CN105153326B - Chitosan alkyl urea and preparation method thereof - Google Patents
Chitosan alkyl urea and preparation method thereof Download PDFInfo
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- CN105153326B CN105153326B CN201510677730.XA CN201510677730A CN105153326B CN 105153326 B CN105153326 B CN 105153326B CN 201510677730 A CN201510677730 A CN 201510677730A CN 105153326 B CN105153326 B CN 105153326B
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Abstract
The present invention relates to chitosan alkyl urea and preparation method thereof, 1) chitosan of the deacetylation more than 98% is dissolved in watery hydrochloric acid, methanol and methylchloroformate are added into resulting solution again, in the pH value for adding triethylamine to control reaction system under low temperature, stirring, obtains chitosan N methoxymethylamides；2) by step 1) obtained chitosan N methoxymethylamides are dissolved in the N of lithium chloride, N dimethylacetamide solutions, add amine, reaction 6 24 chitosan alkyl urea.The beneficial effects of the present invention are：Prepared urea groups chitosan substitution value is high, compound with regular structure, the demand of a variety of applications, and the chitosan using deacetylation more than 98% can be met, without using completely deacetylated chitosan；Obtain the more diversified chitosan derivatives of structure.
Description
Technical field
The present invention relates to natural polymer and its chemical modification method, and in particular to chitosan-alkyl urea and its preparation side
Method.
Background technology
Chitosan, entitled poly- (Isosorbide-5-Nitrae the glycosides) -2- amino-betas-D-Glucose of chemistry, be it is a kind of be present in nature it is natural
Glycosaminoglycan, because it has unique physiology, pharmacological function and good biocompatibility and antibiotic property, and it is nontoxic, harmless,
It is readily biodegradable, therefore is widely used in medicine, food, cosmetics, agricultural, chemical industry, environmental protection, gene transport, cell training
In the multiple fields such as foster and organizational project.Further to expand the application of chitosan, chemistry is carried out to its amino and hydroxyl
Modification exploitation new product, particularly carries out selective modification to its amino and has great importance.
[(1) Zhang L., Shen J., Zuo W., Okamoto Y., Synthesis of chitosan such as Okamoto
3,6-diphenylcarbamate-2-urea derivatives and their applications as chiral
stationary phases for high-performance liquid chromatography,Journal of
Chromatography A,1365:86-93,2014] chitosan with ultrahigh deacetylation degree and isocyanates are reacted, prepared
Chitosan-two (carbamate)-(urea) of complete derivatization.Though prepared chitosan derivatives are with higher regular
Spend, but the reaction does not have hydroxyl and amino in selectivity, chitosan molecule and modified by same substituent, it is impossible to make derivative
Structure diversification, limits its application.
[(2) Cui Yun are opened Yan Fengmei etc., Xu Cheng, Yan Fengmei, the preparation of chitosan nano urea and sign, chemistry world, 9：
552-554,2014；(3) Zhao Yan tinkling of pieces of jade soup is accumulated virtue Yan Fengmei etc., the preparation of polyfluoro phenylcarbamido chitosan nano-material and sign, change
Work new material, 42 (5)：156-160,2014], as urea groups reagent, to splice method using substructure containing fluorophenylisocyanate
The positioning of fluorine-containing phenylisocyanate is incorporated on chitosan, fluorine-containing phenylcarbamido chitosan nano-material has been made.In the reaction,
Using deacetylation be 92% chitosan as raw material, in prepared chitosan derivatives still contain part acetylamino, it is difficult to
Form regular higher structure.
In actual application, the performance of natural polymer and the regularity of its structure are closely related, for example：With urea groups
When changing chitosan derivatives as Chiral selectors, the regularity of derivative is higher, and its chiral separation performance is better[1].Using position
The small primary amine of resistance carries out urea groups to the amino in chitosan molecule, can strengthen the intermolecular hydrogen bond action of chitosan derivatives,
So as to improve the regularity and its stability of chitosan derivatives molecule higher structure.Therefore, urea is introduced in chitosan molecule
Base, can make its derivative have more superior performance and widely application.However, the research on chitosan urea groups at present
It is rarely reported.
In addition, a kind of ripe method is there is no at present, can be under conditions of hydroxyl be by reaction, effectively by chitosan point
The complete urea groups of amino in son.
