CN113603531A

CN113603531A - Pesticide-fertilizer granules containing clothianidin and chlorfenapyr and preparation method thereof

Info

Publication number: CN113603531A
Application number: CN202110920708.9A
Authority: CN
Inventors: 祝春华; 李献; 朱永杰; 余冬冬; 石鹏飞
Original assignee: Zhongcheng Guolian Henan Biotechnology Co ltd
Current assignee: Zhongcheng Guolian Henan Biotechnology Co ltd
Priority date: 2021-08-11
Filing date: 2021-08-11
Publication date: 2021-11-05

Abstract

The invention relates to a pesticide fertilizer granule containing clothianidin and chlorfenapyr and a preparation method thereof, belonging to the technical field of pesticide fertilizers, and the pesticide fertilizer granule comprises the following raw materials: pesticide compound mixture, solvent, surfactant, fertilizer, adsorbent and modified filler; the preparation method of the pesticide fertilizer comprises the following steps: firstly, weighing raw materials according to percentage; secondly, mixing the pesticide compound mixture, a solvent and a surfactant to prepare a mother solution; and thirdly, mixing the mother liquor with a fertilizer, an adsorbent and a filler, and then granulating to obtain the pesticide-fertilizer granules containing clothianidin and chlorfenapyr. The pesticide compound mixture is a mixture of chlorfenapyr and clothianidin, the clothianidin belongs to a neonicotinoid insecticide, and after the chlorfenapyr and the neonicotinoid insecticide are mixed, the dosage of the neonicotinoid insecticide is reduced, the residual risk of the neonicotinoid insecticide is reduced, and the pesticide compound mixture has a good control effect on bradysia odoriphaga.

Description

Pesticide-fertilizer granules containing clothianidin and chlorfenapyr and preparation method thereof

Technical Field

The invention belongs to the technical field of pesticide fertilizers, and particularly relates to pesticide fertilizer granules containing clothianidin and chlorfenapyr and a preparation method thereof.

Background

The chlorfenapyr, the chemical name of which is 4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethyl pyrrole-3-nitrile, is an aryl pyrrole insecticidal and acaricidal agent successfully developed and developed by the cyanamide company in the later 80 s of the 20 th century through the modification of the chemical structure of natural antibiotics, and is a blocker of mitochondrial oxidative phosphorylation in insects; clothianidin belongs to neonicotinoid insecticides; the neonicotinoid insecticide has low toxicity to mammals and high insecticidal activity. However, neonicotinoid insecticides also have some disadvantages, such as a high risk of resistance. In addition, it is harmful to pollinating insects such as bees.

The bradysia odoriphaga, commonly called bradysia odoriphaga, belongs to diptera, hyphomycotina, hymenoptera, and is an important underground pest harming characteristic vegetables in northern China, such as leek, garlic, onion and scallion. The insect pest mainly damages the basal part of the leek leaf sheath and the upper end of the bulb, causes rotting and even death of the whole mound of the leek, and is a key prevention and control object in the leek planting; the existing prevention and control means mostly concentrate on the root irrigation prevention and control of organic phosphorus medicaments, so that serious drug resistance and pesticide pollution are caused, and the problem to be solved in production is to screen out the high-efficiency, safe and environment-friendly prevention and control medicaments.

Disclosure of Invention

The invention aims to provide pesticide fertilizer granules containing clothianidin and chlorfenapyr and a preparation method thereof.

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

a pesticide fertilizer granule containing clothianidin and chlorfenapyr comprises the following raw materials in percentage by weight:

3.01-6% of pesticide compound mixture, 5-15% of solvent, 5-10% of surfactant, 5-7% of fertilizer, 1-2% of adsorbent and the balance of modified filler;

further, the modified filler is prepared by the following steps:

step S11, immersing diatomite in sulfuric acid, stirring and reacting for 3 hours at the temperature of 55-60 ℃, filtering, washing, drying at 70 ℃ to constant weight, then placing in a crucible, roasting and activating for 2 hours at the temperature of 500 ℃, cooling to room temperature after roasting is finished to obtain solid a, and storing in a dryer for later use;

step S12, mixing the auxiliary agent and deionized water, stirring at a constant temperature of 80 ℃, then adding the solid a, maintaining the reaction temperature at 80 ℃, stirring for reaction for 2 hours, filtering while hot, washing to be neutral, and then drying at 40 ℃ to constant weight to obtain a solid b;

step S13, mixing sodium metasilicate nonahydrate with deionized water at 20-30 ℃, then adding humic acid and solid b to obtain suspension, mixing chitosan and acetic acid solution, then adding polyethylene glycol, then dropwise adding the suspension while stirring, after dropwise adding, heating to 50 ℃, adding glutaraldehyde, stirring for reaction for 1h, after reaction, carrying out vacuum filtration, then washing with distilled water and absolute ethyl alcohol, after washing, drying to constant weight at 40 ℃ to obtain the modified filler.

Further, the concentration of the sulfuric acid in the step S11 is 4mol/L, and the ratio of the diatomite to the sulfuric acid is 1 g: 4 mL; in the step S12, the dosage ratio of the auxiliary agent to the deionized water to the solid a is 0.5 g: 80mL of: 15g of the total weight of the mixture; in the step S13, the mass fraction of the acetic acid solution is 2%; the dosage ratio of the sodium metasilicate nonahydrate to the deionized water is 2.4 g: 50mL, the mass ratio of the humic acid to the solid b is 0.1: 1; the dosage ratio of the chitosan, the acetic acid solution and the polyethylene glycol is 1 g: 10mL of: 0.25 g; the dosage mass ratio of the sodium metasilicate nonahydrate to the humic acid to the chitosan is 24: 1: 10.

further, the auxiliary agent is prepared by the following steps:

step S21, adding 2-methylbenzothiazole and 1, 3-propane sultone into toluene, and carrying out heating reflux reaction for 15h at the temperature of 110 ℃ to obtain an intermediate 1; wherein the molar ratio of the 2-methylbenzothiazole to the 1, 3-propane sultone is 1: 1; toluene as a solvent;

the reaction process is as follows:

step S22, mixing the intermediate 1 and methyl phenol, heating to 120 ℃, adding triethoxy propane, keeping the temperature unchanged, continuing to react for 2 hours, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol, separating out solids, filtering, and drying the obtained filter cake to constant weight at 40 ℃ to obtain an intermediate 2; wherein the dosage ratio of the intermediate 1, the methyl phenol, the triethoxy propane and the absolute ethyl alcohol is 14 g: 15mL of: 10 g: 100 mL;

the reaction process is as follows:

step S23, mixing N, N-dimethylformamide and deionized water in equal volume, adding 4-ethylpyridine and an intermediate 2, reacting for 6 hours at 65 ℃ under the protection of nitrogen by using azobisisobutyronitrile as an initiator, and then precipitating with tetrahydrofuran to obtain an intermediate 3; wherein, N, N-dimethylformamide and deionized water are used as solvents; the molar ratio of 4-ethylpyridine to intermediate 2 was 2: 1;

step S24, mixing methanol and ethylene glycol in equal volume, adding the intermediate 3 and n-butyl bromide, stirring and reacting for 5 hours at the temperature of 60 ℃, precipitating with tetrahydrofuran after the reaction is finished, and drying in vacuum to constant weight at room temperature to obtain an auxiliary agent; wherein methanol and ethylene glycol are used as solvents; the mass ratio of the intermediate 3 to the n-butyl bromide is 1: 0.6.

further, the pesticide compound mixture is prepared from clothianidin and chlorfenapyr according to a mass ratio of 1-15: 1-15 are mixed;

further, the solvent is one of N-methyl pyrrolidone, isobutyl alcohol and acetophenone;

further, the surfactant is one of alkylphenol ethoxylates, fatty alcohol-polyoxyethylene ether and lignosulfonate;

further, the fertilizer is at least one of a nitrogen fertilizer, a phosphate fertilizer or a potassium fertilizer; specifically, the ammonium phosphate is at least one of ammonium sulfate, ammonium chloride, ammonium dihydrogen phosphate, urea, potassium dihydrogen phosphate, potassium hydrogen phosphate, potassium chloride, potassium sulfate, potassium nitrate or potassium citrate.

Further, the adsorbent is white carbon black.

A preparation method of insecticide-fertilizer granules containing clothianidin and chlorfenapyr comprises the following steps:

firstly, weighing raw materials according to percentage;

secondly, mixing the pesticide compound mixture, a solvent and a surfactant to prepare a mother solution;

and thirdly, mixing the prepared mother liquor with a fertilizer, an adsorbent and a filler, and then granulating in a fluidized bed granulation mode to obtain the pesticide-fertilizer granules containing clothianidin and chlorfenapyr.

The invention has the beneficial effects that:

because the action mechanisms of the two pesticides of the chlorfenapyr and the neonicotinoid insecticide are different, the application of the composition is beneficial to delaying the development of the drug resistance of pests and prolonging the service life of the pesticides. After the chlorfenapyr and the neonicotinoid insecticide are mixed, the dosage of the neonicotinoid insecticide is reduced, the residual risk of the neonicotinoid insecticide is reduced, and the pesticide has a good control effect on bradysia odoriphaga.

According to the invention, the modified filler is prepared by taking the diatomite as a raw material and organically modifying the diatomite, firstly, the diatomite is modified by using a quaternary ammonium salt polymer containing a quaternary ammonium salt structure, namely an auxiliary agent, so that a solid b is prepared, the adsorption capacity is improved, meanwhile, the antibacterial effect is improved by introducing the quaternary ammonium salt structure, the drug effect is improved, and meanwhile, the problem of drug resistance caused by long-term use of a single bactericide is favorably relieved; in addition, the auxiliary agent contains a benzothiazole structure, and the structure can obviously reduce the hatching rate of mosquito eggs of the leek and the bradysia odoriphaga and the survival rate of the larvae which are hatched initially, and improve the drug effect. Then, humic acid and chitosan are used as modifiers, and the diatomite is modified by combining the humic acid and chitosan which are double-component organic matters, so that the specific surface area of the diatomite is increased, and the drug loading capacity and the adsorption effect are optimized, thereby increasing the release time of the medicament.

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

Preparing an auxiliary agent:

example 2

Preparing a modified filler:

step S11, immersing diatomite in sulfuric acid, stirring and reacting for 3 hours at the temperature of 55 ℃, filtering, washing, drying at 70 ℃ to constant weight, then placing in a crucible, roasting and activating for 2 hours at the temperature of 500 ℃, cooling to room temperature after roasting is finished to obtain solid a, and storing in a dryer for later use;

step S13, mixing sodium metasilicate nonahydrate with deionized water at 20 ℃, then adding humic acid and solid b to obtain a suspension, mixing chitosan and an acetic acid solution, then adding polyethylene glycol, then dropwise adding the suspension while stirring, after dropwise adding, heating to 50 ℃, adding glutaraldehyde, stirring for reaction for 1h, after reaction, carrying out vacuum filtration, then washing with distilled water and absolute ethyl alcohol, after washing, drying to constant weight at 40 ℃ to obtain the modified filler.

Wherein the concentration of the sulfuric acid in the step S11 is 4mol/L, and the dosage ratio of the diatomite to the sulfuric acid is 1 g: 4 mL; in the step S12, the dosage ratio of the auxiliary agent to the deionized water to the solid a is 0.5 g: 80mL of: 15g of the total weight of the mixture; in the step S13, the mass fraction of the acetic acid solution is 2%; the dosage ratio of the sodium metasilicate nonahydrate to the deionized water is 2.4 g: 50mL, the mass ratio of the humic acid to the solid b is 0.1: 1; the dosage ratio of the chitosan, the acetic acid solution and the polyethylene glycol is 1 g: 10mL of: 0.25 g; the dosage mass ratio of the sodium metasilicate nonahydrate to the humic acid to the chitosan is 24: 1: adjuvant 10 was prepared as in example 1.

Example 3

Preparing a modified filler:

step S11, immersing diatomite in sulfuric acid, stirring and reacting for 3 hours at the temperature of 60 ℃, filtering, washing, drying at 70 ℃ to constant weight, then placing in a crucible, roasting and activating for 2 hours at the temperature of 500 ℃, cooling to room temperature after roasting is finished to obtain solid a, and storing in a dryer for later use;

step S13, mixing sodium metasilicate nonahydrate with deionized water at 30 ℃, then adding humic acid and solid b to obtain a suspension, mixing chitosan and an acetic acid solution, then adding polyethylene glycol, then dropwise adding the suspension while stirring, after dropwise adding, heating to 50 ℃, adding glutaraldehyde, stirring for reaction for 1h, after reaction, carrying out vacuum filtration, then washing with distilled water and absolute ethyl alcohol, after washing, drying to constant weight at 40 ℃ to obtain the modified filler.

Example 4

The preparation method of the pesticide-fertilizer granules containing clothianidin and chlorfenapyr comprises the following steps:

firstly, weighing 3.01 percent of pesticide compound mixture, 5 percent of solvent, 5 percent of surfactant, 5 percent of fertilizer, 1 percent of adsorbent and the balance of modified filler according to the percentage;

Wherein the pesticide compound mixture is prepared from clothianidin and chlorfenapyr according to a mass ratio of 1: 15 are mixed; the solvent is N-methyl pyrrolidone; the surfactant is alkylphenol polyoxyethylene; the fertilizer is urea; the adsorbent is white carbon black; the modified filler was prepared as in example 3.

Example 5

firstly, weighing 4% of pesticide compound mixture, 10% of solvent, 8% of surfactant, 6% of fertilizer, 2% of adsorbent and the balance of modified filler according to the percentage;

Wherein the pesticide compound mixture is prepared from clothianidin and chlorfenapyr according to a mass ratio of 1: 1, mixing; the solvent is isobutanol; the surfactant is fatty alcohol-polyoxyethylene ether; the fertilizer is urea; the adsorbent is white carbon black; the modified filler was prepared as in example 3.

Example 6

firstly, weighing 6 percent of pesticide compound mixture, 15 percent of solvent, 10 percent of surfactant, 7 percent of fertilizer, 2 percent of adsorbent and the balance of modified filler according to the percentage;

Wherein the pesticide compound mixture is prepared from clothianidin and chlorfenapyr according to a mass ratio of 15: 1, mixing; the solvent is acetophenone; the surfactant is lignosulfonate; the fertilizer is urea; the adsorbent is white carbon black; the modified filler was prepared as in example 3.

Comparative example 1

and step S12, mixing the auxiliary agent and the deionized water, stirring at a constant temperature of 80 ℃, then adding the solid a, maintaining the reaction temperature at 80 ℃, stirring for reaction for 2 hours, filtering while hot, washing to be neutral, and then drying at 40 ℃ to constant weight to obtain a solid b.

Comparative example 2

The modified filler of example 5 was replaced with solid b prepared in comparative example 1, and the remaining raw materials and preparation process were kept unchanged.

Comparative example 3

The modified filler of example 5 was replaced by diatomaceous earth, and the remaining raw materials and preparation process were kept unchanged.

The samples prepared in examples 4-6 and comparative examples 2 and 3 were tested in a leek field, which had a flat land, moderate fertility, uniform land strength, and severe insect damage in all years. Each group was treated for 4 replicates, the treatment area was 30m²(ii) a The application method comprises the step of spreading the pesticide fertilizer granules into soil when the Chinese chives are sowed. Recording the occurrence condition of the number of the maggots in the leek field after the pesticide is applied, and counting the control effect 60 days after the pesticide is applied and 120 days after the pesticide is applied.

The results are shown in table 1 below:

TABLE 1

From the above table 1, it can be seen that the pesticide fertilizer granules prepared by the invention have a lasting effect on preventing and controlling Chinese chive maggots and have a beneficial effect on improving the yield of Chinese chives.

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.

Claims

1. The pesticide-fertilizer granules containing clothianidin and chlorfenapyr are characterized by comprising the following raw materials in percentage by weight: 3.01-6% of pesticide compound mixture, 5-15% of solvent, 5-10% of surfactant, 5-7% of fertilizer, 1-2% of adsorbent and the balance of modified filler;

the modified filler is prepared by the following steps:

step S11, immersing diatomite in sulfuric acid, stirring and reacting for 3 hours at the temperature of 55-60 ℃, filtering, washing, drying to constant weight at 70 ℃, then placing in a crucible, roasting and activating for 2 hours at the temperature of 500 ℃ to obtain solid a;

step S12, mixing the auxiliary agent and deionized water, stirring at a constant temperature of 80 ℃, then adding the solid a, and stirring and reacting for 2 hours at a reaction temperature of 80 ℃ to obtain a solid b;

and step S13, mixing sodium metasilicate nonahydrate and deionized water at the temperature of 20-30 ℃, then adding humic acid and solid b to obtain a suspension, mixing chitosan and an acetic acid solution, then adding polyethylene glycol, then dropwise adding the suspension while stirring, after dropwise adding, heating to 50 ℃, adding glutaraldehyde, and stirring for reacting for 1h to obtain the modified filler.

2. The insecticide-fertilizer granule containing clothianidin and chlorfenapyr according to claim 1, wherein the concentration of sulfuric acid in step S11 is 4mol/L, and the dosage ratio of diatomite to sulfuric acid is 1 g: 4 mL; in the step S12, the dosage ratio of the auxiliary agent to the deionized water to the solid a is 0.5 g: 80mL of: 15g of the total weight of the mixture; in the step S13, the mass fraction of the acetic acid solution is 2%; the dosage ratio of the sodium metasilicate nonahydrate to the deionized water is 2.4 g: 50mL, the mass ratio of the humic acid to the solid b is 0.1: 1; the dosage ratio of the chitosan, the acetic acid solution and the polyethylene glycol is 1 g: 10mL of: 0.25 g; the dosage mass ratio of the sodium metasilicate nonahydrate to the humic acid to the chitosan is 24: 1: 10.

3. the insecticide-fertilizer granule containing clothianidin and chlorfenapyr as claimed in claim 1, wherein the auxiliary agent is prepared by the following steps:

step S21, adding 2-methylbenzothiazole and 1, 3-propane sultone into toluene, and carrying out heating reflux reaction for 15h at the temperature of 110 ℃ to obtain an intermediate 1;

step S22, mixing the intermediate 1 with methyl phenol, heating to 120 ℃, adding triethoxy propane, keeping the temperature unchanged, and continuing to react for 2 hours to obtain an intermediate 2;

step S23, mixing N, N-dimethylformamide and deionized water in equal volume, adding 4-ethylpyridine and the intermediate 2, reacting for 6 hours at 65 ℃ under the protection of nitrogen by taking azobisisobutyronitrile as an initiator to obtain an intermediate 3;

and step S24, mixing methanol and ethylene glycol in equal volume, adding the intermediate 3 and n-butyl bromide, and stirring and reacting for 5 hours at the temperature of 60 ℃ to obtain the auxiliary agent.

4. The insecticide-fertilizer granule containing clothianidin and chlorfenapyr according to claim 1, characterized in that the pesticide compound mixture is the mixture of clothianidin and chlorfenapyr in a mass ratio of 1-15: 1-15, and mixing.

5. The insecticide-fertilizer granule containing clothianidin and chlorfenapyr as claimed in claim 1, wherein the solvent is one of N-methyl pyrrolidone, isobutyl alcohol and acetophenone.

6. The pesticide-fertilizer granule containing clothianidin and chlorfenapyr as claimed in claim 1, wherein the surfactant is one of alkylphenol ethoxylate, fatty alcohol-polyoxyethylene ether and lignosulfonate.

7. The pesticide-fertilizer granule containing clothianidin and chlorfenapyr as claimed in claim 1, wherein the fertilizer is at least one of a nitrogen fertilizer, a phosphate fertilizer or a potassium fertilizer; the adsorbent is white carbon black.

8. The preparation method of the insecticide-fertilizer granules containing clothianidin and chlorfenapyr according to claim 1, which is characterized by comprising the following steps:

firstly, weighing raw materials according to percentage;

and thirdly, mixing the mother liquor with a fertilizer, an adsorbent and a filler, and then granulating to obtain the pesticide-fertilizer granules containing clothianidin and chlorfenapyr.