CN110359101A - A kind of gel spinning process manufacturing chitin fiber - Google Patents
A kind of gel spinning process manufacturing chitin fiber Download PDFInfo
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- CN110359101A CN110359101A CN201910655449.4A CN201910655449A CN110359101A CN 110359101 A CN110359101 A CN 110359101A CN 201910655449 A CN201910655449 A CN 201910655449A CN 110359101 A CN110359101 A CN 110359101A
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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 present invention relates to a kind of gel spinning process for manufacturing chitin fiber, by spinning solution after spinneret orifice squeezes out, sequentially enter air layer, coagulating bath and plasticizing-bath and chitin fiber is made, wherein spinning solution is weight average molecular weight >=1 × 106Half weak solution of the chitosan of g/mol contains organic sodium phosphate in spinning solution；Before extrusion, spinning solution is heated, temperature rises to 30~40 DEG C by 3~6 DEG C when it being made to reach spinning nozzle；Air layer is equipped with blowing device, and blowing temperature is 30~40 DEG C；The temperature of coagulating bath is 30~40 DEG C；Being plasticized bath temperature is 50~60 DEG C.A kind of gel spinning process of manufacture chitin fiber of the invention, compared to wet spinning perhaps dry-jet wet spinning it is with the obvious advantage can effectively solve the problem that wet process or dry-jet wet spinning preparation chitin fiber poor mechanical property the problem of, great popularization.
Description
Technical field
The invention belongs to chitin fiber technical fields, are related to a kind of gel spinning process for manufacturing chitin fiber.
Background technique
Chitin fiber is a kind of regenerated fiber being usually prepared by wet spinning process, has antibacterial, hemostasis, promotes
Wound healing and other effects is excellent medical and health.But the dry break strength of chitin fiber only has 1.8cN/
Dtex, mechanical property is relatively low, need to be with the blended use such as cotton, viscose rayon, this is because chitin fiber is shaped in wet spinning
In the process, the chitosan molecule chain in spinning solution is random coil conformation, and spinning solution is directly entered coagulating bath, silk after going out spinning nozzle
Tensile stress suffered by item is smaller, and " heredity " occurs for the chitosan molecule chain of random coil conformation in solution, causes the as-spun fibre to be in
Existing isotropic disordered state, and there are stronger interaction of hydrogen bond with molecule interchain in chitosan molecule chain, so that its
Glass transition temperature is much higher than fusing point, and molecule segment orientation is difficult in subsequent drawing process, it is difficult to be stretched through rear road
The crystallinity and the crystalline region degree of orientation for improving fiber, lead to the poor mechanical property of fiber.
In order to improve the mechanical property of chitin fiber, there is researcher to prepare chitin fiber by dry-jet wet spinning
(synthetic fiber industry, 2003,26 (2): 36-38.) are different from wet spinning, the spinning nozzle of dry-jet wet spinning and coagulating bath
Between there are air layer, dynamic analysis of spinning bears positive drawing-off in air section, and the polymer segment in dynamic analysis of spinning can occur centainly to be orientated,
The orientation and crystallinity that can be improved fiber, show as the raising of fibrous mechanical property.However, dry-jet wet spinning and Wet-spinning
Silk preparation fiber structural nature on it is identical, be that chain-folded lamellae and amorphous area are alternately arranged, concentration of tension forces in platelet it
Between amorphous area part, mechanical property determines by the amorphous area comprising many vulnerable areas, therefore, dry-jet wet spinning preparation
The mechanical property of chitin fiber and be not implemented be greatly improved.
Gel spinning belongs to wet spinning field, is that macromolecule spinning solution is extruded into dynamic analysis of spinning, passes through temperature
The method of induced transformation, makes dynamic analysis of spinning be changed into three-dimensional net structure from solution state, expands in subsequent solvent and non-solvent
The stage of dissipating, phase transition occur on the basis of three-dimensional net structure, form uniformly loose network structure, not will form apparent
Skin-core structure, as-spun fibre can bear high drafting, and randomly-oriented macromolecular chain is induced to form orientation texture, promote stress
Induction crystallization, the structure for making fiber that there is amorphous region to be dispersed in continuous crystallisation Medium Culture, mechanical property obtain flying for matter
More.Currently, the commercially produced product power all with higher using gel spinning process preparation such as ultra high molecular weight polyethylene fiber
Learn performance.But the data that yet there are no open report of chitin fiber is prepared about gel spinning.
Therefore, a kind of gel spinning process of manufacture chitin fiber is studied to solve chitin fiber poor mechanical property
Problem has a very important significance.
