CN104726963A - Chitosan fiber and preparation method thereof - Google Patents
Chitosan fiber and preparation method thereof Download PDFInfo
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- CN104726963A CN104726963A CN201510144594.8A CN201510144594A CN104726963A CN 104726963 A CN104726963 A CN 104726963A CN 201510144594 A CN201510144594 A CN 201510144594A CN 104726963 A CN104726963 A CN 104726963A
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Abstract
The invention discloses a chitosan fiber and a preparation method thereof. The method comprises the following steps: stirring chitosan at low temperature or dissolving the chitosan in a solvent composition containing KOH, urea and water by means of freezing-unfreezing circulation to prepare a high-concentration chitosan solution; filtering the high-concentration chitosan solution, defoaming the filtered high-concentration chitosan solution, and spraying the defoamed high-concentration chitosan solution into a coagulating bath for spinning; and further washing with water, drafting, oiling and drying to obtain the chitosan fiber. The method is simple, and mild and easily controllable in operation condition; and the chitosan solution has good stability, is convenient to store and deliver, has proper viscosity and has excellent spinnability. Components of adopted solvent and coagulating bath can be recycled, and a recycling technology is developed and reliable and is suitable for industrial production. The chitosan fiber has a wide application prospect in textile, bio-medical materials and other fields.
Description
Technical field
The invention belongs to natural polymer and chemical fibre field, be specifically related to a kind of chitin fiber and preparation method thereof.
Background technology
Chitin is extensively present in the cell membrane of insects, aquatic crustacean shell and marine alga, and as crab, shrimp, squid parietal bone, fungi etc., its content reserves are only second to cellulose.Have the features such as biological degradability, biocompatibility and Biofunctional due to chitin, therefore chitin fiber has purposes widely in fields such as weaving, suture, medical dressing, antibacterial bacteriostatic material, hemostatic material, material which can retain moisture.But, because chitin degree of crystallinity is high, containing in a large amount of molecules and intermolecular hydrogen bonding, water insoluble and majority of organic solvent.And, once be dissolved in a solvent by chitin, the original aggregated structure of chitin is totally disrupted, and the chitin material aggregated structure formed after regeneration changes, usually its mechanical property is weak and poor, makes the utilization of chitin reach far away its due degree.
Chitin fiber fiber forming process is more more complicated than cellulose, and chitin fiber spining technology basis is still weak.Known chitin solvent, as the concentrated sulfuric acid, concentrated hydrochloric acid, trichloroacetic acid and lithium rhodanate saturated aqueous solution have severe corrosive and toxicity, also can there is obvious degradation in chitin in course of dissolution, therefore prepares chitin fiber by them and rarely have report.Chitin also can adopt the method similar with viscose acetal fibre to carry out wet spinning, needs in the process to use CS in a large number
2, and due to mechanical property not good enough, usually need be mixed with viscose-chitin composite fiber with cellulose viscose liquid.Also be once used to dissolve chitin with the mixed solvent that trichloroacetic acid and formic acid, acetic acid, dichloroacetic acid or chloromethanes etc. form and carried out spinning, but this dicyandiamide solution has high toxicity, and can make chitin that violent degraded occurs, thus there is no the value of practical application.Application number be 201310290963.5 Chinese invention patent with NaOH and aqueous solution of urea for solvent, dissolve after freeze-thaw and obtain chitin solution, and prepare chitin fiber using 5wt% ~ 20wt% aqueous sulfuric acid as coagulating bath.But the chitin fiber that the method obtains is wet strong very low, is difficult to carry out drawing-off and following process.Especially, thisly dissolve the method for chitin by freeze-thaw and prepare that chitin fiber is consuming time, power consumption, be not suitable for large-scale industrial production, be thus difficult to practical application.In addition, research finds that a few organic solvent can dissolve chitin under the condition of heating, and can be used for preparing chitin fiber.Such as, the mixed solvent formed with dimethylacetylamide and LiCl solubilized chitin carry out spinning under the condition heated, the chitin fiber obtained is wet strong lower, but dry strong higher (Progress in Polymer Science, 2009,34,641).In addition, prepare chitin fiber also have report (GreenChemistry, 2006,8,630 with N-methylmorpholine-N-oxide and ion liquid dissolving chitin; Chinese invention patent application 201110043904.0).But with responsive to water and oxidation impurities during organic solvent dissolution chitin, and due to solvent expensive, cause production cost high, at separation, purifying and reclaim and there are problems.
