Polymer nano preparation containing cyflumetofen

Abstract

The invention relates to the technical field of pesticides, and discloses a polymer nano preparation containing cyflumetofen. The nano preparation is prepared by mixing cyflumetofen, spirodiclofen, a polymer nano carrier, an auxiliary agent and water, the weight ratio of cyflumetofen to spirodiclofen is (1: 1)-(1: 2). The nano preparation is used for preventing and treating citrus tree red spider mites, cyflumetofen and spirodiclofen are mixed according to a proper proportion, a synergistic effect on pests can be achieved from multiple aspects, the purpose of effectively controlling the pests to be damaged with a low dosage is achieved, the nano preparation is safe to the environment, the production cost is reduced, and the pesticide effect is improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a polymer nano - preparation containing cyflumetofen. Background Art

[0002] Cyflumetofen is a new acyloxyacetonitrile acaricide developed by Otsuka Chemical Co., Ltd. of Japan, having no cross - resistance with existing insecticides. It was first registered and sold in Japan in 2007, and is used for controlling the main mites parasitizing on crops such as fruit trees, vegetables, tea trees and flowers. This product is a 20% suspension concentrate. It is effective against both the eggs and adult mites of spider mites, and has higher activity against nymphs. According to experimental comparison, cyflumetofen is superior to spirodiclofen and abamectin in all aspects.

[0003] Spirodiclofen is a chemical substance with the molecular formula C21H24Cl2O4. It appears as white powder, has no special smell, has contact killing effect and no systemic activity. It has good killing effects on the eggs, larvae and nymphs of pest mites, has no effect on adult mites, but has the effect of inhibiting the egg - laying and hatching rate of female mites.

[0004] The citrus red mite, the number of generations per year of the citrus red mite is mainly affected by temperature. Generally, when the annual average temperature is about 15 - 17°C, it occurs 12 - 15 generations a year; when the annual average temperature is about 18°C, it occurs 16 - 17 generations a year; when the annual average temperature is about 20°C, it can occur about 20 generations a year. The main factors affecting the population density of red mites include temperature, humidity, food, natural enemies and human factors, etc. Generally, when the temperature is between 12 - 26°C, it is beneficial to the occurrence of red mites, and it is most suitable at about 20°C. Due mainly to the influence of temperature, there are two peak periods for the occurrence of red mites, which generally appear in April - June and September - November all year round. [1] The relative humidity most suitable for the occurrence of red mites is about 70%, and rainy weather is not conducive to their occurrence. The food is preferably the young tissues of citrus. There are many kinds of natural enemies of the citrus red mite, and nearly a hundred have been discovered. Among them, Amblyseius nicholsi, Amblyseius eharai, Amblyseius longispinosus, Stethorus punctillum, Anystis baccarum, Erigonidium graminicolum, Theridion octomaculatum, Chrysopa shansiensis, Chrysopa sinica, Scolothrips takahashii, Stethorus punctillum Weise, Stethorus siphonulus Kapur, Beauveria bassiana, Cladosporium cladosporioides and Nephovirus can significantly control the occurrence of red mites. In orchards with rich natural enemies, red mites can be naturally controlled, especially in the middle and late growth seasons. The main way of human influence on red mites is through orchard spraying. Appropriate spraying can better control red mites, while unreasonable and frequent spraying will kill a large number of natural enemies, making the occurrence of red mites more rampant and showing a multi - peak state.

[0005] The main reasons for the difficulty in preventing and controlling red mites in the prior art are as follows:

[0006] 1. Difficult to control in four generations living together: When spider mites break out, there are often four forms of spider mites on one leaf. Most single acaricides on the market cannot kill both eggs and mites, so the control effect is greatly reduced.

[0007] 2. Diverse reproduction methods and rapid reproduction speed. It often takes only 5 - 7 days to reproduce a generation. Especially under parthenogenesis, spider mites are very likely to develop drug resistance after spraying, increasing the difficulty of prevention and control.

[0008] 3. Stimulation by copper preparations: When preventing and controlling citrus canker, copper preparations are added. Copper preparations can promote egg - laying in female mites, promote the growth of young mites, and can kill the natural enemies of spider mites, promoting the outbreak of spider mites.

[0009] 4. Strong drug resistance due to frequent use of drugs.

[0010] 5. Protection by web - spinning: After spider mites break out, once they spin webs, the webs can play a role in preventing wind, rain, and drugs, making it difficult for the medicament to penetrate.

[0011] 6. Difficult to kill all: Spider mites have few natural enemies and are small in size. After the leaves grow lush, it is very difficult to spray thoroughly, and it is easy to miss spraying or under - spray, allowing spider mites to reproduce quickly.

[0012] The mixture of cyflumetofen and spirodiclofen provided by the applicant, when mixed and used in an appropriate proportion, can synergistically act on pests in many aspects, has good effects on mite pests in all periods, has strong penetration power of the liquid medicine, has good systemic and adhesive properties, can quickly kill mites, and has a long - lasting effect of more than 30 days. One application can effectively control the damage of pests. At the same time, the dosage is reduced, which also alleviates the pressure of chemical pesticides on the environment and can delay the generation of pest drug resistance. Summary of the Invention

[0013] The purpose of the present invention is to provide an application of a high - molecular nano - preparation containing cyflumetofen for preventing and controlling citrus red spider mites, which can effectively prevent and control citrus red spider mites, has both quick - acting and long - lasting effects, is safe for natural enemies and the environment.

[0014] The technical solution of the present invention is:

[0015] A high - molecular nano - preparation containing cyflumetofen, characterized in that: the nano - preparation is made by mixing cyflumetofen, spirodiclofen, a high - molecular nano - carrier, an auxiliary agent, and water to form a suspension. The weight ratio of cyflumetofen to spirodiclofen is 1:1 - 1:2, and the preferred weight ratio is 1:1.

[0016] Furthermore, the content of the effective active ingredient in the nano - preparation is 100 - 500 g / L, and the preferred content of the effective active ingredient is 400 g / L.

[0017] Further, the polymer nano-carrier is selected from one of mesoporous silica and nano-polymer capsules.

[0018] Further, the auxiliaries are selected from one or more of dispersants, wetting agents, antifreeze agents, preservatives, defoaming agents, thickeners, and water.

[0019] Further, the dosage of the active ingredient of the nano-formulation for controlling citrus red spider mites is 50 - 200 mg / kg.

[0020] When the nano-formulation is made into a suspension, it includes the following components and contents in percentage: cyflumetofen 50 - 250 g / L, spirodiclofen 50 - 350 g / L, polymer nano-carrier 0.1 - 30 g / L, dispersant 10 - 100 g / L, wetting agent 10 - 100 g / L, defoaming agent 1 - 20 g / L, thickener 2 - 30 g / L, antifreeze agent 0 - 100 g / L, preservative 0 - 20 g / L, and the balance is water.

[0021] Compared with the prior art, the composition of the present invention has the following beneficial effects: (1) Compared with single agents, the composition has obvious synergistic effects on citrus red spider mites in all stages, significantly improving the control effect; (2) It has strong systemic and penetrative properties; (3) It has both quick and long-lasting effects; (4) It delays the resistance of harmful mites. Detailed implementation methods

[0022] The present invention will be further described below in conjunction with examples, but the present invention is not limited thereto.

[0023] Application Example 1

[0024] Example 1 400 g / L cyflumetofen·spirodiclofen suspension

[0025] 200 g of cyflumetofen technical, 200 g of spirodiclofen technical, 30 g of mesoporous silica, 10 g of EO-PO block copolymer, 25 g of polycarboxylate, 20 g of dodecyl polyoxyethylene ether phosphate, 50 g of glycerol, 3 g of xanthan gum, 2 g of magnesium silicate aluminate, 2 g of silicone defoaming agent, 3 g of isothiazolinone, and water is added to 1000 g to obtain 400 g / L cyflumetofen·spirodiclofen suspension.

[0026] Example 2 400 g / L cyflumetofen·spirodiclofen suspension

[0027] 200 g of cyflumetofen technical, 200 g of spirodiclofen technical, 5 g of styrene, 5 g of divinylbenzene, 10 g of sodium dodecyl sulfate, 50 g of rosin-based vegetable oil, 25 g of fatty alcohol polyoxyethylene ether, 40 g of trisiloxane polyoxyethylene ether, 40 g of propylene glycol, 5 g of polyvinyl alcohol, 2 g of C8-10 fatty alcohols, 3 g of sodium benzoate, 1 g of citric acid, add water to 1000 g to obtain 400 g / L cyflumetofen·spirodiclofen suspension concentrate.

[0028] Example 3: 400 g / L cyflumetofen·spirodiclofen suspension concentrate

[0029] 200 g of cyflumetofen technical, 200 g of spirodiclofen technical, 5 g of styrene, 8 g of divinylbenzene, 5 g of sodium dodecyl sulfate, 40 g of alkyl polyglycoside, 30 g of alkylphenol polyoxyethylene ether formaldehyde condensate sulfate, 20 g of sodium dodecyl sulfate, 10 g of phenethylphenol polyoxyethylene ether phosphate, 30 g of urea, 5 g of xanthan gum, 2 g of C10-20 saturated fatty acid compounds, 0.7 g of glacial acetic acid, 2 g of sorbic acid, add water to 1000 g to obtain 400 g / L cyflumetofen·spirodiclofen suspension concentrate.

[0030] Example 4: 300 g / L cyflumetofen·spirodiclofen suspension concentrate

[0031] 100 g of cyflumetofen technical, 200 g of spirodiclofen technical, 25 g of mesoporous silica, 20 g of alkylnaphthalenesulfonate formaldehyde polymer, 5 g of naphthalene sulfonic acid formaldehyde condensate sodium salt block copolymer, 20 g of fatty alcohol polyoxyethylene ether sulfonate, 40 g of glycerol, 2 g of white carbon black, 10 g of silicone defoamer, 0.4 g of citric acid, add water to 1000 g to obtain 300 g / L cyflumetofen·spirodiclofen suspension concentrate.

[0032] Example 5: 200 g / L cyflumetofen·spirodiclofen suspension concentrate

[0033] 100 g of cyflumetofen technical, 100 g of spirodiclofen technical, 30 g of rosin-based vegetable oil, 20 g of methylene bisnaphthalenesulfonate, 20 g of sodium dodecylbenzenesulfonate, 50 g of propylene glycol, 6 g of guar gum, 0.5 g of C10-20 saturated fatty acid compounds, 5 g of sodium benzoate, add water to 1000 g to obtain 200 g / L cyflumetofen·spirodiclofen suspension concentrate.

[0034] Example 6: 100 g / L cyflumetofen·spirodiclofen suspension concentrate

[0035] 50 g of cyflumetofen technical, 50 g of spirodiclofen technical, 30 g of mesoporous silica, 10 g of styrenephenol polyoxyethylene ether phosphate, 10 g of alkylphenol formaldehyde resin polyoxyethylene ether, 40 g of ethylene glycol, 0.5 g of magnesium aluminum silicate, 10 g of silicone defoamer, 0.3 g of potassium dihydrogen phosphate, and water was added to 1000 g to prepare 100 g / L cyflumetofen·spirodiclofen suspension concentrate.

[0036] Example of implementation and application II:

[0037] Indoor joint toxicity determination experiment of cyflumetofen, spirodiclofen and their mixtures against Panonychus citri 1 Test purpose

[0038] To determine the toxicity of cyflumetofen and spirodiclofen and their different mixed combinations against Panonychus citri indoors, evaluate the synergistic effect, clarify their compatibility, and provide a scientific basis for the research and development of the mixture of cyflumetofen and spirodiclofen.

[0039] 2 Experimental conditions

[0040] 2.1 Test target

[0041] Panonychus citri McGregor, which was collected from citrus leaves with mites in the field and cultured indoors for the test.

[0042] 2. Cultivation conditions

[0043] The cultivation conditions of the test target and the target after the test were temperature (25±1)°C, relative humidity 60% - 80%, and light cycle L:D=(16:8)h.

[0044] 3 Test design

[0045] 3.1 Test agents

[0046] 98% cyflumetofen technical; 98% spirodiclofen technical.

[0047] 3.2 Agent preparation

[0048] Weigh 0.0102 g of 98% cyflumetofen technical, dissolve it with 0.5 mL of DMF, add 0.2 mL of Tween80 emulsifier, stir evenly, add clear water to 100 mL to prepare a stock solution of 100 mg / L, then take 40 mL from the 100 mg / L solution and add it to 60 mL of water containing 0.1% Tween80 emulsifier to prepare a test solution of 40 mg / L, and then dilute it with water containing 0.1% Tween80 emulsifier at a 2-fold ratio to 20, 10, 5, 2.5 and 1.25 mg / L, a total of 6 concentrations for the test.

[0049] Weigh 0.0102 g of spirodiclofen 98% technical material. After dissolving it in 0.5 mL of DMF, add 0.2 mL of Tween 80 emulsifier, stir well, add clear water to 100 mL to prepare a stock solution of 100 mg / L. Then take 40 mL from the 100 mg / L solution and add it to 60 mL of water containing 0.1% Tween 80 emulsifier to prepare a test solution of 40 mg / L. Then dilute it with water containing 0.1% Tween 80 emulsifier at a 2-fold ratio to 20, 10, 5, 2.5, and 1.25 mg / L, and conduct tests at a total of 6 concentrations.

[0050] According to the ratios of cyflumetofen to spirodiclofen of 3:1, 2:1, 1:1, 1:2, and 1:3, respectively measure 15, 13.33, 10, 6.67, and 5 mL of the cyflumetofen stock solution, and then correspondingly measure 5, 6.67, 10, 13.33, and 15 mL of the spirodiclofen stock solution. Mix the two, make up the water with emulsifier to 100 mL, and prepare test solutions of 20 mg / L. Then dilute them with water containing 0.1% Tween 80 emulsifier at a 2-fold ratio to 6 concentrations for testing.

[0051] Add 99.5 mL of water containing 0.1% Tween 80 emulsifier to a beaker containing 0.5 mL of DMF as a blank control.

[0052] 4 Test methods

[0053] Refer to the method of the indoor bioassay test guidelines for pesticides NY / T1154.13 - 2008 and adopt the leaf spraying method. Wash and dry the smooth citrus leaves of the same size, place the leaves face up on a wet sponge, surround the leaves with a moistened cotton strip to prevent the test mites from escaping, put the wet sponge into a petri dish with a diameter of 9 cm, add water to the petri dish, and the water level is slightly lower than the height of the sponge. Inoculate the adult mites reared indoors onto the leaves, about 30 per leaf. Place the petri dish on the bottom plate of the Potter spray tower for spraying, the spraying amount is 1 ml, take it out after the liquid medicine has settled for 1 min, and transfer it to the breeding conditions for breeding. Each treatment has 4 replicates and a blank control is set.

[0054] 5 Data investigation and statistical analysis

[0055] 5.1 Investigation time and method

[0056] After 48 h, check the death situation of the test insects under a dissecting microscope and record it. The judgment standard for the death of the test insects is: count as dead if there is no response when gently touching the test insects with forceps.

[0057] 5.2 Data statistical analysis

[0058] Referring to the Guidelines for Pesticide Bioassay in the Laboratory NY / T 1154.7 - 2006, the co - toxicity coefficient (CTC) of each mixture combination was calculated using the co - toxicity coefficient method of Sun & Johnson (1960). Generally, a co - toxicity coefficient ≥ 120 indicates a synergistic effect, ≤ 80 indicates an antagonistic effect, and between 80 - 120 indicates an additive effect. The formula for calculating the co - toxicity coefficient is as follows:

[0059]

[0060] The theoretical toxicity index (TTI) of the mixture = the toxicity index of agent A × the percentage of agent A in the mixture (%) + the toxicity index of agent B × the percentage of agent B in the mixture (%)

[0061]

[0062] 6 Experimental results

[0063] The toxicity determination results of cyflumetofen, spirodiclofen and their mixtures in the ratios of 3:1, 2:1, 1:1, 1:2 and 1:3 against Panonychus citri are shown in Table 1. It can be seen from the table that when cyflumetofen and spirodiclofen are mixed in the above 5 ratios, they all show a synergistic effect. Their LC50 values are 3.09, 3.22, 2.40, 2.48 and 2.60 mg / L respectively, and the co - toxicity coefficients are 134.09, 124.32, 156.22, 142.16 and 131.68 respectively. Among them, the synergistic effect of the 1:1 ratio is the most significant.

[0064] Table 1 Toxicity determination results of the mixture of cyflumetofen and spirodiclofen against Panonychus citri

[0065]

[0066] The results of this indoor bioassay show that when cyflumetofen and spirodiclofen are mixed in the ratios of 3:1, 2:1, 1:1, 1:2 and 1:3, they all show a synergistic effect, and the synergistic effect of the 1:1 ratio is the most obvious.

[0067] Application Example Three: Field efficacy test of the control of Panonychus citri in Examples 1 - 3 1 Test purpose

[0068] A field efficacy test of 400 g / L cyflumetofen·spirodiclofen suspension concentrate against Panonychus citri was carried out to provide a basis for determining the efficacy of the pesticide, the field application dose, the residual efficacy period, the effects of the pesticide on crops and non - target beneficial organisms, and safe and reasonable application techniques.

[0069] 2 Test basis

[0070] "Rules for Field Efficacy Trials of Pesticides (Part 1): Acaricides against Panonychus citri" (GB / T 17980.11 - 2000) and the operating procedures for field trials of Panonychus citri by Hunan Aimiao Testing Co., Ltd. (AM - GLP - SOP - 09 - 009).

[0071] 3 Experimental Site

[0072] This experiment was arranged in Changsha County, Changsha City, Hunan Province.

[0073] 4 Selection of Test Objects, Crops and Varieties

[0074] Test Object: Red Spider Mite on Citrus Trees (Panonychus citri (Mc Gregor));

[0075] Test Crop: Citrus Trees, the variety is Wogan. The age of the test citrus trees is 4 years, the density is about 80 trees per mu, and the growth is relatively uniform.

[0076] 5 Experimental Design and Arrangement

[0077] 5.1 Dosage and Numbering of Medicaments

[0078] Table 2 Experimental Design of Test Medicaments

[0079]

[0080] 5.2 Application Time and Frequency

[0081] The medicament was applied once in April 2022.

[0082] 5.3 Application Volume

[0083] The liquid volume sprayed per plant is 0.8 liters, and the liquid volume sprayed per mu is about 64 liters.

[0084] 5.4 Investigation Time and Frequency

[0085] The mite population density was investigated before applying the medicament, and the number of live mites was investigated once each on the 1st, 3rd, 7th, 15th, and 30th days after application.

[0086] For each tree in each plot, the tender shoots were marked at five positions: east, west, south, north, and middle. Five leaves were investigated on each tender shoot, and a total of 50 leaves were investigated for the number of live mites. The leaves were examined with a hand - held magnifying glass, the number of live mites was recorded, and the mite reduction rate and control effect were calculated.

[0087] 5.5 Calculation Method of Efficacy

[0088]

[0089]

[0090] 6 Experimental Results

[0091] Table 3 Field control efficacy of Examples 1-3 and control single agents against citrus red mites

[0092]

[0093] In summary, at the tested dosages, the test agent, 400 g / L cyflumetofen·spiromesifen suspension concentrate, had good control efficacy against citrus red mites. Three days after treatment, the control efficacy of each treatment with the test agent was higher than 82%, showing good quick-acting property; 15 and 30 days after treatment, the control efficacy of each dosage of the test agent was higher than 90%, showing obvious long-lasting property, and the control effect was significantly better than that of the two single-agent controls.

[0094] The above content is a further detailed description of the present invention in combination with specific preferred embodiments, and 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, and all should be regarded as belonging to the protection scope of the present invention.

Claims

1. A polymer nano - preparation containing cyflumetofen, characterized in that: The nano - preparation is prepared by mixing cyflumetofen, spirodiclofen, a high - molecular - weight nano - carrier, an auxiliary agent, and water to form a suspension. The weight ratio of cyflumetofen to spirodiclofen is 1:1 to 1:

2.

2. The nano - preparation according to claim 1, characterized in that: The weight ratio of cyflumetofen to spirodiclofen is 1:

1.

3. The nano - preparation according to claim 1 or 2, characterized in that: The total content of cyflumetofen and spirodiclofen is 100 - 500 g / L.

4. The nano - preparation according to claim 3, characterized in that: The total content of cyflumetofen and spirodiclofen is 400 g / L.

5. The nano - preparation according to claim 1, characterized in that: The said high - molecular - weight nano - carrier is selected from one of mesoporous silica and nano - polymeric capsules.

6. The nano - preparation according to claim 1, characterized in that: The said auxiliary agent is selected from one or more of a dispersant, a wetting agent, an antifreeze, a preservative, an antifoaming agent, a thickening agent, and water.

7. The nano - preparation according to claim 1, characterized in that: Application of the nano - preparation in controlling Panonychus citri McGregor on citrus trees.

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