elasticity modulus is 4.18cN/dtex；Regain is 13%, drafting multiple 12.6.
Embodiment 2
It (1) is 10% by water content, the cellulose dissolution that the degree of polymerization is 800 is in P2O5Mass percentage be 80%
In phosphoric acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 20%, is prepared into liquid crystal state by double screw extruder
Stoste glue；
(2) by be preheated to 45 DEG C have cellulose dopes glue be fed in metering pump, setting spin speed 150m/min, pass through
Adjustment setting sprays centainly into glue amount by spinneret, and by air bath, wherein the air gap is 50mm, solidifying using first
Gu bath and the second gelation form nascent strand.Wherein, the volume of ethylene glycol is three component solution volumes in the first coagulating bath
30%, temperature is 45 DEG C, and the volume of ethylene glycol is the 30% of three component solution volumes in the second gelation, and temperature is 40 DEG C；
(3) it neutralized, 80 DEG C of hot water wash, oiled by 30 DEG C of washings, 2% sodium hydroxide solution again, the processes such as dry, wind
And then finished product.
Finally obtained fibrous finished product fiber number is 5.86dtex, and doing breaking strength is 6.98cN/dtex, and elongation at break is
5.8%；Elasticity modulus is 2.21cN/dtex；Regain is 8.6%, drafting multiple 6.3.
Embodiment 3
It (1) is 5% by water content, the cellulose dissolution that the degree of polymerization is 1000 is in P2O5Mass percentage be 78%
In phosphoric acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 30%, is prepared into liquid crystal state by double screw extruder
Stoste glue；
(2) by be preheated to 70 DEG C have cellulose dopes glue be fed in metering pump, setting spin speed 250m/min, pass through
Adjustment setting sprays centainly into glue amount by spinneret, and by air bath, wherein the air gap is 30mm, solidifying using first
Gu bath and the second gelation form nascent strand.Wherein, the volume of acetone is three component solution volumes in the first coagulating bath
10%, temperature is 5 DEG C, and the volume of acetone is the 5% of three component solution volumes in the second gelation, and temperature is 10 DEG C；
(3) it neutralized, 90 DEG C of hot water wash, oiled by 20 DEG C of washings, 2% sodium hydroxide solution again, the processes such as dry, wind
And then finished product.
Finally obtained fibrous finished product fiber number is 1.1dtex, and doing breaking strength is 9.4cN/dtex, and elongation at break is
5.3%；Elasticity modulus is 4.75cN/dtex；Regain is 8.9%, drafting multiple 20.
Embodiment 4
It (1) is 7% by water content, the cellulose dissolution that the degree of polymerization is 700 is in P2O5Mass percentage be 75% phosphorus
In acid/polyphosphoric acids composite solution, the mass fraction of cellulose is 20%, and the original of liquid crystal state is prepared by double screw extruder
Liquid glue；
(2) by be preheated to 20 DEG C have cellulose dopes glue be fed in metering pump, setting spin speed 400m/min, pass through
Adjustment setting sprays centainly into glue amount by spinneret, and by air bath, wherein the air gap is 3mm, using the first solidification
Bath and the second gelation form nascent strand.Wherein, the volume of acetone is the 80% of three component solution volumes in the first coagulating bath,
Temperature is 15 DEG C, and the volume of acetone is the 20% of three component solution volumes in the second gelation, and temperature is 20 DEG C；
(3) it neutralized, 85 DEG C of hot water wash, oiled by 15 DEG C of washings, 0.1%T sodium carbonate liquor again, the works such as dry, wind
Sequence and then finished product.
Finally obtained fibrous finished product fiber number is 6.6dtex, and doing breaking strength is 3.2cN/dtex, and elongation at break is
4.0%；Elasticity modulus is 1.15cN/dtex；Regain is 5.0%, drafting multiple 1.
Test example 15
It (1) is 5% by water content, the cellulose dissolution that the degree of polymerization is 1000 is in P2O5Mass percentage be 75%
In phosphoric acid/polyphosphoric acids composite solution, the stoste glue of liquid crystal state is prepared by double screw extruder, cellulose contains in stoste glue
Amount is 20%；
(2) by be preheated to 70 DEG C have cellulose dopes glue be fed in metering pump, setting spin speed 250m/min, pass through
Adjustment setting sprays by spinneret centainly into glue amount, bathes to form nascent strand by air bath and two step normal propyl alcohols, hollow
Gas gap is 1mm, and the volume of normal propyl alcohol is the 55% of three component solution volumes in the first step coagulating bath, and temperature is 15 DEG C, second
The volume of ethylene glycol is the 35% of three component solution volumes in step coagulating bath, and temperature is 10 DEG C.
(3) it neutralized, 90 DEG C of hot water wash, oiled by 25 DEG C of washings, 2% sodium hydroxide solution again, the processes such as dry, wind
And then finished product.
Test example 16- test example 24
Test example 16- test example 24 respectively by spinning air bath the air gap be respectively set to 3mm, 5mm, 10mm, 20mm,
30mm, 40mm, 50mm, 60mm and 80mm, other parameters are identical with test example 1 with preparation method.
