WO2018058904A1

WO2018058904A1 - Herbicide composition with enhanced effectiveness and application thereof

Info

Publication number: WO2018058904A1
Application number: PCT/CN2017/076782
Authority: WO
Inventors: 金涛; 彭学岗; 张景远; 赵德; 王金信; 路兴涛
Original assignee: 江苏清原农冠杂草防治有限公司
Priority date: 2016-09-30
Filing date: 2017-03-15
Publication date: 2018-04-05
Also published as: CN106472517B; CN106472517A

Abstract

Provided is a herbicide composition with enhanced effectiveness, comprising 1-(2-chloro-3-(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazolo-4-carbonyl)-6-trifluoromethylphenyl)-piperidin-2-one, or a salt or ester thereof. The composition comprises active ingredients A and B provided in an effective dose, wherein A is either the salt, a C1-C4 carboxylic acid ester or a benzoic acid ester; and B is selected from a: 1) phenoxyalkanoic acid; 2) pyridine carboxylic acid; 3) benzoic acid; 4) nitrile; 5) triazole ketone; 6) diphenyl ether; 7) thiadiazole; 8) pyrimidinedione; 9) amide; 10) sulfonylurea; 11) sulfamide; 12) pyrazole; 13) thiocarbamate; 14) bentazon, and the like. The composition can effectively remove a grass weed or a broadleaf weed from a wheat field, and provides features such as large herbicidal spectrum, significant performance enhancement, reduced usage, can be used safely on crops, and the like.

Description

Synergistic herbicidal composition and application thereof

Technical field

The invention belongs to the technical field of pesticide synergy, and particularly relates to a method comprising 1-(2-chloro-3-(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazole-4-carbonyl)-6. A synergistic herbicidal composition of -trifluoromethylphenyl)piperidin-2-one or a salt or ester thereof and use thereof.

Background technique

The use of herbicide chemical weeding is the most economical and effective means of controlling weeds in farmland. However, long-term continuous high-dose use of single-species or single-acting chemical herbicides is likely to cause problems such as weed resistance and resistance evolution. Rational compounding or compounding of herbicide compounds has the advantages of expanding weed spectrum, improving control effect, delaying the occurrence and development of weed resistance and drug resistance, and is one of the most effective methods to solve the above problems.

P-hydroxyphenylpyruvate dioxygenase (HPPD) was discovered following acetyl-CoA carboxylase (ACCase) inhibitors, acetolactate synthase (ALS) inhibitors and protoporphyrin oxidase (Protox) inhibitors. Another class of new herbicides. The action of HPPD inhibitors is characterized by a broad spectrum of herbicidal activity, which can be used before and after emergence, and the weeds die after whitening. Although the symptoms are very similar to those of carotenoid bioinhibitors, their chemical structural features such as polarity and ionization are significantly different from known carotenoid bioinhibitors. The HPPD inhibitor herbicide weed resistance risk is much lower than that of ACCase inhibitors, ALS inhibitors, photosynthesis photosystem II, hormones and other herbicides, and there is no target resistance with these classes of herbicides. Sexually induced cross-resistance.

Acetyl lactate synthase (ALS) inhibitor herbicide, protoporphyrinogen oxidase (PPO) inhibitor herbicide, photosynthesis photosystem II herbicide, hormone herbicide in the wheat field weed control system Important location.

Common acetolactate synthase (ALS) inhibitor herbicides in wheat field include: benzosulfuron, bensulfuron-methyl, thifensulfuron, chloropyrimidene, methyl disulfuron, sulfonylsulfonate, propylbenzene Sulfonamide, flufensulfuron, diflufenazone, flufensulfuron, acesulfame, etc., ALS inhibitor herbicides are selective systemic herbicides, which can be roots and leaves of weeds. Absorbed and transmitted in the body of the plant. By inhibiting the activity of acetolactate synthase (ALS), it affects the biosynthesis of branched chain amino acids (leucine, isoleucine, valine). After the plant is damaged, the growth point is necrotic, the veins are chlorotic, the plant growth is severely inhibited, dwarfed, and finally the whole plant is dead. Sensitive weeds stop growing immediately after absorbing the drug and die after 1-3 weeks. The above herbicides can be used to control the broadleaf weeds such as the sage, the leeks, the wild rape, the porcine, the sorghum, the burdock, and the maiden. Due to repeated and continuous use in successive years, the resistance of weeds is improved, the dosage is increased, the cost is increased, and the safety risk is increased.

Common photosynthesis photosystem II herbicides in wheat field are: bromoxynil, octanoyl bromoxynil, iodobenzonitrile, bentazone, isoproturon, chloromeron, tertidine, chlorpyrifos, oxalofen Photosynthetic photosystem II herbicide is a selective herbicide for post-emergence stem and leaf treatment. It is mainly absorbed by the leaves. It can quickly make tissue necrosis by inhibiting various processes of photosynthesis. The above-mentioned medicaments can be used for controlling broad-leaved weeds such as sage, amaranth, and bristle in the wheat field, but when the medicament is used alone, the amount is large. Moreover, there is a heavier safety risk to wheat. When the dosage is small, the control effect on weeds is poor, and the application technique and dosage are strictly controlled.

Common protoporphyrinogen oxidase (PPO) inhibitor herbicides commonly found in wheat fields include: oxazolone, acesulfame, etc.; azole PPO inhibitor herbicides are a contact-selective herbicide, Under light conditions, in the process of chlorophyll biosynthesis, the accumulation of toxic intermediates is inhibited by inhibiting protoporphyrinogen oxidase, thereby destroying the cell membrane of weeds, causing the leaves to dry quickly and die. The above-mentioned medicaments can be used for controlling broad-leaved weeds such as sage, leeks and piglets in wheat fields, but when the medicaments are used alone, the dosage is high, the cost is high, and the safety risk to wheat is heavier. The control effect of grass is poor, and it is necessary to strictly control the application technology and dosage.

Common hormonal herbicides in wheat fields are: 2, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4, 4 D butyl ester, 2,4-D isooctyl ester, 2,4-dichlorophenoxyacetic acid, 2,4-DB, 2,4-D-propionic acid, flupiric acid, flupiroxine Octyl ester, fluorochloropyridinium ester, triclopyridinic acid, clopyralid, dicamba, etc.; hormone herbicide is a systemic herbicide for post-induction, which is quickly absorbed by plants and makes sensitive plants appear typical. In response to hormonal herbicides, the plants were deformed, distorted, and eventually died. The above-mentioned medicaments can be used for controlling broad-leaved weeds such as Artemisia scoparia, Amaranth, Poria, Poria, and Maijiagong in the wheat field, but when the medicament is used alone, the herbicidal spectrum is narrow, the dosage is high, the cost is high, and the temperature is low. Or there is a heavier safety risk when the cold spring occurs. When the dosage is small, the control effect on weeds is poor. It is necessary to strictly control the application technique and the dosage.

Summary of the invention

In order to solve the above problems in the prior art, the present invention provides a 1-(2-chloro-3-(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazole-4-carbonyl) group. a synergistic herbicidal composition of 6-trifluoromethylphenyl)piperidin-2-one or a salt or ester thereof, and an application thereof, which is effective for controlling grass weeds and broadleaf weeds in a wheat field It has the characteristics of expanding herbicidal spectrum, obvious synergistic effect, reducing application rate, and safety to crops.

A synergistic herbicidal composition comprising a herbicidally effective amount of active ingredient A and active ingredient B, wherein

Active ingredient A is a compound

Or a salt or ester thereof, wherein the ester is a C1-C4 carboxylate or benzoate;

The active ingredient B is selected from one or more of the following compounds:

1) Phenoxycarboxylic acids: 2 methyl 4-chloro, 2 methyl 4-chloroethyl sulfide, MCPB, 2 methyl 4-chloropropionic acid, 2 methyl 4-chloro sodium, 2 methyl 4-chloroisooctyl ester, 2,4-D Ester, 2,4-D isooctyl ester, 2,4-dichlorophenoxyacetic acid, 2,4-DB, 2,4-D-propionic acid;

2) Pyridine carboxylic acids: flupirtoxyacetic acid, isooctyl chlorofluoropyroxyacetate, fluorochloropyridinium ester, trichloropyridinic acid, two Chlorpyridic acid, florpyrauxifen (CAS number 943832-81-3);

3) Benzoic acid: dicamba;

4) Nitriles: bromoxynil, octanoyl bromoxynil, iodobenzonitrile;

5) triazolinones: oxadiazon;

6) Diphenyl ethers: acesulfame, chlorflufen;

7) thiadiazoles: methyl oxazinate;

8) pyrimidinedione: saflufenacil;

9) Amides: acetochlor, flufenacet, mefenacet, metolachlor, dimethoprim, oxalylamine, dipterin, pretilachlor, propisochlor, turfgrass Amine, benzilamide;

10) Sulfonylureas: bensulfuron-methyl, bensulfuron-methyl, thifensulfuron-methyl, chloropyrazine, sulfimsulfuron, trifluoromethanesulfuron, ethersulfuron, chlorsulfuron, metsulfuron, Flunarsulfuron, iodosulfuron sodium, ciprofloxacin;

11) Sulfonamides: diflufenacil, flufensulfuron, sulfoxazolamide;

12) Pyrazoles: oxazolone, oxafluridone, oxazolone, triazosinone;

13) thiocarbamates: benzathine;

14) Others: bentazone, valerian, flupirazone.

Preferably, the active ingredient B is sodium 2, 4-chlorochloride, 2, 4-chloroisooctyl ester, 2,4-D isooctyl ester, flufenoxyacetic acid, isooctyl chlorofluoropyroxyacetate, chlorofluorocarbon. Pyridyl ester, florpyrauxifen, pretilachlor, flufenacet, oxazolone, acesulfame, dipyridamole, tribenuron, bensulfuron-methyl, diflufenacil, bentazone, bromoxynil, One or more of octanoyl bromoxynil, oxazolone, oxafluridone, valerate, and benzathine.

Wherein, the weight ratio of A to B is 1-100:1-100, preferably the weight ratio of A to B is 1-80:1-80, 1-50:1-50, 1-30:1-30, Preferably, the weight ratio of A to B is 1-20:1-20, 1-10:1-10, 1:1-50, 1:1-30, 1-50:1, 1-30:1 is defined Within the range of the weight ratio, the active ingredient A and the active ingredient B are mixed to obtain a synergistic technical effect.

The mass percentage of A and B in the synergistic herbicidal composition is from 1 to 95%, preferably from 5 to 80%, based on the total amount. Generally, the herbicidal compositions of the present invention comprise from 1 to 95 parts by weight of active ingredient and from 5 to 99 parts by weight of a conventional pesticide adjuvant.

Conventional auxiliaries of the compositions of the present invention may be carriers, surfactants and the like.

The term "carrier" as used herein refers to an organic or inorganic, natural or synthetic material. They aid in the administration of the active ingredient which is generally inert and must be agriculturally acceptable, especially accepted by the treated plant. The carrier may be solid, such as clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or waxy hydrocarbons, chlorine Hydrocarbons, liquefied gases, etc.

Surfactants may include emulsifiers, dispersants or wetting agents, which may be ionic or nonionic. Examples which may be mentioned are salts of polyacrylic acid, lignosulfonates, salts of phenolsulfonic or naphthalenesulfonic acid, ethylene oxide with aliphatic alcohols or with fats a family of acids or polymers of aliphatic and substituted phenols (especially alkylphenols or arylphenols), sulfosuccinates, taurine derivatives (especially taurine alkyl esters) and phosphates of alcohols Or polyhydroxyethylated phenol phosphates, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated sixteen, ten Hepta- and stearyl alcohols and sulfated fatty alcohol glycol ethers, in addition to condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol , octylphenol or nonylphenol, alkyl phenyl polyglycol ether, tributyl phenyl polyglycol ether, tristearyl phenyl polyglycol ether, alkyl aryl polyether alcohol, Alcohol and fatty alcohol/ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl polyethylene glycol ether acetal, sorbitol ester, lignin sulfite Waste liquid, as well as proteins, denatured proteins, polysaccharides (such as methyl cellulose), hydrophobically modified starches, polyvinyl alcohol, polycarboxylates, polyalkoxylates, Vinylamine, polyvinylpyrrolidone and copolymers thereof. At least one surfactant is required to facilitate dispersion of the active ingredients in water and to facilitate their proper application to the plants.

The above compositions may also contain various other components such as protective colloids, binders, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents, dyes, colorants, and polymers.

The compositions of the present invention may be diluted or used directly by the user prior to use. The preparation can be prepared by a usual processing method, that is, after mixing the active material with a liquid solvent or a solid carrier, and then adding one or more of a surfactant such as a dispersing agent, a stabilizer, a wetting agent, a binder, an antifoaming agent, and the like. Kind.

Specific formulations of the herbicidal compositions are emulsifiable concentrates, suspensions, microemulsions, suspoemulsions, aqueous emulsions, dispersible oil suspensions, wettable powders or water-dispersible granules (dry suspensions).

When the composition is made into a wettable powder, the content of the following components is: 1 to 70% of the active ingredient A, 1 to 50% of the active ingredient B, 5 to 10% of the dispersing agent, 2 to 10% of the wetting agent, and the balance of the filler.

The active ingredient A, the active ingredient B, the dispersing agent, the wetting agent, and the filler are mixed, uniformly mixed in a mixing tank, pulverized by a jet mill, and then uniformly mixed to obtain a wettable powder product of the composition of the present invention.

When the composition is made into a water-dispersible granule, the content of the following components is as follows: active ingredient A 1 to 70%, active ingredient B 1 to 50%, dispersant 3 to 12%, wetting agent 1 to 8%, disintegrating agent 1 to 10%, binder 1 to 8%, filler balance.

The active ingredient A, the active ingredient B, a dispersing agent, a wetting agent, a disintegrating agent, a filler, and the like are pulverized together to obtain a desired particle diameter, and then a binder or the like is added to obtain a granulation material. The water-dispersible granule product of the composition of the present invention is obtained by quantitatively feeding the product into a fluidized bed granulation dryer, granulating and drying.

When the composition is formulated into a suspending agent, the content of the following components is included: active ingredient A 0.1-40%, active ingredient B 0.1-30%, dispersing agent 2-10%, humectant 2-10%, antifoaming agent 0.1-1%. The binder is 0.1 to 2%, the antifreeze is 0.1 to 8%, and the deionized water is added to 100%.

Dispersing agent, wetting agent, antifoaming agent, thickening agent and antifreezing agent in the above formula are uniformly mixed by high speed shearing, adding active ingredient A and active ingredient B, and ball milling in a ball mill for 2 to 3 hours to make the particles The diameter is all below 5μm. A suspending agent product of the composition of the invention is obtained.

When the composition is made into a suspoemulsion, the content of the following components is included: active ingredient A 0.1-40%, active ingredient B 0.1-30%, emulsifier 2-12%, dispersant 2-10%, defoamer 0.1-2% , thickener 0.1 to 2%, antifreeze 0.1 to 8%, stabilizer 0.05 to 3%, water to 100%.

Dispersing agent, antifoaming agent, thickening agent, antifreeze agent and stabilizer in the above formula are uniformly mixed by high speed shearing, adding active ingredient B to the original drug, and ball milling in a ball mill for 2 to 3 hours to make the particle size all The active ingredient B suspending agent is prepared at 5 μm or less, and then the active ingredient A original drug, emulsifier and various auxiliary agents are directly emulsified into a suspension by a high-speed stirrer to obtain a suspoemulsion product of the composition of the present invention.

When the composition is made into an aqueous emulsion, the content of the following components is included: active ingredient A 0.1% to 40%, active ingredient B 0.1% to 30%, solvent 2% to 10%, emulsifier 2% to 12%, dispersant 2%. ～10%, co-emulsifier 0.2% to 5%, antifreeze 0.1% to 8%, antifoaming agent 0.1% to 2%, thickener 0.1% to 2%, deionized water to 100%.

The original drug, solvent, emulsifier and co-emulsifier are added together in the above formula to dissolve into a uniform oil phase. Deionized water, dispersant, antifreeze, antifoaming agent, thickener are mixed together to form a uniform aqueous phase, and the aqueous phase is slowly dropped into the oil phase under high-speed stirring to prepare the composition of the present invention. Good water emulsion products.

When the composition is made into a microemulsion, the content of the following components is included: active ingredient A 0.1% to 40%, active ingredient B 0.1% to 30%, emulsifier 5% to 15%, solvent 2% to 10%, antifreeze 5 %～10%, stabilizer 0.5%～3%, deionized water added to 100%.

The original drug, solvent and emulsifier in the above formula are added into the mother liquor to prepare a uniform oil phase, and the deionized water and the antifreezing agent are uniformly mixed and injected into the product preparation kettle, and the mixture is uniformly mixed to form the combination of the invention. A transparent or translucent microemulsion product.

Briefly, the compositions of the present invention can be combined with solid and liquid additives conventionally used in prior art formulations.

In a further preferred embodiment, the herbicidal composition further comprises a safener C selected from the group consisting of pyrazolium, detoxification quinone, dibenzoxazole acid, cyclopropanesulfonamide, naphthalic anhydride (NA), Chlorfenac, R-28725, AD-67, CGA-154281 (Benoxacor), CGA-43089 (Cyometrinil), CGA-43089 (Cyometrinil), Hoe-70542 (Fenchlorazole), Fenclorim, and grass An, BAS-145138, MON-13900, quinoline derivatives, sulfonylurea (amine) safeners, 2,4-D (organic acids), new antidote T (main component 4% Ti ⁴⁺ ) and One or more of gibberellins (GA).

The composition of the present invention can be applied to the leaves of the plants to be treated by spraying, i.e., to the weeds, especially on the surface which is infesting or susceptible to weeds which are harmful to the growth of the crop, and the dosage of these active ingredients is usually applied. It is between 15 and 1500 g/ha, preferably between 30 and 750 g/ha.

The herbicidal composition of the present invention has passed the 2-year field efficacy test, showing that in the wheat 3 leaf stage to the regreening stage, weeds 1-5 In the unequal leaves, wheat has no symptoms of phytotoxicity from application to maturity and is safe for wheat. The control effect of weeds reached more than 90% in 45 days. With the increase of drug dosage, the control effect increased significantly. Once applied, the weeds could be controlled during the whole growth period of the crop. Not only the herbicidal effect was significant, but also environmentally friendly. No impact on the next crop.

When the herbicidal compositions of the present invention were applied, unexpected synergistic effects were obtained, and the herbicidal activity was more significant than the expected total activity of the individual herbicides, and the individual herbicides alone were more active. Synergistic effects are shown by reduced application rates, wider weed control profiles, faster and longer herbicidal effects, which are required for weed control practice. These new compositions are clearly superior to existing herbicides in terms of the characteristics described.

The herbicidal composition of the present invention also has the following advantages:

(1) The composition of the present invention is an environmentally friendly herbicide which is easily degraded in the environment and is safe for both glutinous wheat and post-crop crops.

(2) The herbicidal composition of the invention has low cost and convenient use, and has great economic and social benefits for its popularization and application.

(3) Compared with the prior art, the herbicidal composition of the present invention can prevent weeds from resistant broad-leaved weeds and can prevent broad-leaved weeds which are resistant to ALS inhibitors, and is a wheat field weed. An effective solution for resistance management.

detailed description

The following examples are not intended to limit the invention, but are merely illustrative of how the invention can be implemented. These examples show particularly significant effectiveness for certain weeds.

A, the embodiment

1) Cream

1.1) Compound A, when the active ingredient B is 2 methyl 4-chloroisooctyl ester.

The composition of the formula is: 8% A + 40% 2 methyl 4-chloroisooctyl ester + 10% N-methyl pyrrolidone + 7% calcium dodecylbenzenesulfonate + 7% phenethyl phenol polyoxyethylene ether + 200# Aromatic solvent oil

1.2) Compound A, when the active ingredient B is flupiroxine (ester).

Formula composition: 8% A + 6% flupiroxine (ester) + 6% calcium dodecyl benzene sulfonate + 10% castor oil polyoxyethylene ether +15% isophorone + 200 # aromatic solvent Oil supplement

1.3) Compound A, when the active ingredient B is a propanil.

The composition of the formula is: 0.8% A + 25% enemy 稗 + 3% calcium dodecyl benzene sulfonate +15% phenethyl phenol polyoxyethylene ether +15% hydrazine amide + 200 # aromatic hydrocarbon solvent oil

1.4) Compound A, when the active ingredient B is pretilachlor.

The composition of the formula is: 4% A+17.5% pretilachlor + 6% calcium dodecylbenzenesulfonate + 10% nonylphenol polyoxyethylene ether + 10% N-methylpyrrolidone + 200 # aromatic hydrocarbon solvent oil

The above processing equipment for emulsifiable oil: vacuum pump, batching kettle, storage tank.

The processing of the above emulsifiable oil: all materials are put into the batching kettle, stirred and dissolved until completely transparent, and after passing the test, the material is transferred to the tank for filling.

2) Microemulsion

2.1) The compound is A and the active ingredient B is octanoyl bromoxynil.

Formulation composition: 4% A + 10% octanoyl bromoxynil + 10% cyclohexanone + 10% isooctanol + 4% decylamide + 8% sodium di-n-octyl octane sulfonate + 8% phenyl Phenolic polyoxyethylene ether + 4% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate + water complement

2.2) The compound is A and the active ingredient B is acesulfame.

The composition of the formula is: 8% A + 0.8% acesulfame + 10% isophorone + 10% cyclohexanone + 5% ethanol + 8% calcium dodecylbenzenesulfonate + 12% phenethyl phenol Polyoxyethylene ether + 2% phenethyl phenol polyoxyethylene ether formaldehyde resin condensate + water complement

The above microemulsion processing equipment: vacuum pump, batching kettle, storage tank.

The above microemulsion processing process: the original drug and the solvent are put into the batching kettle, stirred and dissolved until completely transparent, then the emulsifier is added, and the mixture is evenly stirred. Finally, water is added, and the mixture is stirred until the solution is completely transparent. After the test is passed, the solution is transferred to the tank for filling.

3) Water emulsion

3.1) The compound is A and the active ingredient B is oxadiazon.

Formulation composition: 4% A + 0.5% oxalofenone + 10% cyclohexanone + 10% 200 # solvent oil + 3% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt + 4% phenethyl phenol poly Oxyethylene ether + 3% castor oil polyoxyethylene ether + 0.1% xanthan gum + 3% ethylene glycol + water to make up

3.2) The compound is A and the active ingredient B is 2,4-D isooctyl ester.

The composition of the formula is: 4% A + 1.25% 2,4-D isooctyl ester + 10% cyclohexanone + 10% 200 # solvent oil + 3% nonylphenol polyoxyethylene ether phosphate triethanolamine salt + 5% hydrazine Sesame oil polyoxyethylene ether + 0.08% xanthan gum + 3% ethylene glycol + water to make up

The above water emulsion processing equipment: vacuum pump, batching kettle, storage tank, shearing kettle.

The above water emulsion processing process: the original drug and the solvent are put into the batching kettle, stirred and dissolved until completely transparent, and then the emulsifier is added, and the mixture is uniformly stirred into an oil phase, and then the ethylene glycol, the defoaming agent and the water are pumped into the shearing kettle. Finally, in the shear state, the oil phase is slowly drawn into the shearing tank. After all the materials are drawn in, the cutting is continued for 1 hour. After the test is passed, the oil is transferred to the tank for filling.

4) Suspending agent

4.1) Compound A, when the active ingredient B is diflufenacil.

Formulation composition: 16% A+1% diflufenacil + 3% polycarboxylate dispersant + 3% EO-PO block polyether + 2% fatty alcohol polyoxyethylene ether + 0.2% xanthan gum +1.5% magnesium aluminum silicate + 5% glycerol + water to make up.

4.2) Compound A, when the active ingredient B is bromoxynil.

Formulation composition: 12% A+24% bromoxynil + 3% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt + 3% polycarboxylic acid Salt dispersant + 2% nonylphenol ethoxylate + 0.2% xanthan gum + 5% glycerol + water to make up.

4.3) Compound A, when the active ingredient B is oxazolone.

The composition is: 32% A + 6% oxazolone + 3% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt + 3% polycarboxylate dispersant + 2% fatty alcohol polyoxyethylene ether + 0.15% xanthan gum + 5% glycerol + water to make up.

4.4) Compound A, when the active ingredient B is Florpyrauxifen.

The composition is: 16% A + 1.2% Florpyrauxifen + 3% phenethyl phenol polyoxyethylene ether phosphate triethanolamine salt + 3% polycarboxylate dispersant + 2% fatty alcohol polyoxyethylene ether + 0.16% yellow The original rubber + 1.5% magnesium silicate aluminum + 5% glycerol + water to make up.

4.5) Compound A, when the active ingredient B is flufenacet.

The composition of the formula is: 8% A + 8% flufenacetate + 3% nonylphenol polyoxyethylene ether phosphate triethanolamine salt + 3% polycarboxylate dispersant + 2% fatty alcohol polyoxyethylene ether + 0.2 % xanthan gum + 1.8% magnesium silicate aluminum + 5% glycerol + water to make up.

The above water suspension processing equipment: mixing tank, colloid mill, sand mill, shearing machine and the like.

The above water suspension agent processing process: all materials are put into the mixing kettle, stirred and mixed, then passed through the colloid mill, then enter the sand mill three-stage sanding, and finally cut evenly in the shearing machine, after passing the test, transfer to storage Tank filling.

5) Dispersible oil suspension agent

5.1) Compound A, when the active ingredient B is fluorochloropyridinium ester.

Formulation composition: 16% A+1% fluorochloropyridinium ester + 4% calcium dodecylbenzenesulfonate + 7% fatty acid polyoxyethylene ether + 2% castor oil polyoxyethylene ether + 1.5% organic bentonite + 1.5% Fumed silica + methyl oleate to make up.

5.2) Compound A, when the active ingredient B is diflufenacil.

The composition of the formula is: 8% A + 0.5% diflufenacil + 3% sodium dodecyl octyl sulfonate + 7% nonylphenol ethoxylate + 5% sorbitan polyoxyethylene + 2% castor oil polyoxyethylene ether + 2.5% organic bentonite + 10% soybean oil + methyl oleate to make up.

5.3) Compound A, when the active ingredient B is flupiroxine (ester).

The composition is: 16% A + 12% flufenoxyacetic acid (ester) + 7% fatty alcohol polyoxyethylene ether + 5% sorbitan fatty acid polyoxyethylene ester + 6% castor oil polyoxyethylene ether + 2.5 % organic bentonite + 20% 200 # solvent oil + methyl oleate to make up.

5.4) Compound A, when the active ingredient B is 2 methyl 4-chloroisooctyl ester.

The composition of the formula is: 8% A + 30% 2 methyl 4-chloroisooctyl ester + 3% calcium dodecylbenzenesulfonate + 5% sorbitan fatty acid polyoxyethylene ester + 6% castor oil polyoxyethylene ether + 3% organic bentonite + 2.5% fumed silica + 10% 200 # solvent oil + methyl oleate to make up.

5.5) Compound A, when the active ingredient B is oxazolone.

Formulation composition: 16% A + 3% oxaconazole + 4% calcium dodecyl benzene sulfonate + 4% sorbitan fatty acid polyoxyethylene ester + 6% castor oil polyoxyethylene ether + 2% organic Bentonite + 2% fumed silica +15% 200 # solvent oil + methyl oleate foot.

5.6) Compound A, when the active ingredient B is valerate.

Formula composition: 1.6% A + 27% valerate + 4% calcium dodecyl benzene sulfonate + 5% sorbitan fatty acid polyoxyethylene ester + 6% castor oil polyoxyethylene ether + 1.5% organic bentonite +1.5% fumed white carbon black +15% 200 #solvent oil + methyl oleate to make up. The above dispersible oil suspension processing equipment: mixing tank, colloid mill, sand mill, shearing machine and the like.

5.7) Compound A, when the active ingredient B is benzathine.

Formula composition: 0.8% A + 24.2% benzalkon + 6% calcium dodecylbenzenesulfonate + 4% sorbitan fatty acid polyoxyethylene ester + 6% castor oil polyoxyethylene ether + 2.2% organic bentonite +2.2% fumed silica + 10% 200 # solvent oil + methyl oleate to make up.

5.8) Compound A, when the active ingredient B is oxazolone.

The composition of the formula is: 8% A + 1% oxazolone + 4% calcium dodecyl benzene sulfonate + 5% sorbitan fatty acid polyoxyethylene ester + 8% castor oil polyoxyethylene ether + 3% organic Bentonite + 2% fumed silica + 10% 200 # solvent oil + methyl oleate to make up.

5.9) Compound A, when the active ingredient B is bensulfuron-methyl.

The composition of the formula is: 8% A + 2% bensulfuron-methyl + 4% sodium sec-octyl sulfosuccinate + 5% sorbitan fatty acid polyoxyethylene ester + 4% castor oil polyoxyethylene ether + fatty alcohol Polyoxyethylene ether + 3% organic bentonite + 2% fumed silica + 10% 200 # solvent oil + methyl oleate to make up.

The above dispersible oil suspension agent processing process: all materials are put into the mixing kettle, stirred and mixed, then passed through the colloid mill, then enter the sand mill three-stage sanding, and finally cut evenly in the shearing machine, after passing the test, transfer To the tank filling.

6) Wettable powder

6.1) Compound A, when the active ingredient B is sodium 2-methyltetrachloride.

The composition of the formula is: 8% A + 25% 2 sodium tetrachloride sodium + 1% citric acid + 10% naphthalene sulfonate dispersant + 5% pull powder + 5% precipitation method white carbon black + diatomaceous earth complement

6.2) Compound A, when the active ingredient B is bentazone.

Formula composition: 8%A+50% bentazone +10% sodium lignosulfonate dispersant +3% sodium lauryl sulfate +10% precipitation method white carbon black + kaolin

6.3) Compound A, when the active ingredient B is bensulfuron.

Formula composition: 32% A + 4% benzenesulfuron + 12% calcium lignin sulfonate dispersant + 3% sodium lauryl sulfate + 10% precipitation method white carbon black + kaolin

The above wettable powder processing equipment: mechanical pulverizer, jet mill.

The above wettable powder processing process: the original drug, the auxiliary agent, the white carbon black, the kaolin, etc. are put into the mechanical pulverizer, and then passed through the airflow pulverizer, and the sample is tested and qualified for use.

7) Water dispersible granules

7.1) Compound A, when the active ingredient B is fluorochloropyridinium ester.

The composition of the formula is: 48% A + 3% chlorofluoropyridyl ester + 10% polycarboxylate dispersant + 5% pull-open powder + 1% disintegrant polyvinyl alcohol + filler diatomaceous earth to make up.

7.2) Compound A, when the active ingredient B is diflufenacil.

Formulation composition: 40% A + 2.5% diflufenacil + 10% naphthalene sulfonate dispersant + 3% sodium dodecyl benzene sulfonate +1% disintegrant polyvinylpyrrolidone + filler diatomaceous earth Make up.

The above water dispersible granule processing equipment: a jet mill, a coulter mixer, a basket granulator, a drying box, a screening machine, and the like.

The above water-dispersible granule processing process: the above materials are uniformly mixed and pulverized by air flow, added with water to knead and granulate, then dried, and finally sieved to obtain a finished product.

B, efficacy test

1) Test conditions

1.1) Test target

Amaranth (Capsella bursa-pastoris) was collected from the wheat fields of Bolip Town, Huangdao District, Shandong Province, Galium aparine and Malachium aquaticum from the small wheat field in Zhumadian, Henan.

The above weeds were cultured by pot culture, and placed in an enamel pan with 180х140mm plastic nutrient bowl. The surface soil was collected from the farmland and passed through the air-screened surface (4/5). The initial humidity of the soil was controlled at 20%. The seeds with full and uniform seeds were soaked in warm water at 25 ° C for 6 hours, germinated in a 28 ° C biochemical incubator (dark), and the white weed seeds were evenly placed on the soil surface, and then covered with soil 0.7 cm. After the treatment, the medicine is placed in a controllable solar greenhouse, and a certain amount of water is regularly added to the enamel tray to keep the soil moist.

1.2) Culture conditions

It is carried out in a controlled solar greenhouse at a temperature of 18 to 30 ° C, natural light, and a relative humidity of 57% to 72%.

The soil type is loam, the organic matter content is 1.63%, pH=7.1, alkali nitrogen is 84.3mg/kg, available phosphorus is 38.5mg/kg, and available potassium is 82.1mg/kg.

1.3) Instrumentation

3WP-2000 Walking Spray Tower, Nanjing Agricultural Machinery Research Institute, Ministry of Agriculture. GA110 type one ten thousand electronic balance (Germany); ZDR2000 intelligent data recorder (Hangzhou Zeda Instrument Co., Ltd.); SPX type intelligent biochemical incubator (Ningbo Jiangnan Instrument Factory).

2) Experimental design

2.1) Reagents

2.1.1) Test agent

The active ingredient B is a commercially available drug, and the active ingredient A is the active ingredient A. For the production method of the compound, see CN2015107506771.

The original drugs were all treated with acetone as a solvent, diluted with 0.1% emulsifier T-80 aqueous solution, and now diluted.

2.2) Test processing

2.2.1) Dose setting

In determining the distribution ratio or content of each component of active ingredient A and active ingredient B, the characteristics of the two agents and their virulence should be measured, and the main purpose of the formulation should also be considered. On the basis of the preliminary pre-test, the active ingredient A and the active ingredient B were used alone and mixedly in the table. A total of 15 groups were designed. Water containing no drug, the same solvent and an emulsifier was used as a blank control.

2.2.2) Repeated test

Each treatment was repeated 4 times, and each time 3 pots were treated, 20 seeds of weed seeds were planted per pot, and 60 plants per treatment.

2.3) Processing method

2.3.1) Processing time and number of times

Test the drug once. Waiting for weeds 2 leaves 1 heart period, intercropping, maintaining 15 weeds per pot, 45 strains per treatment, and then continue to culture until Japan to see Mai Niang, sowing sage 3 leaves 1 heart period for treatment.

2.3.2) Use of instruments and methods of administration

The cultured test materials were evenly placed on a platform with an area of 0.5 m ² , and sprayed with a 3WP-2000 type walking spray tower, and the spray amount was 30 kg/ha. The spray pressure was 0.3 MPa. After all the liquid medicines have been sprayed, close the air valve. After 30 seconds, open the spray tower door and take out the nutrient bowl. Then open the gas valve, spray 50 mL of water, and clean the spray tube.

3) Test method

Potted method is used. For weed culture see 2.1, refer to the "Pesticide Indoor Bioassay Test Guidelines Herbicide". See 3.3.2 for the method of administration, using stem and leaf treatment.

4) Data survey and statistical analysis

4.1) Survey method

Using the absolute number survey method, the whole seedlings of the living weeds were cut along the surface of the soil with a blade, and the fresh weight of the weeds was weighed by an analytical balance. For dead weeds, the fresh weight is zero.

4.2) Survey time and frequency

The investigation was conducted 20 days after the treatment, and a total of 1 investigation was conducted.

4.3) Statistical analysis of data

The Gothe method is used to calculate the theoretical fresh weight inhibition rate of each mixed combination (E0=X+Y-X*Y/100), and then measured with Compared with the inhibition rate (E), the combined effect of the two on weeds was evaluated. When the E-E0 value was greater than 10%, the synergistic effect was less than -10%, and the antagonism was between -10% and 10%. For additive effects. According to the actual control effect and the characteristics of the herbicide, the balance of the formula and other factors determine the best ratio.

Wherein X is the fresh weight inhibition rate when the amount of the active ingredient A is P; and Y is the fresh weight inhibition rate when the amount of the active ingredient B is Q.

The statistical results are shown in the table below.

Table 1A and 2 methyl 4-chlorosodium mixed with the actual control effect on weeds and the combined effect (Gowing method)

The actual control effect and combined effect of the mixture of Table 2A and 2 methyl 4-chloroisooctyl ester on weeds (Gowing method)

Table 3A and 2,4-D isooctyl ester mixed with weeds for practical control and combined effects (Gowing method)

Table 4A. Actual control effect and combined effect on weeds mixed with flufenoxyacetic acid (Gowing method)

Table 5A. Actual control effect and combined effect on weeds mixed with fluorochloropyridinium (Gowing method)

Table 6A combined with bromoxynil for actual control of weeds and combined effects (Gowing method)

Table 7A combined with octanoyl bromoxynil for actual control of weeds and combined effects (Gowing method)

Table 8A The actual control effect and combined effect of weeds mixed with oxazolone on weeds (Gowing method)

The actual control effect and combined effect of the mixture of Table 9A and acesulfame on weeds (Gowing method)

Table 10 The actual control effect of combined use of active ingredient A and diflufenacil on weeds and the combined effect (Gowing method)

Table 11A The actual control effect and combined effect on weeds mixed with bentazone (Gowing method)

Table 12A The actual control effect and combined effect of weeds mixed with oxadiazepine (Gowing method)

Table 13A The actual control effect on the weeds mixed with the enemy and the combined effect (Gowing method)

The actual control effect and combined effect of weeds in Table 14A and valerian (Gowing method)

Table 15A. Actual control effect and combined effect on weeds mixed with benzathine (Gowing method)

Table 16A and Florpyrauxifen mixed with weeds for actual control and combined effects (Gowing method)

Table 17A. Actual control effect and combined effect on weeds mixed with pretilis (Gowing method)

Table 18A. Actual control effect and combined effect on weeds mixed with tribenuron (Gowing method)

Table 19A. Actual control effect and combined effect on weeds mixed with bensulfuron-methyl (Gowing method)

Table 20A The actual control effect and combined effect of weeds mixed with oxazolone (Gowing method)

Table 21A. Actual control effect and combined effect on weeds mixed with flufenacet (Gowing method)

1) The herbicide composition prepared in Examples 1.1-7.2 was used to control weeds in wheat fields.

In 2014, demonstration experiments were carried out at 25 test sites in Zhumadian, Jiangsu, Xiangyang, Anhui Tianchang, Anhui Shouxian, and Xinghua, Jiangsu. See Table 16 for the wheat varieties in different demonstration areas.

Table 22 Wheat varieties in different demonstration areas

示范区Demonstration Area	小麦品种Wheat variety	类型Types of
驻马店Zhumadian	周麦26Zhou Mai 26	硬质白麦Hard white wheat
泗阳Fuyang	扬麦158Yang Mai 158	硬质红麦Hard red wheat
天长Long	扬麦15Yang Mai 15	硬质红麦Hard red wheat
寿县Shouxian	扬麦13Yang Mai 13	硬质红麦Hard red wheat
兴化Xinghua	宁麦13Ning Mai 13	硬质红麦Hard red wheat

Test method: wheat 3 leaves 1 heart, weed 3-5 leaf stage, manual sprayer, water volume 15 kg / 667 m ² , spray evenly with stem and leaf spray, the specific test agent and dosage are shown in Table 23, plot area 50 square meters Repeat 4 times per treatment. The effect of investigation on the 45th day after application is shown in Table 23, and the safety of wheat is shown in Table 24.

Table 23 Datian demonstration effect

Table 24 Safety of demonstration wheat in Daejeon

Note: Weed community types in each demonstration site: Zhumadian: Japan to see Mai Niang + sown sage + Niu Fanzhen; Fuyang: Japan to see Mai Niang + 菵草 + 牛繁缕; Tianchang: Japan to see Mai Niang + Niu Fan缕; Shouxian: Japan to see Mai Niang + Niu Fanzhen; Xinghua: Japan to see Mai Niang + leeks + cattle.

After extensive experimentation and exploration, the present inventors have unexpectedly discovered that 1-(2-chloro-3-(3-cyclopropyl-5-hydroxy-1-methyl-1H-pyrazole-4-carbonyl)-6-three Mixing fluoromethylphenyl)piperidin-2-one with active ingredient B for post-emergence control of grass weeds and broadleaf weeds in wheat fields with surprising, unexpected synergy and expanded herbicide spectrum In particular, it has a particularly obvious synergistic effect on broad-leaved weeds such as amaranth, piglet, wild rape, and cattle fertilization, and at the same time, it can reduce the dosage, improve crop safety, reduce environmental pollution, and reduce the rational compounding. Agricultural costs have good prospects.

Claims

A synergistic herbicidal composition comprising a herbicidally effective amount of active ingredient A and active ingredient B, wherein

Active ingredient A is a compound
Or a salt or ester thereof, wherein the ester is a C1-C4 carboxylate or benzoate;

The active ingredient B is selected from one or more of the following compounds:

1) Phenoxycarboxylic acids: 2 methyl 4-chloro, 2 methyl 4-chloroethyl sulfide, MCPB, 2 methyl 4-chloropropionic acid, 2 methyl 4-chloro sodium, 2 methyl 4-chloroisooctyl ester, 2,4-D Ester, 2,4-D isooctyl ester, 2,4-dichlorophenoxyacetic acid, 2,4-DB, 2,4-D-propionic acid;

2) pyridine carboxylic acid: flupirtoxyacetic acid, isooctyl chlorofluoxetine, fluorochloropyridinium, triclopyridinic acid, clopyralid, florpyrauxifen;

3) Benzoic acid: dicamba;

4) Nitriles: bromoxynil, octanoyl bromoxynil, iodobenzonitrile;

5) triazolinones: oxadiazon;

6) Diphenyl ethers: acesulfame, chlorflufen;

7) thiadiazoles: methyl oxazinate;

8) pyrimidinedione: saflufenacil;

9) Amides: acetochlor, flufenacet, mefenacet, metolachlor, dimethoprim, oxalylamine, dipterin, pretilachlor, propisochlor, turfgrass Amine, benzilamide;

10) Sulfonylureas: bensulfuron-methyl, bensulfuron-methyl, thifensulfuron-methyl, chloropyrazine, sulfimsulfuron, trifluoromethanesulfuron, ethersulfuron, chlorsulfuron, metsulfuron, Flunarsulfuron, iodosulfuron sodium, ciprofloxacin;

11) Sulfonamides: diflufenacil, flufensulfuron, sulfoxazolamide;

12) Pyrazoles: oxazolone, oxafluridone, oxazolone, triazosinone;

13) thiocarbamates: benzathine;

14) Others: bentazone, valerian, flupirazone.
The synergistic herbicidal composition according to claim 1, wherein the active ingredient B is sodium tetramethyl chlorochloride, two methyl tetrachloroisooctyl ester, 2,4-D isooctyl ester, flupiroxyacetic acid, Isooctyl chloroflupirate, fluorochloropyridinium, florpyrauxifen, pretilachlor, flufenacet, oxazolone, flufenacetate, dipyridamole, tribenuron, bensulfuron-methyl, difluorosulfonate One or more of grass amine, bentazone, bromoxynil, octanoyl bromoxynil, oxaconazole, oxafluridone, valerate, and benzathine.
The synergistic herbicidal composition according to claim 1 or 2, wherein the weight ratio of A to B is from 1 to 100:1 to 100.
A synergistic herbicidal composition according to claim 1 or 2, characterized in that the weight ratio of A to B is from 1 to 50:1 to 50.
A synergistic herbicidal composition according to claim 1 or 2, characterized in that the weight ratio of A to B is from 1 to 20:1 to 20.
The synergistic herbicidal composition according to claim 1 or 2, characterized in that the mass percentage of A and B in the herbicidal composition is from 1 to 95%, preferably from 5 to 80%, based on the total amount.
The synergistic herbicidal composition according to claim 1 or 2, wherein the specific preparation of the herbicidal composition is an emulsifiable concentrate, a suspension, a microemulsion, a suspoemulsion, an aqueous emulsion, a dispersible oil suspension, a wettable powder or Water dispersible granules.
A synergistic herbicidal composition according to claim 1 or 2, characterized in that it further comprises a safener C.
The synergistic herbicidal composition according to claim 8, wherein said safener C is selected from the group consisting of pyrazolyl ester, detoxified quinolin, dibenzoxazole acid, cyclopropanesulfonamide, naphthalic anhydride, and chlorfenapyr. An, R-28725, AD-67, CGA-154281, CGA-43089, CGA-43089, Hoe-70542, oxaloacetone, chlorpyrifos, BAS-145138, MON-13900, quinoline derivatives, 2,4 -D, one or more of the new antidote T and gibberellin.
Use of a synergistic herbicidal composition according to any one of claims 1-9 for controlling harmful weeds.