Summary of the invention
The problem of present invention aim to address chitin fiber poor mechanical properties in the prior art, provides a kind of manufacture shell
The gel spinning process of glycan fiber.
In order to achieve the above objectives, the scheme that the present invention uses is as follows:
It is a kind of manufacture chitin fiber gel spinning process sequentially enter air by spinning solution after spinneret orifice squeezes out
Chitin fiber is made in layer, coagulating bath and plasticizing-bath, wherein spinning solution is weight average molecular weight >=1 × 106The chitosan of g/mol
Half weak solution (Polymer Solution that half weak solution, that is, concentration is higher than overlapping concentration), organic sodium phosphate is contained in spinning solution, with
The increase of organic phosphoric acid na concn in system, gel conversion behavior are more significant；Before extrusion, spinning solution is heated, arrives it
Temperature rises to 30~40 DEG C by 3~6 DEG C when up to spinning nozzle；Air layer is equipped with blowing device, and blowing temperature is 30~40 DEG C；Solidification
The temperature of bath is 30~40 DEG C；Being plasticized bath temperature is 50~60 DEG C, and the setting of these temperature is provided to guarantee chitosan solution
Can gelation and carry out preferred.
It, will although gel spinning process is the method for relative maturity for ultra high molecular weight polyethylene fiber
It, which is applied in the preparation of chitin fiber, but has larger difficulty, and main cause is: polyethylene is the simple macromolecule of structure,
Polar group, no strong interaction is not present in strand, and cooling can make polyethylene solution form gel (frozen glue) structure, tension
The polyethylene spun filament of the lower gel structure containing certain solvent of effect, molecule interchain generate sliding, can carry out ultra-drawing,
Very well ordered structure is formed, and chitosan is the different high molecular material of chemical property, and it is special not have solution-gel conversion
Property, there are hydroxyl isopolarity group on strand, molecule interchain easily forms intermolecular interaction, it is not easy to carry out super times and draw
It stretches.
The application is improved by the spinning technique to chitin fiber in the prior art so that chitin fiber coagulates
Glue spinning is possibly realized, and compact structure, uniform, different from common skin-core structure chitin fiber has finally been made, and is improved
Place is as follows:
1) present invention adds organic phosphoric acid sodium, the purpose is to make solution that temperature-induced gelation transition occur, are formed
Gel structure can bear high drafting, the formation of fiber ordered structure is induced, to improve the mechanical property of fiber；It is existing
Wet spinning process and dry-jet wet spinning method organic phosphoric acid sodium is not added, the reason is that using acid solution as the molten of chitosan
Agent, coagulator of the aqueous slkali as chitosan, it is already possible to it is fine to meet chitosan of the preparation mechanical property less than 1.8cN/dtex
The requirement of dimension carries out gelation transition due to not having organic phosphoric acid sodium inducing solution is added, in the prior art chitin fiber
Crystallization is low with the degree of orientation in preparation process, so the mechanical property of fiber is not high；
2) present invention is provided with air layer, plays the role of being to occur that the macromolecule strand in dynamic analysis of spinning centainly
Orientation, conducive to the formation of ordered structure, to improve the mechanical property of fiber；Although dry-jet wet spinning in the prior art
Forming process is also provided with air layer, but air layer of the invention is provided with circular blow wind apparatus, and effect is to provide spinning liquor-
Energy needed for gel conversion promotes the formation of gel structure；Wet spinning forming process in the prior art is not provided with air
Layer, the reason is that the viscosity of spinning solution is low, unbearable spinning tension, therefore, the spinning solution that the prior art goes out spinning nozzle are directly solidifying
Drawing-off or the positive drawing-off of low range Gu spinneret draft is negative；
3) chitosan of the present invention, molecular weight are high, and the concentration of chitosan is in half and dilute non-twines in solution
Concentration area is tied, that is, is higher than overlapping concentration, is less than entanglement concentration, high drafting, high molecular weight chitosan molecular end may be implemented
Few, the tiny flaw on the fibre structure as caused by molecular end is few, and uses the chitosan solution of half dilute concentration, macromolecular chain
Entanglement point it is few, stretchable multiple is just bigger, although being in the chitosan solution in weak solution area, the entanglement point of macromolecular chain is more
It is few, but the chitosan concentration of weak solution is too low, is unfavorable for the formation of fiber compact texture, the fibre strength of preparation remains unchanged not
Height, therefore, the molecular weight of chitosan and concentration range that the present invention selects, be in order to formed orientation, compact texture and carry out excellent
Choosing；Wet spinning and dry-jet wet spinning in the prior art, molecular weight of chitosan is relatively lower, concentration is higher and is in dense molten
Liquid entangled regions, the reason is that, the concentration of solution is higher, corresponding solvent usage amount is reduced, more economical, and concentration height and molecular weight
When big, then the viscosity that will lead to solution is high, is unfavorable for steady extruding, therefore, conventional wet spinning and dry-jet wet spinning are not
Select the chitosan of higher molecular weight；
4) temperature is 3~6 DEG C to spinning solution of the invention before heating, and wet spinning in the prior art and dry squirts method
The spinning solution temperature of spinning is generally near room temperature, and temperature is significantly lower than the prior art to spinning solution of the invention before heating, is
Chitosan system since organic phosphoric acid sodium being added when being in this temperature remains solution state, when the temperature increases, solution
Matter can change, and influence the flowing of solution.