On the other hand, the deacetylated product shitosan of chitin has the advantages such as good biocompatibility, biodegradability, biologically active, has very high Research Significance and using value in biomaterial.Containing a large amount of amino in chitosan molecule, tradition prepares the dilute acetic acid aqueous solution dissolving shitosan that chitin fiber many employings concentration is 2% ~ 5%, prepares chitin fiber (Macromolecular Bioscience, 2004 by wet spinning, 4,811; Progress in Polymer Science, 2009,34,641).Such as, chitosan solution with 5% is spinning solution, 5%NaOH solution and alcohol mixeding liquid are solidification liquid, chitin fiber is obtained by wet spinning process, it is dry, wet break strength is 2.8g/d and 1.2g/d, and dry, wet break elongation is 7% and 6% (Sen-i Gakkaishi, 1987,43,288).But there is the problems such as shitosan dissolves not fully, spinning solution viscosity is high in the method.In addition, shitosan also can dissolve through freeze-thaw in LiOH/ aqueous solution of urea, and the TENSILE STRENGTH of the chitin fiber adopting wet spinning to obtain is about 1.4cN/dtex, elongation at break is 13% (Materials Letters, 2012,84,73).But LiOH is expensive, and prepare chitin fiber not only consuming time, power consumption by the method for freeze-thaw dissolving shitosan, be not suitable for large-scale industrial production.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of chitin fiber and preparation method thereof.
The method preparing chitin fiber provided by the present invention is:
1) 2 ~ 50wt%KOH is contained in solvent for use composition, 0 ~ 20wt% urea, 0 ~ 6wt% thiocarbamide, 0 ~ 10wt%LiOH, 0 ~ 20wt%NaOH, 0 ~ 10wt%ZnO, 0 ~ 10wt% polyethylene glycol, surplus is water, by chitin and solvent compositions after any temperature mixing, be refrigerated to below freezing, then obtain chitin solution above freezing thawing; Or by chitin and solvent compositions after any temperature mixing, above freezing, less than 0 DEG C continuous stirring and dissolving obtains chitin solution;
2) chitin solution is obtained chitin spinning solution below its gelling temperature after filtration, deaeration;
3) chitin spinning solution is prepared chitin fiber through wet spinning or dry-jet wet spinning process: chitin solution is the spinneret orifice of 0.05 ~ 0.5mm by aperture, stop 1 ~ 100s in lower than the coagulating bath below chitin solution gels temperature and be frozen into silk, through washing, drawing-off, oil and obtain chitin fiber after drying.
If chitin stoste is after spinning, washing and drawing-off, more deacetylated through out-phase, wash, to oil and drying can obtain the chitin fiber of different deacetylation.
Originating as above-mentioned chitin, can be the marine organisms such as shrimp, crab, cuttlefish, the insect such as cockroach, silkworm chrysalis, and one or more in mushroom cell.Have no particular limits through the method purifying of known technology before chitin uses, as acid treatment removing calcium salt, alkali treatment removes deproteinized, oxidation processes decolouring etc.
Described solvent compositions, as some preferred versions,
KOH concentration is 8 ~ 20wt%;
Urea concentration is 2 ~ 10wt%;
Thiocarbamide is 0 ~ 4wt%;
LiOH is 0 ~ 6wt%;
NaOH is 0 ~ 12wt%;
ZnO is 0 ~ 5wt%;
Polyethylene glycol is 0 ~ 5wt%.
Wherein, add urea, thiocarbamide, ZnO and polyethylene glycol etc., the continuation contributing to chitin is dissolved, is increased chitin stability of solution, and improves the effects such as chitin fiber intensity.
The method that solvent compositions dissolves chitin is used to have two kinds, Yi Zhongshi: by chitin and solvent compositions after any temperature mixing, to be refrigerated to below freezing, then to obtain chitin solution above freezing thawing.Another kind method is: by chitin and solvent compositions after any temperature mixing, above freezing, less than 0 DEG C continuous stirring and dissolving obtains chitin solution.Use second method, directly can dissolve chitin rapidly, not need freeze-thawing process, for industrialization provides possibility.Use above-mentioned solvent compositions different according to composition, the freezing point of solvent compositions also can change.
The concentration of chitin solution is 1 ~ 12wt%, is preferably 3 ~ 10wt%.
