CN108623706A - Microwave and complexing synergistic oxidation prepare the copper complex formazan method of chitosan oligosaccharide- - Google Patents
Microwave and complexing synergistic oxidation prepare the copper complex formazan method of chitosan oligosaccharide- Download PDFInfo
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- CN108623706A CN108623706A CN201710167956.4A CN201710167956A CN108623706A CN 108623706 A CN108623706 A CN 108623706A CN 201710167956 A CN201710167956 A CN 201710167956A CN 108623706 A CN108623706 A CN 108623706A
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- 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
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Abstract
The present invention is complexed by copper ion and microwave radiation technology, oxidation prepare chitosan oligosaccharide copper complex.The present invention relates to technical field of pesticide, and in particular to technical field prepared by organic copper fungicide.Preparation method of the present invention is：Using chitosan as raw material, it is dissolved in acetic acid aqueous solution, inorganic mantoquita is added, it is 5~10 to make chitosan unit and copper ion molar ratio, and holding forms homogeneous system, and oxidant is added in the mixture, under stiring, by adjusting microwave power, control temperature is at 40~60 DEG C, after reaction, it is cooled to room temperature, pH value is adjusted to neutrality, filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide copper complex after spray drying.The present invention is prepared simply, reduces chitosan molecule intermolecular forces using copper ion complexing, oxidation reaction increases chitosan polar group, oxidation and microwave collective effect degradation chitosan, prepares the uniform chitosan oligosaccharide copper complex of molecular weight.
Description
Technical field
The present invention relates to technical field of pesticide, and in particular to technical field prepared by organic copper fungicide.
Background technology
Fungicide copper agent is by releasing-SH ,-NH in copper ion and fungi vivo protein2,-COOH, the bases such as-OH
Group works, and causes germ dead.Current common organic copper agent has：Thiodiazole-copper (imperial gram bacterium), copper 8-hydroxyquinolinate, nonylphenolsulfonate copper, rosin
Sour copper, copper humate, amino acid copper etc..These copper agent compatibilities are good, have better mixture, can with mostly kill
Microbial inoculum, acaricide, insecticide and plant growth regulator phase mixture；Copper coin cellulose content is generally relatively low, and residual quantity is lower, and environment is dirty
Dye is reduced.
Chitosan oligosaccharide and its derivative are coordinated with copper ion, can be prepared chitosan oligosaccharide-copper complex, be used as fungicide.
Some presently disclosed technical solutions have：《A kind of chitosan oligosaccharide copper complex fungicide and its application》(201410174256.4) it relates to
And the active ingredient of chitosan oligosaccharide copper complex fungicide be that the chitosan oligosaccharide copper complex to be formed is complexed in chitosan oligosaccharide and copper ion,
The mass ratio of middle chitosan oligosaccharide and copper ion is 5: 1~1: 1.2；The average molecular weight of the chitosan oligosaccharide is 161~20000, takes off second
Acyl degree >=85%.The chitosan oligosaccharide copper complex bactericidal agent for preventing and treating bacterial diseases of plants of the invention is all effective, to plant epiphyte
Venereal disease evil only prevents downy mildew, phytophthora root rot, powdery mildew and continuous phytophthora root rot.《A kind of microbicide compositions containing oligosaccharides and copper》
(201010624172.8.) stresses in oligosaccharides in such a way that oligosaccharides is combined with organic copper or inorganic copper fungicide to sterilization
In terms of the synergy of agent.《Chitosan oligosaccharide chelated copper and preparation method thereof》(200816661.6) it is mutual with copper sulphate to report chitosan oligosaccharide
Chitosan oligosaccharide chelated copper is acted on, the utilization rate of copper can be improved and reduce the toxicity of copper.
In terms of chitosan prepares chitosan oligosaccharide by chemical method, mainly by the way of oxidative degradation.In order to be divided
The uniform chitosan oligosaccharide of son amount, is coordinated using copper ion and chitosan, and it is a kind of effective to weaken the active force between chitosan molecule
Mode, Yin Xueqiong carried out more in-depth study, and main paper has：《Oxidative degradation chitosan copper coordination compound prepares oligomeric
Chitosan》(applied chemistry, 2006,23 (7)：729-733)、《The coordination control oxidative degradation of chitosan and quantum Chemical Study》
(chemical research and application, 2004,16 (4)：485-488).The Chen Ping of Zhang Qi seminars《Chitosan copper (II) is coordinated to be controlled with oxidation
The GFC chromatogram research of system degradation oligosaccharides》(spectroscopy and spectrum analysis, 2005,25 (6)：992-995) to the structure of chitosan oligosaccharide into
Analysis is gone.
The introducing of the means such as ultrasound, microwave, nanofiltration, ultrafiltration can improve the efficiency that chitosan prepares chitosan oligosaccharide, increase
The yield of chitosan.Related patents have：《The method that ultrasonic-microwave synergistic oxidation prepares oligomeric narrow molecular weight distributed Chitosan oligosaccharides》
(201310270184.9) and《Ultrasonic-microwave is combined the method for preparing oligomeric narrow molecular weight distributed Chitosan poly sugar》
(201510493810.X) prepares narrow molecular weight distributed Chitosan oligosaccharides using ultrasound and microwave radiation technology oxidative degradation.《It is a kind of to gather shell
The method that sugar is prepared into water-soluble chitosan oligosaccharide》(201310726242.4) degradation of microwave radiation technology hydrogen peroxide is utilized to prepare water soluble shells
Oligosaccharides.《A method of water-soluble chitosan oligosaccharide is prepared using ultrafiltration and nanofiltration》(201310660738.6) ultrafiltration and nanofiltration are used
Means required oligosaccharides can be made to isolate reaction system in time.
On the basis of forefathers study, the present invention is complexed by copper ion and microwave radiation technology, oxidation prepare chitosan oligosaccharide-copper network
Object is closed, has no relevant report.
Invention content
In order to obtain the uniform chitosan oligosaccharide-copper complex of molecular weight, the present invention provides the following technical solutions：
1. a kind of chitosan oligosaccharide-copper complex, which is characterized in that chitosan oligosaccharide molecular weight 300~3000, deacetylation >=
85%, amido, hydroxyl and carbonyl are contained on chitosan oligosaccharide molecule, cooperatively forms chitosan oligosaccharide-copper complex with copper ion, shell is poly-
Sugar unit is 5~10 with copper ion molar ratio.
2. chitosan oligosaccharide-copper complex according to claim 1 carries out as steps described below：Chitosan is dissolved in acetic acid
Inorganic mantoquita is added in aqueous solution, forms homogeneous mixture, under stiring, will by adjusting microwave power after oxidant is added
Reaction temperature is controlled at 40~60 DEG C, reaction a period of time, is cooled to room temperature, and adjusts pH value to neutrality, filtrate is concentrated by evaporation
To the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
3. chitosan molecule amount according to claim 2 is 100,000~300,000, deacetylation >=85%.
4. acetic acid aqueous solution concentration according to claim 2 is in 1%~5% (weight percent).
5. inorganic mantoquita according to claim 2 includes：Cupric sulfate pentahydrate, copper chloride dihydrate.
6. the substance according to claim 2 for adjusting pH value is：Ammonium hydroxide, potassium hydroxide.
7. oxidant according to claim 2 includes：Hydrogen peroxide (30% content), potassium metaperiodate and combinations thereof.
8. reaction temperature according to claim 2 is controlled by microwave, microwave power 0.5kw~1.5kw.
Compared with the existing technology, the present invention has the advantages that：
1. the present invention can prepare chitosan oligosaccharide-copper complex with one-step method by chitosan.
2. the present invention weakens the intermolecular force of chitosan using the complex performance of copper ion, is increased using microwave and aoxidized
The efficiency of agent chain rupture, is acted synergistically by the two, can be quickly obtained chitosan oligosaccharide-copper complex.
3. due to the Complex effect of copper ion, the uniform chitosan oligosaccharide-copper complex of gained molecular weight.
Specific implementation mode
In order to which the technological means for making the present invention realize is apparent to, the present invention is done further with reference to specific embodiment
It illustrates.Following numbers is parts by weight.
Embodiment 1
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 4 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 2
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, and 6 parts of potassium metaperiodates are added
Afterwards, under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, reacts 4 hours, is cooled to room temperature,
PH=7 is adjusted with ammonium hydroxide, filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 3
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, and potassium metaperiodate 0.3 is added
Part, after 6 parts of hydrogen peroxide are added after 1 hour in reaction, under stiring, it is 1kw by adjusting microwave power, reaction temperature control is existed
It 50 DEG C, reacts 3 hours, is cooled to room temperature, pH=7 is adjusted with ammonium hydroxide, filtrate is concentrated by evaporation to the 1/3 of original volume, spraying
Up to chitosan oligosaccharide-copper complex after drying.
Embodiment 4
3 parts of chitosan (molecular weight is 200,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution, and two water chlorine are added
Change 0.44 part of copper, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 14 parts of hydrogen peroxide are added,
Under stirring, it is 1.5kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 5 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 5
3 parts of chitosan (molecular weight is 300,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution, and two water chlorine are added
Change 0.44 part of copper, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 20 parts of hydrogen peroxide are added,
Under stirring, it is 1.5kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 7 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 6
Chitosan (molecular weight is 100,000, deacetylation 85%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts by this, is added five
0.67 part of brochanite, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, and potassium metaperiodate 0.3 is added
Part, after 6 parts of hydrogen peroxide are added after 1 hour in reaction, under stiring, it is 1kw by adjusting microwave power, reaction temperature control is existed
It 50 DEG C, reacts 3 hours, is cooled to room temperature, pH=7 is adjusted with ammonium hydroxide, filtrate is concentrated by evaporation to the 1/3 of original volume, spraying
Up to chitosan oligosaccharide-copper complex after drying.
Embodiment 7
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 5% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 7 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 4 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 8
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 1% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 14 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 4 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 9
3 parts of chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution, and two water chlorine are added
Change 0.44 part of copper, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stirring, it is 0.5kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 6 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 10
3 parts of chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution, and two water chlorine are added
Change 0.44 part of copper, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stirring, it is 1.5kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 3 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 11
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 40 DEG C, is reacted 6 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 12
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 60 DEG C, is reacted 3 hours, is cooled to room temperature, uses ammonia
Water adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper complex after spray drying.
Embodiment 15
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.44 part of copper chloride, it is 7 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 4 hours, is cooled to room temperature, uses hydrogen
Potassium oxide saturated solution adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper after spray drying
Complex compound.
Embodiment 15
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.63 part of copper chloride, it is 5 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, after 10 parts of hydrogen peroxide are added,
Under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, is reacted 4 hours, is cooled to room temperature, uses hydrogen
Potassium oxide saturated solution adjusts pH=7, and filtrate is concentrated by evaporation to the 1/3 of original volume, up to chitosan oligosaccharide-copper after spray drying
Complex compound.
Embodiment 15
Chitosan (molecular weight is 100,000, deacetylation 90%) is dissolved in 100 part of 2% acetic acid aqueous solution for 3 parts, two water are added
0.32 part of copper chloride, it is 10 to keep chitosan unit and copper ion molar ratio, forms homogeneous mixture, and 10 parts of hydrogen peroxide are added
Afterwards, under stiring, it is 1kw by adjusting microwave power, reaction temperature is controlled at 50 DEG C, reacts 4 hours, is cooled to room temperature,
PH=7 is adjusted with potassium hydroxide saturated solution, filtrate is concentrated by evaporation to the 1/3 of original volume, it is few up to shell after spray drying
Sugar-copper complex.
Embodiment of above is merely illustrative of the technical solution of the present invention and unrestricted, and those skilled in the art should manage
Solution, is not departing from the purpose and scope of the invention, can be modified or replaced equivalently to technical scheme of the present invention,
It should cover within the scope of the present invention.
Claims (8)
1. a kind of chitosan oligosaccharide-copper complex, which is characterized in that chitosan oligosaccharide molecular weight is 300~3000, deacetylation >=85%,
Contain amido, hydroxyl and carbonyl on chitosan oligosaccharide molecule, chitosan unit is 5~10 with copper ion molar ratio.
2. chitosan oligosaccharide-copper complex according to claim 1 carries out as steps described below：It is water-soluble that chitosan is dissolved in acetic acid
Inorganic mantoquita is added in liquid, forms homogeneous mixture, after oxidant is added, under stiring, by adjusting microwave power, will react
Temperature is controlled at 40~60 DEG C, reaction a period of time, is cooled to room temperature, and adjusts pH value to neutrality, filtrate is concentrated by evaporation to original
Come the 1/3 of volume, up to chitosan oligosaccharide-copper complex after spray drying.
3. chitosan molecule amount according to claim 2 is 100,000~300,000, deacetylation >=85%.
4. acetic acid aqueous solution concentration according to claim 2 is in 1%~5% (weight percent).
5. inorganic mantoquita according to claim 2 includes：Cupric sulfate pentahydrate, copper chloride dihydrate.
6. the substance according to claim 2 for adjusting pH value is：Potassium hydroxide, ammonium hydroxide.
7. oxidant according to claim 2 includes：Hydrogen peroxide (30% content), potassium metaperiodate and combinations thereof.
8. reaction temperature according to claim 2 is controlled by microwave, microwave power 0.5kw~1.5kw.
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| CN201710167956.4A CN108623706A (en) | 2017-03-21 | 2017-03-21 | Microwave and complexing synergistic oxidation prepare the copper complex formazan method of chitosan oligosaccharide- |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563859A (en) * | 2019-09-19 | 2019-12-13 | 湖北医药学院 | One-pot synthesis method and application of anti-liver cancer drug selenite esterified chitosan copper |
| CN113969298A (en) * | 2021-11-25 | 2022-01-25 | 京博农化科技有限公司 | Preparation method of 6-carboxyl chitosan oligosaccharide-copper complex and application of prepared product |
-
2017
- 2017-03-21 CN CN201710167956.4A patent/CN108623706A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110563859A (en) * | 2019-09-19 | 2019-12-13 | 湖北医药学院 | One-pot synthesis method and application of anti-liver cancer drug selenite esterified chitosan copper |
| CN110563859B (en) * | 2019-09-19 | 2021-07-23 | 湖北医药学院 | One-pot synthesis method and application of anti-liver cancer drug selenite esterified chitosan copper |
| CN113969298A (en) * | 2021-11-25 | 2022-01-25 | 京博农化科技有限公司 | Preparation method of 6-carboxyl chitosan oligosaccharide-copper complex and application of prepared product |
| CN113969298B (en) * | 2021-11-25 | 2024-02-13 | 山东京博农化科技股份有限公司 | Preparation method of 6-carboxyl chitosan oligosaccharide-copper complex and application of prepared product |
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