CN101748499B - Chitin fiber and preparation method thereof - Google Patents
Chitin fiber and preparation method thereof Download PDFInfo
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- CN101748499B CN101748499B CN2008102390406A CN200810239040A CN101748499B CN 101748499 B CN101748499 B CN 101748499B CN 2008102390406 A CN2008102390406 A CN 2008102390406A CN 200810239040 A CN200810239040 A CN 200810239040A CN 101748499 B CN101748499 B CN 101748499B
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Abstract
The invention discloses a chitin fiber and a method for preparing the chitin fiber by taking ionic liquid as solvent, wherein the method comprises the following steps: evenly mixing crushed chitin with the ionic liquid and dissolving the mixture at 50 to 150 DEG C for 1 to 50 hours so as to form homogeneous and stable spinning dope with the concentration of 3-25%; filtering and defoaming the spinning dope and then conducting dry-jet wet spinning, wherein coagulation bath consists of water or the mixture of water and the ionic liquid and the ionic liquid in the coagulation bath has the concentration of 0-60% and the temperature of 0-60%. The method has the advantage that: the ionic liquid adopted includes outstanding dissolution performance toward the chitin and is non-toxic and non-volatile simultaneously, thereby avoiding polluting environment and harming body of operating staff. The ionic liquid can be recovered effectively, which lowers production cost and economizes on resourses.
Description
Technical field
The present invention relates to a kind of fiber, particularly relate to a kind of chitin fiber and preparation method thereof.
Background technology
Chitin claims chitin (Chitin) again, extensively is present in the cell membrane of insects, aquatic crustacean shell and marine alga, and as crab, shrimp, squid bone, eggshell, cockroach, fungi etc., its reserves are only second to string.Deacetyl chitin claims chitosan again, it is the found up to now unique positively charged animal macromolecule of occurring in nature, owing to have undersaturated cation group in its molecular structure, thereby it is to having all kinds of harmful substances of negative electrical charge, harmful bacteria has powerful suction-operated, it just can suppress the activity of harmful bacteria like this, it is lost activity, thereby reach antibiotic purpose, and chitin had both had the structure of string, have again to the human body ossein and organize similar structure, with human body good compatibility is arranged, can be decomposed by the lysozyme of human body and absorb, the human body damaged cells is repaired and activated, thereby make this material that good medical science characteristic be arranged.For simplicity, this paper is referred to as chitin fiber with chitin and chitosan fiber.
As previously mentioned, chitin fiber can be divided into two classes, and a class is a chitin fiber, and raw material is a chitin; Another kind of is chitosan fiber, the deacetyl chitin that raw material is produced for the chitin alkaline hydrolysis, or claim shitosan, chitosan.Fiber production generally will be through two steps, and the first step is that shrimp and crab shells is made chitin again through watery hydrochloric acid holder calcium behind the alkali deproteinization, if further processing promptly can be made into shitosan to chitin through alkali; Second step was with chitin or the certain dissolving of shitosan process, sprayed processes such as silk solidifies and promptly can be made into fiber.
Chitin fiber mainly contains following function: (1), enhancing immunity effect; (2) moisture retention; (3) promote the skin regeneration effect; (4) by the antibiotic enzyme of activating human body, lysozyme, enhance metabolism; (5) antienzyme effect; (6), suppress the bacterial reproduction effect; (7) deodorization; (8) prevent static.So chitin fiber can be made into the chitin health textile of various bacteriostatic deodorizings.
Chitin fiber is produced required solvent at present, as the concentrated sulfuric acid, concentrated hydrochloric acid, trichloroacetic acid/carrene mixed solvent, hexafluoroisopropanol and Hexafluoro acetone, DMAc/LiCl, lithium rhodanate saturated aqueous solution etc., above-mentioned dicyandiamide solution, all have volatility, cause serious pollution to jeopardize operating personnel's health simultaneously environment; Some has very strong corrosive solvent even can make a part of chitin degraded, and is very big to the corrosion of equipment; Thereby some then costs an arm and a leg and causes production cost too high.In addition, the recovery technological process of these chemical reagent is loaded down with trivial details, and can produce a large amount of waste gas and waste water, and environment is caused more serious pollution.In Chinese patent CN1162665A, the chitin adding is contained in the DMAc mixed solvent of 6%LiCl, stirred 3 hours at 20 ℃, make transparent chitin spinning slurry.After filtration, spinning after the deaeration, behind washing and drying, make chitin fiber.This method not only corrosivity is big, the production cost height, and also the physical and mechanical properties of prepared fiber is low, and its dried fracture strength only is 1.34-1.78CN/dtex, and is therefore poor according to this method prepared chitinous spinnability and woven performance.
