Metamifop-halauxifen-cyhalofop-butyl emulsifiable concentrate and preparation method thereof

Abstract

The invention relates to the technical field of pesticide chemistry, in particular to a metamifop-halauxifen-cyhalofop-butyl missible oil agent and a preparation method thereof. The metamifop-halauxifen-cyhalofop-butyl missible oil agent is prepared from the following raw materials in parts by weight: 10 to 20 parts of metamifop, 0.5 to 3 parts of halauxifen, 18 to 36 parts of cyhalofop-butyl, 2 to 5 parts of chlorfenapyr, 2 to 6 parts of dispersing agent, 3 to 8 parts of surfactant, 2 to 5 parts of emulsifying agent, 30 to 60 parts of water and 3 to 8 parts of synergist. The synergist is modified bentonite, and the modified bentonite is metal doped bentonite modified by a triple modifier. According to the invention, the metal-doped and hydroxypropyl-beta-cyclodextrin / PEG / silane coupling agent is added to cooperate with the modified bentonite, so that the loading rate of the pesticide is increased, slow release and synergism are realized, the utilization rate of the pesticide is increased, the ternary compound herbicide has a good control effect on weeding, and a new direction is provided for efficient application of the ternary compound herbicide.

Description

Technical Field

[0001] The present invention relates to the technical field of pesticide chemistry, and particularly relates to an oxaziclomeprop - fluroxypyr - meptyl emulsifiable concentrate and a preparation method thereof. Background Art

[0002] In recent years, paddy weeds (such as barnyard grass, leptochloa chinensis, sedges, etc.) have caused serious harm to the growth of rice, resulting in reduced rice yield and quality decline. Chemical herbicides have become the main means of controlling weeds due to their high efficiency and convenience. However, long - term single use of a certain type of herbicide is likely to lead to enhanced weed resistance, and at the same time, it may have a negative impact on the ecological environment and non - target organisms. Therefore, the development of highly efficient, low - toxic, and broad - spectrum compound herbicides has become a research hotspot in the current agricultural chemistry field.

[0003] Oxaziclomeprop is an acetolactate synthase inhibitor and has excellent efficacy against gramineous weeds; fluroxypyr belongs to synthetic auxin - type herbicides and can cause weed death by interfering with the plant hormone balance; cyhalofop - butyl is an acetyl - CoA carboxylase inhibitor and is effective against a variety of gramineous weeds. However, the above single components have problems such as limited control spectrum, short effective period, or easy development of resistance in actual applications. By scientifically compounding active ingredients with different action mechanisms, the weed control spectrum can be expanded, the development of resistance can be delayed, and the dosage can be reduced.

[0004] As a common dosage form, emulsifiable concentrates have the advantages of high active ingredient content, good stability, and convenient use. However, in the preparation process, key technical problems such as the compatibility of active ingredients, emulsification and dispersion properties, and long - term storage stability need to be solved. Traditional emulsifiable concentrates often use single surfactants or emulsifiers, which are difficult to balance dispersibility and stability, and some formulations have poor environmental safety. In addition, the reasonable application of synergists can significantly improve the bioavailability of herbicides, but existing synergists (such as organosilicon - based) have problems such as high cost or environmental risks.

[0005] Due to its layered structure and cation - exchange ability, bentonite can be used as a carrier or synergist in pesticide formulations. However, natural bentonite has defects such as a single modification method and poor compatibility with organic components. Through metal doping and modification with silane coupling agents, its surface properties can be optimized, the adsorption and slow - release effects on pesticide active ingredients can be enhanced, thereby improving the pesticide efficacy and reducing losses.

[0006] There is an urgent need in the prior art to develop a ternary compound emulsifiable concentrate based on oxaziclomeprop, fluroxypyr, and cyhalofop - butyl. By scientifically formulating active ingredients, optimizing the adjuvant system, and introducing highly efficient modified bentonite synergists, synergistic effects can be achieved, the risk of resistance can be reduced, and environmental compatibility can be improved. Summary of the Invention

[0007] In view of the deficiencies in the above-mentioned existing technologies, the present invention provides an oxaziclome - fluroxypyr - meptyl emulsifiable concentrate and a preparation method thereof.

[0008] To solve the above technical problems, the technical solution adopted by the present invention is:

[0009] An oxaziclome - fluroxypyr - meptyl emulsifiable concentrate is composed of the following raw materials in parts by weight: 10 - 20 parts by weight of oxaziclome, 0.5 - 3 parts by weight of fluroxypyr - meptyl, 18 - 36 parts by weight of cyhalofop - butyl, 2 - 5 parts by weight of dichlormid, 2 - 6 parts by weight of dispersant, 3 - 8 parts by weight of surfactant, 2 - 5 parts by weight of emulsifier, 30 - 60 parts by weight of water, 3 - 8 parts by weight of synergist; the synergist is modified bentonite, and the modified bentonite is metal - doped bentonite modified by a triple modifier.

