CN102704038A - Cyanoethyl chitosan fiber and preparation method thereof - Google Patents
Cyanoethyl chitosan fiber and preparation method thereof Download PDFInfo
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- CN102704038A CN102704038A CN2012102083353A CN201210208335A CN102704038A CN 102704038 A CN102704038 A CN 102704038A CN 2012102083353 A CN2012102083353 A CN 2012102083353A CN 201210208335 A CN201210208335 A CN 201210208335A CN 102704038 A CN102704038 A CN 102704038A
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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 the modified chitosan fiber preparing technical field.
Background technology
Shitosan is widely used on medical textile, life textiles and function textile with its natural caking property, degradability, spinnability, 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, and because of its preparation technology is perfect not enough, the mechanical strength of the finished fiber of preparation is not high.So shitosan is carried out modification, select the good solvent of shitosan, be present problem demanding prompt solution with the intensity that improves chitin fiber.The shitosan powder of deacetylation 40%～70%, molecular weight 200,000～600,000 is scattered in the basic solvent (sodium oxide molybdena 0.2～2%, potassium hydroxide 0.1～5%, all the other be water) of dissolving shitosan like patent 200810059135.X such as Hu Qiaoling; Leave standstill and treat its abundant swelling; The suspension of abundant swelling is freezing repeatedly 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 decreased performance of having avoided the shitosan goods to cause because of degraded.Patent CN201110099174.4 such as Hu Qiaoling are solvent with alkaline hydrogen lithia, NaOH, urea, glycerine mixed solution, dissolving Preparation of Chitosan chitin fiber; It is characterized in that; With basic solvent dissolving shitosan is spinning solution, makes the shitosan macromolecular chain exist with the height solvent swelling state, and the shitosan macromolecular chain is arranged tightr; Overcome shitosan utmost point unsure state in acid solution; Guarantee that shitosan not hydrolysis of macromolecular chain and glycosidic bond do not rupture, more help the macromolecular chain orientations, make the mechanical property of chitin fiber be improved.Chitin fiber is carried out modification also can prepare chitin fiber with specific function; Generate the alkali chitin fiber like patents such as Li Yibin 200510088100.5 glycan fibers through alkalization and carry out etherification reaction with monoxone again; Process the CMC fiber, process 30～200g/m through shredding, one-tenth net, acupuncture again
2Dressing, get final product 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 the body fluid, for wound healing provides positive moist environment, and keeps not hydrops of the surface of a wound; No etch; Isolated bacterial infection can play anti-inflammatory, hemostasis, analgesia, promotes the effect of organization healing.Patent CN200810041340.3 such as Liu Yongle have reported a kind of preparation method of hydroxyethyl group chitosan fiber; Its method splashes into the aqueous isopropanol of oxirane, etherification reaction a period of time then for earlier chitin fiber being immersed preparation alkali shitosan in the aqueous slkali in system; Obtain hydroxyethyl group chitosan fiber; This preparation method introduces hydrophilic ethoxy on the shitosan macromolecular chain, promptly obtain having the hydroxyethyl group chitosan fiber of imbibition liquid-keeping property, and this fiber overflows in many sepages such as empyrosis in the treatment of wound and has potential using value; The preparation method is simple, and substitution value is easy to control.More than two patents all be the chitosan derivative fibres, its common ground is that the preparation method carries out derivative reaction to chitin fiber, the preparation process is simple, but and unstable.This research method is that the chitosan derivatives that makes directly dissolves preparation chitosan derivative fibres, and performance is more stable.Be that solvent prepares chitin fiber report is also arranged with the ionic liquid; Patent CN200910138811.7 such as Yu Shitao with ionic liquid aqueous solution as solvent; Dissolve shitosan at normal temperatures and pressures; Preparation shitosan spinning solution through supersolidification, stretching, washing, drying, obtains chitin fiber at last.The characteristics of this method for overcome in the present preparation chitin fiber process solvent volatile, be difficult for reclaiming, shortcoming such as seriously polluted and three wastes treating capacity is bigger.
Summary of the invention
The purpose of this invention is to provide a kind of cyanoethyl chitin fiber and preparation method thereof.This preparation method adopts wet spinning technology, is solvent with aspartic acid hydrochloride ionic liquid ([Asp] Cl) aqueous solution, and preparation 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: by quality than shitosan: 5 ~ 20% sodium hydroxide solution 1:5 feed intake, and shitosan is uniformly dispersed, and in air, place; At-15 ℃ of freezing 12h, make alkaline chitosan behind the swelling 5h, after thawing; By quality than shitosan: acrylonitrile 1:1 ~ 1:5 adds acrylonitrile, at room temperature reacts 0.5 ~ 24h, and product is washed till neutrality with ethanol; Filter oven dry.
