CN1287017C - Chitin amine/polyviny vinyl alcohol composite fiber and its manufacturing method - Google Patents
Chitin amine/polyviny vinyl alcohol composite fiber and its manufacturing method Download PDFInfo
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- CN1287017C CN1287017C CN 02100120 CN02100120A CN1287017C CN 1287017 C CN1287017 C CN 1287017C CN 02100120 CN02100120 CN 02100120 CN 02100120 A CN02100120 A CN 02100120A CN 1287017 C CN1287017 C CN 1287017C
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Abstract
The present invention discloses a composite chitosan /polyvinyl alcohol fiber in a skin-core structure, and a making method thereof. A spinning stock solution of polyvinyl alcohol is used as a core layer; a spinning stock solution of chitosan or blended chitosan and polyvinyl alcohol is used as a skin layer; the spinning stock solutions are extruded by a skin-core type composite spinning subassembly, are treated by spinning shaping, drafting technology and water washing technology, and the composite fiber is obtained. The composite fiber is further treated by acetalation treatment of methyl aldehyde or glutaric dialdehyde, and a composite chitosan /polyvinyl acetal fiber with raised hot water resistant performance and repeated washing resistant performance is obtained. The composite fiber of the present invention has favorable biological functions and chromaticity because of the high content of a chitosan element in a skin layer. The fiber obtains favorable physical and mechanical performance because a polyethylene element in a core layer has favorable fiber forming performance and drafting performance. The fiber has low producing cost, and can be used for one-off textile raw materials for iatrical application. After acetalation, the fiber can be used for preparing various fabrics with a healthcare function.
Description
Invention field
The present invention relates to a kind of functional fiber material chitosan and polyvinyl alcohol composite fiber and manufacture method thereof, particularly have chitosan and the polyvinyl alcohol composite fiber and the manufacture method thereof of skin-core structure.
Prior art
Chitosan is the product of chitin deacetylate after concentrated base is handled.Chitin is a kind of natural biological high polymer that extracts in the cell membrane by the shell of shrimp, crab, insect and mushroom, algae.At occurring in nature, chitinous year biosynthesis amount is a kind of very abundant organic regenerative resource of cellulosic reserves that is only second to more than 10,000,000,000 tons.In numerous natural polysaccharides, chitin and main derivative chitosan thereof are unique alkaline polysaccharides, have many special biological functions, as high degree of biocompatibility, broad spectrum antibacterial, immunity promote active, promote epithelial cell growth and be suppressed to the short of fibroblast growth and alleviate performance, biodegradation and the absorbability etc. of scar.
Prior art adopts chitin or chitosan solution to be spun into fiber, be used for to absorb medical applications such as sutures and artificial skin, or be used for " drug application principle " health-care underclothes of " transdermal effect activating cell, enhance metabolism and enhancing immunity, antibiotic toxin expelling, Weight-reducing and lipid-lowering, delay senility " etc.But pure chitin or chitosan fiber lack the needed physical and mechanical properties of weaving back processing, and cost is very high, costs an arm and a leg, and its extensive popularization and application is restricted.
Prior art adopts the chitosan minuteness particle added in the rayon spinning stoste and spins antibacterial viscose fiber, but because addition very little (1-2%W/W) does not have due multiple biological function.
JP0347,263,[91 47,2633] method that artificial hair is made in a kind of chitosan and polyvinyl alcohol blending spinning is disclosed, this method is with water-soluble 15% the aqueous solution that makes of the polyvinyl alcohol of alcoholysis degree 98-99%, low-molecular weight crust amine is dissolved in 10% aqueous acetic acid makes 10% chitosan solution, two kinds of solution are got co-blended spinning stoste with poly-vinyl alcohol solution/chitosan solution=80/30 ratio blend, extrude through spinneret orifice, the saltcake coagulating bath is solidified, drawing-off gets blending type chitosan and polyvinyl alcohol composite fiber, makes the fiber of artificial hair purposes again through formalizing technology.But the intensity of this method gained blending type chitosan and vinal is about 2g/d, still can not satisfy the requirement of weaving back processing to the fibrous physics mechanical performance when being used for the thinner weaving purposes of fiber number.
