CN109576803B - Production method of chitosan fiber - Google Patents
Production method of chitosan fiber Download PDFInfo
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- CN109576803B CN109576803B CN201811215761.3A CN201811215761A CN109576803B CN 109576803 B CN109576803 B CN 109576803B CN 201811215761 A CN201811215761 A CN 201811215761A CN 109576803 B CN109576803 B CN 109576803B
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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
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
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Abstract
The invention provides a production method of chitosan fiber, which is characterized in that: the method comprises the following process steps: spinning solution preparation, filtration, deaeration, metering by a metering pump, spinning, coagulation by a coagulating bath, drafting, water washing, oiling, vacuum freeze drying and crimping cutting. The concrete process of coagulation bath coagulation is as follows: the coagulant is one or more of 0.1-5% w/w sodium hydroxide aqueous solution, 2-8% w/w sodium sulfate, sodium bicarbonate, sodium carbonate or sodium phosphate; the spinning solution is extruded from a spinneret plate and then enters a coagulating bath at the temperature of 5-25 ℃ to be coagulated and drafted at the same time, and the draft multiple is 1-2 times. In the whole chitosan fiber wet spinning process, an alcohol solvent is not used, so that potential safety hazards caused by using and storing the alcohol solvent can be thoroughly eliminated, the material cost can be reduced, and the quality of the chitosan fiber can be improved; in addition, the invention realizes continuous production, reduces operators and reduces production cost.
Description
Technical Field
The invention belongs to the technical field of spinning, and particularly relates to a production method of chitosan fibers.
Background
Chitin is a natural polymeric material with earth reserves inferior to cellulose, and is widely found in cell walls of arthropods, mollusks, annelids, protozoa, coelenterates, and fungi and algae. Chitosan is an important derivative of chitin and is obtained by deacetylation of chitin. The chitosan after deacetylation has a large amount of active-NH 2-OH, so that the chitosan fiber obtained by wet spinning has positive charges, good antibacterial property, biocompatibility and adsorptivity. The textile product can resist bacterial infection, prevent and treat skin diseases, and has the advantages of deodorization, sweat absorption, moisture preservation and comfort in wearing. When used as medical dressing, the dressing has the functions of stopping bleeding, reducing pain, accelerating healing speed and promoting new skin generation, can be applied to hemostatic cotton and medical non-woven fabrics,
surgical sutures, artificial skin, and the like.
The chitosan fiber is obtained by wet spinning, and the wet spinning generally comprises the following spinning processes: raw material dissolution, filtration, deaeration, metering, coagulation bath coagulation, drafting, water washing and drying. In the existing patent for producing chitosan fibers, the process for preparing chitosan fibers is many, but most of the processes are not separated from an organic solvent alcohol (most of which are methanol, ethanol, propanol and the like). Because chitosan is mostly dissolved by acid and is coagulated in alkaline coagulating bath, and alcohol is added in the coagulating process, the acid-base reaction speed can be slowed down, and the fiber formation is facilitated; in the drying process, most of water in the chitosan fiber is replaced by alcohol, so that the phenomenon that the fiber is affected due to the formation of doubling in the drying or natural airing process is avoided
Quality is improved.
Alcohols are generally volatile, and the steam and air can form an explosive mixture, so that the steam and air can explode when exposed to open fire and high heat energy, and the chemical reaction of the steam and the oxidant can also cause combustion, and in a fire scene, a heated container has explosion danger. Can spread to a quite far place at a lower part, and can lead to backfire when meeting open fire. Thus, the use of alcohols in production presents a great safety hazard, and is limited by
Therefore, inflammable and explosive products have high requirements on production workshops.
Safety production is an important point of enterprise management, is a fundamental guarantee of enterprise development, and is a daily, accumulated and continuous process. As is well known, the safety matters are large, and once safety accidents occur, huge damages and injuries can be brought to the country, people and enterprises. In the existing chitosan spinning patents, alcohols cannot be completely separated, so that a fiber with high safety is urgently needed at present
A chitosan spinning process with good dimensional performance.
In the technical proposal disclosed in Chinese patent (patent application No. CN 201110222083.5), 4% -8% (w/w) of ethanol is used in the coagulating bath in production, and the ethanol washing process is high-concentration ethanol. In the technical scheme disclosed in China patent (patent application No. CN 201710510660.8), absolute ethyl alcohol is used for soaking and washing for 2-4min in the washing process, in the technical scheme disclosed in China patent (patent application No. CN 200810015053.5), ethyl alcohol is used in the washing process, and after solidification, the once-washed fiber is treated by warm water at 20-30 ℃, and then is soaked and washed by absolute ethyl alcohol for once.
