CN102168323A - Method for preparing chitosan and chitin functional materials by taking ionic liquid as solvent - Google Patents
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- CN102168323A CN102168323A CN2011100439049A CN201110043904A CN102168323A CN 102168323 A CN102168323 A CN 102168323A CN 2011100439049 A CN2011100439049 A CN 2011100439049A CN 201110043904 A CN201110043904 A CN 201110043904A CN 102168323 A CN102168323 A CN 102168323A
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Abstract
The invention relates to a method for preparing chitosan and chitin functional materials by taking ionic liquids as solvents. In the invention, the ionic liquids or the water solutions of the ionic liquids are adopted for dissolving chitosan and chitin so as to prepare chitosan functional fibers, chitin functional fibers, chitosan/chitin blended fibers, chitosan functional films, chitin functional films, and chitosan/chitin films respectively. Imidazole-category ionic liquid, pyridine-category ionic liquid, pyrrole-category ionic liquid, morpholine-category ionic liquid and thiazole-category ionic liquid or water solutions of the ionic liquids are used as solvents, and the solvent selection of chitosan and chitin are broadened. The method utilizes the ionic liquids to prepare chitosan and chitin functional fibers and films, and the method is high in efficient and environment-friendly; in addition, the prepared functional materials have high mechanical strength and stable chemical properties. The functional materials improve the application of the fibers and the films in the fields of medical, health care and textiles.
Description
Technical field
The invention belongs to the preparation of shitosan, chitin functional material, particularly relating to a kind of is the shitosan of solvent, the preparation method of chitin functional material with the ionic liquid.
Background technology
Chitin (chitin) formal name used at school is: β-(1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxy-D-glucose, be white or unformed, the translucent solid of canescence, extensively be present in ocean crustacean shell, mollusk endoskeleton, insect wing, mushroom and the alga cells wall, at occurring in nature, chitinous year biosynthesis amount is to be only second to cellulosic second largest natural resources up to hundred billion tons more than.1811, the Frenchman found chitin the earliest in the Nature, had found the deacetylation product shitosan of chitin---unique a kind of alkaline natural polysaccharide afterwards again in 1859.But human development for a long time and utilize range, the degree of depth and the significant degree of physical resources such as biosynthesis thing to be subjected to the restriction of science and technology and economic condition all the time.In recent decades, chitin and shitosan have become the popular research topic of countries such as Japan and the United States.According to statistics, the patent that Japan on average just applied for 1 relevant chitin or shitosan in per 3 days over past ten years.Research and product development that China also was correlated with since mid-term in 20th century become the major country of studying shitosan and chitin very soon.Owing to contain a large amount of hydrogen bonds, make that it is water insoluble, diluted acid, diluted alkaline, concentrated base and common organic solvents in the chitin, limited its range of application.
Ionic liquid is the new in recent years a kind of environmentally friendly solvent that has prospect that rises.Because it has the characteristics such as electrochemical window of good watery fusion, heat endurance, environmental stability, broad, has been subjected to the extensive concern on chemical boundary.Compare with traditional organic solvent, ionic liquid has following characteristics: (1) liquid condition temperature range is wide, from being lower than or near room temperature to 300 ℃, and has good physics and chemical stability; (2) steam forces down, and is not volatile, eliminated VOC (Volatile Organic Compounds) problem of environmental pollution; (3) a large amount of inorganic and organic substances is all shown good dissolving ability, and have the dual-use function of dissolving and catalysis, can be used as many chemical reaction solvents or catalytic activity carrier; (4) have bigger polarity Modulatory character, viscosity is little, and density is big, can form two-phase or heterogeneous system, is fit to make to separate solvent or constitute reaction-separation coupling new system.Ionic liquid has designability, and the yin, yang ion population by selecting to suit can change ion liquid physicochemical properties, thereby can dissolve multiple organic matter, inorganic matter and macromolecular material.Chitin and shitosan have many natural advantageous properties, cause inflammatory and do not have harmful catabolite etc. as sucting wet air permeability, reactivity, biocompatibility, biodegradability, adsorptivity, cohesiveness, antibiotic property, security, no antigen, nothing, thereby be widely used in aspects such as textile industry, biomedicine and daily environmental protection.Shitosan also has many good functional characters and potential using value in addition, wherein film forming has been subjected to everybody special concern, be cross-linked to form spacial framework between its molecule, easy film forming, this film TENSILE STRENGTH is big, good toughness, alkali resistance material and organic solvent-resistant.Therefore shitosan can be widely used at industrial circles such as food, medicine, weaving, chemical industry, papermaking as a kind of good membranes material.Along with membrane separation technique develops rapidly, reach the shortage of medical fibre in recent years, chitin, chitosan film and fiber become a focus of current research and exploitation.
