CN107897189A - A kind of complex composition and preparation of the lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper - Google Patents
A kind of complex composition and preparation of the lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper Download PDFInfo
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- CN107897189A CN107897189A CN201711218303.0A CN201711218303A CN107897189A CN 107897189 A CN107897189 A CN 107897189A CN 201711218303 A CN201711218303 A CN 201711218303A CN 107897189 A CN107897189 A CN 107897189A
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- adipic acid
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- acid copper
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/46—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom rings with more than six members
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
- A01N37/04—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof polybasic
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Abstract
The present invention discloses a kind of complex composition and preparation of the lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, which is made of isolonglifolene ketoxime lactams and tiger glue adipic acid copper；Wherein the weight ratio of isolonglifolene ketoxime lactams and tiger glue adipic acid copper is preferably (20~1):The weight summation of (1~20), isolonglifolene ketoxime lactams and tiger glue adipic acid copper accounts for the 0.1%~90% of fungicide gross weight.Complex composition provided by the invention is suitable for prevention bacterial disease and fungal disease, obvious synergistic effect is shown, dosage can be reduced, delays the resistance to the action of a drug of the germ to single medicament, ecological disruption and environmental pollution are effectively reduced, and crop yield and quality can be improved.
Description
Technical field
The present invention relates to technical field of pesticide, and in particular to a kind of lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper
Complex composition and preparation.
Background technology
The resistance problem of agricultural pests is a global problem.With the continuity of disease chemical prevention, Pesticide use
The increase of amount and not scientifical use pesticide, the resistance getting worse of germ, the germ species for producing resistance are on the increase.Especially
It is bacterial disease, resistance level is high, and resistance development speed is fast.
As people constantly strengthen the consciousness of environmental protection and social sustainable development, especially 21 century, from plant
New natural drug is found and excavated in resource applied to medicine or agriculturally, has become countries in the world important subject.
It is increasingly difficult to using traditional fungicide of the synthetic method synthesis with excellent activity, and this fungicide that is synthesized is past
It is past that there is certain toxicity, the resistance to the action of a drug and pollution environment etc., for example the pesticide such as DDT, six six six organochlorine is due to environmental disruption
Property it is relatively strong and be gradually backed out market or be eliminated.Therefore, researching and developing and formulate the newtype drug with autonomous property right becomes medicine
Learn the hot spot with Pesticide Science research.Oximido ether compound tool has been widely used, for example as fungicide, antifungal agent, weeding
Agent etc., and there is hypotoxicity, low-residual, high activity, widely attract the research interest of research-on-research.Recently, people
Find 1,2,3,4,5,6- hexahydros -1,1,5,5- tetramethyl -7H-2,4 α-methanonaphthalene -7- ketone (Isolongifolenone) is to suppressing
Junket ammonia enzyme and anti-breast cancer have preferable activity, and Isolongifolenone is highly effective to prevention tick and bite by mosquitos, effect
Fruit is better than traditional Metadelphene.
Tiger glue adipic acid copper has efficient, wide spectrum, safer bactericidal effect, has preferable sterilization to bacterium, fungi etc.
Effect.But because its long-time uses, alone its prevents crop disease, and prevention effect is undesirable, and disease also generates one to it
Determine the resistance to the action of a drug.Therefore, it is necessary to develop a kind of pesticide complex composition efficiently, less toxic, environmentally friendly.
Isolonglifolene ketoxime lactam structure formula is as follows:
The step of preparation process of the compound：Using Isolongifolenone as raw material, different come into leaves is synthesized by addition elimination reaction
Ketenes oxime, then acyl in the isolonglifolene ketoxime should be prepared by the progress Beckmann rearrangement reactions of isolonglifolene ketoxime
Amine.
The content of the invention
Applicant further study show that, show isolonglifolene ketoxime lactams to bacterial disease by substantial amounts of experiment
It is respectively provided with preferable prevention effect and inhibitory action.It can inhibit bacteria such as staphylococcus aureus, escherichia coli, pneumonia gram
The primary Salmonella of thunder, proteus vulgaris and pseudomonas aeruginosa and fungi Ru Aspergillus, Exserohilum turcicum, corn line it is withered, fragrant
Any of several broadleaf plants lotus lattice bacterium, banana anthrax etc.；Superior insecticidal action is shown to insect pests such as aphid and planthoppers.The compound has height
Effect, wide spectrum, it is safe to use the characteristics of, be with exploitation for large tonnage product potential quality fungicide.Acute toxicity and environment poison
Property experiment show that isolonglifolene ketoxime lactams belongs to low toxicity compounds, have good market prospects.
However, a kind of appearance of new drug, if long-term single use, is all inevitably generated resistance, Isolongifolenone
This new type bactericide of oxime lactams is no exception, and single dose uses, its prevention to pest and disease damage is also difficult to obtain its optimum efficiency.
Therefore, it is to improve the effect of prevention crop disease by isolonglifolene ketoxime lactams and tiger glue adipic acid copper compounding by compounding channel
Fruit, and the effective way of delaying drug resistance development.
