Suspension concentrate containing cyflumetofen and spirodiclofen, and use thereof

Abstract

A suspension concentrate containing cyflumetofen and spirodiclofen, and the use thereof. The suspension concentrate comprises the following components in percentages by weight: 10-30% of cyflumetofen, 10-30% of spirodiclofen, 1-10% of a wetting and dispersing agent, 0.05-0.2% of a pH regulator, 1-7% of an anti-freezing agent, 0.05-0.2% of xanthan gum, 0.2-0.8% of magnesium aluminum silicate, 0.05-0.2% of a mildew inhibitor, 0.05-0.2% of a defoaming agent, and the balance of deionized water, wherein the wetting and dispersing agent is prepared from a polycarboxylate and an acrylic copolymer, and the mass ratio of the polycarboxylate to the acrylic copolymer is 1-5:1-5. Suspension concentrate formulas all exhibit relatively good storage results at different temperatures, have a relatively small particle size growth, and all have a suspensibility of 90% or higher. After heat storage and freeze-thaw tests at different temperatures, no solidification occurs upon transfer to room-temperature storage, indicating a significant improvement in the storage stability. Field trial results show that a 38% cyflumetofen-spirodiclofen SC has a good control effect against the citrus red mite, with a stable effective duration being 20-30 days.

Description

A suspension containing dicofol and spirodiclofen and its application Technical Field

[0001] This invention belongs to the field of pesticide formulations, specifically relating to a suspension containing dicofol and spirodiclofen and its application. Background Technology

[0002] Fenfluroxyfen is a novel acylacetonitrile acaricide. It is a non-systemic acaricide that mainly acts through contact. Its mechanism of action is to inhibit mitochondrial protein complex II, hinder electron (hydrogen) transfer, and disrupt phosphorylation reactions.

[0003] Spirodiclofen is a quaternary ketoacid acaricide with contact action and no systemic activity. It mainly inhibits fat synthesis and blocks the energy metabolism of mites. It has excellent ovicidal effect and also has good contact action against nymphs.

[0004] Fenflufenicol and spirodiclofen are representative pesticides used in the production of citrus red spider mites. Their mechanisms of action differ, and mixing them can enhance efficacy and effectively control pesticide resistance in pests. Our company, Shanghai Shengnong, conducted a combined toxicity test on citrus red spider mites using a mixture of fenflufenicol and spirodiclofen. The results showed that a 1:1 mixture of fenflufenicol and spirodiclofen exhibited the highest co-toxicity coefficient and the most significant synergistic effect. Currently, Shaanxi Yitianfeng Crop Technology Co., Ltd. has registered a 400 g / L fenflufenicol·spirodiclofen suspension concentrate (37% mass fraction (fenflufenicol 18.5%, spirodiclofen 18.5%)) for the control of citrus red spider mites; our company, Shanghai Shengnong Biochemical Products Co., Ltd., has registered a 400 g / L fenflufenicol·spirodiclofen suspension concentrate (38% mass fraction (fenflufenicol 19%, spirodiclofen 19%)) for the control of citrus red spider mites. However, existing products suffer from insufficient formulation stability during use, which to some extent affects their control efficacy. Summary of the Invention

[0005] This invention provides a suspension containing fenflurfen and spirodiclofen, and its application. The specific technical solution is as follows:

[0006] A suspension containing dicofol and spirodiclofen, comprising the following components in weight percentage: dicofol 10-30%, spirodiclofen 10-30%, wetting and dispersing agent 1-10%, pH adjuster 0.05-0.2%, antifreeze agent 1-7%, xanthan gum 0.05-0.2%, magnesium aluminum silicate 0.2-0.8%, mildew inhibitor 0.05-0.2%, defoamer 0.05-0.2%, and deionized water to 100%;

[0007] The wetting and dispersing agent is composed of polycarboxylate and acrylic acid copolymer, with a mass ratio of polycarboxylate to acrylic acid copolymer of 1-5:1-5.

[0008] The preferred suspension contains the following components in weight percentage: 15-25% dicofol, 15-25% spirodiclofen, 1-10% wetting and dispersing agent, 0.05-0.2% pH adjuster, 1-7% antifreeze, 0.05-0.2% xanthan gum, 0.2-0.8% magnesium aluminum silicate, 0.05-0.2% antifungal agent, 0.05-0.2% defoamer, and deionized water to 100%.

[0009] The preferred suspension contains the following components in weight percentage: 19% diflubenzuron, 19% spirodiclofen, 1-10% wetting and dispersing agent, 0.05-0.2% pH adjuster, 1-7% antifreeze, 0.05-0.2% xanthan gum, 0.2-0.8% magnesium aluminum silicate, 0.05-0.2% antifungal agent, 0.05-0.2% defoamer, and deionized water to 100%.

[0010] The preferred suspending agent comprises the following components by weight percentage: 19% diflubenzuron, 19% spirodiclofen, 6% wetting and dispersing agent, 0.1% pH adjuster, 5% antifreeze, 0.16% xanthan gum, 0.5% magnesium aluminum silicate, 0.1% antifungal agent, 0.1% defoamer, and deionized water up to 100%; the mass ratio of polycarboxylate to acrylic copolymer is 1:2.

[0011] In this invention, the pH adjuster is citric acid, the mildew inhibitor is sodium benzoate, the defoamer is an organosilicon defoamer, and the antifreeze agent is propylene glycol.

[0012] The suspension provided by this invention is used for controlling red spider mites on citrus trees.

[0013] Compared with the prior art, the present invention has the following beneficial effects:

[0014] The suspension formulations of this invention showed good storage results at different temperatures, with minimal particle size increase and suspension rates all above 90%. After heat storage and freeze-thaw tests at different temperatures, no solidification occurred upon transfer to room temperature storage, indicating significantly improved storage stability. Field trial results show that the 38% diflubenzuron·spirodiclofen SC provided by this invention has a good effect on controlling citrus red spider mites, with a stable effective period of 20-30 days. It is safe for citrus trees and can be promoted for use as a pesticide for controlling citrus red spider mites. A concentration of 5000-4000 times is recommended. The pesticide should be applied once by spraying during the initial peak of red spider mite infestation. Attached Figure Description

[0015] Figure 1: DSC curves of fenfluridine (left) and fenfluridine·spirodiclofen (right, mass ratio 1:1). Detailed Implementation

[0016] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0017] Example 1: DSC test of the melting point of the active ingredient

[0018] As shown in Figure 1, the DSC test results indicate that the initial melting point of the mixture of dicofol and spirodiclofen is 69.75℃, which is 10℃ lower than the melting point of dicofol technical grade. Diflubenzuron's melting point is not very high, and when combined with spirodiclofen, the melting point of the mixture is significantly reduced, presenting processing difficulties for low-melting-point suspensions: it may melt and become pasty during sand milling, making sand milling difficult; during heat storage, the technical grade may melt, crystallize, and increase in particle size; after heat to room temperature, it may crystallize and precipitate, resulting in decreased stability.

[0019] Example 2: Preparation of 38% fenflurfen and spirodiclofen suspension

[0020] Preparation method: According to the formula composition, first add some water, antifreeze, wetting and dispersing agent and some defoamer. After shearing for 3-5 min using a laboratory dispersion mill, add some thickener, mildew inhibitor and original drug. Continue shearing for 5-10 min, then transfer to a laboratory dispersion mill for sand milling (material amount: zirconium bead amount = 1:1.2) for 1.0-1.5 h. Control the particle size D90≤5 μm. After sand milling, filter zirconium beads, then add the remaining thickener, remaining defoamer and remaining water, shear and mix evenly, and perform testing and analysis of various technical indicators.

[0021] Test methods: The mass fraction of the active ingredient was determined by HPLC; pH value, suspension rate, pourability, persistent foaming, wet sieving test, low temperature stability and thermal storage stability test were all determined according to national standards.

[0022] Example of a suspending agent formulation 1

[0023] Table 1 Formulation of Suspension Additives

[0024] Material Name | Example 1 | Comparative Example 1 | Comparative Example 2 | Diflubenzuron / % 19 | 19 | 19 | Spirodiclofen / % 19 | 19 | 19 | Polycarboxylate 26-Acrylic Acid Copolymer 4-6 | pH Adjuster / % 0.1 | 0.1 | 0.1 | Antifreeze / % 5 | 5 | 5 | Xanthan Gum / % 0.16 | 0.16 | 0.16 | Magnesium Aluminum Silicate / % 0.5 | 0.5 | 0.5 | Mildew Inhibitor / % 0.1 | 0.1 | 0.1 | Defoamer / % 0.1 | 0.1 | 0.1 | Deionized Water / % to 100 to 100 to 100

[0025] Notes: pH adjuster citric acid, mildew inhibitor sodium benzoate, defoamer silicone defoamer, antifreeze propylene glycol

[0026] Suspension agent formulation index test 1

[0027] Table 2 Results of Suspension Agent Formulation Indicators

[0028] Attached Figure Description

[0029] Figure 1: DSC curves of fenfluridine (left) and fenfluridine·spirodiclofen (right, mass ratio 1:1).

[0030] Detailed Implementation

[0031] The present invention can be better understood from the following embodiments. However, those skilled in the art will readily understand that the descriptions in the embodiments are for illustrative purposes only and should not, and will not, limit the invention as detailed in the claims.

[0032] Example 1: DSC test of the melting point of the active ingredient

[0033] As shown in Figure 1, the DSC test results indicate that the initial melting point of the mixture of dicofol and spirodiclofen is 69.75℃, which is 10℃ lower than the melting point of dicofol technical grade. Diflubenzuron's melting point is not very high, and when combined with spirodiclofen, the melting point of the mixture is significantly reduced, presenting processing difficulties for low-melting-point suspensions: it may melt and become pasty during sand milling, making sand milling difficult; during heat storage, the technical grade may melt, crystallize, and increase in particle size; after heat to room temperature, it may crystallize and precipitate, resulting in decreased stability.

[0034] Example 2: Preparation of 38% fenflurfen and spirodiclofen suspension

[0035] Preparation method: According to the formula composition, first add some water, antifreeze, wetting and dispersing agent and some defoamer. After shearing for 3-5 min using a laboratory dispersion mill, add some thickener, mildew inhibitor and original drug. Continue shearing for 5-10 min, then transfer to a laboratory dispersion mill for sand milling (material amount: zirconium bead amount = 1:1.2) for 1.0-1.5 h. Control the particle size D90≤5 μm. After sand milling, filter zirconium beads, then add the remaining thickener, remaining defoamer and remaining water, shear and mix evenly, and perform testing and analysis of various technical indicators.

[0036] Test methods: The mass fraction of the active ingredient was determined by HPLC; pH value, suspension rate, pourability, persistent foaming, wet sieving test, low temperature stability and thermal storage stability test were all determined according to national standards.

[0037] Example of a suspending agent formulation 1

[0038] Table 1 Formulation of Suspension Additives

[0039] Material Name | Example 1 | Comparative Example 1 | Comparative Example 2 | Diflubenzuron / % 19 | 19 | 19 | Spirodiclofen / % 19 | 19 | 19 | Polycarboxylate 26-Acrylic Acid Copolymer 4-6 | pH Adjuster / % 0.1 | 0.1 | 0.1 | Antifreeze / % 5 | 5 | 5 | Xanthan Gum / % 0.16 | 0.16 | 0.16 | Magnesium Aluminum Silicate / % 0.5 | 0.5 | 0.5 | Mildew Inhibitor / % 0.1 | 0.1 | 0.1 | Defoamer / % 0.1 | 0.1 | 0.1 | Deionized Water / % to 100 to 100 to 100

[0040] Note: pH adjuster citric acid, mildew inhibitor sodium benzoate, defoamer silicone defoamer, antifreeze propylene glycol suspension formulation index test 1

[0041] Table 2 Results of Suspension Agent Formulation Indicators

[0042] Test Results Example 1 Comparative Example 1 Comparative Example 2 Room Temperature Spinodicarb Content / % 19.07 18.97 19.04 Room Temperature Spirodiclofen Content / % 18.98 18.95 18.90 Room Temperature Spinodicarb Suspension Rate / % 98.43 91.38 90.25 Room Temperature Spirodiclofen Suspension Rate / % 99.64 92.87 91.02 54℃ Heat Storage Spinodicarb Content / % 18.88 18.74 18.83 54℃ Heat Storage Spinodicarb Content / % 18.86 18.71 18.65 54℃ Suspension rate of spirodiclofen at 4℃: 95.50, 88.48, 87.91; Suspension rate of spirodiclofen at 4℃: 96.79, 90.85, 90.01; Suspension rate of spirodiclofen at 60℃: 18.85, 18.70, 18.81; Suspension rate of spirodiclofen at 60℃: 18.73, 18.60, 18.52; Suspension rate of spirodiclofen at 60℃: 91.49, 82.05, 80.16; Suspension rate of spirodiclofen at 60℃: 93.31, 85.91, 84.28; Suspension rate of spirodiclofen in cold storage: 93.31, 85.91, 84.28. / % 18.89 18.79 18.87 Cold-stored spirodiclofen content / % 18.80 18.75 18.72 Cold-stored cyclophosphamide suspension rate / % 97.69 90.32 89.24 Cold-stored spirodiclofen suspension rate / % 99.09 90.97 90.03 Freeze-thawed cyclophosphamide content / % 18.90 18.73 18.86 Freeze-thawed spirodiclofen content / % 18.83 18.68 18.70 Freeze-thawed cyclophosphamide suspension rate / % 94.99 85.86 86.17 Freeze-thawed spirodiclofen suspension Rate / % 96.99 88.25 87.15 Room temperature storage particle size D90 / μm 2.98 23.00 22.995 Freeze-thaw storage particle size / μm 8.00 91 5.40 14.78 Low temperature storage particle size / μm 3.02 74.95 06.60 154℃ hot storage particle size / μm 4.71 71 3.98 21 6.70 560℃ hot storage particle size / μm 5.41 11 5.07 21 8.035 pH value 6.37 6.52 6.06 Foaming property (mL) 30 40 45

[0043] Example of a suspension formulation 2

[0044] Table 3 Formulation of Suspension Additives

[0045] Material Name | Comparative Example 3 | Comparative Example 4 | Fenoxacin / % 19 | Spirodiclofen / % 19 | Atlox 49 | 17 / % 23 | Dispersol PSR 19 / % 2 | Atla G-500 2L / % 23 | Citric Acid / % 0.1 | 0.1 | Glycerol / % 55 | Xanthan Gum / % 0.1 | 0.1 | Magnesium Aluminum Silicate / % 11 | Sodium Benzoate / % 0.5 | 0.5 | Organosilicon Defoamer / % 0.1 | 0.1 | Deionized Water / % to 100

[0046] Note: Comparative Example 3 is a product registered by our company (200g / L of cyclophosphamide and 200g / L of spirodiclofen, with corresponding mass fractions of 19% and 19% respectively).

[0047] Suspension agent formulation index test 1

[0048] Table 4 Results of Suspension Agent Formulation Indicators

[0049] Comparative Example 3 vs. Comparative Example 4: Room Temperature Flufenoxuron Content (%) 18.94 19.05 Room Temperature Flufenoxuron Suspension Rate (%) 93.48 90.35 Room Temperature Spirodiclofen Content (%) 19.02 18.97 Room Temperature Spirodiclofen Suspension Rate (%) 91.27 90.42 Heat Storage Flufenoxuron Content (%) 18.86 18.93 Heat Storage Flufenoxuron Suspension Rate (%) 90.54 85.54 Heat Storage Spirodiclofen Content (%) 18.89 18.83 Heat Storage Spirodiclofen Suspension Rate (%) 90.528 2.97 Cold-stored cyclophosphamide content % 18.79 18.99 Cold-stored cyclophosphamide suspension rate % 91.16 87.48 Cold-stored spirodiclofen content / % 18.95 18.87 Cold-stored spirodiclofen suspension rate / % 89.53 86.08 pH 6.4 16.35 Persistent foaming properties mL 45 53 Room temperature D90 particle size / μm 3.03 83.125 Hot storage D90 particle size / μm 9.72 0 13.144 Cold storage D90 particle size / μm 5.88 48.053

[0050] The suspending agent formulations of this invention showed good storage results at different temperatures, with minimal particle size increase and a suspension rate >90%. After heat storage and freeze-thaw tests at different temperatures, no solidification occurred when transferred to room temperature storage, indicating a significant improvement in storage stability.

[0051] Example 3: Field efficacy trial of 38% fenflurfen and spirodiclofen suspension for controlling citrus red spider mites.

[0052] Experimental Unit: Institute of Plant Protection, Guangxi Academy of Agricultural Sciences

[0053] Test reagent: 38% suspension (Example 1)

[0054] Test crop: Citrus tree

[0055] Target pests: Red spider mites

[0056] Experimental Design:

[0057] Table 5 Experimental Design of Test Reagents

[0058] Treatment Number | Drug Name | Dosage (Dilution Ratio) | 1 | 38% Suspension | 5000 | 2 | 38% Suspension | 4500 | 3 | 38% Suspension | 4000 | 4 | 20% | Fenflufenicol SC | 2500 | 5 | 24% | Spirodiclofen SC | 4000 | 6 | Blank Control | -

[0059] Application method: Apply pesticide during the initial and peak period of red spider mites on citrus trees. First, spray a blank control until the leaves are evenly and thoroughly wetted to the point of dripping. Then, prepare the pesticide solution according to the amount of water used for the control. After diluting the pesticide, spray it in small areas.

[0060] Application equipment: Toyota FT-18 backpack electric sprayer, conical nozzle, nozzle orifice diameter 1.3mm, average spraying speed 1.1L / min.

[0061] Application time and frequency: The drug was applied once in this experiment, on September 1, 2021.

[0062] Survey methods, timing, and frequency: Before and after medication, on days 1, 3, 10, 15, 20, and 30 (i.e., September 1, September 2, September 4, September 11, September 16, September 21, and September 30), for a total of 7 surveys.

[0063] Survey method: Two trees were surveyed in each plot. One tender shoot was marked in each of the five directions (east, west, south, north, and center) of each tree. The number of active mites on five leaves (50 leaves in total) in each direction was investigated. The leaf surface was directly observed with a handheld magnifying glass, the number of mites was counted, and the pest population reduction rate and control effect were calculated.

[0064]

[0065] The experimental data were analyzed for significance using Duncan's new multiple range method in DPS (7.05) statistical analysis software.

[0066] Results and Analysis:

[0067] The results of the experiment on the control of red spider mites on citrus trees with 38% fenflurfen·spirodiclofen SC are shown in Table 2. Analysis using the DMRT method showed that:

[0068] One day after application, the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at 5000 times dilution was significantly lower than that of the control 20% fenflurfen SC, but not significantly different from that of the control 24% spirodiclofen SC. The control efficacy of the 38% fenflurfen·spirodiclofen SC treatments at 4500 times dilution and 4000 times dilution was not significantly different from that of the control 20% fenflurfen SC, but significantly higher than that of the control 24% spirodiclofen SC.

[0069] Three days after application, the control efficacy of the two treatments of 38% dicofol·spirodiclofen SC at 5000x and 4500x dilution was not significantly different from that of the two control compounds; the control efficacy of the treatment of 38% dicofol·spirodiclofen SC at 4000x dilution was significantly higher than that of the control compound 20% dicofol SC, but not significantly different from that of the control compound 24% spirodiclofen SC.

[0070] Ten days after application, the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at a dilution of 5000 times was not significantly different from that of the two control compounds; the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at a dilution of 4500 times was significantly higher than that of the control compound 20% fenflurfen SC, but not significantly different from that of the control compound 24% spirodiclofen SC; the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at a dilution of 4500 times was extremely significantly higher than that of the control compound 20% fenflurfen SC, but not significantly different from that of the control compound 24% spirodiclofen SC.

[0071] Fifteen days after application, the control efficacy of the three treatments of 38% diflubenzuron·spirodiclofen SC at 5000, 4500 and 4000 times dilution was significantly higher than that of the control 20% diflubenzuron SC, but not significantly different from that of the control 24% spirodiclofen SC.

[0072] Twenty days after application, the control efficacy of the two treatments of 38% fenflurfen·spirodiclofen SC at 5000x and 4500x was not significantly different from that of the two control compounds; however, the control efficacy of the 38% fenflurfen·spirodiclofen SC at 4000x was significantly higher than that of the two control compounds.

[0073] Thirty days after application, the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at a dilution of 5000 times was not significantly different from that of the two control compounds; the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at a dilution of 4500 times was significantly higher than that of the control compound 20% fenflurfen SC, but not significantly different from that of the control compound 24% spirodiclofen SC; the control efficacy of the 38% fenflurfen·spirodiclofen SC treatment at a dilution of 4500 times was extremely significantly higher than that of the two control compounds.

[0074] Impact on crops

[0075] Throughout the trial, all doses of 38% fenflurfen·spirodiclofen SC treatment showed no phytotoxicity to citrus trees, and the trees grew normally.

[0076] Impact on other organisms

[0077] The survey results indicate that other pests and non-target organisms were less frequent, and no significant effects of the pesticide on other non-target organisms or its concurrent control effect on other pests were observed.

[0078] Table 6 Results of the trial of 38% fenflurfen·spirodiclofen SC for controlling red spider mites on citrus trees

[0079]

[0080] The above description is only a preferred embodiment of the present invention. For those skilled in the art, appropriate improvements can be made without departing from the original material of the present invention, and these improvements are also within the protection scope of the present invention.

Claims

1. A suspension containing dicofol and spirodiclofen, characterized in that, It contains the following ingredients by weight percentage: 10-30% fenflurfen, 10-30% spirodiclofen, 1-10% wetting and dispersing agent, 0.05-0.2% pH adjuster, 1-7% antifreeze, 0.05-0.2% xanthan gum, 0.2-0.8% magnesium aluminum silicate, 0.05-0.2% mildew inhibitor, 0.05-0.2% defoamer, and deionized water to 100%. The wetting and dispersing agent is composed of polycarboxylate and acrylic acid copolymer, with a mass ratio of polycarboxylate to acrylic acid copolymer of 1-5:1-5.

2. The suspending agent according to claim 1, characterized in that, It contains the following ingredients by weight percentage: 15-25% diflubenzuron, 15-25% spirodiclofen, 1-10% wetting and dispersing agent, 0.05-0.2% pH adjuster, 1-7% antifreeze, 0.05-0.2% xanthan gum, 0.2-0.8% magnesium aluminum silicate, 0.05-0.2% mildew inhibitor, 0.05-0.2% defoamer, and deionized water up to 100%.

3. The suspending agent according to claim 2, characterized in that, It contains the following ingredients by weight percentage: 19% diflubenzuron, 19% spirodiclofen, 1-10% wetting and dispersing agent, 0.05-0.2% pH adjuster, 1-7% antifreeze, 0.05-0.2% xanthan gum, 0.2-0.8% magnesium aluminum silicate, 0.05-0.2% mildew inhibitor, 0.05-0.2% defoamer, and deionized water up to 100%.

4. The suspending agent according to claim 3, characterized in that, It contains the following ingredients by weight percentage: 19% diflubenzuron, 19% spirodiclofen, 6% wetting and dispersing agent, 0.1% pH adjuster, 5% antifreeze, 0.16% xanthan gum, 0.5% magnesium aluminum silicate, 0.1% mildew inhibitor, 0.1% defoamer, and deionized water to 100%. The mass ratio of polycarboxylate to acrylic acid copolymer is 1:

2.

5. The suspending agent according to any one of claims 1-4, characterized in that, The pH adjuster is citric acid, the mildew inhibitor is sodium benzoate, the defoamer is an organosilicone defoamer, and the antifreeze agent is propylene glycol.

6. The use of the suspension agent according to any one of claims 1-4 for the control of red spider mites on citrus trees.

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