Shitosan can be dissolved in many rare inorganic acids or some organic acid, as rare hydrochloric acid, formic acid, acetate, ethanedioic acid etc.The most frequently used dicyandiamide solution is acetic acid,diluted/urea system at present, and is cheap, and it is limited to degrade in the period of storage of slurries spinning and curing time, so have competitive advantage.But the fibrous physics mechanical performance of this system preparation is on the low side.Introduced method as the clear 60-59123 of day disclosure special permission communique: under stirring condition, shitosan is dissolved in the mixed liquor of 5% aqueous acetic acid and 1% urea, makes concentration after filtration after the deaeration and be 3.5%, viscosity is the spinning slurry of 1.52Pas by the Chitosan Preparation fiber.With the spinning head in aperture 0.14mm, 180 holes, spinning slurry is extruded in the room temperature coagulating bath, obtain chitin fiber through washing and drying, its TENSILE STRENGTH is between 0.6～1.5cN/dtex, and the physical and mechanical properties of its fiber is on the low side.
Application number is 200710043563.9, name is called that to disclose a kind of in the patent application of " preparation and the application that with the ionic liquid are the cellulose blending fibre of solvent " be the preparation and the application of the cellulose blending fibre of solvent with the ionic liquid, comminuted fibres element, chitin and ionic liquid mix, and dissolve then, the method for filtration, spinning, post processing prepares cellulose blending fibre.But, this patent application provides a kind of preparation method of cellulose blending fibre, in the method, cellulosic existence must be arranged, just high-intensity cellulose blending fibre can be prepared, and desired one-component chitin fiber among the present invention can't be prepared.Chinese patent CN02100120.0, name is called and discloses a kind of chitosan and polyvinyl alcohol composite fiber and manufacture method thereof with skin-core structure in " chitosan and polyvinyl alcohol composite fiber and manufacture method thereof ", with the polyvinyl alcohol spin dope is sandwich layer, co-blended spinning stoste with chitosan or chitosan and polyvinyl alcohol is cortex, extrude from core-skin layer composite spinneret pack, through spinning moulding, obtain described composite fibre through drawing-off and washing process again.Superior fibre-forming performance and drawing-off performance by polyvinyl alcohol composition in the sandwich layer among the present invention make fiber obtain excellent physical and mechanical properties.
In sum, because chitin solubility in conventional solvent is less and the dissolving difficulty, and traditional dicyandiamide solution, all having volatility, these solvents jeopardize health of operators when environment is caused severe contamination.And, just because its dissolving in conventional solvent is bad, caused the not high defective of mechanical property of chitin fiber in the prior art, made the spinnability of chitin fiber and woven performance poor, need carry out blending to improve its spinnability and stitchability with other fiber.Along with the development of this green solvent of ionic liquid in recent years, because ionic liquid has non-volatility, and be easy to reclaim, can reduce production costs and plurality of advantages such as dissolving cellulos preferably, ionic liquid is more and more by extensive concern.The ionic liquid of many types is very big to the dissolution of chitin degree, and this not only can improve production efficiency greatly, and provides feasibility for the mechanical property that improves chitin fiber.In view of this, special proposition the present invention.
Summary of the invention
First purpose of the present invention is to provide a kind of chitin fiber, and described fiber has remedied the bad defective of chitin fiber mechanical property of prior art, is a kind of chitin fiber of good mechanical performance.
To achieve these goals, the technical solution used in the present invention is:
A kind of chitin fiber, the dried fracture strength of described fiber is 2.5-3.5cN/dtex, and wet breaking strength is 2.0-3.0cN/dtex, and dried elongation at break is 8-12%.
