CN103993380A - Method for preparing high-strength chitosan fiber - Google Patents
Method for preparing high-strength chitosan fiber Download PDFInfo
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- CN103993380A CN103993380A CN201410236193.0A CN201410236193A CN103993380A CN 103993380 A CN103993380 A CN 103993380A CN 201410236193 A CN201410236193 A CN 201410236193A CN 103993380 A CN103993380 A CN 103993380A
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Abstract
The invention relates to the technical field of textiles and in particular relates to a method for preparing a high-strength chitosan fiber. The method for preparing the high-strength chitosan fiber comprises the following steps: step 1, mixing a chitosan solution and a polyvinyl alcohol solution, adding a cross-linking agent, uniformly stirring, and performing vacuum defoamation for 24 hours, thus obtaining a spinning stock solution for later use; and step 2, spinning the obtained spinning stock solution in a coagulating bath at the temperature of 25-45 DEG C, performing thread division and fiber strength improvement by adopting an ultrasonic oscillation method, thus obtaining the chitosan fiber. The chitosan fiber prepared by the method has good mechanical property, and the spinning property and knitting property of the chitosan fiber are improved.
Description
Technical field
The present invention relates to textile technology field, be specifically related to a kind of preparation method of Chitosan Fiber With High Tenacity.
Background technology
The organic matter of occurring in nature, what quantity was maximum is cellulose, is secondly protein, chitin is number three.Shitosan is the important derivatives of chitin, because of the wide material sources of chitin, as the shell of shellfish shrimp, crab, insect, in the cell membrane of fungi (yeast, mould) and the cell membrane of plant (as mushroom), all exists.
Preparation technology, the method for shitosan are also different.Existing preparing chitosan from chitin is mainly alkaline process deacetylation, first, by crust acid soak, demineralizes; Soak with solution again, except deproteinize, after NaOH washing and drying, obtain chitin, then glycan.The process that is obtained shitosan by chitin is referred to as deacetylation.
Shitosan is white in color or canescence more, and slightly pearly luster is translucent, mostly is sheet or powdery, tasteless nontoxic.Can not carry out melting to shitosan, because its pyrolysis temperature is 280-300 DEG C, pyrolysis occur before melting.Because of raw material difference and preparation method's difference, from hundreds thousand of to millions of not etc., because the existence of deacetylation, shitosan is low compared with chitin molecule amount for chitosan molecule amount.Shitosan can dissolve in most rare inorganic acid and organic acid, and organic acid is as the weak solution of the weak acid such as salicylic acid, tartaric acid, lactic acid, formic acid, acetic acid; Inorganic acid is as phosphoric acid, nitric acid, perchloric acid, hydrochloric acid etc., but is insoluble to dilute sulfuric acid and phosphoric acid,diluted.
On chitosan molecule chain, there are hydroxyl and amino that a large amount of chemical reaction abilities are stronger.Under given conditions; can be hydrolyzed, the chemical reaction such as O-acidylate and N-acidylate, acid esters, etherificate, alkylation, carboxy methylation, carboxyethylation, sulfonation, halogenation, nitrated, reduction, oxidation, chelating, condensation and complexing, thereby generate the various chitosan derivatives with different performance.In reaction, in shitosan, introduce large side group, destroyed its crystalline texture, thus its dissolubility raising, water soluble, carboxyl methylation derivant demonstrates the character of polyelectrolyte in solution, thereby has expanded the range of application of shitosan.Although the research and development of chitosan derivatives have obtained certain progress, its application development is still slower.
Its main cause: the one, price is relatively high, more difficult in industrial large-scale application as general material; The 2nd, the research of basis and application foundation is many partially, and application and developmental research are less; The 3rd, the chain of derivative product is shorter.
Shitosan is a kind of macromolecule amine, chitin fiber after moistening due to molecular memory amino with positive electricity, just form the adelphotaxy of positive and negative charge with the cell membrane of the bacterium with negative electricity, bacterium is adsorbed on the surface of fiber by positive electricity, make shitosan have antibiotic property, this is also the most widely used biological characteristics of shitosan.
