CN105131152A - Marine organism polysaccharide copper compound, preparation thereof and application of marine organic polysaccharide copper compound serving as agricultural bactericide - Google Patents
Marine organism polysaccharide copper compound, preparation thereof and application of marine organic polysaccharide copper compound serving as agricultural bactericide Download PDFInfo
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Abstract
The invention belongs to marine chemical engineering technologies, and particularly relates to a marine organism polysaccharide copper compound, preparation thereof and application of the marine organic polysaccharide copper compound serving as agricultural bactericide. The marine organism polysaccharide copper compound is an O-carboxymethyl chitosan diacetone aminobenzoic acid Schiff base copper compound derivative, and the general formula of the compound is shown as the formula I, in the formula I, X is phenyl for replacing carboxyl and methyl at the same time or phenyl or carboxyl phenyl for replacing carboxyl and halogen at the same time, and n=1000-8000. The prepared O-carboxymethyl chitosan diacetone aminobenzoic acid Schiff base copper compound derivative has good solubility, can be dissolved in kinds of solvent, and avoids heavy metal ion residues in soil while improving the antibacterial effect, the application field of the compound is widened, and the compound has potential application value in the field of pesticide.
Description
Technical field
The invention belongs to marine chemical industry engineering, be specifically related to a kind of marine polysaccharide copper composition and preparation and the application as disinfectant use in agriculture.
Background technology
Copper agent obtains long-term widespread use due to plurality of advantages such as it are cheap, using method simply, not easily develops immunity to drugs.It is mainly divided into inorganic and organic two types.Rely on-the SH ,-NH that discharge in cupric ion and germ body internal protein
2, the group such as-COOH ,-OH works, and causes germ dead.But the improper use of traditional copper preparation very easily produces poisoning and brings out the outburst of mite class.Therefore, the content of cupric ion and releasability are the principal elements determining copper agent sterilizing disease-preventing effect, are also to determine that it is to crop safety important factor just simultaneously.
Chitosan is the good ocean glycosaminoglycan of a kind of renewable, nontoxic, biocompatibility and degradation property.Chitosan all has restraining effect to various plants pathogenic fungi, soil-borne disease can be prevented and treated as soil improvement agent in agricultural, prevent and treat seed-borne disease as seed coat agent, preserving fruit and vegetable utilizing controls post-harvest diseases etc., be developed as novel sea biogenic pesticide, have broad application prospects undoubtedly.But chitosan as single-activity component directly use have that drug effect is poor, consumption is large, high in cost of production problem, thus Difficulty.
Summary of the invention
The present invention is exactly for the problems referred to above, provides the good marine polysaccharide copper composition of a kind of novel structure, bacteriostatic activity and preparation and the application as disinfectant use in agriculture.
In order to realize above-mentioned purpose of the present invention, the present invention adopts following technical scheme:
A kind of marine polysaccharide copper composition, marine polysaccharide copper composition is O-CMC methyl ethyl diketone benzaminic acid Schiff's base copper composition derivative, its general formula such as formula shown in I,
In formula I, X is carboxyl, the simultaneously-substituted phenyl of methyl, the simultaneously-substituted phenyl of carboxyl, halogen or carboxyl phenyl; N=1000-8000.
In described formula I, X is carboxyl and methyl or the simultaneously-substituted phenyl of halogen.
A kind of preparation method of marine polysaccharide copper composition:
(1) benzaminic acid is dissolved in solvent, under reflux, carries out reaction with methyl ethyl diketone and generate single cropping amine ligand; Wherein, the volume of solvent and benzaminic acid mass ratio are 30-300:1; The mol ratio of benzaminic acid and methyl ethyl diketone is 1:1-3;
(2) full chitosan is dissolved in solvent, under acid catalysis, carry out reaction generating chitosan methyl ethyl diketone benzaminic acid Schiff base derivatives with single cropping amine ligand, after reaction, generate O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives with chloroacetate reaction again; Wherein, the volume of solvent and full chitosan mass ratio are 50-300:1; The mass ratio of full chitosan and single cropping amine ligand is 1:4-10; Full chitosan and chloroacetic mass ratio are 1:5-10;
(3) O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in solvent, reacts the methyl ethyl diketone of O-CMC shown in production I benzaminic acid Schiff's base copper composition derivative with venus crystals under heated and stirred; Wherein, the volume of solvent and O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives mass ratio are 100-300:1; The mass ratio of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives and venus crystals is 1:3-5; Temperature of reaction is 60-80 DEG C, and the reaction times is 6-12 hour; Filter cake solvent wash, carries out drying at 50-60 DEG C, obtains Chitosan Schiff-base copper composition derivative after drying.