As a preferred option:
A kind of gel spinning process manufacturing chitin fiber as described above, the specific steps are as follows:
(1) organic phosphoric acid sodium solution is slowly injected into chitosan solution to the pH value of system and obtains spinning for 7.2~7.5
Liquid；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 30~40 DEG C by 3~6 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters air layer；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
A kind of gel spinning process for manufacturing chitin fiber as described above, in step (1), organic phosphoric acid sodium solution
Concentration is 0.1~1mol/L, and solvent is water；The concentration of organic phosphoric acid sodium solution and the concentration of chitosan solution match, and make to have
When machine sodium radio-phosphate,P-32 solution additive amount is the 5~10% of chitosan solution quality, the pH value of spinning liquid system is adjusted to 7.2~7.4；
Chitosan solution is made by dissolving the chitosan in the acetum or hydrochloric acid solution of 1~6wt% of concentration
, the mass fraction of chitosan is 1~3wt% in chitosan solution；The concentration of acetum or hydrochloric acid solution is too low, can not make
Chitosan dissolution；It is excessively high, then it will lead to degradation of chitosan.
A kind of gel spinning process for manufacturing chitin fiber as described above, organic phosphoric acid sodium be sodium β-glycerophosphate,
Alpha-D-glucose -1- sodium ascorbyl phosphate or D- grape sugar -6- disodium hydrogen phosphate hydrate；The weight average molecular weight of chitosan is 1 × 106~2
×106G/mol, deacetylation be greater than 90%, the weight average molecular weight of chitosan be set to this be in order to prepare meet the requirements it is molten
Liquid, molecular weight is too low, then is unfavorable for forming highly oriented, highly crystalline structure；Molecular weight is excessively high, then solution viscosity is excessively high, is unfavorable for
It squeezes out.
A kind of gel spinning process for manufacturing chitin fiber as described above, in step (3), the length of air layer is 5
~30mm, the blowing device in air layer are circular blow wind apparatus, and cold air blast velocity is 3~8m/min.Air layer setting purpose be
The macromolecule in spinning solution is set to have certain orientation, length is too short, is orientated insufficient；Too long, dynamic analysis of spinning can be broken.Blowing
The temperature that the purpose of speed setting is to maintain air layer is 30~40 DEG C, makes system in the temperature and extrusion temperature one of air layer
Directly, continue to keep solution-gel state.
A kind of gel spinning process for manufacturing chitin fiber as described above, in step (4), coagulating bath is water, spinneret
Head draft ratio is 2~3.Spinneret draft multiplying power is arranged according to the draw ratio that dynamic analysis of spinning can be born, too low, is taken
To insufficient；Excessively high, dynamic analysis of spinning can be broken.
A kind of gel spinning process for manufacturing chitin fiber as described above, in step (5), plasticizing-bath be concentration 2~
The sodium hydroxide solution of 4wt%, plasticizing-bath draft ratio are 4~5.
A kind of gel spinning process manufacturing chitin fiber as described above, the filament number of chitin fiber are 1.2
~5.0dtex, dry break strength are 2.7~3.8cN/dtex, and water free breaking elongation rate is 8~12%, wet break strength
For 1.9~2.9cN/dtex, wet break elongation is 10~15%；According to FZ/T52012-2011 professional standard, chitosan
Fiber dry break strength is 1.15~1.50cN/dtex, and water free breaking elongation rate is 6~12%, and shell produced by the present invention is poly-
The dry break strength of sugared fiber is much higher than professional standard.
