Preparation method and application of clothianidin-containing nano suspending agent

Abstract

The invention relates to the technical field of pesticides, and discloses a preparation method and application of a clothianidin-containing nano suspending agent. The nano suspending agent comprises effective active components, a hyperbranched dispersant, a wetting agent, a defoaming agent, a preservative, a pH regulator, a thickening agent and water, the effective active components are clothianidin and lufenuron, the weight ratio of clothianidin to lufenuron is 4: 1, and the weight ratio of the thickening agent to the clothianidin is 1: 1. The hyperbranched dispersant is selected from one of a styrene maleic anhydride polymer and a polyoxyethylene ether polyoxypropylene ether polyether amine grafted copolymer. The nano suspending agent is used for preventing and treating Chinese chive maggots, is small in particle size, strong in adhesive force and good in dispersity, can effectively control pests, improves the effect of preventing and treating Chinese chive maggots, and is safe to crops and natural enemies, long in lasting period and small in residue.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and specifically relates to a preparation method and application of a nano-suspension concentrate. Background Art

[0002] Clothianidin is an insecticide in the neonicotinoid class, a type of highly efficient, safe, and highly selective new insecticide. Its action is similar to that of the nicotinic acetylcholine receptor, and it has contact, stomach, and systemic activities. It is mainly used as an insecticide for controlling pests such as aphids, leafhoppers, thrips, and planthoppers of Hemiptera, Coleoptera, Diptera, and certain Lepidoptera on rice, vegetables, fruit trees, and other crops. It has the advantages of high efficiency, broad spectrum, low dosage, low toxicity, long-lasting efficacy, no phytotoxicity to crops, safe use, and no cross-resistance with conventional pesticides. It has excellent systemic and penetration effects and is another variety to replace highly toxic organophosphorus pesticides. Its structure is novel and special, and its performance is more excellent compared with traditional nicotinic insecticides, and it may become a large-scale insecticide variety in the world.

[0003] Lufenuron is mainly used for controlling larvae of Lepidoptera such as cotton, corn, vegetables, and fruit trees; it can also be used as a hygienic pesticide; it can also be used for controlling piercing-sucking mouthpart pests.

[0004] Bradysia odoriphaga belongs to Diptera, Sciaridae, and Bradysia. It mainly harms Liliaceae vegetables such as Chinese chives, welsh onions, onions, scallions, and garlic, and occasionally also harms lettuce, green vegetables, celery, etc. It is distributed in Beijing, Tianjin, Shandong, Shanxi, Liaoning, Jiangxi, Ningxia, Inner Mongolia, Zhejiang, Taiwan and other places and is one of the main pests of alliaceous vegetables. Its insect states include adults, eggs, larvae, and pupae. The larvae gather to harm the bulbs and tender stems at the underground part of Chinese chives. The newly hatched larvae first harm the base of the leaf sheath and the upper end of the bulb of Chinese chives. In spring and autumn, it mainly harms the young stems of Chinese chives, causing rot and the withering and death of the Chinese chive leaves. In summer, the larvae move downward and bore into the bulbs, and in severe cases, the bulbs rot and the whole clump of Chinese chives dies.

[0005] Generally, it occurs in 4 generations a year, respectively in early May, mid-June, early August, and late September. It overwinters as pupae. From late July to early August, adults and larvae occur in large numbers, and the larvae group to harm the underground rhizomes of Chinese chives; adults like shady and humid environments, can fly and walk well, are very active, and often inhabit the crevices of soil blocks around the roots of Chinese chives. The mature larvae or pupae of Bradysia odoriphaga overwinter in the bulbs of Chinese chives and in the soil 3-4 cm deep at the rhizosphere. Adults are light-averse, moisture-loving, and drought-averse, and have an obvious tendency to the odor emitted by alliaceous vegetables. Eggs are mostly laid in the soil around the rhizomes of Chinese chives. The larvae harm the underground leaf sheaths, tender stems, and buds of Chinese chives, bite off the tender stems and bore into the bulbs to harm. In the open-field Chinese chive fields, the larvae of Bradysia odoriphaga are distributed in the soil 2-3 cm from the ground surface, and the deepest does not exceed 5-6 cm. Soil humidity is an important influencing factor for the occurrence of Bradysia odoriphaga. The occurrence amount in clay fields is less than that in sandy fields.

[0006] The mainstream products currently used in the market for controlling Bradysia odoriphaga are organophosphorus or emulsifiable products, most of which are highly toxic and highly residual products, and are unsafe for crops and during use. Therefore, how to improve the control effect and use environmentally friendly and low-toxic products is a difficult problem that urgently needs to be solved at present.

[0007] Through continuous innovative research, the applicant found that by mixing clothianidin and lufenuron with completely different action mechanisms, the product has small particle size, strong adhesion, and good dispersibility, can effectively control the occurrence of pests, improve the control effect of Bradysia odoriphaga on leeks, is safe for crops and natural enemies, has a long lasting period, small residues, and also reduces the pollution of the medicament to the environment. Being safe for natural enemies is the purpose of the present invention. Summary of the Invention

[0008] The purpose of the present invention is to provide a preparation method and application of a nano-suspension agent, which can effectively control Bradysia odoriphaga on leeks, has small particle size, strong adhesion, good dispersibility, can effectively control the occurrence of pests, improve the control effect of Bradysia odoriphaga on leeks, is safe for crops and natural enemies, has a long lasting period, and small residues.

[0009] The technical solution of the present invention is:

[0010] A preparation method and application of a nano-suspension agent, characterized in that: the nano-suspension agent includes an effective active ingredient, a hyperbranched dispersant, a wetting agent, an antifoaming agent, a preservative, a pH regulator, a thickening agent, and water; the effective active ingredient is clothianidin and lufenuron, and the weight ratio of clothianidin to lufenuron is 4:1;

[0011] Further, the weight ratio of the effective active ingredient to the hyperbranched dispersant in the nano-suspension agent is 1:1 to 10:1, and optionally the weight ratio is 1:1 to 5:1.

[0012] Further, the hyperbranched dispersant is selected from one or more of styrene maleic anhydride polymer, polyoxyethylene polyoxypropylene polyetheramine graft copolymer.

[0013] The wetting agent is selected from one or more of alkyl sulfonates, alkyl naphthalene sulfonates, fatty alcohol polyoxyethylene ethers, alkyl glycosides, trisiloxane polyoxyethylene ethers, polyaryl phenolic polyoxyethylene ethers, castor oil polyoxyethylene ethers; the antifreeze is selected from one or more of ethylene glycol, propylene glycol, glycerol, polyethylene glycol, allantoin, sorbitol; the thickening agent is selected from one or more of xanthan gum, polyvinyl alcohol, magnesium aluminum silicate, sodium carboxymethyl cellulose, sodium alginate, guar gum; the antifoaming agent is silicone antifoaming agent, C10-20 saturated fatty acid compounds, C8-10 fatty alcohols; the pH regulator is selected from one or more of citric acid, glacial acetic acid; the preservative is benzoic acid and its sodium salt, isothiazolinone, sorbic acid and its sodium salt or potassium salt.

[0014] Furthermore, the total content of effective active ingredients is 100 to 500 g / L, and optionally the total content is 400 g / L.

[0015] Furthermore, the nanosuspension concentrate is composed of the following components based on 1000 parts by weight: 80 to 400 parts by weight of clothianidin, 20 to 100 parts by weight of lufenuron, 10 to 200 parts by weight of a hyperbranched dispersant, 20 to 80 parts by weight of a wetting agent, 0 to 60 parts by weight of an antifreeze agent, 2 to 25 parts by weight of a thickener, 0.5 to 15 parts by weight of a defoaming agent, 0.05 to 5 parts by weight of a pH adjuster, 0 to 20 parts by weight of a preservative, and the balance being water.

[0016] Furthermore, the nanosuspension concentrate is composed of the following components based on 1000 parts by weight: 320 parts by weight of clothianidin, 80 parts by weight of lufenuron, 50 to 120 parts by weight of a hyperbranched dispersant, 20 to 50 parts by weight of a wetting agent, 30 to 60 parts by weight of an antifreeze agent, 2 to 10 parts by weight of a thickener, 0.5 to 8 parts by weight of a defoaming agent, 0.05 to 2 parts by weight of a pH adjuster, 2 to 8 parts by weight of a preservative, and the balance being water.

[0017] Furthermore, the preparation method of the nano suspension is as follows: first, water, a wetting agent, a hyperbranched dispersant, and a defoamer are put into a stirring tank for high-speed shearing, and after being fully dispersed, clothianidin technical and lufenuron technical are put into the stirring tank for high-speed shearing to form a primary dispersion; then, the suspension is transported to two sand mills connected in series by a diaphragm pump for sand milling, the sand milling feed speed is adjusted to control the sand milling fineness at 4-6 μm, and then, the suspension is transported to a turnover kettle by a diaphragm pump for stirring; the slurry is filtered through 200 meshes and then sand milled with a nano sand mill, and the particle size D 50 Controlled to less than 100 nanometers, particle size D 90 The particle size is controlled to be less than 300 nanometers. Finally, the slurry is transported to a preparation kettle, thickener and defoamer are added, the viscosity of the material is adjusted, and samples are taken for quality inspection to obtain the finished product.

[0018] Furthermore, the nano suspension is used in preventing and controlling leek maggots.

[0019] Compared with the prior art, the composition of the present invention has the following beneficial effects: (1) compared with a single agent, the composition has a significant synergistic effect on leek maggots and significantly improves the control effect; (2) it is low in toxicity and high in efficiency, reduces the amount of pesticide used, reduces the amount of pesticide residues on crops, and has a short safety interval; (3) it has both rapid and long-term effects; (4) it is safe for natural enemies; and (5) the product has a small particle size, good dispersibility, and strong adhesion. DETAILED DESCRIPTION

[0020] The present invention is further described below in conjunction with embodiments, but the present invention is not limited thereto.

[0021] Application Example 1 Preparation Example of Nano-suspension

[0022] The following examples are calculated based on 1000 parts by weight and contain components with the following contents, and 400 g / L clothianidin·lufenuron suspension is prepared according to the preparation method claimed in the present invention:

[0023]

[0024] Control Example: Calculated based on 1000 parts by weight, containing components with the following contents, and 400 g / L clothianidin·lufenuron suspension is prepared according to the conventional preparation method.

[0025] 320 parts by weight of clothianidin, 80 parts by weight of lufenuron, 50 parts by weight of lignosulfonate, 15 parts by weight of alkyl polyglycoside, 8 parts by weight of fatty alcohol polyoxyethylene ether, 40 parts by weight of glycerol, 5 parts by weight of polyvinyl alcohol, 3 parts by weight of silicone defoamer, 1 part by weight of glacial acetic acid, 2 parts by weight of isothiazolinone, and the total is made up to 1000 to obtain 400 g / L cyromazine·cyantraniliprole suspension.

[0026] Application Example 2: Main Technical Indexes of the Example

[0027]

[0028] It can be seen that the particle size of the nano-suspension in the example of the present invention is significantly smaller than that in the control example.

[0029] Application Example 3:

[0030] Indoor Joint Toxicity Determination Experiment 1 of Clothianidin, Lufenuron and Their Mixtures against Bradysia odoriphaga in Chinese Chives - Test Purpose

[0031] To determine the toxicity of clothianidin, lufenuron and their different mixing combinations against Bradysia odoriphaga indoors, and to evaluate the synergistic effect, clarify their compatibility, and provide a scientific basis for the research and development of the mixture of clothianidin and lufenuron.

[0032] 2 Experimental Conditions

[0033] 2.1 Test Target

[0034] Bradysia odoriphaga larvae were collected from the field and reared indoors on Chinese chives for multiple generations. The 3rd instar larvae were used for the bioassay experiment.

[0035] 2. Culture Conditions

[0036] The culture conditions for the test target and the target after the test were temperature (25±1)°C, relative humidity 50% - 70%, and dark conditions.

[0037] 3 Test Design

[0038] 3.1 Test Agents

[0039] Clothianidin 98% technical material, Lufenuron 98% technical material.

[0040] 3.2 Agent Preparation

[0041] Accurately weigh 1.0204 g of clothianidin with a ten-thousandth electronic balance, dissolve it with acetone and make up the volume to 100 mL in a volumetric flask to prepare a 1×10 4 mg / L clothianidin mother liquor for standby.

[0042] Accurately weigh 1.0204 g of lufenuron with a ten-thousandth electronic balance, dissolve it with acetone and make up the volume to 100 mL in a volumetric flask to prepare a 1×10 4 mg / L lufenuron mother liquor for standby.

[0043] Mix clothianidin and lufenuron according to the following ratios: clothianidin:lufenuron = 1:1, 2:1, 4:1, 8:1 and 16:1. For each ratio, also prepare a 1×10 4 mg / L mixed mother liquor for standby.

[0044] Based on the preliminary test, for each single agent and different ratio mixtures of the agents, 5 series of mass concentration treatments are set according to the active ingredient content. The specific treatment doses are as follows:

[0045] Clothianidin (A): 16, 8, 4, 2, 1 mg / L

[0046] Lufenuron (B): 4, 2, 1, 0.5, 0.25 mg / L

[0047] A:B (1:1): 6, 3, 1.5, 0.75, 0.375 mg / L

[0048] A:B (2:1): 6.4, 3.2, 1.6, 0.8, 0.4 mg / L

[0049] A:B (4:1): 8, 4, 2, 1, 0.5 mg / L

[0050] A:B (8:1): 10, 5, 2.5, 1.25, 0.625 mg / L

[0051] A:B (16:1): 12, 6, 3, 1.5, 0.75 mg / L

[0052] 4 Test Methods

[0053] Double filter paper method. Refer to the 6th part: Leaf dipping method (NY / T 1154.14-2008) and the 7th part: Determination of combined effects of mixtures (NY / T 1154.7-2006) of the Agricultural Industry Standard of the People's Republic of China "Guidelines for Pesticide Bioassay in the Laboratory - Insecticides".

[0054] 5 Data investigation and statistical analysis

[0055] 5.1 Investigation time and method

[0056] After 96 h, check the mortality of the test insects and record it. The criterion for judging the death of the test insects is that if there is no response when gently touching the test insects with forceps, it is counted as dead.

[0057] 5.2 Evaluation method for synergistic effect

[0058] Refer to the Guidelines for Pesticide Bioassay in the Laboratory NY / T1154.7-2006, and use the co-toxicity coefficient method of Sun & Johnson (1960) to calculate the co-toxicity coefficient (CTC) of each mixture combination. CTC ≤ 80 indicates antagonistic effect, 80 < CTC < 120 indicates additive effect, and CTC ≥ 120 indicates synergistic effect. The formula for calculating the co-toxicity coefficient is as follows:

[0059]

[0060] Theoretical toxicity index (TTI) of the mixture = Toxicity index of pesticide A × Percentage of pesticide A in the mixture (%) + Toxicity index of pesticide B × Percentage of pesticide B in the mixture (%)

[0061]

[0062] 6 Experimental results

[0063] Table 1 Toxicity determination results of the mixture of clothianidin and lufenuron against Bradysia odoriphaga in Chinese chives

[0064]

[0065] The toxicity determination results of the mixture of clothianidin and lufenuron at the ratios of 1:1, 2:1, 4:1, 8:1 and 16:1 against Bradysia odoriphaga in Chinese chives are shown in Table 1. It can be seen from the table that when clothianidin and lufenuron are mixed at the above 5 ratios, except for 1:1 and 16:1, they all show synergistic effects, and their LC 50The values ​​were 1.5601, 1.7103, 2.0200, 2.5490 and 3.2565 mg / L, and the co-toxicity coefficients were 107.66, 121.89, 127.88, 120.56 and 106.22, respectively. The synergistic effect of 4:1 was the most significant, indicating that the ratio of clothianidin to lufenuron in the preparation process was the most reasonable.

[0066] Application Example 4: Field efficacy test of Examples 1 to 4 for preventing and controlling leek maggots

[0067] 1. Purpose of the experiment

[0068] To verify the control effect of the 400 g / L clothianidin-lufenuron suspension developed by the applicant on leek maggots and its safety to leek, to clarify the field dosage and application technology, and to provide a scientific basis for pesticide registration.

[0069] 2 Test basis

[0070] "Quality Management Specifications for Pesticide Registration Tests", "National Standard of the People's Republic of China - Guidelines for Pesticide Field Efficacy Tests (II) Insecticides for Control of Leek Maggots and Root Maggots (GB / T17980.67-2004)", and "Operational Procedures for Field Tests of Leek Maggots (NWP-SOP-I-017)".

[0071] 3 Experimental location

[0072] This experiment was arranged in Shaanxi Province and Shandong Province.

[0073] 4. Selection of experimental subjects, crops and varieties

[0074] Test subjects: Chinese chive maggots;

[0075] 5 Experimental design and arrangement

[0076] 5.1 Dosage and number of medicines

[0077] Table 2 Experimental design of test drugs

[0078]

[0079] 5.2 Application time and frequency

[0080] In the early stage of the infestation of leek maggots, water the roots.

[0081] 5.3 Usage capacity

[0082] The dosage of the liquid medicine is 4500 liters / hectare.

[0083] 5.4 Survey time and frequency

[0084] The base number was investigated before pesticide application, and the number of damaged plants was investigated 3, 7, 14, and 21 days after pesticide application. The number of live maggots was investigated on the 21st day, for a total of 6 times.

[0085] 5.5 Calculation method of pesticide efficacy The field efficacy of pesticides was calculated according to the formulas in the "Guidelines for Field Efficacy Trials of Pesticides" to calculate the plant protection effect and control effect.

[0086]

[0087]

[0088]

[0089]

[0090] 6 Experimental results

[0091] Table 3 Field efficacy test results of the control of Bradysia odoriphaga in Examples 1-4

[0092]

[0093]

[0094] The experimental results show that: the test substance of 400 g / L clothianidin·lufenuron suspension in the examples is used for the control of Bradysia odoriphaga in leeks. When the medicine is applied at the initial stage of the occurrence of Bradysia odoriphaga in leeks and used by root irrigation, it can be seen from Table 3 that the test drugs in Examples 1-4 of the present invention are used for the control of Bradysia odoriphaga in leeks. After 3 days, 7 days, 14 days, and 21 days of pesticide application, the plant protection effect is significantly better than that of the control agent. After 21 days, the insecticidal effect reaches more than 86%, and the results of some experiments reach more than 95%. Especially in Example 3, the control effect after 21 days reaches more than 99%. Compared with the control single agent, it is significantly different at the 0.01 and 0.05 levels. Therefore, it shows that the test substance of 400 g / L clothianidin·lufenuron suspension has quick-acting and long-lasting effects, is safe for crops and applicators throughout the experimental period.

[0095] Application Example Five: (Examples 1 to 4) Experiment on the determination of environmental impact

[0096] Our company commissioned a third-party company to conduct 10 tests on Examples 1-2, including acute oral toxicity test of bees, acute contact toxicity test of bees, acute oral toxicity test of birds, acute toxicity test of fish, acute toxicity test of silkworms, acute activity inhibition test of daphnia, algal growth inhibition test, acute toxicity test of earthworms, acute toxicity test of natural enemy trichogramma, and acute contact toxicity test of natural enemy ladybugs. The test results are as follows:

[0097] 1) Acute oral toxicity test of bees, the toxicity level is low toxicity.

[0098] 2) Acute contact toxicity test of bees, the toxicity level is low toxicity.

[0099] 3) Acute oral toxicity test in birds, with a low toxicity level.

[0100] 4) Acute toxicity test in fish, with a low toxicity level.

[0101] 5) Acute toxicity test in silkworms, with a low toxicity level.

[0102] 6) Acute activity inhibition test in Daphnia, with a low toxicity level.

[0103] 7) Algae growth inhibition test, with a low toxicity level.

[0104] 8) Acute toxicity test in earthworms, with a slightly toxic level.

[0105] 9) Acute toxicity test in the natural enemy Trichogramma, with a low risk.

[0106] 10) Acute contact toxicity test in the natural enemy ladybug, with a low risk.

[0107] Application Example Six: Acute Toxicology Determination Experiments of Examples 1 - 4

[0108] Our company commissioned a third - party testing agency to conduct acute toxicity determination tests on Examples 1 - 4, and the test results are as follows:

[0109] 1) Acute oral toxicity tests in rats, with all toxicity levels being low.

[0110] 2) Acute percutaneous toxicity test in rats, with a low toxicity level.

[0111] 3) Rabbit eye irritation test, no irritation.

[0112] 4) Skin irritation test, no irritation.

[0113] 5) Skin sensitization test. Experimental animals: guinea pigs; Sensitization intensity: none.

[0114] The above content is a further detailed description of the present invention in combination with specific preferred implementation modes. It cannot be determined that the specific implementation of the present invention is only limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, without departing from the concept of the present invention, several simple deductions or substitutions can still be made, which should all be regarded as belonging to the protection scope of the present invention.

Claims

1. A method for preparing a nano-suspension agent and its application, characterized in that: The described nano-suspension agent comprises an effective active ingredient, a hyperbranched dispersant, a wetting agent, an antifoaming agent, a preservative, a pH regulator, a thickener and water; The effective active ingredient is clothianidin and lufenuron, wherein the weight ratio of clothianidin to lufenuron is 4:

1.

2. The preparation method according to claim 1, wherein: The weight ratio of the effective active ingredient to the hyperbranched dispersant is 1:1 to 10:1, optionally the weight ratio is 1:1 to 5:

1.

3. The preparation method according to claim 1 or 2, characterized in that: The hyperbranched dispersant is selected from one or more of styrene maleic anhydride polymers and polyetheramine graft copolymers of polyethylene oxide polypropylene oxide.

4. The preparation method according to any one of claims 1 to 3, characterized in that: The total content of the effective active ingredient is 100 to 500 g / L, optionally the total content is 400 g / L.

5. The preparation method according to claim 4, wherein: Based on 1000 parts by weight, the nano-suspension agent is composed of the following components in the following contents: Clothianidin 80 to 400 parts by weight, lufenuron 20 to 100 parts by weight, hyperbranched dispersant 10 to 200 parts by weight, wetting agent 20 to 80 parts by weight, antifreeze 0 to 60 parts by weight, thickener 2 to 25 parts by weight, antifoaming agent 0.5 to 15 parts by weight, pH regulator 0.05 to 5 parts by weight, preservative 0 to 20 parts by weight, and the balance being water.

6. The preparation method according to claim 5, characterized in that: Based on 1000 parts by weight, the nano-suspension agent is composed of the following components in the following contents: Clothianidin 320 parts by weight, lufenuron 80 parts by weight, hyperbranched dispersant 50 to 120 parts by weight, wetting agent 20 to 50 parts by weight, antifreeze 30 to 60 parts by weight, thickener 2 to 10 parts by weight, antifoaming agent 0.5 to 8 parts by weight, pH regulator 0.05 to 2 parts by weight, preservative 2 to 8 parts by weight, and the balance being water.

7. The preparation method according to claim 1, characterized in that: First, water, wetting agent, hyperbranched dispersant, and defoamer are put into a stirring tank for high-speed shearing. After being fully dispersed, clothianidin technical and lufenuron technical are put into the stirring tank for high-speed shearing to form a primary dispersion. Then, the dispersion is transported to two sand mills connected in series through a diaphragm pump for sand milling. The sand milling feed speed is adjusted to control the sand milling fineness at 4-6 μm. Then, the dispersion is transported to a turnover kettle through a diaphragm pump for stirring. The slurry is filtered through 200 mesh and then sand milled with a nano sand mill. The particle size D 50 Controlled to less than 100 nanometers, particle size D 90 The particle size is controlled to be less than 300 nanometers. Finally, the slurry is transported to a preparation kettle, thickener and defoamer are added, the viscosity of the material is adjusted, and samples are taken for quality inspection to obtain the finished product.

8. The application according to claim 1, wherein: Application of the nano-suspension agent in controlling Bradysia odoriphaga of Chinese chives.

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