CN102704038B - Cyanoethyl chitosan fiber and preparation method thereof - Google Patents
Cyanoethyl chitosan fiber and preparation method thereof Download PDFInfo
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- CN102704038B CN102704038B CN201210208335.3A CN201210208335A CN102704038B CN 102704038 B CN102704038 B CN 102704038B CN 201210208335 A CN201210208335 A CN 201210208335A CN 102704038 B CN102704038 B CN 102704038B
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- 238000003756 stirring Methods 0.000 description 10
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 235000003704 aspartic acid Nutrition 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- 229910052739 hydrogen Inorganic materials 0.000 description 4
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- 239000004753 textile Substances 0.000 description 3
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
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- JECYNCQXXKQDJN-UHFFFAOYSA-N 2-(2-methylhexan-2-yloxymethyl)oxirane Chemical compound CCCCC(C)(C)OCC1CO1 JECYNCQXXKQDJN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 238000001467 acupuncture Methods 0.000 description 1
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- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
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- 238000005213 imbibition Methods 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
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- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to a preparation method of cyanoethyl chitosan fiber. According to the method, an aspartate hydrochloride ionic liquid water solution is used as a solvent, cyanoethyl chitosan prepared by the reaction of chitosan and acrylonitrile at the normal temperature is dissolved in the solvent, and the cyanoethyl chitosan fiber is prepared in a wet spinning process; the spinning solution has the composition that the [Asp] Cl ionic liquid water solution with the mass fraction of 1-10% is used as the solvent, and the cyanoethyl chitosan prepared by the 0.5-24h of reaction of the acrylonitrile and the alkali chitosan is used as a solute; and the solvent and the solute are fully stirred for dissolving at the temperature of 10-60 DEG C until the solution is clear and transparent. After stewing deaeration, the prepared blended spinning solution is made into fiber in a wet method, and is naturally dried in air to be the fiber after being extended and washed. The fracture strength of the fiber is 2.4cN/dtex, and the thermal decomposition temperature is more than 225 DEG C.
Description
Technical field
The present invention relates to a kind of cyanoethyl chitin fiber and preparation method thereof, belong to modified chitosan fiber preparing technical field.
Background technology
Shitosan, with its natural caking property, degradability, spinnability, is widely used on medical textile, life textiles and function textile, and the huge cellulose that is only second to of its annual production is second largest natural polymer.But chitin fiber is not put on market in a large number, because its preparation technology is perfect not enough, the mechanical strength of the finished fiber of preparation is not high.So shitosan is carried out to modification, select the good solvent of shitosan, to improve the intensity of chitin fiber, be current problem demanding prompt solution.As the patent 200810059135.X such as Hu Qiaoling are scattered in the shitosan powder of deacetylation 40%～70%, molecular weight 200,000～600,000 in the basic solvent (sodium oxide molybdena 0.2～2%, potassium hydroxide 0.1～5%, all the other be water) that dissolves shitosan, standing its abundant swelling for the treatment of, the suspension of abundant swelling is repeatedly freezing at-20 ℃～0 ℃, thaw for several times, obtain transparent chitosan solution.This dissolution with solvents shitosan can obtain stable solution, thereby has avoided the degradation problem of shitosan in acid, the hydraulic performance decline of having avoided shitosan goods to cause because of degraded.The patent CN201110099174.4 such as Hu Qiaoling, with alkaline hydrogen lithia, NaOH, urea, glycerol mixed solution is solvent, dissolve shitosan and prepare chitin fiber, it is characterized in that, it is spinning solution that the basic solvent of take dissolves shitosan, shitosan macromolecular chain is existed with height solvent swelling state, shitosan macromolecular chain is arranged tightr, overcome shitosan utmost point unsure state in acid solution, guarantee that shitosan macromolecular chain is not hydrolyzed and glycosidic bond does not rupture, more be conducive to macromolecular chain orientations, the mechanical property of chitin fiber is improved.Chitin fiber is carried out to modification and also can prepare the chitin fiber with specific function, as generating alkali chitin fiber through alkalization, the patents such as Li Yibin 200510088100.5 glycan fibers carry out etherification reaction with monoxone again, make cm-chitosan fiber, then make 30～200g/m through shredding, one-tenth net, acupuncture