In view of this, the purpose of the present invention solves above-mentioned technical problem, there is provided a kind of lactams of ketoxime containing isolonglifolene with
The complex composition of tiger glue adipic acid copper, the complex composition have obvious synergistic function relative to single dose, reduce pesticide
Dosage, while delay the resistance to the action of a drug of the pathogen to isolonglifolene ketoxime lactams and tiger glue adipic acid copper.
To realize above-mentioned purpose, use following technical scheme of the invention：
A kind of complex composition of the lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, the complex composition is by different length
Leaf ketenes oxime lactams and tiger glue adipic acid copper composition；Wherein, the weight of the isolonglifolene ketoxime lactams and tiger glue adipic acid copper
It is (20~1) to measure ratio:(1~20).
The complex composition of the above-described lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, in order to ensure compounding group
Compound has more preferable preventive effect and synergistic effect, it is further preferred that the isolonglifolene ketoxime lactams and tiger glue adipic acid
The weight ratio of copper is (10~1)：(1~10).
The present invention also provides a kind of lactams of ketoxime containing isolonglifolene and the preparation of tiger glue adipic acid copper, including more than the present invention
Acceptable adjuvant on the complex composition and pesticide of offer, is then prepared into disinfectant use in agriculture.
The preparation of the above-described lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, it is excellent in order to ensure bactericidal effect
Selection of land, the weight percentage that the complex composition accounts for the disinfectant use in agriculture are 0.1%~90%.
The preparation of the above-described lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, in order to ensure bactericidal effect, more
Preferably, the weight percentage that the complex composition accounts for the disinfectant use in agriculture is 1%~80%.
According to different use demands, disinfectant use in agriculture provided by the invention can be made into a variety of formulations.There is provided in the present invention
Some embodiments in, the formulation of fungicide is wettable powder, suspending agent, water dispersible granules, aqueous emulsion, seed treatment dry powder
Agent or granule.It is not limited only to formulation provided by the invention.
According to a variety of formulation different demands of fungicide, acceptable auxiliary material is in filler and solvent on the pesticide
A kind of and mixture of auxiliary agent.
Filler includes kaolin, diatomite, bentonite, attapulgite, white carbon, starch, urea, chitin, composite fertilizer
Or precipitated calcium carbonate.
Solvent includes dimethylbenzene, ethanol, turpentine oil, solvent naphtha, dimethyl carbonate, trimethylbenzene, dimethylformamide, diformazan
Base sulfoxide or water.
Auxiliary agent includes emulsifying agent, wetting agent, dispersant, can also add antifreezing agent, thickener, stabilizer, defoaming if necessary
Other conventional functionality auxiliary agents such as agent, disintegrant, film forming agent.
Emulsifying agent includes polyoxyethylene carboxylate, nonylphenol polyoxyethylene ether, castor oil polyoxyethylene ether, fatty acid polyglycol
Ethylene oxide base ester, agriculture breast 500# or agriculture breast 33#.
Dispersant includes polycarboxylate, lignosulfonates, APES formaldehyde condensation products sulfat, alkyl
Benzene sulfonic acid calcium salt, naphthalene sulfonic acid-formaldehyde condensation product sodium salt, alkylphenol polyoxyethylene ether, aliphatic amine polyoxyethylene ether, aliphatic acid polyoxy
Vinyl acetate or glycerine fatty acid ester APEO.
Wetting agent includes lauryl sodium sulfate, calcium dodecyl benzene sulfonate, pull open powder, alkylnaphthalene sulfonate, polyoxy second
Alkene triphenylethylene phosphenylic acid salt or spaonin powder.
Disintegrant includes sodium chloride, ammonium sulfate or sodium acid carbonate.
Thickener includes xanthans, hydroxymethyl cellulose, hydroxyethyl cellulose, methylcellulose, Magnesiumaluminumsilicate or poly- second
Enol.
Antifreezing agent is selected from least one of ethylene glycol, propane diols, glycerine.
Defoamer is selected from silicone oil, silicone compound.
Binding agent is selected from urea, starch, methylcellulose.
The present invention also provides use of the complex composition in terms of prevention crop bacterium venereal disease evil and fungal disease
On the way.
Bacterial disease is bacterial blight of rice, slice disease, tobacco bacterial wilt, bacterial wilt of tomato, soft rot of cabbage, cucumber
Bacterial angular leaf spot, citrus bacterial canker disease.
Fungal disease is Rhizoctonia solani Kuhn, ulcer bacteria, rhizoctonia, rest fungus and disease caused by sclerotium rolfsii.
The complex composition and its preparation of the present invention has the advantage that：
1st, complex composition and preparation of the invention, have significant synergies, both improve protection effect, reduce
Using preparation and prevention mu cost, and expand fungicidal spectrum；
2nd, complex composition of the invention, can reach and delay the drug-fast occurrence and development of pathogen.
Embodiment
The present invention is illustrated with the following example, but is not limited the scope of the invention.It is used in the present invention different to come into leaves
For ketenes oxime lactams active compound by being provided by Guangxi National Univ., other active compounds used and preparation are purchased in market.Wherein activearm
It is isolonglifolene ketoxime lactams to divide (A), and active component (B) is tiger glue adipic acid copper.
Preparation prepares embodiment：
Embodiment 1：60% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder (4:56)
By isolonglifolene ketoxime lactams 4%, tiger glue adipic acid copper 56%, polyoxyethylene tri-styryl phosphenylic acid salt 5%,
APES formaldehyde condensation products sulfat 3%, attapulgite supply 100% mixing, the uniform stirring in stirred tank,
It is being uniformly mixed after airslide disintegrating mill, that is, 60% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder is made.
Embodiment 2：16% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder (15:1)
By isolonglifolene ketoxime lactams 15%, tiger glue adipic acid copper 1%, pull open powder 4%, alkyl benzene sulfonate calcium salt 5%, height
Ridge soil supplies 100% mixing, the uniform stirring in stirred tank, is being uniformly mixed after airslide disintegrating mill, that is, 16% different length is made
Leaf ketenes oxime lactams tiger glue adipic acid copper wettable powder.
Embodiment 3：80% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder (72:8)
By isolonglifolene ketoxime lactams 72%, tiger glue adipic acid copper 8%, lignosulfonates 6%, lauryl sodium sulfate
2%th, diatomite supplies 100% mixing, the uniform stirring in stirred tank, is being uniformly mixed, that is, is being made after airslide disintegrating mill
80% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder.
Embodiment 4：33% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder (30:3)
By isolonglifolene ketoxime lactams 30%, tiger glue adipic acid copper 3%, alkylphenol polyoxyethylene ether 8%, glycerine fatty acid
Ester APEO 7%, bentonite supply 100% mixing, the uniform stirring in stirred tank, equal in mixing after airslide disintegrating mill
It is even, that is, 33% isolonglifolene ketoxime lactams tiger glue adipic acid copper wettable powder is made.
Embodiment 5：20% isolonglifolene ketoxime lactams tiger glue adipic acid copper suspending agent (1:19)
By glycerine fatty acid ester APEO 10%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 3.5%, ethylene glycol 2%, silicone oil
1%th, hydroxyethyl cellulose 1%, water supply 100% mixing, are uniformly mixed through high speed shear, sequentially add in isolonglifolene ketoxime
Acid amides 1%, tiger glue adipic acid copper 19%, when abrading-ball 2~3 is small in ball crusher, make a diameter that in below 5mm, it is different to be made 20%
Longifolene ketoxime lactams tiger glue adipic acid copper suspending agent.
Embodiment 6：16% isolonglifolene ketoxime lactams tiger glue adipic acid copper suspending agent (8:8)
By polyoxyethylene carboxylate 9%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 2.5%, ethylene glycol 4%, silicone chemical combination
Thing 1%, methylcellulose 1%, water supply 100% mixing, are uniformly mixed through high speed shear, sequentially add in isolonglifolene ketoxime
Acid amides 8%, tiger glue adipic acid copper 8%, when abrading-ball 2~3 is small in ball crusher, make a diameter that in below 5mm, 16% different length be made
Leaf ketenes oxime lactams tiger glue adipic acid copper suspending agent.
Embodiment 7：30% isolonglifolene ketoxime lactams tiger glue adipic acid copper suspending agent (3:27)
By alkylphenol polyoxyethylene ether 8%, calcium dodecyl benzene sulfonate 2%, glycerine 3%, hydroxymethyl cellulose 5%,
Silicone oil 1%, water supply 100% mixing, are uniformly mixed through high speed shear, sequentially add isolonglifolene ketoxime lactams 3%, amber glue
Adipic acid copper 27%, when abrading-ball 2~3 is small in ball crusher, makes a diameter in below 5mm, be made in 30% isolonglifolene ketoxime
Acid amides tiger glue adipic acid copper suspending agent.
Embodiment 8：21% isolonglifolene ketoxime lactams tiger glue adipic acid copper suspending agent (20:1)
By aliphatic amine polyoxyethylene ether 7%, lauryl sodium sulfate 4%, propane diols 1%, silicone compound 1%, Huang
Virgin rubber 0.1%, water supply 100% mixing, are uniformly mixed through high speed shear, sequentially add isolonglifolene ketoxime lactams 20%,
Tiger glue adipic acid copper 1%, when abrading-ball 2~3 is small in ball crusher, makes a diameter that in below 5mm, 21% isolonglifolene ketoxime be made
Lactams tiger glue adipic acid copper suspending agent.
CK1：20% isolonglifolene ketoxime lactams suspending agent
By polyoxyethylene carboxylate 6%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 4%, ethylene glycol 8%, silicone compound
2%th, methylcellulose 2%, water supply 100% mixing, are uniformly mixed through high speed shear, sequentially add acyl in isolonglifolene ketoxime
Amine 20% makes a diameter in below 5mm, 20% isolonglifolene ketoxime lactams be made and hang when abrading-ball 2~3 is small in ball crusher
Floating agent.
Embodiment 9：21% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper (1:20)
By isolonglifolene ketoxime lactams 1%, tiger glue adipic acid copper 20%, solvent naphtha 8%, castor oil polyoxyethylene ether 8%,
Agriculture breast 500#1% is mixed, and is dissolved into uniform oil phase；Part water, glycerine 5%, silicone oil 2% are mixed into
Uniform water phase；Oil phase is added into water phase while high-speed stirred in a kettle, adds xanthans 0.3%, slowly plus water is straight
To phase inversion point is reached, open cutter and carry out high speed shear, and add remaining water and supply 100%, shearing about half an hour, that is, make
Obtain 21% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper.
Embodiment 10：15% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper (5:10)
By isolonglifolene ketoxime lactams 5%, tiger glue adipic acid copper 10%, ethanol 8%, turpentine oil 18%, aliphatic acid polyoxy
Vinyl esters 12%, agriculture breast 33#2% are mixed, and are dissolved into uniform oil phase；By part water, glycerine 5%, silicone oil 2%
Mix into uniform water phase；Oil phase is added into water phase while high-speed stirred in a kettle, adds xanthans
0.3%, add water until reaching phase inversion point, open cutter and carry out high speed shear, and add remaining water and supply 100%, shearing
About half an hour, that is, be made 15% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper.
Embodiment 11：9% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper (1:8)
By isolonglifolene ketoxime lactams 1%, tiger glue adipic acid copper 8%, dimethyl carbonate 15%, trimethylbenzene 10%, fat
Sour polyoxyethylene ester 8%, mix, and is dissolved into uniform oil phase；Part water, propane diols 1%, silicone oil 1.2% are mixed
Together into uniform water phase；Oil phase is added into water phase while high-speed stirred in a kettle, adds Magnesiumaluminumsilicate 3%, is delayed
For slow plus water until reaching phase inversion point, unlatching cutter carries out high speed shear, and adds remaining water and supply 100%, shearing about half
Hour, that is, 9% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper is made.
Embodiment 12：12% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper (9:3)
By isolonglifolene ketoxime lactams 9%, tiger glue adipic acid copper 3%, dimethyl sulfoxide (DMSO) 18%, trimethylbenzene 15%, nonyl
Phenol polyethenoxy ether 8%, mix, and is dissolved into uniform oil phase；Part water, ethylene glycol 5%, silicone oil 2% are blended in
Together into uniform water phase；Oil phase is added into water phase while high-speed stirred in a kettle, adds polyvinyl alcohol 3%, slowly
Add water until reaching phase inversion point, open cutter and carry out high speed shear, and add remaining water and supply 100%, shearing about half is small
When, that is, 12% isolonglifolene ketoxime lactams tiger glue adipic acid aqueous emulsion of copper is made.
Embodiment 13：16% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula (1:15)
By isolonglifolene ketoxime lactams 1%, tiger glue adipic acid copper 15%, aliphatic amine polyoxyethylene ether 10%, alkylnaphthalene sulphur
Hydrochlorate 10%, urea 4%, bentonite supply 100%, are uniformly mixed, are crushed with micro jet, through mediating, Ran Houjia
Be granulated, dried in fluidized bed granulating and drying machine, sieve after through sampling analysis, that is, acyl in 16% isolonglifolene ketoxime is made
Amine tiger glue adipic acid copper water dispersion granula.
Embodiment 14：36% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula (32:4)
By isolonglifolene ketoxime lactams 32%, tiger glue adipic acid copper 4%, polycarboxylate 2%, calcium dodecyl benzene sulfonate
3%th, kaolin is supplied 100% and is uniformly mixed, and is crushed with micro jet, through mediating, then adds fluidized bed prilling and does
Be granulated, dried in dry machine, sieve after through sampling analysis, that is, 36% isolonglifolene ketoxime lactams tiger glue adipic acid copper is made
Water dispersible granules.
Embodiment 15：50% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula (40:10)
By isolonglifolene ketoxime lactams 40%, tiger glue adipic acid copper 10%, polycarboxylate 6%, calcium dodecyl benzene sulfonate
3%th, sodium acid carbonate 5%, precipitated calcium carbonate 15%, diatomite are supplied 100% and are uniformly mixed, and are crushed with micro jet,
Through mediating, then add in fluidized-bed granulation dryer be granulated, dry, sieve after through sampling analysis, i.e., obtained 50% is different
Longifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula.
Embodiment 16：22% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula (2:20)
By isolonglifolene ketoxime lactams 2%, tiger glue adipic acid copper 20%, alkylnaphthalene sulfonate 3%, alkylphenol-polyethenoxy
Ether formaldehyde condensation products sulfate 6%, sodium chloride 4%, starch 10%, kaolin are supplied 100% and are uniformly mixed, with ultra micro air-flow powder
Broken machine crushes, through mediating, then add in fluidized-bed granulation dryer be granulated, dried, sieve after through sampling analysis, that is, make
Obtain 22% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula.
Embodiment 17：90% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula (30:60)
By isolonglifolene ketoxime lactams 30%, tiger glue adipic acid copper 60%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 1%, polyoxy
Ethene triphenylethylene phosphenylic acid salt 2%, ammonium sulfate 2%, white carbon 3%, kaolin are supplied 100% and are uniformly mixed, and use ultra micro
Airslide disintegrating mill crush, through mediate, then add fluidized-bed granulation dryer in be granulated, dry, sieve after through sample divide
Analysis, that is, be made 90% isolonglifolene ketoxime lactams tiger glue adipic acid copper water dispersion granula.
Embodiment 18：6% isolonglifolene ketoxime lactams tiger glue adipic acid copper seed treatment dry powder doses (5:1)
It is isolonglifolene ketoxime lactams 5%, tiger glue adipic acid copper 1%, lauryl sodium sulfate 2.6%, starch 4%, compound
Fertilizer 3%, urea add to 100%, are sufficiently mixed, then by ultra-fine grinding to certain particle diameter, obtain acyl in 6% isolonglifolene ketoxime
Amine tiger glue adipic acid copper seed treatment dry powder doses.
Embodiment 19：5% isolonglifolene ketoxime lactams tiger glue adipic acid copper seed treatment dry powder doses (1:4)
Isolonglifolene ketoxime lactams 1%, tiger glue adipic acid copper 4%, naphthalene sulfonic acid-formaldehyde condensation product sodium salt 3%, spaonin powder
5%th, methylcellulose 5%, urea add to 100%, are sufficiently mixed, then by ultra-fine grinding to certain particle diameter, obtain 5% and different come into leaves
Ketenes oxime lactams tiger glue adipic acid copper seed treatment dry powder doses.
Embodiment 20：0.1% isolonglifolene ketoxime lactams tiger glue adipic acid copper granule (0.05：0.05)
Isolonglifolene ketoxime lactams 0.05%, tiger glue adipic acid copper 0.05%, alkylnaphthalene sulfonate 6.5%, Methyl cellulose
Element 2.5%, supply diatomite 100%, above-mentioned material is uniformly mixed in closed compounding kettle, coating method is granulated, at 120 DEG C
Under the conditions of dry to particle water content 1%, screening, 4000 microns of particle size range (μm), through after the assay was approved, that is, obtaining 0.1%
Isolonglifolene ketoxime lactams tiger glue adipic acid copper granule.
Embodiment 21：1% isolonglifolene ketoxime lactams tiger glue adipic acid copper granule (0.9：0.1)
Isolonglifolene ketoxime lactams 0.9%, tiger glue adipic acid copper 0.1%, polycarboxylate 8.0%, starch 2.0%, kaolinite
Soil supplies 100%, above-mentioned material is uniformly mixed in closed compounding kettle, coating method is granulated, and is dried extremely under the conditions of 120 DEG C
Particle water content 1%, screening, 4000 microns of particle size range (μm), through after the assay was approved, that is, obtaining in 1% isolonglifolene ketoxime
Acid amides tiger glue adipic acid copper granule.
Toxicity Determination：
Following indoor biometrics experiment calculates co-toxicity coefficient (CTC) to evaluate mixed effect using the abundant methods of Sun Yun.
Toxicity index TI (B)=(EC of standard agent A50The EC of ÷ B agent50)×100
Actual toxicity index ATI (AB)=(EC of A50The EC of ÷ AB50)×100
Percentage+TI (B) × B percentages in mixture of theoretical toxicity index TTI (AB)=TI (the A) × A in mixture
Number
Survey toxicity index (ATI)=(standard agent EC50÷ reagent agents EC50)×100
Percentage composition+B the medicament toxicity index of A in theoretical toxicity index (TTI)=A medicament toxicity index × mixture × mixed
The percentage composition of B in agent
Co-toxicity coefficient (CTC)=[mixture surveys toxicity index (ATI) ÷ mixtures theoretical toxicity index (TTI)] × 100
Evaluation criterion is：Co-toxicity coefficient >=120 show as synergistic effect；Co-toxicity coefficient≤80 show as antagonism；80<
Co-toxicity coefficient<120 show as summation action.
Toxicity Determination embodiment：
Toxicity Determination embodiment one
Prevent bacterial leaf streak of rice
Toxicity Determination is carried out using in vitro nephelometry, it is target target to select bacterial leaf streak of rice, repeats 4
It is secondary, after investigating 24 it is small when inspection result.Using drug concentration (mg/l) to numerical value as independent variable x, it is dead with its corresponding correction
The probit value for dying rate is dependent variable y, establishes virulence regression equation respectively, obtains the co-toxicity coefficient of two single dose different ratios, as a result
It see the table below 1. experimental methods and co-toxicity coefficient (CTC) calculated to evaluate mixed effect using the abundant methods of Sun Yun.
Specific method：Using in vitro Nephelometric Determination, the design concentration on the basis of pilot study, each medicament is added respectively
Enter into NA fluid nutrient mediums, pastille culture medium is made in gradient dilution, and Inoculated Rice Xanthomonas campestris PV.oryzicola is placed on 28 DEG C and shakes
Culture 24h or so is swung, its turbidity (change of turbidity and bacterium amount is positively correlated) is measured with transmissometer, according to the turbidity of blank control
The inhibiting rate bred with each chemicals treatment of turbidity calculating of processing to bacterial growth, passes through the probit value of inhibiting rate and serial medicament
Concentration to the linear regression analysis between numerical value, obtain the EC of each medicament50Value, CTC values.
Measurement result see the table below 1
1 isolonglifolene ketoxime lactams of table and the co-toxicity of tiger glue adipic acid copper compounding prevention bacterial leaf streak of rice are surveyed
Determine result
It is (20 by weight by 1 results showed that isolonglifolene ketoxime lactams of table and tiger glue adipic acid copper:1)~(1:
20) co-toxicity coefficient of compounding prevention bacterial leaf streak of rice shows obvious synergistic effect all more than 120 in the range of.
