CN106432543A - O-acetamide chitosan Schiff-base and preparation method thereof - Google Patents
O-acetamide chitosan Schiff-base and preparation method thereof Download PDFInfo
- Publication number
- CN106432543A CN106432543A CN201610865093.3A CN201610865093A CN106432543A CN 106432543 A CN106432543 A CN 106432543A CN 201610865093 A CN201610865093 A CN 201610865093A CN 106432543 A CN106432543 A CN 106432543A
- Authority
- CN
- China
- Prior art keywords
- acetamide
- ethanol
- base
- schiff
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses O-acetamide chitosan Schiff-base and a preparation method thereof. The preparation method includes: benzaldehyde chitosan Schiff-base is allowed to have nucleophilic substitution reaction with chloroacetamide so as to prepare the O-acetamide chitosan Schiff-base. The O-acetamide chitosan Schiff-base has the advantages that the O-acetamide chitosan Schiff-base is definite in modification position, high in purity and good in flocculation and sterilizing effect, and chitosan amino protection is achieved through the Schiff-base reaction to allow hydroxyl to have a fixed-position modification effect.
Description
Technical field
The invention belongs to technical field of fine, it is related to a kind of O- acetamide Chitosan Schiff-base, further relates to above-mentioned O-
The preparation method of acetamide Chitosan Schiff-base.
Background technology
Shitosan is the basic amine group polysaccharide of uniquely a large amount of presence in natural polysaccharide, and its chemical name is (Isosorbide-5-Nitrae) -2- ammonia
Base -2- deoxidation-β-D-Glucose or abbreviation poly glucosamine.Shitosan is obtained through deacetylation by chitin,
It is the most important derivative of chitin.It is a kind of positively charged high molecular polymer, and its wide material sources is nonpoisonous 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 are as certain in all having to SS, organic dyestuff, protein, metal ion, microorganism in waste water etc.
Flocculation.Compared with other flocculants, shitosan is also adding less, the features such as can become salt with organic acid.In addition, shitosan
There is broad spectrum antibacterial, there is to Escherichia coli, hay bacillus, staphylococcus aureus, Bacillus acidi lactici etc. obvious suppression and make
With.The excellent property of shitosan makes it be obtained for extensive application in various fields, but its water-insoluble is to a certain degree
On still can not meet application requirement, significantly limit its range of application.This mainly due to the hydroxyl in chitosan structure and
Amino has certain regularity so that linear chitosan molecule interchain has strong hydrogen bond action, result in arrangement
Lead to shitosan to have higher degree of crystallinity, only can dissolve in part diluted acid.By the method for chemical modification, shitosan is entered
Row is modified, can increase the active group of shitosan and improve its water solubility, so that the condition of its application is more wide in range and carries
Its application performance high.
Shen Hongjie etc. (《Cellulose Science and technology》2014,04:28-33) under ul-trasonic irradiation, with homemade low point
Son amount carboxymethyl chitosan is raw material with vanillic aldehyde, is prepared for low-molecular-weight carboxymethyl chitosan sugar vanillin schiff bases, by anti-
Bacterium experiment finds that it has good anti-microbial property.
Ma Quanhong etc. (《Chemical reagent》2000,06:327-330.) utilize shitosan C2Active amino and α -one penta on position
Diacid carries out macromolecular reaction, has synthesized the functional polymer with schiff bases group, KG modification of chitosan is to Cu
And Zn (II) has good absorption property (II).
Li Yunju etc. (《CDDB》2009, University Of Chongqing's Master's thesis, 2009,10.) to a series of
Corrosion inhibition in 3.5%NaCl medium of the chitosan oligosaccharide of good water solubility and its Schiff bases derivative and mechanism are ground
Study carefully, carboxymethyl chitosan oligosaccharide vanillic aldehyde schiff bases has good corrosion inhibition.
In sum, Chitosan Schiff-base class compound research ratio is wide, can be applicable to antibacterial, catalysis, inhibition, absorption
Deng many-sided, all there is 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.
Content of the invention
It is an object of the invention to provide a kind of O- acetamide Chitosan Schiff-base, its modified position determines, purity is high, has
There are good flocculation and bactericidal effect.