Another object of the present invention is to provide a kind of preparation method of described chitin fiber, described method be a kind of be the method that solvent prepares chitin fiber with the ionic liquid, it has remedied when present chitin fiber is plain to adopt solvent spinning, selected solvent has severe corrosive and volatility thereby causes serious environmental to pollute, and the bad defective of gained fibrous mechanical property.
In order to realize purpose, the technical solution used in the present invention is:
A kind of method for preparing described chitin fiber, described method comprises the steps:
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
(2) described spinning solution is filtered and deaeration, carry out spinning then;
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
Step of the present invention (1) specifically comprises: chitin is pulverized, added ionic liquid then, dissolved 1～50 hour under 50～150 ℃ of temperature, form spinning solution.
The total solid content of spinning solution of the present invention is 5～25%.
Among the present invention, coagulating bath is that 0～60 ℃ of temperature, concentration are 0～60% ionic liquid aqueous solution when carrying out spinning; Preferred described coagulating bath is that 10～40 ℃ of temperature, concentration are 10～40% ionic liquid aqueous solution.
Ionic liquid of the present invention is made up of CATION and anion; Described CATION is a kind of in the following CATION:
Quaternary ammonium ion quaternary phosphonium ion imidazol ion pyridinium ion
Wherein: R
1, R
2, R
3, R
4And R
5Identical or different, be H, C
1～C
8Alkyl, vinyl, propenyl, cyclobutenyl, ethoxy, hydroxypropyl in a kind of;
Described anion is Cl
-, Br
-, CH
3COO
-In a kind of.
The consumption of step of the present invention (1) intermediate ion liquid is the 75-95% of spinning solution weight.
Chitin of the present invention is that deacetylation is 0～100% chitin.Chitin viscosity of the present invention is 20-30cps, purity 〉=90%, protein content≤0.5%, ash content≤1%.
Chitin of the present invention both can be pure chitin, also can be the product that removes behind the part acetyl group.
Post processing of the present invention comprises and tow is stretched, washes, oils and dry step.
Chitin fiber of the present invention can be used as fields such as high-end textile, medical fibre, anti-bacterial fibre.
Specifically, the preparation method of chitin fiber of the present invention comprises the steps:
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make that the fineness of resulting chitin is the 100-500 order.Why needing chitin is crushed to the 100-500 order, is in order to make the chitin after pulverizing can better be dissolved in the ionic liquid, for the chitin fiber of preparation good mechanical performance is got ready.
Chitin after the pulverizing is put into ionic liquid and is dissolved, wherein ion liquid consumption is the 75-95% of spinning solution weight, under 50～150 ℃ of temperature, dissolved 1～50 hour, when dissolving, can stir or carry out ultrasonic concussion, allow chitin in ionic liquid, dissolve fully.Fully after the dissolving, obtain spinning solution, its concentration is 5～25%.
Described ionic liquid is made up of CATION and anion; Described CATION is a kind of in the following CATION:
Quaternary ammonium alkyl ion alkyl quaternary phosphonium ion alkyl imidazole ion alkyl pyridine ion
Wherein: R
1, R
2, R
3, R
4And R
5Identical or different, be H, C
1～C
8Alkyl, vinyl, propenyl, cyclobutenyl, ethoxy, hydroxypropyl in a kind of;
Described anion is Cl
-, Br
-, CH
3COO
-In a kind of.
(2) described spinning solution is filtered and deaeration, do spray-wet spinning then;
With spinning solution filter with deaeration after, do spray-wet spinning, obtain tow after the spinning.Coagulating bath is that 0～60 ℃ of temperature, concentration are 0～60% ionic liquid aqueous solution when doing spray-wet spinning, and described percent concentration is a mass percent.Described ionic liquid kind is an ionic liquid used when dissolving chitin.Spinning speed is 15-100m/min.
Dried spray-wet spinning of the present invention is a kind of method that spins high strength, high-orientation fiber.During spinning, to be dissolved in fully in the ionic liquid and the spinning solution that obtains after high power spinning head (d=0.15-0.3mm) ejection, the spinneret draft multiple is 3～25 times, spinning head is earlier through the long air section of one section 15-25mm, basic curing molding in described air section, make crystalline orientation be fixed, therefore can reach higher intensity.Afterwards, enter coagulating bath, coagulating bath is that 0～60 ℃ of temperature, concentration are 0～60% ionic liquid aqueous solution, and preferred described coagulating bath is that 10～40 ℃ of temperature, concentration are 10～40% ionic liquid aqueous solution.The tow that comes out from coagulating bath does not need to stretch basically, only plays the effect of tensioning tow, and draw ratio helps keeping the crystalline orientation of fiber like this about 1～1.2 times.
Dried spray-wet spinning technology of the present invention not only has dry spinning speed fast, spinning solution concentration height and the advantage that can apply super drawing to thread, and kept wet spinning and can solidify the characteristics that parameter is controlled the as-spun fibre structure by adjusting spinning, thereby this technology has the strong point of dry-spinning and wet spinning concurrently.Owing to after the spinning solution thread is extruded spinneret orifice, by air layer, so just can improve jet stretch ratio earlier, thereby spinning speed than the high 5-10 of common wet spinning doubly, can improve the productivity ratio of spinning machine greatly; Compare the spinning head that the dry-jet wet-spinning usage aperture is bigger with wet spinning; In dried spray of the present invention-wet spinning process, the as-spun fibre surface can form the thin and fine and close cortex of one deck, forms big cavity at fibrous inside when avoiding curing condition to change, and helps improving the mechanical performance of fiber.
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
The resulting tow of step (2) is carried out post processing, obtain described chitin fiber.Described post processing comprises and tow is stretched, washes and dry step.Stretching in the last handling process is minimum, its effect only is in order to allow fiber obtain certain force of strain in the process of road, back washing, ensure carrying out smoothly of later process, its draw ratio is between 1～1.2 times, do drawing medium with hot bath or saturated vapor during stretching, the temperature of stretching is 70-90 ℃, washes afterwards, and then carry out drying, temperature is 90-150 ℃ when dry.
Prior art shows that all there is the not high defective of mechanical property in the chitin fiber for preparing according to conventional method, makes the spinnability of chitin fiber and woven performance poor, need carry out blending to improve its spinnability and stitchability with other fiber.Therefore, be all to need by cellulose and chitin are carried out blend in the patent application of 200710043563.9 grades as application number, prepare cellulose blending fibre, to overcome the above-mentioned defective of chitin fiber, because the ins and outs that cellulose possesses, be that cellulose is that D-glucose is with β-1, the macromolecular polysaccharide that 4 glycosidic bonds are formed, molecular weight about 50000～2500000, be equivalent to 300～15000 glucosyl groups, be vascular plant, the main component of plant and a part of alga cells wall.Chemical cellulose major part wherein is the crystallinity cellulose, and it mixes with chitin, has guaranteed the crystalline orientation of preparation-obtained spinning solution drawing and forming, has avoided fibrous inside to form big cavity, helps improving the mechanical performance of fiber.Yet among the present invention, not needing to add cellulose mixes with chitin, by improvement to the preparation method, as utilize ionic liquid that it is well dissolved to form spinning solution, cooperate then and do spray-wet spinning process, make the crystalline orientation of chitin to be fixed well, avoid that chitin fiber in forming process disorientation takes place and causes the low defective of its mechanical strength in the prior art.
Beneficial effect of the present invention is:
1) ionic liquid of Cai Yonging have good solubility property to crust, ionic liquid is nontoxic, non-volatile simultaneously, can avoid environment is polluted and operating personnel's health is damaged, and ionic liquid can effectively reclaim, reduce production costs, economize on resources.
2) chitin fiber good mechanical performance of the present invention not only has higher dried fracture strength, also has higher wet breaking strength, and dried preferably elongation at break is a kind of chitin fiber of high-quality.
Description of drawings
Fig. 1: a kind of is the process chart that solvent prepares chitin fiber with the ionic liquid.
The specific embodiment
Embodiment 1
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make that the fineness of resulting chitin is about 300 orders.Described chitin is that deacetylation is 0% chitin.Chitin after the pulverizing is put into ionic liquid and is dissolved, and wherein ion liquid consumption is 85% of a spinning solution weight, and dissolving is 50 hours under 50 ℃ of temperature, when dissolving, stirs, and allows chitin dissolve fully in ionic liquid.Fully after the dissolving, obtain spinning solution, its concentration is 15%.
(2) described spinning solution is filtered and deaeration, do spray-wet spinning then;
With spinning solution filter with deaeration after, do spray-wet spinning, obtain tow after the spinning.Coagulating bath is that 25 ℃ of temperature, concentration are [PMIN] Cl of 10% when doing spray-wet spinning
-(Chinese is chlorination 1-propyl group-3-methylimidazole salt) aqueous solution, described percent concentration is a mass percent.Described ionic liquid kind is an ionic liquid used when dissolving chitin.Spinning speed is 15m/min.
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
The resulting tow of step (2) is carried out post processing, obtain described chitin fiber.Described post processing comprises and tow is stretched, washes and dry step.Its draw ratio of described stretching is 1.2 times, does drawing medium with hot bath during stretching, and the temperature of stretching is 85 ℃, washes afterwards, and then carries out drying, and temperature is 105 ℃ when dry.
Resulting chitin fiber fiber number is 1.67dtex, and dried fracture strength is 2.5cN/dtex, and wet breaking strength is 2.0cN/dtex, and dried elongation at break is 10%.
Embodiment 2
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make that the fineness of resulting chitin is about 400 orders.Described chitin is that deacetylation is 40% chitin.Chitin after the pulverizing is put into ionic liquid and is dissolved, wherein ion liquid consumption is 75% of a spinning solution weight, dissolving is 8 hours under 100 ℃ of temperature, described ionic liquid is [EMIN] Ac-(Chinese is acetic acid 1-ethyl-3-methylimidazole salt) aqueous solution, when dissolving, stir, allow chitin in ionic liquid, dissolve fully.Fully after the dissolving, obtain spinning solution, its concentration is 25%.
(2) described spinning solution is filtered and deaeration, do spray-wet spinning then;
With spinning solution filter with deaeration after, do spray-wet spinning, obtain tow after the spinning.Coagulating bath is that 40 ℃ of temperature, concentration are [EMIN] Ac of 10% when doing spray-wet spinning
-(Chinese is acetic acid 1-ethyl-3-methylimidazole salt) aqueous solution, described percent concentration is a mass percent.Described ionic liquid is an ionic liquid used when dissolving chitin.Spinning speed is 50m/min.
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
The resulting tow of step (2) is carried out post processing, obtain described chitin fiber.Described post processing comprises and tow is stretched, washes and dry step.Its draw ratio is 1.1 times in the described stretching, does drawing medium with hot bath during stretching, and the temperature of stretching is 80 ℃, washes afterwards, and then carries out drying, and temperature is 120 ℃ when dry.
Resulting chitin fiber fiber number is 3.33dtex, and dried fracture strength is 3.0cN/dtex, and wet breaking strength is 2.5cN/dtex, and dried elongation at break is 12%.
Embodiment 3
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make that the fineness of resulting chitin is about 500 orders.Described chitin is that deacetylation is 80% chitin.Chitin after the pulverizing is put into ionic liquid and is dissolved, and wherein ion liquid consumption is 95% of a spinning solution weight, and dissolving is 1 hour under 150 ℃ of temperature, when dissolving, stirs, and allows chitin dissolve fully in ionic liquid.Fully after the dissolving, obtain spinning solution, its concentration is 5%.
(2) described spinning solution is filtered and deaeration, do spray-wet spinning then;
With spinning solution filter with deaeration after, do spray-wet spinning, obtain tow after the spinning.Coagulating bath is that 25 ℃ of temperature, concentration are [PMIN] Cl of 10% when doing spray-wet spinning
-(Chinese is chlorination 1-propyl group-3-methylimidazole salt) aqueous solution, described percent concentration is a mass percent.Described ionic liquid kind is an ionic liquid used when dissolving chitin.Spinning speed is 80m/min.
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
The resulting tow of step (2) is carried out post processing, obtain described chitin fiber.Described post processing comprises and tow is stretched, washes and dry step.In the described stretching, its draw ratio is 1.2 times, does drawing medium with hot bath during stretching, and the temperature of stretching is 90 ℃, washes afterwards, and then carries out drying, and temperature is 110 ℃ when dry.
Resulting chitin fiber fiber number is 2.05dtex, and dried fracture strength is 2.8cN/dtex, and wet breaking strength is 2.3cN/dtex, and dried elongation at break is 8%.
Embodiment 4
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make that the fineness of resulting chitin is about 450 orders.Described chitin is that deacetylation is 100% chitin.Chitin after the pulverizing is put into ionic liquid and is dissolved, and wherein ion liquid consumption is 75% of a spinning solution weight, and dissolving is 8 hours under 80 ℃ of temperature, when dissolving, stirs, and allows chitin dissolve fully in ionic liquid.Fully after the dissolving, obtain spinning solution, its concentration is 25%.
(2) described spinning solution is filtered and deaeration, do spray-wet spinning then;
With spinning solution filter with deaeration after, do spray-wet spinning, obtain tow after the spinning.Coagulating bath is that 10 ℃ of temperature, concentration are [PMIN] Cl of 40% when doing spray-wet spinning
-(Chinese is chlorination 1-propyl group-3-methylimidazole salt) aqueous solution, described percent concentration is a mass percent.Described ionic liquid is an ionic liquid used when dissolving chitin.Spinning speed is 100m/min.
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
The resulting tow of step (2) is carried out post processing, obtain described chitin fiber.Described post processing comprises and tow is stretched, washes and dry step.In the described stretching, its draw ratio is 1.2 times, does drawing medium with hot bath during stretching, and the temperature of stretching is 90 ℃, washes afterwards, and then carries out drying, and temperature is 105 ℃ when dry.
Resulting chitin fiber fiber number is 3.0dtex, and dried fracture strength is 3.5cN/dtex, and wet breaking strength is 3.0cN/dtex, and dried elongation at break is 12%.
Table 1 relates to embodiment 5-8
Table 1
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Preparation condition | Other condition is identical with embodiment 1, and different is ionic liquid, and its anion is an acetate ion, and CATION is an imidazol ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4, R5 are H | Other condition is identical with embodiment 2, and different is ionic liquid, and its anion is a chlorion, and CATION is an imidazol ion, and wherein R1 is a hydroxypropyl, and R3 is a cyclobutenyl, and R2, R4, R5 are H | Other condition is identical with embodiment 3, and different is ionic liquid, and its anion is a bromide ion, and CATION is an imidazol ion, and wherein R1 is an ethyl, and R3 is a normal-butyl, and R2, R4, R5 are H | Other condition is identical with embodiment 4, and different is ionic liquid, and its anion is an acetate ion, and CATION is an imidazol ion, and wherein R1 is a hydroxypropyl, and R3 is an ethoxy, and R2, R4, R5 are H |
| Fibre number (dtex) | 1.71 | 3.2 | 2.2 | 2.9 |
| Do fracture strength (cN/dtex) | 2.68 | 3.2 | 2.81 | 3.4 |
| Wet breaking strength (cN/dtex) | 2.12 | 2.65 | 2.36 | 2.8 |
| Dried elongation at break (%) | 9.8 | 10.8 | 12 | 11.5 |
Table 2 relates to embodiment 9-12
Table 2
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Preparation condition | Other condition is identical with embodiment 1, and different is ionic liquid, and its anion is an acetate ion, and CATION is a quaternary ammonium ion, and wherein R1 is | Other condition is identical with embodiment 2, and different is ionic liquid, and its anion is a chlorion, and CATION is a quaternary ammonium ion, and wherein R1 is positive fourth | Other condition is identical with embodiment 3, and different is ionic liquid, and its anion is a bromide ion, and CATION is a quaternary ammonium ion, and wherein R1 is positive fourth | Other condition is identical with embodiment 4, and different is ionic liquid, and its anion is a chlorion, and CATION is a quaternary ammonium ion, and wherein R1 is positive fourth |
| Normal-butyl, R3 are propenyl, and R2, R4 are H | Base, R3 are propenyl, and R2, R4 are H | Base, R3 are propenyl, and R2, R4 are H | Base, R3 are propenyl, and R2, R4 are H | |
| Fibre number (dtex) | 1.58 | 3.0 | 2.15 | 3.1 |
| Do fracture strength (cN/dtex) | 2.6 | 3.04 | 2.94 | 3.35 |
| Wet breaking strength (cN/dtex) | 2.08 | 2.37 | 2.41 | 2.98 |
| Dried elongation at break (%) | 9.0 | 10.3 | 11.2 | 10.9 |
Table 3 relates to embodiment 13-16
Table 3
| Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | |
| Preparation condition | Other condition is identical with embodiment 1, and different is ionic liquid, and its anion is an acetate ion, and CATION is a quaternary phosphonium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4 are H | Other condition is identical with embodiment 2, and different is ionic liquid, and its anion is a chlorion, and CATION is a quaternary phosphonium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4 are H | Other condition is identical with embodiment 3, and different is ionic liquid, and its anion is a bromide ion, and CATION is a quaternary phosphonium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4 are H | Other condition is identical with embodiment 4, and different is ionic liquid, and its anion is a bromide ion, and CATION is a quaternary phosphonium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4 are H |
| Fibre number (dtex) | 1.75 | 3.15 | 2.09 | 3.4 |
| Do fracture strength (cN/dtex) | 2.71 | 3.09 | 2.86 | 3.4 |
| Wet breaking strength (cN/dtex) | 2.16 | 2.62 | 2.37 | 2.98 |
| Dried elongation at break (%) | 10.4 | 11.3 | 9.8 | 11.9 |
Table 4 relates to embodiment 17-20
Table 4
| Embodiment 17 | Embodiment 18 | Embodiment 19 | Embodiment 20 | |
| Preparation condition | Other condition is identical with embodiment 1, and different is ionic liquid, and its anion is an acetate ion, and CATION is a pyridinium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4, R5, R6 are H | Other condition is identical with embodiment 2, and different is ionic liquid, and its anion is an acetate ion, and CATION is a pyridinium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4, R5, R6 are H | Other condition is identical with embodiment 3, and different is ionic liquid, and its anion is an acetate ion, and CATION is a pyridinium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4, R5, R6 are H | Other condition is identical with embodiment 4, and different is ionic liquid, and its anion is an acetate ion, and CATION is a pyridinium ion, and wherein R1 is a normal-butyl, and R3 is a propenyl, and R2, R4, R5, R6 are H |
| Fibre number (dtex) | 1.59 | 3.15 | 2.0 | 3.1 |
| Do fracture strength (cN/dtex) | 2.5 | 3.12 | 2.74 | 3.5 |
| Wet breaking strength (cN/dtex) | 2.1 | 2.9 | 2.3 | 2.99 |
| Dried elongation at break (%) | 9.5 | 11.8 | 9.3 | 11.4 |
Claims (20)
1. a chitin fiber is characterized in that, the dried fracture strength of described fiber is 2.5-3.5cN/dtex, and wet breaking strength is 2.0-3.0cN/dtex, and dried elongation at break is 8-12%, and the preparation of described chitin fiber comprises the steps:
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
(2) described spinning solution is filtered and deaeration, carry out spinning then;
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
2. chitin fiber according to claim 1 is characterized in that, described step (1) specifically comprises: chitin is pulverized, added ionic liquid then, dissolved 1～50 hour under 50～150 ℃ of temperature, form spinning solution.
3. chitin fiber according to claim 1 is characterized in that, the concentration of described spinning solution is 5～25%.
4. chitin fiber according to claim 1 is characterized in that, adopts when carrying out spinning in the described step (2) and does spray-wet spinning technology.
5. according to claim 1 or 4 described chitin fibers, it is characterized in that coagulating bath is that 0～60 ℃ of temperature, concentration are 0～60% ionic liquid aqueous solution when carrying out spinning.
6. chitin fiber according to claim 5 is characterized in that, coagulating bath is that 10～40 ℃ of temperature, concentration are 10～40% ionic liquid aqueous solution when carrying out spinning.
7. chitin fiber according to claim 2 is characterized in that described ionic liquid is made up of CATION and anion; Described CATION is a kind of in the following CATION:
Wherein: R
1, R
2, R
3, R
4And R
5Identical or different, be H, C
1～C
8Alkyl, vinyl, propenyl, cyclobutenyl, ethoxy, hydroxypropyl in a kind of;
Described anion is Cl
-, Br
-, CH
3COO
-In a kind of.
8. chitin fiber according to claim 2 is characterized in that, the consumption of described step (1) intermediate ion liquid is the 75-95% of spinning solution weight.
9. chitin fiber according to claim 2 is characterized in that, described chitin is that deacetylation is 0～100% chitin.
10. chitin fiber according to claim 2 is characterized in that, described post processing comprises and tow stretched, washes and dry step.
11. a method for preparing the described chitin fiber of claim 1 is characterized in that described method comprises the steps:
(1) chitin is pulverized, added ionic liquid then and make its dissolving, obtain spinning solution;
(2) described spinning solution is filtered and deaeration, carry out spinning then;
(3) the resulting tow of step (2) is carried out post processing, obtain described chitin fiber.
12. method according to claim 11 is characterized in that, described step (1) specifically comprises: chitin is pulverized, added ionic liquid then, dissolved 1～50 hour under 50～150 ℃ of temperature, form spinning solution.
13. method according to claim 11 is characterized in that, the concentration of described spinning solution is 5～25%.
14. method according to claim 11 is characterized in that, adopts when carrying out spinning in the described step (2) and does spray-wet spinning technology.
15., it is characterized in that coagulating bath is that 0～60 ℃ of temperature, concentration are 0～60% ionic liquid aqueous solution when carrying out spinning according to claim 11 or 14 described methods.
16. method according to claim 12 is characterized in that, coagulating bath is that 10～40 ℃ of temperature, concentration are 10～40% ionic liquid aqueous solution when carrying out spinning.
17. method according to claim 12 is characterized in that, described ionic liquid is made up of CATION and anion; Described CATION is a kind of in the following CATION:
Wherein: R
1, R
2, R
3, R
4And R
5Identical or different, be H, C
1～C
8Alkyl, vinyl, propenyl, cyclobutenyl, ethoxy, hydroxypropyl in a kind of;
Described anion is Cl
-, Br
-, CH
3COO
-In a kind of.
18. method according to claim 12 is characterized in that, the consumption of described step (1) intermediate ion liquid is the 75-95% of spinning solution weight.
19. method according to claim 12 is characterized in that, described chitin is that deacetylation is 0～100% chitin.
20. method according to claim 12 is characterized in that, described post processing comprises and tow is stretched, washes and dry step.
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| JP5820688B2 (en) * | 2011-03-23 | 2015-11-24 | 株式会社Kri | Solvent used for dissolving polysaccharide, molded product using the solvent, and method for producing polysaccharide derivative |
| CN102534864B (en) * | 2011-11-19 | 2013-10-16 | 青岛科技大学 | Preparation method of alkylation chitosan fiber |
| IN2014DN10349A (en) | 2012-05-21 | 2015-08-07 | Bridgestone Corp | |
| CN102704038B (en) * | 2012-06-21 | 2014-04-09 | 大连工业大学 | Cyanoethyl chitosan fiber and preparation method thereof |
| JP2014227619A (en) | 2013-05-21 | 2014-12-08 | 株式会社ブリヂストン | Method of producing refined polysaccharide fiber, refined polysaccharide fiber and tire |
| CN103409850A (en) * | 2013-08-14 | 2013-11-27 | 江苏盛虹科技股份有限公司 | Chitosan filament and preparation method thereof |
| CN105361551A (en) * | 2015-10-12 | 2016-03-02 | 福建省晋江市恒丰喷胶棉织造有限公司 | Antibacterial cotton quilt with nerve soothing effect |
| CN106868630B (en) * | 2017-02-10 | 2019-03-19 | 青岛科技大学 | A kind of preparation method of squid bone nanofiber |
| CN107715165A (en) * | 2017-09-30 | 2018-02-23 | 河南亚都实业有限公司 | Medical absorbent cotton gauze and its process equipment |
| CN111434817A (en) * | 2019-01-15 | 2020-07-21 | 青岛大学 | Method for preparing chitin fiber fabric by using shrimp and crab shells |
| CN114737277A (en) * | 2021-01-07 | 2022-07-12 | 洛阳常龙新材料科技有限公司 | Glue making method for dissolving chitin and vinylon fibers by using ionic liquid |
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