2dressing, through cutting, pack, sterilizing.This invention is applicable to surgery wound, burn, scald and other chronic wounds etc., flap coverage can prevent the moisture loss in body fluid, for wound healing provides positive moist environment, and keep not hydrops of the surface of a wound, without etch, isolated bacterium infects, and can play anti-inflammatory, hemostasis, analgesia, promotes the effect of organization healing.The patent CN200810041340.3 such as Liu Yongle have reported a kind of preparation method of hydroxyethyl group chitosan fiber, its method is prepared alkali shitosan for first chitin fiber being immersed in aqueous slkali, then in system, splash into the aqueous isopropanol of oxirane, etherification reaction a period of time, obtain hydroxyethyl group chitosan fiber, this preparation method introduces hydrophilic ethoxy on shitosan macromolecular chain, obtain having the hydroxyethyl group chitosan fiber of imbibition liquid-keeping property, this fiber overflows in many sepages such as empyrosis in the treatment of wound and has potential using value, preparation method is simple, substitution value is easy to control.Above two patents are all chitosan derivative fibres, and its common ground is that preparation method carries out derivative reaction to chitin fiber, and preparation process is simple, but and unstable.This research method is that the chitosan derivatives making directly dissolves and prepares chitosan derivative fibres, and performance is more stable.The ionic liquid of take is prepared chitin fiber as solvent also report, the patent CN200910138811.7 such as Yu Shitao are usingd ionic liquid aqueous solution as solvent, dissolve at normal temperatures and pressures shitosan, prepare shitosan spinning solution, through supersolidification, stretching, washing, dry, finally obtain chitin fiber.The feature of the method for overcome prepare at present in chitin fiber process solvent volatile, be difficult for reclaiming, the shortcoming such as seriously polluted and three wastes treating capacity is larger.
Summary of the invention
The object of this invention is to provide a kind of cyanoethyl chitin fiber and preparation method thereof.This preparation method adopts wet spinning technology, and aspartic acid hydrochloride ionic liquid ([Asp] Cl) aqueous solution of take is solvent, prepares cyanoethyl chitin fiber, has the advantages that to improve chitin fiber intensity.
The technical scheme that the present invention deals with problems is: a kind of preparation method of cyanoethyl chitin fiber, comprises following processing step:
1. the preparation of cyanoethyl shitosan: shitosan in mass ratio: 5 ~ 20% sodium hydroxide solution 1:5 feed intake, shitosan is uniformly dispersed, in air, place, after swelling 5h, at-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, shitosan in mass ratio: acrylonitrile 1:1 ~ 1:5 adds acrylonitrile, at room temperature reacts 0.5 ~ 24h, and product is washed till neutrality with ethanol, filter, dry.
2. the preparation of spinning solution: it is [Asp] Cl ionic liquid aqueous solution of 1 ~ 10% that [Asp] Cl ion liquid dissolving is mixed with to mass fraction in deionized water, the cyanoethyl shitosan that 1. step is prepared progressively adds in [Asp] Cl ionic liquid aqueous solution, at 60 ℃, be stirred to completely and dissolve, be mixed with spinning solution, wherein the quality of cyanoethyl shitosan is 5% of ionic liquid aqueous solution quality;
3. the preparation of cyanoethyl chitin fiber: spinning solution is injected to wet-spinning frame syringe, spinning fibre at 10 ~ 60 ℃ of temperature, in coagulating bath, stretched, fully washing, in air, air dry becomes fiber.
Preparation method's step of the present invention 3. described in coagulating bath be preferably 5% sodium hydrate aqueous solution of volume ratio 1:1 and the mixed solution of absolute ethyl alcohol.
It is [Asp] Cl ionic liquid solution of 3% that preparation method's step of the present invention is preferably mixed with [Asp] Cl ion liquid dissolving mass fraction in 2. in deionized water.
Preparation method's step of the present invention 1. in, preferably alkaline chitosan is at room temperature reacted 0.5h, 1h, 3h, 5h or 24h with acrylonitrile after thawing.
Preparation method's step of the present invention 1. in, preferred shitosan in mass ratio: 14% sodium hydroxide solution 1:5 feeds intake.
Preparation method's step of the present invention 1. in, preferred shitosan in mass ratio: acrylonitrile 3:8.06 adds acrylonitrile, at room temperature reacts 0.5 ~ 24h, and product is washed till neutrality with ethanol, filters, and dries.
[Asp] of the present invention Cl ionic liquid be prepared as prior art, person skilled in the art can be prepared as required, the present invention is preparation as follows preferably:
The 1. preparation method of described [Asp] Cl ionic liquid of step in the present invention: aspartic acid powder and deionized water are added in the there-necked flask that condensing unit is housed, magnetic agitation slowly adds 36% hydrochloric acid after 10 minutes, the mol ratio of its hydrogen chloride and aspartic acid is 1 ~ 3; After adding, be warming up to 60 ℃, stop reaction after isothermal reaction 8h, decompression distillation, except anhydrating, obtains white solid product, and ethyl acetate washing 2 times for product is dry at 60 ℃ after suction filtration, finally obtains white solid and is [Asp] Cl ionic liquid.