The present invention also aims to providing the preparation method of above-mentioned O- acetamide Chitosan Schiff-base, by adopting Schiff
Alkali reaction is protected to amino of chitosan, enables hydroxyl to reach the modified effect of positioning.
The purpose of the present invention is achieved through the following technical solutions：
The chemical formula of this O- acetamide Chitosan Schiff-base is：
Wherein, x be 0.13, y be 0.87, z be 0.60-0.95.
Another technical scheme of the present invention is the preparation method of above-mentioned O- acetamide Chitosan Schiff-base, including by benzene first
There is nucleophilic substitution with chloroacetamide in aldehyde Chitosan Schiff-base, obtain O- acetamide Chitosan Schiff-base.
The detailed process of wherein nucleophilic substitution is：
Step 1, takes 1 part of shitosan by mass fraction, takes, by volume parts, the acetic acid solution that 50 parts of concentration is 1%, by shell
Glycan adds in acetic acid solution, obtains lysate；
Step 2, in lysate add sodium hydroxide solution, and adjust lysate pH be 7, then carry out suction filtration and remove
Remove water, and washed using ethanol, obtain filter cake a；
Step 3, is taken 50 parts of ethanol by volume parts, filter cake a is added in ethanol, stirs 1h, and be warming up to 40-80
DEG C, then drip the benzaldehyde ethanol solution that volume parts the are 20 parts and mass fraction benzaldehyde for 0.6-3.2 part, continue reaction
3-7h, obtains suspension a；
Step 4, adds volume parts to be 30 parts of ethanol in suspension a, suction filtration after standing, then use successively ethanol and
Acetone washs, and obtains filter cake b；
Step 5, take 35 parts of isopropanol and 5 parts of sodium hydroxide solution mixing by volume parts after, filter cake b is added it
In, dripping the chloroacetamide aqueous solution that volume parts are 20 parts and mass fraction at 30-50 DEG C is the chloracetyl of 0.6-1.7 part
After amine, continue reaction 4-6h, obtain suspension b；
Step 6, adds the ethanol that volume parts are 30 parts, suction filtration after standing, then successively using ethanol in suspension b
Washed with acetone, reusing ethanol is solvent soxhlet type, obtains O- acetamide shitosan seat after being dried at 30-50 DEG C
Husband's alkali.
Further, the feature of the present invention also resides in：
The molecular weight of the shitosan wherein in step 1 is 700,000, and deacetylation is 87%.
Wherein in step 1, shitosan and acetic acid solution are stirred at room temperature 20min, and mixing speed is 200-300r/min,
It is completely dissolved to shitosan.
Benzaldehyde wherein in step 3 carried out distillation and processed.
Wherein in step 6, the time of Soxhlet extraction is 6-8h.
Wherein described in step 5, the mass concentration of sodium hydroxide solution is 20%, and stirs at room temperature after addition filter cake b
Mix 30min, mixing speed is 200-300r/min.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.60-0.95.
The invention has the beneficial effects as follows：Raw materials of chitosan used by the present invention, benzaldehyde etc., its wide material sources, produce into
This is relatively low, and reaction condition is gentle, and course of reaction is continuous, and simple to operate.Compared with other chitin modified methods, this method has
There is raw material availability high, by protecting to amino of chitosan using schiff base reaction, enable hydroxyl to reach the modified effect of positioning
Really, shitosan carries out selective reaction and makes reaction site clearly, favorable reproducibility, the advantages of the percent grafting of product is easily controlled,
So that its modified position determines, purity is high, there is good flocculation and bactericidal effect.
Further, the O- acetamide Chitosan Schiff-base of present invention synthesis, not only has the typical characteristics of schiff bases,
As to the adsorptivity of metal ion, rust inhibition etc., and by shitosan C6Position-OH grafting acetamido, improves fragrance
The water solubility of base Chitosan Schiff-base, increased the functional activity group of shitosan.
Brief description
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
Below in conjunction with the accompanying drawings the present invention is described in further detail：
The invention provides a kind of O- acetamide Chitosan Schiff-base, its chemical formula is：
Wherein x is 0.13, y is 0.60-0.95 for 0.87, z.
Present invention also offers the preparation method of above-mentioned O- acetamide Chitosan Schiff-base, by benzaldehyde shitosan Schiff
There is nucleophilic substitution with chloroacetamide in alkali, obtain O- acetamide Chitosan Schiff-base, its detailed process is：
Step 1, takes 1 part of shitosan by mass fraction, the molecular weight of shitosan is 700,000, and deacetylation is 87%, by body
Long-pending number takes 50 parts of acetic acid solution, shitosan is added in acetic acid solution, 20min is stirred at room temperature, mixing speed is
200-300r/min, is completely dissolved to shitosan, obtains lysate.
Step 2, in lysate add sodium hydroxide solution, and adjust lysate pH be 7, then carry out suction filtration and remove
Remove water, and washed using ethanol, obtain filter cake a.
Step 3, is taken 50 parts of ethanol by volume parts, filter cake a is added in ethanol, stirs 1h, and be warming up to 40-80
DEG C, then drip the benzaldehyde ethanol solution that volume parts the are 20 parts and mass fraction benzaldehyde for 0.6-3.2 part, wherein benzene first
Aldehyde carried out distillation and processed, and continues reaction 3-7h, obtains suspension a.
Step 4, adds volume parts to be 30 parts of ethanol in suspension a, suction filtration after standing, then use successively ethanol and
Acetone washs, and obtains filter cake b.
Step 5, takes 35 parts of isopropanol by volume parts and sodium hydroxide solution mixing that 5 parts of mass concentrations are 20%
Afterwards, filter cake b is added thereto, 30min is stirred at room temperature, mixing speed is 200-300r/min；Then drip at 30-50 DEG C
Plus the chloroacetamide aqueous solution that volume parts are 20 parts and mass fraction are the chloroacetamide of 0.6-1.7 part, continue reaction 4-6h,
Obtain suspension b.
Step 6, adds the ethanol that volume parts are 30 parts, suction filtration after standing, then successively using ethanol in suspension b
Washed with acetone, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 6-8h, is dried at 30-50 DEG C
After obtain O- acetamide Chitosan Schiff-base.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.60-0.95, wherein z value joins with the reaction temperature in step, material
Than, and the difference in reaction time and change.
The preparation process chemical reaction process of O- acetamide Chitosan Schiff-base of the present invention is as shown in Figure 1：First, shitosan
Carry out nucleophilic addition with benzaldehyde, C on shitosan2- the NH of position2N atom attack carbonyl group upper band with lone electron pair
There is the C atom of positive charge, complete nucleophilic addition, form intermediate product Alpha-hydroxy aminated compounds, be then dehydrated further
Form schiff bases.The schiff bases being formed carries out S with chloroacetamide furtherN2 nucleophilic substitutions, shitosan C6H on the-OH of position
Atom is replaced by acetamido.
In Fig. 2, lines 1 are the nucleus magnetic hydrogen spectrum figure of shitosan raw material, and lines 2 are the nuclear-magnetism of O- acetamide Chitosan Schiff-base
Hydrogen spectrogram.It can be seen that in lines 1, belonging to shitosan sugar ring H-3, H-4 at the multiplet peak of δ=3.4～3.8,
H-5, H-6；Belong to-CH in N- acetamido in unimodal near δ=1.923；Unimodal near δ=3.03 belongs to C2
On amino Hydrogen Proton.Lines 2 compared with lines 1, appearance near δ=1, illustrate to have connected-CH on shitosan2-, in δ
Appearance near=8.0, illustrates that amide group has been connected on shitosan.Resonance bands of a spectrum in δ=7～8 correspond to benzene ring hydrogen
Proton；Prove that O- acetamide Chitosan Schiff-base is successfully synthesized.
The product of the present invention is 60%～95% by the condensation rate that elemental microanalysis method determines schiff bases；By titration
The percent grafting determining chitosan graft acetamide is up to 90%.
Synthetic method of the present invention is simple, strong operability, favorable reproducibility, and the product graft rate being synthesized by this method is controlled
Property strong, molecular weight is big.The O- acetamide Chitosan Schiff-base of synthesis, not only has the typical characteristics of schiff bases, such as to metal from
The adsorptivity of son, rust inhibition, and give shitosan C6The acetamido of position-OH grafting improves aromatic radical Chitosan Schiff-base
Water solubility, increased the functional activity group of shitosan.Therefore, the O- acetamide Chitosan Schiff-base of the present invention is in medical science, work(
Can all there is higher using value in the field such as macromolecular material, Treatment of Industrial Water, food processing, textile and paper.