The present invention uses the chitin fiber of gel spinning preparation, and fibre structure is that amorphous region is dispersed in continuously
In extended chain crystalline matrix, and the chitin fiber of conventional wet lay spinning and dry-jet wet spinning preparation, be chain-folded lamellae with
Amorphous area is alternately arranged in concatenated structure, therefore, is based on chitin fiber prepared by the present invention, dry break strength is higher than
2.7cN/dtex makes fibre because of the optimization of fibre structure much higher than the mechanical strength of the chitin fiber of current large-scale production
Great change has occurred in dimension mechanical property.
The present invention realizes gel spinning process and prepares chitin fiber, compares wet process or dry-jet wet spinning, this hair
It is bright to have a characteristic that using temperature-induced solution-gel conversion characteristic specific to chitosan/organic phosphoric acid sodium system, lead to
The regulation for crossing spinning technique, temperature reaches the requirement of solution-gel transformation before so that spinning solution is gone out spinning nozzle；Containing blowing temperature control
Solution-gel transformation occurs for the air layer of system, dynamic analysis of spinning, forms gel thread, and gel thread occurs certain in coagulating bath
Sovent diffusion, formed gel network structure, positive drawing-off effect under form a small amount of ordered structure；Solidification thread enters plasticizing
Bath is subjected to high drafting, forms high crystallinity, degree of orientation height, fibre structure densification and the chitin fiber without skin-core structure.
The utility model has the advantages that
(1) a kind of gel spinning process of manufacture chitin fiber of the invention belong to it is dry squirt method gel spinning, due to
Drafting multiple of the present invention is high, i.e., winding speed is several times as much as extruded velocity, and therefore, spinning speed is very fast, and spinning speed reaches 50~
100m/min, much higher than the speed of chitosan conventional wet lay spinning；
(2) chitin fiber made from a kind of gel spinning process of manufacture chitin fiber of the invention, crystallinity with
The degree of orientation is high, and fibre structure is fine and close, and without skin-core structure, mechanical strength is fine much higher than chitosan made from conventional wet lay spinning
Dimension；
(3) chitin fiber made from a kind of gel spinning process of manufacture chitin fiber of the invention, due to temperature
The gel structure that mutagens are formed still exists in solidification stages, and fiber skin-core structure is unobvious, also shrinks and is formed without cortex
Gully shape pattern, thus the fineness-unevenness rate of fiber is lower than ± 2%, since the skin-core structure of fiber is unobvious, also without skin
The glossiness of gully form, the smooth densification of fiber sheath, therefore fiber caused by layer is shunk is high.
Specific embodiment
The invention will be further elucidated with reference to specific embodiments.It should be understood that these embodiments are merely to illustrate this hair
It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, art technology
Personnel can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Fixed range.
Embodiment 1
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) the sodium β-glycerophosphate aqueous solution of concentration 1mol/L is slowly injected into the chitosan solution of concentration 1wt% extremely
The pH value of system obtains spinning solution for 7.2, wherein chitosan solution is by being 1 × 10 by weight average molecular weight6G/mol, de- second
The chitosan that acyl degree is 91% is dissolved in the acetum of concentration 1wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 30 DEG C by 3 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 5mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 30 DEG C,
Cold air blast velocity is 3m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 30 DEG C,
Spinneret draft multiplying power is 2；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 2wt%, plasticizing bath temperature is 50 DEG C, and plasticizing-bath draft ratio is 4；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 1.2dtex, dry break strength 2.7cN/dtex, dry state
Elongation at break is 12%, wet break strength 1.9cN/dtex, wet break elongation 15%.
Embodiment 2
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) the sodium β-glycerophosphate aqueous solution of concentration 0.8mol/L is slowly injected into the chitosan solution of concentration 1.5wt%
In to the pH value of system be 7.3 to obtain spinning solution, wherein chitosan solution is by being 1.2 × 10 by weight average molecular weight6g/
Mol, the chitosan that deacetylation is 92% are dissolved in the hydrochloric acid solution of concentration 2wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 35 DEG C by 4 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 10mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 35
DEG C, cold air blast velocity 5m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 35 DEG C,
Spinneret draft multiplying power is 2；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 2.5wt%, plasticizing bath temperature is 54 DEG C, and plasticizing-bath draft ratio is 4；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 2.2dtex, dry break strength 3.1cN/dtex, dry state
Elongation at break is 10%, wet break strength 2.2cN/dtex, wet break elongation 12%.