Wherein, when weight ratio is (10:1)~(1:10) compounded in the range of, for the co-toxicity coefficient respectively handled all more than 160, synergy is non-
Chang Xianzhu.
Toxicity Determination embodiment two
Prevent rice sheath blight disease
Under aseptic technique, the sterilising medium 36ml melted in advance with pipette, extract in sterile conical flask,
Add with the diluted liquid 4ml of 0.1% Tween 80 aqueous solution, fully shake up, then equivalent pours into the training of 4 a diameter of 9cm
Support in ware, drug containing tablet is made, if the processing without medicament is blank control.By cultured pathogen, aseptically
Beaten with the sterilization punchers of diameter 5mm and take bacteria cake, with transfer needle by pure culture biscuits involvng inoculation in drug containing tablet center, mycelia is face-down, lid
Upper ware lid, is placed in moisturizing culture in 26 DEG C of insulating boxs.When the colony diameter of blank control accounts for more than half of ware footpath, with card
Ruler measures colony diameter, and each bacterium colony respectively once, is averaged with crossing method vertical survey diameter, calculates mycelial growth suppression
Rate processed, makees regression analysis to numerical value and corresponding mycelial growth inhibition rate niqueMin according to each drug concentration, calculates each medicament
EC50, and according to the co-toxicity coefficient of the abundant method calculating mixtures of Sun Yun.
Measurement result is shown in Table 2
2 isolonglifolene ketoxime lactams of table and the joint toxicity measuring result of tiger glue adipic acid copper compounding prevention rice sheath blight disease
As seen from the results in Table 2, isolonglifolene ketoxime lactams and tiger glue adipic acid copper are (20 by weight:1)~(1:20)
In the range of compounding prevention rice sheath blight disease co-toxicity coefficient all more than 120, show obvious synergistic effect.Wherein, when
Weight ratio is (10:1)~(1:10) compounding in the range of, respectively handle prevention citrus bacterial canker disease co-toxicity coefficient 153 with
On, the two compound synergic is especially pronounced.
Toxicity Determination embodiment three
Prevent bacterial wilt of peanut
After bacterial wilt of peanut pathogen is activated on NA culture mediums, bacterium stoste is made into sterile water, bacterium stoste is diluted
The clump count grown after into coated plate 100ul is the bacteria suspension of 100 or so, spare.
Take 400ul bacteria suspensions to be mixed with equivalent pesticide single dose, take 100ul with liquid-transfering gun, be placed in the NA tablets being ready for
On, bacteria suspension is coated with to uniform, 28 DEG C of culture 48h, counting clump count with sterilized " L " shape glass bar, and calculate by formula
Bacteriostasis rate, bacterium colony inhibiting rate (%)=(control clump count-processing clump count)/control clump count × 100, often processing repeat 4
It is secondary, replace pesticide-treated to use Excel software analysis as control, the result of gained, calculate the EC of each medicament using sterile water50, and
Co-toxicity coefficient is calculated according to the abundant methods of Sun Yun.
Measurement result is shown in Table 3
The joint toxicity measuring result of 3 isolonglifolene ketoxime lactams of table and tiger glue adipic acid copper compounding prevention bacterial wilt of peanut
As shown in Table 3, isolonglifolene ketoxime lactams and tiger glue adipic acid copper are (20 by weight:1)~(1:20) model
The co-toxicity coefficient of interior compounding prevention bacterial wilt of peanut is enclosed more than 120, shows obvious synergistic effect.Wherein, weight is worked as
Than for (10:1)~(1:10) compounded in the range of, for the co-toxicity coefficient respectively handled more than 160, synergy is especially pronounced.
Toxicity Determination example IV
Prevent peanut beautiful disease in vain
Under aseptic technique, the sterilising medium 36ml melted in advance with pipette, extract in sterile conical flask,
Add with the diluted liquid 4ml of 0.1% Tween 80 aqueous solution, fully shake up, then equivalent pours into the training of 4 a diameter of 9cm
Support in ware, drug containing tablet is made, if the processing without medicament is blank control.By cultured pathogen, aseptically
Beaten with the sterilization punchers of diameter 5mm and take bacteria cake, with transfer needle by pure culture biscuits involvng inoculation in drug containing tablet center, mycelia is face-down, lid
Upper ware lid, is placed in moisturizing culture in 26 DEG C of insulating boxs.When the colony diameter of blank control accounts for more than half of ware footpath, with card
Ruler measures colony diameter, and each bacterium colony respectively once, is averaged with crossing method vertical survey diameter, calculates mycelial growth suppression
Rate processed, makees regression analysis to numerical value and corresponding mycelial growth inhibition rate niqueMin according to each drug concentration, calculates each medicament
EC50, and according to the co-toxicity coefficient of the abundant method calculating mixtures of Sun Yun.
Measurement result is shown in Table 4
The joint toxicity measuring result of 4 isolonglifolene ketoxime lactams of table and tiger glue adipic acid copper compounding prevention peanut sclerotium rolfsii
As shown in Table 4, isolonglifolene ketoxime lactams and tiger glue adipic acid copper are by weight (20~1):The model of (1~20)
The interior white beautiful sick co-toxicity coefficient of compounding prevention peanut is enclosed more than 120, shows obvious synergistic effect.Wherein, weight is worked as
Than for (10:1)~(1:10) compounding, the synergy highly significant respectively handled in ratio range.