The prerequisite that shitosan has spinnability must be high polymer exactly, and the high molecular that high polymer is repeated to be formed by connecting by covalent bond by many identical, simple construction units can reach 10 conventionally
4～10
6compound.And meet following Several Properties: macromolecular chain be straight line, side chain as far as possible less, without larger side base; In molecule, there is the existence of polar group; The relative molecular weight of this material must reach certain scope, to obtain the spinning solution of debita spissitudo; The space structure of its molecular structure and molecules align will have regularity and be beneficial to the formation of supramolecular structure fiber; If fiber-forming polymer amorphism, its serviceability temperature should be lower than vitrification point, if vitrification point all too is low, high polymer should have high degree of crystallinity so; For ensureing to have actual use value after high polymer processing becomes fibre, it should have certain heat endurance.
By finding out to possess above-mentioned Several Properties completely to the introduction of shitosan character above, therefore shitosan has spinnability, and spinning process can continue to carry out.
As far back as nineteen forty-two, the U.S. just first successfully develops chitin fiber, but for the characteristic of chitin fiber, especially less to the research of its antibiotic property.The patent about shitosan that Peniston obtained in 1977, mentions first and prepares chitin fiber with organic solvent.They are dissolved in shitosan in acetic acid and make spinning solution with 5% ratio, and the fiber surface making is coarse, and diameter is approximately 150 μ m, and the acetate fiber that same spinning apparatus forms is only 30 μ m.Mitsubishi prepared chitin fiber for the first time in 1980, the acetic acid solution with 0.5% and 3% shitosan are made spinning solution, and 5% solution is as coagulating bath, and the intensity that makes fiber is 2.2g/dtex.
Qin Yimin etc. have prepared pure chitosan fiber with wet spinning.To adopt deacetylation be 84% shitosan, 5% shitosan and 2% acetic acid solution be as spinning solution, 1% NaOH and 15% Na
2sO
4as coagulating bath, by different drying modes: radiation heating, acetone solvent extraction and air are dried, and in the chitin fiber finally making, maximum intensity is 0.24N/tex.
In the eighties in 20th century, Japan conducts a research to shitosan and chitin derivativ.At the initial stage nineties, Fuji Spinning Co., Ltd. of Japan has just realized the suitability for industrialized production of chitin fiber.The Mitsubishi Rayon (Mitsubishi Rayon Co., Ltd) of Japan is 3% shitosan and 0.5% acetic acid solution at employing spinning solution in 1980, and 5%NaOH is as coagulating bath, system fibre strength be 2.2g/dtex.Other Jia Yue our company Fuji Spinning (Fujiette) also uses different spin solvents: for example trichloroacetic acid, urea-acetic acid, made chitin fiber.
This mole of sea (Hismer) fiber that Shandong Huaxing Haici New Materials Co., Ltd. research and development are produced is granted national inventing patent, it is made by wet spinning, is a kind of medical pure chitosan fiber, containing additive.According to relevant test report, its to the bacteriostasis rate of Escherichia coli and staphylococcus aureus all more than 92%.Fracture strength 1.3-2.5cN/dtex, line density 1.2～3d.
At present, one of them distinct issues that the pure chitosan fiber producer faces are mainly: especially in the application of shitosan, General Requirements chitin fiber has higher mechanical performance, but, chitin fiber is poor compared with other conventional fibre properties in intensity, and elongation at break is also less, and mechanical performance is poor, such as fibre strength, collude with intensity etc., therefore limited the scope of chitin fiber application.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the Chitosan Fiber With High Tenacity with good intensity and sub-wire effect.
A kind of Chitosan Fiber With High Tenacity, it makes certain density shitosan spinning solution after being cross-linked by shitosan and polyvinyl alcohol blending, then filter deaeration, utilize pressure that spinning solution is sprayed into coagulating bath through spinning cap, the fiber of coagulation forming also needs drawn, washing, supersonic oscillations sub-wire, dry, cut-out, post processing etc., finally obtains having high-intensity chitin fiber.
The object of the present invention is achieved like this, and a kind of preparation method of Chitosan Fiber With High Tenacity, comprises the steps:
Step 1, chitosan solution and poly-vinyl alcohol solution are mixed after, add crosslinking agent, stir, vacuum defoamation 24h, obtains spinning solution, for subsequent use;
Step 2, in coagulating bath, by the described spinning solution obtaining, at 25-45 DEG C, carry out spinning, and adopt the method for supersonic oscillations carry out sub-wire and improve fibre strength, obtain chitin fiber.
After chitosan solution and poly-vinyl alcohol solution blend, its solute shitosan and polyvinyl alcohol form blended fiber, and the hydroxyl on the PVA chain in blended fiber and the carboxyl on shitosan and hydroxyl have formed strong hydrogen bond, have improved brute force and the elasticity of fiber.And then make product there is good mechanical performance.
Simultaneously, because the aquogel of shitosan and polyvinyl alcohol formation has very high blood compatibility, so by the superperformance of PVA, add crosslinking agent, by after blend more crosslinked method can make end product chitin fiber obtain good serviceability or processing characteristics.
Prior art shows, the chitin fiber of preparing according to conventional method all exists the defect that mechanical property is not high, makes the spinnability of chitin fiber and woven performance poor, has limited greatly its purposes.The chitin fiber of preparing by such scheme of the present invention has mechanical property well, has improved spinnability and the woven performance of chitin fiber.
Meanwhile, there is the problem of sub-wire weak effect in current chitin fiber on the market, by the inventive method, adopts the method for supersonic oscillations to can solve the problem of shitosan sub-wire difficulty.
Concrete principle is as follows:
After one, shitosan and polyvinyl alcohol blending, be cross-linked again brute force and the elasticity that can improve fiber, make chitin fiber obtain good serviceability or processing characteristics.
Two, chitin fiber adopts the method for supersonic oscillations, tensile fiber effect is increased, improve the degree of orientation of fiber, by making the defect such as micropore, gap that fibrous inside exists reduce even elimination after supersonic oscillations effect, and then improve the compactness of fiber, and it is interior macromolecular regularly arranged to be conducive to fiber, thereby further improve intensity and the elongation at break of fiber; And be more conducive to the sub-wire of chitin fiber.
Further, in step 1, the concentration of described chitosan solution is 0.5%-20%; The concentration of described poly-vinyl alcohol solution is 0.5%-25%;
The mass ratio of the polyvinyl alcohol solute in shitosan solute and described poly-vinyl alcohol solution in described chitosan solution is 9:1-1:1.
Further, in step 1, described shitosan is the shitosan that deacetylation is greater than 85%, and the number-average molecular weight of described shitosan is 1 × 10
4-5 × 10
6.
Further, in step 1, in described chitosan solution, also contain the pure acetic acid of 1-6%.
Further, in step 1, the number-average molecular weight of described polyvinyl alcohol is 1 × 10
4-3 × 10
5.
Further, in step 1, described crosslinking agent is any one or the multiple mixture in oxidized sodium alginate, Geniposide, glutaraldehyde; The addition of described crosslinking agent is the 0.1-5% of the amount of the shitosan solute in described chitosan solution.
Further, in step 2, described coagulating bath is that concentration is the sodium hydroxide solution of 1-6% and the mixture of the ethanolic solution that concentration is 1-3%, and wherein, the content of described sodium hydroxide solution is 1-10%, and the content of described ethanol is 0-10%.
Further, in step 2, described spinning is wet spinning.
By preparation method provided by the invention, the dry fracture strength of the chitin fiber obtaining is 4.2-15cN/dtex, and fibre diameter is 10-50 μ m, and wet breaking strength is 4.0-12cN/dtex, and dry elongation at break is 12-25%.
Brief description of the drawings
Fig. 1 is preparation method's flow chart of a kind of Chitosan Fiber With High Tenacity provided by the invention.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is described in further detail below by specific embodiment.
