CN110359101B - Gel spinning method for manufacturing chitosan fiber - Google Patents

Gel spinning method for manufacturing chitosan fiber Download PDF

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Publication number
CN110359101B
CN110359101B CN201910655449.4A CN201910655449A CN110359101B CN 110359101 B CN110359101 B CN 110359101B CN 201910655449 A CN201910655449 A CN 201910655449A CN 110359101 B CN110359101 B CN 110359101B
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spinning
chitosan
solution
fiber
gel
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CN110359101A (en
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姚勇波
王华平
张玉梅
许志
李海东
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Donghua University
Jiaxing University
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Jiaxing University
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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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/06—Washing or drying
    • 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
    • D01D5/04—Dry spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • 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
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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

Abstract

The invention relates to a gel spinning method for preparing chitosan fiber, which comprises extruding spinning solution through a spinneret orifice, and sequentially entering an air layer, a coagulating bath and a plasticizing bath to prepare the chitosan fiber, wherein the spinning solution has a weight average molecular weight of more than or equal to 1 × 106g/mol of semi-dilute solution of chitosan, wherein the spinning solution contains organic sodium phosphate; before extrusion, heating the spinning solution to raise the temperature of the spinning solution from 3-6 ℃ to 30-40 ℃ when the spinning solution reaches a spinning nozzle; the air layer is provided with a blowing device, and the blowing temperature is 30-40 ℃; the temperature of the coagulating bath is 30-40 ℃; the plasticizing bath temperature is 50-60 ℃. Compared with wet spinning or dry-spray wet spinning, the gel spinning method for manufacturing chitosan fibers has obvious advantages, can effectively solve the problem of poor mechanical properties of the chitosan fibers prepared by wet spinning or dry-spray wet spinning, and has great popularization value.

Description

Gel spinning method for manufacturing chitosan fiber
Technical Field
The invention belongs to the technical field of chitosan fibers, and relates to a gel spinning method for manufacturing chitosan fibers.
Background
The chitosan fiber is a regenerated fiber prepared by a wet spinning method, has the effects of inhibiting bacteria, stopping bleeding, promoting wound healing and the like, and is an excellent medical and health material. However, the dry breaking strength of the chitosan fiber is only 1.8cN/dtex, the mechanical properties are low, and the chitosan fiber needs to be blended with cotton, viscose fiber and the like, because the chitosan fiber is in a random coil conformation in the wet spinning forming process, the spinning solution directly enters a coagulating bath after being discharged from a spinneret orifice, the tensile tension applied to a strand is small, the chitosan molecular chain in the random coil conformation in the solution is inherited, so that the nascent fiber is in an isotropic disordered state, strong hydrogen bond interaction exists between the chitosan molecular chain and the molecular chain, the glass transition temperature of the nascent fiber is far higher than the melting point, the molecular chain segment is difficult to orient in the subsequent stretching process, and the crystallinity and the crystal domain orientation of the fiber are difficult to improve through the subsequent stretching, so that the mechanical properties of the fiber are poor.
In order to improve the mechanical properties of chitosan fibers, researchers prepare chitosan fibers by dry-jet wet spinning (synthetic fiber industry, 2003,26(2): 36-38), and unlike wet spinning, an air layer exists between a spinning nozzle and a coagulation bath of dry-jet wet spinning, spinning trickle bears positive draft in an air section, and a high molecular chain segment in the spinning trickle can be oriented to improve the orientation and crystallinity of fibers, which shows that the mechanical properties of the fibers are improved. However, the structure of the fiber prepared by the dry-jet wet spinning method is essentially the same as that of the fiber prepared by the wet spinning method, the folded chain platelets and the amorphous regions are alternately arranged, the tension is concentrated on the amorphous region part between the platelets, and the mechanical property is determined by the amorphous region containing a plurality of weak parts, so that the mechanical property of the chitosan fiber prepared by the dry-jet wet spinning method is not greatly improved.
