CN112998025A

CN112998025A - Weeding composition containing substituted pyrazolyl pyrazole sulfonylurea compound

Info

Publication number: CN112998025A
Application number: CN201911326530.4A
Authority: CN
Inventors: 葛家成; 闵祥芬; 吕文东; 邢阳阳; 董德臻; 白复芹
Original assignee: Hailir Pesticides and Chemicals Group Co Ltd
Current assignee: Hailir Pesticides and Chemicals Group Co Ltd
Priority date: 2019-12-20
Filing date: 2019-12-20
Publication date: 2021-06-22
Anticipated expiration: 2039-12-20
Also published as: CN112998025B

Abstract

The invention belongs to the technical field of pesticide synergism, and particularly relates to a weeding composition containing a substituted pyrazolyl pyrazole sulfonylurea compound, which comprises an active ingredient A and an active ingredient B with effective weeding, wherein the active ingredient B is one or more compounds selected from aryloxy phenoxy propionate, sulfonamides, sulfonylureas, imidazolinones, pyrimidine salicylic acids, triketones, organophosphorus compounds, carbamates, cyclohexenone compounds, pyridine carboxylic acids, quinoline carboxylic acids and phenoxy carboxylic acids. The composition can effectively prevent and kill weeds in rice fields, and has the characteristics of expanding a weed control spectrum, obvious synergistic effect, reducing application amount, being safe to crops and the like.

Description

Weeding composition containing substituted pyrazolyl pyrazole sulfonylurea compound

Technical Field

The invention belongs to the field of pesticides, and particularly relates to a herbicidal composition containing substituted pyrazolyl pyrazole sulfonylurea or substituted pyrazolyl pyrazole sulfonylurea and application thereof.

Background

Chemical weeding is the most economical and effective means in preventing and removing weeds in farmlands. However, the long-term continuous high-dosage use of a single variety or single action mode of chemical herbicide is easy to cause weed resistance. The reasonable compounding of the weeding compound has the advantages of expanding the weed spectrum, improving the control effect, delaying the generation of weed resistance and the like, and is one of the most effective methods for solving the problems.

Inhibition of plant biosynthesis is a relatively common mechanism of action in known herbicides and is mainly divided into: 1) inhibition of pigment synthesis: firstly, the biosynthesis of chlorophyll and the damage of plasma membrane are inhibited; ② inhibiting the biosynthesis of carotenoids. 2) Inhibition of amino acid, nucleic acid and protein synthesis: firstly, inhibiting the biosynthesis of amino acid; ② inhibiting the synthesis of interfering nucleic acid and protein; 3) inhibit lipid synthesis. Common herbicides that affect plant biosynthesis include aryloxyphenoxypropionates, sulfonamides, sulfonylureas, imidazolinones, pyrimidinylsalicylates, triketones, organophosphates, carbamates, cyclohexenone, pyridine carboxylic acids, quinoline carboxylic acids, phenoxy carboxylic acids.

Through pesticide formula screening, the control effect can be effectively improved, the dosage is reduced, the cost is reduced, and the generation of drug resistance of diseases, insects and weeds is delayed, so that the method is an important means for agricultural comprehensive treatment. The inventor of the invention intensively studies the mixing of the active ingredient A and the photosynthesis inhibitor herbicide, and finds that the compound A and one of the compounds B have good control effect on common weeds in paddy fields within a certain mixing proportion range when mixed.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a weeding composition containing substituted pyrazolyl pyrazole sulfonylurea compounds and application thereof, the composition can effectively prevent and kill the problems of common weeds in paddy fields such as barnyard grass, moleplant seed, monochoria vaginalis, edible tulip, cyperus heterophyllus and the like, and has the characteristics of expanding a weeding spectrum, reducing application amount, being safe to crops, solving resistant weeds and the like.

A weeding composition containing substituted pyrazolyl pyrazole sulfonylurea compounds comprises a weeding active ingredient A and an active ingredient B, wherein the active ingredient A is one of the following general formulas:

in the formula (I), the compound is shown in the specification,

R₁、R₂denotes co-formation of (CH)₂)₄；R₃Represents Cl; r₄Represents CN; r₅Represents H; r₆To represent

One of (1);

the active ingredient B is selected from one or more of the following compounds with herbicidal activity: aryloxyphenoxypropionic acid esters, sulfonamides, sulfonylureas, imidazolinones, pyrimidinylsalicylates, triketones, organophosphates, carbamates, cyclohexenone, pyridine carboxylic acids, quinoline carboxylic acids, phenoxy carboxylic acids;

the further active ingredient B is one or more selected from the following ingredients with herbicidal activity: aryloxy phenoxy propionic acid esters: quizalofop-p-ethyl, haloxyfop-R-methyl, fluazifop-p-butyl, fenoxaprop-p-ethyl, cyhalofop-butyl, quizalofop-p-butyl, haloxyfop-ethyl, quizalofop-p-ethyl, metamifop;

sulfonamides: flumetsulam, pyroxsulam, cloransulam, diclosulam, florasulam, penoxsulam;

sulfonylureas: chlorosulfuron, tribenuron-methyl, bensulfuron-methyl, nicosulfuron, metsulfuron-methyl, chlorimuron-methyl, pyrazosulfuron-ethyl, thifensulfuron-methyl, cinosulfuron-methyl, ethametsulfuron-methyl, cyclosulfamuron-methyl, ethoxysulfuron, rimsulfuron, primisulfuron-methyl, halosulfuron-methyl;

imidazolinones: imazethapyr, imazamox;

pyrimidine salicylic acids: pyrithiobac-sodium, pyriminobac-methyl, pyribenzoxim, bispyribac-sodium and pyriftalid;

triketones: sulcotrione, mesotrione, tembotrione;

organic phosphorus species: glyphosate, glufosinate, anilofos, glufosinate, mephos, butafosinate, propaphos, thiophosphoryl, glufosinate, bialaphos;

carbamates: thiobencarb, prosulfocarb, dichlord, mefenapyr, dichlord, phenmedipham, chlortrimeton, diclofop, and dicamba;

cyclohexenone groups: diclofop-methyl, sethoxydim, cycloxydim, clethodim, tralkoxydim, pyrodim, and clethodim;

pyridine carboxylic acids: fluroxypyr, fluroxypyr-meptyl, triclopyr, clopyralid, flurpyrauxin;

quinoline carboxylic acids: quinclorac;

phenoxy carboxylic acids: 2,4-D, 2 methyl 4 chloro, 2 methyl 4 chloroethyl thioester, MCPB, 2 methyl 4 chloropropionic acid, 2 methyl 4 sodium chloride, 2 methyl 4 chloroisooctyl, 2,4-D sodium salt, potassium salt, ammonium salt dimethylamine salt, 2,4-D methyl ester, ethyl ester and butyl ester.

Further active ingredient B is preferably: 2 methyl 4 chlorine, metamifop, quinclorac, thiobencarb, fenoxaprop-p-ethyl, halosulfuron-methyl, pyriminobac-methyl, pyribenzoxim, cyhalofop-butyl, bispyribac-sodium, penoxsulam and mesotrione.

The weight ratio of the active ingredient A to the active ingredient B in the weeding composition is 1:100-100:1, and the preferable weight ratio of the active ingredient A to the active ingredient B is 1:50-50: 1.

The weight percentage of the active ingredient A and the active ingredient B in the weeding composition accounts for 1-95% of the total amount, and preferably 10-80%.

The weeding composition consists of an active ingredient and a pesticide auxiliary ingredient, wherein the pesticide auxiliary ingredient comprises a carrier and an auxiliary agent;

further, the carrier is one, two or three of water, solvent or filler, and the water is preferably deionized water;

further, the solvent is selected from one or a mixture of more of N, N-dimethylformamide, cyclohexanone, toluene, xylene, dimethyl sulfoxide, methanol, ethanol, trimethylcyclohexanone, N-octylpyrrolidone, ethanolamine, triethanolamine, isopropylamine, N-methylpyrrolidone, propanol, butanol, ethylene glycol, diethylene glycol, ethylene glycol methyl ether, butyl ether, ethanolamine, isopropylamine, ethyl acetate or acetonitrile;

further, the filler is selected from one or a mixture of more of kaolin, diatomite, bentonite, attapulgite, white carbon black, starch or light calcium carbonate;

the auxiliary agent at least comprises a surfactant, and other functional auxiliary agents such as an antifreezing agent, a thickening agent, a stabilizing agent, a disintegrating agent, a defoaming agent, a slow release agent, a binder and the like can be added according to different use occasions and requirements;

the surfactant is selected from one or four of an emulsifier, a dispersant, a wetting agent or a penetrant; the surfactant is a single agent or a compound preparation of a common nonionic surfactant or an anionic surfactant;

further, the emulsifier is selected from one or more of agricultural milk 500# (calcium alkyl benzene sulfonate), OP series phosphate (surfactant phosphate), 600# phosphate (phenyl phenol polyoxyethylene ether phosphate), styrene polyoxyethylene ether wetting agent salt, magnesium salt of alkyl diphenyl ether disulfonate, triethanolamine salt, agricultural milk 400# (benzyl dimethyl phenol polyoxyethylene ether), agricultural milk 700# (alkylphenol formaldehyde resin polyoxyethylene ether), Ning milk 36# (phenethylphenol formaldehyde resin polyoxyethylene ether), agricultural milk 1600# (phenethylphenol polyoxyethylene polypropylene ether), ethylene oxide-propylene oxide block copolymer, OP series (surfactant), BY series (castor oil polyoxyethylene ether), agricultural milk 33# (alkylaryl polyoxyethylene propylene ether), span series (sorbitan monostearate), Tween series (sorbitan fatty acid ester polyoxyethylene ether) or AEO series (fatty alcohol polyoxyethylene ether) An agent;

further, the dispersing agent is selected from one or a mixture of a plurality of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene sulfonate, naphthalene sulfonic acid formaldehyde condensate sodium salt, alkylphenol polyoxyethylene, fatty amine polyoxyethylene, fatty acid polyoxyethylene or glycerol fatty acid ester polyoxyethylene;

further, the wetting agent is selected from one or a mixture of more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, wetting penetrant F, Chinese honeylocust fruit powder, silkworm excrement or soapberry powder;

further, the penetrating agent is selected from a mixture consisting of one or more of penetrating agent JFC (fatty alcohol-polyoxyethylene ether), penetrating agent T (diisooctyl maleate sulfonate), azone or organic silicon;

further, the antifreezing agent is a mixture consisting of one or more of ethylene glycol, propylene glycol, glycerol or urea;

further, the thickening agent is selected from one or more of xanthan gum, a disintegrating agent, bentonite, carboxymethyl cellulose or magnesium aluminum silicate;

further, the stabilizer is selected from one or more of epoxidized soybean oil, epichlorohydrin, BHT, ethyl acetate and triphenyl phosphate;

further, the disintegrating agent is selected from one or more of bentonite, urea, wetting agent, aluminum chloride, low-substituted hydroxypropyl cellulose, lactose, citric acid, succinic acid or sodium bicarbonate;

further, the defoaming agent is selected from one or more of silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds or C8-C10 fatty alcohol compounds.

The weeding composition can be prepared into a preparation form acceptable in pesticides according to a method known by a person skilled in the art, and the preparation form comprises a solid preparation, a liquid preparation and other preparations;

further, the solid preparation is powder, dispersible tablets, granules, soluble powder, soluble granules, soluble tablets, milk powder, milk granules, water dispersible granules, wettable powder, micro-capsule granules, powder, macro-granules and water dispersible tablets;

further, the liquid preparation is microcapsule suspending agent, dispersible agent, missible oil, emulsion granules, oil emulsion, emulsion powder, aqueous emulsion, microemulsion, dispersible oil suspending agent, oil dispersion powder, suspending agent, suspoemulsion, soluble agent and ultra-low volume liquid;

further, the other preparation is bait, concentrated bait, gas preparation, aerosol, smoke agent;

furthermore, the preparation formulation is preferably a suspending agent, a dispersible oil suspending agent, missible oil, a water dispersible granule and a wettable powder.

Further, the herbicidal composition is prepared into a suspending agent, and the components and the content of the suspending agent are preferably as follows: 0.1-80% of active ingredient A, 0.1-80% of active ingredient B, 2-10% of dispersing agent, 2-10% of wetting agent, 0.01-2% of defoaming agent, 0-2% of thickening agent, 0-8% of antifreeze agent and the balance of deionized water;

still further, the processing technology for preparing the herbicide composition into the suspending agent comprises the following steps: sequentially placing the active ingredient A, the active ingredient B, the surfactant and other functional auxiliaries into a reaction kettle, adding water, uniformly mixing, carrying out high-speed shearing and wet sanding, and finally carrying out homogeneous filtration to obtain the suspending agent product.

Further, the dispersible oil suspending agent prepared from the weeding composition preferably comprises the following components in percentage by weight: 0.1-80% of active ingredient A, 0.1-80% of active ingredient B, 1-10% of emulsifier, 1-10% of thickening agent and the balance of oil carrier;

still further, the processing technology for preparing the dispersible oil suspending agent by the weeding composition comprises the following steps: sequentially placing the active ingredient A, the active ingredient B, the emulsifier and other functional additives into a reaction kettle, adding oil, mixing uniformly, shearing at high speed, sanding by a wet method, and finally homogenizing and filtering to obtain the dispersible oil suspending agent product

Furthermore, the weeding composition is prepared into missible oil, and the components and the content of the missible oil are preferably as follows: 0.1-80% of active ingredient A, 0.1-80% of active ingredient B, 5-15% of emulsifier and 2-10% of solvent; the solvent is complemented to the rest;

furthermore, the processing technology for preparing the weeding composition into the missible oil comprises the following steps: adding the active component A and the active component B into a carrier, adding a surfactant and other functional auxiliaries, and uniformly stirring and mixing in a stirring and mixing kettle to obtain the missible oil product

Further, the water dispersible granule prepared from the weeding composition preferably comprises the following components in percentage by weight: 0.1-80% of active ingredient A, 0.1-80% of active ingredient B, 3-12% of dispersing agent, 1-8% of wetting agent, 1-10% of disintegrating agent, 0-8% of binding agent and the balance of filler;

further, the processing technology of the water dispersible granule prepared from the weeding composition comprises the following steps: adding the active ingredient A and the active ingredient B into a carrier, adding a surfactant and other functional auxiliaries, mixing, performing jet milling, adding 10-25% of water, kneading, granulating, drying and screening to obtain a water dispersible granule product; or spraying water to the pulverized powder in a boiling granulator, granulating, drying, and sieving to obtain water dispersible granule

Further, the composition is prepared into wettable powder, and the components and the content of the wettable powder are preferably as follows: 0.1-80% of active ingredient A, 0.1-80% of active ingredient B, 5-20% of wetting agent, 10-20% of dispersing agent and the balance of solid carrier.

Further, the processing technology for preparing the wettable powder from the weeding composition comprises the following steps: adding the active ingredient A and the active ingredient B into a carrier, adding a surfactant and other functional auxiliaries, mixing, carrying out jet milling, and mixing to obtain a wettable powder product

The weeding composition obtains unexpected synergistic effect in the application process, the weeding activity is obviously superior to the effect of applying the weeding compound with single component, the simple accumulation of the simple single component synergism is not realized, and the synergistic effect is represented by reduced application amount, enlarged weed spectrum and delayed weed drug resistance.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more concise and clear, the present invention is described with the following specific embodiments, but the present invention is by no means limited to these embodiments. The following described examples are only preferred embodiments of the present invention, which can be used to describe the present invention and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Active ingredient a example:

when R is₁、R₂Denotes co-formation of (CH)₂)₄；R₃Represents Cl; r₄Represents CN; r₅Represents H; r₆To represent

When is A₁；

When is A₂；

When R is₁、R₂Denotes co-formation of (CH)₂)₄；R₃Represents Cl；R₄Represents CN; r₅Represents H; r₆To represent

When is A₃；

When is A₄。

Formulation preparation example:

dispersible oil suspending agent:

example 1: 22% of A₁Cyhalofop-butyl dispersible oil suspension (2:20) formulation: a. the₁2 percent of cyhalofop-butyl, 20 percent of triphenylethylphenol polyoxyethylene ether, 8 percent of alkyl diphenyl ether disulfonic acid magnesium salt, 2 percent of di-sec-octyl maleate sodium sulfonate, 0.5 percent of fumed silica, 0.3 percent of carboxymethyl cellulose and the balance of methyl oleate;

example 2: 12% of A₁The formula of the halosulfuron-methyl dispersible oil suspending agent (3:9) is as follows: a. the₁3 percent of halosulfuron-methyl 9 percent, 10 percent of octylphenol polyoxyethylene ether, 2 percent of dialkyl succinic acid sodium salt, 0.5 percent of fumed silica, 0.5 percent of bentonite and the balance of methyl oleate;

example 3: 43% A₂Penoxsulam dispersible oil suspension (3:40) formulation: a. the₂3 percent of penoxsulam, 40 percent of sorbitan polyoxyethylene ether, 1 percent of dodecylbenzene sulfonic acid amine, 2 percent of dioctyl sodium sulfosuccinate, 1 percent of fumed silica, 0.6 percent of magnesium aluminum silicate and the balance of methyl oleate;

example 4: 11% of A₂Mesotrione dispersible oil suspension (1:10) formulation: a. the₂1 percent of mesotrione, 10 percent of mesotrione, 8 percent of castor oil polyoxyethylene ether, 3 percent of fatty alcohol polyoxyethylene ether, 2 percent of di-sec-octyl maleate sodium sulfonate, 1 percent of fumed silica, 1 percent of magnesium aluminum silicate and the balance of methyl oleate;

example 5: 11% of A₃Cyhalofop-butyl dispersible oil suspension (1:10) formulation: a. the₃1 percent of cyhalofop-butyl, 10 percent of octyl phenol polyoxyethylene ether, 8 percent of fatty alcohol polyoxyethylene ether, 2 percent of dioctyl sodium sulfosuccinate, 0.6 percent of fumed silica, 0.6 percent of aluminum magnesium silicate and the balance of methyl oleate;

example 6: 16% of A₃Fenoxaprop-p-ethyl dispersible oil suspending agent (1:15) formula: a. the₃1 percent of fenoxaprop-p-ethyl, 15 percent of polyoxyethylene ether oleate, 2 percent of di-sec-octyl maleate sodium sulfonate, 1 percent of fumed silica, 0.8 percent of carboxymethyl cellulose and the balance of corn oil;

example 7: 21% of A₄Formula of penoxsulam dispersible oil suspension (1: 20): a. the₄1 percent of penoxsulam, 20 percent of octyl phenol polyoxyethylene ether, 10 percent of octyl phenol polyoxyethylene ether, 2 percent of di-sec-octyl maleate sodium sulfonate, 0.5 percent of fumed silica, 0.4 percent of magnesium aluminum silicate and the balance of methyl oleate;

example 8: 13% of A₄Pyriminobac-methyl dispersible oil suspending agent (4:9) formula: a. the₄4 percent of pyriminobac-methyl, 9 percent of fatty alcohol-polyoxyethylene ether, 2 percent of dodecylbenzene sulfonic acid amine, 2 percent of dioctyl sodium sulfosuccinate, 1 percent of fumed silica, 1 percent of magnesium aluminum silicate and the balance of methyl oleate;

example 9: 17% of A₄Pyribenzoxim dispersible oil suspension (2:15) formulation: a. the₄2 percent of pyribenzoxim, 15 percent of pyribenzoxim, 8 percent of octyl phenol polyoxyethylene ether, 2 percent of dodecylbenzene sulfonic acid amine, 2 percent of dioctyl sodium sulfosuccinate, 0.5 percent of fumed silica, 0.4 percent of magnesium aluminum silicate and the balance of methyl oleate;

example 10: 9% of A₄Bispyribac-sodium dispersible oil suspending agent (3:6) formula: a. the₄3 percent of bispyribac-sodium, 6 percent of sorbitan polyoxyethylene ether, 15 percent of sorbitan monostearate, 2 percent of dioctyl sodium sulfosuccinate, 1 percent of fumed silica, 1.5 percent of carboxymethyl cellulose and the balance of corn oil;

example 11: 9% of A₄Pyriminobac-methyl dispersible oil suspending agent (3:6) formula: a. the₄3 percent and pyriminobac-methyl 6 percent12% of octyl phenol polyoxyethylene ether, 2% of dodecylbenzene sulfonic acid amine, 2% of dioctyl sodium sulfosuccinate, 1% of fumed silica, 1.2% of magnesium aluminum silicate and the balance of methyl oleate;

example 12: 16% of A₄Formula of penoxsulam dispersible oil suspending agent (1:15): a. the₄1 percent of penoxsulam, 15 percent of castor oil polyoxyethylene ether, 3 percent of dodecylbenzene sulfonic acid amine, 2 percent of di-sec-octyl maleate sodium sulfonate, 1 percent of fumed silica, 1 percent of carboxymethyl cellulose and the balance of methyl oleate.

And (3) preparing an emulsifiable solution preparation:

example 13 11% A₁Pyribenzoxim emulsifiable concentrate (3:7.5) formulation: a. the₁3 percent of pyribenzoxim, 7.5 percent of pyribenzoxim, 21 percent of sorbitan polyoxyethylene ether, 4 percent of sodium dodecyl sulfate and dimethyl sulfoxide;

example 14 28% A₂Metamifop emulsifiable concentrate (4:24) formulation: a. the₂4 percent of metamifop, 24 percent of metamifop, 5 percent of polyoxyethylene ether oleate, 2 percent of sodium dodecyl sulfate and solvent oil for supplementing the balance;

example 15 22% A₂Mesotrione emulsifiable concentrate (2:20) formulation: a. the₂2% of mesotrione, 20% of mesotrione, 6% of octylphenol polyoxyethylene ether, 2% of block polyether and solvent oil for supplementing the balance;

example 16: 32% A₂Formula of penoxsulam emulsifiable concentrate (2: 30): a. the₂2 percent of penoxsulam, 30 percent of sorbitan polyoxyethylene ether, 3 percent of triphenylethylphenol polyoxyethylene allyl ether and trimethylbenzene for balancing;

example 17% A₂Mesotrione emulsifiable concentrate (2:15) formulation: a. the₂2% of mesotrione, 15% of castor oil polyoxyethylene ether, 3% of soapberry powder and the balance of trimethylbenzene;

example 18 31% A₂Formula of penoxsulam emulsifiable concentrate (1:30): a. the₂1 percent of penoxsulam, 30 percent of octaphenyl polyoxyethylene ether, 4 percent of wetting penetrant F2 percent and dimethyl sulfoxide to make up the balance;

example 19: 26% A₃Quinclorac emulsifiable concentrate (1:25)The formula is as follows: a. the₃1 percent of quinclorac 25 percent, 10 percent of castor oil polyoxyethylene ether, 4 percent of Chinese honeylocust fruit powder and trimethylbenzene for balancing;

example 20: 12% A₄Pyriminobac-methyl emulsifiable concentrate (3:9) formula: a. the₄3 percent of pyriminobac-methyl, 9 percent of pyriminobac-methyl, 15 percent of octyl phenol polyoxyethylene ether, a wetting penetrant F5 percent and trimethylbenzene for balancing.

Suspension agent preparation:

example 22: 40% A₂Quinclorac suspending agent (3: 37): a. the₂3 percent of quinclorac, 1 percent of block polyether, 0.5 percent of sodium polyacrylate, 1 percent of fatty alcohol-polyoxyethylene ether, 4 percent of glycol, 0.4 percent of silicone oil, 0.1 percent of xanthan gum and the balance of deionized water;

example 21: 12% of A₁Bispyribac-sodium suspension concentrate (4:8) A₁4 percent of bispyribac-sodium, 3 percent of triphenylethyl phenol polyoxyethylene ether phosphate amine salt, 0.6 percent of sodium polycarboxylate, 1 percent of isomeric tridecanol polyoxyethylene ether, 4 percent of ethylene glycol, 0.5 percent of vegetable oil, 0.08 percent of magnesium aluminum silicate and deionized water for balancing;

example 23: 13% of A₂Metamifop suspension (1:12) A₂1 percent of metamifop, 1 percent of block polyether, 1 percent of alkyl naphthalene sulfonic acid polycondensate, 0.5 percent of fatty alcohol-polyoxyethylene ether, 4 percent of urea, 0.3 percent of mineral oil, 0.1 percent of carboxymethyl cellulose and the balance of deionized water;

example 24: 16% of A₂Mesotrione suspension (1:15) A₂1%, mesotrione, 1% glycol polyether, 0.5% polymaleic anhydride amine salt, 1% lauryl polyoxyethylene ether, 4% glycol, 0.4% mineral oil, 0.12% aluminum magnesium silicate and the balance of deionized water;

example 25: 11% of A₂Pyriminobac-methyl suspending agents (2:9) A₂2 percent of pyriminobac-methyl, 1 percent of block polyether, 0.5 percent of polycarboxylate, 1 percent of isomeric tridecanol polyoxyethylene ether, 4 percent of urea, 0.3 percent of polyether, 0.12 percent of bentonite and the balance of deionized water;

example 26: 31% of A₄Penoxsulam suspension (1:30) A₄1 percent of penoxsulam and propyl3% of glycol block polyether, 1% of alkyl naphthalene sulfonic acid polycondensate, 1% of Guerbet alcohol polyoxyethylene ether, 4% of propylene glycol, 0.4% of higher alcohol, 0.12% of magnesium aluminum silicate and the balance of deionized water;

example 27: 22% of A₄Mesotrione suspension (2:20) A₄2 percent of mesotrione, 2 percent of butanol polyoxyethylene polyoxypropylene ether, 0.5 percent of polymaleic anhydride sodium salt, 1 percent of lauryl alcohol polyoxyethylene ether, 4 percent of glycerol, 0.4 percent of silicone oil, 0.15 percent of carboxymethyl cellulose and the balance of deionized water.

Wettable powder:

example 28: 76% of A₁2 wettable powder of 4-methyl chloride (1:75) formulation: a. the₁1%, 2-methyl-4-chloro-75%, sodium lignosulfonate 4%, sodium methylene dinaphthalene sulfonate 7%, sodium dodecyl sulfate 1% and kaolin for the balance;

example 29: 18% of A₁Pyribenzoxim wettable powder (3:15) formulation: a. the₁3 percent of pyribenzoxim, 15 percent of pyribenzoxim, 5 percent of calcium alkyl benzene sulfonate, 5 percent of methylene dinaphthalene sodium sulfonate, 2 percent of sodium dodecyl sulfate and the balance of white carbon black;

example 30: 26% of A₂Formulation of quinclorac wettable powder (1: 25): a. the₂1%, 25% of quinclorac, 3% of calcium lignosulphonate, 6% of p-methoxy fatty amido sodium benzenesulfonate, 1% of wetting penetrant F, and the balance kaolin;

example 31: 41% A₂Formulation of wettable powder of thiobencarb (1: 40): a. the₂1%, 40% of thiobencarb, 3% of sodium lignosulphonate, 5% of p-methoxy fatty amido sodium benzene sulfonate, 1% of sodium dodecyl sulfate and the balance of kaolin;

example 32: 77% A₃Formulation of quinclorac wettable powder (2: 75): a. the₃2 percent of quinclorac 75 percent, 4 percent of glycerin fatty acid ester polyoxyethylene ether, 5 percent of alkyl naphthalene sulfonic acid polycondensate, 2 percent of sodium dodecyl sulfate and the balance of bentonite;

example 33: 20% of A₃Bispyribac-sodium wettable powder (4:16) formulation: a. the₃4 percent of bispyribac-sodium, 16 percent of wood5% of sodium sulfonate, 4% of sodium methylene dinaphthalene sulfonate, 2% of soapberry powder and the balance of kaolin;

example 34: 33% of A₄Mesotrione wettable powder (3:30) formulation: a. the₄3 percent of mesotrione, 30 percent of sodium lignosulfonate, 5 percent of sodium methylene dinaphthalene sulfonate, 6 percent of wetting penetrant F1 and the balance of white carbon black;

example 35: 43% A₄Formula of penoxsulam wettable powder (3: 40): a. the₄3 percent of penoxsulam, 40 percent of calcium alkyl benzene sulfonate, 4 percent of alkyl naphthalene sulfonic acid polycondensate, 1 percent of Chinese honeylocust fruit powder and the balance of kaolin;

example 36: 18% of A₄Pyribenzoxim wettable powder (3:15) formulation: a. the₄3 percent of pyribenzoxim, 15 percent of sodium lignosulfonate, 3 percent of sodium methylene dinaphthalene sulfonate, 1 percent of sodium dodecyl benzene sulfonate and the balance of kaolin.

Water dispersible granules:

example 37: 21% of A₂The formula of the penoxsulam water dispersible granule (1:20) comprises the following components: a. the₂1%, penoxsulam 20%, lignosulfonate 8%, polycarboxylate 4%, sodium dodecyl sulfate 1%, silicone oil 0.5%, polysaccharide 1%, and kaolin for the balance;

example 38: 77% A₂Formulation of quinclorac water dispersible granules (2: 75): a. the₂2% of quinclorac 75%, alkylphenol polyoxyethylene succinate sulfonic acid 7%, maleic anhydride polymer 6%, soapberry powder 2%, mineral oil 0.5%, xanthan gum 0.1%, and modified corn starch for the balance;

example 39: 18% of A₂Formula of metamifop water dispersible granules (2: 16): a. the₂2%, metamifop 16%, lignosulfonate 6%, polycarboxylate 3%, wetting penetrant F2%, vegetable oil 0.5%, methyl cellulose 0.1%, and kaolin for the balance;

example 40: 16% of A₄Mesotrione water dispersible granule (1:15) formulation: a. the₄1%, mesotrione 15%, sodium alkyl aryl sulfonate polymer 8%, acrylic acid polymer 8%, and dodecyl benzene sulfonic acid2% of sodium, 0.5% of mineral oil, 0.1% of magnesium aluminum silicate and the balance of modified corn starch;

example 41: 11% of A₄Pyriminobac-sodium water dispersible granule (2:9) formula: a. the₄2 percent of pyriminobac-methyl 9 percent, 10 percent of lignosulfonate, 4 percent of acrylic polymer, 2 percent of sodium dodecyl sulfate, 0.5 percent of silicone oil, 0.1 percent of sodium carboxymethyl cellulose and the balance of light calcium carbonate.

Indoor activity test:

the test basis is as follows: NY/T1155.9-2008 "indoor bioassay of pesticides test criteria herbicides part 9: test stem and leaf spraying method for determining activity of herbicide in paddy field, NY/T1155.7-2006 part 7 of herbicide standard for indoor bioassay determination of pesticides: combined action assay of compounding.

Test targets: echinochloa crusgalli (L.) Beauv.), Euphorbia lathyris (Leptochloa chinensis (L.) Nees), Cyperus rotundus (Cyperus difformis L.), Pseudobulbus cremastrae seu pleiones (Sagittaria trifoliata L.), and Monochoria canadensis (Bl.) Kunth.

Preparing a test material: quantifying test soil to 4/5 parts of a pot, irrigating at the top to completely wet the soil to a saturated state, uniformly scattering pretreated weed seeds on the soil surface, respectively covering soil according to seed conditions, keeping the soil fully wet after sowing, transferring to a greenhouse for management, and culturing till weeds are sprayed at the 2-3 leaf stage.

Reagent to be tested: the active component A is a compound created by Helier pharmaceutical industry group Limited company, and is described in detail in patent CN 201910476270.2. The active ingredient B is a conventional herbicide on the market.

Preparing a reagent: all the raw drugs were dissolved in acetone and diluted with 0.1% tween 80 water, and the test drugs were set to 5 series doses each for use.

And (3) test treatment: and (4) culturing the weeds to the 2-3 leaf stage for treatment. Each treatment was repeated 4 times, each time 3 pots, each pot of 20 plants, for a total of 60 weeds per treatment. The weeds are sprayed by a spraying tower to be treated by the agent.

Data investigation: after the treatment for 14 days, the fresh weight of the overground part of each treatment is investigated, and the weed fresh weight inhibition rate is calculated.

The rationality of the type and ratio of the combined action of the 2 herbicides was evaluated by the Gowing method.

The calculation formula is as follows:

the actual measured fresh weight inhibition rate E percent is (fresh weight of weeds in a control area-fresh weight of weeds in a treatment area)/fresh weight of weeds in the control area multiplied by 100

Theoretical fresh weight inhibition E₀Percent fresh weight inhibition ratio of herbicide a + fresh weight inhibition ratio of herbicide B-fresh weight inhibition ratio of herbicide a x fresh weight inhibition ratio of herbicide B/100

E-E₀More than 10% is synergistic effect, E-E₀10% below is antagonistic, E-E₀Addition was found to be within. + -. 10%.

The statistical results are as follows:

TABLE 1 Compound A₁Mixing with other compounds, and treating herba Monochorii, Pseudobulbus Cremastrae seu pleiones, Echinochloa crusgalli, semen Euphorbiae Lathyridis, and herba Cyperi

TABLE 2 Compound A₂Mixing with other compounds, and treating herba Monochorii, Pseudobulbus Cremastrae seu pleiones, Echinochloa crusgalli, semen Euphorbiae Lathyridis, and herba Cyperi

TABLE 3 Compound A₃Mixing with other compounds, and treating herba Monochorii, Pseudobulbus Cremastrae seu pleiones, Echinochloa crusgalli, semen Euphorbiae Lathyridis, and herba Cyperi

TABLE 4 Compound A₄Mixing with other compounds, and treating herba Monochorii, Pseudobulbus Cremastrae seu pleiones, Echinochloa crusgalli, semen Euphorbiae Lathyridis, and herba Cyperi

Test of field drug effect

The herbicidal compositions prepared in examples 1 to 41 were used for controlling weeds in paddy fields.

The conditions of the test base are as follows: in 2018, demonstration tests are respectively carried out in Changsha in Hunan, Wuhan in Hubei, Yingtan in Jiangxi, Changhui dormiton, Jiangsu and the like. The rice varieties are Xiangzao 143, Liangyou 28, Wuyou 286, Sidao 12 and Xudao 4 respectively.

The test method comprises the following steps: and (3) carrying out manual spraying at the weed 3-5 leaf stage, uniformly spraying stem leaves, spraying for 25 square meters in each plot, repeating the spraying for 4 times, and investigating the control effect and checking the safety condition of the rice 30 days after the application.

The weed control effect (%) (% fresh weight of weeds in the clear water control area-fresh weight of weeds in the medicament treatment area)/fresh weight of weeds in the clear water control area x 100.

Grading and evaluating the safety of rice:

level 1: the rice grows normally without any damage symptom;

and 2, stage: the rice has slight phytotoxicity which is less than 10 percent;

and 3, level: the rice can recover after medium phytotoxicity, and the yield is not influenced;

4, level: the rice has serious phytotoxicity and is difficult to recover, thereby causing the reduction of yield;

and 5, stage: the rice has serious phytotoxicity and can not be recovered, thereby causing obvious yield reduction or no yield.

The results of the tests are given in the following table:

TABLE 5 field demonstration test results

TABLE 6 exemplary Rice safety profiles in the field

Through a large number of field efficacy tests of indoor activity screening grade, the invention unexpectedly discovers that the active ingredient A and the active ingredient B are mixed for preventing and killing common weeds such as barnyard grass, sedge heterotropha, monochoria vaginalis, potamogeton indica, edible tulip and other grassy weeds, sedge and broadleaf weeds in the paddy field, have good activity, and the dosage can be reduced.

Claims

1. A weeding composition containing substituted pyrazolyl pyrazole sulfonylurea compounds is characterized by comprising an active ingredient A and an active ingredient B, wherein the active ingredient A is one of the following general formulas:

in the formula (I), the compound is shown in the specification,

One of (1);

the active ingredient B is selected from one or more of the following compounds with herbicidal activity: aryloxyphenoxypropionic acid esters, sulfonamides, sulfonylureas, imidazolinones, pyrimidinylsalicylates, triketones, organophosphates, carbamates, cyclohexenone, pyridinecarboxylic acids, quinolinecarboxylic acids, phenoxycarboxylic acids.

2. The herbicidal composition as claimed in claim 1, wherein the active ingredient B is selected from one or more of the following herbicidally active compounds:

aryloxy phenoxy propionic acid esters: quizalofop-p-ethyl, haloxyfop-R-methyl, fluazifop-p-butyl, fenoxaprop-p-ethyl, cyhalofop-butyl, quizalofop-p-butyl, haloxyfop-ethyl, quizalofop-p-ethyl, metamifop;

imidazolinones: imazethapyr, imazamox;

triketones: sulcotrione, mesotrione, tembotrione;

quinoline carboxylic acids: quinclorac;

Preferably, the active ingredient B is selected from one or more of the following compounds with herbicidal activity: 2-methyl-4-chloro, metamifop, quinclorac, thiobencarb, fenoxaprop-p-ethyl, halosulfuron-methyl, pyriminobac-methyl, pyribenzoxim, cyhalofop-butyl, bispyribac-sodium, penoxsulam and mesotrione.

3. The herbicidal composition as claimed in claim 1, wherein the weight ratio of active ingredient a to active ingredient B in the herbicidal composition is 1:100-100: 1.

4. The herbicidal composition of claim 1, wherein the ratio is from 1:50 to 50: 1.

5. A herbicidal composition according to any one of claims 1 to 4, characterized in that A, B is present in an amount of 1 to 95% by weight, preferably 10 to 80% by weight, based on the total amount.

6. The weeding composition according to any one of claims 1 to 4, further comprising a conventional adjuvant for pesticides, preferably one or both of a carrier and a surfactant.

7. A herbicidal composition according to claim 1, characterized in that the herbicidal composition is formulated in the form of a powder, dispersible tablet, granule, soluble powder, soluble granule, soluble tablet, milk powder, milk granule, water dispersible granule, wettable powder, microcapsule granule, powder, macrogranule, water dispersible tablet, microcapsule suspension, dispersible liquid, emulsifiable concentrate, emulsion granule, oil emulsion, milk powder, emulsion in water, microemulsion, dispersible oil suspension, oil dispersible powder, suspension, suspoemulsion, soluble liquid, ultra-low volume liquid, bait, concentrated bait, gas preparation, aerosol, smoke agent; preferably suspending agent, dispersible oil suspending agent, missible oil, water dispersible granule and wettable powder.

8. Use of the herbicidal composition as claimed in any of claims 1 to 7 for controlling unwanted weeds.

9. Use according to claim 8, wherein the weeds are barnyard grass, moleplant seed, monochoria vaginalis, edible tulip and cyperus heterotropus.