阅读说明：本技术 一种含三氟甲吡醚的杀虫组合物 (Insecticidal composition containing pyridalyl ) 是由 刘言合 陈琦 于 2021-08-24 设计创作，主要内容包括：本发明公开了一种含三氟甲吡醚的杀虫组合物,涉及农药领域,解决了现有的农药组合物在稀释使用时,易发生团聚分散性差,施药时润湿性差、表面张力大,不易在靶标生物叶面上润湿铺展,使药效降低和水溶性差,容易被土壤吸附的问题；本发明是通过静电排斥和空间位阻的增效协同作用实现悬浮体系的物理稳定,甲氧基可凭“伞型”状紧密排列,利于农药在靶标生物叶面上的润湿铺展,提高农药的有效利用率,达到了提升农药组合物的分散性和润湿性的目的。(The invention discloses an insecticidal composition containing pyridalyl, relates to the field of pesticides, and solves the problems that the existing pesticide composition is easy to generate poor agglomeration and dispersibility when diluted for use, has poor wettability and large surface tension when applied, is difficult to wet and spread on the leaf surface of a target organism, reduces the pesticide effect, has poor water solubility and is easy to be adsorbed by soil; the invention realizes the physical stability of a suspension system through the synergistic interaction of electrostatic repulsion and steric hindrance, and the methoxyl groups can be closely arranged in an umbrella shape, thereby being beneficial to wetting and spreading of pesticide on the leaf surface of a target organism, improving the effective utilization rate of the pesticide and achieving the purpose of improving the dispersibility and wettability of the pesticide composition.)

1. The insecticidal composition containing pyridalyl is characterized by comprising the following components in parts by weight:

1-50 parts of pyridalyl, 1-30 parts of component A, 1-50 parts of filler or solvent, 1-10 parts of assistant A and 1-10 parts of assistant B;

the auxiliary A is prepared by the following steps:

s1: adding allyl polyoxyethylene ether into a four-neck flask, adding solvent deionized water, placing the mixture into an oil bath kettle, stirring and heating the mixture to 50-60 ℃, dropwise adding thioglycolic acid into the flask at a dropwise adding speed of 1-2 drops/s, dropwise adding an ammonium persulfate aqueous solution at a dropwise adding speed of 1-2 drops/s, dropwise adding 2-pentenoic acid at a dropwise adding speed of 1-2 drops/s, and obtaining a product A;

s2: adding vinyl trimethoxy silane into the product A, dropwise adding thioglycolic acid into a flask at a speed of 1-2 drops/s, dropwise adding an ammonium persulfate aqueous solution at a speed of 1-2 drops/s, reacting for 1-2h, heating to 70-80 ℃, preserving heat, reacting for 2-3h, cooling to room temperature, and neutralizing pH to 6-7 with a sodium hydroxide solution to obtain the assistant A;

the auxiliary B is prepared by the following steps:

s3: dissolving sodium hydroxide in deionized water, adding the deionized water into a three-neck flask, starting mechanical stirring, adding beta-CD, controlling the temperature at 0-10 ℃, dropwise adding 1, 2-epoxydecane at the dropwise adding speed of 1-2 drops/s, and stirring for 2-3 hours to obtain a product B;

s4: introducing nitrogen into the three-neck flask containing the product B for protection, controlling the temperature at 20-30 ℃, and stirring for reacting for 20-30 hours to obtain a product C;

s5: and (3) cooling the product C in an ice bath, controlling the temperature to be 0-3 ℃, adjusting the pH to 6-7 by using a hydrochloric acid solution, concentrating under reduced pressure, putting into a vacuum drying oven, drying at normal temperature for 3-4h, heating to 50-60 ℃, controlling the heating speed to be 2-5 ℃/min, and drying for 1-2h to obtain the auxiliary B.

2. The insecticidal composition containing pyridalyl as claimed in claim 1, wherein the component A is one of spinosad and ethyl spinosad.