2. the preparation of spinning solution: [Asp] Cl ion liquid dissolving is mixed with mass fraction in deionized water be [Asp] Cl ionic liquid aqueous solution of 1 ~ 10%; The cyanoethyl shitosan that 1. step is prepared progressively adds in [Asp] Cl ionic liquid aqueous solution; Under 60 ℃, be stirred to dissolving fully; Be mixed with spinning solution, wherein the quality of cyanoethyl shitosan is 5% of an ionic liquid aqueous solution quality;
3. the preparation of cyanoethyl chitin fiber: spinning solution is injected the wet-spinning frame syringe, stretched in coagulating bath at 10 ~ 60 ℃ of following spinning fibres of temperature, fully washing, air dry becomes fiber in air.
Preparation method's step according to the 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.
Preparation method's step according to the invention preferably is mixed with mass fraction with [Asp] Cl ion liquid dissolving in 2. in deionized water be [Asp] Cl ionic liquid solution of 3%.
Preparation method's step according to the invention 1. in, 0.5h, 1h, 3h, 5h or 24h are at room temperature reacted with acrylonitrile in the preferred alkaline chitosan back that thaws.
Preparation method's step according to the invention 1. in, preferably by quality than shitosan: 14% sodium hydroxide solution 1:5 feeds intake.
Preparation method's step according to the invention 1. in, preferably by quality than shitosan: acrylonitrile 3:8.06 adds acrylonitrile, at room temperature reacts 0.5 ~ 24h, and product is washed till neutrality with ethanol, filters, and dries.
The ion liquid prior art that is prepared as of [Asp] according to the invention Cl, the person skilled in the art can prepare as required, and the present invention is preparation as follows preferably:
Step 1. said [Asp] Cl preparation method of ionic liquid among the present invention: aspartic acid powder and deionized water adding are equipped with in the there-necked flask of condensing unit; Magnetic agitation slowly adds 36% hydrochloric acid after 10 minutes, the mol ratio of its hydrogen chloride and aspartic acid is 1 ~ 3; Be warming up to 60 ℃ after adding, stop reaction behind the isothermal reaction 8h, decompression distillation removes and anhydrates, and obtains the solid product of white, and product is with ethyl acetate washing 2 times, and is dry under 60 ℃ behind the suction filtration, obtains white solid at last and is [Asp] Cl ionic liquid.
Another object of the present invention provides the cyanoethyl chitin fiber by method for preparing.
The fracture strength of cyanoethyl chitin fiber according to the 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.Wherein the cyanoethyl shitosan is the derivative of shitosan; With a large amount of hydrogen bonds of intermolecular existence, acrylonitrile and chitosan reaction are introduced shitosan with cyanic acid and can be opened hydrogen bond in the chitosan molecule in the chitosan molecule; Improve the shitosan dissolubility; In addition, cyanic acid also belongs to rigid radical, and fibre strength increases.And, containing two carboxyls in the aspartic acid molecular structure, carboxyl is easy to form hydrogen bond with chitosan molecule, so the aspartic acid ionic liquid is more conducive to the dissolving of shitosan, its solubility for shitosan is poor unlike acetate.
The inventive method technology is simple, raw material are easy to get, and ionic liquid is the 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 usually.Two are to use ionic liquid aqueous solution to reduce unlike common solvent acetate as the solvability of solvent to shitosan, but have 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.
Description of drawings
Accompanying drawing 1 width of cloth of the present invention
Fig. 1 is the surperficial POM photo of cyanoethyl chitin fiber.
The specific embodiment
Following embodiment can make those of ordinary skill in the art more fully understand the present invention, but does not limit the present invention in any way.
Raw material: the aspartic acid powder, to analyze purely, Dihua worker Co., Ltd is won in Tianjin; 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 in morning factory;
Used among the following embodiment [Asp] Cl ionic liquid prepares as follows:
13.6g aspartic acid powder and the adding of 30ml deionized water are equipped with in the there-necked flask of condensing unit, and magnetic agitation slowly adds 36% hydrochloric acid of 14.2ml after 10 minutes, and its hydrogen chloride and aspartic acid mol ratio are 1.7; Be warming up to 60 ℃ after adding, stop reaction behind the isothermal reaction 8h, decompression distillation removes and anhydrates; Obtain the solid product of white; Product is with ethyl acetate washing 2 times, and is dry under 60 ℃ behind the suction filtration, obtains white solid at last and is [Asp] Cl ionic liquid.
Embodiment 1
1. the preparation of cyanoethyl shitosan: the 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, behind the 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 oven dry.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with the 40g mass fraction in the 38.8g deionized water be 3% ionic liquid aqueous solution; 2g cyanoethyl shitosan is added in the ionic liquid solution abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare the cyanoethyl chitin fiber: spinning solution is injected the syringe of wet-spinning frame, at 30 ℃ of spinning fibres.Be coagulating bath with 5% (wt) sodium hydrate aqueous solution of volume ratio 1:1 and the mixed solution of absolute ethyl alcohol, stretched, washing 10min, air dry becomes fiber in air.The products obtained therefrom performance parameter is seen table 1.
Embodiment 2
1. the preparation of cyanoethyl shitosan: the 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, behind the 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 oven dry.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with the 40g mass fraction in the 38.8g deionized water be 3% ionic liquid aqueous solution; 2g cyanoethyl shitosan is added in the ionic liquid solution abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare the cyanoethyl chitin fiber: like embodiment 1.The products obtained therefrom performance parameter is seen table 1.