A kind of specific embodiment of the preparation method of present invention O- acetamide Chitosan Schiff-base is：
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, its detailed process is：
Step 1, takes 1g shitosan, the molecular weight of shitosan is 700,000, and deacetylation is 87%, takes 50ml concentration to be 1%
Acetic acid solution, by shitosan add acetic acid solution in, 20min is stirred at room temperature, mixing speed be 240r/min, to shell gather
Sugar is completely dissolved, and obtains lysate.
Step 2, in lysate add 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, Ran Houjin
Row suction filtration removes water, and is washed using ethanol, obtains filter cake a.
Step 3, takes the ethanol of 50ml, filter cake a is added in ethanol, stirs 1h, and be warming up to 60 DEG C, then drip 20ml
Benzaldehyde ethanol solution and 1.9g benzaldehyde, wherein benzaldehyde carried out distillation process, continue reaction 4h, obtain suspension
a.
Step 4, adds the ethanol of 30ml, suction filtration after standing in suspension a, is then washed with ethanol and acetone successively,
Obtain filter cake b.
Step 5, after taking isopropanol and the mixing of sodium hydroxide solution that 5ml mass concentration is 20% of 35ml, filter cake b is added
Enter wherein, 30min is stirred at room temperature, mixing speed is 200r/min；Then drip the chloracetyl aqueous amine of 20ml at 40 DEG C
Solution and the chloroacetamide of 0.6g, continue reaction 5h, obtain suspension b.
Step 6, is added the ethanol of 30ml, suction filtration after standing in suspension b, is then carried out using ethanol and acetone successively
Washing, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 6h, obtains O- acetamide shell after being dried at 40 DEG C
Glycan schiff bases.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.60.
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, its detailed process is：
Step 1, takes 1g shitosan, the molecular weight of shitosan is 700,000, and deacetylation is 87%, takes 50ml concentration to be 1%
Acetic acid solution, by shitosan add acetic acid solution in, 20min is stirred at room temperature, mixing speed be 300r/min, to shell gather
Sugar is completely dissolved, and obtains lysate.
Step 2, in lysate add 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, Ran Houjin
Row suction filtration removes water, and is washed using ethanol, obtains filter cake a.
Step 3, takes the ethanol of 50ml, filter cake a is added in ethanol, stirs 1 hour, and be warming up to 70 DEG C, then drip
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 0.6g, wherein benzaldehyde carried out distillation and processed, and continued reaction 3h, were hanged
Supernatant liquid a.
Step 4, adds the ethanol of 30ml, suction filtration after standing in suspension a, is then washed with ethanol and acetone successively,
Obtain filter cake b.
Step 5, after taking isopropanol and the mixing of sodium hydroxide solution that 5ml mass concentration is 20% of 35ml, filter cake b is added
Enter wherein, 30min is stirred at room temperature, mixing speed is 300r/min；Then drip the chloracetyl aqueous amine of 20ml at 30 DEG C
Solution and the chloroacetamide of 1.1g, continue reaction 4h, obtain suspension b.
Step 6, is added the ethanol of 30ml, suction filtration after standing in suspension b, is then carried out using ethanol and acetone successively
Washing, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 6h, obtains O- acetamide shell after being dried at 30 DEG C
Glycan schiff bases.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.70.
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, its detailed process is：
Step 1, takes 1g shitosan, the molecular weight of shitosan is 700,000, and deacetylation is 87%, takes 50ml concentration to be 1%
Acetic acid solution, by shitosan add acetic acid solution in, 20min is stirred at room temperature, mixing speed be 300r/min, to shell gather
Sugar is completely dissolved, and obtains lysate.
Step 2, in lysate add 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, Ran Houjin
Row suction filtration removes water, and is washed using ethanol, obtains filter cake a.
Step 3, takes the ethanol of 50ml, filter cake a is added in ethanol, stirs 1 hour, and be warming up to 80 DEG C, then drip
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 3.2g, wherein benzaldehyde carried out distillation and processed, and continued reaction 7h, were hanged
Supernatant liquid a.
Step 4, adds the ethanol of 30ml, suction filtration after standing in suspension a, is then washed with ethanol and acetone successively,
Obtain filter cake b.
Step 5, after taking isopropanol and the mixing of sodium hydroxide solution that 5ml mass concentration is 20% of 35ml, filter cake b is added
Enter wherein, 30min is stirred at room temperature, mixing speed is 300r/min；Then drip the chloracetyl aqueous amine of 20ml at 50 DEG C
Solution and the chloroacetamide of 1.7g, continue reaction 6h, obtain suspension b.
Step 6, is added the ethanol of 30ml, suction filtration after standing in suspension b, is then carried out using ethanol and acetone successively
Washing, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 8h, obtains O- acetamide shell after being dried at 50 DEG C
Glycan schiff bases.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.93.
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, its detailed process is：
Step 1, takes 1g shitosan, the molecular weight of shitosan is 700,000, and deacetylation is 87%, takes 50ml concentration to be 1%
Acetic acid solution, by shitosan add acetic acid solution in, 20min is stirred at room temperature, mixing speed be 260r/min, to shell gather
Sugar is completely dissolved, and obtains lysate.
Step 2, in lysate add 1mol/L sodium hydroxide solution, and adjust lysate PH be 7, Ran Houjin
Row suction filtration removes water, and is washed using ethanol, obtains filter cake a.
Step 3, takes the ethanol of 50ml, filter cake a is added in ethanol, stirs 1 hour, and be warming up to 50 DEG C, then drip
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 2.2g, wherein benzaldehyde carried out distillation and processed, and continued reaction 5h, were hanged
Supernatant liquid a.
Step 4, adds the ethanol of 30ml, suction filtration after standing in suspension a, is then washed with ethanol and acetone successively,
Obtain filter cake b.
Step 5, after taking isopropanol and the mixing of sodium hydroxide solution that 5ml mass concentration is 20% of 35ml, filter cake b is added
Enter wherein, 30min is stirred at room temperature, mixing speed is 240r/min；Then drip the chloracetyl aqueous amine of 20ml at 40 DEG C
Solution and the chloroacetamide of 1.1g, continue reaction 5h, obtain suspension b.
Step 6, is added the ethanol of 30ml, suction filtration after standing in suspension b, is then carried out using ethanol and acetone successively
Washing, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 7h, obtains O- acetamide shell after being dried at 40 DEG C
Glycan schiff bases.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.90.
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, its detailed process is：
Step 1, takes 1g shitosan, the molecular weight of shitosan is 700,000, and deacetylation is 87%, takes 50ml concentration to be 1%
Acetic acid solution, by shitosan add acetic acid solution in, 20min is stirred at room temperature, mixing speed be 200r/min, to shell gather
Sugar is completely dissolved, and obtains lysate.
Step 2, in lysate add 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, Ran Houjin
Row suction filtration removes water, and is washed using ethanol, obtains filter cake a.
Step 3, takes the ethanol of 50ml, filter cake a is added in ethanol, stirs 1 hour, and be warming up to 70 DEG C, then drip
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 2.8g, wherein benzaldehyde carried out distillation and processed, and continued reaction 5.5h, obtained
Suspension a.
Step 4, adds the ethanol of 30ml, suction filtration after standing in suspension a, is then washed with ethanol and acetone successively,
Obtain filter cake b.
Step 5, after taking isopropanol and the mixing of sodium hydroxide solution that 5ml mass concentration is 20% of 35ml, filter cake b is added
Enter wherein, 30min is stirred at room temperature, mixing speed is 280r/min；Then drip the chloracetyl aqueous amine of 20ml at 50 DEG C
Solution and the chloroacetamide of 1.0g, continue reaction 4h, obtain suspension b.
Step 6, is added the ethanol of 30ml, suction filtration after standing in suspension b, is then carried out using ethanol and acetone successively
Washing, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 6h, obtains O- acetamide shell after being dried at 35 DEG C
Glycan schiff bases.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.95.
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, its detailed process is：
Step 1, takes 1g shitosan, the molecular weight of shitosan is 700,000, and deacetylation is 87%, takes 50ml concentration to be 1%
Acetic acid solution, by shitosan add acetic acid solution in, 20min is stirred at room temperature, mixing speed be 200r/min, to shell gather
Sugar is completely dissolved, and obtains lysate.