A gel spinning method belongs to the field of wet spinning, and is characterized in that a high-molecular spinning solution is extruded to form a spinning trickle, the spinning trickle is converted into a three-dimensional network structure from a solution state by a temperature-induced phase change method, phase conversion occurs on the basis of the three-dimensional network structure in a subsequent solvent and non-solvent diffusion stage, a uniform and loose network structure is formed, an obvious skin-core structure cannot be formed, a nascent fiber can bear high-power drafting, a randomly-oriented high-molecular chain is induced to form an oriented structure, stress-induced crystallization is promoted, the fiber has a structure that an amorphous region is uniformly dispersed in a continuous crystalline matrix, and mechanical properties are greatly improved. At present, commercial products such as ultra-high molecular weight polyethylene fibers and the like prepared by a gel spinning method have higher mechanical properties. However, there is no published report on the preparation of chitosan fibers by the gel spinning method.
Therefore, the research on a gel spinning method for manufacturing chitosan fibers to solve the problem of poor mechanical properties of the chitosan fibers is of great significance.
Disclosure of Invention
The invention aims to solve the problem of poor mechanical property of chitosan fiber in the prior art and provides a gel spinning method for manufacturing chitosan fiber.
In order to achieve the purpose, the invention adopts the following scheme:
a gel spinning method for preparing chitosan fiber comprises extruding spinning solution through spinneret orifice, sequentially introducing into air layer, coagulating bath and plasticizing bath to obtain chitosan fiber, wherein the weight average molecular weight of the spinning solution is not less than 1 × 106The spinning solution contains organic sodium phosphate, and the gel transformation behavior is more obvious along with the increase of the concentration of the organic sodium phosphate in the system; before extrusion, heating the spinning solution to raise the temperature of the spinning solution from 3-6 ℃ to 30-40 ℃ when the spinning solution reaches a spinning nozzle; the air layer is provided with a blowing device, and the blowing temperature is 30-40 ℃; the temperature of the coagulating bath is 30-40 ℃; the temperature of the plasticizing bath is 50-60 ℃, and the setting of the temperature is preferably carried out to ensure that the chitosan solution can be gelatinized.
Although the gel spinning method is a relatively mature method for ultra-high molecular weight polyethylene fiber, it has great difficulty in applying it to the preparation of chitosan fiber, mainly because: polyethylene is a polymer with a simple structure, polar groups do not exist in molecular chains, strong interaction does not exist, the polyethylene solution can form a gel (jelly) structure through cooling, polyethylene nascent filaments of the gel structure containing a certain solvent under the action of tension slide among the molecular chains, superstretching can be carried out, a very ordered structure is formed, chitosan is a polymer material with different chemical properties, the chitosan does not have the characteristic of solution-gel conversion, hydroxyl groups and other polar groups exist on the molecular chains, intermolecular interaction is easy to form among the molecular chains, and superstretching is not easy to carry out.
According to the method, the gel spinning of the chitosan fiber is possible by improving the spinning process of the chitosan fiber in the prior art, the chitosan fiber with a compact and uniform structure and a skin-core structure different from a common structure is finally prepared, and the improvement is as follows:
1) the organic sodium phosphate is added, so that the solution undergoes temperature-induced gelation transformation, and the formed gel structure can bear high-power drafting and induce the formation of a fiber ordered structure, thereby improving the mechanical property of the fiber; the existing wet spinning method and dry spraying wet spinning method do not add organic sodium phosphate, because acid solution is used as solvent of chitosan, alkali solution is used as coagulant of chitosan, the requirement of preparing chitosan fiber with mechanical property less than 1.8cN/dtex can be met, because organic sodium phosphate is not added to induce solution to carry out gelation transformation, the chitosan fiber in the prior art has low crystallization and orientation degree in the preparation process, so the mechanical property of the fiber is not high;
2) the invention is provided with the air layer which has the function of enabling the macromolecular chains in the spinning trickle to generate certain orientation, and is beneficial to forming an ordered structure, thereby improving the mechanical property of the fiber; although the prior art dry-jet wet spinning forming process is also provided with an air layer, the air layer provided by the invention is provided with a circular air blowing device, and the circular air blowing device is used for providing energy required by the solution-gel transformation of the spinning solution and promoting the formation of a gel structure; in the prior art, an air layer is not arranged in the wet spinning forming process because the viscosity of the spinning solution is low and the spinning solution cannot bear the spinning tension, so that the spinning solution discharged from a spinning nozzle in the prior art is directly solidified, and the drafting of a spinning nozzle is negative drafting or positive drafting with low multiplying power;
3) the chitosan adopted by the invention has high molecular weight, the concentration of the chitosan in the solution is in a semi-dilute non-entanglement concentration region, namely higher than the overlapping concentration and less than the entanglement concentration, high-power drafting can be realized, the molecular terminal of the high molecular weight chitosan is less, and the tiny defects on a fiber structure caused by the molecular terminal are less; in wet spinning and dry-jet wet spinning in the prior art, chitosan has relatively lower molecular weight and higher concentration and is positioned in a concentrated solution entanglement area, because the concentration of a solution is higher, the use amount of a corresponding solvent is reduced, and the solution is more economical, and when the concentration is high and the molecular weight is large, the viscosity of the solution is high, and the solution is not beneficial to stable extrusion, so that the conventional wet spinning and dry-jet wet spinning do not select chitosan with higher molecular weight;
4) the temperature of the spinning solution before heating is 3-6 ℃, while the temperature of the spinning solution for wet spinning and dry-jet wet spinning in the prior art is generally near room temperature, the temperature of the spinning solution before heating is obviously lower than that of the prior art, because the chitosan system added with the organic sodium phosphate is still in a solution state at the temperature, when the temperature is increased, the solution property can be changed, and the flowing of the solution is influenced.
As a preferable scheme:
the gel spinning method for manufacturing the chitosan fiber comprises the following specific steps:
(1) slowly injecting an organic sodium phosphate solution into the chitosan solution until the pH value of the system is 7.2-7.5 to obtain a spinning solution;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is increased from 3-6 ℃ to 30-40 ℃ when the spinning solution reaches the spinning nozzle;
(3) spinning trickle enters an air layer;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation primary structure;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The gel spinning method for preparing chitosan fiber comprises the following steps of (1), wherein the concentration of the organic sodium phosphate solution is 0.1-1 mol/L, and the solvent is water; the concentration of the sodium organophosphate solution is matched with that of the chitosan solution, so that when the addition amount of the sodium organophosphate solution is 5-10% of the mass of the chitosan solution, the pH value of the spinning solution system is adjusted to 7.2-7.4;
the chitosan solution is prepared by dissolving chitosan in an acetic acid solution or hydrochloric acid solution with the concentration of 1-6 wt%, and the mass fraction of chitosan in the chitosan solution is 1-3 wt%; the concentration of the acetic acid solution or the hydrochloric acid solution is too low to dissolve the chitosan; too high, it may result in degradation of chitosan.
In the gel spinning method for manufacturing chitosan fiber, the organic sodium phosphate is β -sodium glycerophosphate, α -D-glucose-1-sodium phosphate or D-glucose-6-disodium phosphate hydrate, and the weight average molecular weight of the chitosan is 1 × 106～2×106g/mol, the deacetylation degree is more than 90%, the weight average molecular weight of the chitosan is set to be the solution meeting the requirement, and if the molecular weight is too low, the formation of a highly-oriented and highly-crystallized structure is not facilitated; if the molecular weight is too high, the solution viscosity becomes too high, which is not favorable for extrusion.
In the gel spinning method for manufacturing chitosan fiber, in the step (3), the length of the air layer is 5-30 mm, the air blowing device in the air layer is a circular air blowing device, and the air blowing speed is 3-8 m/min. The air layer is arranged to ensure that the macromolecules in the spinning solution have certain orientation, the length is too short, and the orientation is insufficient; over-long, the spinning streamlets can break. The blowing speed is set to keep the temperature of the air layer at 30-40 ℃, so that the temperature of the system in the air layer and the extrusion temperature are kept constant, and the solution-gel state is continuously kept.
In the gel spinning method for producing chitosan fiber, in the step (4), the coagulation bath is water, and the drawing magnification of the spinneret is 2-3. The drafting ratio of the spinneret is set according to the drafting ratio which the spinning stream can bear, and is too low and insufficient in orientation; too high, the spinning streamlets can break.
In the gel spinning method for producing chitosan fiber, in the step (5), the plasticizing bath is a sodium hydroxide solution with a concentration of 2-4 wt%, and the drafting ratio of the plasticizing bath is 4-5.
The gel spinning method for manufacturing the chitosan fiber has the advantages that the filament number of the chitosan fiber is 1.2-5.0 dtex, the dry breaking strength is 2.7-3.8 cN/dtex, the dry elongation at break is 8-12%, the wet breaking strength is 1.9-2.9 cN/dtex, and the wet elongation at break is 10-15%; according to the FZ/T52012-2011 industrial standard, the dry breaking strength of the chitosan fiber is 1.15-1.50 cN/dtex, the dry breaking elongation is 6-12%, and the dry breaking strength of the chitosan fiber prepared by the method is far higher than the industrial standard.
The chitosan fiber prepared by the gel spinning method has a fiber structure that amorphous regions are uniformly dispersed in a continuous extended chain crystal matrix, while the chitosan fiber prepared by the conventional wet spinning method and the dry spraying wet spinning method has a structure that folded chain platelets and amorphous regions are alternately arranged in series, so that the dry breaking strength of the chitosan fiber prepared by the gel spinning method is higher than 2.7cN/dtex and is far higher than the mechanical strength of the chitosan fiber produced in large scale at present, and the mechanical property of the fiber is greatly changed due to the optimization of the fiber structure.
Compared with wet spinning or dry-spray wet spinning, the method for preparing the chitosan fiber by the gel spinning method has the following characteristics: the special temperature induction solution-gel transition characteristic of a chitosan/organic sodium phosphate system is utilized, and the temperature of the spinning solution before the spinning solution is discharged from a spinning nozzle meets the requirement of solution-gel transition through the regulation and control of a spinning process; in an air layer containing an air blowing temperature control system, solution-gel conversion is carried out on the spinning trickle to form gel trickle, certain solvent diffusion is carried out on the gel trickle in a coagulating bath to form a gel network structure, and a small amount of ordered structures are formed under the action of positive drafting; and (3) allowing the solidified trickle to enter a plasticizing bath, and performing high-power drafting to form the chitosan fiber with high crystallinity, high orientation degree, compact fiber structure and no skin-core structure.
Has the advantages that:
(1) the gel spinning method for manufacturing chitosan fibers belongs to dry-jet wet-process gel spinning, and is high in drafting multiple, namely the winding speed is several times of the extrusion speed, so that the spinning speed is high, and reaches 50-100 m/min, which is much higher than the conventional wet-process spinning speed of chitosan;
(2) the chitosan fiber prepared by the gel spinning method for preparing chitosan fiber has high crystallinity and orientation degree, compact fiber structure, no skin-core structure and mechanical strength far higher than that of the chitosan fiber prepared by conventional wet spinning;
(3) the chitosan fiber prepared by the gel spinning method for preparing the chitosan fiber has the advantages that the gel structure formed by temperature change still exists in the solidification stage, the skin-core structure of the fiber is not obvious, and the skin layer does not shrink to form a gully shape, so that the linear density irregularity of the fiber is lower than +/-2%, and the glossiness of the fiber is high because the skin-core structure of the fiber is not obvious and the gully shape caused by skin layer shrinkage does not exist, and the surface layer of the fiber is smooth and compact.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting β -sodium glycerophosphate aqueous solution with the concentration of 1mol/L into chitosan solution with the concentration of 1 wt% until the pH value of the system is 7.2 to obtain spinning solution, wherein the chitosan solution is prepared by adding the chitosan solution with the weight-average molecular weight of 1 × 106g/mol, degree of deacetylation 91%The chitosan is dissolved in acetic acid solution with the concentration of 1wt percent to prepare the chitosan;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is increased from 3 ℃ to 30 ℃ when the spinning solution reaches the spinning nozzle;
(3) the spinning trickle enters an air layer with the length of 5mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 30 ℃, and the air blowing speed is 3 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 30 ℃, and the drawing magnification of a spinning jet is 2;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 2 wt%, the temperature of the plasticizing bath is 50 ℃, and the drafting multiplying power of the plasticizing bath is 4;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 1.2dtex, the dry breaking strength of 2.7cN/dtex, the dry elongation at break of 12 percent, the wet breaking strength of 1.9cN/dtex and the wet elongation at break of 15 percent.
Example 2
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting β -sodium glycerophosphate water solution with concentration of 0.8mol/L into chitosan solution with concentration of 1.5 wt% until pH value of system is 7.3 to obtain spinning solution, wherein the chitosan solution is prepared by adding sodium glycerophosphate water solution with weight average molecular weight of 1.2 × 106g/mol, deacetylation degree 92% chitosan dissolved in 2 wt% hydrochloric acid solution;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is raised from 4 ℃ to 35 ℃ when the spinning solution reaches the spinning nozzle;
(3) spinning trickle enters an air layer with the length of 10mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 35 ℃, and the air blowing speed is 5 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 35 ℃, and the drawing magnification of a spinning jet is 2;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 2.5 wt%, the temperature of the plasticizing bath is 54 ℃, and the drafting multiplying power of the plasticizing bath is 4;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 2.2dtex, the dry breaking strength of 3.1cN/dtex, the dry elongation at break of 10 percent, the wet breaking strength of 2.2cN/dtex and the wet elongation at break of 12 percent.
Example 3
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting α -D-glucose-1-sodium phosphate aqueous solution with concentration of 0.3mol/L into chitosan solution with concentration of 2 wt% until pH value of system is 7.4 to obtain spinning solution, wherein the chitosan solution is prepared by adding chitosan with weight average molecular weight of 1.5 × 106g/mol and 93 percent of deacetylation degree in acetic acid solution with the concentration of 4 weight percent;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is raised from 5 ℃ to 36 ℃ when the spinning solution reaches the spinning nozzle;
(3) the spinning trickle enters an air layer with the length of 15mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 36 ℃, and the air blowing speed is 6 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 35 ℃, and the drawing magnification of a spinning jet is 3;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 3 wt%, the temperature of the plasticizing bath is 55 ℃, and the drafting multiplying power of the plasticizing bath is 5;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 3.5dtex, the dry breaking strength of 3.4cN/dtex, the dry elongation at break of 9 percent, the wet breaking strength of 2.5cN/dtex and the wet elongation at break of 11 percent.
Example 4
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting D-glucose-6-disodium phosphate hydrate aqueous solution with concentration of 0.1mol/L into chitosan solution with concentration of 3 wt% until pH value of the system is 7.5 to obtain spinning solution, wherein the chitosan solution is prepared by adding water with weight average molecular weight of 2 × 106g/mol chitosan with deacetylation degree of 95% is dissolved in hydrochloric acid solution with concentration of 6 wt% to prepare the chitosan;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is increased from 6 ℃ to 40 ℃ when the spinning solution reaches the spinning nozzle;
(3) the spinning trickle enters an air layer with the length of 30mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 40 ℃, and the air blowing speed is 8 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 40 ℃, and the drawing magnification of a spinning jet is 3;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 4 wt%, the temperature of the plasticizing bath is 60 ℃, and the drafting multiplying power of the plasticizing bath is 5;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 5.0dtex, the dry breaking strength of 3.8cN/dtex, the dry elongation at break of 12%, the wet breaking strength of 2.9cN/dtex, and the wet elongation at break of 15%.