Prior art spinning vinylon (being commonly called as vinylon or polyvinyl), be that the employing polyvinyl alcohol water solution is a spinning solution, obtain vinal through wet-formed (saltcake or sodium hydrate aqueous solution coagulating bath) or duse process (water evaporates is solidified in the hot-air), drawing-off, make the vinylon polyvinyl through formalizing technology again.The major defect of polyvinyl is that dyeability is poor, and the amount of dying is not high and color and luster is not bright-coloured.Another shortcoming is that elasticity is relatively poor, and the easy wrinkle of PURE YARN FABRIC are so be mainly used in and cotton or wool blend.Its major advantage is intensity height, good hygroscopicity.The performance of polyvinyl long filament and outward appearance and natural silk are closely similar, but because of its not easy dyeing and poor flexibility be difficult to as senior dress material, purposes is restricted.But then, polyvinyl alcohol is a kind of synthetic high polymer that can not rely on petroleum resources, can produce acetylene through cracking from the methane in natural gas or the biogas (plant dead water, rot and produce), acetylene and acetic acid reaction get vinyl acetate, vinyl acetate gets polyvinyl acetate through polymerization, and polyvinyl acetate alcohol under methyl alcohol and NaOH effect solves polyvinyl alcohol.And polyvinyl alcohol belongs to Biodegradable high-molecular, and oxidation at first taking place under microbial action during degraded generates hydrogen peroxide and ketone, and hydrolysis further takes place ketone then, is CO by microbial metabolism at last
2And H
2O (bibliographical information is also arranged, and under some bacterial classification effect, what oxidation generated in polyvinyl alcohol took place is alcohol rather than ketone).Therefore, polyvinyl alcohol is a kind of synthetic high polymer that meets sustainable development and environment protection requirement.
The content of invention
But the object of the present invention is to provide that a kind of raw material can naturally be regenerated, the chitosan of product Natural Degradation and polyvinyl alcohol composite fiber, described composite fibre has skin-core structure, have excellent physical and mechanical properties and dyeability, the individual style and multiple biological health and the medical functions that have biological fiber simultaneously, production cost.
But another object of the present invention is to provide that a kind of raw material can naturally be regenerated, the manufacture method of the chitosan of product Natural Degradation and polyvinyl alcohol composite fiber, described manufacture method adopts the manufacture method of existing skin-core structure composite fibre, technology is simple, is fit to large-scale industrial production.
To achieve these goals, the technical solution used in the present invention is: a kind of chitosan and polyvinyl alcohol composite fiber, have the skin-core structure composite construction, and described cortex is a chitosan, sandwich layer is a polyvinyl alcohol.
The technical solution used in the present invention also can be a kind of chitosan and polyvinyl alcohol composite fiber, has the skin-core structure composite construction, and described cortex is the mixture of chitosan and polyvinyl alcohol, and sandwich layer is polyvinyl alcohol.
Wherein, when described cortex is the mixture of chitosan and polyvinyl alcohol, in the mixture of cortex chitosan content be greater than 0wt%-less than 100wt%, all the other are polyvinyl alcohol, sandwich layer is a polyvinyl alcohol; In described chitosan and the polyvinyl alcohol composite fiber, the content of chitosan be the fiber total amount greater than 0%-80wt%.
In the preferred described cortex, chitosan content is 20-60wt%, and all the other are polyvinyl alcohol, and sandwich layer is a polyvinyl alcohol; In described chitosan and the polyvinyl alcohol composite fiber, the content of chitosan is preferably the 4-30wt% of fiber total amount.
The molecular weight of described chitosan is 15-50 ten thousand, and deacetylation is 70-90%; The degree of polymerization of polyvinyl alcohol is 1700-4000, alcoholysis degree 90-99%.
Further, cortex of the present invention is the cortex of handling through acetalation; Preferred described cortex is the cortex through formaldehyde or the processing of glutaraldehyde acetalation.
The fiber number 2-7d of chitosan of the present invention and polyvinyl alcohol composite fiber, fracture strength 2.5-4.5g/d, extension at break 10-20%.
The manufacture method of chitosan of the present invention and polyvinyl alcohol composite fiber is: the manufacture method of a kind of chitosan and polyvinyl alcohol composite fiber, with the polyvinyl alcohol spin dope is sandwich layer, co-blended spinning stoste with chitosan spinning solution or chitosan and polyvinyl alcohol is cortex, extrude from the core-skin type composite spinneret pack, through spinning technique, obtain having the chitosan and the polyvinyl alcohol composite fiber of skin-core structure again through drawing-off and washing process.
Chitosan of the present invention and the polyvinyl alcohol composite fiber spinning technique after the core-skin type composite spinneret pack is extruded can adopt wet method, do wet method or dry-spinning process.
Chitosan of the present invention and polyvinyl alcohol composite fiber and manufacture method thereof further comprise through the described composite fibre of acetalation PROCESS FOR TREATMENT, obtain chitosan and Polyvinyl acetal composite fibre that heat-resisting water and anti-cyclic washing performance improve; Acetalation is handled and is adopted formaldehyde or glutaraldehyde.
Polyvinyl alcohol spin dope of the present invention is the aqueous solution or the dilute acetic acid aqueous solution of polyvinyl alcohol, and the concentration of polyvinyl alcohol is 5-45wt%, is preferably 15-40wt%.If be the dilute acetic acid aqueous solution of polyvinyl alcohol, it is below the 3wt% that polyvinyl alcohol is dissolved in concentration, preferably in the aqueous acetic acid below the 2wt%, obtains the spinning solution of above-mentioned polyvinyl alcohol concentration.
Chitosan spinning solution of the present invention is the dilute acetic acid aqueous solution of chitosan, and chitosan concentration is 2-10wt% in the spinning solution, is preferably 5-8wt%.Acetate concentration is 1-10wt% in the dilute acetic acid aqueous solution of dissolving chitosan, is preferably 2-5wt%.
The co-blended spinning stoste of chitosan of the present invention and polyvinyl alcohol is meant the chitosan spinning solution is mixed the co-blended spinning stoste that obtains with aforementioned polyvinyl alcohol spin dope.In the solid content of co-blended spinning stoste chitosan content be greater than 0wt%-less than 100wt%, be preferably 20-60wt%.
Polyvinyl alcohol spin dope of the present invention is meant polyvinyl alcohol is dissolved in water or dilute acetic acid aqueous solution under 89-99 ℃, through deaeration and spinning solution.Acetate concentration is below the 3wt%, to be preferably below the 2wt% in the dilute acetic acid aqueous solution of dissolve polyvinyl alcohol.Polyvinyl alcohol concentration is 5-45wt%, is preferably 15-40wt%.Described chitosan spinning solution is configured to the concentration of needs as required, gets the chitosan spinning solution through deaeration; Gained chitosan spinning solution is mixed with aforementioned polyvinyl alcohol spin dope through thermosistor, static mixer, promptly get the co-blended spinning stoste of chitosan and polyvinyl alcohol.When the core-skin type composite spinneret pack is extruded, two kinds of spinning solutions of cortex and sandwich layer are determined according to the solid content weight ratio of skin/core at the metering beguine of cortex inlet and sandwich layer inlet, generally getting cortex solid content/sandwich layer solid content is 10/90-80/20, is preferably 20/80-50/50.
Specifically, the manufacture method of chitosan of the present invention and polyvinyl alcohol composite fiber is: be dissolved in polyvinyl alcohol in water or the dilute acetic acid aqueous solution under 95-98 ℃, obtain the poly-vinyl alcohol solution that concentration is 5-45wt%, get polyvinyl alcohol spin dope through deaeration; Chitosan at room temperature is dissolved in the 1-10wt% dilute acetic acid aqueous solution, and obtaining concentration is the chitosan solution of 2-10wt%, gets the chitosan spinning solution through deaeration; This chitosan spinning solution extrudes the back and is delivered to static mixer by booster pump through thermosistor (95-98 ℃ of temperature control) in dissolution kettle, evenly mix with the polyvinyl alcohol spin dope of direct pump, promptly get the co-blended spinning stoste of chitosan and polyvinyl alcohol to static mixer.Gained chitosan spinning solution is extruded the back be delivered to cortex inlet measuring pump through thermosistor (95-98 ℃ of temperature control), prefilter in dissolution kettle by booster pump, or the co-blended spinning stoste of gained chitosan and polyvinyl alcohol entered cortex inlet measuring pump through prefilter, another road polyvinyl alcohol spin dope is through prefilter pump to the sandwich layer measuring pump that enters the mouth.Cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating speed is 1/0.50-1/1.5.Doubly get core-skin type chitosan and polyvinyl alcohol composite fiber through the fiber of compound stoste thread after wet method, dried wet method or dry spinning are shaped xeothermic stretching 2-5.5 under 180-210 ℃ that the core-skin type composite spinneret is extruded.
Wet method of the present invention, or dried wet method, or dry spinning shaping can adopt the method in the prior art.When wet-formed, the compound stoste thread of extruding from compound spinnerets directly enters coagulating bath, and coagulating agent adopts saltcake (the saturated Na of polyvinyl spinning
2SO
4) aqueous solution or the NaOH aqueous solution; Do when wet-formed, compound stoste thread enters coagulating bath behind the air-gap of one section 1-10cm; During duse process, compound stoste thread makes solvent evaporates through 100-170 ℃ hot-air path and is solidified.
Whether core-skin type chitosan of the present invention and vinal adopt the acetalation treatment process, depend on the final products purposes.When being used for disposable or during medical application, can be without acetalation.When being used for needing heat-resisting water or repeatedly washing purposes, need acetalation.
The core-skin type chitosan and the polyvinyl alcohol composite fiber of Zhi Zaoing has good biological function and dyeability owing to the chitosan component content in the fibrocortex is high according to the method described above; Has low production cost owing to the content of chitosan composition in total fiber is low; Owing to the good fibre-forming performance and the drawing-off performance of polyvinyl alcohol composition in the sandwich layer makes fiber obtain good physical and mechanical properties.Composite fibre of the present invention can be as the textile raw material of disposable or medical application; After acetalation, heat-resisting water reaches repeatedly washing performance and is improved, and can be used to prepare various fabrics with health care.
The specific embodiment
Below be specific embodiments of the invention, described embodiment is used to describe the present invention, rather than restriction the present invention.Unless stated otherwise, the equal weight percentage of the solution concentration among the embodiment.
Embodiment 1
Polyvinyl alcohol (degree of polymerization 1750, alcoholysis degree 99%) is dissolved in the 2wt% dilute acetic acid aqueous solution under 95-98 ℃, obtains the poly-vinyl alcohol solution that concentration is 15wt%, get polyvinyl alcohol spin dope through deaeration.Chitosan (molecular weight 200,000, deacetylation 80%) at room temperature is dissolved in the 2wt% dilute acetic acid aqueous solution, and obtaining concentration is the chitosan solution of 7.5wt%, gets the chitosan spinning solution through deaeration.This chitosan spinning solution extrudes the back and is delivered to static mixer by booster pump through thermosistor (95-98 ℃ of temperature control) in dissolution kettle, evenly mix with the polyvinyl alcohol spin dope of direct pump to static mixer, chitosan stoste/polyvinyl alcohol stoste mixing ratio is 1/0.75 (V/V), enter cortex inlet measuring pump through prefilter then, another road polyvinyl alcohol spin dope is through the direct pump of prefilter to the sandwich layer measuring pump that enters the mouth.Cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating speed is 1/1.32.The compound stoste thread of extruding through the core-skin type composite spinneret directly enters 45 ℃ of nearly saturated aqueous sodium sulfates (410 grams per liter) coagulating bath, solidify 2.5 times of after-drawing through coagulating bath, 1.7 times of drawing-offs in 90 ℃ of aqueous sodium persulfate solutions (370 grams per liter) then, washing, dry back 1.5 times of 210 ℃ of following xeothermic stretchings, get core-skin type chitosan and polyvinyl alcohol composite fiber, the content of chitosan is 40wt% in the cortex, chitosan content is the 14wt% of fiber total amount, the fiber number 6.2d of fiber, intensity 3.1g/d, extension at break 15%.
Embodiment 2
Other is with embodiment 1, different is directly to enter the 30wt%NaOH aqueous coagulation bath through the compound stoste thread that the core-skin type composite spinneret is extruded, solidify 3 times of after-drawing through coagulating bath, 2.2 times of drawing-offs in the sodium hydrate aqueous solution of 90 ℃ of 20wt% then, washing, dry back 1.8 times of 210 ℃ of following xeothermic stretchings, get core-skin type chitosan and polyvinyl alcohol composite fiber, the fiber number 3.9d of fiber, intensity 4.2g/d, extension at break 13%.
Embodiment 3
Polyvinyl alcohol (degree of polymerization 1750, alcoholysis degree 99%) is dissolved in the water under 95-98 ℃, obtains the poly-vinyl alcohol solution that concentration is 45wt%, get polyvinyl alcohol spin dope through deaeration.Chitosan (molecular weight 150,000, deacetylation 85%) at room temperature is dissolved in the 10wt% dilute acetic acid aqueous solution, and obtaining concentration is the chitosan solution of 10wt%, gets the chitosan spinning solution through deaeration.This chitosan spinning solution extrudes the back and is delivered to static mixer by booster pump through thermosistor (95-98 ℃ of temperature control) in dissolution kettle, evenly mix with the 45wt% polyvinyl alcohol spin dope of direct pump to static mixer, mixing ratio chitosan stoste/polyvinyl alcohol stoste is 1/0.6 (V/V), enter cortex inlet measuring pump through prefilter then, another road 45wt% is through the direct pump of prefilter to the sandwich layer measuring pump that enters the mouth.Cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating speed is 1/1.16.The compound stoste thread of extruding through the core-skin type composite spinneret enters 45 ℃ of nearly saturated aqueous sodium sulfates (410 grams per liter) coagulating bath after the jet stretch of 5cm air-gap, solidify 2 times of after-drawing through coagulating bath, 2.1 times of drawing-offs in 90 ℃ of aqueous sodium persulfate solutions (370 grams per liter) then, washing, dry back 1.6 times of 210 ℃ of following xeothermic stretchings, get core-skin type chitosan and polyvinyl alcohol composite fiber, the content of chitosan is 27wt% in the cortex, chitosan content is the 8wt% of fiber total amount, the fiber number 4.3d of fiber, intensity 3.6g/d, extension at break 17%.
Embodiment 4
Polyvinyl alcohol (degree of polymerization 1750, alcoholysis degree 99%) is dissolved in the water under 95-98 ℃, obtains the poly-vinyl alcohol solution that concentration is 38wt%, get polyvinyl alcohol spin dope through deaeration.Chitosan (molecular weight 300,000, deacetylation 75%) at room temperature is dissolved in the 2wt% dilute acetic acid aqueous solution, and obtaining concentration is the chitosan solution of 5wt%, gets the chitosan spinning solution through deaeration.This chitosan spinning solution extrudes the back and is delivered to cortex inlet measuring pump by booster pump through thermosistor (temperature control 95-98 ℃), prefilter in dissolution kettle, another road 38wt% polyvinyl alcohol spin dope is through prefilter pump to the sandwich layer measuring pump that enters the mouth.Cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating speed is 1/0.53.Through compound stoste thread 150 ℃ of following solvent evaporates curing through 6.7 meters dry method paths that the core-skin type composite spinneret is extruded, the fiber after the curing gets core-skin type chitosan and polyvinyl alcohol composite fiber 5.2 times of 180 ℃ of following xeothermic stretchings; The content of chitosan is 100wt% in the cortex, and chitosan content is the 20wt% of fiber total amount, the fiber number 3.1d of fiber, intensity 3.2g/d, extension at break 20%.