3. The insecticidal composition containing pyridalyl as claimed in claim 1, wherein the filler is one or a mixture of two or more of sucrose, mannitol, lactose, potassium sulfate, sodium sulfate, montmorillonite, calcium carbonate, zeolite, acid clay, clay and pyrophyllite in any proportion, and the solvent is water or vegetable oil.

4. The pyridalyl-containing insecticidal composition according to claim 1, wherein the composition is formulated into a pesticide formulation which is one of a suspending agent, a dispersible oil suspending agent and water dispersible granules.

5. The pyridalyl-containing insecticidal composition according to claim 1, characterized in that in step S1, the mass of thioglycolic acid is 2% of the mass of allyl polyoxyethylene ether, the mass fraction of the aqueous solution of ammonium persulfate is 42%, the mass of the aqueous solution of ammonium persulfate is 5% of the mass of allyl polyoxyethylene ether, and the molar ratio of allyl polyoxyethylene ether to 2-pentenoic acid is 3: 1.

6. The insecticidal composition containing pyridalyl as claimed in claim 1, wherein in step S2, the mass of the thioglycolic acid is 2% of the mass of vinyltrimethoxysilane, the mass fraction of the aqueous solution of ammonium persulfate is 42%, the mass of the aqueous solution of ammonium persulfate is 10% of the mass of allyl polyoxyethylene ether, the mass fraction of the solution of sodium hydroxide is 25%, and the molar ratio of vinyltrimethoxysilane to the product a is 1: 2.

7. The insecticidal composition containing pyridalyl as claimed in claim 1, wherein the amount ratio of sodium hydroxide to deionized water in step S3 is 1 g: 15mL, wherein the dosage ratio of the sodium hydroxide, the beta-CD and the 1, 2-epoxydecane is 20 g: 100 g: 50 mL.

8. The insecticidal composition containing pyridalyl according to claim 1, wherein the mass fraction of the hydrochloric acid solution in step S5 is 20%.

Technical Field

The invention relates to the field of pesticides, and particularly relates to an insecticidal composition containing pyridalyl.

Background

The chemical formula of the pyridalyl is C₁₈H₁₄C_l4F₃NO₃Is used for preventing and controlling lepidoptera pest larvae, sprays pesticide at the low-age larvae of diamondback moth, resists rain wash,the spinosad and the ethyl spinosad have quick contact killing and stomach poisoning effects on pests, have stronger osmosis effect on leaves, can kill pests below epidermis, have long residual effect period, have ovicidal effect on some pests, can effectively control lepidoptera, diptera and thysanoptera pests, and can well control certain types of pests eating the leaves in coleoptera and orthoptera, are safer to predatory natural enemy insects, have no phytotoxicity on plants, are suitable for being used on vegetables, fruit trees, gardening and crops, and resist rain wash.

The pyridalyl and the spinosad (ethyl spinosad) are reasonably compounded and are mutually synergistic, so that a more excellent insecticidal effect can be achieved, but the existing pesticide composition is easy to generate poor agglomeration and dispersibility when diluted for use, poor in wettability and large in surface tension when applied, and is not easy to wet and spread on the leaf surface of a target organism, so that the pesticide effect is reduced, the pesticide composition is poor in water solubility, is easy to adsorb by soil, accumulates in the soil and transfers to plants, the pesticide content in crops is increased, the health of a human body is directly threatened, and the environmental pollution is caused;

therefore, an insecticidal composition containing pyridalyl is provided.

Disclosure of Invention

In order to overcome the technical problems, the invention aims to provide an insecticidal composition containing pyridalyl, which comprises the following components in percentage by weight:

(1) the method comprises the steps of adding allyl polyoxyethylene ether into a four-neck flask, dropwise adding aqueous solution of thioglycolic acid and ammonium persulfate into the flask, dropwise adding 2-pentenoic acid to obtain a product A, adding vinyl trimethoxy silane into the product A, and dropwise adding aqueous solution of thioglycolic acid and ammonium persulfate into the flask to obtain an assistant A, wherein the problem that the existing pesticide composition is poor in agglomeration and dispersion easily caused during dilution and application, poor in wettability and large in surface tension, and is not easy to wet and spread on target biological leaf surfaces, so that the pesticide effect is reduced is solved;

(2) the method comprises the steps of dissolving sodium hydroxide in deionized water, starting mechanical stirring, adding beta-CD, dropwise adding 1, 2-epoxydecane to obtain a product B, introducing nitrogen into a three-neck flask containing the product B for protection to obtain a product C, placing the product C in an ice bath for cooling, reducing pressure, concentrating and drying to obtain the auxiliary agent B, and the problems that the existing pesticide composition is poor in water solubility, easy to adsorb by soil, accumulated in the soil and transferred to plants, the pesticide content in crops is increased, the health of human bodies is directly threatened and the environment pollution is caused are solved by adding the auxiliary agent B.

The purpose of the invention can be realized by the following technical scheme:

an insecticidal composition containing pyridalyl comprises the following components in parts by weight:

1-50 parts of pyridalyl, 1-30 parts of component A, 1-50 parts of filler or solvent, 1-10 parts of assistant A and 1-10 parts of assistant B;

the auxiliary A is prepared by the following steps:

s1: adding allyl polyoxyethylene ether into a four-neck flask, adding solvent deionized water, placing the mixture into an oil bath kettle, stirring and heating the mixture to 50-60 ℃, dropwise adding thioglycolic acid into the flask at a dropwise adding speed of 1-2 drops/s, dropwise adding an ammonium persulfate aqueous solution at a dropwise adding speed of 1-2 drops/s, dropwise adding 2-pentenoic acid at a dropwise adding speed of 1-2 drops/s, and obtaining a product A;

s2: adding vinyl trimethoxy silane into the product A, dropwise adding thioglycolic acid into a flask at a speed of 1-2 drops/s, dropwise adding an ammonium persulfate aqueous solution at a speed of 1-2 drops/s, reacting for 1-2h, heating to 70-80 ℃, preserving heat, reacting for 2-3h, cooling to room temperature, and neutralizing pH to 6-7 with a sodium hydroxide solution to obtain the assistant A;

the chemical reaction formula is as follows:

the auxiliary B is prepared by the following steps:

s3: dissolving sodium hydroxide in deionized water, adding the deionized water into a three-neck flask, starting mechanical stirring, adding beta-CD, controlling the temperature at 0-10 ℃, dropwise adding 1, 2-epoxydecane at the dropwise adding speed of 1-2 drops/s, and stirring for 2-3 hours to obtain a product B;

s4: introducing nitrogen into the three-neck flask containing the product B for protection, controlling the temperature at 20-30 ℃, and stirring for reacting for 20-30 hours to obtain a product C;

s5: and (2) cooling the product C in an ice bath, controlling the temperature to be 0-3 ℃, adjusting the pH to 6-7 by using a hydrochloric acid solution, concentrating the neutralized reaction solution under reduced pressure to remove part of water to form thick slurry, adding an ethanol solvent into the thick slurry, stirring, filtering to remove NaCl, concentrating under vacuum to remove ethanol, further removing anion and cation impurities by using ion exchange resin, concentrating under reduced pressure to form syrup, adding acetone into the syrup, stirring to disperse the product into powdery solid in the acetone, filtering to remove acetone, putting the product into a vacuum drying oven, drying at normal temperature for 3-4 hours, removing the acetone, heating to 50-60 ℃, controlling the heating speed to be 2-5 ℃/min, and drying for 1-2 hours to obtain the auxiliary B.

As a further scheme of the invention: the component A is one of spinosad and ethyl spinosad.

As a further scheme of the invention: the filler is one or a mixture of more than two of sucrose, mannitol, lactose, potassium sulfate, sodium sulfate, montmorillonite, calcium carbonate, zeolite, acidic clay, white clay and pyrophyllite in any proportion, and the solvent is water or vegetable oil.

As a further scheme of the invention: the pesticide formulation prepared by the composition is one of suspending agent, dispersible oil suspending agent and water dispersible granule.