Example 5
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting D-glucose-6-disodium phosphate hydrate aqueous solution with concentration of 0.2mol/L into chitosan solution with concentration of 3 wt% until pH value of the system is 7.2 to obtain spinning solution, wherein the chitosan solution is prepared by adding water with weight average molecular weight of 2 × 106g/mol chitosan with deacetylation degree of 95% is dissolved in hydrochloric acid solution with concentration of 6 wt% to prepare the chitosan;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is raised from 5 ℃ to 38 ℃ when the spinning solution reaches the spinning nozzle;
(3) spinning trickle enters an air layer with the length of 25mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 35 ℃, and the air blowing speed is 7 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 38 ℃, and the drawing magnification of a spinning jet is 2;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 4 wt%, the temperature of the plasticizing bath is 56 ℃, and the drafting multiplying power of the plasticizing bath is 4;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 4.8dtex, the dry breaking strength of 3.6cN/dtex, the dry elongation at break of 9 percent, the wet breaking strength of 2.8cN/dtex and the wet elongation at break of 11 percent.
Example 6
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting β -sodium glycerophosphate water solution with concentration of 0.2mol/L into chitosan solution with concentration of 2.5 wt% until pH value of the system is 7.5 to obtain spinning solution, wherein the chitosan solution is prepared by adding sodium glycerophosphate water solution with weight average molecular weight of 1.8 × 106g/mol chitosan with deacetylation degree of 95% is dissolved in acetic acid solution with concentration of 5 wt% to obtain the chitosan-containing aqueous solution;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is raised from 5 ℃ to 38 ℃ when the spinning solution reaches the spinning nozzle;
(3) spinning trickle enters an air layer with the length of 25mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 35 ℃, and the air blowing speed is 7 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 38 ℃, and the drawing magnification of a spinning jet is 2;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 4 wt%, the temperature of the plasticizing bath is 56 ℃, and the drafting multiplying power of the plasticizing bath is 4;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 4.2dtex, the dry breaking strength of 3.3cN/dtex, the dry elongation at break of 10 percent, the wet breaking strength of 2.5cN/dtex and the wet elongation at break of 12 percent.
Example 7
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting α -D-glucose-1-sodium phosphate aqueous solution with the concentration of 1mol/L into chitosan solution with the concentration of 3 wt% until the pH value of the system is 7.4 to obtain spinning solution, wherein the chitosan solution is prepared by adding water with the weight-average molecular weight of 2 × 106g/mol chitosan with deacetylation degree of 96% is dissolved in acetic acid solution with concentration of 5 wt% to obtain the chitosan-containing aqueous solution;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is increased from 3 ℃ to 30 ℃ when the spinning solution reaches the spinning nozzle;
(3) the spinning trickle enters an air layer with the length of 5mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 30 ℃, and the air blowing speed is 3 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 30 ℃, and the drawing magnification of a spinning jet is 2;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 2 wt%, the temperature of the plasticizing bath is 50 ℃, and the drafting multiplying power of the plasticizing bath is 4;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 2.2dtex, the dry breaking strength of 3.1cN/dtex, the dry elongation at break of 11 percent, the wet breaking strength of 2.1cN/dtex and the wet elongation at break of 13 percent.
Example 8
A gel spinning method for manufacturing chitosan fibers comprises the following specific steps:
(1) slowly injecting α -D-glucose-1-sodium phosphate aqueous solution with concentration of 0.4mol/L into chitosan solution with concentration of 3 wt% until pH value of system is 7.2 to obtain spinning solution, wherein the chitosan solution is prepared by adding chitosan with weight average molecular weight of 1.5 × 106g/mol, deacetylation degree 97% chitosan dissolved in 2 wt% hydrochloric acid solution;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extrusion to ensure that the temperature of the spinning solution is raised from 5 ℃ to 35 ℃ when the spinning solution reaches the spinning nozzle;
(3) the spinning trickle enters an air layer with the length of 20mm, the air layer is provided with a circular air blowing device, the air blowing temperature is 35 ℃, and the air blowing speed is 6 m/min;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber, the coagulating bath is water, the temperature of the coagulating bath is 35 ℃, and the drawing magnification of a spinning jet is 2;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation state primary structure, the plasticizing bath is sodium hydroxide solution with the concentration of 3 wt%, the temperature of the plasticizing bath is 27 ℃, and the drafting multiplying power of the plasticizing bath is 4;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
The finally prepared chitosan fiber has the filament number of 3.0dtex, the dry breaking strength of 3.2cN/dtex, the dry elongation at break of 12 percent, the wet breaking strength of 2.9cN/dtex and the wet elongation at break of 13 percent.