Disclosure of Invention
The invention aims at the existing problems and provides a production method of chitosan fibers, wherein an alcohol solvent is not used in the whole chitosan fiber wet spinning process, so that potential safety hazards caused by using and storing the alcohol solvent can be thoroughly eliminated, the material cost can be reduced, and the quality of the chitosan fibers can be improved; further, continuous production is realized, so that operators are reduced, and production cost is reduced.
The invention aims at realizing the following technical scheme:
the production method of the chitosan fiber is characterized by comprising the following process steps:
(1) preparation of spinning solution, (2) filtration, (3) deaeration, (4) metering pump metering, (5) spinning, (6) coagulation bath coagulation, (7) drafting, (8) water washing, (9) oiling, (10) vacuum freeze drying, and (11) crimping cutting;
wherein, the step (6) is characterized in that the coagulating bath is coagulated: the coagulant is one or more of 0.1-5% w/w sodium hydroxide aqueous solution, 2-8% w/w sodium sulfate, sodium bicarbonate, sodium carbonate or sodium phosphate; the spinning solution is extruded from a spinneret plate and then enters a coagulating bath at the temperature of 5-25 ℃ to be coagulated and drafted at the same time, and the draft multiple is 1-2 times.
An improvement of the technical scheme is as follows: after said step (9), performing said step (10) of vacuum freeze-drying: the vacuum freeze drying does not need to pretreat the fibers, the fibers are placed on a tray after being oiled, extruded and dehydrated, then the tray is placed on a tray frame of a material vehicle, the material vehicle sends the tray to a heating plate in a vacuum freeze drying bin, a bin gate is closed to start freeze drying, and the vacuum is pumped to below 200pa, so that the fibers are completely frozen; then, heating the heating plate to raise the temperature, vacuumizing the vacuum freeze drying bin to vacuum degree of 10-800 Pa, controlling the temperature of the heating plate to 30-120 deg.c and the fiber temperature to over 0 deg.c to complete the drying of the fiber.
Another improvement of the technical scheme is as follows: spinning in the step (5): the fiber is long fiber bundle wet spinning; before the step (10), the long fiber bundles are not sheared off, the long fiber bundles are continuously placed on trays, the placed trays are placed on a tray frame of a material vehicle, the long fiber bundles among the trays are also continuously not sheared off, the trays are placed on the tray frame of the material vehicle, the step (10) is started, the material vehicle sends the trays to a heating plate in a vacuum freeze drying bin, a bin door is closed, freeze drying is started, and vacuumizing is carried out until the thickness of the fibers is less than 200pa, so that the fibers are completely frozen; then, heating the heating plate to raise the temperature, vacuumizing the vacuum freeze drying bin to make the vacuum degree in the vacuum freeze drying bin within the range of 10pa to 800pa, controlling the temperature of the heating plate to be 30-120 ℃ and the temperature of the fiber to be more than 0 ℃, pushing the material vehicle out of the vacuum freeze drying bin after the fiber is dried, pulling out one end of the dried long fiber bundle, and introducing the long fiber bundle into buckling cutting equipment through a tension frame guide roller to realize continuous production of the long fiber.
Further improvement of the technical scheme is as follows: in the step (10), the material trolley sends the tray into the vacuum freeze drying bin from a feed inlet at one end of the vacuum freeze drying bin; and after the long fiber bundles are dried, pushing the material vehicle out of a discharge hole at the other end of the vacuum freeze drying bin.
Further improvement of the technical scheme is as follows: the spinning solution prepared in the step (1) is as follows: dissolving a flaky or powdery chitosan raw material into 1-5% w/w of analytically pure acetic acid solution to prepare 2-8% chitosan spinning solution; specifically, a proper amount of deionized purified water is added into a stirring kettle, the temperature of the water is controlled at 20-30 ℃, then chitosan raw material is added and stirred for 1-4 hours, then acetic acid is added and stirring is continued for 3-10 hours; the step (2) is filtering: filtering the stirred spinning solution to a spinning kettle, wherein the filter is a plate frame type or a storage tank type; the filtering process is divided into coarse filtration, primary filtration and secondary filtration, and the pore diameters of filter screens used for the coarse filtration, the primary filtration and the secondary filtration are respectively as follows: 40-80 μm, 20-40 μm and 1-20 μm; the step (3) is defoamed: static or dynamic defoaming is adopted for defoaming, and the required vacuum degree is less than 0Mpa during defoaming.
Further improvement of the technical scheme is as follows: the step (7) is drafting: the drafting is carried out twice, the drafting rollers are 3 rollers or 5 rollers, the drafting bath is divided into a first drafting bath and a second drafting bath, the first drafting bath is composed of one or more of sodium sulfate, sodium chloride, sodium acetate, sodium phosphate or deionized water with the weight of 5-20%, the temperature is 20-60 ℃, and the second drafting bath is composed of one or more of sodium sulfate, sodium chloride, sodium acetate, sodium phosphate or deionized water with the weight of 5-20%, and the temperature is 30-60 ℃.
Further improvement of the technical scheme is as follows: the step (8) is water washing: washing with deionized purified water at 20-50deg.C; and (3) oiling in the step (9): the washed fiber enters an oil feeding groove through a squeeze roll for oiling, and then is dried through the squeeze roll.
Compared with the prior art, the invention has the following advantages and positive effects:
1. according to the invention, alcohols such as methanol, ethanol and the like are not used in the whole chitosan fiber production process, so that potential safety hazards caused by using and storing alcohol substances are thoroughly eliminated;
2. the invention does not use alcohol organic solvent, thus greatly reducing the cost of raw materials;
3. the nature of the coagulation process of the fiber in the coagulation bath is acid-base neutralization reaction, and the acid-base neutralization reaction ratio of NaOH and HAC is severe, so that the fiber can produce a skin-core structure, and the quality of the fiber is not affected due to coagulation, therefore, a certain auxiliary agent is needed to be added to alleviate the neutralization reaction speed of the NaOH and the HAC, and the alcohol organic solvent can play a good role, so that the reaction of the NaOH and the HAC is eased and stable, and the skin-core structure is not produced. In the coagulation bath step, under the condition of not using an alcohol organic solvent, the coagulant is one or more of 0.1-5% w/w sodium hydroxide aqueous solution, 2-8% sodium sulfate, sodium bicarbonate, sodium carbonate or sodium phosphate, so that the reaction speed is slowed down, a skin-core structure is not generated in the coagulation process, and the fiber quality is better;
4. the invention breaks through the intermittent production mode and realizes the continuous production of chitosan fibers;
5. the invention has simple process, short flow, easy operation, low production cost, convenient mass production and great economic and social benefits.
Drawings
FIG. 1 is a schematic top view of a wet spinning vacuum freeze-drying apparatus employed in the present invention.
FIG. 2 is a front view of a vacuum freeze drying chamber employed in the present invention with the feed port door open.
In the figure, 1-a vacuum freeze drying bin; 2-in-bin track; 3-pneumatic connection means; 4-out-of-bin rails; 5-a material vehicle; 6-lifting the silk swinging table; 7. a heating plate; 8. a heating plate support; 9. a temperature probe; 10. a bin gate; 11. a cold trap.
Detailed Description
The invention is described in further detail below with reference to the attached drawings and examples:
referring to fig. 1, an embodiment of wet spinning vacuum freeze-drying equipment adopted by the invention comprises a material vehicle 5, an out-bin guide rail 4 and a vacuum freeze-drying bin 1, wherein a feed inlet and a discharge outlet are respectively arranged at two ends of a bin body of the vacuum freeze-drying bin 1, and bin doors 10 are respectively arranged on the feed inlet and the discharge outlet. The pneumatic connecting devices 3 are respectively arranged at one ends of the guide rails 4 outside the bin, which are close to the feed inlet and the discharge outlet of the vacuum freeze drying bin 1. The vacuum freeze drying bin 1 comprises a bin body, a bin inner guide rail 2, a cold trap 11, a refrigerating system, a vacuumizing system, a temperature probe 9, a heating plate bracket 8 and a heating plate 7.
The in-bin guide rail 2 is arranged at the inner top of the bin body of the vacuum freeze drying bin 1, two ends of the in-bin guide rail 2 are respectively positioned at a feed inlet and a discharge outlet, two ends of the in-bin guide rail 2 are respectively connected with an out-bin guide rail 4 through a pneumatic connecting device 3 to form an annular guide rail, and a lifting wire swinging table 6 is arranged below the out-bin guide rail 4 close to the feed inlet of the vacuum freeze drying bin 1.
The vacuum freeze drying bin 1 is provided with a vacuum fine tuning valve and a deflation valve, and the vacuum fine tuning valve is added, so that the internal heat circulation rate of the vacuum freeze drying bin is improved, air is uniformly supplemented into the freeze drying bin, the air flow speed is increased, and the materials are quickly dried.
The embodiment of the production method of the chitosan fiber comprises the following process steps:
(1) preparation of spinning solution, (2) filtration, (3) deaeration, (4) metering pump metering, (5) spinning, (6) coagulation bath coagulation, (7) drafting, (8) water washing, (9) oiling, (10) vacuum freeze drying, and (11) crimping cutting;
wherein, the concrete process of the coagulation bath coagulation in the step (6) is as follows: the coagulant is one or more of 0.1-5% w/w sodium hydroxide aqueous solution, 2-8% w/w sodium sulfate, sodium bicarbonate, sodium carbonate or sodium phosphate; the spinning solution is extruded from a spinneret plate and then enters a coagulating bath at the temperature of 5-25 ℃ to be coagulated and drafted at the same time, and the draft multiple is 1-2 times.
Further, after the step (9), performing the vacuum freeze-drying of the step (10): the vacuum freeze drying does not need to pretreat the fibers, the fibers are placed on a tray after being oiled, extruded and dehydrated, then the tray is placed on a tray frame of a material vehicle 5, the material vehicle 5 sends the tray to a heating plate 7 in a vacuum freeze drying bin, a bin gate 10 is closed to start freeze drying, and the vacuum is pumped to below 200pa, so that the fibers are completely frozen; then, heating the heating plate 7 to raise the temperature, vacuumizing the vacuum freeze drying bin 1 to make the vacuum degree in the vacuum freeze drying bin be in the range of 10pa to 800pa, controlling the temperature of the heating plate to be 30-120 ℃ and the temperature of the fiber to be more than 0 ℃ and drying the fiber.
Specifically: and (3) preparing spinning solution in the step (1): dissolving a flaky or powdery chitosan raw material into 1-5% w/w of analytically pure acetic acid solution to prepare 2-8% chitosan spinning solution; specifically, a proper amount of deionized purified water is added into a stirring kettle, the temperature of the water is controlled at 20-30 ℃, then chitosan raw material is added and stirred for 1-4 hours, then acetic acid is added, and stirring is continued for 3-10 hours. And (2) filtering: filtering the stirred spinning solution to a spinning kettle, wherein the filter is a plate frame type or a storage tank type; the filtering process is divided into coarse filtration, primary filtration and secondary filtration, and the pore diameters of filter screens used for the coarse filtration, the primary filtration and the secondary filtration are respectively as follows: 40-80 μm, 20-40 μm and 1-20 μm; and (3) defoaming: static or dynamic defoaming is adopted for defoaming, and the required vacuum degree is less than 0Mpa during defoaming.
Drafting in the step (7): the drafting is carried out twice, the drafting rollers are 3 rollers or 5 rollers, the drafting bath is divided into a first drafting bath and a second drafting bath, the first drafting bath is composed of one or more of 5-20% w/w sodium sulfate, sodium chloride, sodium acetate, sodium phosphate or deionized water, the temperature is 20-60 ℃, and the second drafting bath is composed of one or more of 5-20% w/w sodium sulfate, sodium chloride, sodium acetate, sodium phosphate or deionized water, and the temperature is 30-60 ℃.
Washing in the step (8): the water washing tank is used for washing, the deionized purified water at 20-50 ℃ can be divided into 4 layers. And (9) oiling: the washed fiber enters an oil feeding groove through a squeeze roll for oiling, and then is dried through the squeeze roll.
The invention relates to an implementation mode of a wet spinning continuous production method of chitosan fibers, which comprises the following steps:
(1) preparation of spinning solution, (2) filtration, (3) deaeration, (4) metering pump metering, (5) spinning, (6) coagulation bath coagulation, (7) drafting, (8) water washing, (9) oiling, (10) vacuum freeze drying, and (11) crimping cutting;
wherein, spinning in the step (5): the fiber is long fiber bundle wet spinning; before the step (10), the long fiber bundles are not sheared off, the long fiber bundles are continuously placed on trays, the placed trays are placed on a tray frame of a material vehicle, the long fiber bundles among the trays are also continuously not sheared off, the trays are placed on the tray frame of the material vehicle, the step (10) is started, the material vehicle 5 sends the trays to a heating plate in a vacuum freeze drying bin 1, a bin door 10 is closed, freeze drying is started, and vacuumizing is carried out until the thickness of the fibers is less than 200pa, so that the fibers are completely frozen; then, heating the heating plate to raise the temperature, vacuumizing the vacuum freeze drying bin to make the vacuum degree in the vacuum freeze drying bin within the range of 10pa to 800pa, controlling the temperature of the heating plate to be 30-120 ℃ and the temperature of the fiber to be more than 0 ℃, pushing the material 5 out of the vacuum freeze drying bin 1 after the fiber is dried, pulling out one end of the dried long fiber bundle, and introducing the long fiber bundle into buckling cutting equipment through a tension frame guide roller to realize continuous production of the long fiber.
Further, in the step (10), the material vehicle 5 conveys the tray into the vacuum freeze-drying bin 1 from a feed port at one end of the vacuum freeze-drying bin 1; after the long fiber bundles are dried, the material trolley 5 is pushed out from a discharge hole at the other end of the vacuum freeze drying bin 1.
The remaining steps are substantially the same as those of the previous embodiments, and thus will not be described again.
The following is a specific example of a production method of chitosan fiber of the present invention:
example 1:
1. adding deionized water into a stirring kettle, controlling the water temperature to be 20 ℃, adding 3.5% of flaky chitosan raw materials, stirring for 1 hour, then adding acetic acid according to the amount of 1.8%, and continuously stirring for 4 hours to prepare a chitosan spinning solution;
2. filtering the dissolved chitosan spinning solution sequentially through filters with the pore diameters of 50 mu m, 20 mu m and 10 mu m, entering a spinning kettle, vacuumizing and maintaining at-0.05 MPa until the defoaming is finished;
3. is extruded into the coagulation bath after being metered by a metering pump. The coagulating bath is 4% NaOH and 2.5% NaHCO 3， The coagulation bath temperature is 10 ℃;
4. then drafting with a draft ratio of 1.5 times, the first drafting bath being 15% Na at 30deg.C 2 SO 4 The solution, the second drafting bath is deionized water with the temperature of 50 ℃;
5. then cleaning in deionized water at 25 ℃, oiling, squeezing and dehydrating through an oiling agent tank, performing vacuum freeze drying, wherein the vacuum freeze drying does not need to pretreat the fibers, squeezing and dehydrating the fibers, placing the fibers on a tray, placing the tray on a tray rack of a material vehicle, conveying the tray to a heating plate 7 in a vacuum freeze drying bin 1 by the material vehicle, closing a bin gate 10, starting freeze drying, vacuumizing to 180pa, and completely freezing the fibers; then, heating is started, heating is carried out, vacuum is pumped, the vacuum degree in the vacuum freeze drying bin 1 is in the range of 10pa to 800pa, meanwhile, the temperature of the heating plate 7 is controlled to be 60 ℃, the temperature of the fiber reaches 10 ℃, and the fiber is dried;
6. the obtained chitosan fiber index is as follows: water content: 12.3%, linear density: 1.4dtex; intensity: 2.67cN/dtex; elongation at break: 14.8%.
Example 2:
1. adding deionized water into a stirring kettle, controlling the water temperature at 22 ℃, adding 4% of flaky chitosan raw materials, stirring for 1 hour, then adding acetic acid according to the amount of 2%, and continuing stirring for 5 hours to prepare a chitosan spinning solution;
2. filtering the dissolved chitosan spinning solution sequentially through filters with the pore diameters of 60 mu m, 30 mu m and 20 mu m, entering a spinning kettle, vacuumizing and maintaining at-0.06 MPa until the defoaming is finished;
3. extruding into coagulating bath with NaOH 1.0%, sodium sulfate 5%, sodium phosphate 3.0% and coagulating bath temperature 15 deg.c;
4. then drafting, wherein the drafting multiple is 1.8 times, the first drafting bath is 30 ℃ and is 15% sodium chloride aqueous solution, and the second drafting bath is 40 ℃ and is 10% sodium sulfate;
5. then cleaning in deionized water at 35 ℃, oiling, squeezing and dehydrating through an oiling agent tank, performing vacuum freeze drying, wherein the vacuum freeze drying does not need to pretreat the fibers, squeezing and dehydrating the fibers, placing the fibers on a tray, placing the tray on a tray frame of a material vehicle 5, conveying the tray to a heating plate 7 in a vacuum freeze drying bin 1 by the material vehicle 5, sealing a bin gate 10, starting freeze drying, vacuumizing to 150pa, and completely freezing the fibers; then, heating 7 is started to raise the temperature, and vacuum is pumped at the same time, so that the vacuum degree in the vacuum freeze drying bin 1 is in the range of 10pa to 800pa, and meanwhile, the temperature of a heating plate is controlled to be 70 ℃, the temperature of the fiber reaches 12 ℃, and the fiber is dried;
6. the obtained chitosan fiber index is as follows: linear density: 0.8dtex; intensity: 2.9cN/dtex; elongation at break: 12.8%.
Example 3:
1. adding deionized water into a stirring kettle, controlling the water temperature to be 25 ℃, adding 4.5% of flaky chitosan raw materials, stirring for 2 hours, then adding acetic acid according to the amount of 3%, and continuing stirring for 6 hours to prepare a chitosan spinning solution;
2. the dissolved chitosan spinning solution is filtered by a filter with the pore diameter of 40 mu m, 30 mu m and 10 mu m in sequence, enters a spinning kettle, is vacuumized and kept at-0.04 MPa until the deaeration is finished.
3. Is extruded into the coagulation bath after being metered by a metering pump. The coagulation bath was 3.5% sodium carbonate and the coagulation bath temperature was 20 ℃.
4. Then drafting is carried out, the drafting multiple is 2.0 times, the first drafting bath is deionized water at 30 ℃, and the second drafting bath is deionized water at 50 ℃.
5. Then cleaning in deionized water at 35 ℃, carrying out oil coating, extrusion and dehydration in an oiling agent tank, carrying out vacuum freeze drying, wherein the vacuum freeze drying does not need to pretreat the fibers, putting the fibers on a tray after the fiber is subjected to oil coating, extrusion and dehydration, putting the tray on a tray frame of a material vehicle, conveying the tray to a heating plate 7 in a vacuum freeze drying bin 1 by a material vehicle 5, closing a bin door 10, starting freeze drying, vacuumizing to 120pa, and fully freezing the fibers; then, heating is started, heating is carried out 7, vacuum is pumped, the vacuum degree in the vacuum freeze drying bin 1 is in the range of 10pa to 800pa, meanwhile, the temperature of the heating plate is controlled to be 80 ℃, the temperature of the fiber reaches 12 ℃, and the fiber is dried.
6. The obtained chitosan fiber index is as follows: linear density: 2.0dtex; intensity: 2.3cN/dtex; elongation at break: 14.3%.
In the embodiments, alcohols such as methanol, ethanol and the like are not used in the whole chitosan fiber production process, so that potential safety hazards caused by using and storing the alcohols are thoroughly eliminated, and meanwhile, the production cost is reduced.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that various changes, modifications, additions and substitutions can be made without departing from the spirit and scope of the invention.
Claims (6)
1. The production method of the chitosan fiber is characterized by comprising the following process steps:
(1) preparation of spinning solution, (2) filtration, (3) deaeration, (4) metering pump metering, (5) spinning, (6) coagulation bath coagulation, (7) drafting, (8) water washing, (9) oiling, (10) vacuum freeze drying, and (11) crimping cutting;
wherein, in the whole chitosan fiber wet spinning process, an alcohol solvent is not used, and the coagulating bath in the step (6) is used for coagulating: the coagulant is one or more of 0.1-5% w/w sodium hydroxide aqueous solution, 2-8% w/w sodium sulfate, sodium bicarbonate, sodium carbonate or sodium phosphate; extruding the spinning solution from a spinneret plate, and then feeding the spinning solution into a coagulating bath at the temperature of 5-25 ℃ while coagulating and drafting, wherein the drafting multiple is 1-2 times;
spinning in the step (5): the fiber is long fiber bundle wet spinning; before the step (10), the long fiber bundles are not sheared off, the long fiber bundles are continuously placed on trays, the placed trays are placed on a tray frame of a material vehicle, the long fiber bundles among the trays are also continuously not sheared off, the trays are placed on the tray frame of the material vehicle, the step (10) is started, the material vehicle sends the trays to a heating plate in a vacuum freeze drying bin, a bin door is closed, freeze drying is started, and vacuumizing is carried out until the thickness of the fibers is less than 200pa, so that the fibers are completely frozen; then, heating the heating plate to raise the temperature, vacuumizing the heating plate to ensure that the vacuum degree in the vacuum freeze-drying bin is in the range of 10pa to 800pa, controlling the temperature of the heating plate to be 30-120 ℃ and the temperature of the fiber to be more than 0 ℃, pushing a material vehicle out of the vacuum freeze-drying bin after the fiber is dried, pulling out one end of the dried long fiber bundle, and introducing the long fiber bundle into buckling cutting equipment through a tension frame guide roller to realize continuous production of the long fiber;
the step (7) is drafting: the drafting is carried out in two ways, the drafting rollers are 3 rollers or 5 rollers, the drafting bath is divided into a first drafting bath and a second drafting bath, the first drafting bath is composed of one or more of 5% -20% of sodium sulfate, sodium chloride, sodium acetate, sodium phosphate or deionized water, the temperature is 20-60 ℃, and the second drafting bath is composed of one or more of 5% -20% of sodium sulfate, sodium chloride, sodium acetate, sodium phosphate or deionized water, and the temperature is 30-60 ℃.
2. The method for producing chitosan fibers according to claim 1, wherein said step (10) is performed by vacuum freeze-drying after said step (9). The vacuum freeze drying does not need to pretreat the fibers, the fibers are placed on a tray after being oiled, extruded and dehydrated, then the tray is placed on a tray frame of a material vehicle, the material vehicle sends the tray to a heating plate in a vacuum freeze drying bin, a bin gate is closed to start freeze drying, and the vacuum is pumped to below 200pa, so that the fibers are completely frozen; then, heating the heating plate to raise the temperature, vacuumizing the vacuum freeze drying bin to vacuum degree of 10-800 Pa, controlling the temperature of the heating plate to 30-120 deg.c and the fiber temperature to over 0 deg.c to complete the drying of the fiber.
3. The method of producing chitosan fibers according to claim 1, wherein in the step (10), the pallet is fed into the vacuum freeze-drying chamber from a feed port at one end of the vacuum freeze-drying chamber by the pallet carriage; and after the long fiber bundles are dried, pushing the material vehicle out of a discharge hole at the other end of the vacuum freeze drying bin.
4. A method for producing chitosan fibers according to any one of claims 1 to 3, wherein the spinning solution of step (1) is prepared: dissolving a flaky or powdery chitosan raw material into 1-5% w/w of analytically pure acetic acid solution to prepare 2-8% chitosan spinning solution; specifically, a proper amount of deionized purified water is added into a stirring kettle, the temperature of the water is controlled at 20-30 ℃, then chitosan raw material is added and stirred for 1-4 hours, then acetic acid is added and stirring is continued for 3-10 hours; the step (2) is filtering: filtering the stirred spinning solution to a spinning kettle, wherein the filter is a plate frame type or a storage tank type; the filtering process is divided into coarse filtration, primary filtration and secondary filtration, and the pore diameters of filter screens used for the coarse filtration, the primary filtration and the secondary filtration are respectively as follows: 40-80 μm, 20-40 μm and 1-20 μm; the step (3) is defoamed: static or dynamic defoaming is adopted for defoaming, and the required vacuum degree is less than 0Mpa during defoaming.
5. A method for producing chitosan fibers according to any one of claims 1 to 3, wherein said step (8) is water-washed: washing with deionized purified water at 20-50deg.C; and (3) oiling in the step (9): the washed fiber enters an oil feeding groove through a squeeze roll for oiling, and then is dried through the squeeze roll.
6. The method for producing chitosan fibers according to claim 4, wherein the step (8) is water washing: washing with deionized purified water at 20-50deg.C; and (3) oiling in the step (9): the washed fiber enters an oil feeding groove through a squeeze roll for oiling, and then is dried through the squeeze roll.
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| CN115537943A (en) * | 2022-10-31 | 2022-12-30 | 天津天纺投资控股有限公司 | Stretch breaking machine and method for preparing chitosan fiber stretch-breaking strips by utilizing stretch breaking machine |
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