Can select stainless (steel) wire, nonwoven fabric etc. in the chitin solution filter process using above-mentioned two kinds of methods to obtain, filtering accuracy general control is below 5 μm.
Chitin solution can adopt the bubble in ultracentrifugal method removing chitin solution, or the bubble adopting the quiet method that is de-and continuous defoaming of common decompression to remove in chitin solution obtains chitin spinning solution.According to the difference of deaeration mode and chitin solution viscosity, the inclined heated plate of described chitin solution is 0.1 ~ 100h.
Under the prerequisite not affecting chitin stability of solution, auxiliary agent can be added in chitin solution, as dispersant, defoamer, fibre modifier, crosslinking agent etc., the continuation contributing to chitin is dissolved, the bubble removed in chitin solution, and improves the effects such as chitin fiber intensity.Crosslinking agent can be epoxy compounds and/or aldehyde compound and/or borate.This kind of suitable crosslinking agent includes but not limited to epoxychloropropane, epoxy chlorobutane, ethylene glycol diglycidylether, polypropylene glycol diglycidyl ether, glutaraldehyde, borax etc.
In the preparation process of described chitin fiber, described coagulating bath can be single coagulating bath, also can be multistage coagulating bath.
Wherein, coagulating bath is water-soluble low-viscosity organic liquid, or is added with water-soluble low-viscosity organic liquid of monovalent cation wherein, or the mixing material of they and water.Described monovalent cation is H
+, NH
4 +, Li
+, Na
+or K
+, such solution can by water-soluble and obtained to such as hydrochloric acid, sulfuric acid, nitric acid, acetic acid, ammonium sulfate, ammonium acetate, lithium chloride, sodium sulphate, potassium acetate etc.Described water-soluble organic liquid is alcohol, ketone, ester, acid amides, organic sulfide or its mixture, and it is preferred for using methyl alcohol, ethanol, acetone, ethyl acetate, dimethyl formamide, dimethylacetylamide and methyl-sulfoxide to do coagulating bath.
Under the prerequisite not affecting coagulating bath viscosity, polyalcohol can be added in coagulating bath, as ethylene glycol etc. regulates the setting rate of chitin fiber.Can also add crosslinking agent in coagulating bath, as epoxide and aldehyde compound etc., can increase the intensity of fiber, but do not add crosslinking agent after adding crosslinking agent, the chitin fiber of preparation also has good mechanical property.
In the preparation process of described chitin fiber, chitin spinning solution is being frozen into silk lower than the coagulating bath below chitin solution gels temperature.According to solvent compositions composition, chitin source and the difference of chitin solution concentration, the gelling temperature of chitin solution also can change.The temperature of coagulating bath is between-10 DEG C ~ 40 DEG C, even lower.
In the preparation process of described chitin fiber, chitin as-spun fibre can carry out preliminary draft in coagulating bath, multistage coagulating bath plays supplementary coagulation forming and preliminary draft effect, makes the coagulation forming of chitin fiber more abundant, is conducive to follow-up drawing-off to improve fibre property.
Described chitin fiber spinning process, except wet spinning, can also be dry-wet spinning.
In the preparation process of described chitin fiber, post processing comprises washing, drawing-off, oils and the multiple step of drying.
In the preparation process of described chitin fiber, adopt the multiple of a drawing-off limited, can to adopt twice or repeatedly drawing-off improves drafting multiple.Such drawing-off can comprise the multistage drafting process such as hot water drawing-off, boiling water drawing-off and steam drafting, and can with oil, drying steps interts mutually, be conducive to the fibrous inside defect preventing excessive drawing-off from causing, improve the compact structure of fiber, improve the molecularly oriented of fibrous inside, to improve the mechanical property of fiber further.
In the preparation process of described chitin fiber, washing link can utilize common washing methods, progressively can remove the solvent in fiber, reduce the internal voids of fiber as techniques such as multistage gradient washing process.
In the preparation process of described chitin fiber, oil and can prevent adhesion or doubling between monofilament, improve the flexibility of fiber, can oil after a drawing-off, also repeatedly can oil in multistage drafting process.
In the preparation process of described chitin fiber, drying mode can utilize common drying mode, as dry in hot-rolling etc.
In the preparation process of described chitin fiber; under the prerequisite not damaging mechanical property; described deacetylatedly can utilize common out-phase deacetylation procedure, as deacetylated in alkali, biology enzyme is deacetylated, obtains the deacetylated chitin fiber that deacetylation is up to 100%.