Claims (8)

1. A gel spinning method for preparing chitosan fiber is characterized in that a spinning solution is extruded through a spinneret orifice and then sequentially enters an air layer, a coagulating bath and a plasticizing bath to prepare the chitosan fiber, wherein the weight average molecular weight of the spinning solution is more than or equal to 1 × 106g/mol of semi-dilute solution of chitosan, wherein the spinning solution contains organic sodium phosphate; before extrusion, heating the spinning solution to raise the temperature of the spinning solution from 3-6 ℃ to 30-40 ℃ when the spinning solution reaches a spinning nozzle; the air layer is provided with a blowing device, and the blowing temperature is 30-40 ℃; the temperature of the coagulating bath is 30-40 ℃; the plasticizing bath temperature is 50-60 ℃.
2. The gel spinning method for manufacturing chitosan fibers as claimed in claim 1, wherein the specific steps are as follows:
(1) injecting the sodium organophosphate solution into the chitosan solution until the pH value of the system is 7.2-7.5 to obtain a spinning solution;
(2) filtering and metering the spinning solution, extruding the spinning solution through a spinning nozzle to form a spinning trickle, and heating the spinning solution before extruding;
(3) spinning trickle enters an air layer;
(4) the spinning trickle enters a coagulating bath to form gel nascent fiber;
(5) the gel nascent fiber enters a plasticizing bath to form chitosan fiber with an aggregation primary structure;
(6) and (3) washing and drying the chitosan fiber with the aggregation primary structure to obtain the chitosan fiber.
3. The gel spinning method for preparing chitosan fiber according to claim 2, wherein in the step (1), the concentration of the organic sodium phosphate solution is 0.1-1 mol/L, and the solvent is water;
the chitosan solution is prepared by dissolving chitosan in an acetic acid solution or hydrochloric acid solution with the concentration of 1-6 wt%, and the mass fraction of chitosan in the chitosan solution is 1-3 wt%.
4. The gel spinning method for manufacturing chitosan fiber according to claim 3, wherein the sodium organophosphate is β -sodium glycerophosphate, α -D-glucose-1-phosphate sodium salt or D-glucose-6-disodium phosphate hydrate, and the weight average molecular weight of chitosan is 1 × 106～2×106g/mol, degree of deacetylation greater than 90%.
5. The gel spinning method for preparing chitosan fiber according to claim 2, wherein in the step (3), the length of the air layer is 5-30 mm, the blowing device in the air layer is a circular blowing device, and the blowing speed is 3-8 m/min.
6. The gel spinning method for producing chitosan fibers according to claim 2, wherein in step (4), the coagulation bath is water, and the spinneret draw ratio is 2 to 3.
7. The gel spinning method for producing chitosan fiber according to claim 2, wherein in the step (5), the plasticizing bath is a sodium hydroxide solution with a concentration of 2-4 wt%, and the draft ratio of the plasticizing bath is 4-5.
8. The gel spinning method for producing chitosan fibers according to claim 2, wherein the chitosan fibers have a single fiber fineness of 1.2 to 5.0dtex, a dry breaking strength of 2.7 to 3.8cN/dtex, a dry elongation at break of 8 to 12%, a wet breaking strength of 1.9 to 2.9cN/dtex, and a wet elongation at break of 10 to 15%.
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