Pesticide suspending agent containing flubendiamide and preparation method thereof

Abstract

The invention discloses a pesticide suspending agent containing flubendiamide and a preparation method of the pesticide suspending agent, and belongs to the technical field of pesticide preparation processing. The suspending agent is prepared from 1%-30% of flubendiamide, 10%-30% of a second active ingredient, 1%-15% of a performance improver, 1%-10% of a wetting agent, 1%-10% of a dispersing agent, 0.1%-2% of a suspending aid, 2%-10% of an anti-freezing agent and 0.1%-0.6% of a defoaming agent. 0.05%-0.6% of a preservative and the balance of deionized water. The pesticide suspending agent disclosed by the invention has good high-temperature-resistant and low-temperature-resistant storage stability, and is particularly suitable for long-time marine transportation of export preparation products.

Description

Technical Field

[0001] The invention belongs to the technical field of pesticide preparation processing, and in particular relates to a bromofenac-containing pesticide suspension and a preparation method thereof. Background Art

[0002] Broflanilide is an iso-benzamidobenzamide insecticide developed jointly by Japan's Mitsui Agrochemicals and BASF. It is mainly used to control common pests on crops such as Lepidoptera, Coleoptera, termites, mosquitoes and flies. Current studies have shown that broflanilide has excellent activity against both larvae and adults.

[0003] The mechanism of action of brofenac is classified as group 30 in the IRAC mechanism of action classification. Brofenac is an allosteric modulator of GABA-gated chloride channels, which allosterically inhibits GABA-activated chloride channels, causing insects to be overexcited and twitching. Brofenac acts near G336 in the M3 region of the Drosophila RDLGABA receptor after demethylation of Chemicalbook, and is a non-competitively resistant dieldrin (RDL) γ-aminobutyric acid (GABA) receptor antagonist. Although the site of action overlaps with the appearance of macrolides, the mode of action is different from that of macrolides, so it is still effective against pests resistant to cyclodiene and fipronil. Brofenac is mainly used to control lepidoptera, coleoptera, termites, mosquitoes and flies on crops such as green leafy vegetables, perennial crops and cereals. In addition, it can also be used as a seed treatment agent to control nematodes that harm cereals, and for non-crop uses to control termites, ants, cockroaches, flies and other pests. In addition, the agent has high larvicidal activity against Spodopteralitura.

[0004] When pesticide suspension products are exported to Europe and the United States, they often have to go through a 1-2 month sea freight period. They may need to experience high or low temperatures for a long time during the journey, which is a serious test for the quality of pesticide suspension preparations. Pesticide suspension preparations prepared by conventional methods often have unsatisfactory high and low temperature stability (caking, stratification, reduced suspension rate, etc.).

[0005] We know that methyl phenyl silicone oils have the advantages of low temperature resistance, high temperature resistance, lubricity and compatibility. Low phenyl silicone oils have good low temperature resistance, and medium phenyl and high phenyl silicone oils have high thermal stability (Synthesis of Hydroxyl-Terminated Dimethyl-Diphenylsiloxane Oligomers, Organic Silicone Materials. 2018, 32 (S1), 586). The phenyl silicone oil of high phenyl silicone oil can significantly improve the thermal stability of the system by combining with certain additives (An emulsifier for improving the high temperature stability and low temperature stability of cosmetics and its use, CN202210309125.7). After a large number of experimental screenings, we found that mixing low phenyl silicone oil and high phenyl silicone oil in a certain proportion, synergistically emulsifying with W / O emulsifier and O / W emulsifier (such as polyoxyethylene ether emulsifier), and matching with preferred diluents, can effectively improve the high temperature and cold resistance of the preparation when applied to pesticide suspensions, while giving the suspension liquid excellent adhesion properties. Summary of the invention

[0006] The purpose of the present invention is to overcome the above-mentioned defects of the prior art and provide a suspension containing bromofenac, which has excellent high temperature resistance and cold resistance (the quality of the preparation is stable during long-term high temperature (about 65°C) or low temperature sea transportation), is environmentally friendly, has high safety, has good adhesion performance of the liquid medicine on crops and target organisms, has high utilization rate, and has better and more lasting control effect, and a preparation method thereof.

[0007] The composition is composed of 1% to 30% of bromofenac, 10% to 30% of the second active ingredient, 1% to 15% of a performance improver, 1% to 10% of a wetting agent, 1% to 10% of a dispersant, 0.1% to 2% of a suspending agent, 2% to 10% of an antifreeze agent, 0.1% to 0.6% of a defoaming agent, 0.05% to 0.6% of a preservative, and deionized water to make up to 100%.

[0008] The second active ingredient is selected from at least one of spinosad, spinetoram, trifluanid, fluphenazine, sulfoxaflor, methoxyfenozide, fluazifop-pirone, cyantraniliprole, bifenapyr, fluanid, cyprodinil, pyriproxyfen, bifenthrin, chlorantraniliprole, avermectin, avermectin benzoate, flonicamid, cyclobenzaprine and flubendiamide.

[0009] The performance improver: based on the total weight of 100%, 5% to 10% of low-phenyl silicone oil, 10% to 20% of high-phenyl silicone oil, 20% to 30% of diluent, 20% to 30% of O / W emulsifier, and 20% to 35% of W / O emulsifier are homogenized and high-sheared (normal temperature, shear rate of 8000 to 10000 rpm, time of 20 to 30 minutes) for standby use.

[0010] The low-phenyl silicone oil is selected from at least one of methylphenyl silicone oil, ethylphenyl silicone oil and polymethylphenylsiloxane; the high-phenyl silicone oil is selected from at least one of terminal hydroxyl polymethylphenyl silicone oil and divinyl-terminated phenyl silicone oil.

[0011] The diluent is selected from at least one of dimethyl sulfoxide, ethylene glycol, caprylic acid triglyceride, and methyl oleate.

[0012] The emulsifier is selected from a combination of W / O (water-in-oil) emulsifier and O / W (oil-in-water) emulsifier, and the W / O emulsifier is selected from at least one of Atlox4912 and sorbitan trioleate. The O / W emulsifier is selected from at least one of isomeric decanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, castor oil polyoxyethylene ether, and C12-14 secondary alcohol polyoxyethylene ether.

[0013] The wetting agent is Morwet EFW, Ethylan NS-500LQ, One or a combination of several wetting agents in POA.

[0014] The dispersant is one of Tersperse 2500, Petro AA, Morwet D-360, polycarboxylates or a combination of several wetting agents.

[0015] The suspending agent is one or a combination of several thickeners selected from xanthan gum, aluminum magnesium silicate and fumed white carbon black.

[0016] The antifreeze agent is one or a combination of several antifreeze agents selected from propylene glycol, glycerol and urea.

[0017] The defoaming agent is one or a combination of several defoaming agents selected from the group consisting of polyalkylsilicon ethylene oxide, mineral oil and alcohol.

[0018] The mildew preventer is one or a combination of several mildew preventers selected from the group consisting of sodium benzoate, benzoic acid, sorbic acid and propyl polyhydroxybenzoate.

[0019] The invention provides a method for preparing a bromofenac-containing pesticide suspension, comprising the following steps: mixing the required components of a performance improver in a certain proportion, homogenizing and high shearing (normal temperature, shear rate of 8000-10000 rpm, time of 20-30 min) for uniform use. Mixing bromofenac original drug, second active ingredient original drug, performance improver, wetting agent, dispersant, antifreeze agent, suspending agent, preservative, and carrier, stirring and mixing, and then sand milling (sand milling with a pin-type sand mill, controlling the temperature to be below 40°C during the process, and controlling the particle size D90≤4μm) to prepare a bromofenac-containing suspension.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. It has good high and low temperature storage stability, and is especially suitable for long-term marine transportation of export preparations.

[0022] 2. Very good physical and chemical properties, excellent dispersibility and adhesion performance, significantly improve the utilization rate of active ingredients during use, high efficiency, can significantly reduce the use of pesticides, save energy and reduce emissions;

[0023] 3. The additives used in the present invention are safe and environmentally friendly. DETAILED DESCRIPTION

[0024] The present application discloses a bromofenac-containing pesticide suspension and a preparation method thereof. The experimental methods used in the following examples are conventional methods unless otherwise specified; the reagents, materials, etc. used in the following examples are all commercially available unless otherwise specified.

[0025] Example 1

[0026] Preparation method of 15% bromofenac·spinosad suspension:

[0027] 50 kg of brofenac, 100 kg of spinosad, 65 kg of performance improver, 25 kg of Morwet EFW, 10 kg of Tersperse 2500, 50 kg of propylene glycol, 5 kg of sodium benzoate, 2 kg of xanthan gum, 8 kg of magnesium aluminum silicate, 5 kg of polyalkylsilicon oxide and 680 kg of deionized water are mixed evenly and then put into a pin-type sand mill for sand grinding (the temperature is controlled below 40°C and the particle size D90 is controlled to be ≤4μm during the process) to obtain the 15% brofenac·spinosad suspension.

[0028] The preparation of the performance improver is as follows: 50 kg of methylphenyl silicone oil, 100 kg of terminal hydroxyl polymethylphenyl silicone oil, 300 kg of dimethyl sulfoxide, 250 kg of Atlox4912, and 300 kg of isomeric tridecanol polyoxyethylene ether are mixed, homogenized and high sheared (normal temperature, shear rate of 10000 rpm) for 20 minutes, and set aside.

[0029] Example 2

[0030] Preparation method of 35% bromofenac·spinetobacillus suspending agent:

[0031] 100 kg of brofenac, 250 kg of spinetoram, 60 kg of performance improver, 20 kg of EthylanNS-500LQ, 20 kg of a mixture of alkylnaphthalene sulfonate condensate and lignin, 50 kg of glycerol, 5 kg of sodium benzoate, 1.8 kg of xanthan gum, 6 kg of magnesium aluminum silicate, 5 kg of polyalkylsilicon oxide and 482.2 kg of deionized water are mixed evenly and then put into a pin-type sand mill for sand grinding (the temperature is controlled below 40°C and the particle size D90 is controlled to be ≤4μm during the process) to obtain a 35% brofenac·spinetoram suspension.

[0032] The preparation of the performance improver is as follows: 60 kg of ethylphenyl silicone oil, 120 kg of divinyl-terminated phenyl silicone oil, 270 kg of caprylic acid triglyceride, sorbitan trioleate, and 200 kg to 350 kg of isomeric decanol polyoxyethylene ether are mixed, homogenized and high sheared (normal temperature, shear rate of 8000 rpm) for 30 minutes, and set aside.

[0033] Example 3

[0034] Preparation method of 30% bromofenac·trifluanid suspension:

[0035] 100 kg of bromofenac, 200 kg of trifluanid, 50 kg of performance improver, 20 kg of POA, 20 kg of Petro AA, 30 kg of propylene glycol, 5 kg of benzoic acid, 1.8 kg of xanthan gum, 5 kg of magnesium aluminum silicate, 5 kg of polyalkylsilicon oxide and 563.2 kg of deionized water are mixed evenly and then put into a pin-type sand mill for sand grinding (the temperature is controlled below 40° C. and the particle size D90 is controlled to be ≤4 μm during the process) to obtain a 30% bromofenac·trifluanid suspension.

[0036] The performance improver was prepared by mixing 50 kg of ethylphenyl silicone oil, 130 kg of terminal hydroxyl polymethylphenyl silicone oil, 300 kg of ethylene glycol, 220 kg of castor oil polyoxyethylene ether, and 300 kg of Atlox4912, homogenizing and high shearing (normal temperature, shear rate of 9000 rpm) for 25 minutes, and setting aside.

[0037] Example 4

[0038] Preparation method of 30% bromofenac·chlorantraniliprole suspension concentrate:

[0039] 100 kg of brofenac, 200 kg of chlorfenac, 45 kg of performance improver, 30 kg of MorwetEFW, 25 kg of Ethylan NS-500LQ, 50 kg of propylene glycol, 5 kg of sodium benzoate, 1.6 kg of xanthan gum, 7 kg of magnesium aluminum silicate, 5 kg of polyalkylsilicon oxide and 531.4 kg of deionized water are mixed evenly and then put into a pin-type sand mill for sand grinding (the temperature is controlled below 40°C and the particle size D90 is controlled to be ≤4μm during the process) to obtain a 30% brofenac·chlorfenac suspension.

[0040] The preparation of the performance improver is as follows: 90 kg of polymethylphenylsiloxane, 160 kg of terminal hydroxyl polymethylphenyl silicone oil, 280 kg of propylene glycol, 250 kg of C12-14 secondary alcohol polyoxyethylene ether, and 220 kg of Atlox4912 (non-ionic block polyether) are mixed, homogenized and high sheared (normal temperature, shear rate of 8000 rpm) for 30 minutes, and set aside.

[0041] Example 5

[0042] Preparation method of 35% bromofenac·sulfoxaflor suspension concentrate:

[0043] 200 kg of bromofenac, 200 kg of sulfoxaflor, 50 kg of performance improver, 30 kg of Morwet EFW, 15 kg of Tersperse 2500, 30 kg of urea, 4 kg of sodium benzoate, 1.2 kg of xanthan gum, 4 kg of polyalkylsiloxane and 465.8 kg of deionized water were mixed uniformly and then put into a pin-type sand mill for sand milling (the temperature was controlled to be below 40° C. and the particle size D90 was controlled to be ≤4 μm during the process) to obtain a 35% bromofenac·sulfoxaflor suspension.

[0044] The preparation of the performance improver: 70 kg of methylphenyl silicone oil, 130 kg of terminal hydroxyl polymethylphenyl silicone oil, 250 kg of dimethyl sulfoxide, 270 kg of isomeric decanol polyoxyethylene ether, and 280 kg of sorbitan trioleate were mixed, homogenized and high sheared (normal temperature, shear rate of 10000 rpm) for 20 minutes, and set aside.

[0045] Example 6

[0046] Preparation method of 30% bromofenac·methoxyfenozide suspension:

[0047] 100 kg of brofenac, 200 kg of methoxyfenozide, 60 kg of performance improver, 30 kg of polycarboxylate, 10 kg of Ethylan NS-500LQ, 30 kg of glycerol, 5 kg of sodium benzoate, 1.7 kg of xanthan gum, 5 kg of magnesium aluminum silicate, 5 kg of polyalkylsiloxane and 553.3 kg of deionized water were mixed uniformly and then put into a pin-type sand mill for sand milling (the temperature was controlled below 40° C. and the particle size D90 was controlled to be ≤4 μm during the process) to obtain a 30% brofenac·methoxyfenozide suspension.

[0048] The preparation of the performance improver is as follows: 30 kg of methylphenyl silicone oil, 150 kg of terminal hydroxyl polymethylphenyl silicone oil, 120 kg of dimethyl sulfoxide, 150 kg of methyl oleate, 290 kg of isomeric decanol polyoxyethylene ether, and 260 kg of Atlox4912 (non-ionic block polyether) are mixed, homogenized and high sheared (normal temperature, shear rate of 9000 rpm) for 25 minutes, and set aside.

[0049] Comparative Example 1

[0050] Preparation method of 15% bromofenac·spinosad suspension:

[0051] 50 kg of brofenac, 100 kg of spinosad, 60 kg of Morwet EFW, 40 kg of Tersperse 2500, 50 kg of propylene glycol, 5 kg of sodium benzoate, 2 kg of xanthan gum, 8 kg of magnesium aluminum silicate, 5 kg of polyalkylsiloxane and 680 kg of deionized water were mixed evenly and then put into a pin-type sand mill for sand grinding (the temperature was controlled below 40°C and the particle size D90 was controlled ≤ 4 μm during the process) to obtain a control example 15% brofenac·spinosad suspension.

[0052] Quality technical determination

[0053] The prepared suspension was tested under certain conditions, and the obtained data are shown in Table 1.

[0054] Table 1. Technical test results of suspension concentrate quality

[0055]

[0056] From the data in Table 1, it can be seen that the various indicators of Example 1 are significantly better than those of Control Example 1, especially the stability of the preparation under long-term high temperature or cold environment, so it is more suitable for the needs of long-term long-distance sea transportation of export preparation products.

[0057] Determination of drug retention

[0058] Test object: cucumber leaves

[0059] Test agents: Example 1, Control Example 1.

[0060] The specific experimental method is as follows: dilute the drug according to the concentration used and stir evenly. Then, take a φ30mm culture dish and place it on a 1 / 10,000 balance. After zeroing, use a φ16mm puncher to cut off about 2cm 2 For the round cucumber leaves, first weigh and record the mass of the cucumber leaves, pick up the cucumber leaves with pointed tweezers and dip them into the prepared test solution, repeatedly soak for 10 seconds, let them stand in the air for 10 seconds, and then put them in a petri dish to weigh the mass of the cucumber leaves. Each measurement operation was repeated 10 times, and the average value was calculated to obtain the difference in the amount of drug solution retained. The test results are shown in Table 2.

[0061] Table 2 Test data of the amount of liquid retained by the treatment agent on cucumber leaves

[0062]

[0063] It can be seen from Table 2 that the amount of the diluted solution of Example 1 retained on the cucumber leaves is significantly higher than the amount of the diluted solution of Control Example 1 retained on the cucumber leaves.

[0064] Efficacy test

[0065] Test object: Yellow-breasted Thrips of cucumber.

[0066] Test agents: Example 1 and Control Example 1.

[0067] Test method: The test adopts field spray method, and the area of ​​the plot is 5m 2 Three replicates were set for each treatment. A base number survey was conducted before application. The number of live insects was surveyed 1 day, 3 days and 7 days after application. The control effect was calculated and corrected with the clear water control treatment. The test results are shown in Table 3.

[0068] Insect population reduction rate (%) = (number of live insects before application - number of live insects after application) * 100 / number of live insects before application

[0069] Control effect (%) = (pest population reduction rate in the treatment area - insect population reduction rate in the blank control area) * 100 / (100 - insect population reduction rate in the blank control area)

[0070] Table 3. Field efficacy test results of treatment agents against yellow-breasted thrips of cucumber

[0071]

[0072]

[0073] It can be seen from the test results in Table 3 that Example 1 can effectively control yellow-breasted thrips of cucumber at an effective ingredient dosage of 10g / mu and 20g / mu, and the control effect is significantly better than that of Control Example 1. Example 1 controls yellow-breasted thrips of cucumber at an effective ingredient dosage of 10g / mu, and the control effect is significantly better than that of Control Example 1 at an effective ingredient dosage of 20g / mu. Therefore, Example 1 of the present invention, which effectively improves performance, can well achieve pesticide reduction and efficiency improvement.

[0074] Field test observations showed that, within the test concentration range of each treatment agent, cucumbers grew normally without obvious pesticide damage symptoms such as chlorosis, deformity or poor growth, and no obvious harmful effects of the agent on other organisms were found. Therefore, the pesticide suspension containing bromofenac has good safety performance.

Claims

1. A pesticide suspension containing bromofenac, characterized in that: The composition is composed of 1% to 30% of bromofenac, 10% to 30% of the second active ingredient, 1% to 15% of a performance improver, 1% to 10% of a wetting agent, 1% to 10% of a dispersant, 0.1% to 2% of a suspending agent, 2% to 10% of an antifreeze agent, 0.1% to 0.6% of a defoaming agent, 0.05% to 0.6% of a preservative, and deionized water to make up to 100%.

2. The pesticide suspension containing bromofenac according to claim 1, characterized in that: The second active ingredient is selected from at least one of spinosad, spinetoram, trifluanid, fluphenazine, sulfoxaflor, methoxyfenozide, fluazifop-pirone, cyantraniliprole, bifenapyr, fluanid, cyprodinil, pyriproxyfen, bifenthrin, chlorantraniliprole, avermectin, avermectin benzoate, flonicamid, cyclobenzaprine and flubendiamide.

3. The pesticide suspension containing bromofenac according to claim 1, characterized in that: The performance improver: based on the total weight of 100%, 5% to 10% of low-phenyl silicone oil, 10% to 20% of high-phenyl silicone oil, 20% to 30% of diluent, 20% to 30% of O / W emulsifier, and 20% to 35% of W / O emulsifier are homogenized and high-sheared (normal temperature, shear rate of 8000 to 10000 rpm, time of 20 to 30 minutes) for standby use.

4. The pesticide suspension containing bromofenac as claimed in claim 3, characterized in that: The low-phenyl silicone oil is selected from at least one of methylphenyl silicone oil, ethylphenyl silicone oil and polymethylphenylsiloxane; the high-phenyl silicone oil is selected from at least one of terminal hydroxyl polymethylphenyl silicone oil and divinyl-terminated phenyl silicone oil.

5. The pesticide suspension containing bromofenac as claimed in claim 3, characterized in that: The diluent is selected from at least one of dimethyl sulfoxide, ethylene glycol, caprylic acid triglyceride, and methyl oleate.

6. The pesticide suspension containing bromofenac as claimed in claim 3, characterized in that: The emulsifier is selected from a combination of W / O (water-in-oil) emulsifier and O / W (oil-in-water) emulsifier, and the W / O emulsifier is selected from at least one of Atlox4912 and sorbitan trioleate. The O / W emulsifier is selected from at least one of isomeric decanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, castor oil polyoxyethylene ether, and C12-14 secondary alcohol polyoxyethylene ether.

7. The pesticide suspension containing bromofenac as claimed in claim 1, characterized in that: The wetting agent is Morwet EFW, Ethylan NS-500LQ, One or a combination of wetting agents in POA.

8. The pesticide suspension containing bromofenac as claimed in claim 1, characterized in that: The dispersant is one of Tersperse 2500, Petro AA, Morwet D-360, polycarboxylates or a combination of several wetting agents.

9. The pesticide suspension containing bromofenac as claimed in claim 1, characterized in that: The suspending agent is one or a combination of several thickeners selected from xanthan gum, aluminum magnesium silicate and fumed white carbon black.

10. The pesticide suspension containing bromofenac according to claim 1, characterized in that: The antifreeze agent is one or a combination of several antifreeze agents selected from propylene glycol, glycerol and urea.

11. The pesticide suspension containing bromofenac as claimed in claim 1, characterized in that: The defoaming agent is one or a combination of several defoaming agents selected from the group consisting of polyalkylsilicon ethylene oxide, mineral oil and alcohol.

12. The pesticide suspension containing bromofenac according to claim 1, characterized in that: The mildew preventer is one or a combination of several mildew preventers selected from the group consisting of sodium benzoate, benzoic acid, sorbic acid and propyl polyhydroxybenzoate.

13. The method for preparing the bromofenac-containing pesticide suspension according to any one of claims 1 to 12, characterized in that: The following steps are involved: The components required for the performance improver are mixed in a certain proportion, homogenized and high sheared (normal temperature, shear rate of 8000-10000rpm, time of 20-30min) for use. The bromofenac original drug, the second active ingredient original drug, the performance improver, the wetting agent, the dispersant, the antifreeze agent, the suspending agent, the preservative, and the carrier are mixed and stirred evenly, and then sand-milled (sand-milled with a pin-type sand mill, the temperature is controlled below 40°C during the process, and the particle size D90 is controlled to be ≤4μm) to prepare a suspension containing bromofenac.

14. The pesticide suspension containing bromofenac as claimed in claim 1, characterized in that: Calculated by mass content, 50 kg of brofenac, 100 kg of spinosad, 65 kg of performance improver, 25 kg of Morwet EFW, 10 kg of Tersperse 2500, 50 kg of propylene glycol, 5 kg of sodium benzoate, 2 kg of xanthan gum, 8 kg of magnesium aluminum silicate, 5 kg of polyalkylsilicon oxide and 680 kg of deionized water are mixed evenly and then put into a pin-type sand mill for sand milling (the temperature is controlled to be below 40° C. and the particle size D90 is controlled to be ≤4 μm during the process) to obtain the 15% brofenac·spinosad suspension; The performance improver is as follows: 50 kg of methylphenyl silicone oil, 100 kg of terminal hydroxyl polymethylphenyl silicone oil, 300 kg of dimethyl sulfoxide, 250 kg of Atlox4912, and 300 kg of isomeric tridecanol polyoxyethylene ether are mixed, homogenized and high sheared (normal temperature, shear rate of 10000 rpm) for 20 minutes, and set aside.

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