CN115211432A - Bactericide containing pyraclostrobin and bupirimate and preparation method thereof - Google Patents
Bactericide containing pyraclostrobin and bupirimate and preparation method thereof Download PDFInfo
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- CN115211432A CN115211432A CN202111076319.9A CN202111076319A CN115211432A CN 115211432 A CN115211432 A CN 115211432A CN 202111076319 A CN202111076319 A CN 202111076319A CN 115211432 A CN115211432 A CN 115211432A
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- Prior art keywords
- bupirimate
- pyraclostrobin
- bactericide
- aeo
- fatty alcohol
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- 239000005742 Bupirimate Substances 0.000 title claims description 60
- DSKJPMWIHSOYEA-UHFFFAOYSA-N bupirimate Chemical compound CCCCC1=C(C)N=C(NCC)N=C1OS(=O)(=O)N(C)C DSKJPMWIHSOYEA-UHFFFAOYSA-N 0.000 title claims description 60
- 239000005869 Pyraclostrobin Substances 0.000 title claims description 58
- HZRSNVGNWUDEFX-UHFFFAOYSA-N pyraclostrobin Chemical compound COC(=O)N(OC)C1=CC=CC=C1COC1=NN(C=2C=CC(Cl)=CC=2)C=C1 HZRSNVGNWUDEFX-UHFFFAOYSA-N 0.000 title claims description 58
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 51
- 239000003899 bactericide agent Substances 0.000 title claims description 45
- 238000002360 preparation method Methods 0.000 title claims description 19
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- 239000002904 solvent Substances 0.000 claims description 43
- 239000003995 emulsifying agent Substances 0.000 claims description 28
- 239000004480 active ingredient Substances 0.000 claims description 22
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 20
- 239000002612 dispersion medium Substances 0.000 claims description 20
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 20
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 19
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 claims description 18
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 claims description 17
- ZLWPAELISNYYGM-UHFFFAOYSA-N azanium;2-dodecylbenzenesulfonate Chemical compound [NH4+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O ZLWPAELISNYYGM-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
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- 229920000642 polymer Polymers 0.000 claims description 9
- 235000015096 spirit Nutrition 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- PLUHAVSIMCXBEX-UHFFFAOYSA-N azane;dodecyl benzenesulfonate Chemical compound N.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 PLUHAVSIMCXBEX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002609 medium Substances 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000855 fungicidal effect Effects 0.000 claims 2
- 239000000417 fungicide Substances 0.000 claims 2
- NUKZAGXMHTUAFE-UHFFFAOYSA-N hexanoic acid methyl ester Natural products CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims 1
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- 241000510928 Erysiphe necator Species 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- DMAXMXPDVWTIRV-UHFFFAOYSA-N 2-(2-phenylethyl)phenol Chemical group OC1=CC=CC=C1CCC1=CC=CC=C1 DMAXMXPDVWTIRV-UHFFFAOYSA-N 0.000 description 13
- 201000010099 disease Diseases 0.000 description 11
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- 239000000575 pesticide Substances 0.000 description 9
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- 241000219095 Vitis Species 0.000 description 5
- 235000009754 Vitis X bourquina Nutrition 0.000 description 5
- 235000012333 Vitis X labruscana Nutrition 0.000 description 5
- 235000014787 Vitis vinifera Nutrition 0.000 description 5
- -1 polyhydroxyethylene Polymers 0.000 description 5
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- 229940080778 Adenosine deaminase inhibitor Drugs 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 240000000560 Citrus x paradisi Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 206010017533 Fungal infection Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000002487 adenosine deaminase inhibitor Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 239000002552 dosage form Substances 0.000 description 1
- 238000001647 drug administration Methods 0.000 description 1
- BBXXLROWFHWFQY-UHFFFAOYSA-N ethirimol Chemical compound CCCCC1=C(C)NC(NCC)=NC1=O BBXXLROWFHWFQY-UHFFFAOYSA-N 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 208000024386 fungal infectious disease Diseases 0.000 description 1
- 210000004602 germ cell Anatomy 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 230000002438 mitochondrial effect Effects 0.000 description 1
- 230000006540 mitochondrial respiration Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- 230000000361 pesticidal effect Effects 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
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- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Images
Classifications
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Toxicology (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of A01P, and particularly relates to a bactericide containing pyraclostrobin and bupirimate and a preparation method thereof. The bactericide containing pyraclostrobin and bupirimate comprises the following preparation raw materials in parts by weight: 5-50% of active ingredients, 3-30% of emulsifier, 20-50% of solvent and the balance of dispersion medium to 100%; the effective components comprise pyraclostrobin and bupirimate. The bactericide of pyraclostrobin and bupirimate prepared by the invention is especially prepared by using a combined emulsifier of dodecyl benzene sulfonic acid ammonium salt, fatty alcohol polyoxyethylene ether and a polyhydroxyl polyoxyethylene polyoxypropylene formaldehyde polymer in the presence of microemulsion, so that the problem of instability of bupirimate at a temperature of above 37 ℃ can be solved, the effectiveness of the bupirimate in long-term use is ensured, and the use value of the bupirimate is improved.
Description
Technical Field
The invention belongs to the technical field of A01P, and particularly relates to a bactericide containing pyraclostrobin and bupirimate and a preparation method thereof.
Background
Pyraclostrobin and bupirimate have good effects on treating powdery mildew, gibberellic disease and the like as agents for treating injuries caused by fungi to crops, but in a specific using process, the single use of one agent can cause the crops to have drug resistance, so that the crops can be irreversibly damaged.
In order to reduce the influence of such mycosis on crops, a Chinese patent with publication number CN104522012A discloses a bactericidal composition containing pyraclostrobin and bupirimate, in the disclosed patent, the bactericidal composition prepared by pyraclostrobin and bupirimate in different proportions and different dosage forms shows different effects, and particularly when the bactericidal composition is used as a microemulsion, the stability effect becomes a problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a bactericide containing pyraclostrobin and bupirimate, which comprises the following preparation raw materials in parts by weight: 5-50% of active ingredients, 3-30% of emulsifier, 20-50% of solvent and the balance of dispersion medium to 100%; the effective components comprise pyraclostrobin and bupirimate.
In some preferred embodiments, the weight ratio of pyraclostrobin to bupirimate is 1: (1-10).
Further preferably, the amount of the effective components is 20-30% of the total weight of the raw materials for preparation.
Further preferably, the amount of the effective component is 25% of the total weight of the raw materials for preparation.
Further preferably, the weight ratio of the pyraclostrobin to the bupirimate is 1:4.
pyraclostrobin as a bactericide can cause cell death by inhibiting mitochondrial respiration, but when pyraclostrobin is used alone, the use amount and application days of pesticides need to be strictly controlled, otherwise, the pyraclostrobin can affect crops after fruiting and cause phytotoxicity; in order to ensure the bactericidal effect of pesticide and reduce the harm of phytotoxicity to crops or drug applicators to the greatest extent, the applicant discovers through a great amount of creative experiments that the control effect of the bactericide on grape powdery mildew can be improved by adding bupirimate in the presence of pyraclostrobin, and particularly, when the weight ratio of pyraclostrobin to bupirimate is 1:4, the relative humidity is more than 80%, the grape powdery mildew shows better control effect, and the applicant speculates that the reason of the phenomenon is that: when powdery mildew is infected on the surface of grape leaves, bupirimate exists and is taken as an adenosine deaminase inhibitor and can be rapidly absorbed by the grape leaves, the bupirimate after absorption can be combined with germ cells on the surface of the grape leaves to inhibit the formation of germ spores, and at the moment, pyraclostrobin can also be absorbed on the surface of the grape leaves to inhibit the mitochondrial action of the germ, so that the respiration action of the cells is inhibited, and the cells lose activity.
Under the synergistic effect of the two active ingredients, the grape powdery mildew control agent has the control effect of more than 80 percent; however, the applicant has found that when pyraclostrobin is used alone, the amount of pyraclostrobin used needs to be increased, but the increase in the amount of the drug causes harm to the drug applicators; in addition, if bupirimate is used alone, the sterilization effect is greatly reduced when the bupirimate is used at a high stage of powdery mildew after raining.
In some preferred embodiments, the emulsifier comprises at least one of ammonium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, ammonium dodecylsulfate, fatty alcohol polyoxyethylene ether, polyhydroxyethylene oxide-containing polyoxypropylene polymer, polyhydroxyethylene oxide-containing polyoxypropylene formaldehyde polymer.
In some preferred embodiments, the emulsifier comprises an ammonium dodecylbenzenesulfonate, a fatty alcohol-polyoxyethylene ether, a polyhydroxyl polyoxyethylene polyoxypropylene-formaldehyde-containing polymer.
In some preferred embodiments, the polyhydroxylated polyoxyethylene polyoxypropylene formaldehyde polymer is phenethylphenol polyoxyethylene polyoxypropylene and formaldehyde condensate.
In some preferred embodiments, the fatty alcohol-polyoxyethylene ether is at least one selected from the group consisting of AEO-3, AEO-5, AEO-7, AEO-9, and AEO-20.
In some preferred embodiments, the fatty alcohol-polyoxyethylene ether has an HLB value of 10 to 16.
More preferably, the HLB value of the fatty alcohol-polyoxyethylene ether is 12.5.
Further preferably, the fatty alcohol-polyoxyethylene ether is AEO-9.
In the experimental process, the applicant finds that the molecular chains of the fatty alcohol-polyoxyethylene ether added into the system are different, which has great influence on the pourability of the prepared bactericide, and when the used fatty alcohol-polyoxyethylene ether is AEO-9, the better pouring effect can be ensured when the bactericide is in use, so that the bactericide is convenient to use, and the reason for the phenomenon is presumed by the applicant to be probably because: in the system, when the microemulsion is prepared, the effective components are easy to generate flocculation in a dispersion medium, different shearing forces can be generated in the system along with the use of fatty alcohol-polyoxyethylene ethers with different chain lengths, the components which are likely to generate flocculation and sedimentation are decomposed into smaller units, the quick-briss free energy of the system is reduced, the system is ensured to have proper viscosity under the condition of promoting thermodynamic stability and show better effect when being poured.
In addition, the applicant finds that when the added fatty alcohol-polyoxyethylene ether is AEO-5 in the system, the fatty alcohol chain segment in the system is short, so that the dispersing effect is greatly reduced when the fatty alcohol-polyoxyethylene ether is compounded with other emulsifiers; however, when the molecular chain segment of the added fatty alcohol-polyoxyethylene ether is longer, the hydrophilic effect of the added fatty alcohol-polyoxyethylene ether in the system is enhanced, so that the desorption effect is caused, and the stability and the pouring effect of the system are further adversely affected.
In some preferred embodiments, the weight ratio of the dodecyl benzene sulfonic acid ammonium salt, the fatty alcohol-polyoxyethylene ether and the polyhydroxyl polyoxyethylene polyoxypropylene formaldehyde polymer is (1-5): (2-8): (10-20).
In some preferred embodiments, the ammonium dodecylbenzenesulfonate, AEO-9, phenethylphenol polyoxyethylene polyoxypropylene and formaldehyde are condensed in a weight ratio of (1-5): (2-8): (10-20).
More preferably, the weight ratio of the dodecyl benzene sulfonic acid ammonium salt, AEO-9, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde condensation is 3:5:17.
in the experimental process, the applicant finds that when the active ingredient is used in an amount of 25% of the total weight of the preparation raw materials, the phenomenon of reduced control effect may occur when the microemulsion is prepared for use under high-temperature and high-humidity conditions in summer, because the bupirimate per se has instability at a temperature of above 37 ℃, in order to solve the problem, the applicant finds a large number of creative experiments that the addition of the emulsifier in the application can greatly improve the stability of the system, and particularly when the dodecylbenzene sulfonic acid ammonium salt, AEO-9, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde condensation compound emulsifier are used, the applicant speculates that the phenomenon occurs: in the system, with the addition of ammonium dodecylbenzene sulfonate, AEO-9, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde through condensation, hydrophilic groups existing in the system face a dispersion medium, lipophilic groups face a solvent and active ingredient particles, and the addition of the ammonium dodecylbenzene sulfonate can ionize in the system to enable active ingredients to form an electric double layer, so that the ethirimol sulfonate is wrapped between the electric double layers.
In some preferred embodiments, the solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, tripropylene glycol methyl ether, mineral spirits, tetrahydrofuran, methyl acetate, butyl acetate, sec-butyl acetate.
Further preferably, the solvent comprises N, N-dimethylacetamide, tripropylene glycol methyl ether and mineral spirits.
In some preferred embodiments, the mineral spirits are selected from at least one of S-100 mineral spirits, S-150 mineral spirits, and S-200 mineral spirits.
More preferably, the solvent oil is S-200 solvent oil.
More preferably, the weight ratio of the N, N-dimethylacetamide, the tripropylene glycol methyl ether and the S-200 solvent oil is (1-5): 1:1.
more preferably, the weight ratio of the N, N-dimethylacetamide, the tripropylene glycol methyl ether and the S-200 solvent oil is 2:1:1.
in the experimental process, the applicant finds that the selection of a solvent has a great influence on the stability and the transparency of the microemulsion when the microemulsion is prepared, and the applicant finds that solid precipitation can be avoided and the microemulsion is ensured to have better transparency when the N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil are added into a body as the solvent through a great amount of creative experimental researches, and the reason why the phenomenon occurs is presumably that: the existence of N, N-dimethylacetamide as a strong polar aprotic solvent can have better intersolubility with tripropylene glycol methyl ether and better solubility with water as a dispersion medium, so that a foundation is provided for forming a relatively stable thermal stable state of effective components in a water dispersion medium, and in addition, due to the interaction of N, N-dimethylacetamide and S-200 solvent oil added in the system, the bearing capacity of the prepared microemulsion on temperature or storage conditions is improved, and the phenomenon that the color of the microemulsion is darkened possibly caused by the existence of the S-200 solvent oil is avoided.
In addition, the applicant finds that solid precipitation can occur during long-term storage due to the reduced content of the added N, N-dimethylacetamide, so that the color of the microemulsion is changed, and the drug effect of the microemulsion is influenced.
The invention provides a preparation method of a bactericide of pyraclostrobin and bupirimate, which comprises the following steps:
mixing the active ingredients in solvent, adding emulsifier and dispersion medium, and mixing.
Has the advantages that: compared with the bactericide in the prior art, the bactericide of pyraclostrobin and bupirimate prepared by the invention has the following advantages:
1. the bactericide of pyraclostrobin and bupirimate prepared by the invention, especially when existing in microemulsion, can ensure that the bactericide has better prevention and treatment effect on grape powdery mildew under the condition that the relative humidity is more than 80%, and the prevention and treatment effect is as high as more than 80%;
2. the pyraclostrobin and bupirimate bactericide prepared by the invention, especially when the microemulsion exists, can ensure better pouring effect when in use by using fatty alcohol-polyoxyethylene ether AEO-9, improves the stability of the microemulsion, and avoids the phenomena of flocculation, sedimentation and the like in the long-term storage process;
3. the bactericide of pyraclostrobin and bupirimate prepared by the invention is especially prepared in the presence of microemulsion by using a combined emulsifier of dodecyl benzene sulfonic acid ammonium salt, fatty alcohol polyoxyethylene ether and a polyhydroxyl polyoxyethylene polyoxypropylene formaldehyde-containing polymer, so that the problem of instability of bupirimate at a temperature of above 37 ℃ can be solved, the effectiveness of the bupirimate in long-term use is ensured, and the use value of the bupirimate is improved;
4. the bactericide of pyraclostrobin and bupirimate prepared by the invention has better transparency and does not generate solid precipitates in the using process, especially when the bactericide exists in microemulsion and N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil are used as solvents.
Drawings
FIG. 1 is a table of average disease indexes for controlling grape powdery mildew in example 1 of the present application;
FIG. 2 is a table of disease grading indexes 7 days after 3 times of application of example 1 for controlling grape powdery mildew;
FIG. 3 is a table of disease grading 14 days after 3 applications of the composition of example 1 for controlling grape powdery mildew.
Detailed Description
Examples
Example 1
The bactericide containing pyraclostrobin and bupirimate comprises the following preparation raw materials in parts by weight: 25% of active ingredient, 25% of emulsifier, 40% of solvent and the balance of dispersion medium to 100%.
The active ingredients are pyraclostrobin and bupirimate, and the weight ratio of the pyraclostrobin to the bupirimate is 1:4;
the emulsifier is dodecyl benzene sulfonic acid ammonium salt, AEO-9, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde condensation, and the weight ratio is 3:5:17;
dodecyl benzene sulfonic acid ammonium salt, purchased from heian petrochemical plant of Jiangsu province;
AEO-9, HLB 12.5, purchased from Haian petrochemical plant of Jiangsu province;
the condensation of phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde is purchased from Jiangsu Qingyu chemical technology Limited;
the solvent is N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil, and the weight ratio of the N, N-dimethylacetamide to the tripropylene glycol methyl ether to the S-200 solvent oil is 2:1:1;
the dispersion medium is water.
A preparation method of a bactericide of pyraclostrobin and bupirimate comprises the following steps:
mixing the active ingredients in solvent, adding emulsifier and dispersion medium, and mixing.
Example 2
The bactericide containing pyraclostrobin and bupirimate comprises the following preparation raw materials in parts by weight: 25% of active ingredient, 25% of emulsifier, 40% of solvent and the balance of dispersion medium to 100%.
The active ingredients are pyraclostrobin and bupirimate, and the weight ratio of the pyraclostrobin to the bupirimate is 1:4;
the emulsifier is dodecyl benzene sulfonic acid ammonium salt, AEO-15, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde condensation, and the weight ratio is 3:5:17;
dodecyl benzene sulfonic acid ammonium salt, purchased from Haian petrochemical plant of Jiangsu province;
AEO-15 with HLB value of 15-16, purchased from Haian petrochemical plant of Jiangsu province;
the condensation of phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde is purchased from Jiangsu Qingyu chemical technology Limited;
the solvent is N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil, and the weight ratio of the N, N-dimethylacetamide to the tripropylene glycol methyl ether to the S-200 solvent oil is 2:1:1;
the dispersion medium is water.
A preparation method of a bactericide of pyraclostrobin and bupirimate comprises the following steps:
mixing the active ingredients in solvent, adding emulsifier and dispersion medium, and mixing.
Example 3
The bactericide containing pyraclostrobin and bupirimate comprises the following preparation raw materials in parts by weight: 25% of active ingredient, 25% of emulsifier, 40% of solvent and the balance of dispersion medium to 100%.
The active ingredients are pyraclostrobin and bupirimate, and the weight ratio of the pyraclostrobin to the bupirimate is 1:4;
the emulsifier is AEO-9, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde condensation, and the weight ratio is 5:17;
AEO-9, HLB 12.5, purchased from Haian petrochemical plant of Jiangsu province;
phenethylphenol polyoxyethylene polyoxypropylene and formaldehyde are condensed and purchased from Jiangsu Optimus chemical technology Co., ltd;
the solvent is N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil, and the weight ratio of the N, N-dimethylacetamide to the tripropylene glycol methyl ether is 2:1:1;
the dispersion medium is water.
A preparation method of a bactericide of pyraclostrobin and bupirimate comprises the following steps:
mixing the active ingredients in solvent, adding emulsifier and dispersing medium, and mixing.
Example 4
The bactericide containing pyraclostrobin and bupirimate comprises the following preparation raw materials in parts by weight: 25% of active ingredient, 25% of emulsifier, 40% of solvent and the balance of dispersion medium to 100%.
The effective components are pyraclostrobin and bupirimate, and the weight ratio of the pyraclostrobin to the bupirimate is 1:4;
the emulsifier is dodecyl benzene sulfonic acid ammonium salt, AEO-9, phenethyl phenol polyoxyethylene polyoxypropylene and formaldehyde condensation, and the weight ratio is 3:5:17;
dodecyl benzene sulfonic acid ammonium salt, purchased from heian petrochemical plant of Jiangsu province;
AEO-9, HLB 12.5, purchased from Haian petrochemical plant of Jiangsu province;
phenethylphenol polyoxyethylene polyoxypropylene and formaldehyde are condensed and purchased from Jiangsu Optimus chemical technology Co., ltd;
the solvent is N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil, and the weight ratio of the N, N-dimethylacetamide to the tripropylene glycol methyl ether to the S-200 solvent oil is 1:1:1;
the dispersion medium is water.
A preparation method of a bactericide of pyraclostrobin and bupirimate comprises the following steps:
mixing the active ingredients in solvent, adding emulsifier and dispersion medium, and mixing.
Example 5
The bactericide containing pyraclostrobin and bupirimate comprises the following preparation raw materials in parts by weight: 25% of active ingredient, 25% of emulsifier, 40% of solvent and the balance of dispersion medium to 100%.
The effective components are pyraclostrobin and bupirimate, and the weight ratio of the pyraclostrobin to the bupirimate is 1:4;
the emulsifier is dodecyl benzene sulfonic acid ammonium salt and AEO-9, and the weight ratio of the emulsifier is 3:5;
dodecyl benzene sulfonic acid ammonium salt, purchased from Haian petrochemical plant of Jiangsu province;
AEO-9 with HLB value of 12.5, purchased from Haian petrochemical plant of Jiangsu province;
the solvent is N, N-dimethylacetamide, tripropylene glycol methyl ether and S-200 solvent oil, and the weight ratio of the N, N-dimethylacetamide to the tripropylene glycol methyl ether to the S-200 solvent oil is 2:1:1;
the dispersion medium is water.
A preparation method of a bactericide of pyraclostrobin and bupirimate comprises the following steps:
mixing the active ingredients in solvent, adding emulsifier and dispersing medium, and mixing.
And (3) performance testing:
1. testing the field efficacy:
1. and (3) experimental design:
the test samples comprise the bactericide containing the pyraclostrobin and the bupirimate prepared in the embodiment 1 of the application, and the bactericide is subjected to three different dilution times, wherein the dilution times are 2500 times, 1667 times and 1000 times, and the corresponding active ingredient contents are 100 mg/kg, 150 mg/kg and 250 mg/kg and are marked as A, B and C;
the comparative test is as follows:
30% pyraclostrobin suspending agent (purchased, sold on the common market), the dilution is 2500 times, the effective component is 120 mg/kg, and the mark is D;
the 25% bupirimate microemulsion (purchased, generally sold on the market) has the dilution multiple of 700 times, and the effective component of 357 mg/kg is marked as E;
and (4) clear water.
The test types are arranged into the following table;
2. cell arrangement:
the cells are arranged in random blocks, and the protection rows are arranged among the cells, and the schematic diagram is as follows
| C1 | A1 | F1 | D1 | E1 | B1 |
| D2 | B2 | E2 | F2 | C2 | A2 |
| F3 | D3 | C3 | B3 | A3 | E3 |
| E4 | C4 | D4 | A4 | B4 | F4 |
The cell area is 26m 2 4 repeats;
3. the application method comprises the following steps:
1) Application period and method:
crop: grape, variety: fuji, grape fruit expansion period and powdery mildew onset period in the 1 st pesticide application, and occasional disease spots in the field; the liquid medicine is prepared by a secondary dilution method and is evenly sprayed by a sprayer.
2) Applicator device
Spraying with HD400 type sprayer under 0.2-0.3MPa, with orifice diameter of 1mm and flow rate of 730ml/min, with correction error within 10%.
3) Time and frequency of application
4) Capacity of use
The water consumption per district is about 4 liters, and the water consumption per hectare is about 1538 liters;
5) Weather condition table during pesticide application
4. Investigation method, time and number of times
1) Investigation time and number of times
The disease is occasionally developed in the field before the pesticide, the investigation of the base number before the pesticide is not carried out, the investigation is carried out 1 time 7 days after 3 times of pesticide, the prevention effect of the pesticide is evaluated, the investigation is carried out 1 time 14 days after 3 times of pesticide, and the lasting effect of the pesticide effect is evaluated. The specific time is as follows: 30/6/2021 and 7/2021.
2) Investigation method
the blade grading method comprises the following steps:
level 0: no lesion spots;
level 1: the lesion area accounts for less than 5% of the whole leaf area;
and 3, level: the lesion area accounts for 6 to 10 percent of the whole leaf area;
stage 5: the lesion area accounts for 11% -20% of the whole leaf area;
and 7, stage: the lesion area accounts for 21-40% of the whole leaf area;
and 9, stage: the lesion area accounts for more than 40% of the whole leaf area.
3) Drug effect calculation method
5. Analysis of Experimental results
Data in the table are 4-repeat mean values, analysis of variance is processed by DPS (v 7.05 version), and letters indicate significance of difference (upper case 0.01 level, lower case 0.05 level)
The bactericide prepared in the embodiment 1 of the application is diluted 1000 times, 1667 times and 2500 times to prevent and treat grape powdery mildew, the control effect is 84.3 percent, 80.1 percent and 75.8 percent in turn after 3 times of application for 7 days, and the control effect is 79.7 percent, 75.8 percent and 71.5 percent in turn after 3 times of application for 14 days.
In a comparison test, 30% pyraclostrobin suspending agent is diluted 2500 times, and the control effect is 72.7% and 66.1% respectively in 7 days and 14 days after 3 times of drug administration.
In a contrast test, the 25% bupirimate microemulsion is diluted by 700 times, and the control effect is respectively 79.4% and 74.7% 7 and 14 days after 3 times of medicine application.
The control statistical data of 7 days after 3 times of medicines are used for variance analysis, the control effect difference of 1667 times of dilution of the bactericide obtained in the embodiment 1 of the application is not significant compared with 1000 and 2500 times of the bactericide, compared with a comparison test, each dose of a test medicine is equivalent to 700 times of control effect of 25% bupirimate microemulsion, the control effect of 1000 times of dilution of the bactericide obtained in the embodiment 1 of the application is obviously higher than that of 2500 times of dilution of 30% pyraclostrobin suspending agent, and meanwhile, the control effect of 1667 times of dilution of the bactericide obtained in the embodiment 1 of the application is equivalent to that of 2500 times of dilution of the bactericide.
Test results show that the bactericide prepared in the embodiment 1 of the application can prevent and treat grape powdery mildew, the prevention effect is improved along with the reduction of dilution times, the prevention effect is 75.8-84.3% 7 days after 3 times of application, the disease index is controlled to be below 10.8 and is far lower than the clear water control disease index 44.7, the grape powdery mildew harm is reduced, and the prevention effect is good; the control effect is still maintained to be more than 71.5 percent after 3 times of medicine for 14 days, and good persistence is shown. The grapes grew normally during the test period and no phytotoxicity symptoms were observed. The bactericide prepared in the embodiment 1 can be used for preventing and treating grape powdery mildew.
Meanwhile, the average disease index for the test of preventing and treating the grape powdery mildew is shown in figure 1, the grading disease index for 7 days after 3 times of the test of preventing and treating the grape powdery mildew is shown in figure 2, and the grading disease index for 14 days after 3 times of the test of preventing and treating the grape powdery mildew is shown in figure 3.
2. And (3) stability testing:
the bactericidal substances prepared in the examples 1 to 5 are used for stability test, and the test method refers to GB/T1603-2001; standing at 30 deg.C for 1 hr, and observing the stability of microemulsion, if there is no crystallization or if the emulsion and solid are separated out, the emulsion stability is qualified, otherwise it is not qualified. The results of the experiments are reported in the table below.
Claims (10)
1. The bactericide containing pyraclostrobin and bupirimate is characterized by comprising the following preparation raw materials in parts by weight: 5-50% of active ingredients, 3-30% of emulsifier, 20-50% of solvent and the balance of dispersion medium to 100%; the effective components comprise pyraclostrobin and bupirimate.
2. The bactericide containing pyraclostrobin and bupirimate as claimed in claim 1, wherein the weight ratio of pyraclostrobin to bupirimate is 1: (1-10).
3. The bactericidal compound containing pyraclostrobin and bupirimate according to claim 1, wherein the emulsifier comprises at least one of ammonium dodecylbenzene sulfonate, sodium dodecylbenzene sulfonate, ammonium dodecylsulfate, fatty alcohol polyoxyethylene ether, polyhydroxyl polyoxyethylene polyoxypropylene-containing polymer.
4. The bactericide containing pyraclostrobin and bupirimate as claimed in claim 3, wherein the emulsifier comprises dodecyl benzene sulfonic acid ammonium salt, fatty alcohol polyoxyethylene ether, and polyhydroxyl polyoxyethylene polyoxypropylene formaldehyde-containing polymer.
5. The pyraclostrobin-containing and bupirimate-containing bactericide according to claim 4, wherein the weight ratio of the dodecyl benzene sulfonic acid ammonium salt to the fatty alcohol-polyoxyethylene ether to the polyhydroxyl polyoxyethylene polyoxypropylene formaldehyde-containing polymer is (1-5): (2-8): (10-20).
6. The bactericide containing pyraclostrobin and bupirimate as claimed in any one of claims 3 to 5, wherein the fatty alcohol-polyoxyethylene ether is at least one selected from the group consisting of AEO-3, AEO-5, AEO-7, AEO-9 and AEO-20.
7. The bactericide containing pyraclostrobin and bupirimate as claimed in claim 6, wherein the fatty alcohol-polyoxyethylene ether has an HLB value of 10-16.
8. The fungicide according to claim 1, wherein the solvent is at least one selected from N, N-dimethylformamide, N-dimethylacetamide, tripropylene glycol methyl ether, mineral spirits, tetrahydrofuran, methyl acetate, butyl acetate and sec-butyl acetate.
9. The pyraclostrobin-containing bactericide as claimed in claim 8, wherein the mineral spirit is at least one selected from the group consisting of S-100 mineral spirit, S-150 mineral spirit and S-200 mineral spirit.
10. A method for preparing the pyraclostrobin-and bupirimate-containing fungicide according to any one of claims 1 to 9, comprising the steps of:
mixing the active ingredients in solvent, adding emulsifier and dispersing medium, and mixing.
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| CN104522012A (en) * | 2014-12-28 | 2015-04-22 | 海利尔药业集团股份有限公司 | Bactericidal composition containing pyraclostrobin and bupirimate |
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