So, the regular urea groups chitosan of design structure simultaneously sets up effective preparation method, for expanding chitosan
Application is significant.
The content of the invention
The technical problems to be solved by the invention are to fill up existing technological gap there is provided a kind of shell of high substituted degree to gather
Sugar-alkyl urea and preparation method thereof.
In order to solve the above technical problems, the technical solution adopted by the present invention is：Chitosan-alkyl urea, it has following knot
Structure formula：
Wherein：0.98≤x≤1.00；n≥10；R is the aliphatic group of 3-12 carbon atom, but does not include t-butyl form hydrocarbon
Base.
The present invention also provides the preparation method of above-mentioned chitosan-alkyl urea, and its step is as follows：
1) methoxy methyl of amino of chitosan is acylated：Chitosan of the deacetylation more than 98% is dissolved in watery hydrochloric acid,
Or the small water-soluble chitosan of molecular weight is directly dissolved in water, then add into resulting solution appropriate methanol and excess
Methylchloroformate, under low temperature plus triethylamine control reaction system pH value between 2-7, stir 3-8h, obtain chitosan-
N- methoxymethylamides；
2) urea groups of chitosan-N- methoxymethylamides：Chitosan-N- the methoxymethylamides that step (1) is obtained
It is dissolved in the DMA solution of lithium chloride, adds excessive amine, in reaction life in 6-24 hours at 100-130 DEG C
Into chitosan derivatives, i.e. chitosan-alkyl urea.
Reaction equation involved in the present invention is as follows：
It is generally acknowledged that the chemical constitution of macromolecular structure unit is more consistent, its higher structure is more regular.Cellulose gathers with shell
Sugar has closely similar chemical constitution, and Okamoto etc. is once prepared for bonded chiral separation material with cellulose, when cellulose spreads out
When the biological degree of cross linking is 2%, prepared chiral stationary phase still has good separating property [(4) Ikai T., Yamamoto
C.,Kamigaito M.,Okamoto Y.,Immobilized-type chiral packing materials for HPLC
based on polysaccharide derivatives,Journal of Chromatography B,875:2–11,
2008；(5)Ikai T.,Yamamoto C.,Kamigaito M.,Okamoto Y.,Immobilization of
polysaccharide derivatives onto silica gel Facile synthesis of chiral packing
materials by means of intermolecular polycondensation of triethoxysilyl
groups,Journal of Chromatography A,1157:151-158,2007], when the degree of cross linking continues to rise, separation
Performance then declines, and this indicates that its higher structure is still more when the repeat unit structure that cellulose derivative has 98% is identical
It is regular.If such as different with aromatic radical by the chitosan in the present invention-further derivatization of alkyl urea, i.e. systematic function material
Cyanate is modified, and can prepare chiral separation material.The chitosan that the present invention is not less than 98% using deacetylation makees raw material, closes
Into chitosan-alkyl urea, because of the acetylamino content in chitosan-alkyl urea seldom, chitosan-hydrocarbon containing acetylamino on a small quantity
Base urea will also lose during it is isolated and purified, so prepared chitosan-alkyl urea should have regular senior knot
Structure.Functionalization material is prepared by raw material of this chitosan-alkyl urea also has regular higher structure certainly.
Step 1 of the present invention) in dissolve chitosan with watery hydrochloric acid, for (relative point of the small water soluble chitosan of molecular weight
8000) protonatomic mass is less than, and directly can be dissolved in water, and solubility of the methylchloroformate in system can be increased by adding methanol,
Reaction is set to be carried out in homogeneous, triethylamine is used for the HCl produced during neutralization reaction, adjusts the pH value of reaction system.In addition,
Water and methanol can consume excessive methylchloroformate, therefore, it is ensured that the hydroxyl in chitosan molecule is not reacted.
Step 1 of the present invention) described in dissolving chitosan watery hydrochloric acid concentration it is as small as possible, add the amount of methanol poly- with shell
Sugar is separated out not from solution and methylchloroformate can dissolve and be limited；Step 2) described in chitosan-N- methoxymethylamides it is molten
In the DMA solution of lithium chloride, wherein the concentration of lithium chloride can make chitosan-N- methoxymethylamides molten
Solution.
Step 1 of the present invention) described in methylchloroformate molal quantity and chitosan the ratio between the molal quantity of repeat unit no
Less than 3:1, described cryogenic temperature is 2-15 DEG C.
Step 2 of the present invention) if used in amine boiling point be less than reaction temperature, need to react in enclosed system, for boil
The higher amine of point, can directly in dry system back flow reaction.
Step 2 of the present invention) described in amine molal quantity and chitosan-N- methoxymethylamides repeat unit molal quantity
The ratio between be not less than 4:1.
The beneficial effects of the present invention are：
1. the invention provides a kind of complete chitosan urea groups method, prepared urea groups chitosan substitution value
Height, compound with regular structure can meet the demand of a variety of applications, and the chitosan using deacetylation more than 98%, without
Use completely deacetylated chitosan；
2. the invention provides a series of chitosan of almost complete urea groups, and react and only occur on amino, hydroxyl
Base can be further modified, the more diversified chitosan derivatives of preparation structure；
3. a series of urea groups chitosans that the present invention is provided, just can systematic function height after its hydroxyl further modification
Molecular material.Urethane, the chiral separation material regular with regard to that can prepare higher structure such as are carried out to its hydroxyl.
Brief description of the drawings
Fig. 1 is the chitosan-N- methoxymethylamides (a) and chitosan-benzylurea (b) prepared by the embodiment of the present invention 1
Infrared spectrum comparison diagram；
Fig. 2 is chitosan-benzylurea prepared by the embodiment of the present invention 11H NMR spectras；
Fig. 3 is the thermogravimetric analysis figure of chitosan-benzylurea prepared by the embodiment of the present invention 1.
Embodiment
To make those skilled in the art more fully understand the present invention, the present invention is done further in detail with reference to embodiment
Explanation, but present disclosure is not limited solely to the following examples.
The preparation method of chitosan used in the present invention and the equal reference literature of the assay method of molecular weight [(6) Bai Zhengwu
Deng (aromatic radical carbamate)-(acid amides) of chitosan-two and preparation method thereof [P], application number：201410594564.2].
DMAC N,N' dimethyl acetamide (DMAc) used in the present invention uses preceding warpMolecular sieve drying 3 times, LiCl is used
It is preceding to be calcined more than 3 hours within more than 24 hours or 300 DEG C in vacuum drying at 140 DEG C.
Embodiment 1
The synthesis of chitosan-benzylurea：
The synthesis of chitosan-N- methoxymethylamides：By 1.0g (6.2mmol repeat units) chitosan (number-average molecular weight 9
Ten thousand, deacetylation is 99.2%) to be added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Again
35g methanol is added under ice-water bath, after stirring, 5.9g methylchloroformates (62.7mmol) are rapidly joined, control temperature exists
Add triethylamine regulation system pH value in 2-10 DEG C of reaction 8h, course of reaction, control ph is between 2-7.After completion of the reaction, to anti-
Answer and 50mL ethanol is added in bottle and is stirred vigorously, filter, product is washed to neutrality with ethanol, dries, obtains chitosan-N- methoxies
Base formamide 1.27g, yield：93%；Shown in infrared spectrogram such as accompanying drawing 1 (a)：IR(KBr,cm-1)υ:3439,3325(-OH,-
NH-),2950-2887(-C-H),1704(-COOCH3), 1549 (- NH-).
The preparation of chitosan-benzylurea：The LiCl that 1.5g is dried is taken in 100mL three-necked flasks, adds what 20mL was dried
DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.0g chitosan-N- methoxymethylamides
(4.57mmol), stirring and dissolving adds 4.0g benzylamines (37.4mmol) after slightly cooling down, stirs, be warming up to 120 DEG C of reactions
24h, the gel of generation is poured into ethanol smash to pieces after cooling, filtering, solid wash 3 times with ethanol, drying, obtain chitosan-
Benzylurea 1.25g, yield：93%；Shown in infrared spectrogram such as accompanying drawing 1 (b)：IR(KBr,cm-1)υ:3340(-OH,-NH-),
2923-2873 (- C-H), 1643 (- CONH-), 1560 (- NH- ,-Ph), from figure 1 it appears that (a) is in 1704cm-1Place has
Significantly (- CO2-) absworption peak, and 1700cm in (b)-1Neighbouring absworption peak is almost wholly absent, and in 1643cm-1Near
There is stronger (- CONH-) absworption peak, illustrate that amine ester exchange reaction is complete；1H NMR spectras are as shown in Figure 2：1H NMR
(600MHz,25℃,CF3COOD,δ/ppm):5.01-3.97 (- CH on m, 9H, chitosan skeleton H and benzyl2-),7.55(m,
5H, phenyl ring H), amino is almost completely by urea groups in chitosan molecule it can be seen from integral area ratio；Elementary analysis (%)：
Calculated value (C14H18N2O5·1.2H2O)nC 53.23, H 6.51, N 8.87；Measured value C 53.62, H 6.73, N 8.16；Cause
The deacetylation of chitosan is close to 100%, so chitosan derivatives Elemental Analysis theory is just gathered by completely deacetylated shell
Sugar derivatives repeat unit molecular formula is calculated.Due to containing great amount of hydroxy group and acid amides in prepared chitosan-benzylurea, therefore
It easily absorbs water.Thermogravimetric analysis is as shown in Figure 3：When temperature is by rising to 180 DEG C for 25 DEG C, the weight of chitosan-benzylurea
It is gradually reduced, shows gradually dehydration, it is about 7.0% to calculate water content according to figure, and this result according to elemental analysis value with calculating
Water content (6.8%) match.
Embodiment 2
The synthesis of chitosan-normal-butyl urea：
The preparation of chitosan-N- methoxymethylamides：By 1.0g (6.2mmol repeat units) chitosan (number-average molecular weight 3
Ten thousand, deacetylation 99.7%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Exist again
28g methanol is added under ice-water bath, after stirring, 4.82g methylchloroformates (51.3mmol) are rapidly joined, control temperature is in 2-
Add triethylamine regulation system pH value in 8 DEG C of reaction 8h, course of reaction, control ph is between 2-7.After completion of the reaction, to reaction
50mL ethanol is added in bottle and is stirred vigorously, is filtered, product is washed to neutrality with ethanol, dries, obtains chitosan-N- methoxyl groups
Formamide 1.25g, yield：92%.
The preparation of chitosan-normal-butyl urea：The LiCl that 1.2g is dried is taken in 50mL three-necked flasks, adds what 15mL was dried
DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.0g chitosan-N- methoxymethylamides
(4.57mmol), stirring and dissolving adds 3.33g n-butylamines (45.7mmol) after slightly cooling down, stirs, reaction solution is transferred to
In closed container, 120 DEG C of reaction 24h are maintained the temperature at, the gel of generation is poured into ethanol after cooling and smashed to pieces, is filtered, will be solid
Body is washed 3 times with ethanol, is dried, is obtained chitosan-normal-butyl urea 1.1g, yield：92%.
Embodiment 3
The synthesis of chitosan-n-octyl urea：
The preparation of chitosan-N- methoxymethylamides：By 2.0g (12.4mmol repeat units) chitosan (number-average molecular weight
60000, deacetylation 98.7%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Again
60g methanol is added under ice-water bath, after stirring, 9.5g methylchloroformates (101.1mmol) are rapidly joined, control temperature exists
Add triethylamine regulation system pH value in 2-7 DEG C of reaction 6h, course of reaction, control ph is between 2-7.After completion of the reaction, to anti-
Answer and 100mL ethanol is added in bottle and is stirred vigorously, filter, product is washed to neutrality with ethanol, dries, obtains chitosan-N- first
Epoxide formamide 2.44g, yield：90%.
The preparation of chitosan-n-octyl urea：The LiCl that 2.50g is dried is taken in 100mL three-necked flasks, 50mL is added and dries
DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 2.0g chitosan-N- methoxymethylamides
(9.14mmol), stirring and dissolving so adds 9.4g n-octyl amines (73.0mmol), stirred, and is warming up to 115 DEG C and keeping temperature
8h is reacted at 115-120 DEG C, the gel of generation is poured into ethanol after cooling and smashed to pieces, filters, solid is washed 3 times with ethanol,
Dry, obtain chitosan-n-octyl urea 2.75g, yield：96%.
Embodiment 4
The synthesis of chitosan-dodecyl urea：
The preparation of chitosan-N- methoxymethylamides：By 3.0g (18.6mmol repeat units) chitosan (number-average molecular weight
0.2 ten thousand, deacetylation 100%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Again
90g methanol is added under ice-water bath, after stirring, 12g methylchloroformates (127.6mmol) are rapidly joined, control temperature exists
Add triethylamine regulation system pH value in 5-13 DEG C of reaction 5h, course of reaction, control ph is between 2-7.After completion of the reaction, to anti-
Answer and 150mL ethanol is added in bottle and is stirred vigorously, filter, product is washed to neutrality with ethanol, dries, obtains chitosan-N- first
Epoxide formamide 3.9g, yield：96%.
The preparation of chitosan-dodecyl urea：The LiCl that 1.2g is dried is taken in 50mL three-necked flasks, 12mL is added and does
Dry DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.0g chitosan-N- methoxymethylamides
Then (4.57mmol), stirring and dissolving adds 7.0g n-dodecylamines (37.8mmol), stirs, be warming up to 130 DEG C of reactions
6h, the gel of generation is poured into ethanol smash to pieces after cooling, filtering, and solid wash 3 times with ethanol, and drying obtains chitosan-just
Dodecyl urea 1.60g, yield：95%.
Embodiment 5
The synthesis of chitosan-cyclohexyl urea：
The preparation of chitosan-N- methoxymethylamides：By 2.0g (12.4mmol repeat units) chitosan (number-average molecular weight
140000, deacetylation 99.4%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Again
60g methanol is added under ice-water bath, after stirring, 7.0g methylchloroformates (74.5mmol) are rapidly joined, control temperature exists
Add triethylamine regulation system pH value in 5-12 DEG C of reaction 5h, course of reaction, control ph is between 2-7.After completion of the reaction, to anti-
Answer and 100mL ethanol is added in bottle and is stirred vigorously, filter, product is washed to neutrality with ethanol, dries, obtains chitosan-N- first
Epoxide formamide 2.56g, yield：94%.
The preparation of chitosan-cyclohexyl urea：The LiCl that 1.3g is dried is taken in 50mL three-necked flasks, adds what 30mL was dried
DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.0g chitosan-N- methoxymethylamides
(4.57mmol), stirring and dissolving adds 3.65g cyclohexylamine (39.7mmol), stirs, be warming up to 100 DEG C of reactions after dissolving
14h, the gel of generation is poured into ethanol smash to pieces after cooling, filtering, solid wash 3 times with ethanol, drying, obtain chitosan-
Cyclohexyl urea 1.20g, yield：94%
Embodiment 6
The synthesis of chitosan-(4- methyl-benzyls)-urea：
The preparation of chitosan-N- methoxymethylamides：By 1.0g (6.2mmol repeat units) chitosan (number-average molecular weight
350000, deacetylation 98.4%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Again
40g methanol is added under ice-water bath, after stirring, 5.0g methylchloroformates (53.2mmol) are rapidly joined, control temperature exists
Add triethylamine regulation system pH value in 5-15 DEG C of reaction 3h, course of reaction, control ph is between 2-7.After completion of the reaction, to anti-
Answer and 50mL ethanol is added in bottle and is stirred vigorously, filter, product is washed to neutrality with ethanol, dries, obtains chitosan-N- methoxies
Base formamide 1.25g, yield：92%.
The preparation of chitosan-(4- methyl-benzyls)-urea：Take the LiCl that 1.8g is dried in 50mL three-necked flasks, add
The DMAc that 25mL is dried, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.18g chitosan-N- methoxyl group formyls
Amine (5.39mmol), stirring and dissolving is warming up to after 100 DEG C and adds 5.31g 4- methylbenzylamines (43.5mmol), stirs, and protects
Hold temperature and react 24h at 100-105 DEG C, the gel of generation is poured into ethanol after cooling and smashed to pieces, filter, solid is washed with ethanol
Wash 3 times, dry, obtain chitosan-(4- methyl-benzyls)-urea 1.60g, yield：96%.
Embodiment 7
The synthesis of chitosan-isobutyl group urea：
The preparation of chitosan-N- methoxymethylamides：By 2.0g (12.4mmol repeat units) chitosan (number-average molecular weight
40000, deacetylation 99.4%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for watery hydrochloric acid stirring.Again
60g methanol is added under ice-water bath, after stirring, 10.0g methylchloroformates (106.4mmol) is rapidly joined, controls temperature
Add triethylamine regulation system pH value in 5-13 DEG C of reaction 3h, course of reaction, control ph is between 2-7.After completion of the reaction, to
100mL ethanol is added in reaction bulb and is stirred vigorously, is filtered, product is washed to neutrality with ethanol, dries, obtains chitosan-N-
Methoxymethylamide 2.54g, yield：93%
The preparation of chitosan-isobutyl group urea：The LiCl that 2.0g is dried is taken in 50mL three-necked flasks, adds what 30mL was dried
DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.8g chitosan-N- methoxymethylamides
(8.23mmol), stirring and dissolving adds 6.00g isobutyl amines (82.2mmol) after slightly cooling down, stirs, reaction solution is transferred to
In closed container, 120 DEG C of reaction 12h are maintained the temperature at, the gel of generation is poured into ethanol after cooling and smashed to pieces, is filtered, will be solid
Body is washed 3 times with ethanol, is dried, is obtained chitosan-isobutyl group urea 2.00g, yield：94%.
Embodiment 8
The synthesis of chitosan-isopropyl urea：
The preparation of chitosan-N- methoxymethylamides：By 1.0g (6.2mmol repeat units) chitosan (number-average molecular weight
0.2 ten thousand, deacetylation 100%) it is added in 250mL there-necked flasks, plus to be dissolved to chitosan as clear as crystal for distilled water stirring.Again
20g methanol is added under ice-water bath, after stirring, 1.75g methylchloroformates (18.6mmol) are rapidly joined, control temperature exists
Add triethylamine regulation system pH value in 2-7 DEG C of reaction 3h, course of reaction, control ph is between 2-7.After completion of the reaction, to anti-
Answer and 50mL ethanol is added in bottle and is stirred vigorously, filter, product is washed to neutrality with ethanol, dries, obtains chitosan-N- methoxies
Base formamide 1.27g, yield：93%
The preparation of chitosan-isopropyl urea：The LiCl that 1.0g is dried is taken in 50mL three-necked flasks, adds what 15mL was dried
DMAc, heating is completely dissolved LiCl, maintains the temperature at 80 DEG C, adds 1.0g chitosan-N- methoxymethylamides
(4.57mmol), stirring and dissolving is cooled to after room temperature and adds 2.7g isopropylamines (45.7mmol), stirs, and reaction solution is turned
Move in closed container, react 12h at 120 DEG C, the gel of generation is poured into ethanol after cooling and smashed to pieces, filter, solid is used
Ethanol is washed 3 times, is dried, is obtained chitosan-isopropyl urea 1.05g, yield：94%.
Claims (2)
1. the preparation method of chitosan-alkyl urea, described chitosan-alkyl urea has following general structure：
Wherein：0.98≤x≤1.00；n≥10；R is the aliphatic group of 3-12 carbon atom, but including t-butyl form alkyl,
It is characterized in that step is as follows：
1) methoxy methyl of amino of chitosan is acylated：Chitosan of the deacetylation more than 98% is dissolved in watery hydrochloric acid, or
The small water-soluble chitosan of molecular weight is directly dissolved in water, then adds into resulting solution appropriate methanol and excessive chlorine
Methyl formate, the amount of described addition methanol is separated out with chitosan not from solution and methylchloroformate can dissolve and be limited, in low
The lower pH value for adding triethylamine control reaction system of temperature stirs 3-8h, obtains chitosan-N- methoxymethylamides, institute between 2-7
The ratio between the molal quantity for the methylchloroformate stated and the molal quantity of repeat unit of chitosan are not less than 3:1, described cryogenic temperature
For 2-15 DEG C；
2) urea groups of chitosan-N- methoxymethylamides：Chitosan-N- methoxymethylamides the dissolving that step (1) is obtained
In the DMA solution of lithium chloride, excessive amine is added, shell is generated in reacting 6-24 hours at 100-130 DEG C
Polysaccharid derivative, i.e. chitosan-alkyl urea.
2. the preparation method of chitosan according to claim 1-alkyl urea, it is characterised in that step 2) described in amine rub
The ratio between molal quantity of repeat unit of that number and chitosan-N- methoxymethylamides is not less than 4:1.
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