Embodiment 3
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) shell that the alpha-D-glucose -1- sodium ascorbyl phosphate aqueous solution of concentration 0.3mol/L is slowly injected into concentration 2wt% is gathered
To the pH value of system be 7.4 to obtain spinning solution in sugar juice, wherein chitosan solution be by be 1.5 by weight average molecular weight ×
106G/mol, the chitosan that deacetylation is 93% are dissolved in the acetum of concentration 4wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 36 DEG C by 5 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 15mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 36
DEG C, cold air blast velocity 6m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 35 DEG C,
Spinneret draft multiplying power is 3；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 3wt%, plasticizing bath temperature is 55 DEG C, and plasticizing-bath draft ratio is 5；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 3.5dtex, dry break strength 3.4cN/dtex, dry state
Elongation at break is 9%, wet break strength 2.5cN/dtex, wet break elongation 11%.
Embodiment 4
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) the D- grape sugar -6- disodium hydrogen phosphate aqueous solution of concentration 0.1mol/L is slowly injected into the shell of concentration 3wt%
To the pH value of system be 7.5 to obtain spinning solution in glycan solution, wherein chitosan solution be by be 2 by weight average molecular weight ×
106G/mol, the chitosan that deacetylation is 95% are dissolved in the hydrochloric acid solution of concentration 6wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 40 DEG C by 6 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 30mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 40
DEG C, cold air blast velocity 8m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 40 DEG C,
Spinneret draft multiplying power is 3；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 4wt%, plasticizing bath temperature is 60 DEG C, and plasticizing-bath draft ratio is 5；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 5.0dtex, dry break strength 3.8cN/dtex, dry state
Elongation at break is 12%, wet break strength 2.9cN/dtex, wet break elongation 15%.
Embodiment 5
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) the D- grape sugar -6- disodium hydrogen phosphate aqueous solution of concentration 0.2mol/L is slowly injected into the shell of concentration 3wt%
To the pH value of system be 7.2 to obtain spinning solution in glycan solution, wherein chitosan solution be by be 2 by weight average molecular weight ×
106G/mol, the chitosan that deacetylation is 95% are dissolved in the hydrochloric acid solution of concentration 6wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 38 DEG C by 5 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 25mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 35
DEG C, cold air blast velocity 7m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 38 DEG C,
Spinneret draft multiplying power is 2；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 4wt%, plasticizing bath temperature is 56 DEG C, and plasticizing-bath draft ratio is 4；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 4.8dtex, dry break strength 3.6cN/dtex, dry state
Elongation at break is 9%, wet break strength 2.8cN/dtex, wet break elongation 11%.
Embodiment 6
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) the sodium β-glycerophosphate aqueous solution of concentration 0.2mol/L is slowly injected into the chitosan solution of concentration 2.5wt%
In to the pH value of system be 7.5 to obtain spinning solution, wherein chitosan solution is by being 1.8 × 10 by weight average molecular weight6g/
Mol, the chitosan that deacetylation is 95% are dissolved in the acetum of concentration 5wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 38 DEG C by 5 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 25mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 35
DEG C, cold air blast velocity 7m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 38 DEG C,
Spinneret draft multiplying power is 2；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 4wt%, plasticizing bath temperature is 56 DEG C, and plasticizing-bath draft ratio is 4；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 4.2dtex, dry break strength 3.3cN/dtex, dry state
Elongation at break is 10%, wet break strength 2.5cN/dtex, wet break elongation 12%.
Embodiment 7
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) alpha-D-glucose -1- sodium ascorbyl phosphate aqueous solution of concentration 1mol/L is slowly injected into the chitosan of concentration 3wt%
Spinning solution is obtained for 7.4 to the pH value of system in solution, wherein chitosan solution is by being 2 × 10 by weight average molecular weight6g/
Mol, the chitosan that deacetylation is 96% are dissolved in the acetum of concentration 5wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 30 DEG C by 3 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 5mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 30 DEG C,
Cold air blast velocity is 3m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 30 DEG C,
Spinneret draft multiplying power is 2；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 2wt%, plasticizing bath temperature is 50 DEG C, and plasticizing-bath draft ratio is 4；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 2.2dtex, dry break strength 3.1cN/dtex, dry state
Elongation at break is 11%, wet break strength 2.1cN/dtex, wet break elongation 13%.