Another object of the present invention is to provide the cyanoethyl chitin fiber of being prepared by said method.
The fracture strength of cyanoethyl chitin fiber of the present invention is 1.2 ~ 2.4cN/dtex, heat decomposition temperature >=225 ℃.
Spinning solution of the present invention relates to aspartic acid hydrochloride ionic liquid, cyanoethyl shitosan.The derivative that wherein cyanoethyl shitosan is shitosan, in chitosan molecule and a large amount of hydrogen bonds of intermolecular existence, acrylonitrile and chitosan reaction, cyano group is introduced to shitosan and can open hydrogen bond in chitosan molecule, improve shitosan dissolubility, in addition, cyano group also belongs to rigid radical, and fibre strength increases.And, in aspartic acid molecular structure, containing two carboxyls, carboxyl is easy to form hydrogen bond with chitosan molecule, so aspartic acid ionic liquid is more conducive to the dissolving of shitosan, its solubility for shitosan is poor unlike acetic acid.
The inventive method technique is simple, raw material are easy to get, and ionic liquid is safety and environmental protection solvent, can not cause the pollution of environment at all.Meet the requirement of low-carbon environment-friendly.
Compared with prior art, preparation method involved in the present invention, has following outstanding advantage.The one, improved spinnability and fibrous mechanical property simultaneously.Common existing method of modifying, the viscosity of reduction shitosan spinning solution, fibre strength can reduce conventionally.The 2nd, use ionic liquid aqueous solution as solvent, the solvability of shitosan to be reduced unlike common solvent acetic acid, but avoided the corrosion of diluted acid solvent to spinning equipment.The 3rd, the fiber safety non-toxic that spinning forms, meets the requirement of medical material.
Accompanying drawing explanation
Accompanying drawing 1 width of the present invention
Fig. 1 is the surperficial POM photo of cyanoethyl chitin fiber.
The specific embodiment
The following examples can make the present invention of those of ordinary skill in the art's comprehend, but do not limit the present invention in any way.
Raw material: aspartic acid powder, analyze pure, Tianjin Bo Di Chemical Co., Ltd.; Concentrated hydrochloric acid, analyze pure, Tianjin Kermel Chemical Reagent Co., Ltd.; Ethyl acetate, analyze pure, Tianjin Kermel Chemical Reagent Co., Ltd..Shitosan: Jinhu County, Huantai County crust Products Co., Ltd; Acrylonitrile, analyze pure, Tianjin good fortune chemical reagent factory in morning;
[Asp] used in following embodiment Cl ionic liquid is prepared as follows:
13.6g aspartic acid powder and 30ml deionized water are added in the there-necked flask that condensing unit is housed, magnetic agitation slowly adds 36% hydrochloric acid of 14.2ml after 10 minutes, its hydrogen chloride and aspartic acid mol ratio are 1.7, after adding, be warming up to 60 ℃, stop reaction after isothermal reaction 8h, decompression distillation is except anhydrating, obtain white solid product, ethyl acetate washing 2 times for product, dry at 60 ℃ after suction filtration, finally obtain white solid and be [Asp] Cl ionic liquid.
Embodiment 1
1. the preparation of cyanoethyl shitosan: 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, after swelling 5h ,-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, with 8.06g acrylonitrile stirring reaction 30min at room temperature, product is washed till neutrality with ethanol, filters, and dries.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with 40g mass fraction in 38.8g deionized water be 3% ionic liquid aqueous solution, 2g cyanoethyl shitosan is added in ionic liquid solution to abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare cyanoethyl chitin fiber: spinning solution is injected to the syringe of wet-spinning frame, at 30 ℃ of spinning fibres.Take the 5%(wt of volume ratio 1:1) mixed solution of sodium hydrate aqueous solution and absolute ethyl alcohol is coagulating bath, stretched, washing 10min, in air, air dry becomes fiber.Products obtained therefrom performance parameter is in Table 1.
Embodiment 2
1. the preparation of cyanoethyl shitosan: 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, after swelling 5h, at-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, with 8.06g acrylonitrile stirring reaction 1h at room temperature, product is washed till neutrality with ethanol, filters, and dries.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with 40g mass fraction in 38.8g deionized water be 3% ionic liquid aqueous solution, 2g cyanoethyl shitosan is added in ionic liquid solution to abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare cyanoethyl chitin fiber: as embodiment 1.Products obtained therefrom performance parameter is in Table 1.
Embodiment 3
1. the preparation of cyanoethyl shitosan: 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, after swelling 5h, at-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, with 8.06g acrylonitrile stirring reaction 3h at room temperature, product is washed till neutrality with ethanol, filters, and dries.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with 40g mass fraction in 38.8g deionized water be 3% ionic liquid aqueous solution, 2g cyanoethyl shitosan is added in ionic liquid solution to abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare cyanoethyl chitin fiber: as embodiment 1.Products obtained therefrom performance parameter is in Table 1.
Embodiment 4
1. the preparation of cyanoethyl shitosan: 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, after swelling 5h, at-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, with 8.06g acrylonitrile stirring reaction 5h at room temperature, product is washed till neutrality with ethanol, filters, and dries.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with 40g mass fraction in 38.8g deionized water be 3% ionic liquid aqueous solution, 2g cyanoethyl shitosan is added in ionic liquid solution to abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare cyanoethyl chitin fiber: as embodiment 1.Products obtained therefrom performance parameter is in Table 1.
Embodiment 5
1. the preparation of cyanoethyl shitosan: 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, after swelling 5h, at-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, with 8.06g acrylonitrile stirring reaction 24h at room temperature, product is washed till neutrality with ethanol, filters, and dries.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with 40g mass fraction in 38.8g deionized water be 3% ionic liquid aqueous solution, 2g cyanoethyl shitosan is added in ionic liquid solution to abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare cyanoethyl chitin fiber: as embodiment 1.Products obtained therefrom performance parameter is in Table 1.
The partial properties parameter of table 1 embodiment 1 ~ 5 product
Claims (3)
1. a preparation method for cyanoethyl chitin fiber, comprises following processing step:
1. the preparation of cyanoethyl shitosan: shitosan in mass ratio: 5～20% sodium hydroxide solution 1:5 feed intake, shitosan is uniformly dispersed, in air, place, after swelling 5h, at-15 ℃ of freezing 12h, make alkaline chitosan, after thawing, shitosan in mass ratio: acrylonitrile 1:1～1:5 adds acrylonitrile, at room temperature reacts 3～24h, and product is washed till neutrality with ethanol, filter, dry;
2. the preparation of spinning solution: it is 3% aspartic acid hydrochloride ionic liquid aqueous solution that aspartic acid hydrochloride ion liquid dissolving is mixed with to mass fraction in deionized water, the cyanoethyl shitosan that 1. step is prepared progressively adds in aspartic acid hydrochloride ionic liquid aqueous solution, at 60 ℃, be stirred to completely and dissolve, be mixed with spinning solution, wherein the quality of cyanoethyl shitosan is 5% of ionic liquid aqueous solution quality;
3. the preparation of cyanoethyl chitin fiber: spinning solution is injected to wet-spinning frame syringe, spinning fibre at 10～60 ℃ of temperature, in coagulating bath, stretched, washing, in air, air dry becomes fiber.
2. the preparation method of cyanoethyl chitin fiber according to claim 1, is characterized in that: described coagulating bath is to be the volume ratio 5wt% sodium hydroxide solution that is 1:1 and the mixed solution of absolute ethyl alcohol.
3. a cyanoethyl chitin fiber, is characterized in that: described cyanoethyl chitin fiber is made by method described in claim 1 or 2.
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| CN103572596A (en) * | 2013-10-24 | 2014-02-12 | 浙江理工大学 | Method for reinforcing fragile cotton fabrics with cyanoethyl chitosan |
| CN104313717B (en) * | 2014-11-06 | 2018-01-12 | 西安元创化工科技股份有限公司 | A kind of production method with high-strength polypropylene nitrile fiber |
| CN113845678B (en) * | 2021-11-30 | 2023-06-09 | 安徽理工大学 | Preparation method of high-transparency flame-retardant polyvinyl alcohol film |
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| CN101089249A (en) * | 2007-07-06 | 2007-12-19 | 东华大学 | Preparation and application of cellulose mixed fibre using ion liquid as solvent |
| CN101748499B (en) * | 2008-12-05 | 2011-10-05 | 中国纺织科学研究院 | Chitin fiber and preparation method thereof |
| CN101550610A (en) * | 2009-04-29 | 2009-10-07 | 青岛科技大学 | Preparation method of chitosan fiber |
| CN102168323A (en) * | 2011-02-24 | 2011-08-31 | 天津工业大学 | Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent |
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2012
- 2012-06-21 CN CN201210208335.3A patent/CN102704038B/en not_active Expired - Fee Related
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