Embodiment 3
1. the preparation of cyanoethyl shitosan: the 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, behind the 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 oven dry.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with the 40g mass fraction in the 38.8g deionized water be 3% ionic liquid aqueous solution; 2g cyanoethyl shitosan is added in the ionic liquid solution abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare the cyanoethyl chitin fiber: like embodiment 1.The products obtained therefrom performance parameter is seen table 1.
Embodiment 4
1. the preparation of cyanoethyl shitosan: the 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, behind the 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 oven dry.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with the 40g mass fraction in the 38.8g deionized water be 3% ionic liquid aqueous solution; 2g cyanoethyl shitosan is added in the ionic liquid solution abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare the cyanoethyl chitin fiber: like embodiment 1.The products obtained therefrom performance parameter is seen table 1.
Embodiment 5
1. the preparation of cyanoethyl shitosan: the 3g shitosan is fully mixed with 14% sodium hydroxide solution 15g, behind the 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 oven dry.
2. the preparation of spinning solution: [Asp] Cl ionic liquid 1.2g is dissolved in to be mixed with the 40g mass fraction in the 38.8g deionized water be 3% ionic liquid aqueous solution; 2g cyanoethyl shitosan is added in the ionic liquid solution abundant stirring and dissolving 8h under 30 ℃ of conditions;
3. prepare the cyanoethyl chitin fiber: like embodiment 1.The products obtained therefrom performance parameter is seen table 1.
The partial properties parameter of table 1 embodiment 1 ~ 5 product
Claims (5)
1. the preparation method of a cyanoethyl chitin fiber comprises following processing step:
1. the preparation of cyanoethyl shitosan: by quality than shitosan: 5 ~ 20% sodium hydroxide solution 1:5 feed intake, and shitosan is uniformly dispersed, and in air, place; At-15 ℃ of freezing 12h, make alkaline chitosan behind the swelling 5h, after thawing; By quality than shitosan: acrylonitrile 1:1 ~ 1:5 adds acrylonitrile, at room temperature reacts 0.5 ~ 24h, and product is washed till neutrality with ethanol; Filter oven dry;
2. the preparation of spinning solution: [Asp] Cl ion liquid dissolving is mixed with mass fraction in deionized water be [Asp] Cl ionic liquid aqueous solution of 1 ~ 10%; The cyanoethyl shitosan that 1. step is prepared progressively adds in [Asp] Cl ionic liquid aqueous solution; Under 60 ℃, be stirred to dissolving fully; Be mixed with spinning solution, wherein the quality of cyanoethyl shitosan is 5% of an ionic liquid aqueous solution quality;
3. the preparation of cyanoethyl chitin fiber: spinning solution is injected the wet-spinning frame syringe, stretched in coagulating bath at 10 ~ 60 ℃ of following spinning fibres of temperature, washing, air dry becomes fiber in air.
2. the preparation method of cyanoethyl chitin fiber according to claim 1 is characterized in that: said coagulating bath be for volume ratio be the 5wt% sodium hydroxide solution of 1:1 and the mixed solution of absolute ethyl alcohol.
3. the preparation method of cyanoethyl chitin fiber according to claim 1 is characterized in that: step 2. in, [Asp] Cl ion liquid dissolving is mixed with mass fraction in deionized water be [Asp] Cl ionic liquid solution of 3%.
4. cyanoethyl chitin fiber, it is characterized in that: said cyanoethyl chitin fiber is made by the said method of claim 1 ~ 3.
5. a kind of cyanoethyl chitin fiber according to claim 4 is characterized in that: the fracture strength of said cyanoethyl chitin fiber is 1.2 ~ 2.4cN/dtex, heat decomposition temperature >=225 ℃.
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Cited By (4)
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| CN103061109A (en) * | 2012-12-14 | 2013-04-24 | 青岛海蓝生物制品有限公司 | Method for modifying non-water-soluble chitosan fiber into water-soluble chitosan fiber |
| CN103572596A (en) * | 2013-10-24 | 2014-02-12 | 浙江理工大学 | Method for reinforcing fragile cotton fabrics with cyanoethyl chitosan |
| CN104313717A (en) * | 2014-11-06 | 2015-01-28 | 西安元创化工科技股份有限公司 | Production method of polyacrylonitrile fiber with high strength |
| CN113845678A (en) * | 2021-11-30 | 2021-12-28 | 安徽理工大学 | Preparation method of high-transparency flame-retardant polyvinyl alcohol film |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103061109A (en) * | 2012-12-14 | 2013-04-24 | 青岛海蓝生物制品有限公司 | Method for modifying non-water-soluble chitosan fiber into water-soluble chitosan fiber |
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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 |
| CN104313717A (en) * | 2014-11-06 | 2015-01-28 | 西安元创化工科技股份有限公司 | Production method of polyacrylonitrile fiber with high strength |
| 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 |
| CN113845678A (en) * | 2021-11-30 | 2021-12-28 | 安徽理工大学 | Preparation method of high-transparency flame-retardant polyvinyl alcohol film |
| 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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