CN101565508B - Method and application for dissolving chitosan by salt solvent - Google Patents
Method and application for dissolving chitosan by salt solvent Download PDFInfo
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- CN101565508B CN101565508B CN2009103011825A CN200910301182A CN101565508B CN 101565508 B CN101565508 B CN 101565508B CN 2009103011825 A CN2009103011825 A CN 2009103011825A CN 200910301182 A CN200910301182 A CN 200910301182A CN 101565508 B CN101565508 B CN 101565508B
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- Prior art keywords
- chitosan
- dissolving
- solvent
- salt solvent
- salt
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 67
- 239000002904 solvent Substances 0.000 title claims abstract description 26
- 150000003839 salts Chemical class 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 15
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 3
- 230000006196 deacetylation Effects 0.000 claims abstract description 3
- 238000003381 deacetylation reaction Methods 0.000 claims abstract description 3
- 238000011010 flushing procedure Methods 0.000 claims abstract description 3
- 239000007787 solid Substances 0.000 claims abstract description 3
- 239000000835 fiber Substances 0.000 claims description 14
- 238000002525 ultrasonication Methods 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000004744 fabric Substances 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 230000007928 solubilization Effects 0.000 abstract 1
- 238000005063 solubilization Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a chitosan salt solvent and its application, belonging to high molecule material technology field, which is characterized in that the salt solvent is 40-65 mass.% of sodium rhodanate. The steps of dissolving the chitosan by solvent are: pretreating, dispersing chitosan powder with 70-95% of deacetylation degree and 20000-600000 of viscosity average molecular weight into an alkali liquor with a certain concentration, filtering after ultrasonic treatment, flushing the collected solid with water; dissolving, dispersing the pretreated chitosan in water, adding NaSCN, stirring the formed suspension liquid for 2-5 hours at 60-90 DEG C, obtaining the transparent chitosan solution. The invention can produce the stable chitosan solution by the salt solvent and provides new method for searching the chitosan solubilization mechanism and is widely applied in the machining for the functional composite materials such as chitosan film, fabric and polyacrylonitrile.
Description
Technical field
The invention belongs to technical field of polymer materials, relate to a kind of method and application thereof of dissolving chitosan by salt solvent, particularly a kind of salt solvent is used to dissolve chitosan.
Background technology
Chitosan mainly is made up of β-(1,4)-2-amino-2-deoxidation-D-glycosamine and β-(1,4)-2-acetylaminohydroxyphenylarsonic acid 2-deoxidation-two kinds of sugar units of D-glycosamine, and wherein, β-(1,4)-2-amino-2-deoxidation-D-glucosamine units content accounts for more than 60%.Chitosan is nontoxic, hydrophilic, characteristics such as biological degradability, biocompatibility, reproducibility and germ resistance are arranged, biomedicine, pharmacy, food, papermaking, weaving, water purify and wastewater treatment in be widely used.Preparation chitosan goods generally need earlier chitosan to be dissolved, and then carry out forming process.Since between chitosan molecule the intensive hydrogen bond action is arranged, can be less as the solvent of chitosan.Solvent commonly used both at home and abroad is various diluted acids, example hydrochloric acid, acetate, citric acid, formic acid, lactic acid, Mono Chloro Acetic Acid, propanedioic acid, oxyacetic acid, phenylformic acid and several nitration mixture thereof.The chitosan chain is rich in free amino group, by protonated and make chitosan be dissolved in acidic medium, so there is the part degraded in chitosan regular meeting in acidic solution, makes product not reach requirement in acidic solution; And during polymer manufacture functional composite material such as chitosan and polyacrylonitrile, because chitosan is poorly soluble, general to use after the modification polymkeric substance such as water-soluble chitosan and polyacrylonitrile to carry out compound, and cost can increase much like this, has limited many ranges of application of chitosan.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method and application thereof of dissolving chitosan by salt solvent.
Chitosan salt solvent composition of the present invention and mass percentage content thereof are: Sodium Thiocyanate 99 40%～65%, all the other are water.
This dissolving chitosan by salt solvent step is:
(1) pre-treatment: the chitosan powder of deacetylation 70%～95%, viscosity-average molecular weight 20,000～600,000 is scattered in the certain density alkali lye, with filtering after the ultrasonication, with the solid water flushing of collecting;
(2) dissolving: pretreated chitosan is scattered in the water, adds NaSCN salt, then the suspension that forms was stirred 2～5 hours down at 60 ℃～90 ℃, can obtain transparent chitosan solution.
In addition, this salt solvent also can be used for the research of chitosan dissolution mechanism, is used for the forming process of chitosan system film, fiber, is used for the forming process with functional composite materials such as polyacrylonitrile.
Beneficial effect of the present invention is:
1, adopt salt solvent of the present invention can obtain stable chitosan solution, for research chitosan dissolution mechanism provides new method;
2, adopt the ultrasonic pretreatment chitosan that the chitosan specific surface area is increased greatly, improved dissolved efficiency;
3,, avoided chitosan in acid, degrade and caused the problem of chitosan product properties decline because right and wrong acid solvent;
4, the mensuration that is used for the chitosan molecule amount provides parameters such as solubility product parameter for chitosan;
5, because this salt solvent is the good solvent of polymkeric substance such as polyacrylonitrile, can directly use polymer manufacture functional composite materials such as unmodified chitosan and polyacrylonitrile, having saved like this is chitin modified cost.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.
Embodiment 1:
At first 3g being taken off acetyl 75%, viscosity-average molecular weight and be 50,000 chitosan powder is scattered in the sodium hydroxide solution of 8%～10% (massfraction), then, be washed to neutrality with collecting the chitosan that contains some water with 10 minutes after-filtration of 40KMHz ultrasonication; To go up the step is scattered in the water through pretreated chitosan, adds NaSCN salt, and making NaSCN concentration is 50%, then the suspension that forms is stirred 2 hours at 80 ± 1 ℃ of lower magnetic forces, can obtain transparent chitosan solution.Again above-mentioned solution is dripped 2% acetate and produce to no longer including to precipitate, collecting precipitation, washing, dry, weighing, the chitosan preceding with dissolving compares, and finds that dissolving chitosan rate of loss is 3.1%
Embodiment 2:
At first 3g being taken off acetyl 85%, viscosity-average molecular weight and be 110,000 chitosan powder is scattered in the sodium hydroxide solution of 8%～10% (massfraction), then, be washed to neutrality with collecting the chitosan that contains some water with 10 minutes after-filtration of 40KHz ultrasonication; To go up the step is scattered in the water through pretreated chitosan, adds NaSCN salt, and making NaSCN concentration is 55%, then the suspension that forms is stirred 2 hours at 90 ± 1 ℃ of lower magnetic forces, can obtain transparent chitosan solution.Again above-mentioned solution is dripped 2% acetate and produce to no longer including to precipitate, collecting precipitation, washing, dry, weighing, the chitosan preceding with dissolving compares, and finds that dissolving chitosan rate of loss is 3.7%
Embodiment 3:
Get the made chitosan solution 100g of embodiment 1, under agitation add 13.64g polyacrylonitrile powder (chitosan mass mark 1%, polyacrylonitrile massfraction 12%), system temperature is risen to 75 ± 1 ℃ then, dissolved 2～3 hours, and can obtain the compound stoste of chitosan/polyacrylonitrile of homogeneous.The compound stoste that makes is delivered to spinning-drawing machine carry out spinning after vacuum defoamation is handled, former liquid temp is controlled at 75 ± 1 ℃.Spinning condition: spinneret orifice diameter 0.1mm, it is 0.40cc/min that setting pressure makes extruded velocity, spinning speed is controlled at 5m/min.The stoste of ejection enters precipitation bath and forms nascent fibre, and precipitation bath is 10% the NaSCN aqueous solution, bathes 10 ± 2 ℃ of temperature.The nascent fibre that forms enters one-level solvent stretch bath to carry out just stretching, and draw ratio is 3～7 times.The solvent stretch bath is 15% the NaSCN aqueous solution, bathes 85 ± 2 ℃ of temperature.Carry out secondary stretch through steam bath again through solvent tensile fiber, draw ratio is 2～5 times.The fiber of secondary stretch is through washing, the dry sample filaments that gets.The sample filaments performance is tested, find that the mechanical property of conjugated fibre remains on former polyacrylonitrile fibre level substantially.
Embodiment 4:
Get the made chitosan solution 100g of embodiment 2, under agitation add 14.94g polyacrylonitrile powder (chitosan mass mark 1%, polyacrylonitrile massfraction 13%), system temperature is risen to 75 ± 1 ℃ then, dissolved 2～3 hours, and can obtain the compound stoste of chitosan/polyacrylonitrile of homogeneous.The compound stoste that makes is delivered to spinning-drawing machine carry out spinning after vacuum defoamation is handled, former liquid temp is controlled at 75 ± 1 ℃.Spinning condition: spinneret orifice diameter 0.1mm, it is 0.40cc/min that setting pressure makes extruded velocity, spinning speed is controlled at 5m/min.The stoste of ejection enters precipitation bath and forms nascent fibre, and precipitation bath is 10% the NaSCN aqueous solution, bathes 10 ± 2 ℃ of temperature.The nascent fibre that forms enters one-level solvent stretch bath to carry out just stretching, and draw ratio is 3～7 times.The solvent stretch bath is 15% the NaSCN aqueous solution, bathes 85 ± 2 ℃ of temperature.Carry out secondary stretch through steam bath again through solvent tensile fiber, draw ratio is 2～5 times.The fiber of secondary stretch is through washing, the dry sample filaments that gets.The sample filaments performance is tested, find that the mechanical property of conjugated fibre remains on former polyacrylonitrile fibre level substantially.
Claims (2)
1. the method for a dissolving chitosan by salt solvent is characterized in that using method is as follows:
(1) composition of salt solvent and mass percentage content thereof are Sodium Thiocyanate 99 40%～65%;
(2) the use step of dissolving chitosan:
1) pre-treatment: the chitosan powder of deacetylation 70%～95%, viscosity-average molecular weight 20,000～600,000 is scattered in the certain density alkali lye, with filtering after the ultrasonication, with the solid water flushing of collecting;
2) dissolving: pretreated chitosan is scattered in the water, adds NaSCN salt, then the suspension that forms was stirred 2～5 hours down at 60 ℃～90 ℃, obtain transparent chitosan solution.
2. the application of the described method of claim 1 is characterized in that: be used for the research of chitosan dissolution mechanism; Or be used for the forming process of chitosan system film, fiber; Or be used for forming process with the polyacrylonitrile functional composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103011825A CN101565508B (en) | 2009-03-27 | 2009-03-27 | Method and application for dissolving chitosan by salt solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103011825A CN101565508B (en) | 2009-03-27 | 2009-03-27 | Method and application for dissolving chitosan by salt solvent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101565508A CN101565508A (en) | 2009-10-28 |
| CN101565508B true CN101565508B (en) | 2011-07-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103011825A Expired - Fee Related CN101565508B (en) | 2009-03-27 | 2009-03-27 | Method and application for dissolving chitosan by salt solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101565508B (en) |
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- 2009-03-27 CN CN2009103011825A patent/CN101565508B/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN101565508A (en) | 2009-10-28 |
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Granted publication date: 20110706 Termination date: 20120327 |