In chitin fiber of the present invention, under the prerequisite not damaging mechanical property, can add containing additive in chitin fiber is shaped, as plasticizer, dyestuff, light stabilizer etc.Filler can also be added, as organic and inorganic filler in chitin spinning solution.Organic filler is as conducting polymer, hydrophilic high molecular material etc.; Inorganic filler is as Graphene, CNT, carbon black, silica, clay, titanium dioxide etc.One or more of these additives or filler can be added, filler can be added before chitin solution-polymerized SBR, and/or add additive before chitin fiber drying.
Compared with prior art, beneficial effect is chitin fiber provided by the invention and preparation method thereof:
1) be chitin is stirred at low temperature or is dissolved in the solvent compositions containing KOH (and/or LiOH, NaOH), urea (and/or thiocarbamide) and water through freeze-thaw circulation, the chitin solution of obtained high concentration after filtration, deaeration, operating condition relaxes easily control, and chitin stability of solution is good, be convenient to storage and conveying, solution viscosity is moderate, has good spinnability.
2) in the present invention, sprayed in coagulating bath by chitin solution and be frozen into silk, described coagulating bath is based on water-soluble low-viscosity organic liquid.And the Chinese invention patent of 201310290963.5 is using 5wt% ~ 20wt% aqueous sulfuric acid as coagulating bath.Find in inventor's practice, wet very poor by force with the filament that 5wt% ~ 20wt% sulfuric acid obtains for coagulating bath.And higher to wet strong requirement in spinning technique, because spinning is continued operation, and very short through the time of coagulating bath, with 5wt% ~ 20wt% sulfuric acid for coagulating bath is almost difficult to continued operation.The intensity of last shredded dried bean curd is also barely satisfactory.The present invention take organic liquid as the main body of coagulating bath, obtains well wet strong and dry strong, meets the requirement of continuous spinning.
3) solvent adopted and coagulating bath component can repeat to recycle, and recovery technology mature and reliable.Whole technique is simple and convenient, safety and environmental protection drops into low, with low cost, is suitable for suitability for industrialized production.This new method obtaining chitin fiber by gentle, simple method is the important breakthrough to prior art, thus has industrial prospect.
Detailed description of the invention
Below in conjunction with specific embodiment, technical scheme of the present invention is described further; limiting the scope of the invention can not be interpreted as; those skilled in the art makes some nonessential change and adjustment according to the content of foregoing invention, all belongs to protection scope of the present invention.
Embodiment 1:
1g chitin powder (commercially available) is added in 99g 2 ~ 50wt%KOH aqueous solution of 0 ~ 25 DEG C, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after evacuation and centrifugal degassing, obtain the chitin solution that concentration is 1wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.07mm by aperture under the pressure of 0.1MPa enters and stops 10s in-10 DEG C of methanol solutions and be frozen into silk.By gained strand with after deionized water removing chemical reagent, oil, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 0.9 ~ 1.2cN/dtex, and elongation at break is 16% ~ 21%.
Embodiment 2:
On freezing point ~ 2 ~ 50wt%KOH of the 97g 25 ~ 50 DEG C of 0 DEG C, add 3g chitin powder (commercially available) in 0 ~ 20wt% aqueous solution of urea, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after evacuation and centrifugal degassing, obtain the chitin solution that concentration is 3wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.05mm by aperture under the pressure of 0.1MPa enters and stops 20s in the mixed solution of-5 DEG C of water and ethanol and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.2, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.1 ~ 1.6cN/dtex, and elongation at break is 12% ~ 25%.
Embodiment 3:
5g chitin powder (commercially available) is added in the aqueous solution of the 2 ~ 40wt%KOH of the 95g on 25 DEG C, 0 ~ 6wt% thiocarbamide, 0 ~ 10wt%ZnO, 0 ~ 10wt% polyethylene glycol, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after vacuum deaerator, obtain the chitin solution that concentration is 5wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.08mm by aperture under the pressure of 0.1MPa enters and stops 20s in the mixed solution of 0 DEG C of acetic acid and ethanol and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.3 ~ 1.8cN/dtex, and elongation at break is 8% ~ 16%.
Embodiment 4:
9g chitin powder is added in the aqueous solution of 91g 8 ~ 20wt%KOH, the 0 ~ 6wt%LiOH of 0 ~ 25 DEG C, 0 ~ 4wt% thiocarbamide, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after evacuation and centrifugal degassing, obtain the chitin solution that concentration is 9wt%.This chitin solution prepares chitin fiber through wet spinning technology.Chitin solution is under the pressure of 0.1MPa, and the spinneret orifice spray silk being 0.05mm by aperture enters and stops 30s in the mixed solution of 10 DEG C of acetic acid, potassium acetate, second alcohol and water and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.2 ~ 2.0cN/dtex, and elongation at break is 11% ~ 18%.
Embodiment 5:
12g chitin powder is added in the aqueous solution of 88g 2 ~ 30wt%KOH, the 0 ~ 10wt%LiOH of 0 ~ 25 DEG C, 0 ~ 4wt% thiocarbamide, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after evacuation and centrifugal degassing, obtain the chitin solution that concentration is 12wt%.This spinning solution prepares chitin fiber through dry-wet spinning technique.Then under the pressure of 0.2MPa by the spinneret orifice ejection that aperture is 0.5mm, enter after 20cm air-gap and stop 50s in the water of 5 DEG C and dimethylacetamide solution mixing and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.5 ~ 2.4cN/dtex, and elongation at break is 9% ~ 19%.
Embodiment 6:
7g chitin powder is added in the aqueous solution of the 93g 2 ~ 25wt%KOH of 0 ~ 25 DEG C, 2 ~ 10wt% urea, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after vacuum deaerator, obtain the chitin solution that concentration is 7wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.08mm by aperture under the pressure of 0.1MPa enters and stops 50s in the mixed solution of 10 DEG C of methyl-sulfoxides and water and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.4 ~ 2.2cN/dtex, and elongation at break is 10% ~ 20%.
Embodiment 7:
10g chitin powder is added in the aqueous solution of 90g 8 ~ 20wt%KOH, the 0 ~ 12wt%NaOH of 0 ~ 25 DEG C, 2 ~ 10wt% urea, stir and be placed on refrigerator and cooled and freeze to 12h below freezing, then at room temperature thaw, after evacuation and centrifugal degassing, obtain the chitin solution that concentration is 10wt%.Chitin solution evacuation and centrifugal degassing 0.5h at 0 DEG C obtains chitin spinning solution.This spinning solution prepares chitin fiber through dry-wet spinning technique.Then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.3mm, enter after 10cm air-gap and stop 50s in the water of 0 DEG C and dimethyl sulfoxide solution mixing and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.3 ~ 2.2cN/dtex, and elongation at break is 11% ~ 21%.
Embodiment 8:
On freezing point ~ the 94g 8 ~ 20wt%KOH of 0 DEG C, 0 ~ 20wt% urea, 0 ~ 5wt%ZnO, 0 ~ 5wt% polyethylene glycol the aqueous solution in add 6g chitin powder, be refrigerated to placement 12h below freezing after stirring, then at room temperature thaw and obtain the chitin solution that concentration is 6wt%.Chitin solution evacuation and centrifugal degassing 0.1h at 5 DEG C obtains chitin spinning solution.This spinning solution prepares chitin fiber through dry-wet spinning technique.Then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.4mm, enter after 10cm air-gap and stop 50s in the water of 5 DEG C and dimethyl formamide solution mixing and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.1 ~ 2.2cN/dtex, and elongation at break is 9% ~ 18%.
Embodiment 9:
On freezing point ~ the 93g 8 ~ 20wt%KOH of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C of continuous stirring dissolves completely, obtains through filtering, after vacuum deaerator the chitin solution that concentration is 7wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.05mm by aperture under the pressure of 0.1MPa enters in the mixed solution of 0 DEG C of second alcohol and water and stops 50s, and then stops 50s in the mixed solution entering 15 DEG C of second alcohol and waters and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.3 ~ 2.2cN/dtex, and elongation at break is 10% ~ 17%.
Embodiment 10:
On freezing point ~ the 93g 8 ~ 20wt%KOH of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C of continuous stirring dissolves completely, obtains through filtering, after vacuum deaerator 12h the chitin solution that concentration is 7wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.05mm by aperture under the pressure of 0.1MPa enters in the mixed solution of the dimethylacetylamide of 5 DEG C and water and stops 20s, and then stops 50s in the mixed solution entering 30 DEG C of dimethylacetylamides and water and be frozen into silk.Gained strand deionized water removing chemical reagent is carried out drawing-off, and draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.2 ~ 2.3cN/dtex, and elongation at break is 13% ~ 23%.