Step 2, in lysate add 1mol/L sodium hydroxide solution, and adjust lysate pH be 7, Ran Houjin
Row suction filtration removes water, and is washed using ethanol, obtains filter cake a.
Step 3, takes the ethanol of 50ml, filter cake a is added in ethanol, stirs 1 hour, and be warming up to 50 DEG C, then drip
The benzaldehyde ethanol solution of 20ml and the benzaldehyde of 1.9g, wherein benzaldehyde carried out distillation and processed, and continued reaction 5h, were hanged
Supernatant liquid a.
Step 4, adds the ethanol of 30ml, suction filtration after standing in suspension a, is then washed with ethanol and acetone successively,
Obtain filter cake b.
Step 5, after taking isopropanol and the mixing of sodium hydroxide solution that 5ml mass concentration is 20% of 35ml, filter cake b is added
Enter wherein, 30min is stirred at room temperature, mixing speed is 270r/min；Then drip the chloracetyl aqueous amine of 20ml at 35 DEG C
Solution and the chloroacetamide of 1.6g, continue reaction 5h, obtain suspension b.
Step 6, is added the ethanol of 30ml, suction filtration after standing in suspension b, is then carried out using ethanol and acetone successively
Washing, reusing ethanol is solvent soxhlet type, and the time of soxhlet type is 7h, obtains O- acetamide shell after being dried at 40 DEG C
Glycan schiff bases.
The chemical formula of the O- acetamide Chitosan Schiff-base wherein obtaining in step 6 is：
In chemical formula x be 0.13, y be 0.87, z be 0.89.
Claims (9)
1. a kind of O- acetamide Chitosan Schiff-base is it is characterised in that its chemical formula is：
Wherein, x be 0.13, y be 0.87, z be 0.60-0.95.
2. a kind of preparation method of O- acetamide Chitosan Schiff-base is it is characterised in that include by benzaldehyde shitosan Schiff
There is nucleophilic substitution with chloroacetamide in alkali, obtain O- acetamide Chitosan Schiff-base.
3. the preparation method of O- acetamide Chitosan Schiff-base according to claim 2 is it is characterised in that described nucleophilic takes
For the detailed process reacted it is：
Step 1, takes 1 part of shitosan by mass fraction, takes, by volume parts, the acetic acid solution that 50 parts of concentration is 1%, by shitosan
Add in acetic acid solution, obtain lysate；
Step 2, in lysate add sodium hydroxide solution, and adjust lysate pH be 7, then carry out suction filtration removing
Water, and washed using ethanol, obtain filter cake a；
Step 3, is taken 50 parts of ethanol by volume parts, filter cake a is added in ethanol, stirs 1h, and be warming up to 40-80 DEG C,
Dripping the benzaldehyde ethanol solution that volume parts are 20 parts and mass fraction again is the benzaldehyde of 0.6-3.2 part, continues reaction 3-
7h, obtains suspension a；
Step 4, adds the ethanol that volume parts are 30 parts, suction filtration after standing in suspension a, then uses ethanol and acetone successively
Washing, obtains filter cake b；
Step 5, take 35 parts of isopropanol and 5 parts of sodium hydroxide solution mixing by volume parts after, filter cake b is added thereto,
After at 30-50 DEG C, dropping volume parts are 20 parts of the chloroacetamide aqueous solution and chloroacetamide that mass fraction is 0.6-1.7 part,
Continue reaction 4-6h, obtain suspension b；
Step 6, adds the ethanol that volume parts are 30 parts, suction filtration after standing, then successively using ethanol and third in suspension b
Ketone is washed, and reusing ethanol is solvent soxhlet type, obtains O- acetamide shitosan Schiff after being dried at 30-50 DEG C
Alkali.
4. the preparation method of O- acetamide Chitosan Schiff-base according to claim 3 is it is characterised in that described step 1
In shitosan molecular weight be 700,000, deacetylation be 87%.
5. the preparation method of the O- acetamide Chitosan Schiff-base according to claim 3 or 4 any one, its feature exists
In in described step 1, shitosan and acetic acid solution are stirred at room temperature 20min, and mixing speed is 200-300r/min, gathers to shell
Sugar is completely dissolved.
