CN111328821A - Bactericide composition containing pyraclostrobin and mancozeb - Google Patents
Bactericide composition containing pyraclostrobin and mancozeb Download PDFInfo
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- CN111328821A CN111328821A CN202010139472.0A CN202010139472A CN111328821A CN 111328821 A CN111328821 A CN 111328821A CN 202010139472 A CN202010139472 A CN 202010139472A CN 111328821 A CN111328821 A CN 111328821A
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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
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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
- A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
- A01N47/14—Di-thio analogues thereof
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Abstract
The invention relates to the technical field of pesticides, and particularly relates to a bactericide composition containing pyraclostrobin and mancozeb. The pyraclostrobin accounts for 3-15% of the bactericide composition by weight; the weight percentage of the mancozeb accounts for 20-75% of the bactericide composition; the bactericide composition further comprises alkoxylated tallow alcohol.
Description
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a bactericide composition containing pyraclostrobin and mancozeb.
Background
Pyraclostrobin, also known as pyraclostrobin, is mainly used for various crops such as wheat, peanuts, rice, vegetables, fruit trees, tobacco, tea trees, ornamental plants, lawns and the like, and preventing and treating various diseases such as leaf blight, rust disease, powdery mildew, downy mildew, epidemic disease, anthracnose, scab, brown spot, damping-off and the like caused by ascomycetes, basidiomycetes, deuteromycetes and oomycetes fungi. Has better control effects on powdery mildew, downy mildew, banana scab, leaf spot disease, grape downy mildew, anthracnose, powdery mildew, early blight, late blight, powdery mildew, leaf blight and the like of tomatoes and potatoes. It can control most diseases of ascomycetes, basidiomycetes, deuteromycetes and oomycetes. Has strong inhibiting effect on spore germination and growth of leaf mycelium, and has protective and therapeutic activity. Has permeability, local systemic activity, long lasting period and rain wash resistance. Is widely used for preventing and treating diseases of wheat, rice, peanuts, grapes, vegetables, potatoes, bananas, lemons, coffee, fruit trees, walnuts, tea trees, tobacco, ornamental plants, lawns and other field crops.
However, the single pyraclostrobin bactericide component has resistance to pathogenic bacteria after long-term use, and the bacteriostatic control effect of the pyraclostrobin is seriously affected. In addition, the stability of the existing bactericide obtained by compounding pyraclostrobin and other components has some problems, the instability phenomenon is easily caused to influence the exertion of the efficacy of the bactericide, and particularly the prevention and treatment effect is greatly different from the effect obtained in a laboratory test when the climate change is frequent.
Disclosure of Invention
In order to solve the technical problems, the invention provides a bactericide composition containing pyraclostrobin and mancozeb, wherein the weight ratio of pyraclostrobin to mancozeb is (3-20): (5-80); the bactericide composition further comprises alkoxylated tallow alcohol.
As a preferred technical scheme, the bactericide composition also comprises polyether modified siloxane.
As a preferable technical scheme, the dosage form of the bactericidal composition comprises wettable powder, seed coating agent, dispersible oil suspending agent and water dispersible granule.
As a preferable technical scheme, the dispersible oil suspending agent is prepared from 1-5 wt% of an antifreezing agent, 1-5 wt% of a thickening agent, 1-4 wt% of a stabilizer, 30-35 wt% of mancozeb, 5-10 wt% of pyraclostrobin, 1-10 wt% of alkoxylated tallow alcohol, 1-10 wt% of polyether modified siloxane and the balance of a dispersing medium; the antifreeze is selected from one or more of ethylene glycol, propylene glycol, glucose, glycerol and polyethylene glycol.
As a preferable technical scheme, the preparation method of the dispersible oil suspending agent comprises the following steps:
adding a dispersion medium, a stabilizer, alkoxylated tallow alcohol and polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding pyraclostrobin and mancozeb raw medicines, a thickening agent and an antifreezing agent under a high-speed shearing state, and grinding the materials by a sand mill until the particle size is less than 5 micrometers to obtain the composite material.
As a preferable technical scheme, the weight ratio of the alkoxylated tallow alcohol to the polyether modified siloxane is (1: 4) - (4: 1).
As a preferable technical scheme, the preparation raw materials of the polyether modified siloxane comprise unsaturated polyether and hydrogen-containing silicone oil; the unsaturated polyether includes allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether.
As a preferable technical scheme, the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether is (2-3): 1.
as a preferred technical scheme, the bactericide composition also comprises disproportionated potassium rosinate.
The second aspect of the invention provides the application of the bactericide composition containing pyraclostrobin and mancozeb in preventing and treating vegetable and fruit tree sand skin disease, downy mildew and epidemic disease.
The bactericidal composition is prepared by combining pyraclostrobin and mancozeb, and the control effect of the bactericidal composition on the vegetable and fruit tree sand skin disease, downy mildew and epidemic disease is improved by utilizing the synergistic effect between the pyraclostrobin and the mancozeb. Meanwhile, the synergistic effect of the auxiliaries such as the alkoxylated tallow alcohol and the polyether modified organic siloxane is utilized, the stability of the composition is improved, the suspension rate of the dispersible oil suspending agent prepared from the bactericide composition is improved, the sterilization prevention and control effect is improved, the spreading property of the liquid medicine on leaf surfaces is improved, and the like.
Detailed Description
The technical features of the technical solutions provided by the present invention are further clearly and completely described below with reference to the specific embodiments, and the scope of protection is not limited thereto.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The invention provides a bactericide composition containing pyraclostrobin and mancozeb, which is prepared from the following components in parts by weight (3-20): (5-80); the germicidal composition also includes an alkoxylated tallow alcohol.
Preferably, the weight of the alkoxylated tallow alcohol accounts for 1-10 wt% of the bactericide composition.
Further preferably, the weight ratio of the pyraclostrobin to the mancozeb is (5-10): (30 to 35).
The pyraclostrobin in the invention has a chemical name of N- [2- [ [1- (4-chlorophenyl) pyrazol-3-yl ] oxymethyl ] phenyl ] -N-methoxy methyl carbamate, and has a molecular structure as follows:
pyraclostrobin belongs to strobilurin fungicide, and is a mitochondrial respiration inhibitor. It inhibits mitochondrial respiration by blocking electron transfer between the mitogen b and C1, rendering mitochondria unable to produce and supply energy (ATP) required for normal cellular metabolism, ultimately leading to cell death. Pyraclostrobin has strong capability of inhibiting germ spore germination, and has good inhibition effect on hypha growth in leaves. It has long lasting period and potential therapeutic activity. The compound has weak conduction and fumigation effects towards the leaf tip or leaf base in the leaf, but has strong conduction activity in the plant body. The pyraclostrobin has the advantages of protective effect, therapeutic effect, systemic conductivity, rain erosion resistance and wide application range. Although pyraclostrobin has inhibitory effect on the pathogenic strains tested, it should be used in the recommended dose and mixed with other bactericide without cross resistance in the barrel or directly, and the number of times of application in each growing season is strictly limited to delay the occurrence and development of resistance.
The mancozeb chemical name of the invention is complex salt of manganese ethylene bis-dithiocarbamate and zinc, CAS number 8010-01-7, molecular formula (C)4H6MnN2S4) xZny, relative molecular mass (265.24) x + (65.38) y, molecular structure as follows:
the mancozeb in the invention can be purchased from the market and can also be prepared by oneself,the synthesis steps are as follows: 1) slowly dripping carbon disulfide into an aqueous solution of ethylenediamine and sodium hydroxide to react to generate sodium metiram; 2) adding MnSO into sodium metiram4Reacting to generate maneb; 3) adding ZnSO continuously4Generating mancozeb, and mixing the obtained mancozeb wet product with an organic solvent after the reaction is finished, distilling and dehydrating.
The alkoxylated tallow alcohol in the invention is a compound which is alkoxylated by the reaction of tallow alcohol with monomers with epoxy groups and has an alkoxy chain segment with a long aliphatic carbon chain. The applicant finds that a certain amount of alkoxylated tallow alcohol is added into the bactericidal composition compounded by pyraclostrobin and mancozeb, so that the bactericidal composition can play a role in resisting rain wash, the inhibition of the bactericidal composition on citrus sand skin disease, cucumber downy mildew, cucumber epidemic disease, grape downy mildew and the like is improved to a certain extent, and the drug effect of the bactericidal composition is not obviously influenced even if the bactericidal composition is flushed by rain after being sprayed with a drug. Probably because the alkoxylated tallow alcohol has better acting force with the pyraclostrobin and the mancozeb, the pyraclostrobin and the mancozeb are well dispersed mutually by utilizing the long carbon chain on the tallow alcohol molecule and the alkoxy chain segment with certain hydrophilicity, and are spread on the surfaces of the crop leaves. Meanwhile, as the hydrophobic effect of the larger carbon chain of the tallow alcohol and the hydrophilic effect of the alkoxy group reach a certain balance, the surface tension of the bactericide composition can reach a very low level, the wetting capability and the spreading capability of the composition are further improved, the bactericide composition can better penetrate into the surfaces of crop leaves and form a film layer on the surfaces of the leaves, the adhesive force between the film layer and the surfaces of the leaves is realized, and the sterilization time of the composition is prolonged.
The source of the alkoxylated tallow alcohol in the present invention is not particularly limited, and can be prepared by the alkoxylation method of alcohols well known to those skilled in the art, or can be obtained commercially, or can be purchased from Yongchuang Woodbisan.
In some preferred embodiments, the antimicrobial composition further comprises a polyether modified siloxane. Preferably, the preparation raw materials of the polyether modified siloxane comprise unsaturated polyether and hydrogen-containing silicone oil; the unsaturated polyether includes allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether.
The polyether modified siloxane in the invention utilizes unsaturated double bonds in polyether to react with terminal hydrogen in organosiloxane, and polyether chain segments are grafted to organosiloxane frameworks to increase polar groups on organosiloxane molecular chains. The mancozeb molecule structure contains strong polar imino groups, sulfur atoms and other groups, so that the acting force in the molecule is strong, the molecules are easy to agglomerate together and are not easy to dissolve and disperse, and the acting force between the molecule and the pyraclostrobin needs to be improved. The applicant finds that by adding a certain amount of polyether modified organosiloxane into the compounded pyraclostrobin and mancozeb and simultaneously performing synergistic action with a certain amount of alkoxylated tallow alcohol, the intramolecular acting force of mancozeb can be well broken, the acting force between the pyraclostrobin and the polyether modified organosiloxane is improved, the dispersity and the stability of the components in a dispersing medium are improved, the spreading of the bactericidal composition on the surface of an object to be applied to vegetables, fruit trees and the like is facilitated, the drifting of the bactericidal composition in the using process is avoided, the film forming on the surface of crops is facilitated, the bactericidal time of the composition is prolonged, and the bactericidal rate is improved.
The polyether modified siloxane is prepared by the following method:
1) adding 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high hydrogen-containing silicone oil with hydrogen content of 1.56% and 6g of acid clay into a reaction kettle, heating to 60 ℃ and reacting for 4 hours to obtain low hydrogen-containing silicone oil with hydrogen content of 0.3%;
2) adding 50g of low-hydrogen silicone oil, 95g of unsaturated polyether, 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution into a reaction kettle, reacting for 5 hours at the reaction temperature of 110 ℃ and normal pressure, and cooling after no redundant Si-H bonds exist.
Preferably, the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether is (2-3): 1; further preferably, the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether is 2.5: 1. the allyl alcohol polyether is selected from allyl alcohol polyether HMS-232R (hydroxyl value is about 75mgKOH/g) of Huangjiang Huangma chemical industry Co., Ltd, the allyl polyoxyethylene polyoxypropylene epoxy ether is selected from HY series products of Nanjing Zhongshan chemical industry Co., Ltd, and the average molecular weight is 1000.
The applicant finds that the dispersion stability, low-temperature stability, high-temperature stability and the like of the dispersible oil suspending agent of the bactericidal composition can be remarkably improved by regulating the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether. Probably, the cohesive energy density of the polyether modified siloxane can be well regulated and controlled by the two monomers, the interaction force between the polyether modified organosiloxane, the pyraclostrobin and the mancozeb is improved, the medicines are promoted to be fully dispersed along with the polyether modified siloxane and other components, and the problems of agglomeration, flocculation and the like caused by the change of factors such as temperature and the like among medicine particles are avoided.
In some embodiments, the dosage form of the bactericidal composition comprises wettable powder, seed coating agent, dispersible oil suspending agent and water dispersible granule.
Preferably, the dispersible oil suspending agent also comprises 1-5 wt% of an antifreezing agent, 1-5 wt% of a thickening agent and 1-4 wt% of a stabilizing agent; the antifreezing agent is one or more selected from ethylene glycol, propylene glycol, glucose, glycerol and polyethylene glycol.
The thickening agent is not specially limited, and fumed silica, polyvinyl alcohol, bentonite, attapulgite, magnesium lithium silicate and the like can be selected.
In the present invention, the stabilizer is not particularly limited, and organic acids, organic bases, esters, alcohols, ethers (such as castor oil polyoxyethylene ether), and the like can be selected.
In some embodiments, the method for preparing the dispersible oil suspension comprises the following steps:
adding a dispersion medium, a stabilizer, alkoxylated tallow alcohol and polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding pyraclostrobin and mancozeb raw medicines, a thickening agent and an antifreezing agent under a high-speed shearing state, and grinding the materials by a sand mill until the particle size is less than 5 micrometers to obtain the composite material.
Preferably, the dispersible oil suspension is prepared by grinding with a sand mill to a particle size of less than 1 micron.
The dispersion medium is a solvent, and includes but is not limited to methyl oleate or soybean oil.
In some embodiments, the alkoxylated tallow alcohol and polyether modified siloxane are present in a weight ratio of (1: 4) to (4: 1); preferably, the weight ratio of the alkoxylated tallow alcohol to the polyether modified siloxane is 2: 3.
The second aspect of the invention provides a use method of the dispersible oil suspending agent, and besides the conventional use method, the dispersible oil suspending agent can be sprayed on corresponding crops for use by adopting a low-volume spraying technology.
The main difference between the low-volume spraying technology and the high-volume spraying technology is that the diameters of the adopted spray holes are different during spraying. The high volume spray is a spray method in which the diameter of the nozzle of the spray nozzle is 1.3 mm, and the low volume spray is a spray method in which the unit volume of the spray is less than a constant volume. By reducing the diameter of the spray hole of the sprayer, the spray hole is changed to be small when the pressure is constant, the fog drops become thin, the coverage area is increased, the spray liquid consumption per unit area is obviously reduced, and even is reduced to one tenth of the conventional spray amount. By the use method, the pesticide application efficiency can be obviously improved, unnecessary labor energy consumption is reduced, the pesticide dosage can be effectively reduced, a better prevention and treatment effect is achieved, and environmental pollution and cost pressure are avoided.
In some embodiments, the biocide composition further comprises disproportionated potassium rosinate; preferably, the use amount of the disproportionated potassium rosinate accounts for 20-50 wt% of the mass of the alkoxylated tallow alcohol.
The disproportionated potassium abietate is obtained by the disproportionation reaction of rosin in the presence of catalyst to make acidic resin acid molecules rearranged by hydrogen transfer and eliminate conjugated double bond system. The structural formula is as follows:
the applicant finds that a certain amount of disproportionated potassium rosinate is added into the sterilization composition, so that the exertion of the efficacy of the composition can be well improved, and the composition is favorable for improving the bacteriostasis rate to a certain extent. When the sterilization composition is prepared into the dispersible oil suspending agent and the alkylated tallow alcohol and polyether modified siloxane are used simultaneously, the dispersible oil suspending agent has good dispersion stability even if the components such as pyraclostrobin, mancozeb and the like are ground into particles with the particle size of less than 1 micron and are dispersed in a dispersion medium such as methyl oleate or soybean oil, the dispersible oil suspending agent can be uniformly sprayed and used by adopting WFB-18A type and 3MF-4 type ultralow-capacity spraying machines, the size of fog drops is proper, good sedimentation and coverage can be obtained on the surface of a plant, and the dispersible oil suspending agent has good penetrability in a plant cluster due to the relatively small size. In addition, under the interaction among the components, the low-temperature stability and the high-temperature stability of the dispersible oil suspending agent are improved, and the control rate of the vegetable and fruit tree sand skin disease, downy mildew, epidemic disease and the like are obviously improved. Probably, under the interaction of the disproportionated potassium rosinate, the alkylated tallow alcohol and the polyether modified siloxane, micelles with small particle size and high thickness can be formed in a dispersing medium of the dispersible oil suspending agent, and the pyraclostrobin and the mancozeb are coated in the micelles to be fully dispersed, so that agglomeration and sedimentation are avoided. Meanwhile, mancozeb is a complex of organic molecules and metal ions, has high sensitivity to the pH value, the temperature and the like of a system, and is easy to cause the problems of agglomeration, caking and the like along with the change of the environment. Under the synergistic action of the disproportionated potassium rosinate, the alkylated tallow alcohol and the polyether modified siloxane, mancozeb is coated in the micelle with a specific particle size, the charge characteristics of the three components are utilized, the micelle surface is charged specifically, the friction agglomeration between adjacent micelles is avoided, the stability of the dispersible oil suspending agent is further improved, and the sterilization effect of the bactericide composition is remarkably improved.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention. In addition, all the raw materials used were ordinary commercial products unless otherwise specified.
Examples
Embodiment 1 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 2 wt% of castor oil polyoxyethylene ether, 5 wt% of alkoxylated tallow alcohol and 7 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 6 wt% of pyraclostrobin, 25 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 3 micrometers.
The preparation method of the polyether modified siloxane comprises the following steps:
1) adding 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high hydrogen-containing silicone oil with hydrogen content of 1.56% and 6g of acid clay into a reaction kettle, heating to 60 ℃ and reacting for 4 hours to obtain low hydrogen-containing silicone oil with hydrogen content of 0.3%;
2) adding 50g of the low-hydrogen silicone oil, 95g of allyl alcohol polyether (allyl alcohol polyether HMS-232R of Huangjiang Huangma chemical Co., Ltd.), 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution into a reaction kettle, reacting for 5 hours at the reaction temperature of 110 ℃ and under normal pressure, and cooling after no redundant Si-H bonds exist.
Embodiment 2 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 2 wt% of castor oil polyoxyethylene ether, 8 wt% of alkoxylated tallow alcohol and 4 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 10 wt% of pyraclostrobin, 35 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 3 micrometers.
Wherein the polyether modified siloxane is the same as in example 1.
Embodiment 3 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 30 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 3 micrometers.
Wherein the polyether modified siloxane is the same as in example 1.
Embodiment 4 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 30 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 3 micrometers.
The preparation method of the polyether modified siloxane comprises the following steps:
1) adding 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high hydrogen-containing silicone oil with hydrogen content of 1.56% and 6g of acid clay into a reaction kettle, heating to 60 ℃ and reacting for 4 hours to obtain low hydrogen-containing silicone oil with hydrogen content of 0.3%;
2) 50g of the low hydrogen silicone oil, 95g of unsaturated polyether (a mixture of allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether, in a weight ratio of 2.5: 1) adding 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution into a reaction kettle, reacting for 5 hours at the reaction temperature of 110 ℃ and normal pressure, and cooling after no more Si-H bonds exist.
Embodiment 5 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the oil dispersible suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 20 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 6 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the oil dispersible suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 10 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 7 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 5 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 8 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 3 wt% of pyraclostrobin, 24 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 9 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 3 wt% of pyraclostrobin, 30 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 10 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the oil dispersible suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 20 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 11 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol and 1.6 wt% of disproportionated potassium rosinate into a reaction kettle, mixing and dispersing; adding 5 wt% of pyraclostrobin, 20 wt% of Dyson manganese zinc original drug, 3 wt% of bentonite, 2 wt% of ethylene glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 microns.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 12 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 20 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
Wherein the polyether modified siloxane is the same as in example 4.
Embodiment 13 provides a dispersible oil suspension comprising a fungicide composition comprising pyraclostrobin and mancozeb.
The preparation method of the dispersible oil suspending agent comprises the following steps:
adding 3 wt% of castor oil polyoxyethylene ether, 4 wt% of alkoxylated tallow alcohol, 1.6 wt% of disproportionated potassium rosinate and 6 wt% of polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding 5 wt% of pyraclostrobin, 20 wt% of mancozeb technical, 3 wt% of bentonite, 2 wt% of glycol and the balance of methyl oleate under a high-speed shearing state, and grinding until the particle size is less than 5 micrometers.
The preparation method of the polyether modified siloxane comprises the following steps:
1) adding 100g of octamethylcyclotetrasiloxane, 7.2g of hexamethyldisiloxane, 28.5g of high hydrogen-containing silicone oil with hydrogen content of 1.56% and 6g of acid clay into a reaction kettle, heating to 60 ℃ and reacting for 4 hours to obtain low hydrogen-containing silicone oil with hydrogen content of 0.3%;
2) adding 50g of low-hydrogen silicone oil, 95g of unsaturated polyether (allyl polyoxyethylene polyoxypropylene epoxy ether), 20g of diethylene glycol and 6.8mg of platinum-rhodium complex solution into a reaction kettle, reacting for 5 hours at the reaction temperature of 110 ℃ and under normal pressure, and cooling after no redundant Si-H bonds exist.
Evaluation of Performance
Toxicity tests of the bactericidal composition in the examples on cucumber epidemic disease, grape downy mildew, cucumber downy mildew and citrus sand disease are determined by a drug-containing culture method according to standards of NY/T1156.2-2006 and NY/T1156.2-2006 specified in pesticide indoor bioassay experimental criteria bactericides. Specifically, the method comprises the following steps:
1) according to the standard method NY/T1156.2-2006 for biological measurement, a drug-containing culture medium method is adopted: 3mL of liquid medicine with each single dose and mixed dose series concentration is added into 27mL of PDA culture medium cooled to 45 ℃ to prepare a medicine-containing culture medium plate with the required final concentration. Then, 6mm diameter hypha blocks were prepared from the edges of the colonies of citrus resiniferous (sand skin disease) fungi cultured for 7 days, and transferred to each series of drug-containing media with the hypha facing downward, and the treatment was repeated 4 times. After the treatment, the mixture is placed in a constant temperature biochemical incubator at 28 ℃ for culture.
The statistical classification method comprises the following steps: the colony diameter was measured 7 days after the experimental treatment, and the growth inhibition (%) was calculated.
D＝D1-D2；
Wherein: d represents the colony growth diameter; d1Represents the colony diameter; d2The cake diameter is indicated.
I(％)＝(D0-Dt)/D0*100
Wherein: i represents the hypha growth inhibition rate; d0Indicates the growing diameter of the blank control colony; dtIndicating the growth diameter of the agent-treated colonies.
The synergy of the mixed medicament is evaluated according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960) by referring to the bioassay standard NY/T1156.6-2006, namely that CTC is less than or equal to 80 as antagonistic action, CTC is more than 80 and less than 120 as additive action, and CTC is more than or equal to 120 as synergistic action.
Measured virulence index (ATI) ═ standard agent EC50Reagent for test EC50)*100
Theoretical virulence index (TTI) of the mixture agent a percent (%) of agent a in the mixture agent + virulence index of agent B percent (%) of the mixture agent B
Co-toxicity coefficient (CTC) ═ mix observed virulence index (ATI)/mix theoretical virulence index (TTI) ] + 100. The test results are shown in Table 1.
2) Referring to a sound measurement standard method NY/T1156.3-2006, a plate blade method is adopted.
Preparing a sporangia suspension: selecting cucumber diseased leaves, washing the leaf with distilled water at 4 deg.C to obtain leaf-back downy mildew sporangium, and making into suspension (concentration controlled at 1 x 10/ml)51 to 107Sporangia) and storing at 4 ℃ for later use.
Uniformly spraying the prepared liquid medicine on the back of the donor blade, after the liquid medicine is naturally dried, enabling the back of each treated blade to face upwards, and discharging the liquid medicine in a moisture preserving box according to treatment marks. At 24 hours after the treatment, 10 microliters of the prepared fresh sporangium suspension was spotted on the back of the leaf. 4 drops were inoculated per leaf, 5 leaves per treatment, and the test was blanked with treatments containing no agent. And covering the inoculated cell with a dish cover, placing the cell in an artificial climate box, and culturing under the conditions of continuous illumination/darkness for 12h alternation every day, the temperature of 17-22 ℃ and the relative humidity of more than 90%.
The statistical method comprises the following steps: after 7 days of culture, the disease spot diameter is measured and recorded according to the disease condition of the blank control, and the control effect (%) is calculated.
P＝(D0-D1/D0)*100
Wherein: p represents the Down-preventing Effect, D0Indicates the diameter of blank control lesion, D1Indicates the lesion diameter to be treated.
The synergy of the mixed medicament is evaluated according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960) by referring to the bioassay standard NY/T1156.6-2006, namely that CTC is less than or equal to 80 as antagonistic action, CTC is more than 80 and less than 120 as additive action, and CTC is more than or equal to 120 as synergistic action.
Measured virulence index (ATI) ═ standard agent EC50Reagent for test EC50)*100
Theoretical virulence index (TTI) of the mixture agent a percent (%) of agent a in the mixture agent + virulence index of agent B percent (%) of the mixture agent B
Co-toxicity coefficient (CTC) ═ mix observed virulence index (ATI)/mix theoretical virulence index (TTI) ] + 100. The test results are shown in Table 2.
3) Referring to sound test standard method NY/T1156.3-2006, a drug-containing culture medium method is adopted: 3mL of liquid medicine with each single agent and mixed agent series concentration is taken and added into 27mL of PDA culture medium cooled to 45 ℃ to prepare a medicine-containing culture medium plate with the required final concentration. Then, 6mm diameter hypha blocks are prepared from the edges of the cucumber phytophthora colonies cultured for 7 days, and the hypha blocks are transferred to each series of drug-containing culture media with the hypha facing downwards, and the treatment is repeated for 4 times. After the treatment, the mixture is placed in a constant temperature biochemical incubator at 28 ℃ for culture.
The statistical classification method comprises the following steps: the colony diameter was measured 5 days after the experimental treatment, and the growth inhibition (%) was calculated.
D＝D1-D2；
Wherein: d represents the colony growth diameter; d1Represents the colony diameter; d2The cake diameter is indicated.
I(％)＝(D0-Dt)/D0*100
Wherein: i represents the hypha growth inhibition rate; d0Indicates the growing diameter of the blank control colony; dtIndicating the growth diameter of the agent-treated colonies.
The synergy of the mixed medicament is evaluated according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960) by referring to the bioassay standard NY/T1156.6-2006, namely that CTC is less than or equal to 80 as antagonistic action, CTC is more than 80 and less than 120 as additive action, and CTC is more than or equal to 120 as synergistic action.
Measured virulence index (ATI) ═ standard agent EC50Reagent for test EC50)*100
Theoretical virulence index (TTI) of the mixture agent a percent (%) of agent a in the mixture agent + virulence index of agent B percent (%) of the mixture agent B
Co-toxicity coefficient (CTC) ═ mix observed virulence index (ATI)/mix theoretical virulence index (TTI) ] + 100. The test results are shown in Table 3.
4) Referring to a sound measurement standard method NY/T1156.3-2006, a plate blade method is adopted.
Preparing a sporangia suspension: selecting grape diseased leaf, washing leaf with distilled water at 4 deg.C to obtain leaf-back downy mildew sporangium, and making into suspension (concentration controlled at 1 × 10 per ml)51 to 107Sporangia) and storing at 4 ℃ for later use.
Uniformly spraying the prepared liquid medicine on the back of the donor blade, after the liquid medicine is naturally dried, enabling the back of each treated blade to face upwards, and discharging the liquid medicine in a moisture preserving box according to treatment marks. At 24 hours after the treatment, 10 microliters of the prepared fresh sporangium suspension was spotted on the back of the leaf. 4 drops were inoculated per leaf, 5 leaves per treatment, and the test was blanked with treatments containing no agent. And covering the inoculated cell with a dish cover, placing the cell in an artificial climate box, and culturing under the conditions of continuous illumination/darkness for 12h alternation every day, the temperature of 17-22 ℃ and the relative humidity of more than 90%.
The statistical method comprises the following steps: after 7 days of culture, the disease spot diameter is measured and recorded according to the disease condition of the blank control, and the control effect (%) is calculated.
P＝(D0-D1/D0)*100
Wherein: p represents the Down-preventing Effect, D0Indicates the diameter of blank control lesion, D1Indicates the lesion diameter to be treated.
The synergy of the mixed medicament is evaluated according to the co-toxicity coefficient method (CTC) of Sun & Johnson (1960) by referring to the bioassay standard NY/T1156.6-2006, namely that CTC is less than or equal to 80 as antagonistic action, CTC is more than 80 and less than 120 as additive action, and CTC is more than or equal to 120 as synergistic action.
Measured virulence index (ATI) ═ standard agent EC50Reagent for test EC50)*100
Theoretical virulence index (TTI) of the mixture agent a percent (%) of agent a in the mixture agent + virulence index of agent B percent (%) of the mixture agent B
Co-toxicity coefficient (CTC) ═ mix observed virulence index (ATI)/mix theoretical virulence index (TTI) ] + 100. The test results are shown in Table 4.
TABLE 1 virulence assay results of fungicidal compositions against citrus resinifera (Cortinarius) bacteria
Indoor bioassay results show that the ratio of pyraclostrobin to mancozeb is 1: 1,1: 2,1: 4,1: 6,1: 8,1: the citrus resinifera is mixed at a ratio of 10 to show a synergistic effect on citrus resinifera, wherein the ratio of the citrus resinifera to citrus resinifera is 1: 6,1: 8,1: 10, the synergistic effect is most obvious. In actual production, special environment, processing technology, virulence and other factors are needed for further comprehensive consideration.
TABLE 2 virulence test results of the fungicidal compositions against Pseudoperonospora cubensis
Indoor bioassay results show that the ratio of pyraclostrobin to mancozeb is 1: 1,1: 2,1: 4,1: 6,1: 8,1: 10, the ratio of the two components is 1: 6,1: 8,1: 10, the synergistic effect is most obvious. In actual production, special environment, processing technology, virulence and other factors are needed for further comprehensive consideration.
TABLE 3 virulence test results of the fungicidal compositions against cucumber phytophthora
Indoor bioassay results show that the ratio of pyraclostrobin to mancozeb is 1: 1,1: 2,1: 4,1: 6,1: 8,1: 10, the ratio of the two components is 1: 6,1: 8, 1: 10, the synergistic effect is most obvious. In actual production, specific factors such as environment, processing technology and toxicity are required to be further comprehensively considered.
TABLE 4 virulence assay results for P.viticola for fungicidal compositions
Indoor bioassay results show that the ratio of pyraclostrobin to mancozeb is 1: 1,1: 2,1: 4,1: 6,1: 8,1: the mixture with the proportion of 10 shows synergistic effect on the plasmopara viticola, wherein the ratio of the two is 1: 6,1: 8,1: 10, the synergistic effect is most obvious. In actual production, special environment, processing technology, virulence and other factors are needed for further comprehensive consideration.
In addition, the applicant performed a dispersion stability test, a low temperature stability test, a high temperature stability test, and the like on the dispersible oil suspension agent in the example of the present invention. Specifically, the method comprises the following steps:
1. the test method for high temperature stability was carried out according to the "liquid formulation" test method in GB/T19136-2003: after the dispersible oil suspending agent prepared by the embodiment is stored for 4 weeks at 54 ℃, the dispersible oil suspending agent is tested to be in a stable liquid state, and the dispersible oil suspending agent is qualified without the phenomena of layering, solidification, precipitation and the like; otherwise, it is not satisfactory.
2. And (3) testing dispersion stability: the test was carried out according to the method described in HG/T2467.11-2003, essentially preparing a dispersion at a given concentration, placing it in two graduated emulsion tubes respectively, standing for a certain period of time, pouring the tubes several times, and observing the dispersion initially, after standing for a certain period of time and after redispersion. Wherein
The superior grade: initial dispersibility-complete dispersion; dispersibility-precipitation <5.0ml, cream or oil slick <3.0ml for 30 min; redispersion-24 h precipitation <1.0ml, cream or oil slick <2.0 ml.
Good grade: initial dispersibility-complete dispersion; dispersibility-precipitation <8.0ml, cream or oil slick <5.0ml for 30 min; redispersion for 24h <1.5ml of sediment, cream or creme <3.0 ml.
Unqualified: initial dispersability-incomplete dispersion; dispersibility-precipitation >8.0ml, cream or oil slick >5.0ml for 30 min; redispersion-24 h >1.5ml pellet, cream or creme >3.0 ml.
3. The low temperature stability was performed according to "oil suspension" in GB/T19137-: if the phenomena such as precipitation, delamination and the like do not occur, the initial properties can be reproduced after the room temperature is recovered and the stirring is carried out, the product is qualified, otherwise, the product is not qualified.
TABLE 5 test chart for physical and chemical properties
| High temperature stability | Stability of dispersion | Freeze thaw stability | |
| Example 3 | Qualified | Good wine | Fail to be qualified |
| Example 4 | Qualified | Superior food | Qualified |
| Example 5 | Qualified | Superior food | Qualified |
| Example 6 | Qualified | Superior food | Qualified |
| Example 7 | Qualified | Superior food | Qualified |
| Example 8 | Qualified | Superior food | Qualified |
| Example 9 | Qualified | Superior food | Qualified |
| Example 10 | Fail to be qualified | Good wine | Fail to be qualified |
| Example 11 | Fail to be qualified | Good wine | Fail to be qualified |
| Example 12 | Fail to be qualified | Good wine | Fail to be qualified |
| Example 13 | Fail to be qualified | Superior food | Fail to be qualified |
Field test
The applicant entrusts Sichuan Hebei science and technology company Limited to carry out field test on the pyraclostrobin and mancozeb composite dispersible oil suspending agent to observe the control effect on alternaria leaf spot and citrus resinifera of apple trees, and the method comprises the following specific steps:
alternaria leaf spot of first and second apple trees
1.1 crop and target: crop/apple tree/red Fuji
target/Alternaria leaf spot [ Alternaria mali; marssonina coronara ]
1.2 test conditions: the test was conducted in apple plots of Taiping village in Fulin town of Hanyuan county, Sichuan province, 7/19/2019/8/9/2019. The test area is 1.5 mu, and the apple tree varieties are: hongfush, clean crop, 8 years old tree, 60 apple plants per mu, applying the pesticide at the fruit expanding period. The field is red brown sandy loam, the pH value is 6.1, and the organic matter content is 24.5 g/kg. The medicine is not applied at the early stage.
2 test design and arrangement
2.1.1 test Agents
410 g/l pyraclostrobin mancozeb dispersible oil suspending agent (Shanghai Yue Lian biotechnology Co., Ltd.)
2.1.2 control Agents
30% pyraclostrobin suspension concentrate (Shanghai Yueji Biotech Co., Ltd.)
80% mancozeb wettable powder (Shanghai Yue chemical Co., Ltd.)
2.1.3 test treatment
TABLE 62.1.3 test treatments
2.2 cell arrangement
2.2.1 cell arrangement: the cells are arranged in random blocks, which is shown as follows
Table 72.1.3 cell arrangements
| A1 | C1 | B1 | D1 | F1 | E1 |
| D2 | B2 | E2 | F2 | C2 | A2 |
| F3 | E3 | C3 | B3 | A3 | D3 |
| E4 | F4 | D4 | A4 | B4 | C4 |
2.2.2 cell area and repetition: repeating for 4 times, wherein each cell comprises 2 trees, and protection rows are arranged among the cells.
2.3 modes of application
2.3.1 application time and frequency: the application is started before the apple trees are attacked, and the application is continuously carried out for 2 times. The specific time is as follows: 19/7/2019 and 30/7/2019.
2.3.2 instruments used and methods of application: the liquid medicine is prepared by adopting a secondary dilution method, and the main preparation tools comprise: scales, graduated cylinders, pipettes, glass rods, and the like. Spraying with PB-16 type sprayer under 0.2-0.4Mpa and with diameter of spray orifice of 1mm, and water consumption of each tree is about 1.25L.
2.3.4 soil data: the red brown sandy loam has a pH value of 6.1 and an organic matter content of 24.5 g/kg.
2.3.5 prevention of non-target biological conditions: no other agents were administered during the trial.
3 investigation and results
3.1 investigation method: 2 trees are investigated in each cell, each tree is divided into 5 directions of east, west, south, north and middle, 2 new tips (spring tips and autumn tips) are fixed respectively, all leaves are investigated regularly, and the total leaf number and the leaf number of each disease are recorded. The grading method comprises the following steps: level 0: no disease spots; level 1: the lesion area accounts for less than 10% of the whole leaf area; and 3, level: the lesion area accounts for 11 to 25 percent of the whole leaf area; and 5, stage: the lesion area accounts for 26-40% of the whole leaf area; and 7, stage: the lesion area accounts for 41 to 65 percent of the whole leaf area; and 9, stage: the lesion area accounts for more than 66% of the whole leaf area.
3.2 survey time and number: the test was performed 1 time when the clear water control symptoms were evident. The specific time is as follows: 8 and 9 months in 2019.
3.3 the test complies with the quality management standard of pesticide registration test, the standard of pesticide field efficacy test GB/T17980.124-2004 and the SOP-TM-149a test for alternaria leaf spot of apple trees, and the calculation formula is as follows
3.4 Effect on other organisms: no significant effect of the test agent on other organisms was observed during the test.
3.5 test results
3.5.1 prevention and treatment effects: the average control effect is shown in table 8.
TABLE 8410 g/L pyraclostrobin mancozeb dispersible oil suspending agent average control effect table for preventing and treating alternaria leaf spot of apple trees
| Treatment of | Finger for disease | Control effect% |
| A | 5.75 | 76.5bA |
| B | 4.39 | 82abA |
| C | 3.59 | 85.3aA |
| D | 4.15 | 83aA |
| E | 8.07 | 67cB |
| F | 24.44 |
The data in the table are 4 replicate means, the analysis of variance is processed by DPS (v version 7.05), and the alphabet shows significance of differences (upper case 0.01 level, lower case 0.05 level, DMRT method).
3.5.2 safety: during the test period, apple trees grow normally, and no phytotoxicity symptoms are observed.
4 evaluation and discussion
The pyraclostrobin mancozeb dispersible oil suspending agent of 410 g/L can prevent and treat alternaria leaf spot of apple trees by 800, 1000 and 1200 times, and the control effect is 85.3 percent, 82 percent and 76.5 percent when the control symptom of clear water is obvious. The control medicament 30% pyraclostrobin suspending agent is 2500 times, 80% mancozeb wettable powder is 600 times, and the control effect is 83% and 67% respectively when clear water control symptoms are obvious. The result of the anova shows that the 1000 times of the reagent to be tested has equivalent control effect to 800 times and 1200 times. Compared with a control medicament, the control effect difference of 800 and 1000 times of the test medicament and 2500 times of the 30% pyraclostrobin suspending agent is not significant, and the control effect of each dose of the test medicament is significantly higher than 600 times of that of 80% mancozeb wettable powder.
Test results show that the pyraclostrobin mancozeb dispersible oil suspending agent of 410 g/L can prevent and treat alternaria leaf spot of apple trees, and the prevention effect is improved along with fold reduction. When the clear water control symptom is obvious, the control effect is 76.5-85.3%, the disease index is controlled below 5.75 and is far lower than the clear water control disease index 24.44, the harm of apple tree alternaria leaf spot is reduced, and the control effect is good. During the test period, apple trees grow normally, and no phytotoxicity symptoms are observed. 410 g/L pyraclostrobin mancozeb dispersible oil suspending agent can be used for preventing and treating alternaria leaf spot of apple trees.
According to the test result in the year, the 410 g/L pyraclostrobin mancozeb dispersible oil suspension provided by Shanghai Yuejie Biotech company Limited prevents and treats alternaria leaf spot of apple trees, and the 800-fold dilution (341.7-512.5 mg/kg of active ingredient) is recommended to be used for 2 times before or at the early stage of the alternaria leaf spot of the apple trees at intervals of 7-10 days.
Resinosis of citrus trees
1.1 crop and target: crop/citrus aurantium
Target/resinoid disease [ Phomopsis scytosporella ]
The test conditions of 1.2 are that the test is carried out in a Ziyun orchard of filial piety county at Sichuan castration from 20 days at 4 months in 2019 to 30 days at 5 months in 2019, the field is yellow loam, the pH value is 5.8, the test area of organic matter content is 21.6 g/kg. is 1.5 mu, the orchard is put into production 4 years after high-speed change, the variety is Wo gan, the plant row spacing is 3m × 4m, 55 plants are planted per mu, and no bactericide is used 50 days before the test.
2 test design and arrangement
2.1.1 test Agents
410 g/l pyraclostrobin-mancozeb dispersible oil suspension concentrate (Shanghai Yue Lian biotechnology Co., Ltd.)
2.1.2 control Agents
30% pyraclostrobin suspension concentrate (Shanghai Yueji Biotech Co., Ltd.)
80% mancozeb wettable powder (Shanghai Yue chemical Co., Ltd.)
2.1.3 test treatment
TABLE 92.1.3 test treatments
2.3 modes of application
2.3.1 application time and frequency: in the period of withering to blossom 2/3, young fruit period and fruit expansion period, the medicine is applied 1 time and 3 times at an interval of 10 days. 2.3.2 instruments used and methods of application: the liquid medicine is prepared by adopting a secondary dilution method, and the main preparation tools comprise: scales, graduated cylinders, pipettes, glass rods, and the like. Spraying with HD400 type sprayer under spraying pressure of 0.2-0.4MPa and with spraying hole diameter of 1mm, and water consumption of each tree of about 1.5L.
2.3.4 soil data: yellow loam, pH value 5.8, organic matter content 21.6 g/kg.
2.3.5 prevention of non-target biological conditions: no other agents were administered during the trial.