3 gained cellulose fibre performance parameter of table
As shown in Table 3, air layer length has certain influence to drawing of fiber multiple and fibre property.When air layer length is spent
When small or excessive, spinning can not be normally carried out, such as test example 16 and test example 25.The drawing-off of test example 18- test example 21 times
Several and fibrous fracture intensity is better than test example 17- test example 23, therefore selects the air gap for 3mm~50mm, preferably 5~
30mm。
Test example 25- test example 32
Spinning process is identical as test example 15, and the air gap 30mm, other conditions are shown in Table 4.
4 first coagulation bath condition of table and fibre property
As shown in Table 4,30 fibre property of test example 25- test example is substantially better than test example 31-32, therefore selects first to coagulate
Gu the volumetric concentration of normal propyl alcohol is 10%~85%, preferably 30%~80% in bath, temperature is 5~45 DEG C.
Using other organic solvents such as acetone, ethyl alcohol, ethyl acetate, ethylene glycol in the first coagulating bath, obtained result
It is similar to the above results.
Comparative example 15
It (1) is 5% by water content, the cellulose dissolution that the degree of polymerization is 1000 is in P2O5Mass percentage be 75%
In phosphoric acid/polyphosphoric acids composite solution, the stoste glue of liquid crystal state is prepared by double screw extruder, cellulose contains in stoste glue
Amount is 20%；
(2) by be preheated to 70 DEG C have cellulose dopes glue be fed in metering pump, setting spin speed 250m/min, pass through
Adjustment setting sprays by spinneret centainly into glue amount, bathes to form nascent strand by air bath and a step normal propyl alcohol, 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) it neutralized, 90 DEG C of hot water wash, oiled by 25 DEG C of washings, 30% sodium hydroxide solution again, the works such as dry, wind
Sequence and then finished product.
Test example 33- test example 40
40 spinning process of test example 33- test example is identical as comparative example 15, but passes through the second gelation normal propyl alcohol, and second is solidifying
Admittedly bath condition is shown in Table 5.
5 Second Gelation Condition of table and fibre property
As shown in Table 5, compared with the comparative example 15 without the second gelation, 40 fiber of test example 33- test example is dry disconnected
Resistance to spalling and elongation at break are considerably higher, therefore have remarkable result for fibre property raising using two step coagulating bath spinning,
And when the second gelation concentration is 5%~50%, preferably 20%~40%, and temperature is 10~40 DEG C, fibre property is best.
Using other organic solvents such as acetone, ethyl alcohol, ethyl acetate, ethylene glycol in the second gelation, obtained result
It is similar to the above results.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention
Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.
Claims (8)
1. a kind of method that dry-wet spinning prepares cellulose fibre, which is characterized in that preparation step is as follows:
(1) cellulose and phosphoric acid/polyphosphoric acids composite solution that the degree of polymerization is 500~1000, water content is 1%~10% are mixed
It closes, the stoste glue of liquid crystal state is prepared by double screw extruder；
(2) preheating of stoste glue described in step (1) is fed in metering pump, adjusts into glue amount, is sprayed by spinneret；
(3) air bath, the first coagulating bath and the second gelation are passed sequentially through and forms nascent strand, wherein the air gap be 3~
50mm, first coagulating bath and the second gelation are three component solutions；
(4) pass through washing again, neutralization, hot water wash, oil, drying, rolling step and then finished product fiber；
Mass fraction of the cellulose as described in step (1) in composite solution is 25~30%；
Three component solutions described in step (3) include water, phosphoric acid and organic solvent, and the organic solvent is acetone, ethyl alcohol, positive third
One of alcohol, ethyl acetate or ethylene glycol；The volume of organic solvent is three component solution volumes in first coagulating bath
30%~80%；The volume of organic solvent is the 20%~40% of three component solution volumes in the second gelation.
2. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that first is solidifying
Admittedly the temperature bathed is 5 DEG C~45 DEG C.
3. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that second is solidifying
Admittedly the temperature bathed is 10~40 DEG C.
4. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that the step
Suddenly mass fraction of the cellulose in composite solution described in (1) is 25% or 30%.
5. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that the step
Suddenly P in phosphoric acid/polyphosphoric acids composite solution in (1)2O5Mass percentage be 72~80%.
6. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that the step
Suddenly the air gap in (3) is 5mm~30mm.
7. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that the step
Suddenly the neutralization in (4) refers to the sodium carbonate or sodium hydrate aqueous solution that fiber is 0.1-5% by concentration.
8. the method that a kind of dry-wet spinning according to claim 1 prepares cellulose fibre, which is characterized in that it is described at
The fiber number of product fiber is 1.1~6.6dtex, and doing breaking strength is 3.2~9.4 cN/dtex, and elongation at break is 4.0~11%；
Regain is 5.0~13%, and drafting multiple is 1~20.
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| CN110129901A (en) * | 2019-05-05 | 2019-08-16 | 江阴芗菲服饰有限公司 | A kind of preparation method of creeping chill fiber |
| CN110057644B (en) * | 2019-05-13 | 2020-08-04 | 中国科学院山西煤炭化学研究所 | Method for measuring limiting oxygen index of spinning solution |
| CN112779612B (en) * | 2021-01-07 | 2023-11-14 | 山东鸿泰鼎新材料科技有限公司 | Efficient production and manufacturing method and equipment for lyocell fibers |
| CN113150310B (en) * | 2021-04-02 | 2022-08-23 | 东华大学 | Method for dissolving cellulose at low temperature by phosphoric acid with controllable polymerization degree |
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