Embodiment 8
A kind of gel spinning process manufacturing chitin fiber, the specific steps are as follows:
(1) shell that the alpha-D-glucose -1- sodium ascorbyl phosphate aqueous solution of concentration 0.4mol/L is slowly injected into concentration 3wt% is gathered
To the pH value of system be 7.2 to obtain spinning solution in sugar juice, wherein chitosan solution be by be 1.5 by weight average molecular weight ×
106G/mol, the chitosan that deacetylation is 97% are dissolved in the hydrochloric acid solution of concentration 2wt% obtained；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, to spinning solution
It is heated, temperature rises to 35 DEG C by 5 DEG C when it being made to reach spinning nozzle；
(3) dynamic analysis of spinning enters the air layer that length is 20mm, and air layer is equipped with circular blow wind apparatus, and blowing temperature is 35
DEG C, cold air blast velocity 6m/min；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre, and coagulating bath is water, and the temperature of coagulating bath is 35 DEG C,
Spinneret draft multiplying power is 2；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure, and plasticizing-bath is concentration
The sodium hydroxide solution of 3wt%, plasticizing bath temperature is 27 DEG C, and plasticizing-bath draft ratio is 4；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
The filament number of final chitin fiber obtained is 3.0dtex, dry break strength 3.2cN/dtex, dry state
Elongation at break 12%, wet break strength 2.9cN/dtex, wet break elongation 13%.
Claims (8)
1. a kind of gel spinning process for manufacturing chitin fiber, it is characterized in that: by spinning solution after spinneret orifice squeezes out, successively into
Enter air layer, coagulating bath and plasticizing-bath and chitin fiber is made, wherein spinning solution is weight average molecular weight >=1 × 106G/mol's
Half weak solution of chitosan contains organic sodium phosphate in spinning solution；Before extrusion, spinning solution is heated, it is made to reach spinning nozzle
Shi Wendu rises to 30~40 DEG C by 3~6 DEG C；Air layer is equipped with blowing device, and blowing temperature is 30~40 DEG C；The temperature of coagulating bath
It is 30~40 DEG C；Being plasticized bath temperature is 50~60 DEG C.
2. a kind of gel spinning process for manufacturing chitin fiber according to claim 1, which is characterized in that specific steps
It is as follows:
(1) organic phosphoric acid sodium solution is injected in chitosan solution and obtains spinning solution to the pH value of system for 7.2~7.5；
(2) spinning solution is filtered, measured and spinning nozzle is extruded into dynamic analysis of spinning, and before extrusion, spinning solution is carried out
Heating；
(3) dynamic analysis of spinning enters air layer；
(4) dynamic analysis of spinning enters coagulating bath formation gel as-spun fibre；
(5) gel as-spun fibre enters the chitin fiber that plasticizing-bath forms state of aggregation primary structure；
(6) chitin fiber is washed and be dried to obtain to the chitin fiber of state of aggregation primary structure.
3. a kind of gel spinning process for manufacturing chitin fiber according to claim 2, which is characterized in that step (1)
In, the concentration of organic phosphoric acid sodium solution is 0.1~1mol/L, and solvent is water；
Chitosan solution is the shell as made from dissolving the chitosan in the acetum or hydrochloric acid solution of 1~6wt% of concentration
The mass fraction of chitosan is 1~3wt% in glycan solution.
4. a kind of gel spinning process for manufacturing chitin fiber according to claim 3, which is characterized in that organic phosphoric acid
Sodium is sodium β-glycerophosphate, alpha-D-glucose -1- sodium ascorbyl phosphate or D- grape sugar -6- disodium hydrogen phosphate hydrate；The weight of chitosan is equal
Molecular weight is 1 × 106~2 × 106G/mol, deacetylation are greater than 90%.
5. a kind of gel spinning process for manufacturing chitin fiber according to claim 2, which is characterized in that step (3)
In, the length of air layer is 5~30mm, and the blowing device in air layer is circular blow wind apparatus, and cold air blast velocity is 3~8m/min.
6. a kind of gel spinning process for manufacturing chitin fiber according to claim 2, which is characterized in that step (4)
In, coagulating bath is water, and spinneret draft multiplying power is 2~3.
7. a kind of gel spinning process for manufacturing chitin fiber according to claim 2, which is characterized in that step (5)
In, plasticizing-bath is the sodium hydroxide solution of 2~4wt% of concentration, and plasticizing-bath draft ratio is 4~5.
8. a kind of gel spinning process for manufacturing chitin fiber according to claim 2, which is characterized in that chitosan is fine
The filament number of dimension be 1.2~5.0dtex, dry break strength be 2.7~3.8cN/dtex, water free breaking elongation rate be 8~
12%, wet break strength is 1.9~2.9cN/dtex, and wet break elongation is 10~15%.
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