6. the preparation method of O- acetamide Chitosan Schiff-base according to claim 3 is it is characterised in that described step 3
In benzaldehyde carried out distillation process.
7. the preparation method of O- acetamide Chitosan Schiff-base according to claim 3 is it is characterised in that described step 6
The time of middle Soxhlet extraction is 6-8h.
8. the preparation method of O- acetamide Chitosan Schiff-base according to claim 3 is it is characterised in that described step 5
Described in sodium hydroxide solution mass concentration be 20%, and add filter cake b after 30min, mixing speed are stirred at room temperature
For 200-300r/min.
9. the preparation method of O- acetamide Chitosan Schiff-base according to claim 3 is it is characterised in that described step 6
In the chemical formula of O- acetamide Chitosan Schiff-base that obtains be：
Wherein x is 0.13, y is 0.60-0.95 for 0.87, z.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610865093.3A CN106432543B (en) | 2016-09-29 | 2016-09-29 | A kind of O- acetamide Chitosan Schiff-base and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610865093.3A CN106432543B (en) | 2016-09-29 | 2016-09-29 | A kind of O- acetamide Chitosan Schiff-base and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106432543A true CN106432543A (en) | 2017-02-22 |
| CN106432543B CN106432543B (en) | 2019-01-15 |
Family
ID=58170065
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610865093.3A Active CN106432543B (en) | 2016-09-29 | 2016-09-29 | A kind of O- acetamide Chitosan Schiff-base and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106432543B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905445A (en) * | 2017-03-30 | 2017-06-30 | 广州振清环保技术有限公司 | A kind of Polyaminated shitosan decolorising agent of carboxymethyl and its preparation method and application |
| CN114892173A (en) * | 2022-05-23 | 2022-08-12 | 安徽绿洲危险废物综合利用有限公司 | Alkaline etching solution recycling process |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701044A (en) * | 2009-11-09 | 2010-05-05 | 烟台海岸带可持续发展研究所 | Chitosan hyamine and preparation and application thereof |
| CN102153674A (en) * | 2011-03-15 | 2011-08-17 | 中国海洋大学 | Chitosan ester p-aminobenzoate and preparation method thereof |
| CN102464729A (en) * | 2010-11-09 | 2012-05-23 | 北京联合大学生物化学工程学院 | O-quaternary ammonium salt oligochitosan vanillina Schiff base bacteriostatic agent and preparation method thereof |
| CN102532345A (en) * | 2010-12-24 | 2012-07-04 | 大连中科格莱克生物科技有限公司 | O-unsaturated fatty acid acylated chitosan oligosaccharides as well as preparation and application thereof |
| CN105085715A (en) * | 2015-09-10 | 2015-11-25 | 江苏双林海洋生物药业有限公司 | Preparation method of O-carboxymethyl chitosan |
| CN105237655A (en) * | 2015-10-08 | 2016-01-13 | 中国科学院海洋研究所 | Marine organism polysaccharide Schiff base derivative, preparation method thereof, and application thereof as agricultural bactericide |
-
2016
- 2016-09-29 CN CN201610865093.3A patent/CN106432543B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101701044A (en) * | 2009-11-09 | 2010-05-05 | 烟台海岸带可持续发展研究所 | Chitosan hyamine and preparation and application thereof |
| CN102464729A (en) * | 2010-11-09 | 2012-05-23 | 北京联合大学生物化学工程学院 | O-quaternary ammonium salt oligochitosan vanillina Schiff base bacteriostatic agent and preparation method thereof |
| CN102532345A (en) * | 2010-12-24 | 2012-07-04 | 大连中科格莱克生物科技有限公司 | O-unsaturated fatty acid acylated chitosan oligosaccharides as well as preparation and application thereof |
| CN102153674A (en) * | 2011-03-15 | 2011-08-17 | 中国海洋大学 | Chitosan ester p-aminobenzoate and preparation method thereof |
| CN105085715A (en) * | 2015-09-10 | 2015-11-25 | 江苏双林海洋生物药业有限公司 | Preparation method of O-carboxymethyl chitosan |
| CN105237655A (en) * | 2015-10-08 | 2016-01-13 | 中国科学院海洋研究所 | Marine organism polysaccharide Schiff base derivative, preparation method thereof, and application thereof as agricultural bactericide |
Non-Patent Citations (4)
| Title |
|---|
