CN106432538A - Method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides - Google Patents
Method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides Download PDFInfo
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Abstract
The invention belongs to the technical field of fine chemical industry and particularly relates to a method for preparing chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides, of which the molecular weight is 50,000 or below. The method comprises the steps of firstly, dissolving chitin in a certain solvent, carrying out homogeneous degradation under acid catalysis so as to obtain the chitin oligosaccharides with certain molecular weight, and subjecting the chitin oligosaccharides to deacetylating treatment by a strong base, thereby preparing the chitooligosaccharides and the chitosan oligosaccharides. After the chitin oligosaccharides are subjected to deacetylating treatment by the strong base, the chitooligosaccharides or the chitosan oligosaccharides with the degree of deacetylation of 50% to 98% is obtained. Glycosidic bonds among acetylglucosamine are more easily degraded under the condition of acid catalysis, so that a chitin degradation reaction can be carried out under mild conditions, the yield is high, and the control on molecular weight is effectively achieved. According to the chitin oligosaccharides, chitooligosaccharides and chitosan oligosaccharides prepared by the method, the molecular weight can be continuously adjustable in the range of 1,000 to tens of thousands, the distribution of the molecular weight is relatively narrow, the product quality is high, and the production cost is reduced remarkably.
Description
Technical field
The invention belongs to technical field of fine is and in particular to a kind of molecular weight chitin below 50,000 is oligomeric
The preparation method of sugar, Chitosan Oligosacchaides and oligochitosan.
Background technology
As the second largest Renewable resource being only second to cellulose, chitin is widely present outside Yu Haiyang crustacean
In shell, Mollusca Endoskeleton, insect wing, mushroom and alga cells wall, reserves are huge, not yet obtain
Effective exploitation.Shitosan is the product after the deacetylated process of chitin, is the positively charged of only a large amount of presence
Basic amine group natural polysaccharide, good biocompatibility, there is many special physics, chemistry and physiologically active, quilt
It is considered " human body the 6th vital principle ".But because shitosan is macromolecular compound, relative molecular mass is usual
In hundreds of thousands to up to a million, and molecular structure, closely it is impossible to be dissolved in some usual vehicles such as water, is difficult in vivo
Degraded and absorbed, thus have impact on its range of application.
Chitosan Oligosacchaides are products when shitosan is degraded to mean molecule quantity under proper condition less than 10,000.Shell is few
2~10 glucosamine that sugar is commonly considered as being formed after shitosan is degraded further are bonded with β -1,4 glucosides
The Chitosan Oligosacchaides connecing.Compared with shitosan, Chitosan Oligosacchaides and oligochitosan possess good water solubility, biological activity
High, function is big, the features such as be easily absorbed by the body and other unique function, have shitosan incomparable
Superiority.
Research shows, Chitosan Oligosacchaides or oligochitosan directly can be absorbed by animal intestinal epithelial cell, and human body is inhaled
Yield can reach 99.88%, shows antibacterial, antitumor, Adjust-blood lipid, regulation immunity and activates intestinal bifid bar
The different physiological roles such as bacterium.The free amine group protonation in acid condition of Chitosan Oligosacchaides or oligochitosan, can with thin
The cell membrane effect of bacterium, disturbs bacterial cell membrane function, the growth of suppression funguses and microorganism, shows substantially
Antibacterial and bacteriostasis.Chitosan Oligosacchaides or oligochitosan have regulating plant growth, growth, breeding, disease resistance
Etc. aspect function, can stimulate the immune system response of plant, activate defense reaction, produce and there is disease resistance
Active substance, suppression disease formation, induction plant disease resistance, to multiple funguses, antibacterial and virus produce
Raw immunity and killing action.Chitosan Oligosacchaides or oligochitosan product chemistry, medicine, food, cosmetics,
All many-sides such as agricultural, environmental protection, poultry industry are widely applied.
At present, the approach of preparing of Chitosan Oligosacchaides or oligochitosan is mainly the acid degradation by shitosan
The degraded of (JPS6121103, KR100296738), hydrogen peroxide oxidation (CN200410020831.1,
CN201010172203.0, CN201110125040.5) and enzymolysis (US4970150, CN200510019438.5,
CN01126457.8, CN201010172203.0, CN200710051931.4) etc. technology path.Acid degradation method
Simple to operate, but the more difficult control of degradation condition, water volume used is big, power consumption is big, in degradation products monosaccharide and
Two sugared contents are high, water solublity oligosaccharide low yield.Oxidation degradation method ionizes formation in aqueous using hydrogen peroxide
The various free groups with extremely strong oxidisability attack the glycosidic bond on shitosan, and acutely, degradation speed is relatively for reaction
Hurry up, oligosaccharide structure is readily broken, the oligochitosan product quality obtaining is wayward.Enzymatic isolation method hydrolytic enzyme pair
Shitosan carries out biodegradation, and reaction condition is gentle, and energy consumption is low, and side reaction is few, is to study both at home and abroad at present
Emphasis.But enzymatic isolation method complex procedures, degradation efficiency are low, and the time is long, investment is big.Presently used enzymatic activity is not
Height, purification difficulty is big, and specificity is not strong, causes product yield low, and production cost is high.
Molecular size range all has a significant impact to many physical propertys of Chitosan Oligosacchaides, such as:Molecular weight is less, shell
The dissolubility of oligosaccharide, rheological characteristic and permeability are better, and liquid crystal liquid crystal property and film property are poorer.Research shows that shell is oligomeric
Sugar bacteriostasis gradually strengthen with the reduction of mean molecule quantity, molecular weight be 1500 when fungistatic effect
Good;And the Chitosan Oligosacchaides of higher molecular weight are higher to the activity reducing liver total lipid content and reduction cholesterol;When
The degree of polymerization of oligochitosan is to have best anticancer, suppression cancer isoreactivity when 6.Therefore, control Chitosan Oligosacchaides and shell few
The biological activity to systematic study Chitosan Oligosacchaides and oligochitosan for the molecular weight of sugar, lifts Related product quality, controls
Product quality has great importance.And existing Chitosan Oligosacchaides and oligochitosan preparation of industrialization technology be also difficult to right
Molecular weight is effectively controlled.
The research such as Varum shows that, under acid catalysiss, between acetylglucosamine, the degradation rate of glycosidic bond is amino
100 to 1000 times (Carbohydr.Polym.46,89 (2001)) of glycosidic bond degradation rate between glucose.?
Under equal conditions, chitinous degradation speed will be far above shitosan, and therefore chitinous degraded can be warmer
With under conditions of carry out.But due to intramolecular and intermolecular there is strong hydrogen bonding interact, chitin forms densification
Crystal structure, water insoluble, diluted acid, diluted alkaline and general organic solvent.Under out-phase reaction condition, warp
Strong acid and heat effect chitin can degradable become acetylglucosamine or glucosamine it is impossible to realize right
The control of catabolite molecular weight.
Content of the invention
The problem existing for prior art, the invention provides a kind of new chitin oligosaccharide, Chitosan Oligosacchaides
With the preparation method of oligochitosan, the molecular weight of the chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan of preparation can be
1000 to continuously adjustabe in tens thousand of scopes, and molecular weight distribution is narrower.
The present invention provide technical scheme be:
The preparation method of a kind of chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, makes chitin in a solvent first
Dissolving, even mutually degraded under acid catalysiss obtains chitin oligosaccharide, and chitin oligosaccharide is deacetylated through highly basic again
Chitosan Oligosacchaides and oligochitosan are prepared in process.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, comprises the following steps that:
1) chitin pulverizer is scattered in solvent after pulverizing, and under strong stirring, chitin fills in a solvent
Divide swelling or dissolving;
2) chitin starts to degrade, and molecular weight gradually reduces, and through separation, purification, dry run, obtains first
Chitin oligosaccharide;
3) chitin oligosaccharide is added in strong base solution and carries out deacetylation, through separation, purification, drying
Process, obtains Chitosan Oligosacchaides and oligochitosan product.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, after chitin is dried through rinsing,
Again 80~200 mesh are crushed to using pulverizer.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, dissolving chitinous solvent is
Hexafluoroisopropanol, Hexafluoro acetone, dichlroroethanol, the dimethylformamide containing lithium chloride, containing lithium chloride
Dimethyl acetylamide, N- methyl morpholine oxide, concentrated hydrochloric acid, concentrated sulphuric acid, strong phosphoric acid, pyrovinic acid, formic acid,
One of dichloroacetic acid, trichloroacetic acid or two or more mixture, solvent load be chitin quality 5~
50 times.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, when using faintly acid solvent:
Hexafluoroisopropanol, Hexafluoro acetone, dichlroroethanol, the dimethylformamide containing lithium chloride, containing lithium chloride
Dimethyl acetylamide, N- methyl morpholine oxide, formic acid, dichloroacetic acid, trichloroacetic acid one or more
When, by adding hydrochloric acid or sulphuric acid, to improve chitinous degradation speed.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, adds in faintly acid solvent
Hydrochloric acid or sulphuric acid quality are the 0.2~12% of solvent quality.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, the separation of chitin oligosaccharide,
Purification, dry run, are isolated and purified using solvent evaporation, precipitate with ethanol, column chromatography, membrane separation technique, and
Through vacuum drying, it is spray-dried or forced air drying, obtain the oligomeric sugar product of chitin;Chitin oligosaccharide takes off
The reacted separation of acetyl, purification, dry run, carry out separating using precipitate with ethanol, column chromatography, membrane separation technique
Purification, and through vacuum drying, spray drying or forced air drying, obtain Chitosan Oligosacchaides and oligochitosan product.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, the precipitate with ethanol examination that alcohol deposition method adopts
Agent be one of methanol, ethanol, propanol, isopropanol, butanol, isoamyl alcohol, acetone, butanone or two kinds with
On.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, chitin oligosaccharide is deacetylated
Base is to carry out in strong base solution, and deacetylated process reaction temperature is 40~140 DEG C, and the response time 1~20 is little
When;Strong base solution adopts the NaOH solution of 10~60wt% or the KOH solution of 10~60wt%, and highly basic is molten
Liquid consumption is 5~20 times of chitin oligosaccharide quality.
The preparation method of described chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan, chitin oligosaccharide is through highly basic
Deacetylated process after, obtain deacetylation 50% to 98% Chitosan Oligosacchaides or oligochitosan;Degraded by controlling
Time obtains the chitin oligosaccharide of different molecular weight, after deacetylated, when molecular weight obtains when higher than 3000
Be Chitosan Oligosacchaides, obtain when molecular weight is below 3000 is oligochitosan.
The design philosophy of the present invention is:
The present invention dissolves first first with dense strong acid, intensive polar solvent, fluorated solvent or amide/lithium chloride solvent etc.
Chitin, the chitin after dissolving is degraded into chitin oligosaccharide, chitin oligosaccharide warp again under acid catalysed conditions
The deacetylated process of highly basic prepares Chitosan Oligosacchaides and oligochitosan.Through over half a century research it has been found that
Multiple can dissolve chitinous solution system, including strong acid such as the hydrochloric acid of high concentration, nitric acid, sulphuric acid, phosphoric acid,
The intensive polar solvents such as trichloroacetic acid, dichloroacetic acid, formic acid, pyrovinic acid, chlorhydrin, amide/lithium chloride system,
Fluorated solvent etc..Utilization of the present invention can dissolve chitinous solvent, makes chitin even phase condition upon dissolution
Lower degraded.Glycosidic bond between due to acetylglucosamine under acid catalysed conditions it is easier to be degraded, carapace
Matter degradation reaction can be carried out under mild conditions, be capable of the effective control to molecular weight simultaneously.
Advantages of the present invention and beneficial effect are:
1st, change the conventional first deacetylated preparation method being degraded into Chitosan Oligosacchaides and oligochitosan again of chitin, this
Invention, using making chitin be degraded into chitin oligosaccharide technology path deacetylated first, significantly reduces life
Produce cost.
2nd, compared with shitosan, chitin can be degraded under conditions of milder, and course of reaction is easy to
Control, by-product is few, and yield is higher.
3rd, the molecular weight of chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan can be in 1,000 to tens thousand of scopes
Continuously adjustabe, molecular weight distribution is narrower, and product quality is high, and performance is easily controllable.
Brief description
Fig. 1 is the GPC gel chromatography of Chitosan Oligosacchaides and oligochitosan.
Specific embodiment
In a specific embodiment, the preparation method of chitin oligosaccharide of the present invention, Chitosan Oligosacchaides and oligochitosan,
Comprise the steps:
(1) with pulverizer, lamellar chitin powder is broken to suitable granularity, typically about (80~200 mesh).
(2) chitin granules are scattered in 5 times to 50 times solvents, and under strong stirring, chitin is in solvent
In fully swelling or dissolving.
(3) reactant is incubated 1 to 10 hour at 0 DEG C~100 DEG C, and chitin starts to degrade, and molecular weight is progressively
Reduce, obtain chitin oligosaccharide, the chitin that can obtain different molecular weight by the control response time is oligomeric
Sugar.
(4) method such as vacuum decompression evaporation solvent, precipitate with ethanol, column chromatography, membrance separation is adopted to remove reaction liquid
The chitin oligosaccharide that solvent purification reaction obtain.
(5) chitin oligosaccharide adds the strong base solution of 5 to 50 times of volumes, is heated to 40 DEG C to 140 DEG C simultaneously
Insulation carries out deacetylation in 1 to 20 hour.
(6) remove alkali using methods such as column chromatography, membrance separation or precipitate with ethanol after highly basic is deacetylated and be further purified,
Again through drying meanss such as forced air drying, spray drying or vacuum drying, obtain deacetylation 50% to 98%
Chitosan Oligosacchaides and oligochitosan.During deacetylated, the change of molecular weight of polysaccharide less, is degraded by controlling
Time obtains the chitin oligosaccharide of different molecular weight.After deacetylated, when molecular weight obtains when higher than 3000
Be Chitosan Oligosacchaides, obtain when molecular weight is below 3000 is oligochitosan.
In order that technical scheme and advantage are clearer, carry out in detail below in conjunction with specific embodiment
Description.
Embodiment 1
At 10 DEG C, 10g chitin is slowly added in 200mL concentrated hydrochloric acid (36wt%).Stirring 6 hours
Afterwards, chitin is completely dissolved.Improve reaction temperature to 30 DEG C, stir 1 hour, and slow in backward reactant liquor
Add NaOH pressed powder neutralization reaction solution.Reaction solution adds 1000mL ethanol to carry out precipitate with ethanol, separates out
Solid precipitation through filter, ethanol purge, forced air drying obtains 8 grams of chitin oligosaccharide.
8 grams of chitin oligosaccharide are added in the 50wt%NaOH solution of 160g.90 DEG C of insulations 6 of reaction temperature
Hour.After reaction terminates, 800mL ethanol is added to carry out precipitate with ethanol., through filtering, ethanol is clear for the solid precipitation separating out
Wash, lyophilization obtains the white Chitosan Oligosacchaides powder of 6g.The molecular weight of Chitosan Oligosacchaides is 11000, deacetylated
Spend for 92%.
Embodiment 2
At 10 DEG C, 10g chitin is slowly added in 200mL concentrated hydrochloric acid (36wt%).Stirring 6 hours
Afterwards, chitin is completely dissolved.Improve reaction temperature to 30 DEG C, stir 1.5 hours, and slow in backward reactant liquor
Slow addition NaOH pressed powder neutralization reaction solution.Reaction solution adds 1000mL ethanol to carry out precipitate with ethanol, analysis
Through filtration, ethanol purge, forced air drying obtains 7.5 grams of chitin oligosaccharide to the solid precipitation going out.
7.5 grams of chitin oligosaccharide are added in the 50wt%NaOH solution of 160g.90 DEG C of insulations of reaction temperature
6 hours.After reaction terminates, 800mL ethanol is added to carry out precipitate with ethanol.The solid precipitation separating out is through filtration, ethanol
Cleaning, lyophilization obtains the white Chitosan Oligosacchaides powder of 5.8g.The molecular weight of Chitosan Oligosacchaides is 5000, de- second
Acyl degree is 93%.
Embodiment 3
At 10 DEG C, 10g chitin is slowly added in 200mL concentrated hydrochloric acid (36wt%).Stirring 6 hours
Afterwards, chitin is completely dissolved.Improve reaction temperature to 30 DEG C, stir 2 hours, and slow in backward reactant liquor
Add NaOH pressed powder neutralization reaction solution.Reaction solution adds 1000mL ethanol to carry out precipitate with ethanol, separates out
Solid precipitation through filter, ethanol purge, forced air drying obtains 6.8 grams of chitin oligosaccharide.
6.8 grams of chitin oligosaccharide are added in the 45wt%NaOH solution of 160g.80 DEG C of insulations of reaction temperature
4 hours.After reaction terminates, 800mL ethanol is added to carry out precipitate with ethanol.The solid precipitation separating out is through filtration, ethanol
Cleaning, lyophilization obtains the faint yellow oligochitosan powder of 4.9g.The molecular weight of oligochitosan is 2500, deacetylated
Spend for 90%.
Embodiment 4
At 30 DEG C, 10g chitin is slowly added in 500mL hexafluoroisopropanol.Stirring 6 hours, carapace
Matter adds 25mL concentrated hydrochloric acid after being completely dissolved.Improve reaction temperature to 50 DEG C, after stirring 1 hour, at 50 DEG C
Vacuum revolving, makes most reaction dissolvent evaporations reclaim.Product adds ethanol purge, filters, air blast
It is dried to obtain 8.5 grams of chitin oligosaccharide.
8.5 grams of chitin oligosaccharide are added in the 40wt%NaOH solution of 160g.80 DEG C of insulations of reaction temperature
4 hours.After reaction terminates, 800mL ethanol is added to carry out precipitate with ethanol.The solid precipitation separating out is through filtration, ethanol
Cleaning, lyophilization obtains the faint yellow oligochitosan powder of 5.4g.The molecular weight of oligochitosan is 3000, deacetylated
Spend for 86%.
Embodiment 5
At 20 DEG C, 10g chitin is slowly added into 300mL formic acid.Stirring 6 hours, chitin is completely molten
21mL concentrated hydrochloric acid is added after solution.Improve reaction temperature to 64 DEG C, after stirring 1 hour, revolve in 50 DEG C of vacuum
Steam, so that most reaction dissolvent evaporations is reclaimed.Product adds ethanol purge, filters, and forced air drying obtains
To 7.6 grams of chitin oligosaccharide.
7.6 grams of chitin oligosaccharide are added in the 40wt%NaOH solution of 160g.80 DEG C of insulations of reaction temperature
4 hours.After reaction terminates, 800mL ethanol is added to carry out precipitate with ethanol.The solid precipitation separating out is through filtration, ethanol
Cleaning, lyophilization obtains the yellow oligochitosan powder of 4.5g.The molecular weight of oligochitosan is 1800, deacetylation
For 83%.
Embodiment 6
At 20 DEG C, 10g chitin is slowly added into 300mL dichloroacetic acid.Stirring 6 hours, chitin is complete
5mL concentrated hydrochloric acid is added after CL.Improve reaction temperature to 70 DEG C, after stirring 1.5 hours, true at 60 DEG C
Empty revolving, makes most reaction dissolvent evaporations reclaim.Product adds ethanol purge, filters, and air blast is done
Dry obtain 7.0 grams of chitin oligosaccharide.
7.0 grams of chitin oligosaccharide are added in the 40wt%NaOH solution of 160g.80 DEG C of insulations of reaction temperature
4 hours.After reaction terminates, 800mL ethanol is added to carry out precipitate with ethanol.The solid precipitation separating out is through filtration, ethanol
Cleaning, lyophilization obtains the yellow oligochitosan powder of 4.1g.The molecular weight of oligochitosan is 2100, deacetylation
For 84%.
Embodiment result shows, the present invention makes chitin be dissolved in certain solvent and even phase under acid catalysiss first
Degraded obtains the chitin oligosaccharide of certain molecular weight, and chitin oligosaccharide is prepared through deacetylated process of highly basic again
Chitosan Oligosacchaides and oligochitosan.Glycosidic bond between due to acetylglucosamine is easier to be dropped under acid catalysed conditions
Solution, chitin degradation reaction can be carried out under mild conditions, and yield is high, and effectively realizes to molecular weight
Control.As shown in figure 1, showing from GPC gel chromatography, the present invention preparation Chitosan Oligosacchaides and oligochitosan point
Son amount can in the range of 1 thousand to 4 ten thousand continuously adjustabe, molecular weight distribution is narrower.
Claims (10)
1. a kind of chitin oligosaccharide, Chitosan Oligosacchaides and oligochitosan preparation method it is characterised in that:Make first
Chitin dissolves in a solvent, and even mutually degraded under acid catalysiss obtains chitin oligosaccharide, and chitin oligosaccharide is again
Prepare Chitosan Oligosacchaides and oligochitosan through the deacetylated process of highly basic.
2. the preparation method of chitin oligosaccharide according to claim 1, Chitosan Oligosacchaides and oligochitosan, its
It is characterised by, comprise the following steps that:
1) chitin pulverizer is scattered in solvent after pulverizing, and under strong stirring, chitin fills in a solvent
Divide swelling or dissolving;
2) chitin starts to degrade, and molecular weight gradually reduces, and through separation, purification, dry run, obtains first
Chitin oligosaccharide;
3) chitin oligosaccharide is added in strong base solution and carries out deacetylation, through separation, purification, drying
Process, obtains Chitosan Oligosacchaides and oligochitosan product.
3. the preparation method of chitin oligosaccharide according to claim 2, Chitosan Oligosacchaides and oligochitosan, its
It is characterised by, after chitin is dried through rinsing, then 80~200 mesh are crushed to using pulverizer.
4. the preparation method of chitin oligosaccharide according to claim 1 and 2, Chitosan Oligosacchaides and oligochitosan,
It is characterized in that, the chitinous solvent of dissolving is hexafluoroisopropanol, Hexafluoro acetone, dichlroroethanol, contains chlorination
The dimethylformamide of lithium, the dimethyl acetylamide containing lithium chloride, N- methyl morpholine oxide, concentrated hydrochloric acid, dense
One of sulphuric acid, strong phosphoric acid, pyrovinic acid, formic acid, dichloroacetic acid, trichloroacetic acid or two or more mixing
Compound, solvent load is 5~50 times of chitin quality.
5. the preparation method of chitin oligosaccharide according to claim 1 and 2, Chitosan Oligosacchaides and oligochitosan,
It is characterized in that, when using faintly acid solvent:Hexafluoroisopropanol, Hexafluoro acetone, dichlroroethanol, contain chlorination
The dimethylformamide of lithium, the dimethyl acetylamide containing lithium chloride, N- methyl morpholine oxide, formic acid, dichloro
Acetic acid, trichloroacetic acid one or more when, by adding hydrochloric acid or sulphuric acid, to improve chitinous fall
Solution speed.
6. the preparation method of chitin oligosaccharide according to claim 5, Chitosan Oligosacchaides and oligochitosan, its
It is characterised by, the hydrochloric acid adding in faintly acid solvent or sulphuric acid quality are the 0.2~12% of solvent quality.
7. the preparation method of chitin oligosaccharide according to claim 2, Chitosan Oligosacchaides and oligochitosan, its
It is characterised by, the separation of chitin oligosaccharide, purification, dry run, using solvent evaporation, precipitate with ethanol, post layer
Analysis, membrane separation technique are isolated and purified, and through vacuum drying, spray drying or forced air drying, obtain first
The oligomeric sugar product of chitin;Separation after chitin oligosaccharide deacetylation, purification, dry run, using alcohol
Heavy, column chromatography, membrane separation technique are isolated and purified, and through vacuum drying, spray drying or forced air drying,
Obtain Chitosan Oligosacchaides and oligochitosan product.
8. the preparation method of chitin oligosaccharide according to claim 7, Chitosan Oligosacchaides and oligochitosan, its
Be characterised by, alcohol deposition method adopt precipitate with ethanol reagent be methanol, ethanol, propanol, isopropanol, butanol, isoamyl alcohol,
One of acetone, butanone or two or more.
9. the preparation method of chitin oligosaccharide according to claim 2, Chitosan Oligosacchaides and oligochitosan, its
It is characterised by, chitin oligosaccharide deacetylation is to carry out in strong base solution, deacetylated process reaction temperature is
40~140 DEG C, 1~20 hour response time;Strong base solution adopt the NaOH solution of 10~60wt% or 10~
The KOH solution of 60wt%, strong base solution consumption is 5~20 times of chitin oligosaccharide quality.
10. the preparation method of chitin oligosaccharide according to claim 2, Chitosan Oligosacchaides and oligochitosan,
It is characterized in that, after chitin oligosaccharide is processed through highly basic is deacetylated, obtain deacetylation 50% to 98%
Chitosan Oligosacchaides or oligochitosan;Obtain the chitin oligosaccharide of different molecular weight by controlling degradation time, in de- second
After acyl, obtain when higher than 3000 when molecular weight is Chitosan Oligosacchaides, obtains when molecular weight is below 3000
Be oligochitosan.
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