Embodiment 11:
On freezing point ~ 8 ~ 20wt%KOH of the 93g of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C of continuous stirring dissolves completely, obtains through filtering, after vacuum deaerator 12h the chitin solution that concentration is 7wt%.This chitin solution prepares chitin fiber through wet spinning technology.The spinneret orifice spray silk that chitin solution is 0.05mm by aperture under the pressure of 0.1MPa enters in the mixed solution of the methyl-sulfoxide of 10 DEG C and water and stops 30s, and then stops 50s in the mixed solution entering 40 DEG C of methyl-sulfoxides and water and be frozen into silk.Carry out drawing-off by after gained strand deionized water removing chemical reagent, draw ratio is 1.0 ~ 1.4, then through oiling, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.4 ~ 2.5cN/dtex, and elongation at break is 11% ~ 18%.
Embodiment 12:
In the aqueous solution of the 93g 8 ~ 20wt%KOH of 0 ~ 25 DEG C, 2 ~ 10wt% urea, add 7g chitin powder, on freezing point ~ 0 DEG C continuously stir 2h after chitin dissolve obtain the chitin solution that concentration is 7wt% completely.Chitin solution evacuation and centrifugal degassing 0.1h at 5 DEG C obtains chitin spinning solution.This spinning solution prepares chitin fiber through dry-wet spinning technique.Then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.5mm, enter after 20cm air-gap and stop 50s in the ethanolic solution of 5 DEG C and be frozen into silk.By gained strand with after deionized water removing chemical reagent, drawing-off, oil, obtain chitin fiber after drying.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.3 ~ 1.5cN/dtex, and elongation at break is 16% ~ 20%.
Embodiment 13:
In the aqueous solution of the 93g 8 ~ 20wt%KOH of 0 ~ 25 DEG C, 2 ~ 10wt% urea, add 7g chitin powder, on freezing point ~ 0 DEG C continuously stir 2h after chitin dissolve obtain the chitin solution that concentration is 7wt% completely.Chitin solution evacuation and centrifugal degassing 0.1h at 5 DEG C obtains chitin spinning solution, then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.5mm, enter after 20cm air-gap and stop 50s in the ethanolic solution of 5 DEG C and be frozen into silk.By gained strand deionized water removing chemical reagent after carry out drawing-off, draw ratio is 1.2, then carry out oiling and drying obtain chitin fiber.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 1.4 ~ 1.7cN/dtex, and elongation at break is 14% ~ 20%.
Embodiment 14:
Add 7g chitin powder in 93g 8 ~ 20wt%KOH on 25 DEG C, the aqueous solution of 2 ~ 10wt% urea, after stirring 1h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution evacuation and centrifugal degassing 0.1h at 5 DEG C obtains chitin spinning solution, then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.5mm, enter after 20cm air-gap and stop 30s in the ethanolic solution of 5 DEG C and be frozen into silk.By gained strand deionized water removing chemical reagent after carry out drawing-off, draw ratio is 1.4, then carry out oiling and drying obtain chitin fiber.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 2.1 ~ 2.4cN/dtex, and elongation at break is 11% ~ 16%.
Embodiment 15:
In the aqueous solution of the 93g 8 ~ 20wt%KOH of 0 ~ 25 DEG C, 2 ~ 10wt% urea, add 7g chitin powder, after stirring 1h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution evacuation and centrifugal degassing 0.1h at 5 DEG C obtains chitin spinning solution, then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.5mm, enter after 20cm air-gap and stop 30s in the ethanolic solution of 5 DEG C and be frozen into silk.By gained strand deionized water removing chemical reagent after carry out drawing-off, draw ratio is 1.6, then carry out oiling and drying obtain chitin fiber.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 2.3 ~ 2.6cN/dtex, and elongation at break is 10% ~ 16%.
Embodiment 16:
In the aqueous solution of the 93g 8 ~ 20wt%KOH of 0 ~ 25 DEG C, 2 ~ 10wt% urea, add 7g chitin powder, after stirring 1h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution evacuation and centrifugal degassing 0.1h at 5 DEG C obtains chitin spinning solution, then under the pressure of 0.1MPa by the spinneret orifice ejection that aperture is 0.5mm, enter after 20cm air-gap and stop 100s in the ethanolic solution of 5 DEG C and be frozen into silk.By gained strand deionized water removing chemical reagent after carry out drawing-off, draw ratio is 1.8, then carry out oiling and drying obtain chitin fiber.Carry out Mechanics Performance Testing to the above-mentioned chitin fiber prepared, its TENSILE STRENGTH is 2.7 ~ 3.2cN/dtex, and elongation at break is 10% ~ 14%.
Embodiment 17:
On freezing point ~ the 93g 8 ~ 20wt%KOH of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C stir 2h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution filters at 5 DEG C, and obtains chitin spinning solution after vacuum decompression deaeration 12h.This spinning solution prepares chitin fiber through wet spinning technology.Chitin spinning solution is under the pressure of 0.1MPa, and the spinneret orifice spray silk being 0.07mm by aperture enters and stops 15s in the 80wt% ethanol/5wt% aqueous acetic acid of 5 DEG C and be frozen into silk.By gained strand with after deionized water removing chemical reagent; in the 10wt%NaOH aqueous solution of 60 DEG C, react 2h carries out deacetylated; with chemical reagent after washing residual in 50% ethanol water removing fiber, oil and drying, obtain the deacetylated chitin fiber that deacetylation is 40%.
Embodiment 18:
On freezing point ~ the 93g 8 ~ 20wt%KOH of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C stir 2h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution filters at 5 DEG C, and obtains chitin spinning solution after vacuum decompression deaeration 12h.This spinning solution prepares chitin fiber through wet spinning technology.Chitin spinning solution is under the pressure of 0.1MPa, and the spinneret orifice spray silk being 0.07mm by aperture enters and stops 15s in the 80wt% ethanol/5wt% aqueous acetic acid of 5 DEG C and be frozen into silk.By gained strand with after deionized water removing chemical reagent; in the 15wt%NaOH aqueous solution of 50 DEG C, react 4h carries out deacetylated; with chemical reagent after washing residual in 50% ethanol water removing fiber, oil and drying, obtain the deacetylated chitin fiber that deacetylation is 65%.
Embodiment 19:
On freezing point ~ the 93g 8 ~ 20wt%KOH of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C stir 2h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution filters at 5 DEG C, and obtains chitin spinning solution after vacuum decompression deaeration 12h.This spinning solution prepares chitin fiber through wet spinning technology.Chitin spinning solution is under the pressure of 0.1MPa, and the spinneret orifice spray silk being 0.07mm by aperture enters and stops 15s in the 80wt% ethanol/5wt% aqueous acetic acid of 5 DEG C and be frozen into silk.By gained strand with after deionized water removing chemical reagent; in the 30wt%NaOH aqueous solution of 50 DEG C, react 6h carries out deacetylated; with chemical reagent after washing residual in 50% ethanol water removing fiber, oil and drying, obtain the deacetylated chitin fiber that deacetylation is 86%.
Embodiment 20:
On freezing point ~ the 93g 8 ~ 20wt%KOH of 0 DEG C, 2 ~ 10wt% urea the aqueous solution in add 7g chitin powder, then on freezing point ~ 0 DEG C stir 2h continuously, chitin dissolves obtain the chitin solution that concentration is 7wt% completely.Chitin solution filters at 5 DEG C, and obtains chitin spinning solution after vacuum decompression deaeration 12h.This spinning solution prepares chitin fiber through wet spinning technology.Chitin spinning solution is under the pressure of 0.1MPa, and the spinneret orifice spray silk being 0.07mm by aperture enters and stops 15s in the 80wt% ethanol/5wt% aqueous acetic acid of 5 DEG C and be frozen into silk.By gained strand with after deionized water removing chemical reagent; in the 30wt%NaOH aqueous solution of 50 DEG C, react 6h carries out deacetylated; after 50% ethanol water process; again in the 30wt%NaOH aqueous solution of 50 DEG C, reacting 6h carries out deacetylated; use 50% ethanol water and washing successively, oil and obtain the deacetylated chitin fiber that deacetylation is 100% after drying.
Claims (17)
1. a preparation method for chitin fiber, is characterized in that its step is as follows:
1) 2 ~ 50 wt% KOH are contained in solvent for use composition, 0 ~ 20 wt% urea, 0 ~ 6 wt% thiocarbamide, 0 ~ 10 wt% LiOH, 0 ~ 20 wt% NaOH, 0 ~ 10 wt% ZnO, 0 ~ 10 wt% polyethylene glycol, surplus is water, by chitin with mix under solvent compositions arbitrary temp after be refrigerated to below freezing, then obtain chitin solution above freezing thawing; Or after being mixed under arbitrary temp with solvent compositions by chitin, above freezing, less than 0 DEG C continuous stirring and dissolving obtains chitin solution;
2) chitin solution is obtained chitin spinning solution below its gelling temperature after filtration, deaeration;
3) chitin spinning solution is prepared chitin fiber through wet method and dry-jet wet-spinning spinning technique: chitin spinning solution is the spinneret orifice of 0.05 ~ 0.5 mm by aperture, stop 1 ~ 100 s in lower than the coagulating bath below chitin solution gels temperature and be frozen into silk, then through washing, drawing-off, oil and obtain chitin fiber after drying, described coagulating bath is water-soluble low-viscosity organic liquid, or be added with water-soluble low-viscosity organic liquid of monovalent cation wherein, or the mixing material of they and water.
2. preparation method according to claim 1, is characterized in that: in described solvent compositions, and KOH concentration is 8 ~ 20 wt%.
3. preparation method according to claim 1, is characterized in that: in described solvent compositions, and urea concentration is 2 ~ 10 wt%.
4. preparation method according to claim 1, is characterized in that: in described solvent compositions, and thiourea concentration is 0 ~ 4 wt%.
5. preparation method according to claim 1, is characterized in that: in described solvent compositions, and LiOH concentration is 0 ~ 6 wt%.
6. preparation method according to claim 1, is characterized in that: in described solvent compositions, and NaOH concentration is 0 ~ 12 wt%.
7. preparation method according to claim 1, is characterized in that: in described solvent compositions, and ZnO concentration is 0 ~ 5 wt%.
8. preparation method according to claim 1, is characterized in that: in described solvent compositions, and Polyethylene glycol is 0 ~ 5 wt%.
9. preparation method according to claim 1, is characterized in that: described chitin solution concentration is 1 ~ 12 wt%.
10. preparation method according to claim 1, is characterized in that: the inclined heated plate of described chitin solution is 0.1 ~ 100 h.
11. preparation methods according to claim 1, is characterized in that: described coagulating bath is single coagulating bath or multistage coagulating bath.
12. preparation methods according to claim 1, is characterized in that: in described coagulating bath, monovalent cation is H
+, NH
4 +, Li
+, Na
+or K
+; Described water-soluble low-viscosity organic liquid is alcohol, ketone, ester, acid amides, organic sulfide or its mixture.
13. preparation methods according to claim 12, is characterized in that: described alcohol is methyl alcohol or ethanol; Described ketone is acetone; Described ester is ethyl acetate; Described acid amides is dimethyl formamide or dimethylacetylamide; Described organic sulfide is methyl-sulfoxide.
14. preparation methods according to claim 1, is characterized in that: the temperature of solidifying is-10 DEG C ~ 40 DEG C.
The preparation-obtained chitin fiber of 15. any one of claim 1 ~ 14 method.
The preparation method of 16. 1 kinds of deacetylated chitin fibers, is characterized in that its step is as follows:
1) 2 ~ 50 wt% KOH are contained in solvent for use composition, 0 ~ 20 wt% urea, 0 ~ 6 wt% thiocarbamide, 0 ~ 10 wt% LiOH, 0 ~ 20 wt% NaOH, 0 ~ 10 wt% ZnO, 0 ~ 10 wt% polyethylene glycol, surplus is water, by chitin with mix under solvent compositions arbitrary temp after be refrigerated to below freezing, then obtain chitin solution above freezing thawing; Or after being mixed under arbitrary temp with solvent compositions by chitin, above freezing, less than 0 DEG C continuous stirring and dissolving obtains chitin solution;
2) chitin solution is placed below its gelling temperature, and obtain chitin spinning solution after filtration, deaeration;
3) chitin spinning solution is prepared chitin fiber through wet method and dry-jet wet-spinning spinning technique: the spinneret orifice by chitin solution by aperture being 0.05 ~ 0.5 mm, in the coagulating bath of-10 DEG C ~ 40 DEG C, stop 1 ~ 100 s be frozen into silk, then deacetylated through washing, drawing-off, out-phase, wash, oil and after drying, obtain deacetylated chitin fiber; Described coagulating bath is water-soluble low-viscosity organic liquid, or is added with water-soluble low-viscosity organic liquid of monovalent cation wherein, or the mixing material of they and water.
17. preparation methods according to claim 16, is characterized in that: the deacetylation of described deacetylated chitin fiber can reach 100%.
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