| GUO-QING YING 等: "Preparation, water solubility and antioxidant activity of branched-chain chitosan derivatives", 《CARBOHYDRATE POLYMERS》 * |
| JOSE´ E. DOS SANTOS等: "Synthesis and characterization of Schiff bases from chitosan and salicylaldehyde derivatives", 《CARBOHYDRATE POLYMERS》 * |
| 李秋萍: "O-羧甲基壳聚糖制备工艺研究", 《安徽医药》 * |
| 韩永萍 等: "低聚壳聚糖芳香醛席夫碱中酚羟基的抑菌活性研究", 《食品与机械》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106905445A (en) * | 2017-03-30 | 2017-06-30 | 广州振清环保技术有限公司 | A kind of Polyaminated shitosan decolorising agent of carboxymethyl and its preparation method and application |
| CN106905445B (en) * | 2017-03-30 | 2019-02-26 | 广州振清环保技术有限公司 | A kind of Polyaminated chitosan decolorising agent of carboxymethyl-and its preparation method and application |
| CN114892173A (en) * | 2022-05-23 | 2022-08-12 | 安徽绿洲危险废物综合利用有限公司 | Alkaline etching solution recycling process |
| CN114892173B (en) * | 2022-05-23 | 2023-07-18 | 安徽绿洲危险废物综合利用有限公司 | Alkaline etching solution circulating regeneration process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106432543B (en) | 2019-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101033264B (en) | Chitosan biguanide hydrochloride, preparation method and use thereof | |
| CN100360036C (en) | Preparation method of chitin/metal copper composite antibactericidal agent | |
| CN100360035C (en) | Preparation method of chitin/zinc compound bactericide | |
| CN104672348B (en) | Chitosan quaternary ammonium salt derivatives with good aqueous solubility and antibacterial activity and preparation method thereof | |
| CN103980385B (en) | O-quaternized-N-thiocarbamide chitosan and method for making thereof and application | |
| CN106995502B (en) | Bifunctional group modified chitosan derivative and preparation method thereof | |
| El Knidri et al. | Chitin and chitosan: chemistry, solubility, fiber formation, and their potential applications | |
| CN106496358A (en) | Amphiphilic chitosan quaternary ammonium salt derivatives and its preparation and application | |
| CN105237655A (en) | Marine organism polysaccharide Schiff base derivative, preparation method thereof, and application thereof as agricultural bactericide | |
| CN107216408A (en) | A kind of preparation method of antibacterial functionalized chitosan derivatives | |
| CN105131152A (en) | Marine organism polysaccharide copper compound, preparation thereof and application of marine organic polysaccharide copper compound serving as agricultural bactericide | |
| CN105218700A (en) | A kind of oligochitosan-O-kojic acid-Mannich base derivative antibacterial agent and preparation method thereof | |
| CN107043432A (en) | A kind of both sexes carboxymethyl chitosan guanidine salt derivative and preparation method thereof | |
| CN106432543B (en) | A kind of O- acetamide Chitosan Schiff-base and preparation method thereof | |
| CN106380526A (en) | O-alpha-methyl mandelate-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof | |
| CN103936885A (en) | O-fumarate-N-trimethyl chitosan quaternary ammonium salt as well as preparation method and application thereof | |
| CN107602726B (en) | Low molecular weight C6-carboxyl chitin and preparation method thereof | |
| CN103965374A (en) | O-imidazate-N-trimethyl chitosan quaternary ammonium salt, as well as preparation method and application thereof | |
| CN105669878B (en) | A kind of modification chitosan oligomer for aquaculture and preparation method thereof | |
| Barwin Vino et al. | Physicochemical characterization of biopolymers chitin and chitosan extracted from squid Doryteuthis sibogae adam, 1954 pen | |
| Li et al. | Recent progress in the utilization of chitin/chitosan for chemicals and materials | |
| CN100443505C (en) | 2-chitose-salicylic acid graft compound and its preparing method | |
| KR100441270B1 (en) | The Method for Preparation of Water Soluble Free Amine Chitosan | |
| CN109354632B (en) | Carboxymethyl aminopolysaccharide derivative and preparation method and application thereof | |
| CN110343195A (en) | A kind of readily soluble chitosan of long-chain and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |