CN114586799A - Pine wood nematode disease treating agent and preparation method thereof - Google Patents

Pine wood nematode disease treating agent and preparation method thereof Download PDF

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CN114586799A
CN114586799A CN202210301567.7A CN202210301567A CN114586799A CN 114586799 A CN114586799 A CN 114586799A CN 202210301567 A CN202210301567 A CN 202210301567A CN 114586799 A CN114586799 A CN 114586799A
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agent
penetration
solvent
synergist
piperonyl butoxide
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徐福元
柴忠心
陈凤毛
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Nanjing Shengxing Harmful Biological Control Technology Co ltd
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Nanjing Shengxing Harmful Biological Control Technology Co ltd
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/30Biocides, 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
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N43/00Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N51/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds having the sequences of atoms O—N—S, X—O—S, N—N—S, O—N—N or O-halogen, regardless of the number of bonds each atom has and with no atom of these sequences forming part of a heterocyclic ring
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/02Sulfur; Selenium; Tellurium; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/08Alkali metal chlorides; Alkaline earth metal chlorides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D317/00Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/50Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/54Radicals substituted by oxygen atoms
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against 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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Abstract

The application relates to the technical field of forestry disease control, and particularly discloses a pine wood nematode disease treating agent and a preparation method thereof. The ingredients of the curing agent for the pine wood nematode disease comprise a medicament and an auxiliary agent, wherein the medicament is formed by mixing emamectin benzoate and thiamethoxam; the auxiliary agent comprises a surfactant, a penetration auxiliary agent, a solvent, a defoaming agent and a synergist; the solvent comprises at least one organic solvent, the components of the synergist comprise piperonyl butoxide and a chloride concentrate, and the penetration assistant is used for accelerating the penetration rate of chloride ions in the trunk. The chlorine salt concentrated solution reduces the limitation of the concentration of chlorine ions on the insecticidal effect of emamectin benzoate, and meanwhile, under the combined action of the concentration difference of the chlorine ions and the permeation assistant, the treatment agent is easier to diffuse into gaps of duct cells of pine trees, so that the insecticidal effect of the treatment agent is improved.

Description

Pine wood nematode disease treating and curing agent and preparation method thereof
Technical Field
The application relates to the technical field of forestry disease control, in particular to a pine wood nematode disease treating agent and a preparation method thereof.
Background
Pine trees are one of the main economic tree species in China, and pine forest regions with huge areas exist in China. The pine wood nematode disease is a high-risk disease of pine trees, on one hand, the pine wood nematode disease has great influence on the growth of the pine trees, and on the other hand, because pathogenic nematodes are usually hidden in the trunks of the pine trees, the pine trees are difficult to show abnormality at the early stage of pine wood nematode infection and can be discovered by people after the disease is serious. In recent years, in order to effectively control the pine wilt disease, researchers screen out a batch of insecticide varieties with the potential of controlling the pine wilt disease, such as imidacloprid, fosthiazate, thiamethoxam, emamectin benzoate, Lofogda and the like, from harmful biological control agents. The insecticide is prepared into a curing agent, and the curing agent is injected into the trunk of the pine wood, so that the effect of killing the nematodes can be achieved.
In the related technology, the treatment agent for the pine wood nematode disease comprises the following components in percentage by weight: 0.5-3.0% of emamectin benzoate, 10-20% of thiamethoxam, 20-30% of surfactant, 0.1-0.5% of defoaming agent, 0.1-0.8% of synergist, and the balance of solvent to make up to 100%, wherein the synergist is piperonyl butoxide.
In view of the above-mentioned related technologies, the inventors believe that although the treatment agent for pine wood nematode disease is obtained by compounding the emamectin benzoate, thiamethoxam and piperonyl butoxide with the rest of the components in the related technologies, and the insecticidal effect of the emamectin benzoate is improved by using the piperonyl butoxide, a large amount of chloride ions need to be transported into the nematode when the emamectin benzoate exerts the insecticidal effect, and the concentration of the chloride ions in the trunk of the pine is limited, so that the improvement of the insecticidal effect of the piperonyl butoxide on the emamectin benzoate is limited.