As a further scheme of the invention: in the step S1, the mass of the thioglycolic acid is 2% of the mass of the allyl polyoxyethylene ether, the mass fraction of the ammonium persulfate aqueous solution is 42%, the mass of the ammonium persulfate aqueous solution is 5% of the mass of the allyl polyoxyethylene ether, and the molar ratio of the allyl polyoxyethylene ether to the 2-pentenoic acid is 3: 1.

As a further scheme of the invention: in the step S2, the mass of the thioglycolic acid is 2% of that of the vinyltrimethoxysilane, the mass fraction of the ammonium persulfate aqueous solution is 42%, the mass of the ammonium persulfate aqueous solution is 10% of that of the allyl polyoxyethylene ether, the mass fraction of the sodium hydroxide solution is 25%, and the molar ratio of the vinyltrimethoxysilane to the product A is 1: 2.

As a further scheme of the invention: in step S3, the ratio of the sodium hydroxide to the deionized water is 1 g: 15mL, wherein the dosage ratio of the sodium hydroxide, the beta-CD and the 1, 2-epoxydecane is 20 g: 100 g: 50 mL.

As a further scheme of the invention: the mass fraction of the hydrochloric acid solution in step S5 is 20%.

The invention has the beneficial effects that:

the invention adds allyl polyoxyethylene ether into a four-neck flask, adds thioglycolic acid and ammonium persulfate aqueous solution into the flask, adds 2-pentenoic acid into the flask to obtain a product A, adds vinyl trimethoxy silane into the product A, adds thioglycolic acid and ammonium persulfate aqueous solution into the flask to obtain the assistant A, a large number of anchoring points on the long chain of the assistant A molecule are beneficial to the adsorption of the assistant A on dispersed particles, the hydrophilic long chain extends into water and wraps the surface of the dispersed particles to form a three-dimensional barrier to prevent aggregation among the particles, thereby realizing the physical stability of a suspension system through the synergistic and synergistic effects of electrostatic repulsion and steric hindrance, enabling the suspension system to have excellent dispersibility, replacing the hydrocarbon chain of a hydrophobic group by silane, easily rotating the molecular structure after replacement, enabling methoxy groups to be closely arranged in an umbrella shape and showing stronger hydrophobicity, the pesticide composition has the characteristics of heat resistance, ageing resistance and high safety, thereby achieving the purpose of improving the dispersibility and wettability of the pesticide composition;

sodium hydroxide is dissolved in deionized water, mechanical stirring is started, beta-CD is added, 1, 2-epoxy decane is dripped to obtain a product B, nitrogen is introduced into a three-neck flask containing the product B for protection, a product C is obtained, the product C is placed in an ice bath for cooling, reduced pressure concentration and drying are carried out to obtain the auxiliary agent B, the special molecular structure of beta-CD with internal hydrophobicity and external hydrophilicity and the characteristics of no toxicity, no soil adsorption and easy biodegradation are utilized, the cavity structure of the molecules is more matched with the geometric shape of the molecules of the pesticide composition through modification, and the auxiliary agent B acts on the pesticide composition to form a clathrate compound with large water solubility so as to improve the water solubility of the pesticide composition, improve the bioavailability of the pesticide composition, reduce the dosage of the pesticide composition, reduce the adsorption of the pesticide composition by soil and promote the transmission and degradation of the pesticide composition in soil, reduces the environmental pollution, thereby achieving the purpose of improving the solubilization of the pesticide composition.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1:

the embodiment is an insecticidal composition containing pyridalyl, which comprises the following components in parts by weight:

20 parts of pyridalyl, 30 parts of a component A, 20 parts of a filler or a solvent, 2 parts of an auxiliary agent A and 5 parts of an auxiliary agent B;

the auxiliary A is prepared by the following steps:

s1: adding allyl polyoxyethylene ether into a four-neck flask, adding solvent deionized water, placing the mixture into an oil bath kettle, stirring and heating the mixture to 50 ℃, dropwise adding thioglycolic acid into the flask, controlling the dropwise adding speed to be 1 drop/s, dropwise adding an ammonium persulfate aqueous solution, controlling the dropwise adding speed to be 1 drop/s, dropwise adding 2-pentenoic acid, and controlling the dropwise adding speed to be 1 drop/s to obtain a product A;

s2: adding vinyl trimethoxy silane into the product A, dropwise adding thioglycolic acid into a flask at a speed of 1 drop/s, dropwise adding an ammonium persulfate aqueous solution at a speed of 1 drop/s, reacting for 1h, heating to 70 ℃, preserving heat for reacting for 2h, cooling to room temperature, and neutralizing pH to 6 with a sodium hydroxide solution to obtain the assistant A;

the auxiliary B is prepared by the following steps:

s3: dissolving sodium hydroxide in deionized water, adding the deionized water into a three-neck flask, starting mechanical stirring, adding beta-CD, controlling the temperature at 0 ℃, dropwise adding 1, 2-epoxydecane at the dropwise adding speed of 1 drop/s, and stirring for 2 hours to obtain a product B;

s4: introducing nitrogen into the three-neck flask containing the product B for protection, controlling the temperature at 20 ℃, and stirring for reacting for 20 hours to obtain a product C;

s5: and (3) cooling the product C in an ice bath, controlling the temperature to be 0 ℃, adjusting the pH to 6 by using a hydrochloric acid solution, concentrating under reduced pressure, putting into a vacuum drying oven, drying at normal temperature for 3h, heating to 50 ℃, controlling the heating speed to be 2 ℃/min, and drying for 1h to obtain the auxiliary B.

The components are prepared into water dispersible granules with the mass percentage of 50 percent according to a conventional preparation method to prepare pesticide spraying liquid.

Example 2:

the embodiment is an insecticidal composition containing pyridalyl, which comprises the following components in parts by weight:

30 parts of pyridalyl, 20 parts of a component A, 30 parts of a filler or a solvent, 5 parts of an auxiliary agent A and 2 parts of an auxiliary agent B;

the auxiliary A is prepared by the following steps:

s1: adding allyl polyoxyethylene ether into a four-neck flask, adding solvent deionized water, placing the mixture into an oil bath kettle, stirring and heating the mixture to 50 ℃, dropwise adding thioglycolic acid into the flask, controlling the dropwise adding speed to be 1 drop/s, dropwise adding an ammonium persulfate aqueous solution, controlling the dropwise adding speed to be 1 drop/s, dropwise adding 2-pentenoic acid, and controlling the dropwise adding speed to be 1 drop/s to obtain a product A;

s2: adding vinyl trimethoxy silane into the product A, dropwise adding thioglycolic acid into a flask at a speed of 1 drop/s, dropwise adding an ammonium persulfate aqueous solution at a speed of 1 drop/s, reacting for 1h, heating to 70 ℃, preserving heat for reacting for 2h, cooling to room temperature, and neutralizing pH to 6 with a sodium hydroxide solution to obtain the assistant A;

the auxiliary B is prepared by the following steps:

s3: dissolving sodium hydroxide in deionized water, adding the deionized water into a three-neck flask, starting mechanical stirring, adding beta-CD, controlling the temperature at 5 ℃, dropwise adding 1, 2-epoxydecane at the dropwise adding speed of 2 drops/s, and stirring for 3 hours to obtain a product B;

s4: introducing nitrogen into the three-neck flask containing the product B for protection, controlling the temperature at 30 ℃, and stirring for reacting for 30 hours to obtain a product C;

s5: and (3) cooling the product C in an ice bath, controlling the temperature to be 3 ℃, adjusting the pH to 7 by using a hydrochloric acid solution, concentrating under reduced pressure, putting into a vacuum drying oven, drying at normal temperature for 4 hours, heating to 60 ℃, controlling the heating speed to be 5 ℃/min, and drying for 2 hours to obtain the auxiliary B.

The components are prepared into water dispersible granules with the mass percentage of 50 percent according to a conventional preparation method to prepare pesticide spraying liquid.

Example 3:

the embodiment is an insecticidal composition containing pyridalyl, which comprises the following components in parts by weight:

30 parts of pyridalyl, 40 parts of a component A, 20 parts of a filler or a solvent, 2 parts of an assistant A and 3 parts of an assistant B;

the auxiliary A is prepared by the following steps:

s1: adding allyl polyoxyethylene ether into a four-neck flask, adding solvent deionized water, placing the mixture into an oil bath kettle, stirring and heating the mixture to 60 ℃, dropwise adding thioglycolic acid into the flask, controlling the dropwise adding speed to be 2 drops/s, dropwise adding an ammonium persulfate aqueous solution, controlling the dropwise adding speed to be 2 drops/s, dropwise adding 2-pentenoic acid, and controlling the dropwise adding speed to be 2 drops/s to obtain a product A;

s2: adding vinyl trimethoxy silane into the product A, dropwise adding thioglycolic acid into a flask at the speed of 2 drops/s, dropwise adding an ammonium persulfate aqueous solution at the speed of 2 drops/s, reacting for 2 hours, heating to 80 ℃, preserving heat for reacting for 3 hours, cooling to room temperature, and neutralizing the pH value to 7 with a sodium hydroxide solution to obtain the assistant A;

the auxiliary B is prepared by the following steps:

s3: dissolving sodium hydroxide in deionized water, adding the deionized water into a three-neck flask, starting mechanical stirring, adding beta-CD, controlling the temperature at 10 ℃, dropwise adding 1, 2-epoxydecane at the dropwise adding speed of 2 drops/s, and stirring for 3 hours to obtain a product B;

s4: introducing nitrogen into the three-neck flask containing the product B for protection, controlling the temperature at 30 ℃, and stirring for reacting for 30 hours to obtain a product C;

s5: and (3) cooling the product C in an ice bath, controlling the temperature to be 3 ℃, adjusting the pH to 7 by using a hydrochloric acid solution, concentrating under reduced pressure, putting into a vacuum drying oven, drying at normal temperature for 4 hours, heating to 60 ℃, controlling the heating speed to be 5 ℃/min, and drying for 2 hours to obtain the auxiliary B.

The components are prepared into water dispersible granules with the mass percentage of 50 percent according to a conventional preparation method to prepare pesticide spraying liquid.

Comparative example 1:

comparative example 1 differs from example 1 in that no pyridalyl was added.

Comparative example 2:

comparative example 2 differs from example 1 in that no adjuvant a was added.

Comparative example 3:

comparative example 3 differs from example 1 in that no auxiliary B was added.

Comparative example 4:

this comparative example used a pyridalyl-containing pesticidal composition disclosed in chinese patent CN 201710336386.7.

Selecting diamondback moth larvae with consistent growth, respectively placing the larvae in the cabbage of different test fields in an equivalent manner, diluting the pesticides of examples 1-3 and comparative examples 1-4 by 1000 times, respectively spraying the diluted pesticides on the cabbage of different test fields, simultaneously selecting the cabbage of one test field without pesticide application, spraying equivalent clear water as a control group, checking the number of dead and live insects at intervals of 3, 7 and 15 days, and calculating the death rate;

the results are shown in the following table:

as can be seen from the data in the above table, the rate of decline after the experimental example is 88.3-91.2% for three days, the corrected control effect after the experimental example is 88.4-90.2% for three days, the rate of decline after the comparative example is 54.2-70.3% for three days, the corrected control effect after the comparative example is 55.3-71.5% for three days, the rate of decline after the experimental example is 88.1-90.6% for seven days, the corrected control effect after the experimental example is 88.4-89.5% for seven days, the rate of decline after the comparative example is 55.9-75.4% for seven days, the corrected control effect after the comparative example is 56.1-73.2% for seven days, the rate of decline after the experimental example is 90.1-92.1% for fifteen days, the corrected control effect after the experimental example is 91.1-93.4% for fifteen days, the rate of decline after the comparative example is 55.2-60.2% for fifteen days, and the corrected control effect after the comparative example is 56.7-64% for fifteen days, fifteen days after the pesticide is applied, the population reduction rate and the correction control effect of the embodiment are both more than 90%, the data of the experimental example is obviously superior to that of the comparative example, the reasonable compounding of the pyridalyl and the component A is demonstrated, and the pesticide effect can be effectively improved by adding the auxiliary agent A and the auxiliary agent B.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.