3 investigation and results
3.1 investigation method: 2 plants in each cell are investigated at each point according to a 5-point sampling method in east, west, south and north, 4 leaves and all fruits below the top leaf of each branch are examined, and disease index and prevention and treatment effect are calculated. The classification method comprises the following steps: level 0: the leaves and fruits have no disease spots; level 1: the area of brown spot disease spots on leaves and fruits accounts for less than 5% of the area of the leaves and fruits; and 3, level: the area of brown spot disease spots on leaves and fruits accounts for 6-10% of the area of the leaves and fruits; and 5, stage: the area of brown spot lesions on the leaves and the fruits accounts for 11 to 25 percent of the area of the leaves and the fruits; and 7, stage: the area of brown spot lesions on the leaves and the fruits accounts for 26 to 50 percent of the area of the leaves and the fruits; and 9, stage: the area of brown spot disease spots on leaves and fruits accounts for more than 51 percent of the area of the leaves and the fruits.
3.2 survey time and number: each of the test was conducted 1 time and 2 times before and 20 days after the 3 times of treatment. The specific time is as follows: 20 days in 2019 and 5 and 30 days in 2019.
3.3 test basis and calculation: the test complies with the quality management standard of pesticide registration test, the pesticide field efficacy test criterion, and the SOP-TM-073a Citrus resinifera disease test, and has the following calculation formula
3.4 Effect on other organisms: no significant effect of the test agent on other organisms was observed during the test.
3.5 test results
3.5.1 prevention and treatment effects: the average control effect is shown in table 10.
TABLE 10410 g/L pyraclostrobin-mancozeb dispersible oil suspension agent average control effect table for preventing and controlling citrus tree resinoid disease
The data in the table are mean values of 4 replicates, the analysis of variance was treated by DPS (v version 7.05), and the letters indicate significance of difference (upper case 0.01 level, lower case 0.05 level, DMRT method).
3.5.2 safety: during the test period, the citrus trees grow normally, and no phytotoxicity symptoms are observed.
4 evaluation and discussion
During the investigation period of the experiment, the fruits are in the expansion stage, and the resin disease symptoms are not shown, so that only the leaves are investigated for disease condition analysis. The pyraclostrobin mancozeb dispersible oil suspending agent of 410 g/L can prevent and treat citrus resin diseases by 800, 1000 and 1200 times, the control effect of the leaves is 85.1 percent, 83.0 percent and 78.3 percent in sequence 20 days after 3 times of pesticide application, the control agent is 30 percent of pyraclostrobin suspending agent 2500 times, and the 80 percent of mancozeb wettable powder is 600 times, and the control effect of the leaves is 78.6 percent and 79.0 percent in 20 days after 3 times of pesticide application. The result of the anova shows that the control effect of the tested medicament 800 and 1000 is obviously higher than 1200 times. Compared with the control medicament, the 800-1000-time control effect of the test medicament is obviously higher than that of the two groups of control medicaments, and 1200-time control effect is equivalent to that of the control medicaments.
Test results show that 410 g/L pyraclostrobin and mancozeb dispersible oil suspending agent can prevent and control citrus tree resinoid diseases, the prevention effect is increased along with the reduction of multiple, 78.3-85.1% of the leaf control effect 20 days after 800 times of 1200 times of 3 times of medicine, the leaf control effect is controlled to be below 4.06 and is far lower than 18.02 of the leaf control effect, the harm of the citrus tree resinoid diseases is effectively reduced, and the prevention effect is good. During the test, the citrus grows normally, no phytotoxicity symptom is observed, and 410 g/L pyraclostrobin mancozeb dispersible oil suspending agent can be used for preventing and treating citrus resin diseases.
According to the test result in the year, the dispersible oil suspending agent of pyraclostrobin and mancozeb provided by Shanghai Yuejie Biotech company Limited at 410 g/L is recommended to be diluted by 800-fold for preventing and treating citrus resinifera, and is continuously applied for 3 times at intervals of 7-14 days at each new top emergence period, blossom metabolism 2/3, and before or at the initial stage of emergence of young fruits of citrus trees.
In addition, in order to ensure the repeatability of the technical scheme, the applicant entrusts Shanxi university of agriculture to carry out field tests on the pyraclostrobin mancozeb dispersible oil suspending agent in the invention again, which specifically comprises the following steps:
and (3) test crops: apple trees; the control object is: alternaria alternata of Alternaria mali
Reagent to be tested: 410 g/l pyraclostrobin mancozeb dispersible oil suspending agent
3 environmental and facility cultivation conditions
3.1 test site location
Shanxi province Taigu county, Yangyi county, Hui Ma village.
3.2 assay target conditions
In the past, the apple trees have alternaria leaf spot, the test is carried out for the first time in the early stage of disease occurrence, and the apple trees have sporadic scabs in the field.
3.3 test crop varieties and growth conditions
The variety of the test crop: fuji; growth conditions were as follows: the apple trees are 8 years old, and the planting density is 50 plants/mu.
3.4 soil type of test plot
The test field is loam with pH of about 7.2 and no interplanted crops.
3.5 Water and Fertilizer management of test field
Management conditions such as fertilizer, water and the like are uniform and consistent, management levels such as irrigation and drainage and the like are medium, and the operation is carried out according to conventional farming before and after the test.
3.6 weather data
The first application (7 months and 21 days) is cloudy and cloudy, the temperature is 23-34 ℃, the average temperature is 26.9 ℃, and the relative humidity is 66%. The second application (7 months and 31 days) is carried out at 20-33 deg.C, the average temperature is 26.2 deg.C, and the relative humidity is 64%. The third application (8 months and 10 days) is clear, the temperature is 18-30 ℃, the average temperature is 24.6 ℃, and the relative humidity is 69%. In the test period, the effective rainfall is 8 days, the total rainfall is 79.1mm, the maximum rainfall is 29 days in 7 months in 2019, and the rainfall is 27.9 mm. The maximum temperature during the test was 36 ℃ and the minimum temperature was 13 ℃. There is no disaster climate which affects the efficacy of the drug, but the disease is relatively dry and slow in the past year.
3.7 information of pesticide for preventing and treating other diseases and pests
No bactericide or insecticide was used during the test, and the test results were not affected.
4 test design and arrangement
4.1 test agent dosage and numbering
TABLE 11 test design for test agents
4.2 cell arrangement
The experiment has 6 treatments, each treatment has 4 cells, and the cells adopt random block arrangement to total 24 cells.
TABLE 12 cell arrangement Table
4.2.2 cell area and repetition
Cell area: each plot was 2 mature apple trees.
The number of repetitions: repeat 4 times.
4.3 methods of application
4.3.1 administration periods and methods
The pesticide is applied at the early stage of the apple alternaria leaf spot, the pesticide is weighed according to the dosage required by each treatment, and the water is added for conventional spraying, so that the spraying is required to be uniform and consistent, and no heavy spraying or missed spraying is required. And spraying clear water to the blank control.
4.3.2 applicator devices
Instrument numbering: SP-F-003
The instrument model is as follows: a petrel back-carrying electric sprayer, 3WBD-16 type, with working pressure of 0.2-0.4 MPa.
4.3.3 application time and frequency
The test is performed 3 times in total, the first time in 21 days 7 and 7 months in 2019, the second time in 31 days 7 and 7 months in 2019, and the third time in 10 days 8 and 8 months in 2019.
4.3.4 volume of application
Spraying 2 liters of liquid to each tree.
4.4 methods of investigation, time and frequency
Reference agricultural ministry of agriculture "test criteria of pesticide field efficacy (two): the bactericide for preventing and treating alternaria mali (GB/T17980.124-2004) is carried out according to the test unit SOP (bactericide for preventing and treating alternaria mali) (SXAU-SOP-F-015).
4.4.1 investigation time and number of surveys
First investigation: and 7, 9, 21 days, the first investigation is carried out before drug application, sporadic disease spots appear on apple trees at the moment, and the disease index is recorded as zero.
And (4) second investigation: the control effect is investigated 12 days after the last application of the drug in 8 and 22 months in 2019, and the disease occurrence condition is recorded according to the grading standard.
4.4.2 methods of investigation
Two plants in each cell are investigated, each plant is respectively fixed with two new tips in the east, south, west, north and middle five directions, all the leaves are investigated, and the total leaf number and the leaf number of each grade disease are recorded. Each leaf was graded as the percentage of lesion area.
Leaf damage grading method (taking leaves as a unit):
level 0: no disease spots;
level 1: the disease spots account for less than 10% of the whole leaf area;
and 3, level: the disease spots account for 11 to 25 percent of the whole leaf area;
and 5, stage: the lesion spots account for 26 to 40 percent of the whole leaf area;
and 7, stage: the lesion spots account for 41 to 65 percent of the whole leaf area;
and 9, stage: the lesion spots account for more than 66% of the total leaf area.
4.4.3 method for calculating drug efficacy
The method and formula for calculating the drug effect are as follows: calculating disease index and prevention and treatment effect of each cell, calculating average prevention and treatment effect of each treatment, and analyzing difference significance between treatments by adopting an SPSS 17.0 software DMRT method.
4.5 direct effects on crops
After 1 day, 3 days and 5 days after each application, no phytotoxicity of the pesticide on apple trees and fruits is observed.
4.6 yield and quality of product
At the end of the experiment, yield and quality were not investigated.
4.7 Effect on other organisms
4.7.1 Effect on other pests
In the test, other diseases of the apple trees are not found, and the apple trees have no influence on insect pests.
4.7.2 Effect on other non-target organisms and surrounding crops
There was no effect on other non-target organisms and surrounding crops in the experiment.
5 test results and analysis
The results of the control effect investigation 10 days after the last drug show that (table 2): when the dosage of the active ingredients of the test medicament 410 g/L pyraclostrobin mancozeb dispersible oil suspending agent is 341.7 mg/kg, 410 mg/kg and 512.5 mg/kg, the control effect is 81.23%, 85.83% and 86.70% respectively; when the dosage of the active ingredient of the 30% pyraclostrobin suspending agent of the control medicament is 200 mg/kg, the control effect is 84.22%, and when the dosage of the active ingredient of the 80% dyssomnion zinc wettable powder of the control medicament is 1000 mg/kg, the control effect is 82.92%.
The analysis of the test result by a Duncan new complex pole difference method shows that: at the levels of 0.05 and 0.01, the differences between the high concentration, the medium concentration and the low concentration of the pyraclostrobin mancozeb dispersible oil suspending agent of 410 g/L and the control agent are not significant.
TABLE 13410 g/L pyraclostrobin mancozeb dispersible oil suspending agent pesticide effect test result for preventing and treating apple alternaria leaf spot
Conclusion 6
The pyraclostrobin mancozeb dispersible oil suspending agent of 410 g/L is recommended to be popularized and used in production for spraying prevention and treatment before the onset of apple alternaria leaf spot or in the initial stage of the onset of the apple alternaria leaf spot, the application time is 3 times at intervals of 7-14 days, and the dosage of effective components is 341.7-512.5 mg/kg (the dilution multiple of the preparation is 800-1200 times). The tested dosage of the tested medicament is safe for apple trees and fruits.
The foregoing examples are illustrative only, and serve to explain some of the features of the present disclosure. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. And that advances in science and technology will result in possible equivalents or sub-substitutions not now considered due to the imprecision of language representation, and such variations should also be construed where possible to be covered by the appended claims.
Claims (10)
1. A bactericide composition containing pyraclostrobin and mancozeb is characterized in that the weight ratio of pyraclostrobin to mancozeb is (3-20): (5-80); the bactericide composition further comprises alkoxylated tallow alcohol.
2. The bactericide composition containing pyraclostrobin and mancozeb according to claim 1, which further comprises polyether modified siloxane.
3. The bactericide composition containing pyraclostrobin and mancozeb according to claim 2, wherein the bactericide composition comprises wettable powder, seed coating agent, dispersible oil suspending agent and water dispersible granule.
4. The bactericide composition containing pyraclostrobin and mancozeb according to claim 3, wherein the dispersible oil suspending agent is prepared from 1-5 wt% of an antifreezing agent, 1-5 wt% of a thickening agent, 1-4 wt% of a stabilizer, 30-35 wt% of mancozeb, 5-10 wt% of pyraclostrobin, 1-10 wt% of alkoxylated tallow alcohol, and 1-10 wt% of polyether modified siloxane; the antifreeze is one or more selected from ethylene glycol, propylene glycol, glucose, urea, glycerol, polyethylene glycol and inorganic salt.
5. The bactericide composition containing pyraclostrobin and mancozeb as claimed in claim 4, wherein the preparation method of the dispersible oil suspending agent comprises the following steps:
adding a dispersion medium, a stabilizer, alkoxylated tallow alcohol and polyether modified siloxane into a reaction kettle, and mixing and dispersing; adding pyraclostrobin and mancozeb raw medicines, a thickening agent and an antifreezing agent under a high-speed shearing state, and grinding the materials by a sand mill until the particle size is less than 5 micrometers to obtain the composite material.
6. The bactericide composition containing pyraclostrobin and mancozeb according to claim 2, wherein the weight ratio of the alkoxylated tallow alcohol to the polyether modified siloxane is (1: 4) - (4: 1).
7. The bactericide composition containing pyraclostrobin and mancozeb as claimed in claim 2, wherein the raw materials for preparing the polyether modified siloxane comprise unsaturated polyether and hydrogen-containing silicone oil; the unsaturated polyether includes allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether.
8. The bactericide composition containing pyraclostrobin and mancozeb as claimed in claim 7, wherein the weight ratio of allyl alcohol polyether to allyl polyoxyethylene polyoxypropylene epoxy ether is (2-3): 1.
9. the bactericide composition containing pyraclostrobin and mancozeb according to any one of claims 1 to 8, further comprising disproportionated potassium rosinate.
10. The application of the bactericide composition containing pyraclostrobin and mancozeb in any one of claims 1 to 9 in preventing and treating vegetable and fruit tree sand skin disease, downy mildew and epidemic disease.
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| CN114176092A (en) * | 2021-12-28 | 2022-03-15 | 利民化学有限责任公司 | Nano oil suspending agent containing mancozeb and prothioconazole and preparation method thereof |
| CN115316397A (en) * | 2022-09-08 | 2022-11-11 | 利民化学有限责任公司 | Application of bactericidal composition for preventing and treating diaporthe citri |
| WO2024131338A1 (en) * | 2022-12-18 | 2024-06-27 | 张子勇 | Nanosuspension for fruit disease control |
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