Disclosure of Invention
In the related art, the concentration of chloride ions in the trunk of the pine tree is limited, so that the improvement of the insecticidal effect of piperonyl butoxide on emamectin benzoate is limited. In order to overcome the defect, the application provides a pine wood nematode disease curing agent and a preparation method thereof.
In a first aspect, the application provides a treatment agent for pine wood nematode disease, which adopts the following technical scheme:
the pine wood nematode disease curing agent comprises a medicament and an auxiliary agent, wherein the medicament is formed by mixing emamectin benzoate and thiamethoxam; the auxiliary agent comprises a surfactant, a penetration auxiliary agent, a solvent, a defoaming agent and a synergist; the solvent comprises at least one organic solvent, the components of the synergist comprise piperonyl butoxide and a chloride salt concentrated solution, and the penetration assistant is used for accelerating the penetration rate of chloride ions in the trunk.
By adopting the technical scheme, the chlorine salt concentrated solution is added into the components of the synergist, and the chlorine salt concentrated solution improves the initial chlorine salt content of the injection part of the therapeutic agent. After the curing agent is injected into the trunk, the drug effect of the emamectin benzoate starts to be developed, so that not only the original chloride ions in the trunk enter the body of the nematode, but also the chloride ions provided by the chloride salt concentrated solution enter the body of the nematode, and the nematode is killed. The chloride concentrated solution reduces the limitation of the concentration of chloride ions on the insecticidal effect of the emamectin benzoate, so that the piperonyl butoxide can more effectively improve the insecticidal effect of the emamectin benzoate.
Meanwhile, the chlorine ion concentrated solution is added, the chlorine ion concentration difference is generated between the treating agent and the trunk, and under the action of the chlorine ion concentration difference, water in the trunk diffuses to the injection part of the treating agent, so that gaps among duct cells of xylem are enlarged. Although the xylem of the pine tree is highly dense, the treatment agent is easily diffused into the gaps between the cells of the catheter with the aid of the penetration assisting agent, and the absorption amount of the treatment agent by the trunk is increased, thereby improving the effect of the treatment agent on the pine wood nematode disease.
Preferably, the weight percentage of each component in the pine wilt disease treatment agent is as follows: 0.5-3.0% of emamectin benzoate, 10-20% of thiamethoxam, 20-30% of surfactant, 5.0-15.0% of permeation aid, 0.1-0.5% of defoaming agent, 0.5-4.0% of synergist, and the balance of solvent to 100%, wherein the weight percentage of the piperonyl butoxide in the synergist is at least 20%.
By adopting the technical scheme, the weight percentages of the components in the nematode disease are optimized, and the restriction of the concentration of chloride ions in the trunk on the emamectin benzoate insecticidal effect is reduced.
Preferably, the piperonyl butoxide is prepared as follows:
(1) uniformly mixing dihydrosafrole, paraformaldehyde, an extracting agent and a catalyst to obtain a mixed solution 1, adding hydrochloric acid into the mixed solution 1 under the water bath heating condition, sequentially preserving heat and cooling the mixed solution 1 after the addition is finished, adding the extracting agent into the mixed solution 1, and extracting and separating to obtain chloromethyl dihydrosafrole;
(2) uniformly stirring chloromethyl dihydrosafrole, inorganic base, diethylene glycol monobutyl ether and an extractant to obtain a mixed solution 2, carrying out water bath heating reflux treatment on the mixed solution 2, adding water into the remaining mixed solution 2 after the reflux is finished, uniformly stirring, and standing and separating to obtain an etherified solution;
(3) and removing the extractant in the etherification solution to obtain piperonyl butoxide.
By adopting the technical scheme, the chloromethyl dihydrosafrole is prepared by taking dihydrosafrole, paraformaldehyde and hydrochloric acid as raw materials, then chlorine atoms in the chloromethyl dihydrosafrole are hydrolyzed under the participation of inorganic base, and then the chlorine atoms and diethylene glycol monobutyl ether are etherified to obtain the piperonyl butyl ether.
Preferably, the chlorine salt concentrate is prepared as follows:
(1) mixing two waste liquids generated by extracting the split solutions in the steps (1) and (2) for preparing piperonyl butoxide until the pH value of the mixed liquid is 7 for later use;
(2) evaporating the residual unused waste liquid in the step (1), collecting hydrogen chloride, and absorbing the hydrogen chloride by using water to obtain a hydrochloric acid product;
(3) and (2) evaporating and concentrating the mixed liquid of the two waste liquids obtained in the step (1) until crystals are generated in the mixed liquid to obtain a chlorine salt concentrated solution.
By adopting the technical scheme, the waste liquid generated in the process of preparing the piperonyl butoxide is used as the raw material, and the chlorine salt concentrated solution is obtained through evaporation and concentration, so that the reaction by-product is recycled. Besides the chlorine salt concentrated solution, the method also carries out evaporation treatment on the residual unused acidic waste liquid to obtain a byproduct hydrochloric acid.
Preferably, in the step (1) of preparing the piperonyl butoxide, the inorganic base is potassium hydroxide or sodium hydroxide.
By adopting the technical scheme, both sodium hydroxide and potassium hydroxide can be used for preparing piperonyl butoxide, wherein when potassium hydroxide is selected, the main component in the chloride salt concentrated solution is potassium chloride. The potassium chloride can be directly absorbed by plants and can promote the growth of the plants, thereby improving the resistance of the pine trees to nematode diseases and reducing the damage of the pine trees caused by the nematode diseases.
Preferably, the solvent in the adjuvant further comprises water.
By adopting the technical scheme, although the emamectin benzoate and the thiamethoxam are sufficiently dissolved by only using the organic solvent in the formula system, when the solvent contains water, the water can dissolve chloride salt crystals in the chloride salt concentrated solution, so that the total amount of chloride ions in the treatment agent is increased, and the insecticidal effect of the emamectin benzoate can be better improved.
Preferably, the surfactant comprises at least one of tween 80, polyoxyethylene fatty alcohol ether, styrylphenol polyoxyethylene ether, sodium dodecyl benzene sulfonate and dodecyl glucoside.
By adopting the technical scheme, the surfactant for preparing the pine wood nematode disease curing agent is preferably selected, wherein the dodecyl glucose is a nontoxic substance for pine trees and causes relatively small obstruction to the growth of the pine trees.
Preferably, the component of the penetration aid comprises a sulfite.
By adopting the technical scheme, the sulfite can play an anti-oxidation role on one hand, and is beneficial to reducing the possibility of oxidation of the damaged part of the trunk generated when the curing agent is injected. On the other hand, the sulfite can also partially dissolve lignin in the trunk, and preferably increases the penetration effect of the treatment agent in the trunk, contributing to enhancement of the medicinal effect of the treatment agent, and the component of the penetration aid includes aluminum chloride.
By adopting the technical scheme, the lignin in the trunk is negatively charged when in a wet state, and is easy to adsorb cations. When the aluminum chloride in the penetration auxiliary agent contacts with the moisture in the trunk, the aluminum chloride is ionized to generate chloride ions and aluminum ions, the aluminum ions are combined with the lignin and neutralize the charges of the lignin, and the chloride ions released by the aluminum chloride further increase the total amount of the chloride ions, so that the piperonyl butoxide can more effectively improve the insecticidal effect of the emamectin benzoate.
In a second aspect, the application provides a preparation method of the treating agent for the pine wood nematode disease, which adopts the following technical scheme.
A preparation method of a bursaphelenchus xylophilus disease treating and treating agent comprises the following steps:
(1) uniformly mixing emamectin benzoate and thiamethoxam to obtain a medicament; uniformly mixing a surfactant, a penetration aid, a solvent, a defoaming agent and a synergist to obtain an aid;
(2) and mixing the medicament and the auxiliary agent and uniformly stirring to obtain the pine wood nematode disease treating agent.
By adopting the technical scheme, the agent and the auxiliary agent are prepared respectively and then are uniformly mixed to obtain the treatment agent for the pine wood nematode disease.
In summary, the present application has the following beneficial effects:
1. through the cooperation of the chlorine salt concentrated solution and the synergist, the chlorine salt concentrated solution provides enough chloride ions for the emamectin benzoate to exert the pesticide effect while the piperonyl butoxide serving as the synergist exerts the synergistic effect, so that the limitation of the concentration of the chloride ions in the trunk on the pesticide effect of the emamectin benzoate is reduced, and the piperonyl butoxide can more effectively improve the insecticidal effect of the emamectin benzoate.
2. The waste liquid of the piperonyl butoxide is preferably prepared in the application as the raw material for preparing the chloride concentrate, the waste liquid of the piperonyl butoxide is recycled, and the byproduct hydrochloric acid is generated, so that the waste water amount of the production process is reduced, and the utilization rate of the raw material is increased.
3. According to the method, the agent and the auxiliary agent are prepared respectively, and then the agent and the auxiliary agent are uniformly mixed, so that the treatment agent for the pine wood nematode disease is obtained.
Detailed Description
The present application will be described in further detail with reference to examples.
The starting materials used in the preparation examples of the present application are all commercially available.
Preparation of piperonyl butoxide and chloride concentrate
The following will explain preparation example 1 as an example.
Preparation example 1
In the present application, piperonyl butoxide is prepared according to the following process:
(1) uniformly mixing 700g of dihydrosafrole, 195g of paraformaldehyde, 575g of extractant and 2g of catalyst to obtain a mixed solution 1, adding 2150g of hydrochloric acid into the mixed solution 1 within 2.5h under the water bath heating condition, heating the mixed solution 1 to 56 ℃ after the addition is finished, preserving the heat for 7h, then cooling the temperature to 48 ℃, supplementing 450g of the extractant into the mixed solution 1, stirring for 30min, and extracting and separating the mixed solution 1 to obtain chloromethyl dihydrosafrole; in the step, the extractant is petroleum ether, the catalyst is anhydrous zinc chloride, and the hydrochloric acid is industrial grade hydrochloric acid with the hydrogen chloride mass fraction of 36%;
(2) uniformly stirring 732g of chloromethyl dihydrosafrole, 248g of inorganic base, 600g of diethylene glycol monobutyl ether and 480g of extractant at 35 ℃ to obtain a mixed solution 2, carrying out water bath heating reflux treatment on the mixed solution 2 for 7.5h, adding 960g of water into the residual mixed solution 2 after the reflux is finished, stirring for 20min, standing the mixture of the mixed solution 2 and the water until the mixture is layered, and then carrying out liquid separation to obtain an etherified liquid; in the step, the inorganic base is sodium hydroxide;
(3) and removing the extractant in the etherification solution in vacuum to obtain piperonyl butoxide.
In this preparation example, the chloride salt concentrate was prepared as follows:
(1) mixing two waste liquids generated by extracting the split solutions in the steps (1) and (2) for preparing piperonyl butoxide until the pH value of the mixed liquid is 7 for later use;
(2) heating and evaporating the rest unused waste liquid in the step (1), and absorbing the evaporated hydrogen chloride by using water to obtain a hydrochloric acid product;
(3) and (2) heating and evaporating the mixed liquid of the two waste liquids obtained in the step (1) until crystals begin to precipitate in the mixed liquid, thus obtaining the chloride concentrated solution.
Preparation example 2
This preparation example is different from preparation example 1 in that sodium hydroxide used in step (2) of preparing piperonyl butoxide is replaced with potassium hydroxide in the same molar number.
Examples
The starting materials used in the examples of the present application are all commercially available.
Examples 1 to 5
The following description will be given by taking example 1 as an example.
Example 1
In this embodiment, the pine wood nematode disease treatment agent comprises a medicament and an auxiliary agent, wherein the medicament comprises 0.5g of emamectin benzoate and 10g of thiamethoxam, and the auxiliary agent comprises 20g of a surfactant, 5g of a penetration auxiliary agent, 0.1g of an antifoaming agent, 0.5g of a synergist and 63.9g of a solvent. Wherein the surfactant is sodium dodecyl benzene sulfonate; the penetration auxiliary agent is sodium sulfite; the defoaming agent is a silicone defoaming agent with the solid content of 33 percent, the silicone content of 20 percent and the solvent of water; the synergist is prepared by mixing piperonyl butoxide purchased from the market and the chlorine salt concentrated solution prepared in preparation example 1 according to the weight ratio of 1: 4; the solvent is DMF.
In this example, the treatment agent for pine wood nematode disease was prepared according to the following steps:
(1) uniformly mixing 0.5g of emamectin benzoate and 10g of thiamethoxam to obtain a medicament; uniformly mixing 20g of surfactant, 5g of penetration aid, 0.1g of defoaming agent, 0.5g of synergist and 63.9g of solvent to obtain the aid;
(2) and mixing the medicament and the auxiliary agent and uniformly stirring to obtain the pine wood nematode disease treating agent.
As shown in Table 1, examples 1 to 5 differ mainly in the ratio of raw materials
TABLE 1
Figure BDA0003565830420000051
Figure BDA0003565830420000061
Example 6
This example differs from example 3 in that the solvent was a mixture of 35.4g of DMF and 10g of water.
Example 7
This example differs from example 6 in that the surfactant is dodecyl glucoside.
Example 8
This example differs from example 7 in that the permeation aid is aluminum chloride.
Example 9
This example differs from example 8 in that the permeation aid is a mixture of 5g of aluminum chloride and 5g of sodium sulfite.
Preparation example 10
This example differs from example 9 in that the synergist was prepared by mixing piperonyl butoxide of preparation example 1 and the chloride salt concentrate of preparation example 1 in a weight ratio of 1:4
Example 11
This example differs from example 10 in that the synergist was mixed with piperonyl butoxide of preparation 2 and the chloride salt concentrate of preparation 1 in a weight ratio of 1: 4.
Comparative example
Comparative example 1
A wood nematode disease curing agent is prepared by compounding the following components: 1.8g of emamectin benzoate, 15g of thiamethoxam, 25g of sodium dodecyl sulfate, 0.3g of silicone defoamer, 0.5g of piperonyl butoxide, and 57.4g of solvent which is DMF.
Comparative example 2
This comparative example differs from example 3 in that the medicament comprises only thiamethoxam.
Comparative example 3
This comparative example differs from example 3 in that the agent only comprises thiamethoxam and the synergist does not comprise a chloride salt concentrate.
Comparative example 4
This comparative example differs from example 3 in that the synergist only comprises a chlorine salt concentrate.
Comparative example 5
This comparative example differs from example 3 in that the permeation aid is not included and the weight of the permeation aid is made up with water.
Performance detection test method
Three test areas I, II and III are set, the area is 10 mu each, the soil type is mountain forest soil, and the pine samples are 20-year-old healthy masson pine (5 plants are selected per mu). The control experiment was set up by inoculating the same nematode load in pine trees under the same conditions outside the test area.
The test method comprises the steps of artificially inoculating 5000 nematodes per pine strain of a sample strain, carrying out spray treatment by using the pine wood nematode disease treatment agent combination of the application after inoculation for one month, and spraying the tree crowns and the tree trunks by using a ground spraying method during spraying.
After 28 days of treatment, the treatment effect is evaluated and quantified according to the following formula:
Figure BDA0003565830420000071
wherein IP is the susceptible index of the test pine tree. And (3) carrying out IP inspection, namely grading the incidence symptom grade of the pine trees, namely grading the incidence index IP (grade 0-4) of the pine trees, wherein the incidence degree is increased gradually, the grade 0 represents no incidence, the grade 1 represents that about 10% of branches and leaves are browned, the grade 2 represents that 30-40% of branches and leaves are browned, the grade 3 represents that more than 50% of branches and leaves are browned, and the grade 4 represents that the whole pine tree is dead.
After the evaluation was completed, the average of the treatment effects of the three test areas was calculated, and the results are shown in table 2.
TABLE 2
Sample(s) Therapeutic effect/%) Sample(s) Rescue effect/%)
Example 1 72.6 Example 9 79.2
Example 2 73.8 Example 10 79.2
Example 3 75.9 Example 11 82.5
Example 4 74.6 Comparative example 1 42.1
Example 5 73.1 Comparative example 2 18.8
Example 6 77.8 Comparative example 3 18.8
Example 7 77.9 Comparative example 4 20.6
Example 8 78.5 Comparative example 5 57.3
As can be seen by combining examples 1-5 and comparative example 1 and combining Table 2, the curing effect measured by examples 1-5 is obviously better than that of comparative example 1, which shows that after the chlorine salt concentrated solution is added into the prescription system of the curing agent, the application is helpful to providing enough chlorine ions for the emamectin benzoate to exert the drug effect, so that the limitation of the concentration of the chlorine ions on the insecticidal effect of the emamectin benzoate is reduced; meanwhile, under the combined action of the concentration difference of the chloride ions and the penetration auxiliary agent, the curing agent is easier to diffuse into the gaps of the duct cells of the pine trees, so that the piperonyl butoxide can more effectively improve the insecticidal effect of the emamectin benzoate.
As can be seen by combining example 3 and comparative examples 2 to 3 with Table 2, the curing effect measured in example 3 is superior to that of comparative examples 2 to 3, and the results of comparative examples 2 and 3 are the same, indicating that even if the chlorine salt concentrate is added, the total amount of chlorine ions in the curing agent has no significant effect on the insecticidal effect of the curing agent in the absence of emamectin benzoate.
It can be seen by combining example 3 and comparative example 4 and combining table 2 that the rescue effect measured in example 3 is better than that in comparative example 4, which shows that when piperonyl butoxide is not included in the synergist, the emamectin benzoate does not need extra chloride ions because the emamectin benzoate does not undergo synergism, so that the rescue effect of the rescue agent is poor.
Combining example 3 and comparative example 5 with table 2, it can be seen that the curing effect measured in example 3 is better than that of comparative example 5, which shows that in the case of not containing the penetration aid, the movement of the curing agent in the trunk of the pine tree is hindered to a greater extent, and therefore, the number of nematodes contacted is insufficient, resulting in poor insecticidal effect of the curing agent.
Combining example 3 and example 6 and combining table 2, it can be seen that the rescue effect measured in example 6 is better than that of example 3, and it is demonstrated that the total amount of chloride ions in the rescue agent is increased by dissolving the chlorine salt crystals in the chlorine salt concentrated solution with water in the solvent, so that piperonyl butoxide can better improve the insecticidal efficiency of emamectin benzoate.
As can be seen by combining example 7 with example 6 and by combining Table 2, the therapeutic effect measured in example 7 is slightly better than that of example 6, indicating that the dodecyl glucoside selected in example 7 has relatively low toxicity to pine trees and therefore has relatively little effect on the growth of pine trees.
As can be seen by combining examples 8-9, example 7 and Table 2, the remedial effect measured in example 8 is superior to that of example 8, indicating that aluminum chloride is more helpful in promoting penetration of the remedial agent than sodium sulfite. The curing effect measured in example 9 is superior to that of examples 7 to 8, which shows that when aluminum chloride and sodium sulfite are used in combination, the aluminum chloride neutralizes the charge of lignin and increases the total amount of chloride ions in the curing agent, and the sodium sulfite dissolves the lignin and promotes the penetration of the components in the curing agent including chloride ions, thereby improving the curing effect of the curing agent on the infected pine trees.
As can be seen by combining example 10 and example 9 with Table 2, the curative effect measured in example 9 is the same as that measured in example 10, which shows that the piperonyl butoxide of the present application reaches the level of the same kind of commercial products.
It can be seen from the combination of example 11 and example 10 and the combination of table 2 that the treatment effect measured in example 11 is better than that of example 10, which illustrates that in example 11, potassium hydroxide is used as an inorganic base, so that the main component in the chlorine salt concentrated solution is potassium chloride, and the potassium chloride provides potassium ions for pine trees, thereby promoting the growth of the pine trees, reducing the severity of the disease after the pine trees are infected with diseases, and improving the treatment effect.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (10)

1. The treatment agent for the pine wood nematode disease is characterized by comprising a medicament and an auxiliary agent, wherein the medicament is formed by mixing emamectin benzoate and thiamethoxam; the auxiliary agent comprises a surfactant, a penetration auxiliary agent, a solvent, a defoaming agent and a synergist; the solvent comprises at least one organic solvent, the components of the synergist comprise piperonyl butoxide and a chloride salt concentrated solution, and the penetration assistant is used for accelerating the penetration rate of chloride ions in the trunk.
2. The bursaphelenchus xylophilus disease treatment agent according to claim 1, wherein the weight percentage of each component in the bursaphelenchus xylophilus disease treatment agent is as follows: 0.5-3.0% of emamectin benzoate, 10-20% of thiamethoxam, 20-30% of surfactant, 5.0-15.0% of permeation assistant, 0.1-0.5% of defoaming agent, 0.5-4.0% of synergist, and the balance of solvent to 100%, wherein the weight percentage of the piperonyl butoxide in the synergist is at least 20%.
3. The bursaphelenchus xylophilus disease treatment agent of claim 1, wherein the piperonyl butoxide is prepared according to the following method:
(1) uniformly mixing dihydrosafrole, paraformaldehyde, an extracting agent and a catalyst to obtain a mixed solution 1, adding hydrochloric acid into the mixed solution 1 under the water bath heating condition, sequentially preserving heat and cooling the mixed solution 1 after the addition is finished, adding the extracting agent into the mixed solution 1, and extracting and separating to obtain chloromethyl dihydrosafrole;
(2) uniformly stirring chloromethyl dihydrosafrole, inorganic base, diethylene glycol monobutyl ether and an extractant to obtain a mixed solution 2, carrying out water bath heating reflux treatment on the mixed solution 2, adding water into the remaining mixed solution 2 after the reflux is finished, uniformly stirring, and standing and separating to obtain an etherified solution;
(3) and removing the extractant in the etherification solution to obtain piperonyl butoxide.
4. The bursaphelenchus xylophilus disease treatment agent of claim 3, wherein the chlorine salt concentrate is prepared according to the following method:
(1) mixing two waste liquids generated by extracting the split solutions in the steps (1) and (2) for preparing piperonyl butoxide until the pH value of the mixed liquid is 7 for later use;
(2) evaporating the residual unused waste liquid in the step (1), collecting hydrogen chloride, and absorbing the hydrogen chloride by using water to obtain a hydrochloric acid product;
(3) and (2) evaporating and concentrating the mixed liquid of the two waste liquids obtained in the step (1) until crystals are generated in the mixed liquid to obtain a chlorine salt concentrated solution.
5. The bursaphelenchus xylophilus disease remedy according to claim 3, wherein in the step (1) of preparing the piperonyl butoxide, the inorganic base is potassium hydroxide or sodium hydroxide.
6. The bursaphelenchus xylophilus disease treatment agent of claim 4, wherein the solvent in the adjuvant further comprises water.
7. The bursaphelenchus xylophilus disease remedy according to claim 1, wherein the surfactant comprises at least one of tween 80, polyoxyethylene fatty alcohol ether, styrylphenol polyoxyethylene ether, sodium dodecylbenzenesulfonate, and dodecyl glucoside.
8. The bursaphelenchus xylophilus disease treatment agent as claimed in claim 1, wherein the component of the penetration aid comprises sulfite.
9. The bursaphelenchus xylophilus disease treatment agent of claim 8, wherein the components of the penetration aid further comprise aluminum chloride.
10. The method for preparing the bursaphelenchus xylophilus disease remedy according to any one of claims 1 to 9, comprising the steps of:
(1) uniformly mixing emamectin benzoate and thiamethoxam to obtain a medicament; uniformly mixing a surfactant, a penetration aid, a solvent, a defoaming agent and a synergist to obtain an aid;
(2) and mixing the medicament and the auxiliary agent and uniformly stirring to obtain the pine wood nematode disease treating agent.
CN202210301567.7A 2022-03-25 2022-03-25 Pine wood nematode disease treating agent and preparation method thereof Pending CN114586799A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2157298A1 (en) * 1970-11-19 1972-06-08 FMC Corp, New York, N Y (VStA) Process for the production of piperonyl butoxide
CN106699721A (en) * 2015-11-13 2017-05-24 重庆宏兆科技有限公司 Production technology of piperonyl butoxide composited by sassafras oil
CN113115783A (en) * 2021-04-12 2021-07-16 南京生兴有害生物防治技术股份有限公司 Preparation method of curing agent for pine wood nematode disease

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2157298A1 (en) * 1970-11-19 1972-06-08 FMC Corp, New York, N Y (VStA) Process for the production of piperonyl butoxide
CN106699721A (en) * 2015-11-13 2017-05-24 重庆宏兆科技有限公司 Production technology of piperonyl butoxide composited by sassafras oil
CN113115783A (en) * 2021-04-12 2021-07-16 南京生兴有害生物防治技术股份有限公司 Preparation method of curing agent for pine wood nematode disease

Non-Patent Citations (1)

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梅家庆 等: "杀虫增效剂胡椒基丁醚的合成及应用", 中华卫生杀虫药械 *

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