The report of ion liquid dissolving shitosan, chitin that sees report at present is very few, and Chinese patent CN200710043563.9 has openly reported to be the preparation and the application of the cellulose blending fibre of solvent with the ionic liquid; Chinese patent CN200810157372.X has openly reported the composite fibre of regenerated cellulose/chitin composite material preparation method and preparation; Chinese patent CN200810239040.6 has openly reported a kind of chitin fiber and preparation method thereof; Chinese patent CN201010257904.4 has openly reported a kind of preparation method of shitosan/cellulose composite material; Yusong Wu in 2008 etc. are at periodical Polymer (2008, reported 3:1-7) that the 1-butyl-3-methylimidazole acetate ionic liquid has been done dissolution with solvents chitin and shitosan, 1-allyl-3 methylimidazole villaumite ionic liquid and 1-butyl-3-methylimidazole villaumite can both dissolve shitosan, but can not dissolve chitin fully, these document institute reported method all adopt pure ionic liquid as solvent, the solution temperature height, dissolution time is long, the viscosity of gained solution is bigger, and these technical measures are very unfavorable to spinning.The Chinese patent CN200910138811.7 of Yu Shitao has openly reported a kind of preparation method of chitin fiber, but dissolution time is long, and bad separating out.Tinghua Wu in 2010 etc. are at Carbohydrate Polymers 83 (2011, reported ionic liquid 1 233-238), 3-methylimidazole villaumite and 1-hydrogen-3-methylimidazole villaumite can dissolve shitosan as mixed solvent, and the shitosan of dissolving can be regenerated.
Summary of the invention
The purpose of this invention is to provide a kind of is the shitosan of solvent with the ionic liquid or the ion liquid aqueous solution, the preparation method of chitin functional material, the present invention adopts ionic liquid or ion liquid aqueous solution dissolving shitosan, chitin, the time of ion liquid aqueous solution dissolving and the pure ion liquid dissolving shitosan of employing in the past, chitin is compared, the time of dissolving is shorter, and the ionic liquid that expends is few, reduce cost, the present invention also adopts the ionic liquid of thiazoles to dissolve shitosan in addition, chitin, this is again a shitosan, dissolution of chitin has been widened choice of Solvent, shitosan in the inventive method, the dissolution of chitin gelation, spinning, film forming all is physical change, and chemical change does not take place.Shitosan, chitin fiber and film have antibiotic, suction-operated simultaneously, also have good biocompatibility, easily degraded, environmentally safe.Method efficient height of the present invention, environmental protection can be satisfied production requirement.
Of the present invention a kind of be that the shitosan of solvent, the preparation method of chitin functional material comprise the following steps: with the ionic liquid or the ion liquid aqueous solution
(1) shitosan, chitin and the ionic liquid of pulverizing mixed, dissolving is 1-10 hour under 25-160 ℃ of temperature, obtains the spinning solution of stable homogeneous, and the total solid content of spinning solution is 1-20%;
(2) will through filtration, spinning solution after the deaeration carry out spinning, wherein coagulating bath is temperature 0-95 ℃, the ionic liquid aqueous solution of mass concentration 0-50%, spinning speed be 5-150 rice/minute;
(3) stretched, the washing, the bleaching, again through oiling, drying process, obtain the functional material fiber;
(4) shitosan, chitin and the ionic liquid of pulverizing mixed, dissolving is 1-10 hour under 20-170 ℃ of temperature, obtains the transparent casting solution of stable homogeneous;
(5) with the casting solution standing and defoaming, curtain coating straticulation on glass plate is put into the coagulating bath immersion and is made its gelation form film;
(6) with the film washing, the drying that obtain, can obtain shitosan, chitin functional membrane.
