CN101748503B - Method for preparing chitin/acrylic composite fiber by using ionic liquid as solvent - Google Patents
Method for preparing chitin/acrylic composite fiber by using ionic liquid as solvent Download PDFInfo
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- CN101748503B CN101748503B CN2008102403800A CN200810240380A CN101748503B CN 101748503 B CN101748503 B CN 101748503B CN 2008102403800 A CN2008102403800 A CN 2008102403800A CN 200810240380 A CN200810240380 A CN 200810240380A CN 101748503 B CN101748503 B CN 101748503B
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- 229920002101 Chitin Polymers 0.000 title claims abstract description 158
- 239000000835 fiber Substances 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 87
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims description 29
- 239000002904 solvent Substances 0.000 title abstract description 15
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000012792 core layer Substances 0.000 claims abstract 6
- 239000010410 layer Substances 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 74
- 238000000465 moulding Methods 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 150000001450 anions Chemical class 0.000 claims description 10
- -1 Alkyl imidazolium ion Chemical compound 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 7
- 230000006196 deacetylation Effects 0.000 claims description 4
- 238000003381 deacetylation reaction Methods 0.000 claims description 4
- 238000001891 gel spinning Methods 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 238000002166 wet spinning Methods 0.000 claims description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims 1
- 230000001054 cortical effect Effects 0.000 claims 1
- 238000002788 crimping Methods 0.000 claims 1
- 238000007493 shaping process Methods 0.000 claims 1
- 238000007711 solidification Methods 0.000 claims 1
- 230000008023 solidification Effects 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 68
- 230000001112 coagulating effect Effects 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000004753 textile Substances 0.000 abstract description 3
- 230000008827 biological function Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract 1
- 238000011045 prefiltration Methods 0.000 description 16
- 229920001661 Chitosan Polymers 0.000 description 12
- 229920002239 polyacrylonitrile Polymers 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 description 9
- 229920002678 cellulose Polymers 0.000 description 8
- 239000001913 cellulose Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- ZXLOSLWIGFGPIU-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;acetate Chemical group CC(O)=O.CCN1CN(C)C=C1 ZXLOSLWIGFGPIU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- 241000238557 Decapoda Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 102000016943 Muramidase Human genes 0.000 description 2
- 108010014251 Muramidase Proteins 0.000 description 2
- 108010062010 N-Acetylmuramoyl-L-alanine Amidase Proteins 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229960000274 lysozyme Drugs 0.000 description 2
- 239000004325 lysozyme Substances 0.000 description 2
- 235000010335 lysozyme Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004060 metabolic process Effects 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- 241000238366 Cephalopoda Species 0.000 description 1
- 241000238424 Crustacea Species 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
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- 241000233866 Fungi Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
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- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000003544 deproteinization Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
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- 231100000765 toxin Toxicity 0.000 description 1
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- Multicomponent Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses chitin/acrylic composite fiber with a skin-core structure and a manufacturing method thereof. Acrylic fiber spinning solution is used as a core layer, chitin or mixed spinning solution of chitin and acrylic fiber is used as a skin layer, the solution is extruded from a skin-core composite spinneret assembly, and composite fiber is obtained through spinning and forming, drafting and water washing; and ionic liquid is used as solvent for the preparation of composite fiber spinning solution, coagulating bath is formed by water or mixture of water and ionic liquid, and the concentration of ionic liquid in the coagulating bath is 0 to 60 percent. The composite fiber has the advantages that the biological functions are good because the chitin is used in the skin layer, the physical and mechanical performance is good because the acrylic fiber with good fiber forming property and draftability is used in the core layer and the production cost is low; and the composite fiber can be widely used as textile raw material for disposable or medical use, medical fiber, antibacterial fiber and the like.
Description
Technical field
The present invention relates to a kind of preparation method of chitin/acrylic composite fiber, particularly relating to a kind of is the preparation method of the chitin/acrylic composite fiber with skin-core structure of solvent with the ionic liquid.
