CN101606521B - Synergic acaricide - Google Patents

Abstract

The invention provides a synergistic acaricide, which contains: an effective amount of spirodiclofen; an effective amount of a solvent capable of dissolving the spirodiclofen, the solvent at least including d-limonene; and an effective amount of an emulsifier. The synergistic acaricide of the present invention utilizes the strong dissolving properties of d-limonene, uses d-limonene as a solvent for spirodiclofen, and replaces toxic and environmentally friendly aromatic hydrocarbon solvents, reducing the impact of acaricides on pollution of the environment. In addition, d-limonene is used as a solvent for spirodiclofen, which can dissolve and destroy the waxy layer on the surface of the mites, making it easier for the acaricide to enter the interior of the mites, increasing the quick-acting properties of spirodiclofen , thereby improving the acaricidal effect. Moreover, the synergistic acaricide of the present invention can be processed into dosage forms such as emulsifiable concentrate, microemulsion, water emulsion, etc. as required.

Description

A synergistic acaricide

technical field

The invention belongs to the field of pesticides, in particular to a synergistic acaricide.

Background technique

Spirodiclofen is a tetronic acid acaricide (tetronic acid), chemical name: 3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4,5]-decane- 3-en-4-yl-2,2-dimethylbutyl ester; molecular formula: C ₂₁ H ₂₄ C ₁₂ O ₄ ; relative molecular weight: 411.32. Spirodiclofen has the following characteristics:

1. The mechanism of action is unique: it mainly inhibits the fat synthesis in harmful mites. It has no cross-resistance with existing acaricides, and is suitable for the prevention and treatment of harmful mites that are resistant to existing acaricides.

2. Wide spectrum of killing acarids and strong adaptability. Spirodifen has a good control effect on spider mite, yellow spider, rust lice, tea yellow mite, cinnabarinus and two-spotted spider mite, etc. Control of mite infestation of family crops. In addition, spirodiclofen also has a good control effect on pests such as pear psyllid, elm oyster scale and leafhopper.

3. Egg and young killing: the egg killing effect is particularly excellent, and it also has a good contact killing effect on young nymphs. Although it cannot kill female adult mites quickly, it has a good sterilization effect on female adult mites. 96% of the eggs laid by the female adult mites could not hatch and died in the late embryonic stage after being exposed to the pesticide.

4. Long duration: spirodiclofen has a long duration of effect, and 5000 times dilution can be used in production to control the whole claw of citrus for 40-50 days. Spirodiclofen is resistant to rain erosion after spraying on crop leaves, and the normal performance of the drug effect will not be affected by moderate rain after 2 hours of spraying.

5. Low toxicity, low residue and good safety. It is very safe to crops under different temperature conditions, safe to humans, animals and crops, low-toxic, and suitable for pollution-free production.

6. No mutual resistance: It can be mixed and used with most pesticides (except strong basic pesticides and copper preparations). It can not only improve the quick-acting property of spirodiclofen, but also benefit the resistance control of mite infestation.

The solubility of spirodiclofen in water is very small (0.05g/1000ml, 20°C), so when it is processed into pesticide emulsifiable concentrate, emulsion in water, and microemulsion, it must first be dissolved in a solvent. Therefore, solvents are essential auxiliaries in the production of these dosage forms. At present, spirodiclofen is mainly processed into emulsifiable concentrates. The production of emulsifiable concentrates requires a large amount of aromatic solvents, causing serious environmental pollution. New environmentally friendly solvents are being sought to replace aromatic solvents at home and abroad. Moreover, although the current spirodiclofen preparations have a long duration of action (up to 60 days), their quick-acting properties are relatively poor.

d-limonene (d-limonene), also known as D-limonene, limonene, limonene or limonene, is a monocyclic citrus terpene that exists most widely in natural plant essential oils, mostly from orange peels with a high content Extracted from middle-aged food, it is a food additive with strong volatility and permeability. It is used as a household sanitation insecticide and limonene insecticide in tea gardens in the United States. It can destroy the waxy layer on the body surface of pests and cause body fluids to lose water and die .

At present, there is no report on the mixed use of spirodiclofen and d-limonene.

Contents of the invention

The purpose of the embodiments of the present invention is to provide a synergistic acaricide, aiming to solve the serious environmental pollution caused by the production of the existing spirodiclofen pesticide using a large amount of aromatic solvents, and the problems of poor quick-acting properties.

The embodiment of the present invention is achieved in this way, a synergistic acaricide, which contains: an effective amount of spirodiclofen; an effective amount of a solvent capable of dissolving spirodiclofen, the solvent at least including d-limonene; and an effective amount emulsifier.

Compared with the prior art, the synergistic acaricide of the embodiment of the present invention utilizes the strong solubility characteristics of d-limonene, and uses d-limonene as a solvent for spirodiclofen instead of highly toxic and environmentally friendly Aromatic hydrocarbon solvents can reduce the pollution of acaricides to the environment.

In addition, d-limonene is used as a solvent for spirodiclofen, which can dissolve and destroy the waxy layer on the surface of the mites, making it easier for the acaricide to enter the interior of the mites, increasing the quick-acting properties of spirodiclofen , thereby improving the acaricidal effect. Therefore, using d-limonene compound acaricide to control mites has obvious synergistic effect.

Moreover, after dissolving spirodiclofen with d-limonene, the acaricide can be processed into formulations such as emulsifiable concentrate, microemulsion, and water emulsion as required.

Detailed ways

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

The embodiment of the present invention provides an environmentally friendly and quick-acting synergistic acaricide compared with the prior art, specifically, it contains:

An effective amount of spirodiclofen;

An effective amount of a solvent capable of dissolving spirofen, said solvent comprising at least d-limonene; and

An effective amount of emulsifier.

The emulsifier in the embodiment of the present invention is not particularly limited, and it is an emulsifier commonly used in the field, for example, one or a mixture of alkylbenzene sulfonates, phosphoric acid esters, and polyethers can be selected.

The solvent of the embodiment of the present invention also includes an environmentally friendly organic solvent capable of dissolving spirodiclofen in addition to d-limonene, for example, it can be selected from ethanol, isopropanol, glycerol, pyrrolidone, dibasic acid ester, vegetable oil and vegetable oil One or more mixtures of esters.

The synergistic acaricide of the embodiment of the present invention can be formulated into various pesticide formulations, such as emulsifiable concentrate, microemulsion or water emulsion, by adding various auxiliary agents commonly used in the field as required. If the above-mentioned synergistic acaricide is formulated into an emulsifiable concentrate, the solvent can be only d-limonene, or a mixture of d-limonene and other organic solvents capable of dissolving spirodiclofen; if it is formulated into a microemulsion or an emulsion in water, the The synergistic acaricide also includes the amount of water needed to formulate it into a microemulsion or water emulsion. When it is formulated into a microemulsion, a co-surfactant commonly used in the art, such as one or a mixture of ethanol and isopropanol, can also be added to expand the temperature range. When formulated into water emulsion, antifreeze agents commonly used in this field, such as glycerol, isopropanol, etc., can also be added.

More specifically, the synergistic acaricide of the embodiment of the present invention is formulated into an emulsifiable concentrate, which contains 2-25% of spirodiclofen, 3-50% of d-limonene, emulsifier 3-25%, and 0-92% other organic solvents that can dissolve spirodiclofen except d-limonene. Further, wherein the emulsifying dose is preferably 5 to 25% (weight), and other organic solvents capable of dissolving spirodiclofen except d-limonene are preferably 0 to 90% (weight), and the organic solvent can be selected from ethanol, One or a mixture of isopropanol, glycerol, pyrrolidone, dibasic esters, vegetable oils and vegetable oil esters. The emulsifier is a mixture of calcium alkylbenzene sulfonate, styrene phenol polyoxyethylene ether, alkylphenol formaldehyde resin polyoxyethylene ether, or other emulsifier monomers or compound emulsifiers well known to those skilled in the art. Yes, in order to achieve the best emulsifying performance, the proportion of emulsifier should be properly adjusted within the above range. The preparation method of the emulsifiable concentrate is: first add d-limonene in the preparation kettle, then add spirodiclofen, stir for about 20 minutes to dissolve completely, then add emulsifier and make up the solvent, continue to stir evenly for about 15 minutes to complete the spirodiclofen of the present invention Cream products.

When the synergistic acaricide of the embodiment of the present invention is formulated into a microemulsion or water emulsion, based on the total weight of the synergistic acaricide, it contains 2-25% of spirodiclofen, 3-50% of d-limonene, emulsifier 3-25%, 0-92% water.

More specifically, when producing microemulsions, it is preferred to use 5-20% of spirodiclofen, 10-30% of d-limonene, 5-25% of emulsifier, 0-10% co-surfactant, 15% by weight. ~80% water for preparation. The emulsifier is a mixture of calcium alkylbenzene sulfonate, styrene phenol polyoxyethylene ether phosphate and alkylphenol formaldehyde resin polyoxyethylene ether, or other emulsifier monomers or compound emulsifiers well known to those skilled in the industry can be. By adding co-surfactant (such as ethanol, isopropanol, etc.) microemulsion transparent temperature zone scope (that is to add or not add co-surfactant also can prepare complete microemulsion; when not adding co-surfactant, formed The transparent temperature range of microemulsion is 10-30°C. When co-surfactant is added, the transparent temperature range of microemulsion formed is -5-60°C, which can be stored at room temperature throughout the year in most places in China). The preparation method of the microemulsion is: first add d-limonene in the preparation kettle, then add spirodiclofen, add or not add ethanol or isopropanol, stir and dissolve completely for about 20 minutes, then add emulsifier and continue to stir evenly for about 10 minutes minutes, continue to stir for about 15 minutes to obtain a homogeneous transparent liquid after making up with water, and complete the spirodiclofen microemulsion product of the present invention.

More specifically, when producing water emulsion, it is preferred to use spirodiclofen 5-20%, d-limonene 10-30%, emulsifier 5-25%, antifreeze agent 0-10%, water 15% by weight. ~80%. The emulsifier can be styrene phenol polyoxyethylene ether phosphate, or other emulsifier monomers or compound emulsifiers well known to those skilled in the industry. In order to achieve uniform emulsification and dispersion of the water emulsion, the ratio of the emulsifier should be within the above range Make appropriate adjustments within. The preparation method of water emulsion is: first add d-limonene in the preparation kettle, then add spirodiclofen, stir and dissolve completely for about 20 minutes, then add emulsifier and continue stirring for about 10 minutes to complete the preparation of the oil phase. Add water to the mixture, slowly add the oil phase under stirring, so that the oil phase is dispersed in the water phase to form a milky white water emulsion. For antifreeze needs, you can also add the above-mentioned antifreeze agent (such as glycerin), and stir to complete the spiral mite of the present invention. Ester water emulsion products.

Example 1

According to the formula of Example 1 in Table 1, first add d-limonene to the preparation kettle, then add spirodiclofen, stir for about 20 minutes to dissolve completely, add emulsifier and make up the solvent, continue to stir evenly for about 15 minutes to prepare 5% For the spirodiclofen emulsifiable concentrate preparation, the content of each component in the formula is calculated by mass percentage. The prepared preparations were sealed in 10ml ampoules, and 2 sealed bottles of each agent were stored in a refrigerator at 0°C and an oven at 54°C for 14 days, and the content was analyzed at the end of the day to obtain the decomposition rate. The results are shown in Table 1.

Comparative example 1

Use xylene as solvent, formulate 5% spirodiclofen emulsifiable concentrate by the method of Example 1 according to the formula of comparative example 1 in Table 1, seal the prepared preparation in a 10ml ampoule, and seal 2 bottles of each medicament respectively in Store in a refrigerator at 0°C and an oven at 54°C for 14 days, and analyze the content at maturity to obtain the decomposition rate. See Table 1 for the results.

Example 2

According to the formula of Example 2 in Table 1, first add d-limonene in the preparation kettle, then add spirodiclofen, stir and dissolve completely for about 20 minutes, then add emulsifier and continue stirring for about 10 minutes, and continue stirring for about 10 minutes after making up with water. A homogeneous and transparent liquid was obtained in 15 minutes, which was prepared into 5% spirodiclofen microemulsion. The prepared preparations were sealed in 10ml ampoules, and 2 sealed bottles of each agent were stored in a refrigerator at 0°C and an oven at 54°C for 14 days, and the content was analyzed at the end of the day to obtain the decomposition rate. The results are shown in Table 1.

Comparative example 2

Use xylene as solvent, formulate 5% spirodiclofen microemulsion by the method of Example 2 according to the formula of comparative example 2 in table 1, seal the prepared preparation in a 10ml ampoule, and seal 2 bottles of each medicament respectively Store in a refrigerator at 0°C and an oven at 54°C for 14 days, and analyze the content at the expiration date to obtain the decomposition rate. See Table 1 for the results.

Example 3

According to the formula of Example 3 in Table 1, first add d-limonene in the preparation kettle, then add spirodiclofen, stir and dissolve completely for about 20 minutes, then add emulsifier and continue to stir evenly for about 10 minutes to complete the preparation of the oil phase. Add water into the mixing tank, and slowly add the oil phase under stirring, so that the oil phase is dispersed in the water phase to form a milky white water emulsion, add antifreeze and stir evenly to prepare a 5% spirodiclofen water emulsion. The prepared preparations were sealed in 10ml ampoules, and 2 sealed bottles of each agent were stored in a refrigerator at 0°C and an oven at 54°C for 14 days, and the content was analyzed at the end of the day to obtain the decomposition rate. The results are shown in Table 1.

Comparative example 3

Use xylene as a solvent, formulate 5% spirodiclofen water emulsion according to the formula of comparative example 3 in table 1 with the method of embodiment 3, seal the prepared preparation in a 10ml ampoule, and seal 2 bottles of each medicament respectively Store in a refrigerator at 0°C and an oven at 54°C for 14 days, and analyze the content at the expiration date to obtain the decomposition rate. See Table 1 for the results.

Table 1 embodiment and comparative example specific consumption

It can be seen from Table 1 that the synergistic acaricide of the embodiment of the present invention has good stability.

Example 4

According to the method of Example 1, the 25% spirodiclofen emulsifiable concentrate preparation was prepared according to the following formula.

Spirodiclofen 25%, d-limonene 50%, calcium alkylbenzene sulfonate 10%, alkylphenol formaldehyde resin polyoxyethylene ether 10%, EO/PO block polyether 5%.

Example 5

According to the method of Example 1, the 20% spirodiclofen emulsifiable concentrate preparation was prepared according to the following formula.

Spirodifen 20%, d-limonene 15%, dimethyl succinate 30%, ethanol 10%, calcium alkylbenzene sulfonate 8%, alkylphenol formaldehyde resin polyoxyethylene ether 10%, EO/PO Block polyether 7%.

Example 6

According to the method of Example 2, the 20% spirodiclofen microemulsion was prepared according to the following formula.

Spirodiclofen 20%, d-limonene 20%, ethanol 10%, calcium alkylbenzenesulfonate 11%, alkylphenol formaldehyde resin polyoxyethylene ether 9%, EO/PO block polyether 8%, water supplement 100%.

Example 7

According to the method of Example 2, the 15% spirodiclofen microemulsion was prepared according to the following formula.

Spirodiclofen 15%, d-limonene 20%, isopropanol 3%, alkylphenol formaldehyde resin polyoxyethylene ether 5%, EO/PO block polyether phosphate 18%, water supplement 100%.

Example 8

According to the method of Example 2, the 2% spirodiclofen microemulsion was prepared according to the following formula.

Spirodiclofen 2%, d-limonene 10%, isopropanol 3%, alkylphenol formaldehyde resin polyoxyethylene ether 2%, EO/PO block polyether phosphate 8%, water supplement 100%.

Example 9

According to the method of Example 3, the 25% spirodiclofen emulsion in water was prepared according to the following formula.

Spirodiclofen 25%, d-limonene 30%, EO/PO block polyether phosphate emulsifier 8%, glycerol 5%, water supplement 100%.

Example 10

According to the method of Example 3, the 2% spirodiclofen emulsion in water was prepared according to the following formula.

Spirodiclofen 2%, d-limonene 20%, EO/PO block polyether phosphate emulsifier 5%, water supplement 100%.

Toxicity test

Each agent in Examples 1-3 and Comparative Example 1-3 was diluted with tap water to a specific concentration, and the toxicity of the agents to adults of Tetranychus cinnabarinus was tested by the leaf dipping method. Immerse the whole tomato leaves in the prepared medicinal solution for 5 seconds, remove and quickly absorb the medicinal solution of the leaves with filter paper, pick 20 adults of tomato cinnabarinus cinnabarinus with a small brush and place them on the tomato leaves that have been soaked and dried Put it into a 9cm petri dish that is lined with filter paper (a few drops of water are dripped on the filter paper to moisten it), one tomato leaf in each petri dish, and cover the petri dish. Each treatment was repeated 3 times, and the results observed under a microscope after 72 hours are shown in Table 2. Death standard: under the microscope, the worm body does not move as the standard.

Table 2: Comparative test results of different solvents in different formulations of spirodiclofen

It can be seen from Table 2 that the introduction of d-limonene as a synergist in the spirodiclofen preparation has greatly improved the quick-acting acaricidal properties of the spirodiclofen preparation, and has obvious synergistic effect. Therefore, the amount of spirodiclofen can be reduced to further reduce production and use costs. In addition, the d-limonene in the synergistic acaricide of the embodiment of the present invention can dissolve spirodiclofen, so the aromatic organic solvent can be completely used, and all d-limonene is used as the solvent or only a small amount of ethanol or other environmentally friendly solvents are added. Solvent, green and environmental protection, the solvent is basically non-toxic and pollution-free.

The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. within range.

Claims (2)

1. A synergistic acaricide, the dosage form is an emulsifiable concentrate, in terms of the synergistic acaricide gross weight, which contains:

2. A synergistic acaricide, the dosage form is a microemulsion, in terms of synergistic acaricide gross weight, which contains: