A kind of insecticide containing deltamethrin with stable components and preparation method thereof

Abstract

The present invention relates to the technical field of insecticides containing deltamethrin, and specifically discloses an insecticide containing deltamethrin with stable components and a preparation method thereof, wherein the deltamethrin insecticide comprises deltamethrin, a solvent capable of dissolving the deltamethrin, an emulsifier, an inhibitor capable of inhibiting the isomer conversion of the deltamethrin, and an acidity regulator, wherein the inhibitor is an alkyl aromatic sulfonate. The insecticide containing deltamethrin provided by the present invention has the characteristics of high insecticidal activity, broad insecticidal spectrum, good stability, rapid drug effect, safety to crops, etc., in particular, deltamethrin has good stability, low isomerization degree, and does not affect the stability and insecticidal effect of its highest active isomer after long-term storage or obvious temperature changes, and has a longer shelf life.

Description

Technical Field

[0001] The invention relates to the technical field of insecticides containing deltamethrin, and in particular to an insecticide containing deltamethrin with stable components and a preparation method thereof. Background Art

[0002] Deltamethrin is an organic compound with the English name Deltamethrin. Its chemical formula is C 22 H 19 Br2NO3, molecular weight is 505.2, melting point is 98℃, boiling point is 300℃, density is 1.595g / cm 3 , the flash point is 277.8℃, the appearance is white to off-white crystalline powder, and its molecular structure is as follows: The chemical name is: (S)-α-cyano-3-phenoxybenzyl-(1R,3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate.

[0003] Deltamethrin is a pyrethroid insecticide with high insecticidal activity, broad insecticidal spectrum, rapid efficacy and safety for crops. It mainly acts on contact and stomach poison, and has certain repellent and antifeedant effects, without systemic and fumigation effects. It can control cotton bollworm, cotton bollworm, leaf springtail, cotton aphid, thrips, cabbage worm, diamondback moth, Spodoptera litura, tea geometrid, and rice stem borer, rice thrips, rice leaf roller, soybean borer, citrus leaf miner, pear borer, peach borer, etc.

[0004] Although insecticides containing cypermethrin have the characteristics of high insecticidal activity, broad insecticidal spectrum, rapid efficacy and safety to crops, there are 3 asymmetric carbon atoms in the cypermethrin molecule, there are 8 isomers, and only one of them has the highest activity (as shown in the above structural formula).

[0005] The structures and insecticidal activities of these 8 isomers are shown in the following table:

[0006]

[0007]

[0008] Among them, * is the most active deltamethrin structure; ** is the inactive R isomer.

[0009] After being formulated into emulsifiable concentrate, cis-, trans- and optical isomerization of deltamethrin will occur during long-term storage or after application, generating other isomers with reduced efficacy, affecting the overall stability of the formulation and causing a certain degree of fluctuation in insecticidal effect. Especially for the R isomer, when formulated into a preparation, especially into an emulsifiable concentrate, the benzyl central carbon will undergo a racemization reaction, resulting in a loss of half of its activity. Therefore, the proportion and content of the R isomer in the raw material or product has always been an indicator that needs to be controlled. The generation of the R isomer is mainly due to the racemization of benzyl alcohol, and ultimately a basically 1:1 ratio of deltamethrin and R isomer is obtained. Therefore, if this reaction can be hindered, the rate at which deltamethrin generates the R isomer can be greatly suppressed.

[0010] Therefore, a formula with longer storage stability, especially a formula that can inhibit the racemization of the benzyl center of cypermethrin, can greatly avoid the reduction of activity, which is more practical for the production, storage, transportation and use of cypermethrin emulsifiable concentrate. Summary of the invention

[0011] In view of the above-mentioned deficiencies in the prior art, the purpose of the present invention is to provide a stable component-containing insecticide containing deltamethrin and a preparation method thereof, aiming to solve the problem that deltamethrin undergoes isomer conversion after long-term storage or application in existing insecticides containing deltamethrin, which affects the overall stability of the formula and leads to poor insecticide efficacy. The applicant discovered by chance that a very small amount of calcium dodecyl arylsulfonate can effectively inhibit the generation rate of the R isomer in deltamethrin emulsifiable concentrate, and on this basis, a series of experiments were conducted to complete the present invention.

[0012] The technical solution of the present invention is as follows:

[0013] A deltamethrin-containing insecticide with stable components, wherein the deltamethrin insecticide comprises deltamethrin, a solvent capable of dissolving the deltamethrin, an emulsifier, an inhibitor capable of inhibiting the isomer conversion of the deltamethrin, and an acidity regulator, wherein the inhibitor is an alkyl aromatic sulfonate.

[0014] The insecticide containing deltamethrin with stable components comprises, by weight percentage, 1-10% of deltamethrin, 10-90% of solvent, 8-40% of emulsifier, 0.1-1% of inhibitor, and 0.1-1% of acidity regulator.

[0015] Furthermore, the insecticide containing deltamethrin is in the form of an emulsifiable concentrate.

[0016] The component-stabilized insecticide containing deltamethrin, wherein the alkyl aromatic sulfonate is alkylbenzene sulfonate or alkylnaphthalene sulfonate, and more preferably calcium salt or magnesium salt; further, the number of carbon atoms in the alkyl group of the alkylbenzene sulfonate is 6-20; further, the alkylbenzene sulfonate is one or more of calcium hexylbenzene sulfonate, magnesium hexylbenzene sulfonate, calcium octylbenzene sulfonate, magnesium octylbenzene sulfonate, calcium decylbenzene sulfonate, magnesium decylbenzene sulfonate, calcium dodecylbenzene sulfonate, magnesium dodecylbenzene sulfonate, calcium tetradecylbenzene sulfonate, magnesium tetradecylbenzene sulfonate, calcium hexadecylbenzene sulfonate, magnesium hexadecylbenzene sulfonate, calcium octadecylbenzene sulfonate, magnesium octadecylbenzene sulfonate, calcium eicosylbenzene sulfonate, and magnesium eicosylbenzene sulfonate; the alkylnaphthalene sulfonate is one or more of calcium decylnaphthalene sulfonate, magnesium decylnaphthalene sulfonate, calcium dodecylnaphthalene sulfonate, magnesium dodecylnaphthalene sulfonate, calcium tetradecylnaphthalene sulfonate, and magnesium tetradecylnaphthalene sulfonate. Furthermore, the alkylbenzene sulfonate is one or both of calcium dodecylbenzene sulfonate and magnesium dodecylbenzene sulfonate.

[0017] The component-stabilized insecticide containing deltamethrin, wherein the emulsifier comprises an ionic emulsifier and / or a nonionic emulsifier, the ionic emulsifier is an anionic surfactant, preferably the anionic surfactant is one or more of carboxylates, sulfonates, sulfates and phosphates; the nonionic emulsifier is one or more of castor oil polyoxyethylene ether (EL series), hydrogenated castor oil polyoxyethylene ether (HEL series) and polysorbate (Tween series). The HLB value is further preferably 10-17.

[0018] The component-stabilized insecticide containing deltamethrin, wherein the solvent is an aromatic organic solvent or an ester organic solvent; further, the ester solvent also contains an ether bond.

[0019] The described component-stabilized insecticide containing deltamethrin, wherein the described aromatic organic solvent is one or more of toluene, xylene, isopropylbenzene, n-propylbenzene, trimethylolene, aromatic solvent S100, aromatic solvent S150, and aromatic solvent S200; the described ester solvent containing ether bonds at the same time is a polyol in which one of the hydroxyl groups is capped by an ester bond and one of the hydroxyl groups is capped by an ether bond; further, the described ester solvent containing ether bonds in the general formula is a substance in which one of the hydroxyl groups of ethylene glycol, propylene glycol, butylene glycol, and glycerol forms an ester bond with formic acid, acetic acid, or propionic acid, and the other hydroxyl group forms an ether bond with methanol, ethanol, or propanol, and further preferably one or more of ethylene glycol methyl ether formate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether formate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether formate, propylene glycol methyl ether acetate, propylene glycol ethyl ether formate, propylene glycol ethyl ether acetate and butylene glycol methyl ether formate, butylene glycol methyl ether acetate.

[0020] The component-stabilized insecticide containing deltamethrin, wherein the acidity regulator is one or more of citric acid, salicylic acid, benzoic acid, formic acid, acetic acid, propionic acid, n-butyric acid and lactic acid.

[0021] The component-stabilized insecticide containing deltamethrin, wherein when the solvent is an aromatic organic solvent, the acidity regulator is preferably one or both of acetic acid and propionic acid; when the solvent is an ester organic solvent, the acidity regulator is preferably citric acid.

[0022] A method for preparing a deltamethrin-containing insecticide with stable components, wherein each component is formulated in a reasonable manner;

[0023] Further preferably comprises the steps of:

[0024] Mixing a nonionic emulsifier, an ionic emulsifier and an inhibitor to obtain a first mixed solution;

[0025] mixing deltamethrin with a solvent to obtain a second mixed solution;

[0026] adding the first mixed solution to the second mixed solution and stirring evenly to obtain a third mixed solution;

[0027] An acidity regulator is added to the third mixed solution, and the volume is fixed with a solvent, and the mixture is stirred evenly to obtain the insecticide containing deltamethrin with stable components; or the acidity regulator can be added when preparing the second mixed solution.

[0028] Beneficial effects: The present invention adds alkyl aromatic sulfonate as an inhibitor to the deltamethrin emulsifiable concentrate system containing an emulsifier, and the alkyl aromatic sulfonate can effectively inhibit the conversion of deltamethrin isomers, thereby stabilizing the effective ingredients of the deltamethrin insecticide; in particular, calcium dodecylbenzenesulfonate is used as the R isomerization inhibitor, and a significant inhibitory effect can be obtained when the addition amount is less than 1%; and the present invention also adds an acidity regulator to the deltamethrin emulsifiable concentrate system containing a nonionic emulsifier, and deltamethrin can exert a more excellent insecticidal effect in an acidic medium environment. Therefore, the insecticide containing deltamethrin provided by the present invention has the characteristics of high insecticidal activity, broad insecticidal spectrum, good stability, rapid drug effect, safety to crops, etc., in particular, deltamethrin has good stability, low isomerization degree, especially low R isomerization degree, and the stability and insecticidal effect of its highest active isomer are not affected by long-term storage or obvious temperature changes, and has a longer shelf life. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 This is the detection spectrum of the insecticide containing cypermethrin in Example 1 on the 0th day.

[0030] Figure 2This is the detection spectrum of the insecticide containing cypermethrin in Example 1 on the 5th day.

[0031] Figure 3 This is the detection spectrum of the insecticide containing cypermethrin in Example 1 on the 60th day.

[0032] Figure 4 This is the detection spectrum of the insecticide containing cypermethrin in Example 4 on the 0th day.

[0033] Figure 5 This is the detection spectrum of the insecticide containing cypermethrin in Example 4 on the 5th day.

[0034] Figure 6 This is the detection spectrum of the insecticide containing cypermethrin in Example 4 on the 60th day.

[0035] Figure 7 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 1 on the 0th day.

[0036] Figure 8 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 1 on the 5th day.

[0037] Fig. 9 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 1 on the 60th day.

[0038] Fig.10 This is the detection spectrum of the insecticide containing cypermethrin in Example 6 on the 5th day.

[0039] Fig.11 This is the detection spectrum of the insecticide containing cypermethrin in Example 6 on the 60th day.

[0040] Fig.12 This is the detection spectrum of the insecticide containing cypermethrin in Example 10 on the 5th day.

[0041] Fig.13 This is the detection spectrum of the insecticide containing cypermethrin in Example 10 on the 60th day.

[0042] Fig.14 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 2 on Day 0.

[0043] Fig.15 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 2 on the 5th day.

[0044] Fig.16 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 2 on the 60th day.

[0045] Fig.17 This is the detection spectrum of the insecticide containing cypermethrin in Example 11 on the 0th day.

[0046] Fig.18 This is the detection spectrum of the insecticide containing cypermethrin in Example 11 on the 10th day.

[0047] Fig.19 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 3 on the 0th day.

[0048] Fig. 20 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 3 on the 10th day.

[0049] Fig.21 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 4 on the 8th day.

[0050] Fig. 22 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 5 on the 8th day. DETAILED DESCRIPTION

[0051] The present invention provides a stable component-containing insecticide containing deltamethrin and a preparation method thereof. To make the purpose, technical scheme and effect of the present invention clearer and more specific, the present invention is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0052] The chemical structure of deltamethrin is From the chemical formula, it can be seen that there are 3 asymmetric carbon atoms in the deltamethrin molecule and there are 8 isomers. However, the one with the highest insecticidal activity is only the above-mentioned deltamethrin, whose chemical name is: (S)-α-cyano-3-phenoxybenzyl-(1R, 3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate. After the deltamethrin is formulated into an emulsifiable insecticide, it will undergo cis, trans and optical isomerization during long-term storage or after application, generating other isomers with poor efficacy, especially the R isomer, whose chemical name is: (R)-α-cyano-3-phenoxybenzyl-(1R, 3R)-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate, which has no insecticidal activity. Deltamethrin will undergo racemization at the benzyl carbon atom, and in extreme cases can lose nearly half of its insecticidal activity, thus affecting the overall stability of the formula and causing a certain degree of fluctuation in the insecticidal effect.

[0053] Based on this, the present invention provides a deltamethrin-containing insecticide with stable components, wherein the deltamethrin insecticide comprises deltamethrin, a solvent capable of dissolving the deltamethrin, an emulsifier, an inhibitor capable of inhibiting the isomer conversion of the deltamethrin, and an acidity regulator, wherein the inhibitor is an alkyl aromatic sulfonate.

[0054] In the present invention, the deltamethrin is used as the main insecticide component, the main function of the solvent is to dissolve the deltamethrin, and the emulsifier is the main component for preparing the emulsifiable concentrate formulation, and can partially dissolve deltamethrin and / or promote the dissolution of deltamethrin.

[0055] The applicant discovered in an accidental experiment that although the alkyl aromatic sulfonate is an anionic surfactant, it can act as an inhibitor at a very low content and can effectively inhibit the R isomer conversion of deltamethrin in a system containing a nonionic emulsifier and / or an ionic emulsifier, especially in an emulsifiable concentrate system.

[0056] Specifically, because the cyanide in deltamethrin makes the benzyl hydrogen atom active, according to the actual reaction results, nearly half of the R isomer will eventually be generated, so the reaction should be a single-molecule electrophilic reaction SE1, and a positively charged ion will be generated at the benzyl carbon atom, forming a planar configuration at this time. After that, the hydrogen ion can in principle obtain equal opportunities to attack from both sides, which will generate the racemization of the product, and the process of generating carbon anions itself is an energy-requiring process. When a small amount of alkyl aromatic sulfonate exists in molecular form, it may provide some protection for the benzyl carbon, making it difficult for the hydrogen ion to leave there, thereby limiting the production of R isomerization products, thereby improving the stability of deltamethrin.

[0057] This racemization is generally easier to carry out under alkaline conditions, and alkyl aromatic sulfonates such as calcium dodecylbenzene sulfonate and magnesium dodecylbenzene sulfonate can be regarded as Lewis acids, which can inhibit this possible racemization. However, sodium dodecylbenzene sulfonate has an alkaline reaction and therefore does not have this effect, which is also confirmed by experimental results.

[0058] The present invention also adds an acidity regulator to the deltamethrin emulsifiable concentrate system, so that deltamethrin can exert a more excellent insecticidal effect in an acidic medium environment. The acidity regulator has a promoting effect on the stability of deltamethrin, but relying solely on the acidity regulator cannot effectively eliminate the racemization of deltamethrin in the emulsifiable concentrate system, and there will still be some isomerization products. Therefore, relying solely on the acidity regulator cannot completely prevent the racemization of deltamethrin.

[0059] Therefore, the insecticide containing deltamethrin provided by the present invention has the characteristics of high insecticidal activity, broad insecticidal spectrum, good stability, rapid drug effect, safety to crops, etc., in particular, deltamethrin has good stability, low R isomerization degree, and the stability and insecticidal effect of its most active isomer are not affected by long-term storage or obvious temperature changes, and has a longer shelf life.

[0060] That is to say, for the cypermethrin system without alkyl aromatic sulfonates, especially for the emulsifiable concentrate system without alkyl aromatic sulfonates, further for the emulsifiable concentrate system without calcium alkyl aromatic sulfonate, and further for the emulsifiable concentrate system containing non-ionic emulsifier without calcium alkyl aromatic sulfonate, obvious R isomerization will occur after standing, and R isomers with no insecticidal activity will be generated, resulting in a decrease in the effective content of cypermethrin and a decrease in the insecticidal effect; while for the system with the addition of alkyl aromatic sulfonates, especially alkylbenzene sulfonates, and further for the cypermethrin system with calcium alkyl aromatic sulfonate, even a very small amount of addition can significantly reduce the effect of R isomerization of cypermethrin, thereby greatly improving the stability of the cypermethrin emulsifiable concentrate.

[0061] In the emulsifiable concentrate system containing nonionic surfactants, calcium alkyl sulfonate, especially calcium dodecylbenzene sulfonate, is very effective in inhibiting the generation of R isomers. However, in the aqueous microemulsion system, it is found that even if nonionic surfactants such as Tween 20 are included, the generation of R isomers is very small. Even if it is placed for more than one year, the content of R isomers is only less than 1% of deltamethrin. The specific reason is still under study. That is to say, calcium dodecylbenzene sulfonate and the like have a very effective effect on inhibiting the generation of isomers in the emulsifiable concentrate system containing nonionic surfactants.

[0062] Furthermore, the present invention also provides a cypermethrin-containing insecticide with stable components and a clear ratio range, wherein the composition of the cypermethrin-containing insecticide comprises, by weight percentage, 1-10% of cypermethrin, 10-90% of a solvent, 8-40% of an emulsifier, 0.1-1% of an inhibitor, and 0.1-1% of an acidity regulator.

[0063] In this embodiment, in order to ensure that the insecticide has a better insecticidal effect, the content of deltamethrin is 1-10%, preferably 2.5-10%. For example, the content of deltamethrin can be 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc.

[0064] In this embodiment, the solvent is used to dissolve the deltamethrin, and as an example, its content can be 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, etc. Since deltamethrin is almost insoluble in water at room temperature, in order to dissolve the deltamethrin, the solvent is preferably an aromatic organic solvent or an ester organic solvent, and the ester solvent preferably contains an ether bond at the same time. As an example, the aromatic organic solvent is one or more of toluene, xylene, isopropylbenzene, n-propylbenzene, trimethylolene, aromatic solvent S100, aromatic solvent S150, and aromatic solvent S200, but is not limited thereto; the ester solvent containing ether bonds at the same time is a polyol in which one of the hydroxyl groups is capped with an ester bond and one of the hydroxyl groups is capped with an ether bond; further, the ester solvent containing ether bonds in the general formula is a substance in which one of the hydroxyl groups in ethylene glycol, propylene glycol, butanediol, and glycerol forms an ester bond with acid, acetic acid, or propionic acid, and the other section forms an ether bond with methanol, ethanol, or propanol, and is further preferably one or more of ethylene glycol methyl ether formate, ethylene glycol methyl ether acetate, ethylene glycol ethyl ether formate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether formate, propylene glycol methyl ether acetate, propylene glycol ethyl ether formate, propylene glycol ethyl ether acetate and butanediol methyl ether formate, butanediol methyl ether acetate.

[0065] In this embodiment, the 8-40 parts of emulsifier are nonionic surfactants and / or ionic surfactants; further, the ionic surfactant is preferably an anionic surfactant; preferably, it can be composed of 4-20 parts of ionic emulsifiers and 4-20 parts of nonionic emulsifiers. According to different emulsification properties and requirements, the nonionic emulsifier is preferably castor oil polyoxyethylene ether (EL series) and / or hydrogenated castor oil polyoxyethylene ether (HEL series) and / or polysorbate. It is further preferred that the HLB value of the emulsifier is between 10-17. For example, the castor oil polyoxyethylene ether can be EL-20, EL-30, EL-40, EL-80, EL-90, etc., but not limited thereto; the hydrogenated castor oil polyoxyethylene ether can be HEL-20, HEL-30, HEL-40, HEL-80, HEL-90, etc., but not limited thereto; the polysorbate can be Tween-20, Tween-40, Tween-60, Tween-80, Tween 85, etc., but not limited thereto. In order to ensure the emulsification effect, the content of the nonionic emulsifier can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc. The ionic emulsifier is preferably an anionic surfactant, and the anionic surfactant is further preferably a carboxylate, sulfonate, sulfate ester and phosphate ester. The content of the ionic emulsifier can also be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, etc.

[0066] The alkyl aromatic sulfonate is preferably alkyl benzene sulfonate or alkyl naphthalene sulfonate, more preferably calcium salt or magnesium salt; furthermore, the alkyl group is an alkyl group with less than 20 carbon atoms, more preferably 6-20 carbon atoms. For example, one or more of calcium hexylbenzene sulfonate, magnesium hexylbenzene sulfonate, calcium octylbenzene sulfonate, magnesium octylbenzene sulfonate, calcium decylbenzene sulfonate, magnesium decylbenzene sulfonate, calcium undecylbenzene sulfonate, calcium undecylbenzene sulfonate, calcium dodecylbenzene sulfonate, magnesium dodecylbenzene sulfonate, calcium tridecylbenzene sulfonate, magnesium tridecylbenzene sulfonate, calcium tetradecylbenzene sulfonate, magnesium tetradecylbenzene sulfonate, calcium pentadecylbenzene sulfonate, magnesium pentadecylbenzene sulfonate, calcium hexadecylbenzene sulfonate, magnesium heptadecanylbenzene sulfonate, calcium heptadecanylbenzene sulfonate, magnesium heptadecanylbenzene sulfonate, calcium octadecylbenzene sulfonate, magnesium octadecylbenzene sulfonate, calcium nonadecanylbenzene sulfonate, magnesium nonadecanylbenzene sulfonate, calcium eicosylbenzene sulfonate, magnesium eicosylbenzene sulfonate, calcium decylnaphthalene sulfonate, magnesium decylnaphthalene sulfonate, calcium dodecylnaphthalene sulfonate, magnesium dodecylnaphthalene sulfonate, calcium tetradecylnaphthalene sulfonate, and magnesium dodecylnaphthalene sulfonate. Further preferably, the alkylbenzene sulfonate is preferably one or more of calcium nonylbenzene sulfonate, magnesium nonylbenzene sulfonate, calcium dodecylbenzene sulfonate, magnesium dodecylbenzene sulfonate, calcium tetradecylbenzene sulfonate, and magnesium tetradecylbenzene sulfonate, but is not limited thereto. In this embodiment, alkyl aromatic sulfonate is used to prevent deltamethrin from undergoing R isomer conversion in an emulsifiable concentrate system containing a nonionic emulsifier and / or an ionic emulsifier. This effect has not been disclosed in the literature so far. As long as a small amount of alkyl aromatic sulfonate is added to the emulsifiable concentrate system containing a nonionic emulsifier, even if it is under high temperature for a long time, the occurrence of R isomerization can be suppressed, meeting the product quality requirements; and more importantly, only a very small amount needs to be added to achieve the effect of suppressing deltamethrin R isomerization, so that deltamethrin emulsifiable concentrate or water emulsion can maintain a higher shelf life. As an example, the content of the alkyl aromatic sulfonate can be 0.1%, 0.5%, or 1.0%. Moreover, the amount used to inhibit isomerization is very small, generally below 1% to achieve a very good inhibitory effect; if the content exceeds 1%, the excess can be used as an anionic emulsifier.

[0067] In this embodiment, although inorganic acids such as sulfuric acid and phosphoric acid can also play a role in maintaining the acidic environment of the system, considering biocompatibility and safety of use, organic carboxylic acids are preferably selected as acidity regulators in this embodiment. Organic carboxylic acids are milder and have better biocompatibility than inorganic acids. Based on this, the acidity regulator in this embodiment is preferably one or more of citric acid (citric acid), salicylic acid (o-hydroxybenzoic acid), benzoic acid, formic acid, acetic acid, propionic acid, n-butyric acid and lactic acid, but is not limited thereto.

[0068] Furthermore, from the perspective of ease of use, acidity and irritation, acetic acid, propionic acid and citric acid are preferred as acidity regulators. Furthermore, different organic carboxylic acids are selected as acidity regulators according to the type of solvent used. Specifically, when the solvent is an aromatic organic solvent, the acidity regulator is preferably one or both of acetic acid and propionic acid; when the solvent is an ester organic solvent, the acidity regulator is preferably citric acid. When using aromatic solvents, liquid acids such as acetic acid and propionic acid can be better dissolved in the system; and for ester solvents, especially when using solvents containing both ester bonds and ether bonds, solid acids such as citric acid have better solubility therein.

[0069] In some embodiments, a method for preparing a deltamethrin-containing insecticide with stable components is also provided, and each component can be formulated in a reasonable manner.

[0070] The preparation of emulsifiable concentrate further comprises the following steps: mixing a nonionic emulsifier, an ionic emulsifier and an inhibitor to obtain a first mixed solution; mixing deltamethrin with a solvent to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly to obtain a third mixed solution; adding an acidity regulator to the third mixed solution, and adjusting the volume with a solvent, stirring evenly to obtain the insecticide containing deltamethrin with stable components. The acidity regulator may also be added when preparing the second mixed solution.

[0071] The present invention will be further explained below by means of specific embodiments:

[0072] Example 1

[0073] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 5 g of deltamethrin, 9 g of EL-40, 8 g of calcium dodecylbenzenesulfonate, 0.2 g of glacial acetic acid, 25 g of xylene, and an S200 solvent diluted to 100 mL.

[0074] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0075] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material and dissolving it in xylene to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the first mixed solution, then quantitatively adding an S200 solvent, and stirring evenly to obtain the third mixed solution.

[0076] Example 2

[0077] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 5 g of deltamethrin, 9 g of EL-40, 5 g of calcium dodecylbenzenesulfonate, 0.2 g of glacial acetic acid, 25 g of xylene, and an S200 solvent diluted to 100 mL.

[0078] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0079] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it in xylene to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, then fixing the volume with an S200 solvent, and stirring evenly to obtain the third mixed solution.

[0080] Example 3

[0081] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 5 g of deltamethrin, 9 g of EL-40, 2.5 g of calcium dodecylbenzenesulfonate, 0.2 g of glacial acetic acid, 25 g of xylene, and an S200 solvent diluted to 100 mL.

[0082] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0083] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it in xylene to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, then fixing the volume with an S200 solvent, and stirring evenly to obtain the third mixed solution.

[0084] Example 4

[0085] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 5 g of deltamethrin, 9 g of EL-40, 0.1 g of calcium dodecylbenzenesulfonate, 0.2 g of glacial acetic acid, 25 g of xylene, and an S200 solvent diluted to 100 mL.

[0086] In this formulation, 0.1 g of calcium dodecylbenzene sulfonate serves as an R isomerization inhibitor.

[0087] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it in xylene to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, then fixing the volume with an S200 solvent, and stirring evenly to obtain the third mixed solution.

[0088] Example 5

[0089] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 5 g of deltamethrin, 9 g of EL-40, 0.5 g of calcium dodecylbenzenesulfonate, 0.2 g of glacial acetic acid, 25 g of xylene, and S200 solvent quantified to 100 g.

[0090] In this formulation, 0.5 g of calcium dodecylbenzene sulfonate serves as an R isomerization inhibitor.

[0091] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it in xylene to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then quantitatively adding an S200 solvent, and stirring evenly to obtain the third mixed solution.

[0092] Comparative Example 1

[0093] Provided is a deltamethrin-containing insecticide, wherein the deltamethrin-containing insecticide comprises, by weight, 5 g of deltamethrin, 9 g of EL-40, 0.2 g of glacial acetic acid, 25 g of xylene, and an S200 solvent diluted to 100 mL.

[0094] The preparation of the insecticide containing deltamethrin comprises the following steps: weighing a deltamethrin raw material, dissolving it in xylene to obtain a first mixed solution; adding EL-40 to the first mixed solution and stirring evenly to obtain a second mixed solution; adding glacial acetic acid to the second mixed solution, then fixing the volume with S200 solvent, and stirring evenly to obtain the second mixed solution.

[0095] The cypermethrin solution was prepared according to the above preparation method and detected by high performance liquid chromatography. The detection method is as follows.

[0096] Chromatographic conditions and system suitability test: Lichrosorb 60A was used as filler (250 mm×4.6 mm, 5 μm), n-hexane-ethyl acetate (95:5) was used as mobile phase; the detection wavelength was 278 nm; the flow rate was 1.5 ml per minute.

[0097] Determination method: Take about 1g of this product, weigh it accurately, put it in a 50ml volumetric flask, add an appropriate amount of n-hexane-ethyl acetate-100% ethanol (70:30:2), dilute to the scale, accurately measure 20μl and inject it into the liquid chromatograph, and record the chromatogram; take an appropriate amount of cypermethrin reference substance (approximately equivalent to 50mg of cypermethrin) and determine it in the same way.

[0098] According to the main peak position of the deltamethrin reference substance, find the main peak position of the deltamethrin solution. If there are other peaks besides the main peak, record their peak time and area ratio to the main peak.

[0099] Stability test: In order to confirm that calcium dodecylbenzene sulfonate has the effect of inhibiting the conversion of deltamethrin isomers in the above formula, the following experiments were conducted: In order to ensure that the stability of the solution is not affected by its packaging materials, it was sealed with a glass bottle and placed in a 40°C stability test box. The isomers were tested at 0 days, 5 days, and 60 days. The results are shown in Tables 1-3 and Figure 1-Figure 9 As shown, Figure 1-Figure 3 They are the detection spectra of the insecticide containing deltamethrin in Example 1 on the 0th day, the 5th day and the 60th day respectively. The two large peaks in the front are the peaks of xylene and aromatic solvents, and the peak at about 4.5 minutes is the main peak of deltamethrin. Figure 4-Figure 6 They are the detection spectra of the insecticide containing cypermethrin in Example 5 on the 0th day, the 5th day and the 60th day respectively. The two large peaks in the front are the peaks of xylene and aromatic solvents, and the peak at about 4.5 minutes is the main peak of cypermethrin. Figure 7-Figure 9 These are the detection spectra of the insecticide containing cypermethrin in Comparative Example 1 on the 0th, 5th and 60th days. The first two large peaks are the peaks of xylene and aromatic solvents, the peak at around 4.5 minutes is the main peak of cypermethrin, and the peak at around 4.2 minutes is the isomer peak.

[0100] Table 1 Test results on day 0

[0101] serial number Isomer situation Example 1 No significant changes in isomers Example 2 No significant changes in isomers Example 3 No significant changes in isomers Example 4 No significant changes in isomers Example 5 No significant changes in isomers Comparative Example 1 There is a smaller isomer peak

[0102] Table 2 Test results on the 5th day

[0103]

[0104] Table 3 Test results on day 60

[0105]

[0106] From Table 1-Table 3 and Figure 1-Figure 9The results show that only 0.1% of calcium dodecylbenzene sulfonate is needed to be added to the insecticide system containing deltamethrin in aromatic hydrocarbon solvents to achieve the effect of inhibiting the isomer conversion of deltamethrin. After 60 days at 40°C, almost no R isomer is produced; while in Comparative Example 1, in which calcium dodecylbenzene sulfonate was not added, obvious isomer products were produced in 5 days, and the ratio of isomerized product to deltamethrin reached nearly 1:1 in about 60 days, with a loss of almost half.

[0107] Example 6

[0108] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 4.5 g of EL-40, 4 g of calcium dodecylbenzenesulfonate, 0.05 g of glacial acetic acid, and ethylene glycol methyl ether acetate diluted to 50 mL.

[0109] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it with an appropriate amount of ethylene glycol methyl ether acetate to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then fixing the volume with ethylene glycol methyl ether acetate, and stirring evenly to obtain the third mixed solution.

[0110] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0111] Example 7

[0112] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 4.5 g of EL-40, 2.5 g of calcium dodecylbenzenesulfonate, 0.05 g of glacial acetic acid, and ethylene glycol methyl ether acetate diluted to 50 mL.

[0113] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it with an appropriate amount of ethylene glycol methyl ether acetate to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then fixing the volume with ethylene glycol methyl ether acetate, and stirring evenly to obtain the third mixed solution.

[0114] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0115] Example 8

[0116] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 4.5 g of EL-40, 1.25 g of calcium dodecylbenzenesulfonate, 0.05 g of glacial acetic acid, and ethylene glycol methyl ether acetate diluted to 50 mL.

[0117] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it with an appropriate amount of ethylene glycol methyl ether acetate to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then fixing the volume with ethylene glycol methyl ether acetate, and stirring evenly to obtain the third mixed solution.

[0118] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0119] Example 9

[0120] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 4.5 g of EL-40, 0.6 g of calcium dodecylbenzenesulfonate, 0.05 g of glacial acetic acid, and ethylene glycol methyl ether acetate diluted to 50 mL.

[0121] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it with an appropriate amount of ethylene glycol methyl ether acetate to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then fixing the volume with ethylene glycol methyl ether acetate, and stirring evenly to obtain the third mixed solution.

[0122] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0123] Example 10

[0124] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 4.5 g of EL-40, 0.25 g of calcium dodecylbenzenesulfonate, 0.05 g of glacial acetic acid, and ethylene glycol methyl ether acetate diluted to 50 mL.

[0125] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it with an appropriate amount of ethylene glycol methyl ether acetate to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then fixing the volume with ethylene glycol methyl ether acetate, and stirring evenly to obtain the third mixed solution.

[0126] In this formulation, 0.25 g of calcium dodecylbenzene sulfonate serves as an R isomerization inhibitor.

[0127] Comparative Example 2

[0128] Provided is a deltamethrin-containing insecticide, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 4.5 g of EL-40, 0.05 g of glacial acetic acid, and ethylene glycol methyl ether acetate diluted to 50 mL.

[0129] The preparation of the insecticide containing deltamethrin comprises the following steps: weighing a deltamethrin raw material, dissolving it with an appropriate amount of ethylene glycol methyl ether acetate to obtain a first mixed solution; adding EL-40 to the first mixed solution and stirring it evenly to obtain a second mixed solution; adding glacial acetic acid to the second mixed solution, then quantitatively adding ethylene glycol methyl ether acetate, and stirring it evenly to obtain the second mixed solution.

[0130] The cypermethrin solution was prepared according to the above preparation method and detected by high performance liquid chromatography. The detection method is as follows.

[0131] Chromatographic conditions and system suitability test: Lichrosorb 60A was used as filler (250 mm×4.6 mm, 5 μm), n-hexane-ethyl acetate (95:5) was used as mobile phase; the detection wavelength was 278 nm; the flow rate was 1.5 ml per minute.

[0132] Determination method: Take about 1g of this product, weigh it accurately, put it in a 50ml volumetric flask, add an appropriate amount of n-hexane-ethyl acetate-100% ethanol (70:30:2), dilute to the scale, accurately measure 20μl and inject it into the liquid chromatograph, and record the chromatogram; take an appropriate amount of cypermethrin reference substance (approximately equivalent to 50mg of cypermethrin) and determine it in the same way.

[0133] According to the main peak position of the deltamethrin reference substance, find the main peak position of the deltamethrin solution. If there are other peaks besides the main peak, record their peak time and area ratio to the main peak.

[0134] Stability test: In order to confirm that calcium dodecylbenzene sulfonate has an inhibitory effect on the isomer conversion of deltamethrin in the above formula, the following experiments were conducted: In order to ensure that the stability of the solution is not affected by its packaging material, it was sealed with a glass bottle and placed in a 40°C stability test box. The isomers were tested at 0 days, 5 days, and 60 days. The results are shown in Tables 4-6 and Figure 10-Figure 16 As shown, Figure 10-11 They are the detection spectra of the insecticide containing deltamethrin in Example 6 on the 5th day and the 60th day respectively. The front peak is the peak of calcium dodecylbenzene sulfonate, and the peak at about 4.5 minutes is the main peak of deltamethrin. Figure 12-13 They are the detection spectra of the insecticide containing deltamethrin in Example 10 on the 5th day and the 60th day respectively. The front peak is the peak of calcium dodecylbenzene sulfonate, and the peak at about 4.5 minutes is the main peak of deltamethrin. Figure 14-16 It is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 2 on the 0th day, the 5th day and the 60th day. The front peak is the peak of calcium dodecylbenzene sulfonate, the peak around 4.5 minutes is the main peak of cypermethrin, and the peak around 4.0 minutes is the isomer peak.

[0135] Table 4 Test results on day 0

[0136]

[0137]

[0138] Table 5 Test results on the 5th day

[0139]

[0140] Table 6 Test results on day 60

[0141]

[0142] From Tables 4 to 6 and Figure 10-Figure 16 The results show that in the insecticide system containing deltamethrin in an ester solvent, only 0.5% of calcium dodecylbenzene sulfonate is needed to inhibit the isomer conversion of deltamethrin, while obvious isomerization occurs in the system without calcium dodecylbenzene sulfonate.

[0143] Embodiment 11

[0144] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 6.25 g of Tween-20, 6.25 g of calcium dodecylbenzenesulfonate, 0.05 g of glacial acetic acid, and propylene glycol methyl ether acetate quantified to 50 ml.

[0145] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing Tween-20 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, and dissolving it with an appropriate amount of propylene glycol methyl ether acetate to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; adding glacial acetic acid to the third mixed solution, and then quantitatively adding propylene glycol methyl ether acetate, and stirring evenly to obtain the third mixed solution.

[0146] In this formulation, a small amount of calcium dodecylbenzene sulfonate acts as an R isomerization inhibitor, and the rest acts as an anionic emulsifier component.

[0147] Comparative Example 3

[0148] Provided is a deltamethrin-containing insecticide, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 6.25 g of Tween-20, 0.05 g of glacial acetic acid, and propylene glycol methyl ether acetate quantified to 50 ml.

[0149] The preparation of the insecticide containing deltamethrin comprises the following steps: weighing a deltamethrin raw material, dissolving it with an appropriate amount of propylene glycol methyl ether acetate to obtain a first mixed solution; adding Tween-20 to the first mixed solution and stirring it evenly to obtain a second mixed solution; adding glacial acetic acid to the second mixed solution, then quantitatively adding propylene glycol methyl ether acetate, and stirring it evenly to obtain the second mixed solution.

[0150] Comparative Example 4

[0151] Provided is a deltamethrin-containing insecticide, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 22.5 g of Tween-20, 0.05 g of glacial acetic acid, 0.025 g of BHT, and ethylene glycol methyl ether acetate quantified to 50 ml.

[0152] The preparation of the insecticide containing deltamethrin comprises the following steps: weighing deltamethrin raw materials and BHT, dissolving them with an appropriate amount of ethylene glycol methyl ether acetate to obtain a first mixed solution; adding Tween-20 to the first mixed solution and stirring evenly to obtain a second mixed solution; adding glacial acetic acid to the second mixed solution, then quantitatively adding ethylene glycol methyl ether acetate, and stirring evenly to obtain the second mixed solution.

[0153] Comparative Example 5

[0154] Provided is a deltamethrin-containing insecticide, wherein the deltamethrin-containing insecticide comprises, by weight, 2.5 g of deltamethrin, 12.5 g of EL-40, 0.05 g of glacial acetic acid, 0.025 g of BHT, and ethylene glycol methyl ether acetate quantified to 50 ml.

[0155] The preparation of the insecticide containing deltamethrin comprises the following steps: weighing deltamethrin raw materials and BHT, dissolving them with an appropriate amount of ethylene glycol methyl ether acetate to obtain a first mixed solution; adding EL-40 to the first mixed solution and stirring evenly to obtain a second mixed solution; adding glacial acetic acid to the second mixed solution, then quantitatively adding ethylene glycol methyl ether acetate, and stirring evenly to obtain the second mixed solution.

[0156] The cypermethrin solution was prepared according to the above preparation method and detected by high performance liquid chromatography. The detection method is as follows.

[0157] Chromatographic conditions and system suitability test: Lichrosorb 60A was used as filler (250 mm×4.6 mm, 5 μm), n-hexane-ethyl acetate (95:5) was used as mobile phase; the detection wavelength was 278 nm; the flow rate was 1.5 ml per minute.

[0158] Determination method: Take about 1g of this product, weigh it accurately, put it in a 50ml volumetric flask, add an appropriate amount of n-hexane-ethyl acetate-100% ethanol (70:30:2), dilute to the scale, accurately measure 20μl and inject it into the liquid chromatograph, and record the chromatogram; take an appropriate amount of cypermethrin reference substance (approximately equivalent to 50mg of cypermethrin) and determine it in the same way.

[0159] According to the main peak position of the deltamethrin reference substance, find the main peak position of the deltamethrin solution. If there are other peaks besides the main peak, record their peak time and area ratio to the main peak.

[0160] Stability test: In order to confirm that calcium dodecylbenzene sulfonate has an inhibitory effect on the isomer conversion of deltamethrin in the above formula, the following experiment was conducted: In order to ensure that the stability of the solution is not affected by its packaging material, it is sealed with a glass bottle and placed in a 40°C stability test box. The isomers are tested at 0 days and 10 days respectively. The results are shown in Tables 7-8 and Figure 17-Figure 20 As shown, Figure 17-Figure 18 They are the detection spectra of the insecticide containing deltamethrin in Example 11 on the 0th day and the 10th day respectively. The front peak is the peak of calcium dodecylbenzene sulfonate, and the peak at about 4.5 minutes is the main peak of deltamethrin. Figure 19-20 This is the detection spectrum of the insecticide containing cypermethrin in Comparative Example 3 on the 0th day and the 10th day. The front peak is the peak of calcium dodecylbenzene sulfonate, the peak around 4.7 minutes is the main peak of cypermethrin, and the peak around 4.2 minutes is the isomer peak.

[0161] Stability test: In order to confirm that BHT has an inhibitory effect on the isomer conversion of deltamethrin in the above formula, the following experiment was conducted: In order to ensure that the stability of the solution is not affected by its packaging material, a glass bottle was sealed and placed in a 40°C stability test box. After 8 days, its isomerization was tested. The results are shown in Table 9 and Figure 21-22 shown.

[0162] Table 7 Test results on day 0

[0163] serial number Isomer situation Embodiment 11 No significant changes in isomers Comparative Example 3 There is a smaller isomer peak

[0164] Table 8 Test results on day 10

[0165]

[0166] Table 9 Test results on day 8

[0167]

[0168]

[0169] From Table 7-Table 8 and Figure 17-Figure 20 It can be seen from the results that although the above Example 11 and Comparative Example 3 did not further reduce the amount of calcium dodecylbenzene sulfonate in proportion to conduct multiple tests, it can be clearly seen from the perspective of simply inhibiting the conversion of deltamethrin isomers that calcium dodecylbenzene sulfonate plays a significant role in inhibiting the conversion of deltamethrin isomers.

[0170] From Table 9 and Figure 21-22 The results show that the addition of BHT has no obvious inhibitory effect on the isomerization of cypermethrin.

[0171] Example 12

[0172] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 0.5 g of deltamethrin, 4.5 g of EL-40, 0.25 g of calcium dodecylbenzenesulfonate, 0.05 g of citric acid, and propylene glycol methyl ether acetate diluted to 50 mL.

[0173] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40 with calcium dodecylbenzene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, dissolving it with an appropriate amount of propylene glycol methyl ether acetate, and adding citric acid to dissolve it to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; and then quantifying the amount of propylene glycol methyl ether acetate and stirring evenly to obtain the third mixed solution.

[0174] According to a test method similar to the above method, it was found that no obvious isomerization products of deltamethrin were observed after 10 days.

[0175] Embodiment 13

[0176] Similar to Example 12, except that calcium nonylbenzenesulfonate was used instead of calcium dodecylbenzenesulfonate as the inhibitor, preparation and testing were performed, and it was found that the inhibitor also had the effect of inhibiting the isomerization of deltamethrin.

[0177] Embodiment 14

[0178] Provided is a deltamethrin-containing insecticide with stable components, wherein the deltamethrin-containing insecticide comprises, by weight, 4.0 g of deltamethrin, 4.5 g of EL-40, 4 g of nonylphenol polyoxyethylene (4) ether ammonium sulfate, 0.25 g of calcium dodecylbenzene naphthoate, 0.05 g of citric acid, and propylene glycol methyl ether acetate diluted to 50 mL.

[0179] The preparation of the insecticide containing deltamethrin comprises the following steps: premixing EL-40, nonylphenol polyoxyethylene (4) ether ammonium sulfate and calcium dodecylnaphthalene sulfonate to obtain a first mixed solution; weighing a deltamethrin raw material, dissolving it with an appropriate amount of propylene glycol methyl ether acetate, and adding citric acid to dissolve it to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly so that the first mixed solution is fully dissolved in the second mixed solution to obtain a third mixed solution; and then quantifying the amount of propylene glycol methyl ether acetate and stirring evenly to obtain the third mixed solution.

[0180] According to a test method similar to the above method, it was found that no obvious isomerization products of deltamethrin were observed after 10 days.

[0181] It should be understood that the application of the present invention is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to the present invention.

Claims

1. Application of calcium dodecylbenzene sulfonate as a deltamethrin R isomerization inhibitor in deltamethrin emulsifiable concentrate, characterized in that: The composition of the deltamethrin emulsifiable concentrate includes 1-10% of deltamethrin, 10-90% of solvent, 8-40% of emulsifier, 0.1-1% of calcium dodecylbenzene sulfonate, and 0.1-1% of acidity regulator by weight percentage; the emulsifier includes EL-40; the solvent is an aromatic organic solvent or an ester organic solvent; the aromatic organic solvent is one or more of xylene, isopropylbenzene, n-propylbenzene, trimethylbenzene, aromatic solvent S100, aromatic solvent S150, and aromatic solvent S200; the ester organic solvent is one or more of ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and butylene glycol methyl ether acetate; the sum of the weight percentages of each component is equal to 100%.

2. The use according to claim 1, characterized in that: The acidity regulator is one or more of citric acid, salicylic acid, benzoic acid, formic acid, acetic acid, propionic acid, n-butyric acid and lactic acid.

3. The use according to claim 2, characterized in that: When the solvent is an aromatic organic solvent, the acidity regulator is one or both of acetic acid and propionic acid; when the solvent is an ester organic solvent, the acidity regulator is citric acid.

4. A method for preparing deltamethrin emulsifiable concentrate in the application as claimed in any one of claims 1 to 3, characterized in that: Includes steps: Mixing an emulsifier including EL-40 and calcium dodecylbenzene sulfonate to obtain a first mixed solution; mixing deltamethrin with part of the solvent to obtain a second mixed solution; adding the first mixed solution to the second mixed solution and stirring evenly to obtain a third mixed solution; The acidity regulator is added to the third mixed solution, and the volume is fixed with a solvent, and the mixture is stirred evenly to obtain the deltamethrin emulsifiable concentrate; or the acidity regulator is added when preparing the second mixed solution.

Images