Benzaminic acid is dissolved in solvent by described step (1), reacts generate single cropping amine ligand in 6-12 hour with methyl ethyl diketone at 60-80 DEG C under refluxing; Wherein, solvent is methyl alcohol and/ethanol.
Described benzaminic acid is 4-Amino-3-methylbenzoic acid, 4-amino-2-methyl phenylformic acid, 3-amino-2-methyl phenylformic acid, 3-amino-4-tolyl acid, 3-amino-4-chloro-benzoic acid or 4-amino-2-chloro-benzoic acid; Solvent is methyl alcohol and/ethanol.
Described step (2) step is that full chitosan is dissolved in solvent, at 60-80 DEG C, 6-12 hour generating chitosan methyl ethyl diketone benzaminic acid Schiff base derivatives is reacted with single cropping amine ligand, react at 60-80 DEG C with Mono Chloro Acetic Acid again after reaction and react for 6-12 hour, then filter filter cake organic solvent washing, at 50-60 DEG C, carry out drying, after drying, obtain O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives; Wherein, solvent is alcohol and water, and alcohol is methyl alcohol and/ethanol; Organic solvent is ethanol or acetone.
Described step (3) O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in solvent, 6-12 hour is reacted under stirring at 60-80 DEG C with venus crystals, filter filter cake after reaction and use ethanol, water washing successively, at 50-60 DEG C, carry out drying, after drying, obtain the methyl ethyl diketone of O-CMC shown in formula I benzaminic acid Schiff's base copper composition derivative; Wherein, solvent is alcohol and water, and alcohol is methyl alcohol and/ethanol.
An application for marine polysaccharide copper composition, polysaccharide copper composition shown in described formula I is used as the application of sterilant in agricultural, forestry and health field.
Principle: containing-NH in chitosan structure
2benzaminic acid can be introduced in chitosan structure with single cropping amine ligand generation schiff base reaction, use two N coordination cupric ions in chitosan and benzaminic acid again, namely number of amino groups is added, enhance by force bioactive, and then to produce with chitosan and act synergistically, significantly improve the biological activity of derivative.
Specifically, in the present invention, benzaminic acid and methyl ethyl diketone react and generate single cropping amine ligand, single cropping amine ligand and full chitosan C
2-NH on position
2react generating chitosan Schiff's base, and reacting with Mono Chloro Acetic Acid afterwards generates O-CMC derivative, C on this chitosan derivatives
2-N=on position, phenyl ring connect-NH-and venus crystals cupric ion coordination generate O-CMC copper composition derivative, the derivative of gained determines its structure through Infrared spectroscopy, and chitosan and the group of access are effectively combined and generate O-CMC methyl ethyl diketone benzaminic acid Schiff's base copper composition derivative.
Advantage of the present invention:
1. introduce aminobenzoic acid groups and cupric ion in chitosan structure of the present invention, three produces synergistic function, significantly improves the bacteriostatic activity of chitosan.
2. the O-CMC methyl ethyl diketone benzaminic acid Schiff's base copper composition derivative that prepared by the present invention has good solubility, dissolve in multi-solvents, heavy metal ion is also avoid residual in soil while raising fungistatic effect, expand its Application Areas, have potential using value at pesticide field.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of full chitosan, and its infrared signature absorbs (cm
-1): 1556,1069.
The infrared spectrogram of the chitosan derivatives 1 that Fig. 2 provides for the embodiment of the present invention, its infrared signature absorbs (cm
-1): 3426,3345,2922,1682,1596,1541,1434,1320,1280,1247.
The infrared spectrogram of the chitosan derivatives 2 that Fig. 3 provides for the embodiment of the present invention, its infrared signature absorbs (cm-1): 3426,3337,2923,1682,1596,1541,1434,1320,1280,1246.
The infrared spectrogram of the chitosan derivatives 3 that Fig. 4 provides for the embodiment of the present invention, its infrared signature absorbs (cm-1): 3422,3335,1672,1595,1542,1418,1320,1279,1246.
The infrared spectrogram of the chitosan derivatives 4 that Fig. 5 provides for the embodiment of the present invention, its infrared signature absorbs (cm-1): 3311,2877,1556,1397,1314.
The infrared spectrogram of the chitosan derivatives 5 that Fig. 6 provides for the embodiment of the present invention, its infrared signature absorbs (cm-1): 3422,3336,1683,1596,1542,1418,1317.
The infrared spectrogram of the chitosan derivatives 6 that Fig. 7 provides for the embodiment of the present invention, its infrared signature absorbs (cm-1): 3422,3336,2926,1683,1595,1542,1419,1318,1279,1246.
Embodiment
Below in conjunction with Figure of description, the invention will be further described, and protection scope of the present invention is not only confined to following examples.
The present invention adopts active substructure to splice principle, the bio-active group of benzaminic acid Schiff base derivatives is incorporated in natural product chitosan skeleton, utilize the amino complex copper ion in molecule, prepare the chitosan derivative that antibacterial and inducing anti-disease activity all improves, open new way for development of new biological pesticide.
The preparation of embodiment 1 derivative 1
Join in 70mL dehydrated alcohol by 2.5 grams of 4-Amino-3-methylbenzoic acids, 1.66 grams of methyl ethyl diketones, 60 DEG C are reacted 12 hours, and reactant revolves steaming, and cold ethanol is washed, dry at 60 DEG C, obtain single cropping amine ligand.
By 0.5 gram molecular weight be 1,300,000 full chitosan join in 20mL dehydrated alcohol and 25mL water, drip 0.5mL acetic acid to it under stirring; 2.0 grams of single cropping amine ligands join in 50mL dehydrated alcohol, are added drop-wise in reaction system, and 60 DEG C are reacted 12 hours; 2.5 grams of Mono Chloro Acetic Acids are joined in 10mL dehydrated alcohol, be added drop-wise in reaction system, 60 DEG C are reacted 6 hours, be cooled to room temperature, add dehydrated alcohol precipitation, precipitation suction filtration, absolute ethanol washing, dry at 60 DEG C, obtain pale yellow powder, be O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives.
0.3 gram of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram of Cu (OAc)
22H
2o is dissolved in 50mL water, under 70 DEG C of stirrings, the venus crystals aqueous solution is added drop-wise in the Schiff's base aqueous solution, react 6 hours, be cooled to room temperature, centrifugal, washing, 60 DEG C of dryings, obtain dark green powder, are the copper composition of O-CMC shown in formula I derivative 1, wherein X is 2-methyl-4-carboxyl phenyl, n=1000-8000.
Infrared spectra shows: the infrared spectrum (Fig. 2) of O-CMC copper composition derivative 1, compared with the infrared spectrum (Fig. 1) of full chitosan, is positioned at 1556cm
-1the charateristic avsorption band of NH weaken, show NH
2react; 1596,1434cm
-1for the charateristic avsorption band of C=N and C-N; 1541cm
-1for the characteristic absorbance of phenyl ring; Prove that order derivative 1 synthesizes successfully.
The preparation of embodiment 2 derivative 2
Join in 70mL dehydrated alcohol by 2.5 grams of 4-amino-2-methyl phenylformic acid, 1.66 grams of methyl ethyl diketones, 60 DEG C are reacted 12 hours, and reactant revolves steaming, and cold ethanol is washed, dry at 60 DEG C, obtain single cropping amine ligand.
By 0.5 gram molecular weight be 1,300,000 full chitosan join in 20mL dehydrated alcohol and 25mL water, drip 0.5mL acetic acid to it under stirring; 2.0 grams of single cropping amine ligands join in 50mL dehydrated alcohol, are added drop-wise in reaction system, and 60 DEG C are reacted 12 hours; 2.5 grams of Mono Chloro Acetic Acids are joined in 10mL dehydrated alcohol, be added drop-wise in reaction system, 60 DEG C are reacted 6 hours, be cooled to room temperature, add dehydrated alcohol precipitation, precipitation suction filtration, absolute ethanol washing, dry at 60 DEG C, obtain faint yellow toner end, be O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives.
0.3 gram of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram of Cu (OAc)
22H
2o is dissolved in 50mL water, under 70 DEG C of stirrings, the venus crystals aqueous solution is added drop-wise in the Schiff's base aqueous solution, react 6 hours, be cooled to room temperature, centrifugal, washing, 60 DEG C of dryings, obtain dark green powder, are the copper composition of O-CMC shown in formula I derivative 1, wherein X is 3-methyl-4-carboxyl phenyl, n=1000-8000.
Infrared spectra shows: the infrared spectrum (Fig. 3) of O-CMC derivative 2, compared with the infrared spectrum (Fig. 1) of full chitosan, is positioned at 1556cm
-1the charateristic avsorption band of NH weaken, show NH
2react; 1596,1434cm
-1for the charateristic avsorption band of C=N and C-N; 1541cm
-1for the characteristic absorbance of phenyl ring; Prove that order derivative is 2-in-1 successfully.
The preparation of embodiment 3 derivative 3
Join in 70mL dehydrated alcohol by 2.5 grams of 3-amino-2-methyl phenylformic acid, 1.66 grams of methyl ethyl diketones, 60 DEG C are reacted 12 hours, and reactant revolves steaming, and cold ethanol is washed, dry at 60 DEG C, obtain single cropping amine ligand.
By 0.5 gram molecular weight be 1,300,000 full chitosan join in 20mL dehydrated alcohol and 25mL water, drip 0.5mL acetic acid to it under stirring; 2.0 grams of single cropping amine ligands join in 50mL dehydrated alcohol, are added drop-wise in reaction system, and 60 DEG C are reacted 12 hours; 2.5 grams of Mono Chloro Acetic Acids are joined in 10mL dehydrated alcohol, be added drop-wise in reaction system, 60 DEG C are reacted 6 hours, be cooled to room temperature, add dehydrated alcohol precipitation, precipitation suction filtration, absolute ethanol washing, dry at 60 DEG C, obtain faint yellow toner end, be O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives.
0.3 gram of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram of Cu (OAc)
22H
2o is dissolved in 50mL water, under 70 DEG C of stirrings, the venus crystals aqueous solution is added drop-wise in the Schiff's base aqueous solution, react 6 hours, be cooled to room temperature, centrifugal, washing, 60 DEG C of dryings, obtain dark green powder, are the copper composition of O-CMC shown in formula I derivative 1, wherein X is 2-methyl-3-carboxyl phenyl, n=1000-8000.
Infrared spectra shows: the infrared spectrum (Fig. 4) of O-CMC derivative 3, compared with the infrared spectrum (Fig. 1) of full chitosan, is positioned at 1556cm
-1the charateristic avsorption band of NH weaken, show NH
2react; 1595,1418cm
-1for the charateristic avsorption band of C=N and C-N; 1541cm
-1for the characteristic absorbance of phenyl ring; Prove that order derivative 3 synthesizes successfully.
The preparation of embodiment 4 derivative 4
Join in 70mL dehydrated alcohol by 2.5 grams of 3-amino-4-tolyl acids, 1.66 grams of methyl ethyl diketones, 60 DEG C are reacted 12 hours, and reactant revolves steaming, and cold ethanol is washed, dry at 60 DEG C, obtain single cropping amine ligand.
By 0.5 gram molecular weight be 1,300,000 full chitosan join in 20mL dehydrated alcohol and 25mL water, drip 0.5mL acetic acid to it under stirring; 2.0 grams of single cropping amine ligands join in 50mL dehydrated alcohol, are added drop-wise in reaction system, and 60 DEG C are reacted 12 hours; 2.5 grams of Mono Chloro Acetic Acids are joined in 10mL dehydrated alcohol, be added drop-wise in reaction system, 60 DEG C are reacted 6 hours, be cooled to room temperature, add dehydrated alcohol precipitation, precipitation suction filtration, absolute ethanol washing, dry at 60 DEG C, obtain faint yellow toner end, be O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives 4.
0.3 gram of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram of Cu (OAc)
22H
2o is dissolved in 50mL water, under 70 DEG C of stirrings, the venus crystals aqueous solution is added drop-wise in the Schiff's base aqueous solution, react 6 hours, be cooled to room temperature, centrifugal, washing, 60 DEG C of dryings, obtain dark green powder, are the copper composition of O-CMC shown in formula I derivative 1, wherein X is 2-methyl-5-carboxyl phenyl, n=1000-8000.
Infrared spectra shows: the infrared spectrum (Fig. 5) of O-CMC derivative 4, compared with the infrared spectrum (Fig. 1) of full chitosan, is positioned at 1556cm
-1the charateristic avsorption band of NH weaken, show NH
2react; 1556cm
-1for the characteristic absorbance of phenyl ring; Prove that order derivative 4 synthesizes successfully.
The preparation of embodiment 5 derivative 5
Join in 70mL dehydrated alcohol by 2.5 grams of 3-amino-4-chloro-benzoic acids, 1.66 grams of methyl ethyl diketones, 60 DEG C are reacted 12 hours, and reactant revolves steaming, and cold ethanol is washed, dry at 60 DEG C, obtain single cropping amine ligand.
By 0.5 gram molecular weight be 1,300,000 full chitosan join in 20mL dehydrated alcohol and 25mL water, drip 0.5mL acetic acid to it under stirring; 2.0 grams of single cropping amine ligands join in 50mL dehydrated alcohol, are added drop-wise in reaction system, and 60 DEG C are reacted 12 hours; 2.5 grams of Mono Chloro Acetic Acids are joined in 10mL dehydrated alcohol, be added drop-wise in reaction system, 60 DEG C are reacted 6 hours, be cooled to room temperature, add dehydrated alcohol precipitation, precipitation suction filtration, absolute ethanol washing, dry at 60 DEG C, obtain faint yellow toner end, be O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives.
0.3 gram of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram of Cu (OAc)
22H
2o is dissolved in 50mL water, under 70 DEG C of stirrings, the venus crystals aqueous solution is added drop-wise in the Schiff's base aqueous solution, react 6 hours, be cooled to room temperature, centrifugal, washing, 60 DEG C of dryings, obtain dark green powder, are the copper composition of O-CMC shown in formula I derivative 1, wherein X is 3-carboxyl-5-chloro-phenyl-, n=1000-8000.
Infrared spectra shows: the infrared spectrum (Fig. 6) of O-CMC derivative 5, compared with the infrared spectrum (Fig. 1) of full chitosan, is positioned at 1556cm
-1the charateristic avsorption band of NH weaken, show NH
2react; 1596,1418cm
-1for the charateristic avsorption band of C=N and C-N; 1542cm
-1for the characteristic absorbance of phenyl ring; Prove that order derivative 5 synthesizes successfully.
The preparation of embodiment 6 derivative 6
Join in 70mL dehydrated alcohol by 2.5 grams of 4-amino-2-chloro-benzoic acids, 1.66 grams of methyl ethyl diketones, 60 DEG C are reacted 12 hours, and reactant revolves steaming, and cold ethanol is washed, dry at 60 DEG C, obtain single cropping amine ligand.
By 0.5 gram molecular weight be 1,300,000 full chitosan join in 20mL dehydrated alcohol and 25mL water, drip 0.5mL acetic acid to it under stirring; 2.0 grams of single cropping amine ligands join in 50mL dehydrated alcohol, are added drop-wise in reaction system, and 60 DEG C are reacted 12 hours; 2.5 grams of Mono Chloro Acetic Acids are joined in 10mL dehydrated alcohol, be added drop-wise in reaction system, 60 DEG C are reacted 6 hours, be cooled to room temperature, add dehydrated alcohol precipitation, precipitation suction filtration, absolute ethanol washing, dry at 60 DEG C, obtain faint yellow toner end, be O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives.
0.3 gram of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in 30mL water, 0.5 gram of Cu (OAc)
22H
2o is dissolved in 50mL water, under 70 DEG C of stirrings, the venus crystals aqueous solution is added drop-wise in the Schiff's base aqueous solution, react 6 hours, be cooled to room temperature, centrifugal, washing, 60 DEG C of dryings, obtain dark green powder, are the copper composition of O-CMC shown in formula I derivative 1, wherein X is 4-carboxyl-3-chloro-phenyl-, n=1000-8000.
Infrared spectra shows: the infrared spectrum (Fig. 7) of O-CMC derivative 6, compared with the infrared spectrum (Fig. 1) of full chitosan, is positioned at 1556cm
-1the charateristic avsorption band of NH weaken, show NH
2react; 1595,1419cm
-1for the charateristic avsorption band of C=N and C-N; 1542cm
-1for the characteristic absorbance of phenyl ring; Prove that order derivative 6 synthesizes successfully.
Antibacterial Activity
Adopt growth rate method working sample to the bacteriostatic activity of Phytophthora capsici pathogenic bacteria.Test under 3 sample concentrations namely: 100 μ g/mL, 200 μ g/mL, 400 μ g/mL are to the inhibition of Phytophthora capsici.
Testing with the good general oligosaccharides medicament of the same concentrations aqua of 2% (commercially available be) and the Thiodiazole-copper suspension agent of 20% (commercially available be) medicament for positive control, take distilled water as negative control.Substratum evenly being poured into 1 diameter is in the culture dish of 9cm, after solidifying completely, inoculates the bacterium cake that 3 pieces of diameters are 5mm in each culture dish.Cultivate at 27 DEG C after 72 hours, measure colony diameter, the bacteriostasis rate of calculation sample.Each process arranges 1 culture dish, and 3 bacterium colonies inoculated by every ware, to each Detection of colony maximum diameter (D
max) and minimum diameter (D
min), average as sample antibacterial circle diameter D
sample, total Test repeats once.Bacteriostasis rate (table 1) is calculated according to following formula.
Bacteriostasis rate (%)=(D
blank-d
sample)/(D
blank-5) × 100
Experimental result shows that O-CMC methyl ethyl diketone benzaminic acid Schiff's base copper composition derivative generally has good fungistatic effect to Phytophthora capsici, is significantly better than present existing good general oligosaccharides and Thiodiazole-copper product.
Table 1 partial Formula 1 chitosan derivatives is to the inhibit activities of Phytophthora capsici
| Compound | Concentration (μ g/mL) | To Phytophthora capsici inhibiting rate (%) |
| 2 | 100 | 28.6 |
| 200 | 63.3 | |
| 400 | 73.5 | |
| 3 | 100 | 38.0 |
| 200 | 100.0 | |
| 400 | 100.0 | |
| 4 | 100 | 28.6 |
| 200 | 100.0 | |
| 400 | 100.0 | |
| 5 | 100 | 22.9 |
| 200 | 83.7 | |
| 400 | 100.0 | |
| 6 | 100 | 24.1 |
| 200 | 73.1 | |
| 400 | 100.0 | |
| Good general oligosaccharides | 100 | 45.7 |
| 200 | 58.0 | |
| 400 | 75.5 | |
| Thiodiazole-copper | 100 | -1.6 |
| 200 | -9.0 | |
| 400 | 35.9 | |
| Chitosan | 100 | 14.3 |
| 200 | 16.3 | |
| 400 | 42.0 |
Claims (8)
1. a marine polysaccharide copper composition, is characterized in that: marine polysaccharide copper composition is O-CMC methyl ethyl diketone benzaminic acid Schiff's base copper composition derivative, its general formula such as formula shown in I,
In formula I, X is carboxyl, the simultaneously-substituted phenyl of methyl, the simultaneously-substituted phenyl of carboxyl, halogen or carboxyl phenyl; N=1000-8000.
2. marine polysaccharide copper composition according to claim 1, is characterized in that: in described formula I, and X is carboxyl and methyl or the simultaneously-substituted phenyl of halogen.
3. a preparation method for marine polysaccharide copper composition according to claim 1, is characterized in that:
(1) benzaminic acid is dissolved in solvent, under reflux, carries out reaction with methyl ethyl diketone and generate single cropping amine ligand; Wherein, the volume of solvent and benzaminic acid mass ratio are 30-300:1; The mol ratio of benzaminic acid and methyl ethyl diketone is 1:1-3;
(2) full chitosan is dissolved in solvent, under acid catalysis, carry out reaction generating chitosan methyl ethyl diketone benzaminic acid Schiff base derivatives with single cropping amine ligand, after reaction, generate O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives with chloroacetate reaction again; Wherein, the volume of solvent and full chitosan mass ratio are 50-300:1; The mass ratio of full chitosan and single cropping amine ligand is 1:4-10; Full chitosan and chloroacetic mass ratio are 1:5-10;
(3) O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in solvent, reacts the methyl ethyl diketone of O-CMC shown in production I benzaminic acid Schiff's base copper composition derivative with venus crystals under heated and stirred; Wherein, the volume of solvent and O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives mass ratio are 100-300:1; The mass ratio of O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives and venus crystals is 1:3-5; Temperature of reaction is 60-80 DEG C, and the reaction times is 6-12 hour; Filter cake solvent wash, carries out drying at 50-60 DEG C, obtains Chitosan Schiff-base copper composition derivative after drying.
4. the preparation method of marine polysaccharide copper composition according to claim 3, it is characterized in that: benzaminic acid is dissolved in solvent by described step (1), react under refluxing at 60-80 DEG C with methyl ethyl diketone and generate single cropping amine ligand in 6-12 hour; Wherein, solvent is methyl alcohol and/ethanol.
5. the preparation method of the marine polysaccharide copper composition according to claim 3 or 4, is characterized in that: described benzaminic acid is 4-Amino-3-methylbenzoic acid, 4-amino-2-methyl phenylformic acid, 3-amino-2-methyl phenylformic acid, 3-amino-4-tolyl acid, 3-amino-4-chloro-benzoic acid or 4-amino-2-chloro-benzoic acid; Solvent is methyl alcohol and/ethanol.
6. the preparation method of marine polysaccharide copper composition according to claim 3, it is characterized in that: described step (2) step is that full chitosan is dissolved in solvent, at 60-80 DEG C, 6-12 hour generating chitosan methyl ethyl diketone benzaminic acid Schiff base derivatives is reacted with single cropping amine ligand, react at 60-80 DEG C with Mono Chloro Acetic Acid again after reaction and react for 6-12 hour, then filter filter cake organic solvent washing, at 50-60 DEG C, carry out drying, after drying, obtain O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives; Wherein, solvent is alcohol and water; Organic solvent is ethanol or acetone.
7. the preparation method of marine polysaccharide copper composition according to claim 3, it is characterized in that: described step (3) O-CMC methyl ethyl diketone benzaminic acid Schiff base derivatives is dissolved in solvent, 6-12 hour is reacted under stirring at 60-80 DEG C with venus crystals, filter filter cake after reaction and use ethanol, water washing successively, at 50-60 DEG C, carry out drying, after drying, obtain the methyl ethyl diketone of O-CMC shown in formula I benzaminic acid Schiff's base copper composition derivative; Wherein, solvent is alcohol and water.
8. an application for marine polysaccharide copper composition according to claim 1, is characterized in that: polysaccharide copper composition shown in described formula I is used as the application of sterilant in agricultural, forestry and health field.
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| CN105801722A (en) * | 2016-03-28 | 2016-07-27 | 中国科学院海洋研究所 | Marine organism polysaccharide copper compound and preparation method and application thereof |
| CN107188993A (en) * | 2017-07-17 | 2017-09-22 | 中国科学院海洋研究所 | A kind of marine polysaccharide copper composition and its preparation method and application |
| CN107200791A (en) * | 2017-07-17 | 2017-09-26 | 中国科学院海洋研究所 | A kind of marine polysaccharide nickel composite and its preparation method and application |
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| CN107200791A (en) * | 2017-07-17 | 2017-09-26 | 中国科学院海洋研究所 | A kind of marine polysaccharide nickel composite and its preparation method and application |
| CN107232202A (en) * | 2017-07-23 | 2017-10-10 | 青岛海大生物集团有限公司 | A kind of preparation method of sea grass polysaccharide network ammonia copper fungicide |
| CN107746437A (en) * | 2017-11-23 | 2018-03-02 | 中国科学院海洋研究所 | A kind of marine polysaccharide quaternary ammonium salt derivative and its preparation and application |
| CN108424467A (en) * | 2018-04-16 | 2018-08-21 | 陕西科技大学 | A kind of preparation method of cellulose base composite antibacterial material |
| CN114805637A (en) * | 2022-05-31 | 2022-07-29 | 中国科学院海洋研究所 | Marine organism polysaccharide Schiff base derivative and preparation method and application thereof |
| CN114805637B (en) * | 2022-05-31 | 2023-02-03 | 中国科学院海洋研究所 | Marine organism polysaccharide Schiff base derivative and preparation method and application thereof |
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