Embodiment 5
Other is with embodiment 4, different is that gained core-skin type chitosan and polyvinyl alcohol composite fiber are placed glutaraldehyde water solution (32 grams per liter), reaction was taken out after 2 hours under the room temperature, washing, dry chitosan and the polyvinyl alcohol glutaraldehyde composite fibre that contracts, the intensity 3.9g/d of fiber, extension at break 12%, hot water resistance significantly improves.
Embodiment 6
Other is with embodiment 2, different is to place the hydroformylation of being made up of formaldehyde (25 grams per liter), sulfuric acid (225 grams per liter), sodium sulphate (70 grams per liter) to bathe 70 ℃ of reactions taking-up after 30 minutes gained chitosan and polyvinyl alcohol composite fiber, washing, dry chitosan and the polyvinyl formal composite fibre of getting, the intensity 3.9g/d of fiber, extension at break 12%, hot water resistance significantly improves.
Embodiment 7
Other is with embodiment 1, different is that polyvinyl alcohol (degree of polymerization 2400, alcoholysis degree 98%) is dissolved in the spirit of vinegar of 3wt%, get polyvinyl alcohol spin dope concentration 30wt%, chitosan (molecular weight 500,000, deacetylation 70%) at room temperature is dissolved in the 1wt% dilute acetic acid aqueous solution, obtaining concentration is the chitosan solution of 2wt%, the content of chitosan is 8wt% in the cortex of product chitosan and polyvinyl alcohol composite fiber, and chitosan content is the 2wt% of fiber total amount.The fiber number 2.1d of fiber, intensity 4.2g/d, extension at break 18%.
Embodiment 8
Other is with embodiment 4, different is that polyvinyl alcohol (degree of polymerization 4000, alcoholysis degree 92%) is dissolved in the water, get polyvinyl alcohol spin dope concentration 5wt%, chitosan (molecular weight 150,000, deacetylation 90%) at room temperature is dissolved in the 1wt% dilute acetic acid aqueous solution, obtaining concentration is the chitosan solution of 10wt%, the content of chitosan is 100wt% in the cortex of product chitosan and polyvinyl alcohol composite fiber, and chitosan content is the 79wt% of fiber total amount.The fiber number 2.8d of fiber, intensity 2.6g/d, extension at break 11%.
Embodiment 9
Other is with embodiment 1, that different is polyvinyl alcohol spin dope concentration 30wt%, the concentration of chitosan solution is 2wt%, and control suitable chitosan stoste/polyvinyl alcohol stoste and mix cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating ratio when, the content that obtains chitosan in the cortex of product chitosan and polyvinyl alcohol composite fiber is 1wt%, and chitosan content is the 0.1wt% of fiber total amount.The fiber number 2.2d of fiber, intensity 4.5g/d, extension at break 20%.
Embodiment 10
Other is with embodiment 1, that different is polyvinyl alcohol spin dope concentration 30wt%, the concentration of chitosan solution is 4wt%, and control suitable chitosan stoste/polyvinyl alcohol stoste and mix cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating ratio when, the content that obtains chitosan in the cortex of product chitosan and polyvinyl alcohol composite fiber is 20wt%, and chitosan content is the 6wt% of fiber total amount.The fiber number 4.9d of fiber, intensity 4.0g/d, extension at break 15%.
Embodiment 11
Other is with embodiment 1, that different is polyvinyl alcohol spin dope concentration 20wt%, the concentration of chitosan solution is 6wt%, and control suitable chitosan stoste/polyvinyl alcohol stoste and mix cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating ratio when, the content that obtains chitosan in the cortex of product chitosan and polyvinyl alcohol composite fiber is 60wt%, and chitosan content is the 10wt% of fiber total amount.The fiber number 5.5d of fiber, intensity 3.5g/d, extension at break 18%.
Claims (15)
1. chitosan and polyvinyl alcohol composite fiber have the core-skin type composite construction, and described cortex is a chitosan, and sandwich layer is a polyvinyl alcohol.
2. chitosan and polyvinyl alcohol composite fiber have the core-skin type composite construction, and described cortex is the mixture of chitosan and polyvinyl alcohol, and sandwich layer is a polyvinyl alcohol.
3. chitosan according to claim 2 and polyvinyl alcohol composite fiber, in the wherein said cortex in the mixture of chitosan and polyvinyl alcohol chitosan content be greater than 0wt%-less than 100wt%, all the other are polyvinyl alcohol, sandwich layer is a polyvinyl alcohol.
4. chitosan according to claim 1 and 2 and polyvinyl alcohol composite fiber, in described chitosan and the polyvinyl alcohol composite fiber, the content of chitosan be the fiber total amount greater than 0wt%, less than 80wt%.
5. chitosan according to claim 2 and polyvinyl alcohol composite fiber, described cortex are the 20-60wt% chitosan, and all the other are polyvinyl alcohol, and sandwich layer is a polyvinyl alcohol.
6. chitosan according to claim 5 and polyvinyl alcohol composite fiber, wherein the content of chitosan is the 4-30wt% of fiber total amount.
7. chitosan according to claim 1 and 2 and polyvinyl alcohol composite fiber, wherein said fiber are the fibers of handling through acetalation.
8. chitosan according to claim 7 and polyvinyl alcohol composite fiber, wherein said fiber are the fibers through formaldehyde or the processing of glutaraldehyde acetalation.
9. a kind of chitosan according to claim 1 and 2 and polyvinyl alcohol composite fiber, the molecular weight of described chitosan are 15-50 ten thousand, and deacetylation is 70-90%; The degree of polymerization of polyvinyl alcohol is 1700-4000, and alcoholysis degree is 90-99%; The fiber number 2-7d of described composite fibre, fracture strength 2.5-4.5g/d, extension at break 10-20%.
10. the manufacture method of claim 1 or 2 described-kind of chitosan and polyvinyl alcohol composite fiber, with the polyvinyl alcohol spin dope is sandwich layer, co-blended spinning stoste with chitosan or chitosan and polyvinyl alcohol is cortex, extrude from the core-skin type composite spinneret pack, through spinning technique, obtain having the chitosan and the polyvinyl alcohol composite fiber of skin-core structure again through drawing-off and washing process.
11. the manufacture method of a kind of chitosan according to claim 10 and polyvinyl alcohol composite fiber, with the degree of polymerization is 1700-4000, alcoholysis degree is that the polyvinyl alcohol of 90-99% is dissolved under 95-98 ℃ in water or the dilute acetic acid aqueous solution below the 3wt%, obtain the poly-vinyl alcohol solution that concentration is 5-45wt%, get polyvinyl alcohol spin dope through deaeration; With molecular weight is 15-50 ten thousand, and deacetylation is that the chitosan of 70-90% at room temperature is dissolved in the 1-10wt% dilute acetic acid aqueous solution, and obtaining concentration is the chitosan solution of 2-10wt%, gets the chitosan spinning solution through deaeration; This chitosan spinning solution extrudes the back and is controlled to be 95-98 ℃ thermosistor by booster pump through temperature and is delivered to static mixer in dissolution kettle, evenly mix with the polyethylene spinning solution of direct pump, promptly get the co-blended spinning stoste of chitosan and polyvinyl alcohol to static mixer; Described chitosan spinning solution is extruded the back be controlled to be 95-98 ℃ thermosistor through temperature in dissolution kettle by booster pump, prefilter is delivered to cortex inlet measuring pump, or the co-blended spinning stoste of gained chitosan and polyvinyl alcohol entered cortex inlet measuring pump through prefilter, another road polyvinyl alcohol spin dope is through prefilter pump to the sandwich layer measuring pump that enters the mouth, cortex inlet measuring pump rotating speed/sandwich layer inlet measuring pump rotating speed is 1/0.50-1/1.5, doubly get core-skin type chitosan and polyvinyl alcohol composite fiber through the fiber of compound stoste thread behind spinning technique xeothermic stretching 2-5.5 under 180-210 ℃ that the core-skin type composite spinneret is extruded.
12. the manufacture method of a kind of chitosan according to claim 11 and polyvinyl alcohol composite fiber, wherein said chitosan and the polyvinyl alcohol composite fiber spinning technique after the core-skin type composite spinneret pack is extruded can adopt wet method, do wet method or dry-spinning process shaping;
Describedly wet-formedly be, the compound stoste thread of extruding from compound spinnerets directly enters coagulating bath, and coagulating agent adopts the saturated Na of polyvinyl spinning
2SO
4The aqueous solution or the NaOH aqueous solution;
It is described that to do wet-formed be that compound stoste thread enters coagulating bath behind the air-gap of one section 1-10cm;
Described duse process is that compound stoste thread makes solvent evaporates through 100-170 ℃ hot-air path and solidified.
13. according to the manufacture method of claim 10 or 11 described a kind of chitosan and polyvinyl alcohol composite fiber, wherein said chitosan and polyvinyl alcohol composite fiber further carry out acetalation to be handled.
14. handling, the manufacture method of a kind of chitosan according to claim 13 and polyvinyl alcohol composite fiber, wherein said acetalation adopt formaldehyde or glutaraldehyde.
15. the manufacture method of a kind of chitosan according to claim 14 and polyvinyl alcohol composite fiber, wherein said acetalation is treated to: place the hydroformylation that contains formaldehyde or glutaraldehyde to bathe core-skin type chitosan and polyvinyl alcohol composite fiber, room temperature-70 ℃ reaction taking-up after 0.5-2 hour down, washing, dry chitosan and the Polyvinyl acetal composite fibre of getting.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100120 CN1287017C (en) | 2002-01-04 | 2002-01-04 | Chitin amine/polyviny vinyl alcohol composite fiber and its manufacturing method |
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|---|---|---|---|
| CN 02100120 CN1287017C (en) | 2002-01-04 | 2002-01-04 | Chitin amine/polyviny vinyl alcohol composite fiber and its manufacturing method |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100430535C (en) * | 2005-12-21 | 2008-11-05 | 青岛大学 | Alginate/polyvinyl alcohol composite fiber and its preparing process |
| CN101748503B (en) * | 2008-12-18 | 2011-11-16 | 中国纺织科学研究院 | Method for preparing chitin/acrylic composite fiber by using ionic liquid as solvent |
| CN103505758B (en) * | 2013-09-17 | 2015-02-11 | 南通南京大学材料工程技术研究院 | Chitosan-nanofiber hemostatic material and preparation method thereof |
| CN106175018A (en) * | 2016-07-08 | 2016-12-07 | 华南理工大学 | A kind of degradable disponsable hair care towel and preparation method thereof |
| CN106521697A (en) * | 2016-11-17 | 2017-03-22 | 无锡明盛纺织机械有限公司 | Carboxyethyl chitosan and polyvinyl alcohol composite fiber and preparation method and application thereof |
| CN106521698A (en) * | 2016-11-17 | 2017-03-22 | 无锡明盛纺织机械有限公司 | Composite fiber for medical dressing and preparation method and application thereof |
| CN106400191A (en) * | 2016-11-17 | 2017-02-15 | 无锡明盛纺织机械有限公司 | Composite fiber adopting skin-core type structure as well as preparation method and application of composite fiber |
| CN107034548A (en) * | 2016-11-18 | 2017-08-11 | 无锡明盛纺织机械有限公司 | A kind of composite fibre and its preparation method and application |
| CN107164831A (en) * | 2017-06-28 | 2017-09-15 | 华杰 | A kind of composite fibre and its preparation method and application |
| CN112545404B (en) * | 2020-12-08 | 2022-05-17 | 湖北魔洗高新材料制品有限公司 | Improved method for preparing PVA collodion cotton head with high-efficiency production |
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2002
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