CN106432543B - A kind of O- acetamide Chitosan Schiff-base and preparation method thereof - Google Patents
A kind of O- acetamide Chitosan Schiff-base and preparation method thereof Download PDFInfo
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- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
The invention discloses a kind of O- acetamide Chitosan Schiff-bases and preparation method thereof, and nucleophilic substitution occurs by benzaldehyde Chitosan Schiff-base and chloroacetamide, O- acetamide Chitosan Schiff-base is made.The modified position of O- acetamide Chitosan Schiff-base of the invention determines that purity is high has flocculation and bactericidal effect well, and protects by using schiff base reaction to amino of chitosan, and hydroxyl is enable to achieve the effect that positioning is modified.
Description
Technical field
The invention belongs to technical field of fine, are related to a kind of O- acetamide Chitosan Schiff-base, further relate to above-mentioned O-
The preparation method of acetamide Chitosan Schiff-base.
Background technique
Chitosan is unique a large amount of existing basic amine group polysaccharide in natural polysaccharide, and its chemical name is (Isosorbide-5-Nitrae) -2- ammonia
Base -2- deoxidation-β-D-Glucose or abbreviation poly glucosamine.Chitosan is to be obtained by chitin through deacetylation,
It is the most important derivative of chitin.It is a kind of positively charged high molecular polymer, it is from a wealth of sources, non-toxic and tasteless, tool
There are good biocompatibility and biological degradability.Its C2Position-NH2, C6Position-OH and C3It is a series of special that position-OH makes it have
Function and property, such as have to suspended solid particles, organic dyestuff, protein, metal ion, microorganism in waste water certain
Flocculation.Compared with other flocculants, chitosan there are also adding less, can with organic acid at salt the features such as.In addition, chitosan
With broad spectrum antibacterial, there is apparent inhibition to make Escherichia coli, hay bacillus, staphylococcus aureus, Bacillus acidi lactici etc.
With.The excellent property of chitosan is widely applied it all in various fields, however its water-insoluble is to a certain degree
On be not able to satisfy application requirement still, significantly limit its application range.This is mainly due in chitosan structure hydroxyl and
Amino has certain regularity in arrangement, so that there are strong hydrogen bond actions for linear chitosan molecule interchain, as a result
Cause chitosan to have higher crystallinity, can only be dissolved in the diluted acid of part.By the method for chemical modification to chitosan into
Row is modified, and can be increased the active group of chitosan and be improved its water solubility, so that the condition for applying it is more wide in range and mentions
Its high application performance.
Shen Hongjie etc. (" Cellulose Science and technology " 2014,04:28-33) is under ultrasonic wave effect, with homemade low point
Son amount carboxymethyl chitosan and vanillic aldehyde are raw material, are prepared for low molecular weight carboxymethyl chitosan sugar vanillin schiff bases, by anti-
Bacterium experiment finds it with good anti-microbial property.
Ma Quanhong etc. (" chemical reagent " 2000,06:327-330.) utilizes chitosan C2Active amino and α -one penta on position
Diacid carries out macromolecular reaction, has synthesized the functional polymer with schiff bases group, α-ketoglutaric acid modification of chitosan is to Cu
(II) and Zn (II) has good absorption property.
Li Yunju etc. (" China Dissertation Database " 2009, University Of Chongqing's Master's thesis, 2009,10.) is to a series of
Corrosion inhibition and mechanism of the chitosan oligosaccharide and its Schiff bases derivative of good water solubility in 3.5%NaCl medium are ground
Study carefully, carboxymethyl chitosan oligosaccharide vanillic aldehyde schiff bases has good corrosion inhibition.
In conclusion the research of Chitosan Schiff-base class compound can be applicable to antibacterial, catalysis, inhibition, absorption than wide
Etc. various aspects, have application in fields such as medicine, weaving, papermaking, water process.Therefore, Chitosan Schiff-base is carried out further
Study on the modification is very necessary.
Summary of the invention
The purpose of the present invention is to provide a kind of O- acetamide Chitosan Schiff-bases, are modified position and determine, purity is high, tool
There are flocculation and bactericidal effect well.
The object of the invention is also to provide the preparation methods of above-mentioned O- acetamide Chitosan Schiff-base, by using Schiff
Amino of chitosan is protected in alkali reaction, and hydroxyl is enable to achieve the effect that positioning is modified.
The purpose of the present invention is achieved through the following technical solutions:
The chemical formula of this O- acetamide Chitosan Schiff-base are as follows:
Wherein, 0.13 x, y 0.87, z 0.60-0.95.
Another technical solution of the invention is the preparation method of above-mentioned O- acetamide Chitosan Schiff-base, including passes through benzene first
Nucleophilic substitution occurs for aldehyde Chitosan Schiff-base and chloroacetamide, obtains O- acetamide Chitosan Schiff-base.
Wherein the detailed process of nucleophilic substitution is:
Step 1,1 part of chitosan is taken by mass fraction, taking 50 parts of concentration by volume parts is 1% acetic acid solution, by shell
Glycan is added in acetic acid solution, obtains lysate；
Step 2, the pH that sodium hydroxide solution is added into lysate, and adjusts lysate is 7, then carries out filtering and remove
Water is removed, and is washed using ethyl alcohol, filter cake a is obtained；
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol that 50 parts are taken by volume parts, stirs 1h, and be warming up to 40-80
DEG C, then the benzaldehyde ethanol solution that volume parts are 20 parts and the benzaldehyde that mass fraction is 0.6-3.2 parts is added dropwise, the reaction was continued
3-7h obtains suspension a；
Step 4, it is 30 parts of ethyl alcohol that volume parts are added into suspension a, is filtered after standing, then successively with ethyl alcohol and
Acetone washing obtains filter cake b；
Step 5, after 35 parts of isopropanol and 5 parts of sodium hydroxide solution mixing are taken by volume parts, it is added in filter cake b
In, the chloroacetamide aqueous solution that volume parts are 20 parts and the chloracetyl that mass fraction is 0.6-1.7 parts are added dropwise at 30-50 DEG C
After amine, the reaction was continued 4-6h obtains suspension b；
Step 6, the ethyl alcohol that volume parts are 30 parts is added into suspension b, is filtered after standing, then successively uses ethyl alcohol
It is washed with acetone, reusing ethyl alcohol is solvent soxhlet type, obtains O- acetamide chitosan seat after dry at 30-50 DEG C
Husband's alkali.
Further, the features of the present invention also characterized in that:
Wherein the molecular weight of the chitosan in step 1 is 700,000, deacetylation 87%.
Wherein 20min, mixing speed 200-300r/min is stirred at room temperature in chitosan and acetic acid solution in step 1,
It is completely dissolved to chitosan.
Wherein the benzaldehyde in step 3 carried out distillation processing.
Wherein the time of Soxhlet extraction is 6-8h in step 6.
Wherein the mass concentration of sodium hydroxide solution described in step 5 is 20%, and filter cake b is added and stirs at room temperature later
Mix 30min, mixing speed 200-300r/min.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.60-0.95 in chemical formula.
The beneficial effects of the present invention are: raw materials of chitosan used in the present invention, benzaldehyde etc., from a wealth of sources, it is produced into
This is lower, and reaction condition is mild, and reaction process is continuous, and easy to operate.Compared with other chitin modified methods, this method tool
There is raw material availability height, amino of chitosan is protected by using schiff base reaction, hydroxyl is enable to reach the modified effect of positioning
The advantages that fruit, chitosan carry out selective reaction and make reaction site clear, favorable reproducibility, the grafting rate of product is easy to control,
Determine, purity is high that there is flocculation and bactericidal effect well so that it is modified position.
Further, the O- acetamide Chitosan Schiff-base that the present invention synthesizes not only has the typical characteristics of schiff bases,
Such as to the adsorptivity of metal ion, rust inhibition, and by giving chitosan C6Position-OH is grafted acetamido, improves fragrance
The water solubility of base Chitosan Schiff-base increases the functional activity group of chitosan.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram of O- acetamide Chitosan Schiff-base of the present invention；
Fig. 2 is the contrast schematic diagram of nucleus magnetic hydrogen spectrum of the present invention.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawing:
The present invention provides a kind of O- acetamide Chitosan Schiff-base, chemical formulas are as follows:
Wherein x is 0.13, y 0.87, z 0.60-0.95.
The present invention also provides the preparation methods of above-mentioned O- acetamide Chitosan Schiff-base, pass through benzaldehyde chitosan Schiff
Nucleophilic substitution occurs for alkali and chloroacetamide, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1 part of chitosan is taken by mass fraction, the molecular weight of chitosan is 700,000, deacetylation 87%, by body
Product number takes 50 parts of acetic acid solution, and chitosan is added in acetic acid solution, 20min is stirred at room temperature, mixing speed is
200-300r/min obtains lysate until chitosan is completely dissolved.
Step 2, the pH that sodium hydroxide solution is added into lysate, and adjusts lysate is 7, then carries out filtering and remove
Water is removed, and is washed using ethyl alcohol, filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol that 50 parts are taken by volume parts, stirs 1h, and be warming up to 40-80
DEG C, then the benzaldehyde ethanol solution that volume parts are 20 parts and the benzaldehyde that mass fraction is 0.6-3.2 parts is added dropwise, wherein benzene first
Aldehyde carried out distillation processing, and the reaction was continued 3-7h obtains suspension a.
Step 4, it is 30 parts of ethyl alcohol that volume parts are added into suspension a, is filtered after standing, then successively with ethyl alcohol and
Acetone washing obtains filter cake b.
Step 5,35 parts of isopropanol is taken by volume parts and sodium hydroxide solution that 5 parts of mass concentrations are 20% mixes
Afterwards, filter cake b is added thereto, 30min, mixing speed 200-300r/min is stirred at room temperature；Then it is dripped at 30-50 DEG C
Add the chloroacetamide aqueous solution that volume parts are 20 parts and the chloroacetamide that mass fraction is 0.6-1.7 parts, the reaction was continued 4-6h,
Obtain suspension b.
Step 6, the ethyl alcohol that volume parts are 30 parts is added into suspension b, is filtered after standing, then successively uses ethyl alcohol
It is washed with acetone, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 6-8h, dry at 30-50 DEG C
After obtain O- acetamide Chitosan Schiff-base.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87 in chemical formula, and z 0.60-0.95, wherein z value is matched with the reaction temperature in step, material
Than and the reaction time difference and change.
The preparation process chemical reaction process of O- acetamide Chitosan Schiff-base of the present invention is as shown in Figure 1: firstly, chitosan
Nucleophilic addition, C on chitosan are carried out with benzaldehyde2- the NH of position2Band on N atom attack carbonyl group with lone electron pair
There is the C atom of positive charge, complete nucleophilic addition, form intermediate product Alpha-hydroxy aminated compounds, then further dehydration
Form schiff bases.The schiff bases of formation further carries out S with chloroacetamideN2 nucleophilic substitutions, chitosan C6H on the-OH of position
Atom is replaced by acetamido.
Lines 1 are the nucleus magnetic hydrogen spectrum figure of chitosan raw material in Fig. 2, and lines 2 are the nuclear-magnetism of O- acetamide Chitosan Schiff-base
Hydrogen spectrogram.It can be seen from the figure that chitosan saccharide ring H-3, H-4 are belonged at the multiplet peak of δ=3.4~3.8 in lines 1,
H-5, H-6；Unimodal near δ=1.92 belongs to-CH in N- acetamido3；Unimodal near δ=3.03 belongs to C2
On amino Hydrogen Proton.Compared with lines 1, the appearance near δ=1 illustrates to have connected-CH on chitosan lines 22, in δ
Appearance near=8.0, illustrates that amide group connects on chitosan.Resonance spectrum band in δ=7~8 corresponds to the hydrogen on phenyl ring
Proton；Prove that O- acetamide Chitosan Schiff-base is successfully synthesized.
Product of the invention is 60%~95% by the condensation rate that elemental microanalysis method determines schiff bases；Pass through titration
The grafting rate of chitosan graft acetamide is determined up to 90%.
Synthetic method of the present invention is simple, strong operability, favorable reproducibility, and controllable by the product graft rate that this method synthesizes
Property is strong, and molecular weight is big.The O- acetamide Chitosan Schiff-base of synthesis, not only with schiff bases typical characteristics, such as to metal from
The adsorptivity of son, rust inhibition, and give chitosan C6The acetamido of position-OH grafting improves aromatic radical Chitosan Schiff-base
Water solubility increases the functional activity group of chitosan.Therefore, O- acetamide Chitosan Schiff-base of the invention is in medicine, function
There is higher application value in the fields such as energy high molecular material, Treatment of Industrial Water, food processing, textile and paper.
A kind of specific embodiment of the preparation method of O- acetamide Chitosan Schiff-base of the present invention are as follows:
Embodiment 1
A kind of preparation method of O- acetamide Chitosan Schiff-base is sent out by benzaldehyde Chitosan Schiff-base and chloroacetamide
Raw nucleophilic substitution, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1g chitosan is taken, the molecular weight of chitosan is 700,000, and deacetylation 87%, taking 50ml concentration is 1%
Acetic acid solution, chitosan is added in acetic acid solution, 20min, mixing speed 240r/min is stirred at room temperature, until shell is poly-
Sugar is completely dissolved, and obtains lysate.
Step 2, into lysate be added 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, then into
Row, which filters, removes water, and is washed using ethyl alcohol, and filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol for taking 50ml, stirs 1h, and be warming up to 60 DEG C, then 20ml is added dropwise
Benzaldehyde ethanol solution and 1.9g benzaldehyde, wherein benzaldehyde carried out distillation processing, and the reaction was continued 4h obtains suspension
a。
Step 4, the ethyl alcohol of 30ml is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone washing,
Obtain filter cake b.
Step 5, after taking isopropanol and the 5ml mass concentration of 35ml to mix for 20% sodium hydroxide solution, filter cake b is added
Enter wherein, 30min, mixing speed 200r/min is stirred at room temperature；Then the chloracetyl aqueous amine of 20ml is added dropwise at 40 DEG C
The chloroacetamide of solution and 0.6g, the reaction was continued 5h obtain suspension b.
Step 6, the ethyl alcohol of 30ml is added into suspension b, is filtered after standing, is then successively carried out using ethyl alcohol and acetone
Washing, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 6h, obtains O- acetamide shell after dry at 40 DEG C
Glycan schiff bases.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.60 in chemical formula.
Embodiment 2
A kind of preparation method of O- acetamide Chitosan Schiff-base is sent out by benzaldehyde Chitosan Schiff-base and chloroacetamide
Raw nucleophilic substitution, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1g chitosan is taken, the molecular weight of chitosan is 700,000, and deacetylation 87%, taking 50ml concentration is 1%
Acetic acid solution, chitosan is added in acetic acid solution, 20min, mixing speed 300r/min is stirred at room temperature, until shell is poly-
Sugar is completely dissolved, and obtains lysate.
Step 2, into lysate be added 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, then into
Row, which filters, removes water, and is washed using ethyl alcohol, and filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol for taking 50ml, stirs 1 hour, and be warming up to 70 DEG C, then be added dropwise
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 0.6g, wherein benzaldehyde carried out distillation processing, and the reaction was continued 3h is hanged
Supernatant liquid a.
Step 4, the ethyl alcohol of 30ml is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone washing,
Obtain filter cake b.
Step 5, after taking isopropanol and the 5ml mass concentration of 35ml to mix for 20% sodium hydroxide solution, filter cake b is added
Enter wherein, 30min, mixing speed 300r/min is stirred at room temperature；Then the chloracetyl aqueous amine of 20ml is added dropwise at 30 DEG C
The chloroacetamide of solution and 1.1g, the reaction was continued 4h obtain suspension b.
Step 6, the ethyl alcohol of 30ml is added into suspension b, is filtered after standing, is then successively carried out using ethyl alcohol and acetone
Washing, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 6h, obtains O- acetamide shell after dry at 30 DEG C
Glycan schiff bases.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.70 in chemical formula.
Embodiment 3
A kind of preparation method of O- acetamide Chitosan Schiff-base is sent out by benzaldehyde Chitosan Schiff-base and chloroacetamide
Raw nucleophilic substitution, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1g chitosan is taken, the molecular weight of chitosan is 700,000, and deacetylation 87%, taking 50ml concentration is 1%
Acetic acid solution, chitosan is added in acetic acid solution, 20min, mixing speed 300r/min is stirred at room temperature, until shell is poly-
Sugar is completely dissolved, and obtains lysate.
Step 2, into lysate be added 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, then into
Row, which filters, removes water, and is washed using ethyl alcohol, and filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol for taking 50ml, stirs 1 hour, and be warming up to 80 DEG C, then be added dropwise
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 3.2g, wherein benzaldehyde carried out distillation processing, and the reaction was continued 7h is hanged
Supernatant liquid a.
Step 4, the ethyl alcohol of 30ml is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone washing,
Obtain filter cake b.
Step 5, after taking isopropanol and the 5ml mass concentration of 35ml to mix for 20% sodium hydroxide solution, filter cake b is added
Enter wherein, 30min, mixing speed 300r/min is stirred at room temperature；Then the chloracetyl aqueous amine of 20ml is added dropwise at 50 DEG C
The chloroacetamide of solution and 1.7g, the reaction was continued 6h obtain suspension b.
Step 6, the ethyl alcohol of 30ml is added into suspension b, is filtered after standing, is then successively carried out using ethyl alcohol and acetone
Washing, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 8h, obtains O- acetamide shell after dry at 50 DEG C
Glycan schiff bases.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.93 in chemical formula.
Embodiment 4
A kind of preparation method of O- acetamide Chitosan Schiff-base is sent out by benzaldehyde Chitosan Schiff-base and chloroacetamide
Raw nucleophilic substitution, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1g chitosan is taken, the molecular weight of chitosan is 700,000, and deacetylation 87%, taking 50ml concentration is 1%
Acetic acid solution, chitosan is added in acetic acid solution, 20min, mixing speed 260r/min is stirred at room temperature, until shell is poly-
Sugar is completely dissolved, and obtains lysate.
Step 2, into lysate be added 1mol/L sodium hydroxide solution, and adjust lysate PH be 7, then into
Row, which filters, removes water, and is washed using ethyl alcohol, and filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol for taking 50ml, stirs 1 hour, and be warming up to 50 DEG C, then be added dropwise
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 2.2g, wherein benzaldehyde carried out distillation processing, and the reaction was continued 5h is hanged
Supernatant liquid a.
Step 4, the ethyl alcohol of 30ml is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone washing,
Obtain filter cake b.
Step 5, after taking isopropanol and the 5ml mass concentration of 35ml to mix for 20% sodium hydroxide solution, filter cake b is added
Enter wherein, 30min, mixing speed 240r/min is stirred at room temperature；Then the chloracetyl aqueous amine of 20ml is added dropwise at 40 DEG C
The chloroacetamide of solution and 1.1g, the reaction was continued 5h obtain suspension b.
Step 6, the ethyl alcohol of 30ml is added into suspension b, is filtered after standing, is then successively carried out using ethyl alcohol and acetone
Washing, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 7h, obtains O- acetamide shell after dry at 40 DEG C
Glycan schiff bases.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.90 in chemical formula.
Embodiment 5
A kind of preparation method of O- acetamide Chitosan Schiff-base is sent out by benzaldehyde Chitosan Schiff-base and chloroacetamide
Raw nucleophilic substitution, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1g chitosan is taken, the molecular weight of chitosan is 700,000, and deacetylation 87%, taking 50ml concentration is 1%
Acetic acid solution, chitosan is added in acetic acid solution, 20min, mixing speed 200r/min is stirred at room temperature, until shell is poly-
Sugar is completely dissolved, and obtains lysate.
Step 2, into lysate be added 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, then into
Row, which filters, removes water, and is washed using ethyl alcohol, and filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol for taking 50ml, stirs 1 hour, and be warming up to 70 DEG C, then be added dropwise
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 2.8g, wherein benzaldehyde carried out distillation processing, and the reaction was continued 5.5h is obtained
Suspension a.
Step 4, the ethyl alcohol of 30ml is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone washing,
Obtain filter cake b.
Step 5, after taking isopropanol and the 5ml mass concentration of 35ml to mix for 20% sodium hydroxide solution, filter cake b is added
Enter wherein, 30min, mixing speed 280r/min is stirred at room temperature；Then the chloracetyl aqueous amine of 20ml is added dropwise at 50 DEG C
The chloroacetamide of solution and 1.0g, the reaction was continued 4h obtain suspension b.
Step 6, the ethyl alcohol of 30ml is added into suspension b, is filtered after standing, is then successively carried out using ethyl alcohol and acetone
Washing, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 6h, obtains O- acetamide shell after dry at 35 DEG C
Glycan schiff bases.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.95 in chemical formula.
Embodiment 6
A kind of preparation method of O- acetamide Chitosan Schiff-base is sent out by benzaldehyde Chitosan Schiff-base and chloroacetamide
Raw nucleophilic substitution, obtains O- acetamide Chitosan Schiff-base, detailed process is:
Step 1,1g chitosan is taken, the molecular weight of chitosan is 700,000, and deacetylation 87%, taking 50ml concentration is 1%
Acetic acid solution, chitosan is added in acetic acid solution, 20min, mixing speed 200r/min is stirred at room temperature, until shell is poly-
Sugar is completely dissolved, and obtains lysate.
Step 2, into lysate be added 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, then into
Row, which filters, removes water, and is washed using ethyl alcohol, and filter cake a is obtained.
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol for taking 50ml, stirs 1 hour, and be warming up to 50 DEG C, then be added dropwise
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 1.9g, wherein benzaldehyde carried out distillation processing, and the reaction was continued 5h is hanged
Supernatant liquid a.
Step 4, the ethyl alcohol of 30ml is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone washing,
Obtain filter cake b.
Step 5, after taking isopropanol and the 5ml mass concentration of 35ml to mix for 20% sodium hydroxide solution, filter cake b is added
Enter wherein, 30min, mixing speed 270r/min is stirred at room temperature；Then the chloracetyl aqueous amine of 20ml is added dropwise at 35 DEG C
The chloroacetamide of solution and 1.6g, the reaction was continued 5h obtain suspension b.
Step 6, the ethyl alcohol of 30ml is added into suspension b, is filtered after standing, is then successively carried out using ethyl alcohol and acetone
Washing, reusing ethyl alcohol is solvent soxhlet type, and the time of soxhlet type is 7h, obtains O- acetamide shell after dry at 40 DEG C
Glycan schiff bases.
The wherein chemical formula of O- acetamide Chitosan Schiff-base obtained in step 6 are as follows:
X is 0.13, y 0.87, z 0.89 in chemical formula.
Claims (8)
1. a kind of O- acetamide Chitosan Schiff-base, which is characterized in that its chemical formula are as follows:
Wherein, 0.13 x, y 0.87, z 0.60-0.95.
2. a kind of preparation method of O- acetamide Chitosan Schiff-base, which is characterized in that including passing through benzaldehyde chitosan Schiff
Nucleophilic substitution occurs for alkali and chloroacetamide, obtains O- acetamide Chitosan Schiff-base；The nucleophilic substitution it is specific
Process is:
Step 1,1 part of chitosan is taken by mass fraction, taking 50 parts of concentration by volume parts is 1% acetic acid solution, by chitosan
It is added in acetic acid solution, obtains lysate；
Step 2, the pH that sodium hydroxide solution is added into lysate, and adjusts lysate is 7, then carries out suction filtration removing
Water, and washed using ethyl alcohol, obtain filter cake a；
Step 3, filter cake a is added in ethyl alcohol the ethyl alcohol that 50 parts are taken by volume parts, stirs 1h, and be warming up to 40-80 DEG C,
The benzaldehyde ethanol solution that volume parts are 20 parts and the benzaldehyde that mass fraction is 0.6-3.2 parts are added dropwise again, the reaction was continued 3-
7h obtains suspension a；
Step 4, the ethyl alcohol that volume parts are 30 parts is added into suspension a, is filtered after standing, then successively uses ethyl alcohol and acetone
Washing, obtains filter cake b；
Step 5, after 35 parts of isopropanol and 5 parts of sodium hydroxide solution mixing are taken by volume parts, filter cake b is added thereto,
After the chloroacetamide aqueous solution that volume parts are 20 parts and the chloroacetamide that mass fraction is 0.6-1.7 parts are added dropwise at 30-50 DEG C,
The reaction was continued 4-6h, obtains suspension b；
Step 6, the ethyl alcohol that volume parts are 30 parts is added into suspension b, is filtered after standing, then successively uses ethyl alcohol and third
Ketone is washed, and reusing ethyl alcohol is solvent soxhlet type, obtains O- acetamide chitosan Schiff after dry at 30-50 DEG C
Alkali.
3. the preparation method of O- acetamide Chitosan Schiff-base according to claim 2, which is characterized in that the step 1
In chitosan molecular weight be 700,000, deacetylation 87%.
4. according to the preparation method of O- acetamide Chitosan Schiff-base described in Claims 2 or 3 any one, feature exists
In 20min, mixing speed 200-300r/min is stirred at room temperature in chitosan and acetic acid solution in the step 1, until shell is poly-
Sugar is completely dissolved.
5. the preparation method of O- acetamide Chitosan Schiff-base according to claim 2, which is characterized in that the step 3
In benzaldehyde carried out distillation processing.
6. the preparation method of O- acetamide Chitosan Schiff-base according to claim 2, which is characterized in that the step 6
The time of middle Soxhlet extraction is 6-8h.
7. the preparation method of O- acetamide Chitosan Schiff-base according to claim 2, which is characterized in that the step 5
Described in the mass concentration of sodium hydroxide solution be 20%, and be added after filter cake b and be stirred at room temperature 30min, mixing speed
For 200-300r/min.
8. the preparation method of O- acetamide Chitosan Schiff-base according to claim 2, which is characterized in that the step 6
Obtained in O- acetamide Chitosan Schiff-base chemical formula are as follows:
Wherein x is 0.13, y 0.87, z 0.60-0.95.
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