A preparation method for Chitosan Fiber With High Tenacity, as shown in Figure 1, comprises the steps:
Step 1, chitosan solution and poly-vinyl alcohol solution are mixed after, add crosslinking agent, stir, vacuum defoamation 24h, obtains spinning solution, for subsequent use;
Wherein, in order to improve the utilization rate of raw material, preferably, the concentration of described chitosan solution is 0.5%-20%, is preferably 3%-6%; The concentration of described poly-vinyl alcohol solution is 0.5%-25%, is preferably 5%-15%;
The mass ratio of the solute in solute and poly-vinyl alcohol solution in chitosan solution is 9:1-1:1.
In order to improve the purity of raw material, wherein shitosan is the shitosan that deacetylation is greater than 85% simultaneously, and the number-average molecular weight of described shitosan is 1 × 10
4-5 × 10
6; In order to improve textile performance and the machining property of end product, preferred number average molecular weight is 5 × 10
4-5 × 10
6shitosan, further preferably 2 × 10
5-5 × 10
6shitosan.In the time that the number-average molecular weight of shitosan is larger, the mechanical performance of its end product chitin fiber is better, is also conducive to moisturizing simultaneously.
In aforesaid chitosan solution, also contain the pure acetic acid of 1-6%.Acetic acid can promote the dissolving of shitosan.
In the time that the number-average molecular weight of polyvinyl alcohol is too small, in preparation process, easily carry, still, the mechanical performance of the chitin fiber finally making is poor, and in the time that data molecular weight is excessive, viscosity is too high, carries difficulty large.
In order to improve the degree of cross linking of polyvinyl alcohol and shitosan, meanwhile, preparation process is easy, and preferably, the number-average molecular weight of described polyvinyl alcohol is 1 × 10
4-3 × 10
5, more preferably number-average molecular weight is 5 × 10
4-2.5 × 10
5, further preferred number average molecular weight is 7 × 10
4-1.5 × 10
5.
In the process of shitosan and polyvinyl alcohol cross-linking reaction, can add and promote that crosslinked crosslinking agent, this crosslinking agent can be any one or the multiple mixture in oxidized sodium alginate, Geniposide, glutaraldehyde; Wherein the component in every kind of composition is mixed according to any proportioning.Wherein, preferential oxidation sodium alginate and/or Geniposide, more preferably oxidized sodium alginate.Because oxidized sodium alginate can make the biocompatibility of chitin fiber better.
The addition of crosslinking agent is the 0.1-5% of the amount of the shitosan solute in chitosan solution.
Step 2, in coagulating bath, the described spinning solution obtaining is carried out to spinning at 25-45 DEG C, and adopts the method for supersonic oscillations carry out sub-wire and improve fibre strength, obtain chitin fiber.
Wherein, coagulating bath is that concentration is the sodium hydroxide solution of 1-6% and the mixture of the ethanol that concentration is 1-3%, and wherein, the content of described sodium hydroxide solution is 1-10%, and the content of described ethanol is 0-10%.
In spinning process, adopt wet spinning.In order to improve the intensity of chitin fiber, after the stoste thread extruding enters coagulating bath, in order to reduce the crude degree of fiber surface, can make it again enter the stretch bath being formed by sodium hydroxide solution from spinneret orifice eye.The concentration of the sodium hydroxide solution in stretch bath is 3-6%.
After chitosan solution and poly-vinyl alcohol solution blend, its solute shitosan and polyvinyl alcohol form blended fiber, and the hydroxyl on the PVA chain in blended fiber and the carboxyl on shitosan and hydroxyl have formed strong hydrogen bond, have improved brute force and the elasticity of fiber.And then make product there is good mechanical performance.
Simultaneously, because the aquogel of shitosan and polyvinyl alcohol formation has very high blood compatibility, so by the superperformance of PVA, add crosslinking agent, by after blend more crosslinked method can make end product chitin fiber obtain good serviceability or processing characteristics.
Prior art shows, the chitin fiber of preparing according to conventional method all exists the defect that mechanical property is not high, makes the spinnability of chitin fiber and woven performance poor, has limited greatly its purposes.The chitin fiber of preparing by such scheme of the present invention has mechanical property well, has improved spinnability and the woven performance of chitin fiber.
Meanwhile, there is the problem of sub-wire weak effect in current chitin fiber on the market, by the inventive method, adopts the method for supersonic oscillations to can solve the problem of shitosan sub-wire difficulty.
Concrete principle is as follows:
After one, shitosan and polyvinyl alcohol blending, be cross-linked again brute force and the elasticity that can improve fiber, make chitin fiber obtain good serviceability or processing characteristics.
Two, chitin fiber adopts the method for supersonic oscillations, tensile fiber effect is increased, improve the degree of orientation of fiber, by making the defect such as micropore, gap that fibrous inside exists reduce even elimination after supersonic oscillations effect, and then improve the compactness of fiber, and it is interior macromolecular regularly arranged to be conducive to fiber, thereby further improve intensity and the elongation at break of fiber; And be more conducive to the sub-wire of chitin fiber.
By preparation method provided by the invention, the dry fracture strength of the chitin fiber obtaining is 4.2-15cN/dtex, and fibre diameter is 10-50 μ m, and wet breaking strength is 4.0-12cN/dtex, and dry elongation at break is 12-25%.
Next, introduce in detail the synthetic method of heliotropin provided by the invention by following several specific embodiments:
Embodiment 1:
A kind of preparation method of Chitosan Fiber With High Tenacity:
Compound concentration is polyvinyl alcohol (PVA) solution that 2.5% chitosan solution and concentration are 8%, mass ratio according to the solute of chitosan solution and poly-vinyl alcohol solution (being shitosan and polyvinyl alcohol) is 3:1, chitosan solution and poly-vinyl alcohol solution are mixed, stir, vacuum defoamation 24h, obtain spinning solution, for subsequent use; Wherein, the number-average molecular weight of the shitosan of employing is 2 × 10
5, the number-average molecular weight of polyvinyl alcohol is 8 × 10
4.
Control spinning solution and at 40 DEG C, carry out spinning, by the spinning solution process wet spinning obtaining, and the method that adopts supersonic oscillations is carried out sub-wire and improves fibre strength, obtain chitin fiber, the sodium hydrate aqueous solution that the coagulating bath using in wet spinning is 2wt% and 2wt% ethanol, it is 5% that secondary solidifies naoh concentration in stretch bath;
The dry fracture strength of the chitin fiber finally obtaining is 6cN/dtex, and wet breaking strength is 5.5cN/dtex, and dry elongation at break is 14.3%.
Example 2:
A kind of preparation method of Chitosan Fiber With High Tenacity:
Compound concentration is polyvinyl alcohol (PVA) solution that 2% chitosan solution and concentration are 10%, mass ratio according to the solute of chitosan solution and poly-vinyl alcohol solution (being shitosan and polyvinyl alcohol) is 4:1, chitosan solution and poly-vinyl alcohol solution are mixed, stir, vacuum defoamation 24h, obtain spinning solution, for subsequent use; Wherein the number-average molecular weight of shitosan is 2 × 10
5, the number-average molecular weight of polyvinyl alcohol is 8 × 10
4.
Control spinning solution and carry out spinning at 40 DEG C, by the spinning solution process wet spinning obtaining, and the method that adopts supersonic oscillations is carried out sub-wire and improves fibre strength, obtain chitin fiber, the coagulating bath using in wet spinning is 1% sodium hydrate aqueous solution and 2wt% ethanol, and in stretch bath, naoh concentration is 4%;
The dry fracture strength of the chitin fiber finally obtaining is 12cN/dtex, and wet breaking strength is 10.5cN/dtex, and dry elongation at break is 22%.
Example 3:
A kind of preparation method of Chitosan Fiber With High Tenacity:
Compound concentration is polyvinyl alcohol (PVA) solution that 2.5% chitosan solution and concentration are 8%, mass ratio according to the solute of chitosan solution and poly-vinyl alcohol solution (being shitosan and polyvinyl alcohol) is 5:1, chitosan solution and poly-vinyl alcohol solution are mixed, after mixing, add oxidized sodium alginate crosslinking agent, its quality is 0.5% of chitosan mass, stirs, and vacuum defoamation 24h, obtain spinning solution, for subsequent use; Wherein the number-average molecular weight of shitosan is 2 × 10
5, the number-average molecular weight of described polyvinyl alcohol is 8 × 10
4.
Control spinning solution and at 40 DEG C, carry out spinning, by the spinning solution process wet spinning obtaining, and the method that adopts supersonic oscillations is carried out sub-wire and improves fibre strength, obtain chitin fiber, sodium hydrate aqueous solution and 2wt% ethanol that the coagulating bath wherein using is 2wt%, in stretch bath, naoh concentration is 5%;
The dry fracture strength of the chitin fiber finally obtaining is 7.3cN/dtex, and wet breaking strength is 6.5cN/dtex, and dry elongation at break is 12%.
Example 4:
A kind of preparation method of Chitosan Fiber With High Tenacity:
Compound concentration is polyvinyl alcohol (PVA) solution that 2% chitosan solution and concentration are 10%, mass ratio according to the solute of chitosan solution and poly-vinyl alcohol solution (being shitosan and polyvinyl alcohol) is 6:1, chitosan solution and poly-vinyl alcohol solution are mixed, after mixing, add oxidized sodium alginate crosslinking agent, its quality is 1% of chitosan mass, stirs, and vacuum defoamation 24h, obtain spinning solution, for subsequent use;
Wherein the number-average molecular weight of shitosan is 2 × 10
5.The number-average molecular weight of described polyvinyl alcohol is 8 × 10
4.
Control spinning solution and at 40 DEG C, carry out spinning, by the spinning solution process wet spinning obtaining, and the method that adopts supersonic oscillations carry out sub-wire with improve fibre strength, obtain chitin fiber, the sodium hydrate aqueous solution that the coagulating bath wherein using in wet spinning process is 3wt%;
The dry fracture strength of the chitin fiber finally obtaining is 15cN/dtex, and wet breaking strength is 12cN/dtex, and dry elongation at break is 25%.
Example 5:
A kind of preparation method of Chitosan Fiber With High Tenacity:
Compound concentration is polyvinyl alcohol (PVA) solution that 0.5% chitosan solution and concentration are 0.5%, mass ratio according to the solute of chitosan solution and poly-vinyl alcohol solution (being shitosan and polyvinyl alcohol) is 9:1, chitosan solution and poly-vinyl alcohol solution are mixed, after mixing, add oxidized sodium alginate crosslinking agent, its quality is 1% of chitosan mass, stirs, and vacuum defoamation 24h, obtain spinning solution, for subsequent use;
Wherein the number-average molecular weight of shitosan is 1 × 10
4.The number-average molecular weight of described polyvinyl alcohol is 1 × 10
4.
Control spinning solution and at 40 DEG C, carry out spinning, by the spinning solution process wet spinning obtaining, and the method that adopts supersonic oscillations is carried out sub-wire and improves fibre strength, obtain chitin fiber, the sodium hydrate aqueous solution that the coagulating bath wherein using in wet spinning process is 1wt% and 1wt% ethanol, in stretch bath, naoh concentration is 3%;
The dry fracture strength of the chitin fiber finally obtaining is 7cN/dtex, and wet breaking strength is 7cN/dtex, and dry elongation at break is 12%.
Example 6:
A kind of preparation method of Chitosan Fiber With High Tenacity:
Compound concentration is polyvinyl alcohol (PVA) solution that 20% chitosan solution and concentration are 25%, mass ratio according to the solute of chitosan solution and poly-vinyl alcohol solution (being shitosan and polyvinyl alcohol) is 1:1, chitosan solution and poly-vinyl alcohol solution are mixed, after mixing, add oxidized sodium alginate crosslinking agent, its quality is 1% of chitosan mass, stirs, and vacuum defoamation 24h, obtain spinning solution, for subsequent use;
Wherein the number-average molecular weight of shitosan is 5 × 10
6.The number-average molecular weight of described polyvinyl alcohol is 3 × 10
5.
Control spinning solution and at 40 DEG C, carry out spinning, by the spinning solution process wet spinning obtaining, and the method that adopts supersonic oscillations is carried out sub-wire and improves fibre strength, obtain chitin fiber, the sodium hydrate aqueous solution that the coagulating bath wherein using in wet spinning process is 6wt% and 3wt% ethanol, in stretch bath, naoh concentration is 5%;
The dry fracture strength of the chitin fiber finally obtaining is 8cN/dtex, and wet breaking strength is 6cN/dtex, and dry elongation at break is 13%.
Wherein, taking acquired results in embodiment 4 as best.
Each raw material that the present invention is cited, and the bound of the each raw material of the present invention, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. a preparation method for Chitosan Fiber With High Tenacity, is characterized in that, comprises the steps:
Step 1, chitosan solution and poly-vinyl alcohol solution are mixed after, add crosslinking agent, stir, vacuum defoamation 24h, obtains spinning solution, for subsequent use;
Step 2, in coagulating bath, the described spinning solution obtaining is carried out to spinning at 25-45 DEG C, and adopts the method for supersonic oscillations carry out sub-wire and improve fibre strength, obtain chitin fiber.
2. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 1, is characterized in that:
In step 1, the concentration of described chitosan solution is 0.5%-20%; The concentration of described poly-vinyl alcohol solution is 0.5%-25%;
The mass ratio of the polyvinyl alcohol solute in shitosan solute and described poly-vinyl alcohol solution in described chitosan solution is 9:1-1:1.
3. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 2, is characterized in that:
In step 1, described shitosan is the shitosan that deacetylation is greater than 85%, and the number-average molecular weight of described shitosan is 1 × 10
4-5 × 10
6.
4. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 3, is characterized in that:
In step 1, in described chitosan solution, also contain the pure acetic acid of 1-6%.
5. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 4, is characterized in that:
In step 1, the number-average molecular weight of described polyvinyl alcohol is 1 × 10
4-3 × 10
5.
6. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 5, is characterized in that:
In step 1, described crosslinking agent is any one or the multiple mixture in oxidized sodium alginate, Geniposide, glutaraldehyde;
The addition of described crosslinking agent is the 0.1-5% of the amount of the shitosan solute in described chitosan solution.
7. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 4, is characterized in that:
In step 2, described coagulating bath is that concentration is the sodium hydroxide solution of 1-6% and the mixture of the ethanol that concentration is 1-3%;
Wherein, the content of described sodium hydroxide solution is 1-10%, and the content of described ethanol is 0-10%.
8. the preparation method of a kind of Chitosan Fiber With High Tenacity according to claim 4, is characterized in that:
In step 2, described spinning is wet spinning.
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| CN108823805A (en) * | 2018-06-13 | 2018-11-16 | 福建翔丰华新能源材料有限公司 | A kind of novel method for preparing chitin fiber felt |
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| CN112952215A (en) * | 2021-01-31 | 2021-06-11 | 复旦大学 | Water-based fiber battery and preparation method thereof |
| CN113636779A (en) * | 2021-07-02 | 2021-11-12 | 海南胜凯建材有限公司 | Self-curing high-expansion fiber anti-cracking agent and preparation method thereof |
| CN113862830A (en) * | 2021-10-18 | 2021-12-31 | 扬州日兴生物科技股份有限公司 | Method for preparing chitosan/polyvinylpyrrolidone composite fiber |
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| CN115198390A (en) * | 2022-07-28 | 2022-10-18 | 南京林业大学 | High-strength partially deacetylated chitin nanofiber-based composite silk thread and forming preparation method thereof |
| CN115198390B (en) * | 2022-07-28 | 2024-03-19 | 南京林业大学 | A high-strength partially chitosan nanofiber-based composite thread and its molding and preparation method |
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