Crop field test examples
In order to clear and definite isolonglifolene ketoxime lactams and tiger glue adipic acid copper it is alone with it is mixed when to rice, fruit tree, melon etc.
The prevention effect of crop disease, and compounding use whether synergy and synergy it is whether obvious, present invention applicant is different at home
Area has carried out substantial amounts of field trial.Illustrated below with several field embodiments.
CK1：20% isolonglifolene ketoxime lactams wettable powder suspending agent is made by oneself.
CK2：240g/L tiger glue adipic acid copper suspending agents, it is purchased in market.
Field trial embodiment one：Prevent the field control effectiveness test of bacterial leaf streak of rice
Test method：According to《Pesticide field efficacy medicine test criterion two (GB/T17980.105-2004)》Provide dispenser side
Method, in the early stages of disease first time spray pesticide, second of spray pesticide after 7d.It is total to dispenser twice, each 20 squares of cell
Rice is repeated four times.According to Chinese pesticide Information Network, dosage is 300 grams/ha, 350 grams/ha, 400 grams/ha and 500
Gram/ha.
Investigation method：According to《Pesticide field efficacy medicine test criterion two (GB/T17980.105-2004)》Provide investigation side
Method, is sampled per cell using 5 diagonal, and every takes 25 clumps, and every plant is investigated boot leaf and the following two panels leaf of boot leaf.
X. c. pv. oryzicola Seriousness gradation standard：
0 grade：Rice disease-free spot；
1 grade：Blade only has half past one transparent water stain shape scab, and lesion area accounts for less than the 1% of full wafer leaf area；
3 grades：Blade has fragmentary short and narrow strip scab, lesion area account for the 1%-5% of full wafer leaf area；
5 grades：Leaf spot lesion is more, and lesion area accounts for the 6%-25% of full wafer leaf area；
7 grades：Scab is closeer on blade, and lesion area accounts for the 26%-50% of full wafer leaf area；
9 grades：Scab gathers on blade, and lesion area accounts for more than the 51% of full wafer leaf area.
Result of the test is shown in Table 5.
Table 5 prevents the field test results of bacterial leaf streak of rice
From result of the test table 5, handled in bacterial leaf streak of rice early stage, single dose is less than in dosage
In the case of, 5 compositions of isolonglifolene ketoxime lactams and tiger glue adipic acid copper compounding after second of medicine 7d and 14d it is anti-
Effect is alone higher than the two, and complex composition active ingredient dosage is also fewer than alone, in this explanation isolonglifolene ketoxime
Acid amides and tiger glue adipic acid copper compound synergic are obvious, not only improve protection effect, but also reduce mu dosage and cost.
Field trial embodiment two：Prevent the field control effectiveness test of rice sheath blight disease
Test method：According to《Pesticide field efficacy medicine test criterion two (GB/T17980.20-2000)》Provide application method,
First time spray pesticide in the early stages of disease, second of spray pesticide after 7d.It is total to dispenser twice, each 20 weight per square meter of cell
It is four times multiple.According to Chinese pesticide Information Network, dosage is 50 grams/ha, 60 grams/ha, 70 grams/ha and 80 grams/ha.
Investigation method：According to《Pesticide field efficacy medicine test criterion two (GB/T17980.105-2004)》Provide investigation side
Method, is sampled per cell using 5 diagonal, and every takes 25 clumps, record total strain number, diseased plant number and sick series.
Rice sheath blight disease Seriousness gradation standard (by units of)：
0 grade：Complete stool is disease-free；
1 grade：Quaterfoil and its following leaf sheath, blade morbidity are (using sword-like leave as first leaf)；
3 grades：Third blade and its following leaf sheath, blade morbidity；
5 grades：Second blade and its following leaf sheath, blade morbidity；
7 grades：Sword-like leave blade and its following leaf sheath, blade morbidity；
9 grades：Complete stool falls ill, withered ahead of time.
Result of the test is shown in Table 6.
Table 6 prevents the field test results of rice sheath blight disease
From result of the test table 6, dispenser is carried out in rice sheath blight disease early period of origination, the situation of single dose is less than in dosage
Under, the preventive effect of 4 composition 7d and 14d after second of medicine of isolonglifolene ketoxime lactams and tiger glue adipic acid copper compounding compares
The two alone height, and complex composition active ingredient dosage is also fewer than alone, both this explanations compounding use, and synergy is bright
It is aobvious, protection effect is not only improved, but also reduce mu dosage and cost.
Field trial embodiment three：Prevent the field control effectiveness test of bacterial wilt of peanut
Test method：According to《Pesticide field efficacy medicine test criterion Part IX (NY/T 1464.49-2013)》Regulation is applied
Prescription method, first time spray pesticide is carried out when beginning to see scab, second of spray pesticide is carried out after 7d.It is total to dispenser twice, each
20 square metres of cell, is repeated 4 times.According to Chinese pesticide Information Network, dosage is 45 grams/ha, 60 grams/ha, 75 grams/public
Just, 90 grams/ha.
Investigation method：According to《Pesticide field efficacy medicine test criterion Part IX (NY/T 1464.49-2013)》Regulation is adjusted
Checking method, is sampled per cell using 5 diagonal, and every takes 20 clumps, record total strain number, diseased plant number and sick series.Apply for the second time
7d, 14d investigation, record investigation total strain number and diseased plant number are distinguished after medicine, calculates diseased plant rate and prevention preventive effect.
Result of the test is shown in Table 7.
Table 7 prevents the field test results of bacterial wilt of peanut
From result of the test table 7, bacterial wilt of peanut is prevented, in the case where dosage is less than single dose, of the invention answers
With composition, the prevention effect of 7d is above single dose after second of medicine, this explanation isolonglifolene ketoxime lactams and tiger glue adipic acid
Copper compounding has obvious synergistic effect.Lasting period is grown, and the preventive effect of 14d is remained to up to more than 78.5% after second of medicine.
Field example IV：Prevent the white beautiful sick field control effectiveness test of peanut
Test method：According to《Pesticide field efficacy medicine test criterion nine (NY/T 1464.49-2013)》Provide application method,
Spray for the first time is carried out when beginning to see scab and pours root application, second of dispenser is carried out after 7d, compares to pour clear water.Apply altogether
Twice, each 20 square metres of cell, is repeated 4 times medicine.
Investigation method：According to《Pesticide field efficacy medicine test criterion nine (NY/T 1464.49-2013)》Provide investigation method,
Sampled per cell using 5 diagonal, every takes 20 clumps, record total strain number, diseased plant number and sick series.After second of dispenser respectively
7d, 14d are investigated, and record investigation total strain number and diseased plant number, calculate diseased plant rate and prevention preventive effect.
Result of the test is shown in Table 8.
Table 8 prevents the white beautiful sick field test results of peanut
From result of the test table 8, in the case where dosage is less than single dose, built composition for preventing and controlling peanut of the invention
Bacterial wilt prevention effect of 7d after second of medicine is above single dose；And after second of medicine the preventive effect of 14 days remain to reach 79% with
On, lasting period length.
Claims (8)
- A kind of 1. complex composition of lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, it is characterised in that the compounding group Compound is made of isolonglifolene ketoxime lactams and tiger glue adipic acid copper；The wherein described isolonglifolene ketoxime lactams and amber glue fertilizer The weight ratio of sour copper is (20~1):(1~20).
- 2. the complex composition of the lactams of ketoxime containing isolonglifolene according to claim 1 and tiger glue adipic acid copper, its feature It is, the weight ratio of the isolonglifolene ketoxime lactams and tiger glue adipic acid copper is (10~1)：(1~10).
- 3. the preparation of a kind of lactams of ketoxime containing isolonglifolene and tiger glue adipic acid copper, it is characterised in that including claim 1~2 Acceptable adjuvant on any complex composition and pesticide, is then prepared into disinfectant use in agriculture.
- 4. the preparation of the lactams of ketoxime containing isolonglifolene according to claim 3 and tiger glue adipic acid copper, it is characterised in that institute The weight percentage that the complex composition stated accounts for the disinfectant use in agriculture is 0.1%~90%.
- 5. the preparation of the lactams of ketoxime containing isolonglifolene according to claim 4 and tiger glue adipic acid copper, it is characterised in that institute The weight percentage that the complex composition stated accounts for the disinfectant use in agriculture is 1%~80%.
- 6. the preparation of the lactams of ketoxime containing isolonglifolene according to claim 3 and tiger glue adipic acid copper, it is characterised in that institute The formulation for stating disinfectant use in agriculture is wettable powder, suspending agent, water dispersible granules, aqueous emulsion, seed treatment dry powder doses or particle Agent.
- 7. application of any complex composition of claim 1~2 in prevention crop bacterium venereal disease evil.
- 8. application of any complex composition of claim 1~2 in crop fungal disease is prevented.
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Citations (3)
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|---|---|---|---|---|
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| CN104521988A (en) * | 2014-12-18 | 2015-04-22 | 广西田园生化股份有限公司 | Compound composition containing 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and Copper(succinate+glutarate+adipate) and preparation |
| CN106588772A (en) * | 2016-12-19 | 2017-04-26 | 广西中医药大学 | Heavy turpentine longifolene derivative, preparation thereof and application |
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2017
- 2017-11-28 CN CN201711218303.0A patent/CN107897189A/en active Pending
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|---|---|---|---|---|
| CN104488926A (en) * | 2014-12-18 | 2015-04-08 | 广西田园生化股份有限公司 | Compound composition containing methanesulphonyl myclobutanil and thifluzamide and preparation |
| CN104521988A (en) * | 2014-12-18 | 2015-04-22 | 广西田园生化股份有限公司 | Compound composition containing 2-(p-fluorophenyl)-5-methanesulfonyl-1,3,4-oxadiazole and Copper(succinate+glutarate+adipate) and preparation |
| CN106588772A (en) * | 2016-12-19 | 2017-04-26 | 广西中医药大学 | Heavy turpentine longifolene derivative, preparation thereof and application |
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| WU ZHANG，等: "Design, Synthesis, and Bioassay of Novel Compounds of Isolongifolenone Oxime Derivatives", 《HELV. CHIM. ACTA》 * |
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