Described shitosan/chitin η=25-590cps, granularity are 80 orders, purity 〉=90%, moisture≤9%, ash≤1%.
Described ionic liquid is formed by CATION and anion, and described ionic liquid comprises: be anionic alkyl imidazo ion liquid, be anionic pyridine ion liquid, be anionic pyrroles's ionic liquid, be anionic alkyl morpholine ionic liquid, be anionic alkyl indoles ionic liquid, alkyl thiazole ionic liquid with bisulfate ion with bisulfate ion with bisulfate ion with bisulfate ion with bisulfate ion.Its general structure is:
(1) be anionic alkyl imidazo ion liquid with bisulfate ion
(6) alkyl thiazole ionic liquid
(7) alkyl imidazo ion liquid
R in the structural formula wherein
1, R
2, R
4Be the alkyl of H or C1-C8, can be identical or different; R
3, R
5And R
6Alkyl, vinyl, propenyl, cyclobutenyl, alkoxyl, ethoxy and hydroxypropyl for H, C1-C8; R
3, R
5And R
6Selected group can be identical or different; Xn
-Be Cl
-, Br
-, I
-, CH
3PhSO
3 -, CH
3COO
-, SO
4 -, NO
3 -, HSO
4 -, BF
4 -, PF
6 -, SCN
-, CF
3SO
4 -, CH
3SO
3 -, CF
3COO
-, (CH
3O)
2PO
2 -, (CF
3SO
2)
2N
-Or (CF
3SO
2)
3C
-A kind of.
Described coagulating bath is temperature 0-95 ℃, the ionic liquid aqueous solution of mass concentration 0-50%, spinning speed be 5-150 rice/minute.Described stretching is selected from one or more in nervous stretching, jet stretch, plasticization drawing, air bath after-drawing or the retraction, and total drawing ratio is 20-180%.Described spinning process is dry spinning, wet spinning or dry-jet wet spinning.
Functions such as that chitin, shitosan have is antibacterial, antipruritic, deodorization, anti-inflammatory, pain relieving, described functional material can be made into fiber, is used for the manufacturing and the medical fibre of textiles, also can be used for hollow-fibre membrane, is used for the film of using of manufacture of intraocular internal organs and water purifier.
Provided by the invention is that the shitosan of solvent, the preparation of chitin functional material compared with prior art have following beneficial effect with the ionic liquid or the ion liquid aqueous solution:
(1) lyate ion liquid provided by the invention or ionic liquid aqueous solution, it is volatile to have overcome conventional solvent, be difficult for to reclaim, seriously polluted, etching apparatus serious shortcoming, compare with traditional organic solvent, be a kind of relatively green solvent of environmental protection.(2) coagulating bath in the preparation process of functional material provided by the invention is the ion liquid aqueous solution or water, and cost is low, and is pollution-free.(3) the used ionic liquid of the present invention is pollution-free, can also reuse, and reduces production costs, and meets the theory of modern recycling economy.(4) preparation process of functional material provided by the invention does not produce pollutant, is environmentally friendly green preparation process.
The specific embodiment
Below be used to further specify the method that the present invention describes by specific embodiment, but be not intended that the invention be limited to these embodiment.
Embodiment 1
With 10 parts of shitosans that viscosity is 590cps pulverizing, with 90 parts of mass fractions be ionic liquid N-(4-sulfonic group) butyl-imidazole bisulfate [(CH of 10%
2)
4SO
3HMIM] [HSO
4] aqueous solution even, 80 ℃ of following mechanical agitation 4 hours, obtain the homogeneous spinning solution, carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is the above-mentioned ion liquid aqueous solution, and the mass concentration of coagulating bath intermediate ion liquid is 10%, and coagulation bath temperature is 25 ℃.Spinning speed is 40 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, makes the chitin fiber that intensity is 4.2cN/dtex.
Embodiment 2
With 20 parts of shitosans that viscosity is 590cps pulverizing, with 80 parts of mass fractions be ionic liquid N-butyl imidazole disulfate [BMIM] HSO of 20%
4Aqueous solution even, stirred 1 hour down at 100 ℃, obtain the homogeneous spinning solution, carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is above-mentioned ionic liquid aqueous solution, and the mass concentration of coagulating bath intermediate ion liquid is 10%, and coagulation bath temperature is 25 ℃.Spinning speed is 20 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, makes the chitin fiber that intensity is 3.6cN/dtex.
Embodiment 3
With 19 parts of shitosans that viscosity is 590cps pulverizing, with 81 parts of mass fractions be ionic liquid N-(4-sulfonic group) butyl-imidazole bisulfate [(CH of 15%
2)
4SO
3HMIM] [HSO
4] aqueous solution even, 80 ℃ of following mechanical agitation 6 hours, obtain the clear solution of stable homogeneous; With 2 parts of chitins, mix with ionic liquid 1-butyl-3-methylimidazole acetate [BMIM] Ac of 98 parts, stirred 3 hours down at 120 ℃, obtain the clear solution of stable homogeneous; Above-mentioned two kinds of solution are mixed, obtain the spinning solution of stable homogeneous, will carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is above-mentioned ionic liquid aqueous solution, the mass concentration of coagulating bath intermediate ion liquid is 12% the aqueous solution, and coagulation bath temperature is 40 ℃.Spinning speed is 25 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, and making intensity is shitosan/chitin blending fiber of 5.05cN/dtex.
Embodiment 4
With 5 parts of shitosans that viscosity is 590cps pulverizing, with mass fraction be 95 parts of ionic liquid N-(4-sulfonic group) butyl-imidazole bisulfate [(CH of 1%
2)
4SO
3HMIM] [HSO
4] aqueous solution even, 90 ℃ of following mechanical agitation 0.5 hour, obtain the clear solution of stable homogeneous; With 5 parts chitin, mix with ionic liquid 3-butyl-4-methylthiazol acetate [BMTHI] Ac of 95 parts, stirred 2 hours down at 110 ℃, obtain the clear solution of stable homogeneous; Above-mentioned two kinds of solution are mixed, obtain the spinning solution of stable homogeneous, carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is above-mentioned ionic liquid aqueous solution, the mass concentration of coagulating bath intermediate ion liquid is 15%, and coagulation bath temperature is 35 ℃.Spinning speed is 30 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, and making intensity is shitosan/chitin blending fiber of 3.95cN/dtex.
Embodiment 5
With 5 parts of shitosans that viscosity is 590cps pulverizing, with mass fraction be 95 parts of ionic liquid N-(4-sulfonic group) butyl-imidazole bisulfate [(CH of 1%
2)
4SO
3HMIM] [HSO
4] aqueous solution even, 90 ℃ of following mechanical agitation 0.5 hour, obtain the clear solution of stable homogeneous; With 5 parts chitin, mix with the mixed ionic liquid 3-allyl of 95 parts ionic liquid-4-methylthiazol bromine salt [AMTHI] Br, stirred 2 hours down at 110 ℃, obtain the clear solution of stable homogeneous; Above-mentioned two kinds of solution are mixed, obtain the spinning solution of stable homogeneous, carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is above-mentioned ionic liquid aqueous solution, the mass concentration of coagulating bath intermediate ion liquid is 15%, and coagulation bath temperature is 35 ℃.Spinning speed is 30 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, and making intensity is shitosan/chitin blending fiber of 3.20cN/dtex.
Embodiment 6
With 10 parts of chitins pulverizing and ionic liquid 3-allyl-4-methylthiazol villaumite [AMTHI] Cl of 90 parts, 100 ℃ of following mechanical agitation 2 hours, obtain the spinning solution of stable homogeneous, carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is above-mentioned ionic liquid aqueous solution, the mass concentration of coagulating bath intermediate ion liquid is 15%, and coagulation bath temperature is 30 ℃.Spinning speed is 40 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, makes the chitin fiber that intensity is 4.50cN/dtex.
Embodiment 7
15 parts of viscosity pulverizing shitosan that is 590cps and ionic liquid 3-allyl-4-methylthiazol bromine salt [AMTHI] Br of 85 parts are mixed, 100 ℃ of following mechanical agitation 1.5 hours, obtain the spinning solution of stable homogeneous, carry out dry-jet wet-spinning after the filtration of spinning solution process, the deaeration, coagulating bath is above-mentioned ionic liquid aqueous solution, the mass concentration of coagulating bath intermediate ion liquid is 20%, and coagulation bath temperature is 45 ℃.Spinning speed is 40 meters/minute, and the strand after solidifying passes through and washes, stretches, oils, the processing of dry supervisor, makes the chitin fiber that intensity is 4.50cN/dtex.
Embodiment 8
2 parts of viscosity pulverizing shitosan that is 590cps and ionic liquid 3-butyl-4-methylthiazol villaumite [BMTHI] Cl of 98 parts are mixed, stirred 1.5 hours down at 80 ℃, obtain the spinning solution of stable homogeneous, spinning solution is through after filtering, be placed in the reactor of doughnut spinning machine and carry out deaeration, 80 ℃ of spinning temperatures are set, core liquid is DMSO, the solid bath temperature of water-setting is 35 ℃, the doughnut that makes is placed in the water coagulating bath and soaked 25 hours, remove survivor ion liquid, can make shitosan/chitin doughnut.
Embodiment 9
2 parts of chitins pulverizing and ionic liquid 3-butyl-4-methylthiazol bromine salt [BMTHI] Br of 98 parts are mixed, stirred 2 hours down at 80 ℃, obtain the spinning solution of stable homogeneous, spinning solution is through after filtering, be placed in the reactor of doughnut spinning machine and carry out deaeration, 80 ℃ of spinning temperatures, core liquid is DMSO, the solid bath temperature of water-setting is 30 ℃, the doughnut that makes is placed in the water coagulating bath and soaked 30 hours, remove survivor ion liquid, can make shitosan/chitin doughnut.
Embodiment 10
With 10 parts of shitosans that viscosity is 590cps pulverizing, with ionic liquid N-(4-sulfonic group) butyl-imidazole bisulfate [(CH of 90 parts
2)
4SO
3HMIM] [HSO
4] aqueous solution even, stirred 4 hours down at 90 ℃, obtain the stable homogeneous clear solution, with its standing and defoaming, longshore current straticulation on glass plate is put into and is solidified bath water and soak and to make its gelation form film, soaks 24 hours, to remove most ionic liquid, coagulation bath temperature is 40 ℃, washes residual ionic liquid in the flush away film again with water, pass through dried at last again, obtain the shitosan functional membrane.
Embodiment 11
With 5 parts of chitins pulverizing, mix with ionic liquid 3-butyl-4-methylthiazol bromine salt [BMTHI] Br of 95 parts, stirred 3 hours down at 120 ℃, obtain the stable homogeneous clear solution, with its standing and defoaming, longshore current straticulation on glass plate, put into and solidify bath water and soak and to make its gelation form film, soaked 35 hours, to remove most ionic liquid, coagulation bath temperature is 45 ℃, washes residual ionic liquid in the flush away film again with water, pass through dried at last again, obtain the chitin functional membrane.
Embodiment 12
With 2 parts of viscosity pulverizing be 2 parts of shitosans of 590cps that pulverize with ionic liquid N-(4-sulfonic group) butyl-imidazole bisulfate [(CH 98 parts
2)
4SO
3HMIM] [HSO
4] aqueous solution even, stirred 20 minutes down at 90 ℃, obtain the stable homogeneous clear solution, the 3 parts of chitins and 97 parts of ionic liquids [BMIM] Ac that pulverize are mixed,, obtain clear solution 110 ℃ of following mechanical agitation 0.5 hour, above-mentioned two kinds of solution are mixed, obtain the stable homogeneous clear solution, with its standing and defoaming, longshore current straticulation on glass plate, put into and solidify bath water and soak and to make its gelation form film, soaked 30 hours, to remove most ionic liquid, coagulation bath temperature is 25 ℃, wash with water again, residual ionic liquid in the flush away film passes through dried at last again, obtains shitosan/chitin functional membrane.
Claims (8)
1. one kind is the shitosan of solvent, the preparation method of chitin functional material with the ionic liquid, comprises the following steps:
(1) shitosan, chitin and ionic liquid or the ion liquid aqueous solution of pulverizing is even, dissolving is 1-10 hour under 25-160 ℃ of temperature, obtains the spinning solution of stable homogeneous, and the total solid content of spinning solution is 1-20%;
(2) will through filtration, spinning solution after the deaeration carry out spinning, wherein coagulating bath is temperature 0-95 ℃, the ionic liquid aqueous solution of mass concentration 0-50%, spinning speed be 5-150 rice/minute;
(3) stretched, the washing, the bleaching, again through oiling, drying process, obtain the functional material fiber;
(4) shitosan, chitin and the ionic liquid of pulverizing mixed, dissolving is 1-10 hour under 20-170 ℃ of temperature, obtains the transparent casting solution of stable homogeneous;
(5) with the casting solution standing and defoaming, curtain coating straticulation on glass plate is put into the coagulating bath immersion and is made its gelation form film;
(6) with the film that obtains through washing, drying, can obtain shitosan, chitin functional membrane.
2. according to claim 1 is the shitosan of solvent, the preparation method of chitin functional material with the ionic liquid, it is characterized in that: described shitosan/chitin η=25-590cps, granularity are 80 orders, purity 〉=90%, moisture≤9%, ash≤1%.
3. according to claim 1 is the shitosan of solvent with the ionic liquid, the preparation method of chitin functional material, it is characterized in that: (1) described ionic liquid is formed by CATION and anion, described ion comprises: with bisulfate ion is anionic alkyl imidazo ion liquid, with bisulfate ion is anionic pyridine ion liquid, with bisulfate ion is anionic pyrroles's ionic liquid, with bisulfate ion is anionic alkyl morpholine ionic liquid, with bisulfate ion is anionic alkyl indoles ionic liquid, alkyl thiazole ionic liquid, its general structure is:
(1) be anionic alkyl imidazo ion liquid with bisulfate ion
(2) be anionic pyridine ion liquid with bisulfate ion
(3) be anionic pyrroles's ionic liquid with bisulfate ion
(4) be anionic alkyl morpholine ionic liquid with bisulfate ion
(5) be anionic alkyl indoles ionic liquid with bisulfate ion
(6) alkyl thiazole ionic liquid
(7) alkyl imidazo ion liquid
R in the structural formula wherein
1, R
2, R
4Be the alkyl of H or C1-C8, can be identical or different; R
3, R
5And R
6Alkyl, vinyl, propenyl, cyclobutenyl, alkoxyl, ethoxy and hydroxypropyl for H, C1-C8; R
3, R
5And R
6Selected group can be identical or different; Xn
-Be Cl
-, Br
-, I
-, CH
3PhSO
3 -, CH
3COO
-, SO
4 -, NO
3 -, HSO
4 -, BF
4 -, PF
6 -, SCN
-, CF
3SO
3 -, CH
3SO
3 -, CF
3COO
-, (CH
3O)
2PO
2 -, (CF
3SO
2)
2N
-Or (CF
3SO
2)
3C
-A kind of.
4. according to claim 1 is the shitosan of solvent, the preparation method of chitin functional fibre with the ionic liquid, it is characterized in that: described coagulating bath is temperature 0-95 ℃, the ionic liquid aqueous solution of mass concentration 0-50%, spinning speed be 5-150 rice/minute.
5. according to claim 1 is the shitosan of solvent, the preparation method of chitin functional fibre with the ionic liquid or the ion liquid aqueous solution, it is characterized in that: described stretching is selected from one or more in nervous stretching, jet stretch, plasticization drawing, air bath after-drawing or the retraction, and total drawing ratio is 20-180%.
6. according to claim 1 is the shitosan of solvent, the preparation method of chitin functional fibre with the ionic liquid or the ion liquid aqueous solution, and it is characterized in that: described spinning process is dry spinning, wet spinning or dry-jet wet spinning.
7. according to claim 1 is the shitosan of solvent, the preparation method of chitin functional membrane with the ionic liquid or the ion liquid aqueous solution, and it is characterized in that: the coagulating bath in the step (5) is a water, and temperature is 0-60 ℃.
8. according to claim 1 is the shitosan of solvent, the preparation method of chitin functional membrane with the ionic liquid or the ion liquid aqueous solution, and it is characterized in that: the immersion in the step (6), mode of washing are for being soaked in water, washing with water.
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