Background technology
Polyacrylonitrile fibre is commonly called as acrylic fibers, be a kind of synthetic fiber, the dyeability of good warmth retention property, excellence is arranged and do not have moth erosion and mould sex change, can obtain than wool gay colours more after its dyeing, polyacrylonitrile fibre is widely used in makes the simulate wool goods, therefore polyacrylonitrile fibre is called artificial wool again, but polyacrylonitrile fibre also has a lot of shortcomings: hydrophily is poor, causes at easy static electrification of dry weather and human body compatibility relatively poor.Fiber itself does not have anti-microbial property simultaneously.
Chitin is a kind of linear polysaccharide class boiomacromolecule, 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, have undersaturated cation group in the molecular structure, thereby it has powerful suction-operated to all kinds of harmful substances, the harmful bacteria that has negative electrical charge, it just can suppress the activity of harmful bacteria like this, it is lost activity, thereby reach antibiotic purpose.The structure that had both had the similar plants fiber has again to the human body ossein and organizes similar structure, with human body good compatibility is arranged, and can be decomposed by the lysozyme of human body to absorb, and the human body damaged cells is repaired and is activated, thereby good medical science characteristic is 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 big 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.Fiber production generally will be through two steps, and the first step is that shrimp and crab shells is made chitin again through the watery hydrochloric acid decalcification 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 health textile of various bacteriostatic deodorizings.
Chitin solution can be spun into fiber, be used for to absorb fields such as operation suture thread 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 fiber lacks the needed physical and mechanical properties of weaving back processing, and cost is very high, costs an arm and a leg, and popularization and application is restricted.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 physical and mechanical properties 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, preparation comprises: (1) comminuted fibres element, chitin/shitosan and ionic liquid mix, dissolving is 1-80 hour under 25-160 ℃ of temperature, and forming total solid content is the stable homogeneous spinning solution of 3-40%; (2) filter, after the deaeration, enter in the coagulating bath through single hole or porous spinnerets and to solidify, spinning speed be 5-150 rice/minute; (3) behind plasticization drawing, again through wash, bleach, oil, drying, obtain the cellulose blending fibre goods.This method process energy consumption and operating cost are low, environmental protection, and the cellulose blending fibre of preparation has excellent mechanical intensity.
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.
Application number is CN200810034673.3, name is called in the patent application of " a kind of polyacrylonitrile-chitin composite fiber and manufacture method thereof " provides a kind of polyacrylonitrile-chitin composite fiber and manufacture method thereof, this composite fibre is made up of chitin and polyacrylonitrile, chitin accounts for the 1-20% of composite fibre solid content, and acrylonitrile accounts for the 80-99% of fiber solid content; Its manufacture method comprises: (1) is dissolved in acrylonitrile in the solvent, is made into the polyacrylonitrile solution that content is 3-45%; (2) chitin is added in the polyacrylonitrile solution, addition is the 1-20% of polyacrylonitrile dry weight, is made into polyacrylonitrile, chitin spinning solution, standing and defoaming; (3) with spinning solution curing molding after the spinneret orifice ejection, make finished product in conventional operations such as stretched, washing, dryings.
In sum, though it is the preparation and the application of the cellulose blending fibre of solvent with the ionic liquid that prior art discloses, comprise chitin and cellulose in the described blended fiber, because chitin solubility in conventional solvent is less and the dissolving difficulty, and traditional dicyandiamide solution, all have volatility, these solvents jeopardize health of operators when environment is caused severe contamination.And, just because its dissolving in conventional solvent is bad, caused chitin fiber mechanical property not high defective simple in the prior art, make the spinnability and the woven performance of chitin fiber poor, need carry out blending improving its spinnability and stitchability with other fiber, so provide in the prior art that to adopt chitin and cellulose be that blended material prepares cellulose blending fibre to improve the intensity of fiber.But for intensity and the dyeability that improves composite fibre, prior art has also proposed the composite fibre of preparation chitin and polyvinyl alcohol skin-core structure, 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 make fiber obtain excellent physical and mechanical properties.
But, prior art does not also disclose a kind of composite fibre for preparing chitin and acrylic fibers skin-core structure and preparation method thereof, though disclose polyacrylonitrile-chitin composite fiber, but this composite fibre is not a skin-core structure, and because chitin and polyacrylonitrile all have polar group, and chitin can only be dissolved in the partial solvent of polyacrylonitrile, therefore this composite fibre can only improve polypropylene fibre hydrophily, antistatic behaviour and with the affine antibiotic property of human body.And do not have the advantageous property of skin-core structure composite fibre, different as composition in composition and the sandwich layer in the skin-core structure composite fibre mediopellis, thereby make itself performance of composition performance in the cortex, composition in the sandwich layer is brought into play its original effect, and its overall performance of the compound back of core-skin layer can be greatly improved.
Summary of the invention
The purpose of this invention is to provide a kind of is the method that solvent prepares the chitin/acrylic fiber with the ionic liquid, when remedying present chitin and adopting solvent spinning, spinning solution is inhomogeneous, the cost height, the defective of fibre machinery poor performance, described composite fibre has skin-core structure, has excellent physical and mechanical properties and good dyeability, have the individual style and the multiple biological health medical functions of biogenic fiber simultaneously, reduced production cost simultaneously.
To achieve these goals, the technical solution used in the present invention is:
A kind of chitin and acrylic composite fiber, described chitin and acrylic composite fiber have the core-skin type composite construction, and its fracture strength is 2.8～4.5cN/dtex, and elongation at break is 15～25%, and fiber number is 1.67～3.33dtex.
In the core-skin type composite construction of the present invention, cortex is the mixture of chitin or chitin and acrylic fibers, and sandwich layer is acrylic fibers.
In the mixture of chitin of the present invention and acrylic fibers, the content of chitin is the 20-70% of described mixture total weight amount; The content of preferred described chitin is the 20-50% of described mixture total weight amount.
Another object of the present invention is to provide a kind of method for preparing chitin and acrylic composite fiber, and described manufacture method adopts existing skin-core structure composite fibre manufacture method, and technology is simple, is fit to large-scale production.
To achieve these goals, the technical solution used in the present invention is:
A kind of method for preparing described chitin and acrylic composite fiber is characterized in that, described method comprises:
1) chitin is pulverized, obtained the superfine powder of chitin; Add ionic liquid then and make its dissolving in the superfine powder of chitin, obtaining mass percent concentration is the chitin solution of 3-25%;
2) utilize ionic liquid to dissolve acrylic fibers, obtaining mass percent concentration is the acrylic fibers solution of 3-25%;
3) the chitin solution and the step 2 that step 1) are obtained) obtain acrylic solution and mix, obtain the mixed solution of chitin and acrylic fibers, wherein the mass ratio of chitin and acrylic fibers is 1: 9～7: 3 in the mixed solution;
4) with step 2) described acrylic fibers solution is as being sandwich layer, by the sandwich layer measuring pump; With the mixed solution of the described chitin solution of step 1) or described chitin of step 3) and acrylic fibers as cortex, by the cortex measuring pump; Enter core-skin type composite spinneret pack ejection back curing molding then, stretched again, washing, curl, typing, drying steps make described composite fibre, obtains described chitin and acrylic composite fiber.
Ionic liquid of the present invention is made up of CATION and anion; Wherein said CATION is:
The alkyl imidazole 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 one or several;
Described anion is Cl
-, Br
-, CH
3COO
-In a kind of.
THE MOLECULAR WEIGHT OF CHITIN of the present invention is 15-50 ten thousand, and deacetylation is 0-95%.
Dissolving of the present invention is included under 50～150 ℃ of temperature dissolved 1～50 hour, formed concentration and be the solution of 3～25% stable homogeneous.
Cortex inlet measuring pump conveying capacity of the present invention is 1/9～8/2 with the ratio of sandwich layer inlet measuring pump conveying capacity.
Curing molding of the present invention comprises through wet spinning or dry-wet spinning moulding.
Draw ratio of the present invention is 3～20 times.
Specifically, the described method for preparing chitin and acrylic composite fiber of the present invention comprises:
1) chitin is pulverized, obtained the superfine powder of chitin; Add ionic liquid then and make its dissolving in the superfine powder of chitin, obtaining mass percent concentration is the chitin solution of 3-25%;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make the particle size range of pulverizing the resulting chitin in back at the 100-800 order.Why needing chitin is crushed to the 100-800 order, is in order to make the chitin after pulverizing can better be dissolved in the ionic liquid, for the skin-core structure composite fibre of preparation good mechanical performance is prepared.Molecular weight 15～500,000 just, deacetylation are that 0～95% chitin evenly mixes with ionic liquid, dissolve 1～50 hour under 50～150 ℃ of temperature, form the spinning solution of stable homogeneous, and the concentration of spinning solution is 3～25%.In these preferred 80～120 ℃ of dissolvings 10～30 hours, spinning solution concentration preferred 10～20%.
Described ionic liquid is made up of CATION and anion;
Described CATION is:
The alkyl imidazole 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 one or several;
Described anion is Cl
-, Br
-, CH
3COO
-In a kind of.
2) utilize ionic liquid to dissolve acrylic fibers, obtaining mass percent concentration is the acrylic fibers solution of 3-25%;
The acrylic fibers of molecular weight 5～300,000 are evenly mixed with ionic liquid dissolve, dissolved 1～50 hour under 50～150 ℃ of temperature, forming concentration is 3～25%, the spinning solution of stable homogeneous;
3) the chitin solution and the step 2 that step 1) are obtained) obtain acrylic solution and mix, obtain the mixed solution of chitin and acrylic fibers, wherein the mass ratio of chitin and acrylic fibers is 1: 9～7: 3 in the mixed solution;
When above-mentioned two kinds of solution are mixed, can stir in the time of necessary, the speed of stirring is 10～100rpm, and mixing time is 10-30 minute, the mixed solution that obtains like this can fully mix, and gets ready for preparing high performance skin-core structure composite fibre.
4) with step 2) described acrylic fibers solution is as being sandwich layer, by the sandwich layer measuring pump; With the mixed solution of the described chitin solution of step 1) or described chitin of step 3) and acrylic fibers as cortex, by the cortex measuring pump; Enter core-skin type composite spinneret pack ejection back curing molding then, make described composite fibre through 3～20 times of stretching, washing, curling, typing, drying steps again, obtain described chitin and acrylic composite fiber.
Chitin solution is delivered to cortex inlet measuring pump through prefilter, or gained chitin and acrylic spinning stoste evenly mixed the co-blended spinning stoste that obtains and enter cortex inlet measuring pump through prefilter, acrylic fibers solution enters the sandwich layer measuring pump through prefilter.Cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 1/9～8/2.After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.As optimized technical scheme, in the described cortex, the content of chitin is 25～65wt%; In the described chitin/acrylic composite fiber, the content of chitin is 2.5～52wt% of fiber total amount.
Curing molding method of the present invention comprises wet spinning or dry-wet spinning.
Described wet spinning comprises: enter through the composite spinning stoste that skin-core composite spinneret is extruded and contain curing molding in 0～60% the ion liquid coagulating bath, drawn, washing again, curl, make chitin/acrylic composite fiber after the typing, drying.
Described dry-wet spinning comprises: the composite spinning stoste of extruding through skin-core composite spinneret, after the air gap layer cooling curing stretching through 1～25cm, enter again to contain in 0～60% the ion liquid coagulating bath and further improve fibre structure, then through after the road stretch, washing, curl, make chitin/acrylic composite fiber after the drying.
Chitin of the present invention and acrylic composite fiber are owing to the chitin composition in the cortex has good biological function and dyeability; Has lower production cost owing to chitin content content in total fiber is lower; Owing to the good fibre forming property of acrylic fibers in the sandwich layer makes fiber have good physical and mechanical properties.Described composite fibre can be used as the textile raw material of medical application.
In addition, chitin of the present invention and acrylic composite fiber, has skin-core structure, its cortex is chitin or chitin and the mixing of acrylic fibers, because chitin is the found up to now unique positively charged natural polymer of occurring in nature, have undersaturated cation group in the molecular structure, thereby it has powerful suction-operated to all kinds of harmful substances, the harmful bacteria that has negative electrical charge, it just can suppress the activity of harmful bacteria like this, it is lost activity, thereby reach antibiotic purpose.And described chitin and acrylic composite fiber have good dyeability and mechanical strength, is a kind of skin-core structure fiber of high-quality.
Beneficial effect of the present invention is:
1) ionic liquid of Cai Yonging all has good solubility property to chitin and acrylic fibers, and ionic liquid is nontoxic, non-volatile simultaneously, can avoid environment is polluted and operating personnel's health is damaged.
2) ionic liquid can effectively reclaim, and reduces production costs, and economizes on resources.
3) skin-core structure makes described composite fibre have good biological property and physical and mechanical properties simultaneously, reduces cost.
Description of drawings
Fig. 1 is the process chart that solvent prepares chitin/acrylic composite fiber with the ionic liquid for the present invention.
The specific embodiment
The present invention is further elaborated in conjunction with specific embodiments.
Embodiment 1
Chitin is evenly mixed with ionic liquid, and dissolving is 50 hours under 50 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 9%.Acrylic fibers are evenly mixed with ionic liquid, and dissolving is 50 hours under 50 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 15%.The chitin spinning solution is delivered to cortex inlet measuring pump through prefilter, and acrylic spinning stoste enters the sandwich layer measuring pump through prefilter.Cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 3/7;
After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.Coagulating bath is [PMIN] Cl-(Chinese is chlorination 1-propyl group-3-methylimidazole salt) aqueous solution, and coagulating bath intermediate ion strength of fluid is 10%, and temperature is 25 ℃.Chitin content is the 20wt% of fiber total content, and fibre number is that 3.33dtex, intensity are 3.8cN/dtex.
Embodiment 2
Chitin is evenly mixed with ionic liquid, and dissolving is 1 hour under 150 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 7%.Acrylic fibers are evenly mixed with ionic liquid, and dissolving is 1 hour under 150 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 15%.The chitin spinning solution is delivered to cortex inlet measuring pump through prefilter, and acrylic spinning stoste enters the sandwich layer measuring pump through prefilter.Cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 3/7;
After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.Coagulating bath is [EMIN] Ac-(Chinese is acetic acid 1-ethyl-3-methylimidazole salt) aqueous solution, and coagulating bath intermediate ion strength of fluid is 10%, and temperature is 20 ℃.Chitin content is the 17.5wt% of fiber total content, and fibre number is that 1.67dtex, intensity are 4.5cN/dtex.
Embodiment 3
Chitin is evenly mixed with ionic liquid, and dissolving is 5 hours under 100 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 15%.Acrylic fibers are evenly mixed with ionic liquid, and dissolving is 3 hours under 100 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 15%.The chitin spinning solution is delivered to cortex inlet measuring pump through prefilter, and acrylic spinning stoste enters the sandwich layer measuring pump through prefilter.Cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 5/5;
After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.Coagulating bath is [PMIN] Cl-(Chinese is chlorination 1-propyl group-3-methylimidazole salt) aqueous solution, and coagulating bath intermediate ion strength of fluid is 5%, and temperature is 25 ℃.Chitin content is the 50wt% of fiber total content, and fibre number is that 3.33dtex, intensity are 2.8cN/dtex.
Embodiment 4
Chitin is evenly mixed with ionic liquid, and dissolving is 6.5 hours under 80 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 20%.Acrylic fibers are evenly mixed with ionic liquid, and dissolving is 3 hours under 80 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 15%.The chitin spinning solution is delivered to cortex inlet measuring pump through prefilter, and acrylic spinning stoste enters the sandwich layer measuring pump through prefilter.Cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 2/8;
After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.Coagulating bath is [EMIN] Ac-(Chinese is acetic acid 1-ethyl-3-methylimidazole salt) aqueous solution, and coagulating bath intermediate ion strength of fluid is 10%, and temperature is 25 ℃.Chitin content is the 25wt% of fiber total content, and fibre number is that 2.5dtex, intensity are 3.2cN/dtex.
Embodiment 5
Chitin is evenly mixed with ionic liquid, and dissolving is 6.5 hours under 80 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 10%.Acrylic fibers are evenly mixed with ionic liquid, and dissolving is 3 hours under 80 ℃ of temperature, and through the spinning solution of deaeration formation stable homogeneous, the concentration of spinning solution is 20%.The chitin spinning solution is extruded the back be delivered to static mixer in dissolution kettle by booster pump, evenly mix with direct pump to the acrylic spinning stoste of static mixer, chitin/acrylic stoste conveying capacity ratio is 5/5, enter cortex inlet measuring pump through prefilter, acrylic spinning stoste enters the sandwich layer measuring pump through prefilter.The ratio of cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 4/6;
After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.Coagulating bath is [EMIN] Ac-(Chinese is acetic acid 1-ethyl-3-methylimidazole salt) aqueous solution, and coagulating bath intermediate ion strength of fluid is 10%, and temperature is 25 ℃.Chitin content is the 15wt% of fiber total content, and fibre number is that 3.33dtex, intensity are 3.5cN/dtex.
Embodiment 6
(1) chitin is pulverized, obtained the superfine powder of chitin; In the superfine powder of chitin, add ionic liquid then and make its dissolving, obtain mass percent concentration and be 3% chitin solution;
At first chitin is pulverized, adopted the special-purpose pulverizer of chitin during pulverizing, make the particle size range of pulverizing the resulting chitin in back at 100 orders.Why needing chitin is crushed to 100 orders, is in order to make the chitin after pulverizing can better be dissolved in the ionic liquid, for the skin-core structure composite fibre of preparation good mechanical performance is prepared.With molecular weight 150,000, deacetylation is that 0～5 chitin evenly mixes with ionic liquid, and dissolving is 10 hours under 50 ℃ of temperature, forms the spinning solution of stable homogeneous, and the concentration of spinning solution is 3%.
Described ionic liquid is made up of CATION and anion;
Described CATION is:
The alkyl imidazole ion
Wherein: R
1, R
2, R
3, R
4And R
5Identical, be vinyl;
Described anion is CH
3COO
-
(2) utilize ionic liquid to dissolve acrylic fibers, obtain mass percent concentration and be 3% acrylic fibers solution;
The acrylic fibers of molecular weight 50,000 are evenly mixed with ionic liquid dissolve, dissolving is 1 hour under 50 ℃ of temperature, forms concentration and be 3%, the spinning solution of stable homogeneous;
(3) the chitin solution and the step 2 that step 1) are obtained) obtain acrylic solution and mix, obtain the mixed solution of chitin and acrylic fibers, wherein the conveying capacity ratio of chitin and acrylic fibers is 1: 9 in the mixed solution;
When above-mentioned two kinds of solution are mixed, can stir in the time of necessary, the speed of stirring is 10rpm, and mixing time is 10 minutes, and the mixed solution that obtains like this can fully mix, and gets ready for preparing high performance skin-core structure composite fibre.
4) with step 2) described acrylic fibers solution is as being sandwich layer, by the sandwich layer measuring pump; With the described chitin solution of step 1) as cortex, by the cortex measuring pump; Enter core-skin type composite spinneret pack ejection back curing molding then, make described composite fibre through 10 times of stretching, washing, curling, typing, drying steps again, obtain described chitin and acrylic composite fiber.
Chitin solution is delivered to cortex inlet measuring pump through prefilter, or gained chitin and acrylic spinning stoste evenly mixed the co-blended spinning stoste that obtains and enter cortex inlet measuring pump through prefilter, acrylic fibers solution enters the sandwich layer measuring pump through prefilter.Cortex inlet measuring pump conveying capacity/sandwich layer inlet measuring pump conveying capacity is 1/9.After stretching, spinning moulding obtains the core-skin type chitin/acrylic composite fiber through the compound stoste that the core-skin composite spinneret is extruded.
The fracture strength of the fiber that obtains is 2.8cN/dtex, and elongation at break is 12%, and fiber number is 1.67dtex.
Below be embodiments of the invention 7-11:
The ionic liquid of embodiment 7-11 is made up of CATION and anion, wherein cationic structure as shown in the formula, substituting group and anion structure are as shown in table 1, concrete operations are with embodiment 6, related parameter of per step is as shown in table 1:
The alkyl imidazole ion
Table 1
Claims (10)
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