[0010] Oxaziclome is an aryloxyphenoxypropionate herbicide, mainly used for weed control in paddy fields, especially having significant effects on gramineous weeds such as barnyard grass and goosegrass. It achieves the weed control effect by inhibiting the growth and reproduction of weeds, and at the same time has high safety for rice.

[0011] Fluroxypyr - meptyl is a selective herbicide, mainly used for controlling annual gramineous weeds and some broad - leaf weeds. It has a certain control effect on young barnyard grass, and can also control crabgrass, sprangletop, green foxtail, goosegrass, and Alopecurus aequalis Sobol., etc.

[0012] Cyhalofop - butyl is a selective herbicide, mainly used for weed control in paddy fields, especially having high control efficiency on barnyard grass. It has a certain control effect on young barnyard grass, and can also control crabgrass, sprangletop, green foxtail, goosegrass, and Alopecurus aequalis Sobol., etc.

[0013] Bentonite is a natural layered silicate mineral, having a large specific surface area and cation - exchange capacity, and can be used as a pesticide carrier or synergist. However, if used directly, it has poor compatibility with organic pesticide components, limited surface - active sites, and is prone to agglomeration due to too small interlayer spacing, and thus cannot achieve the adsorption purpose. Therefore, the present invention optimizes its performance through modification.

[0014] Metal ions are introduced through ion exchange to enhance the interlayer charge distribution, improve the specific surface area and adsorption capacity, and graft organic functional groups on the surface of bentonite to improve its compatibility with organic pesticides and enhance the slow - release effect.

[0015] Hydroxypropyl-β-cyclodextrin has a cavity structure with hydrophilic exterior and hydrophobic interior, which can adsorb and include pesticide molecules (such as halauxifen-methyl), forming a "host-guest complex". After inclusion, the release rate of the pesticide is controllable, reducing photolysis and degradation, improving the solubility and stability of the pesticide, and prolonging the effective period. The long-chain structure of polyethylene glycol can prevent the aggregation of bentonite particles, improve its dispersibility in the emulsifiable concentrate system, improve the compatibility between the pesticide and water, and promote the emulsification of the emulsifiable concentrate. The siloxane group of the silane coupling agent can condense with the hydroxyl groups of bentonite to form stable chemical bonds. Silane coupling agents such as mercapto group and amino group can enhance the adsorption and slow-release ability of pesticides. Combining the respective advantages of the above three modifiers, the modifier combines with the surface hydroxyl groups of metal-doped bentonite through siloxane bonds, and the end of the polyethylene glycol chain reacts with the active groups (-COOH, -NH2 or -SH) of the silane coupling agent to form a stable organic-inorganic hybrid structure, and finally forms a "bentonite-silane-polyethylene glycol-hydroxypropyl-β-cyclodextrin" multi-layer modified structure.

[0016] Preferably, the preparation method of the metal-doped bentonite is as follows: Mix 8-14 parts by weight of bentonite and 150-300 parts by weight of water, disperse by ultrasonic wave, adjust the pH to 7 with hydrochloric acid, add 3-8 parts by weight of metal chloride, and stir at room temperature and 400-800 rpm for 4-10 h to obtain metal-doped bentonite.

[0017] Reaction mechanism of metal-doped bentonite: Na + , Ca 2+ Through cation exchange, metal cations enter the interlayer of bentonite, and finally metal-doped bentonite is obtained.

[0018] Preferably, the preparation method of the triple modifier is as follows: Mix 0.3-1 part by weight of hydroxypropyl-β-cyclodextrin and 2-6 parts by weight of polyethylene glycol, add 30-70 parts by weight of 30-50 wt% ethanol aqueous solution, stir at 70-90 °C and 200-400 rpm for 0.5-3 h, add it to 3-7 parts by weight of silane coupling agent, and stir at 30-50 °C and 200-400 rpm for 1-4 h to obtain the modifier.

[0019] Combination mechanism of the modifier: The combination of hydroxypropyl-β-cyclodextrin and polyethylene glycol can partially include the hydrophobic chain segment of polyethylene glycol through the cavity of hydroxypropyl-β-cyclodextrin to form a supramolecular complex. The ethoxy group, amino group or carboxyl group of the silane coupling agent condenses with the hydroxyl group of polyethylene glycol, and the remaining mercapto group, amino group and carboxyl group in the silane coupling agent can condense and combine with the surface hydroxyl groups in bentonite, and finally obtain bentonite co-modified by cyclodextrin-polyethylene glycol-silane coupling agent.

[0020] Preferably, the preparation method of the modified bentonite is as follows: Under nitrogen protection, 1.5 - 4 parts by weight of the above-mentioned modifier is mixed with 40 - 100 parts by weight of dimethyl sulfoxide, 0.2 - 0.7 parts by weight of NaH is added, and after stirring at room temperature and 100 - 300 rpm for 10 - 40 min, 3 - 8 parts by weight of the above-mentioned metal-doped bentonite is added, and the reaction is carried out at 80 - 110 °C and 100 - 300 rpm for 6 - 18 h to obtain the modified bentonite.

[0021] The reason why the inventor uses three modifiers to modify bentonite is that the modified bentonite has a larger interlayer spacing, a higher specific surface area, and a stronger adsorption capacity. Metal doping increases the interlayer spacing of bentonite, providing space to accommodate pesticide molecules, especially the relatively large chlorfluropyrid. Due to the adsorption effect, chlorfluropyrid is released relatively fast in the initial stage; the sulfonamide group of metazachlor can form a coordination bond with metal cations, the ester group of chlorfluropyrid can be electrostatically attracted to the amino group in the amino silane coupling agent, and the pyridine nitrogen of chlorfluropyrid and the cyano group of cyhalofop-butyl can also coordinate with cations. Because the coordination bond has a strong effect, it is released relatively fast in the middle and late stages. Thus, the slow release of pesticides can be achieved, thereby reducing the number and dosage of pesticide applications. The modified bentonite greatly improves the pesticide loading rate; the combined action of polyethylene glycol and silane coupling agent prevents particle sedimentation, enhances the stability of the emulsifiable concentrate, and extends the storage period; the slow-release design reduces pesticide runoff, improves targeting, reduces the impact on non-target organisms, improves the adsorption and slow release of pesticides, and improves pesticide utilization efficiency.

[0022] In summary, through the synergistic modification of metal doping + hydroxypropyl-β-cyclodextrin / PEG / silane coupling agent, the present invention upgrades bentonite from a simple carrier to a multifunctional synergist, which not only optimizes the dispersibility and stability of pesticides, improves the pesticide loading rate, but also realizes slow-release synergism, reduces the dosage of pesticides, improves the utilization efficiency of pesticides, and reduces the application amount of pesticides, etc., providing a new direction for the efficient application of ternary compound herbicides.

[0023] Preferably, the metal chloride is at least one of ferric chloride, copper chloride, calcium chloride, and magnesium chloride; further, the metal chloride is a mixture composed of ferric chloride and copper chloride in a mass ratio of (1 - 3):1.

[0024] The metal chlorides used in the present invention are a combination of ferric chloride and copper chloride. The reason is that ferric chloride has a high charge density and strong Lewis acidity, and can preferentially bind to mefenoxam (sulfonamide group) through coordination bonds, hydrogen bonds, and electrostatic attraction; while copper chloride is more likely to form coordination bonds or π-π stacking with the aromatic ring or heteroatoms of pesticides (such as pyridine nitrogen, cyano - CN), compensating for the limitations of iron ions. Therefore, through the synergism of iron and copper ions, the modified bentonite not only achieves efficient loading of the multi-component compound pesticide, but also reaches the synergistic effect of 1 + 1 > 2 through the cascade mechanism of chemical adsorption - physical inclusion - environmentally responsive release, providing a more efficient control effect for herbicides in complex farmland environments.

[0025] Preferably, the silane coupling agent is at least one of 3-mercaptopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, and N-[β-(N,N-diacetylamino)ethyl]-γ-(N-acetylamino)propyltrimethoxysilane.

[0026] Preferably, the dispersant is at least one of lauroyl glycinate, alkylphenol polyoxyethylene ether formaldehyde condensate, glycerol borate fatty acid ester, and polycarboxylate.

[0027] Preferably, the surfactant is at least one of isooctyl alcohol polyoxyethylene ether, lauryl alcohol ether phosphate, sodium dodecyl sulfate, calcium dodecylbenzenesulfonate, sodium lignin sulfonate, and carboxymethyl cellulose.

[0028] Preferably, the emulsifier is at least one of the Tween series, alkylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether, and calcium alkylbenzenesulfonate.

[0029] The preparation method of the mefenoxam - halauxifen - methyl - cyhalofop - butyl emulsifiable concentrate includes the following steps: Mix water, synergist, and dispersant, and stir at room temperature for 30 - 60 min; add mefenoxam, halauxifen - methyl, cyhalofop - butyl, cloquintocet - mexyl, surfactant, and emulsifier, and homogenize at 10000 - 15000 rpm for 5 - 15 min to obtain the mefenoxam - halauxifen - methyl - cyhalofop - butyl emulsifiable concentrate.

[0030] The beneficial effects of the present invention are as follows: 1. The present invention provides a mefenoxam - halauxifen - methyl - cyhalofop - butyl emulsifiable concentrate and its preparation method. By mixing these three herbicides, the weed control spectrum can be expanded, the weed control effect can be improved, and various weeds in paddy fields, including barnyard grass, crabgrass, goosegrass, and Alopecurus aequalis, can be effectively controlled, especially for resistant weeds, it has a better control effect.

[0031] 2. By mixing oxaziclomefone, fluroxypyr-methyl, and cyhalofop-butyl, herbicides with different mechanisms of action can be used to effectively solve the problem of resistant weeds, reduce the dependence on a single herbicide. A reasonable ratio can not only improve the herbicidal effect but also increase economic benefits and reduce the overall cost.

[0032] 3. Through the synergistic modification of metal doping + hydroxypropyl-β-cyclodextrin / PEG / silane coupling agent, bentonite is upgraded from a simple carrier to a multifunctional synergist. It not only optimizes the dispersibility and stability of pesticides, improves the loading rate of pesticides, but also realizes slow release and synergistic effects, reduces the dosage of pesticides, improves the utilization rate of pesticides, has a good control effect on weed control, and reduces the dosage of pesticides, etc. It provides a new direction for the efficient application of ternary compound herbicides. Detailed implementation manners

[0033] The following further describes in detail the above-mentioned invention content of the present invention in combination with specific implementation manners, but this should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following embodiments.

[0034] The introduction of some raw materials in this application, and other raw material substances not introduced are all commercially available:

[0035] Phenethylphenol polyoxyethylene ether was purchased from Xingtai Xinlanxing Technology Co., Ltd., model: agricultural emulsifier 601.

[0036] Bentonite is commercially available sodium-based bentonite, purchased from Tianbao Haotong Stone Processing Factory in Hongqiao District, Tianjin, model TB-200, 325 mesh.

[0037] Hydroxypropyl-β-cyclodextrin was purchased from Kunshan Sheng'an Biotechnology Co., Ltd., product number: 9957.

[0038] Polyethylene glycol was purchased from Shanghai Yushicheng Chemical Technology Co., Ltd., model: Pluriol E4000.

[0039] Example 1

[0040] An oxaziclomefone - fluroxypyr-methyl - cyhalofop-butyl emulsifiable concentrate is composed of the following raw materials in parts by weight: 15 parts by weight of oxaziclomefone, 1 part by weight of fluroxypyr-methyl, 24 parts by weight of cyhalofop-butyl, 3 parts by weight of dichlormid, 4 parts by weight of dispersant, 6 parts by weight of surfactant, 3 parts by weight of emulsifier, 40 parts by weight of water, and 4 parts by weight of synergist.

[0041] The dispersant is sodium lauroyl glycinate.

[0042] The surfactant is sodium dodecyl sulfate.

[0043] The emulsifier is phenethylphenol polyoxyethylene ether.

[0044] The synergist bentonite.

[0045] The preparation method of the metamifop - fluroxypyr - mepiquat chloride emulsifiable concentrate comprises the following steps: Mix water, a synergist, and a dispersant, and stir at room temperature for 45 min; add metamifop, fluroxypyr - mepiquat chloride, cyhalofop - butyl, cloquintocet - mexyl, a surfactant, and an emulsifier, and homogenize at 12000 rpm for 10 min to obtain the metamifop - fluroxypyr - mepiquat chloride emulsifiable concentrate.

[0046] Example 2

[0047] A metamifop - fluroxypyr - mepiquat chloride emulsifiable concentrate is composed of the following raw materials in parts by weight: 15 parts by weight of metamifop, 1 part by weight of fluroxypyr - mepiquat chloride, 24 parts by weight of cyhalofop - butyl, 3 parts by weight of cloquintocet - mexyl, 4 parts by weight of a dispersant, 6 parts by weight of a surfactant, 3 parts by weight of an emulsifier, 40 parts by weight of water, and 4 parts by weight of a synergist.

[0048] The dispersant is sodium lauroyl glycinate.

[0049] The surfactant is sodium dodecyl sulfate.

[0050] The emulsifier is phenethylphenol polyoxyethylene ether.

[0051] The synergist is modified bentonite, and the preparation method of the modified bentonite is as follows:

[0052] Mix 10 parts by weight of bentonite and 200 parts by weight of water, ultrasonically disperse in an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz for 2 h, add 0.15 mol / L hydrochloric acid to adjust the pH to 7, add 5 parts by weight of metal chloride, stir at room temperature and 600 rpm for 6 h, centrifuge, wash, and dry to obtain modified bentonite; the metal chloride is ferric chloride.

[0053] The preparation method of the metamifop - fluroxypyr - mepiquat chloride emulsifiable concentrate comprises the following steps: Mix water, a synergist, and a dispersant, and stir at room temperature for 45 min; add metamifop, fluroxypyr - mepiquat chloride, cyhalofop - butyl, cloquintocet - mexyl, a surfactant, and an emulsifier, and homogenize at 12000 rpm for 10 min to obtain the metamifop - fluroxypyr - mepiquat chloride emulsifiable concentrate.

[0054] Example 3

[0055] A metamifop - fluroxypyr - mepiquat chloride emulsifiable concentrate is composed of the following raw materials in parts by weight: 15 parts by weight of metamifop, 1 part by weight of fluroxypyr - mepiquat chloride, 24 parts by weight of cyhalofop - butyl, 3 parts by weight of cloquintocet - mexyl, 4 parts by weight of a dispersant, 6 parts by weight of a surfactant, 3 parts by weight of an emulsifier, 40 parts by weight of water, and 4 parts by weight of a synergist.

[0056] The dispersant is sodium lauroyl glycinate.

[0057] The surfactant is sodium dodecyl sulfate.

[0058] The emulsifier is phenethyl phenol polyoxyethylene ether.

[0059] The synergist is modified bentonite, and the preparation method of the modified bentonite is as follows:

[0060] A1. Mix 10 parts by weight of bentonite and 200 parts by weight of water, ultrasonically disperse for 2 h at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, adjust the pH to 7 with 0.15 mol / L hydrochloric acid, add 5 parts by weight of metal chloride, stir at room temperature and 600 rpm for 6 h, centrifuge, wash and dry to obtain metal-doped bentonite; the metal chloride is ferric chloride;

[0061] A2. Mix 0.5 part by weight of hydroxypropyl-β-cyclodextrin and 4 parts by weight of polyethylene glycol, add 40 parts by weight of 40 wt% ethanol aqueous solution, and stir at 80 °C and 300 rpm for 1 h to obtain a modifier;

[0062] A3. Under nitrogen protection, mix 2.5 parts by weight of the above modifier with 60 parts by weight of dimethyl sulfoxide, add 0.3 part by weight of NaH, stir at room temperature and 200 rpm for 20 min, then add 5 parts by weight of the above metal-doped bentonite, react at 100 °C and 200 rpm for 10 h, centrifuge, wash, dry, grind, and pass through a 200-mesh sieve to obtain modified bentonite.

[0063] The preparation method of the metamifop-chlorfluropyr- cyhalofop-butyl emulsifiable concentrate includes the following steps: Mix water, synergist, and dispersant, and stir at room temperature for 45 min; add metamifop, chlorfluropyr, cyhalofop-butyl, cloquintocet-mexyl, surfactant, and emulsifier, and homogenize at 12,000 rpm for 10 min to obtain the metamifop-chlorfluropyr- cyhalofop-butyl emulsifiable concentrate.

[0064] Example 4

[0065] A metamifop-chlorfluropyr- cyhalofop-butyl emulsifiable concentrate is composed of the following raw materials in parts by weight: 15 parts by weight of metamifop, 1 part by weight of chlorfluropyr, 24 parts by weight of cyhalofop-butyl, 3 parts by weight of cloquintocet-mexyl, 4 parts by weight of dispersant, 6 parts by weight of surfactant, 3 parts by weight of emulsifier, 40 parts by weight of water, and 4 parts by weight of synergist.

[0066] The dispersant is sodium lauroyl glycinate.

[0067] The surfactant is sodium dodecyl sulfate.

[0068] The emulsifier is phenethylphenol polyoxyethylene ether.

[0069] The synergist is modified bentonite, and the preparation method of the modified bentonite is as follows:

[0070] A1. Mix 10 parts by weight of bentonite and 200 parts by weight of water, ultrasonically disperse for 2 h at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, adjust the pH to 7 by adding 0.15 mol / L hydrochloric acid, add 5 parts by weight of metal chloride, stir at room temperature and 600 rpm for 6 h, centrifuge, wash and dry to obtain metal-doped bentonite; the metal chloride is ferric chloride;

[0071] A2. Mix 0.5 part by weight of hydroxypropyl-β-cyclodextrin and 4 parts by weight of polyethylene glycol, add 40 parts by weight of 40 wt% ethanol aqueous solution, stir at 80 °C and 300 rpm for 1 h, add to 5 parts by weight of silane coupling agent, and stir at 40 °C and 300 rpm for 2 h to obtain a modifier; the silane coupling agent is N-[β-(N,N-diacetyl)aminoethyl]-γ-(N-acetyl)aminopropyltrimethoxysilane;

[0072] A3. Under nitrogen protection, mix 2.5 parts by weight of the above modifier and 60 parts by weight of dimethyl sulfoxide, add 0.3 part by weight of NaH, stir at room temperature and 200 rpm for 20 min, then add 5 parts by weight of the above metal-doped bentonite, react at 100 °C and 200 rpm for 10 h, centrifuge, wash, dry, grind, and pass through a 200-mesh sieve to obtain modified bentonite.

[0073] The preparation method of the metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate includes the following steps: Mix water, synergist, and dispersant, and stir at room temperature for 45 min; add metamifop, chlorfluropyr-methyl, cyhalofop-butyl, cloquintocet-mexyl, surfactant, and emulsifier, and homogenize at 12,000 rpm for 10 min to obtain the metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate.

[0074] Example 5

[0075] A metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate is composed of the following raw materials in parts by weight: 15 parts by weight of metamifop, 1 part by weight of chlorfluropyr-methyl, 24 parts by weight of cyhalofop-butyl, 3 parts by weight of cloquintocet-mexyl, 4 parts by weight of dispersant, 6 parts by weight of surfactant, 3 parts by weight of emulsifier, 40 parts by weight of water, and 4 parts by weight of synergist.

[0076] The dispersant is sodium lauroyl glycinate.

[0077] The surfactant is sodium dodecyl sulfate.

[0078] The emulsifier is phenethylphenol polyoxyethylene ether.

[0079] The synergist is modified bentonite, and the preparation method of the modified bentonite is as follows:

[0080] A1. Mix 10 parts by weight of bentonite and 200 parts by weight of water, ultrasonically disperse for 2 h at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, adjust the pH to 7 by adding 0.15 mol / L hydrochloric acid, add 5 parts by weight of metal chloride, stir at room temperature and 600 rpm for 6 h, centrifuge, wash and dry to obtain metal-doped bentonite; the metal chloride is copper chloride;

[0081] A2. Mix 0.5 part by weight of hydroxypropyl-β-cyclodextrin and 4 parts by weight of polyethylene glycol, add 40 parts by weight of 40 wt% ethanol aqueous solution, stir at 80 °C and 300 rpm for 1 h, add to 5 parts by weight of silane coupling agent, and stir at 40 °C and 300 rpm for 2 h to obtain a modifier; the silane coupling agent is N-[β-(N,N-diacetyl)aminoethyl]-γ-(N-acetyl)aminopropyltrimethoxysilane;

[0082] A3. Under nitrogen protection, mix 2.5 parts by weight of the above-mentioned modifier with 60 parts by weight of dimethyl sulfoxide, add 0.3 part by weight of NaH, stir at room temperature and 200 rpm for 20 min, then add 5 parts by weight of the above-mentioned metal-doped bentonite, react at 100 °C and 200 rpm for 10 h, centrifuge, wash, dry, grind, and pass through a 200-mesh sieve to obtain modified bentonite.

[0083] The preparation method of the metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate includes the following steps: Mix water, synergist, and dispersant, and stir at room temperature for 45 min; add metamifop, chlorfluropyr-methyl, cyhalofop-butyl, dichlormid, surfactant, and emulsifier, and homogenize at 12,000 rpm for 10 min to obtain the metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate.

[0084] Example 6

[0085] A metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate is composed of the following raw materials in parts by weight: 15 parts by weight of metamifop, 1 part by weight of chlorfluropyr-methyl, 24 parts by weight of cyhalofop-butyl, 3 parts by weight of dichlormid, 4 parts by weight of dispersant, 6 parts by weight of surfactant, 3 parts by weight of emulsifier, 40 parts by weight of water, and 4 parts by weight of synergist.

[0086] The dispersant is sodium lauroyl glycinate.

[0087] The surfactant is sodium dodecyl sulfate.

[0088] The emulsifier is phenethylphenol polyoxyethylene ether.

[0089] The synergist is modified bentonite, and the preparation method of the modified bentonite is as follows:

[0090] A1. Mix 10 parts by weight of bentonite and 200 parts by weight of water, ultrasonically disperse for 2 h at an ultrasonic power of 100 W and an ultrasonic frequency of 40 kHz, adjust the pH to 7 by adding 0.15 mol / L hydrochloric acid, add 5 parts by weight of metal chloride, stir at room temperature and 600 rpm for 6 h, centrifuge, wash and dry to obtain metal-doped bentonite; the metal chloride is a mixture composed of ferric chloride and copper chloride in a mass ratio of 2:1;

[0091] A2. Mix 0.5 part by weight of hydroxypropyl-β-cyclodextrin and 4 parts by weight of polyethylene glycol, add 40 parts by weight of 40 wt% ethanol aqueous solution, stir at 80 °C and 300 rpm for 1 h, add to 5 parts by weight of silane coupling agent, and stir at 40 °C and 300 rpm for 2 h to obtain a modifier; the silane coupling agent is N-[β-(N,N-diacetyl)aminoethyl]-γ-(N-acetyl)aminopropyltrimethoxysilane;

[0092] A3. Under nitrogen protection, mix 2.5 parts by weight of the above-mentioned modifier with 60 parts by weight of dimethyl sulfoxide, add 0.3 part by weight of NaH, stir at room temperature and 200 rpm for 20 min, then add 5 parts by weight of the above-mentioned metal-doped bentonite, react at 100 °C and 200 rpm for 10 h, centrifuge, wash, dry, grind, and pass through a 200-mesh sieve to obtain modified bentonite.

[0093] The preparation method of the metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate includes the following steps: Mix water, synergist, and dispersant, and stir at room temperature for 45 min; add metamifop, chlorfluropyr-methyl, cyhalofop-butyl, cyometrinil, surfactant, and emulsifier, and homogenize at 12000 rpm for 10 min to obtain the metamifop-chlorfluropyr-methyl-cyhalofop-butyl emulsifiable concentrate.

[0094] Test Example 1

[0095] Determination of drug loading: Dissolve emamectin benzoate in tetrahydrofuran to prepare a mixed solution of 0.15 g / mL. Take 300 mL of the above-mentioned mixed solution and add 10 g of the modified bentonite prepared in Examples 1, 2, and 6 respectively. After stirring at 500 rpm for 4 h, evaporate the tetrahydrofuran to dryness to obtain the modified bentonite loaded with emamectin benzoate.

[0096] Weigh 0.25 g of the modified bentonite of emamectin benzoate mentioned above and mix it with 60 mL of acetone. Ultrasonic for 12 h, take out 2 mL of the supernatant after centrifugation to test the ultraviolet absorption spectrum, quantitatively determine the content of emamectin benzoate through the standard concentration curve and calculate the drug loading. The drug loading is the effective mass of emamectin benzoate loaded by the adsorption and slow-release agent per unit mass. The results are shown in Table 1.

[0097] Table 1 Determination of drug loading

[0098] Drug loading amount (mg / g) Example 1 131 Example 2 227 Example 3 261 Example 6 293

[0099] Test Example 2

[0100] Pharmacodynamic performance test: Use the metamifop - fluroxypyr - mefenpyr - diethyl emulsifiable concentrate prepared in Examples 1 - 6 respectively to conduct pharmacodynamic and phytotoxicity tests. The specific methods are as follows:

[0101] Test weeds: Echinochloa crusgalli, Eleusine indica, Digitaria sanguinalis, Portulaca oleracea, Alopecurus aequalis. Investigate the control effect of weeds on the 15th day and 45th day after application.

[0102] Experimental design: Conduct experiments on the metamifop - fluroxypyr - mefenpyr - diethyl emulsifiable concentrate prepared in Examples 1 - 6 mentioned above and the clear water control group. Each treatment has 4 replicates, the dosage is 400 g / hm2, and spray evenly on the stems and leaves. Take samples of 50 m in each plot 2 , and arrange them in a randomized block design. Calculate the fresh weight control effect of each agent on the 15th day and 45th day after application. Control effect = [(number of weed plants (or fresh weight) in the control area - number of weed plants or fresh weight in the treatment area)] / number of weed plants (or fresh weight) in the control area × 100%. The results are shown in Table 2.

[0103] Table 2 Herbicidal pharmacodynamic performance test

[0104]

[0105] It can be seen from the above results that the metamifop - fluroxypyr - mefenpyr - diethyl emulsifiable concentrate prepared by the present invention has good herbicidal effects and long - lasting pharmacodynamic effects. Comparing Examples 1 - 3, it can be known that introducing metal ions through ion exchange can enhance the interlayer charge distribution, increase the specific surface area and adsorption capacity, graft organic functional groups on the surface of bentonite, improve its compatibility with organic pesticides, and enhance the slow - release effect.

[0106] Hydroxypropyl-β-cyclodextrin has a cavity structure with hydrophilic exterior and hydrophobic interior, which can adsorb and include pesticide molecules (such as halauxifen-methyl), forming a "host-guest complex". After inclusion, the release rate of the pesticide is controllable, reducing photolysis and degradation, improving the solubility and stability of the pesticide, and prolonging the effective period. The long-chain structure of polyethylene glycol can prevent the aggregation of bentonite particles, improve its dispersibility in the emulsifiable concentrate system, improve the compatibility of the pesticide with water, and promote the emulsification of the emulsifiable concentrate. The siloxane group of the silane coupling agent can condense with the hydroxyl groups of bentonite to form stable chemical bonds. Mercapto, amino and other silane coupling agents can enhance the adsorption and slow-release ability of pesticides.

[0107] Further comparing Examples 3-4, it can be seen that in Example 4, three modifiers are used to modify bentonite. The reason is that the modified bentonite has a larger layer spacing, a higher specific surface area and a stronger adsorption capacity. Metal doping increases the layer spacing of bentonite, providing space to accommodate pesticide molecules, especially the relatively large-sized halauxifen-methyl. Due to the adsorption effect, halauxifen-methyl is released relatively fast in the initial stage; the sulfonamide group of mefenoxam can form a coordination bond with metal cations, the ester group of halauxifen-methyl can have electrostatic attraction with the amino group in the amino-silane coupling agent, and the pyridine nitrogen of halauxifen-methyl and the cyano group of cyhalofop-butyl can also coordinate with cations. Because the coordination bond has a strong effect, the release is relatively fast in the middle and late stages. Thus, the slow release of pesticides can be achieved, reducing the application frequency and dosage of pesticides. The modified bentonite greatly improves the loading rate of pesticides; the combined action of polyethylene glycol and silane coupling agent prevents particle sedimentation, enhances the stability of the emulsifiable concentrate, and prolongs the storage period; the slow-release design reduces pesticide runoff, improves targeting, reduces the impact on non-target organisms, improves the adsorption and slow release of pesticides, and improves pesticide utilization efficiency.

[0108] Finally, comparing Examples 4-6, it can be seen that the metal chlorides used in the present invention are a mixture of ferric chloride and copper chloride. The reason is that ferric chloride has a high charge density and strong Lewis acidity, and can preferentially combine with mefenoxam (sulfonamide group) through coordination bonds, hydrogen bonds and electrostatic attraction; while copper chloride is more likely to form coordination bonds or π-π stacking with the aromatic ring or heteroatoms (such as pyridine nitrogen, cyano group -CN) of pesticides, compensating for the limitations of ferric ions. Therefore, through the synergistic effect of iron and copper ions, the modified bentonite not only realizes the efficient loading of multi-component compound pesticides, but also achieves a synergistic effect of 1+1>2 through the cascade mechanism of chemisorption-physical inclusion-environment-responsive release, providing a more efficient control effect for herbicides in complex farmland environments.

[0109] In summary, through the synergistic modification of metal doping + hydroxypropyl-β-cyclodextrin / PEG / silane coupling agent, the bentonite is upgraded from a simple carrier to a multifunctional synergist, which not only optimizes the dispersibility and stability of pesticides, improves the loading rate of pesticides, but also realizes slow-release synergism, reduces the dosage of pesticides, improves the utilization rate of pesticides, has good herbicidal efficacy, reduces the application amount of pesticides and other objectives, providing a new direction for the efficient application of ternary compound herbicides.

Claims

1. A propyzamide - fluroxypyr - meptyl - cyhalofop - butyl emulsifiable concentrate, characterized in that, It consists of the following raw materials in parts by weight: 10 - 20 parts by weight of mefenoxam, 0.5 - 3 parts by weight of halauxifen-methyl, 18 - 36 parts by weight of cyhalofop-butyl, 2 - 5 parts by weight of dichlormid, 2 - 6 parts by weight of dispersant, 3 - 8 parts by weight of surfactant, 2 - 5 parts by weight of emulsifier, 30 - 60 parts by weight of water, 3 - 8 parts by weight of synergist; the synergist is modified bentonite, and the modified bentonite is metal-doped bentonite modified by a triple modifier.

2. The pretilachlor - fluroxypyr - meptyl EC according to claim 1, characterized in that, The preparation method of the metal-doped bentonite is as follows: Mix 8 - 14 parts by weight of bentonite and 150 - 300 parts by weight of water, disperse them by ultrasonic wave, adjust the pH to 7 with hydrochloric acid, add 3 - 8 parts by weight of metal chloride, and stir at room temperature and 400 - 800 rpm for 4 - 10 h to obtain metal-doped bentonite.

3. The oxaziclomefone - fluroxypyr - meptyl - cyhalofop - butyl emulsifiable concentrate according to claim 1, characterized in that, The preparation method of the triple modifier is as follows: Mix 0.3 - 1 part by weight of hydroxypropyl-β-cyclodextrin and 2 - 6 parts by weight of polyethylene glycol, add an ethanol aqueous solution, stir at 70 - 90 °C and 200 - 400 rpm for 0.5 - 3 h, and then add it to 3 - 7 parts by weight of silane coupling agent, and stir at 30 - 50 °C and 200 - 400 rpm for 1 - 4 h to obtain a modifier.

4. The mefenoxam - fluroxypyr - meptyl - cyhalofop - butyl emulsifiable concentrate according to claim 1, characterized in that, The preparation method of the modified bentonite is as follows: Under nitrogen protection, mix 1.5 - 4 parts by weight of the above-mentioned modifier with 40 - 100 parts by weight of dimethyl sulfoxide, add 0.2 - 0.7 part by weight of NaH, stir at room temperature and 100 - 300 rpm for 10 - 40 min, and then add 3 - 8 parts by weight of the above-mentioned metal-doped bentonite, and react at 80 - 110 °C and 100 - 300 rpm for 6 - 18 h to obtain modified bentonite.

5. The mefenoxam - halauxifen - methyl - cyhalofop - butyl emulsifiable concentrate according to claim 2, wherein The metal chloride is at least one of ferric chloride, copper chloride, calcium chloride, and magnesium chloride.

6. The mefenoxam - fluroxypyr - meptyl - cyhalofop - butyl emulsifiable concentrate according to claim 3, wherein The silane coupling agent is at least one of 3-mercaptopropyltriethoxysilane, 3-(2-aminoethylamino)propylmethyldimethoxysilane, and N-[β-(N,N-diacetyl)aminoethyl]-γ-(N-acetyl)aminopropyltrimethoxysilane.

7. The pretilachlor - fluroxypyr - meptyl EC according to claim 1, characterized in that, The dispersant is at least one of lauroyl glycinate, alkylphenol polyoxyethylene ether formaldehyde condensate, glycerol borate fatty acid ester, and polycarboxylate.

8. The oxazolyloxy-methyl - fluroxypyr - meptyl - cyhalofop - butyl emulsifiable concentrate according to claim 1, wherein, The surfactant is at least one of isooctanol polyoxyethylene ether, lauryl alcohol ether phosphate, sodium dodecyl sulfate, calcium dodecylbenzenesulfonate, sodium lignosulfonate, and carboxymethyl cellulose.

9. The mefenoxam - fluroxypyr - mepiquat chloride emulsifiable concentrate according to claim 1, characterized in that, The emulsifier is at least one of the Tween series, alkylphenol polyoxyethylene ether, phenethylphenol polyoxyethylene ether, and calcium alkylbenzenesulfonate.

10. The preparation method of the mefenoxam - fluroxypyr - mepiquat chloride - cyhalofop - butyl emulsifiable concentrate according to any one of claims 1 - 9, characterized in that, It includes the following steps: Mix water, synergist, and dispersant, and stir at room temperature for 30 - 60 min; add mefenoxam, halauxifen-methyl, cyhalofop-butyl, dichlormid, surfactant, and emulsifier, and homogenize at 10000 - 15000 rpm for 5 - 15 min to obtain mefenoxam-halauxifen-methyl-cyhalofop-butyl emulsifiable concentrate.

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