A pesticide polymer synergist and its application in glyphosate formulations

Abstract

This invention relates to a pesticide polymeric synergist and its application in glyphosate formulations. The synergist comprises a high molecular weight polymer, is water-soluble, and has a solid content of 5-75%. When diluted with water to a 1% solid content aqueous solution, the pH value is 5-8. When diluted with water to a 200 ppm solid content solution, the conductivity of the aqueous solution is 100-250 μS / cm. Applying this pesticide polymeric synergist can improve the efficacy of existing pesticide active ingredient formulations, including both the rapid and sustained effects of the active ingredient.

Description

Technical Field

[0001] This invention relates to a synergist, and more particularly to a pesticide polymeric synergist and its application in glyphosate formulations. The invention also relates to a method for preparing the pesticide polymeric synergist and its application in glyphosate formulations or herbicides with glyphosate as the main component. Background Technology

[0002] Enhancing the efficacy of pesticide active ingredients, such as herbicides, insecticides, acaricides, nematicides, fungicides, and plant growth regulators, during formulation and application has always been a highly complex process. Currently, there are relatively few adjuvants that can achieve both stable and enhanced formulation efficacy; most only maintain formulation stability, while high-molecular-weight adjuvants that significantly improve formulation effectiveness are even rarer.

[0003] Among the active ingredients in pesticides, improving the efficacy of herbicides such as glyphosate, especially its rapid and sustained effects, is a crucial research area. Glyphosate's chemical name is N-(phosphonocarboxymethyl)glycine, also known as Roundup, glyphosate, and phosphonoglycine, and is usually used in its salt form (referred to as glyphosate in this article). Pure glyphosate is a non-volatile white solid, stable at room temperature, and insoluble in common organic solvents. Its isopropylamine salt, sodium salt, potassium salt, and ammonium salt are completely soluble in water. It is commonly used to process glyphosate aqueous solutions of different concentrations, such as 10%, 41%, and 62% (hereinafter collectively referred to as glyphosate aqueous solutions, and all percentages are by mass). Glyphosate is a non-selective, residue-free, non-selective herbicide that is very effective against perennial rooted weeds. Plants mainly absorb it through their leaves, and the absorbed herbicide is quickly translocated through the phloem, with most of it being transferred to the underground roots and rhizomes within 24 hours, thus killing weeds in non-cultivated land. It is one of the most widely used broad-spectrum non-selective herbicides in agricultural production.

[0004] When glyphosate is formulated into an aqueous solution, its high surface tension prevents it from wetting, spreading, and adhering to the target surface. Therefore, surfactants are often added to reduce the surface tension of the aqueous solution, increasing its spreadability, wettability, and adhesion to the target surface, thereby increasing the deposition rate. However, the number of surfactants suitable for glyphosate aqueous solutions is limited, and most anionic and nonionic surfactants cause turbidity in glyphosate aqueous systems. This significantly restricts the selection of surfactants for glyphosate aqueous solutions. Developing an aqueous solution that achieves both good apparent viscosity and significantly improved glyphosate activity from this limited pool of available surfactants is a common challenge in the industry.

[0005] Currently, while the glyphosate formulation industry has identified several effective surfactants, such as alkyl glycosides (APG), imidazoline amphoteric surfactants, betaine-type surfactants, plant-derived surfactants (such as glyphosate saponins), alkyl ammonium chloride, fatty alcohol ether wetting and penetrating agents (for tank mixing), and tallow amine polyoxyethylene ether (TAEO), tallow amine surfactants are used in large quantities, are costly, and have poor environmental compatibility. Conventional surfactants also suffer from low efficacy and difficulty in eliminating foam. Therefore, it is particularly important to develop a pesticide synergist that can be used in glyphosate aqueous formulations and herbicide formulations with glyphosate as the main component, to overcome its various shortcomings and limitations of existing technologies.

[0006] Currently, patent applications for pesticide formulations, such as patent publication number CN106259456A, disclose pesticide slow-release synergists. The adjuvants include solubilizers, emulsifiers, and thickeners. These adjuvants can shape the active ingredient of the synergist into micro-clusters, facilitating encapsulation by a polymer material. The polymer material is polysulfide, which has high permeability and easily encapsulates the active ingredient. However, the influence of this polymer on glyphosate formulations is not mentioned. Patent publication number CN101475691A discloses acrylamide-modified polymer micro-crosslinked gel, prepared using anionic, cationic, and nonionic methods; however, the product prepared using this method is unsuitable for use in glyphosate formulations. Summary of the Invention

[0007] To address the aforementioned problems, the present invention aims to provide a pesticide polymer synergist. The synergist comprises a high molecular weight polymer, is water-soluble, has a solid content of 5-75%, and when diluted with water to a 1% solid content aqueous solution, the pH value is 5-8. When diluted with water to a 200ppm solid content solution, the conductivity of the aqueous solution is 100-250μs / cm.

[0008] Preferably, in the above-mentioned pesticide polymer synergist, the conductivity of the aqueous solution is 100-150 μs / cm.

[0009] Preferably, in the above-mentioned pesticide polymer synergist, when the synergist is diluted with water or concentrated to a solid content of 25%, the apparent viscosity of the synergist at 25°C is 500-100,000 centipoise.

[0010] Preferably, when the synergist is diluted with water or concentrated to a solid content of 25%, the apparent viscosity of the synergist at 25°C is 3000-30000 centipoise.

[0011] Preferably, in the above-mentioned pesticide polymer synergist, the polymer is obtained by solution polymerization of raw materials containing anionic monomers, cationic monomers, and / or nonionic monomers.

[0012] Preferably, in the above-mentioned pesticide polymer synergist, the weight ratio of the anionic monomer, cationic monomer and nonionic monomer is 5-95:5-95:0-30.

[0013] Preferably, in the above-mentioned pesticide polymer synergist, the anionic monomer is selected from one or more of acrylic acid, methacrylic acid, styrene sulfonate, acryloyl dimethyl taurate, and itaconic acid; the cationic monomer is selected from one or more of dimethylaminoethyl methacrylate, dimethyl diallyl ammonium chloride, methacryloylpropyltrimethyl ammonium chloride, and methacryloyloxyethyltrimethyl ammonium chloride; and the nonionic monomer is selected from one or more of styrene, vinylpyrrolidone, methacrylamide, and acrylamide.

[0014] Particularly preferred is that, in the above-mentioned pesticide polymer synergist, the anionic monomer is selected from one or two of acryloyldimethyl taurate and itaconic acid; the cationic monomer is selected from one or two of methacryloylpropyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride; and the nonionic monomer is selected from one or two of methacrylamide and acrylamide.

[0015] Preferably, in the above-mentioned pesticide polymer synergists, the solution polymerization method includes the following steps:

[0016] (1) Add water and neutralizing agent to the reactor. Under stirring, slowly pump the anionic monomer into the reactor. Control the temperature of the reactor to not exceed 60°C, the stirring speed to be within 60 rpm, and the pH value of the system to be controlled between 5 and 9.

[0017] (2) Add cationic monomers and nonionic monomers, and stir until homogeneous;

[0018] (3) Control the system temperature at 55-65℃, add 2 / 3 of the initiator, stir evenly, control the stirring speed to within 30 rpm, and keep the reaction slow.

[0019] (4) When the system temperature reaches 90℃, add the remaining initiator, keep the reactor temperature between 90℃ and 98℃, keep it at that temperature for 2-4 hours, and then lower the reactor temperature to 50-70℃.

[0020] (5) Add a chain terminator to terminate the reaction and obtain the pesticide polymer synergist of the present invention.

[0021] Preferably, in the above-mentioned pesticide polymer synergist, the neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, ethanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and ammonia water.

[0022] Preferably, in the above-mentioned pesticide polymer synergist, the initiator is an inorganic peroxide or an organic peroxide. Preferably, the inorganic peroxide is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate, or it can be a commonly used inorganic peroxide. Preferably, the organic peroxide is benzoyl peroxide, or it can be a commonly used organic peroxide.

[0023] Preferably, in the above-mentioned pesticide polymer synergist, the chain terminator is selected from one or more of hydroquinone, p-tert-butylcatechol, sodium dimethyl dithiocarbamate, sodium polysulfide, sodium nitrite, and sodium sulfite.

[0024] The present invention also provides a white to slightly yellow powdery or granular pesticide polymer synergist, characterized in that it is obtained by drying and pulverizing the above-mentioned pesticide polymer synergist.

[0025] This invention also provides a method for preparing the above-mentioned pesticide polymer synergist, the method comprising the following steps: polymerizing raw materials containing anionic monomers and cationic monomers, and / or nonionic monomers by solution polymerization, controlling the solid content of the product to be 5-75%, diluting the product with water to an aqueous solution with a solid content of 1% at a pH of 5-8, and when the product is diluted with water to a solution with a solid content of 200ppm, the conductivity of the aqueous solution is 100-250μs / cm, thereby obtaining the pesticide polymer synergist.

[0026] Preferably, in the above preparation method, the conductivity of the aqueous solution is 100-150 μs / cm.

[0027] Preferably, in the above method, the anionic monomer is selected from one or more of acrylic acid, methacrylic acid, styrene sulfonate, acryloyl dimethyl taurate, and itaconic acid; the cationic monomer is selected from one or more of dimethylaminoethyl methacrylate, dimethyl diallyl ammonium chloride, methacryloylpropyltrimethyl ammonium chloride, and methacryloyloxyethyltrimethyl ammonium chloride; and the nonionic monomer is selected from one or more of styrene, vinylpyrrolidone, methacrylamide, and acrylamide.

[0028] Particularly preferred is that, in the above method, the anionic monomer is selected from one or two of acryloyldimethyl taurate and itaconic acid; the cationic monomer is selected from one or two of methacryloylpropyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride; and the nonionic monomer is selected from one or two of methacrylamide and acrylamide.

[0029] Preferably, the above method further includes a drying and pulverizing step of the obtained pesticide polymer synergist, and the dried and pulverized product is a white to slightly yellow powder granule.

[0030] Specifically, the preparation method of the above-mentioned pesticide polymer synergist includes the following steps in sequence:

[0031] (1) Add water and neutralizing agent to the reactor. Under stirring, slowly pump the anionic monomer into the reactor. Control the temperature of the reactor to not exceed 60°C, the stirring speed to be within 60 rpm, and the pH value of the system to be controlled between 5 and 9.

[0032] (2) Add cationic monomers and nonionic monomers, and stir until homogeneous;

[0033] (3) Control the system temperature at 55-65℃, add 2 / 3 of the initiator, stir evenly, control the stirring speed to within 30 rpm, and keep the reaction slow.

[0034] (4) When the system temperature reaches 90℃, add the remaining initiator, keep the reactor temperature between 90℃ and 98℃, keep it at that temperature for 2-4 hours, and then lower the reactor temperature to 50-70℃.

[0035] (5) Add a chain terminator to terminate the reaction and obtain the pesticide polymer synergist of the present invention.

[0036] Preferably, in the above-mentioned method for preparing pesticide polymer synergists, the neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, ethanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and ammonia.

[0037] Preferably, in the above-mentioned method for preparing pesticide polymeric synergists, the initiator is an inorganic peroxide or an organic peroxide. Preferably, the inorganic peroxide is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate, or it can be a commonly used inorganic peroxide. Preferably, the organic peroxide is benzoyl peroxide, or it can be a commonly used organic peroxide.

[0038] Preferably, in the above-mentioned method for preparing pesticide polymer synergists, the chain terminator is selected from one or more of hydroquinone, p-tert-butylcatechol, sodium dimethyl dithiocarbamate, sodium polysulfide, sodium nitrite, and sodium sulfite.

[0039] The present invention also provides a pesticide formulation comprising the above-mentioned pesticide polymeric synergist and active ingredient, wherein the pesticide polymeric synergist accounts for 0.01-5.0% of the pesticide formulation by weight, and the weight of the added pesticide polymeric synergist is calculated based on the percentage of solids.

[0040] Preferably, in the above-mentioned pesticide formulation, the pesticide polymer synergist accounts for 0.1-1.0% of the pesticide formulation by weight.

[0041] Based on the calculation of 100%, adding 5% of pesticide polymer synergist to 100g of pesticide formulation means that if the solid content of the pesticide polymer synergist is 50%, then the amount of pesticide polymer synergist needed to prepare 100g of pesticide formulation is 10g.

[0042] In the above-mentioned pesticide formulations, the active ingredient is one or more of the following: herbicides, insecticides, acaricides, nematicides, fungicides, and plant growth regulators.

[0043] Preferably, in the above-mentioned pesticide formulation, the herbicide is one or more of a cytotoxic herbicide or a selective herbicide, or the herbicide is at least two of a cytotoxic herbicide and a selective herbicide, wherein the cytotoxic herbicide is one or more of glyphosate, glyphosate isopropylamine salt, glyphosate diammonium salt, glyphosate ammonium salt, glyphosate dimethylamine salt, glyphosate sodium salt, glyphosate potassium salt, and paraquat.

[0044] Preferred selective herbicides are one or more of the following: 2,4-D, MCPA, quizalofop-P-ethyl, pyrazosulfuron, pendimethalin, atrazine, atrazine, metolachlor, butachlor, acetochlor, propachlor, bensulfuron-methyl, isoproturon, diuron, oxyfluorfen, flusulfanilamide, ethoxysulfuron, quizalofop-P-ethyl, oxadiazon, bensulfuron-methyl, bensulfuron-methyl, chlorpyrifos, nicosulfuron, pyrazosulfuron-methyl, bensulfuron-methyl, sulfadiazon, trifluralin sodium salt, chlorpyrifos, bromobenzyl, dicamba, diquat, clethodim, bentazon, quinclorac, isoxaflutole, fluroxypyr, and chlorpyrifos.

[0045] Preferably, the above-mentioned herbicide also includes a safener, wherein the safener is one or more of the following: cyclopropanesulfonamide, ...

[0046] Preferably, the insecticide, acaricide, or nematicide is selected from one or more active ingredients from the following categories:

[0047] (1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, including carbamates such as carbamate, thiamethoxam, propoxur, carbamate, thiamethoxam, methyl sulfone, methyl sulfone, oxadiazon, imidacloprid, fenvalerate, carbamate, carbamate, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, thiamethoxam, dichlorvos, dichlorvos, butylpyridinium, chlorpyrifos, parathion, diazinon, etc., or organophosphates, such as acetamiprid, phosmet, fenthion, fenthion, pyrazophos, pyrazophos, thiamethoxam, dichlorvos, dichlorvos, butylpyridinium, chlorpyrifos, methyl parathion, diazinon, etc. Phosphorus dibromophos, phosmet, phosmet, heptenphos, methamidophos, phorate, methyl pyridinium, methyl pyrazophos, methyl chlorpyrifos, methyl glutathione, methyl demeton-methyl, methyl ethione, phosmet, quinalphos, dimethoate, isopropyl phthalate of o-(methoxyaminothiophosphoryl)salicylate, phosphamidon, thion, chloromethionine, oxychloride, malathion, phosmet, thiamethoxam, thiamethoxam, triazophos, chlorpyrifos, fenitrothion, pyridaben, dichlorvos, phosmet, terbufos, oximethion, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, phosmet, methamidophos, ethione, acephate, isoxazoline, isofenphos, phosmet and phosmet.

[0048] (2) Sodium channel modulators, such as pyrethroids, including d-trans-propenylpyrethrin, d-cis-trans-propenylpyrethrin, α-cypermethrin, β-cyhalothrin, β-cypermethrin, γ-cyhalothrin, ζ-cypermethrin, θ-cypermethrin, λ-cyhalothrin, τ-cyhalothrin, pyrethrin, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, propenylpyrethrin, pyrethrin, flufenacet, flusilylpyrethrin, flufenacetylpyrethrin, flufenacetylpyrethrin, and high-potassium cypermethrin. Cypermethrin, cypermethrin, methoxybenzylflumethrin, bifenthrin, cyhalothrin, cypermethrin, fenvalerate, cypermethrin, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate, fenvalerate S-cyclopentenyl isomer, tetrafluorobenzyl, tetrabromopyrethrin, fenvalerate, fenvalerate [(1R) isomer], DDT, methoxychloride, deltamethrin, dextromethorphan [(EZ)-(1R) isomer] and fenvalerate [(1R)-trans isomer].

[0049] (3) Competitive regulators of nicotinic acetylcholine receptors (nAChR), such as neonicotinoids, such as acetamiprid, thiamethoxam, dinotefuran, imidacloprid, acetamiprid, thiamethoxam and thiamethoxam, nicotine, flupyridine, and flupyrflufenone.

[0050] (4) Nicotinic acetylcholine receptor allosteric modulators, such as spinosads, such as ethyl spinosad and spinosad.

[0051] (5) Glutamate-gated chloride channel allosteric modulators, such as avermectin / milbemycin, such as avermectin, emamectin benzoate, rapamectin and mitoxin.

[0052] (6) Juvenile hormone mimics, such as acetamiprid, acetamiprid, acetamiprid, phenoxycarb or fenvalerate.

[0053] (7) Various non-specific (multi-site) inhibitors, such as alkyl halides, such as methyl bromide and other alkyl halides, chloropicrin, thiocyanate, borax, tartaric acid, or methyl isocyanate generating agents, such as dazomet and thiamethoxam.

[0054] (8) Microbial disruptors of the intestinal membrane in insects, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and Bt plant protein.

[0055] (9) Inhibitors of mitochondrial ATP synthase, such as ATP interfering agents, such as butyl ether urea, or organotin compounds, such as triazole tin, tricyclic tin, phenylbutyl tin, chlorfenapyr or tetrachlorpyrifos.

[0056] (10) Nicotinic acetylcholine receptor channel blockers, such as chlorpyrifos, fenitrothion hydrochloride, chlorpyrifos or chlorpyrifos.

[0057] (11) Inhibitors of chitin biosynthesis, such as diflubenzuron, diflubenzuron, diflubenzuron, flucyclobenzuron, flufenoxuron, flufenoxuron, fenflurfen, diphenylfluorourea, polyfluorourea, flufenoxuron or fenflurfen.

[0058] (12) Ecdyskin disruptors, such as cyromazine, ecdyskin receptor agonists, such as cyclotetracycline, chlorfenapyr, methoxyfenozide and tebufenozide.

[0059] (13) Other active ingredients, such as quaternary acid, spirodiclofen, spirodiclofen, spirotetramat, amitraz, thiamethoxam, chlorfenapyr, dinitrate (DNOC), fipronil, flufenoxuron, cypermethrin, pyrimethanil, quinacrine, azoxystrobin, pyrimethanil, pyridaben, pyridaben, pyridaben, rotenone, indoxacarb, cyfluthrin, pymetrozine, flonicamid, tetradifon, thiamethoxam, flufenoxuron, or etoxazole, chlordane, endosulfan, etoxuron, fipronil, pyrimethanil, diflubenzuron, chlorantraniliprole, bromine Cyanobacterium, flufenoxuron, afranal, azadirachtin, benzimidazole, bifenazate, bromopropylate, manganese chlorpyrifos, cypermethrin, cyclopyridamole, chlorfenapyr, trichlorfon, ε-cypermethrin, flufenoxuron sulfone, pyrimethanil, flufenoxuron, difenoconazole, fluopyram, furazolidone, pendimethalin, chlorthiazoline, isopyrazosulfuron, κ-bifenthrin, κ-heptafluthrin, chlorfenapyr, piperazine, trifluralin, pyrimethanil, tetrafluthrin, flufenoxuron, thioflufenoxuron, or iodomethacin.

[0060] Preferred fungicides include 8-hydroxyquinoline copper, acetamiprid, pyraclostrobin, chlorothalonil, benzothiadiazole, benzo[a]fluoroquinolones, benomyl, benomyl thiamethoxam, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, benzalkonium chloride, pyraclostrobin, pyraclostrobin, propiconazole, prothioconazole, propineb, propoxyquin, Bordeaux mixture, kasugamycin, mancozeb, mancozeb zinc, mancozeb, mancozeb, captan, butylmorpholine, butylpyromorpholine, eugenol, cyproconazole, azoxystrobin, and other fungicides. Fungicides include: Carbendazim, Calcium Polysulfide, Paclobutrazol, Oxadiazon, Oxadiazon, Dithionol, Tebuconazole, Furazolidone, Fluopyram, Fluopyram, Fluopyram, Fluazinam, Flutriafol, Flufenoxuron, Fluazinam, Fluazinam, Fluazinam, Fluazinam, Fluazinam, Fluazinam, Fluazinam, Fluazinam, Fluazinam, Zinc Fibram, Iprodione, High-efficiency Benzopyr, High-efficiency Metalaxyl, Fludioxonil, Silthiamethoxam, Cyproconazole, Cyproconazole, Cyclofluopyram, Copper Naphthalate, Cyclopyridamole, Methoxyfenozide, and others. Phosphatidylcholine, Thiophanate-methyl, Metalaxyl, Azoxystrobin, Cyproconazole, Carbazin, Captan, Clomid, Quinoxystrobin, Bifenpyroxim, Phosphonic acid and its salts, Copper sulfate, Thiazol, Spirocyclohexane, Chlorpyrifos, Prochloraz, Imidacloprid, Azoxystrobin, Azoxystrobin, Azoxystrobin, Azoxystrobin, Pyrimethanil, Fenoxam, Captan, Fenoxam, Abamectin, Copper hydroxide, Cyazofamid, Thiabenazole, Thifenoxam, Thiamethoxam, Thiazithromycin, Aluminum triethylphosphonate, Triazole, Dipyridamole Amine, cymoxanil, cymoxanil, oxytetracycline, abscisic acid, carbofuran, azoxystrobin, azoxystrobin, pentachlorophenol, pendimethalin, tebuconazole, tebuconazole, tebuconazole, tebuconazole, dimethomorph, carvone, chlorpyrifos, valamethoxam, valamethoxam, copper oxide, copper oxychloride, tebuconazole, tebuconazole, calcium fosetyl-aluminate, sodium fosetyl-aluminate, tebuconazole, vinclozolin, iprodione, methyl isothiocyanate, isothiazamide, imazalil sulfate, cymoxanil, styrazocarb, azoxystrobin, azoxystrobin, and one or more of azoxystrobin and pyraclostrobin.

[0061] Preferably, the plant growth regulators are selected from 2,4-D chlorobutyric acid, S-inducer, chlormequat chloride, chlormequat chloride, aminopyridinic acid, paraquat, chlorothalonil, benzopyrazine, benomyl, benzylaminopurine, glyphosate, hypersensitive protein, gibberellic acid, gibberellic acid 4, gibberellic acid 7, growth promoters, cyanamide, isoprothiolane, diquat, diuron, diflubenzuron, butyrylhydrazine, p-bromophenoxyacetic acid, paclobutrazol, diphenylurea, dinitrophenol, actinomycete ketone, and fenidyl alcohol. Flusulfanilamide, flubendiamide, humic acid, chlorothalonil, succinic acid, cypropyrimidinol, cyprosulfanilamide, sulfadiazine, sulfadiazine, chitosan, toluenephthaline, metolachlor, methylcyclopropene, methyl imazalil, carbaryl, methoxyrone, furfurylaminopurine, anti-dampness amine, anti-dampness ester, ascorbic acid, Bacillus cereus, chloraniline, chlorophenoxyacetic acid, chlorpyrifos, choline chloride, magnesium chlorate, methylparaben, methylphenoxyacetic acid, chlorpyrifos, methylparaben, methylparaben Jasmonic acid, naphthoxyacetic acid, naphthaleneacetic acid, methyl naphthaleneacetate, ethyl naphthaleneacetate, naphthylacetamide, allantoin, hydroxyethylhydrazine, thiamethoxam, thiabendazole, triiodobenzoic acid, tributylbenzyl chloride, trifluoroindolebutyrate, triacontanol, phosphatidylcholine, cyhalothrin, undecanoic acid, salicylic acid, tetracycline, pinoresindiene, glycidyl acid, furfural, cytosolic acid, cyclohexane, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, chlorpyrifos, defoliant Fluorobutyric acid, fluorobutyric acid amine, uniconazole, adenine, nicotinamide, bisphosphonic acid, oxime, ethylene silicon, ethephon, ethoxyquinoline, sapote, sapote ether, sapote azole, sapote acetic acid, indolepropionic acid, indolebutyric acid, indoleacetic acid, indole ester, zeatin, zeaxanthin, brassinolide, sapote amine, sapote oxime, sapote phosphonate, sapote amine, sapote amine, sapote amine, sapote amine, sapote amine, n-decyl alcohol, sec-butylamine, and sapote acid are among one or more of these.

[0062] In the above-mentioned pesticide formulations, the formulation is in the form of granules, powders, or liquids, and more preferably, the formulation is in the form of aqueous solutions, wettable powders, or soluble granules.

[0063] Generally, granular and powder formulations can also be referred to as solid dosage forms.

[0064] The present invention also provides the use of the above-mentioned pesticide polymer synergist, which is used to enhance the effect of pesticide active ingredients.

[0065] In the above-mentioned uses, the active ingredient is one or more of the following: herbicides, insecticides, acaricides, nematicides, fungicides, and plant growth regulators.

[0066] Preferably, the herbicide is one or more of a cytotoxic herbicide or a selective herbicide, or the herbicide is at least two of a cytotoxic herbicide and a selective herbicide, wherein the cytotoxic herbicide is one or more of glyphosate, glyphosate isopropylamine salt, glyphosate diammonium salt, glyphosate ammonium salt, glyphosate dimethylamine salt, glyphosate sodium salt, glyphosate potassium salt, and paraquat.

[0067] In the above-mentioned uses, the selective herbicide is one or more of the following: 2,4-D, 2,4-D, quizalofop-P-ethyl, pyrazosulfuron, pendimethalin, atrazine, atrazine, metolachlor, butachlor, acetochlor, propachlor, bensulfuron-methyl, isoproturon, diuron, oxyfluorfen, flusulfanilamide, ethoxysulfuron, quizalofop-P-ethyl, oxadiazon, bensulfuron-methyl, bensulfuron-methyl, chlorpyrifos, nicosulfuron, pyrazosulfuron-methyl, bensulfuron-methyl, sulfadiazon, trifluralin sodium salt, chlorpyrifos, chlorpyrifos, bromobenzonitrile, dicamba, diquat, clethodim, bentazon, quinclorac, isoxaflutole, fluroxypyr, and chlorpyrifos.

[0068] Beneficial effects of the present invention

[0069] The pesticide polymer synergist of the present invention is a polymer with a certain molecular weight and physicochemical characteristics prepared by solution polymerization of anionic monomers, cationic monomers and / or nonionic monomers with specific structures. By utilizing the synergistic effect of the polymer with small molecule surface activity and the properties of polymer monomers, the efficacy of pesticide active ingredients can be effectively improved, such as improving the herbicidal effect of glyphosate formulations.

[0070] The application of the pesticide polymer synergist of the present invention can improve the efficacy of existing pesticide active ingredient formulations, including both rapid and sustained effects. For example, in the efficacy of glyphosate formulations, rapid effect ensures that the herbicide rate of glyphosate formulations is increased by more than 10% in 7 days, and sustained effect ensures that weeds treated with glyphosate formulations do not basically turn green again in 30 days.

[0071] In the preparation of pesticide formulations, the use of the pesticide polymer synergist of the present invention can improve the stability of the formulation. For example, in the preparation of glyphosate formulations, the use of the pesticide polymer synergist can achieve the stability of glyphosate formulations, and at the same time improve the rapid effect and sustained effect of glyphosate formulations. Detailed Implementation

[0072] Example 1: Preparation of pesticide polymeric synergists

[0073] The raw material formulations for preparing pesticide polymer synergists are shown in Table 1 below. Raw materials for pesticide polymer synergists with codes A1, A2, A3, A4, A5 and A6 are prepared respectively. The raw material components and weights of the products are shown in Table 1 below (weight unit is kg).

[0074] Table 1. Raw material formulation of pesticide polymer synergists A1-A6

[0075]

[0076] The total amount of water used to supplement the raw materials during the production process of each product is 100kg.

[0077] The preparation methods for each of the above products are as follows:

[0078] (1) Add water and neutralizing agent to the reactor according to the formula in Table 1. Under stirring, slowly pump the anionic monomer into the reactor, control the temperature at 55℃±3℃, the stirring speed at 50 rpm, and the pH value at around 6.5.

[0079] (2) Add cationic monomers and nonionic monomers, and stir until homogeneous;

[0080] (3) Control the temperature at about 60℃, add 2 / 3 of the initiator, stir evenly, control the stirring speed at 20 rpm, and keep the reaction proceeding slowly;

[0081] (4) When the temperature is controlled at 90℃, add the remaining initiator, keep the reactor temperature between 90℃ and 98℃, keep it at that temperature for 2.5 hours, and then lower the reactor temperature to 60℃.

[0082] (5) Add chain terminator to terminate the reaction and obtain pesticide polymer synergists A1, A2, A3, A4, A5 and A6.

[0083] (6) The pesticide polymer synergists obtained in step (5) can be dried and pulverized to obtain powdered and granular pesticide polymer synergists A1F, A2F, A3F, A4F, A5F and A6F.

[0084] Example 2: Performance Testing of Pesticide Polymer Synergists

[0085] The performance of synergists A1, A2, A3, A4, A5, and A6 was tested, and the data are shown in Table 2 below. The solid content testing method for the synergists followed industry standard methods. The pH measurement method involved diluting the synergist with water until the solid content of the solution reached 1%, then measuring the pH value of the aqueous solution. The conductivity measurement method involved diluting the pesticide polymeric synergist with water until the solid content of the aqueous solution reached 200 ppm, then measuring the conductivity of the aqueous solution. The viscosity measurement method involved diluting or concentrating the pesticide polymeric synergist to a solid content of 25% and then measuring the viscosity.

[0086] Table 2 Performance of Synergist Products A1-A6

[0087]

[0088] Example 3: Effect test of pesticide polymer synergist on glyphosate formulation synergism

[0089] Add 0.01-5.0% (calculated based on 100% solids content, the same below) of pesticide polymer synergists A1, A2, A3, A4, A5 and A6 to 30% glyphosate aqueous solution. Generally, the percentage added is calculated based on the 100% solids content of the pesticide polymer synergist. Then test the herbicidal effect of the original glyphosate aqueous solution with and without pesticide polymer synergist.

[0090] The glyphosate weed control effect was tested in an orchard in Shantou, Guangdong Province. The average height of the weeds at the time of application was 30-50 cm, and no herbicides had been applied during this growth period. Micro-sprayers were used to control the orchard weeds. The concentration and amount of pesticide were applied according to the dilution ratio specified in the pesticide formulation instructions, diluted to a glyphosate content of 4000 ppm. Both formulations with and without added polymeric synergists were diluted to the same active ingredient content (4000 ppm glyphosate). Application was conducted uniformly in windless and sunny weather. Each test sample area was approximately 0.4 square meters, and each formulation was tested three times, with the average value taken as the final result. The weed mortality rate at 7 and 14 days and the weed regrowth rate at 30 days were investigated. The standard for weeds to be killed by herbicides is that all the leaves of the weeds turn yellow and wither, and the heart leaves of grass weeds and the top leaves of broadleaf weeds turn yellow and wither.

[0091] Regardless of whether pesticide polymer synergists are added, the application methods and statistical methods for the effectiveness against the target of pesticide formulations are all based on the original product standard requirements of the pesticide formulations. The weed kill rate is calculated by dividing the number of dead weeds by the number of surviving weeds before application, and the regrowth rate is calculated by dividing the number of regrowth weeds by the number of dead weeds counted 7 days and 14 days after application. The test results for each mixed sample are the average of the three test plots.

[0092] Table 3 Synergistic effect of pesticide polymeric synergists on 30% glyphosate aqueous solution

[0093]

[0094] The test results above show that the pesticide polymer synergist of this invention has a synergistic effect on increasing the efficacy of 30% glyphosate aqueous solution. This is mainly manifested in two aspects: firstly, it improves the weed control rate after 7 days, enhancing the speed of weed control and significantly increasing the weed mortality rate by more than 10%, with a maximum increase of approximately 21%. Secondly, the effect on the 30-day greening rate is even better; using the polymer synergist of this invention, we can achieve virtually no greening after 30 days. Even in the worst case, the greening rate using the pesticide polymer synergist of this invention is only 0.7%, which is far better than pesticide formulations without the polymer synergist of this invention.

[0095] Following the above experimental methods, the effects of the pesticide polymer synergist of the present invention on the efficacy of other commercially available glyphosate-related formulations were measured. The activity of 41% glyphosate isopropylamine salt solution, 62% glyphosate isopropylamine salt solution, 30% glyphosate aqueous solution, 50% glyphosate ammonium salt wettable powder, 75.7% glyphosate ammonium salt soluble granules, 50.2% glyphosate dimethylammonium salt solution, and 42% glyphosate potassium salt solution was verified by adding the pesticide polymer synergists A1, A2, A3, A4, A5, and A6 prepared in Example 1, or pesticide polymer synergists A1F, A2F, A3F, A4F, A5F, and A6F. Based on dry matter calculations, the addition amount of the pesticide polymer synergist varied between 0.01% and 5.00%. To obtain better results while ensuring the cost of the synergist, the addition amount was controlled between 0.1% and 1.0%. The type of pesticide polymeric synergist added is randomly selected from the above 12 types. Generally, liquid formulations are supplemented with pesticide polymeric synergists A1, A2, A3, A4, A5, or A6, while solid granular or powder formulations are generally supplemented with pesticide polymeric synergists A1F, A2F, A3F, A4F, A5F, and A6F. The amount of synergist added is calculated based on the solid content converted to a percentage.

[0096] Following the method described above for conducting field trials on 30% glyphosate aqueous solution with the addition of a pesticide polymer synergist, the 14-day weed control rate and 30-day greening rate of the glyphosate formulation with and without the pesticide polymer synergist were measured. The results showed that the 14-day weed control rate was above 95% and was more than 5% higher than that without the pesticide polymer synergist, while the 30-day greening rate was below 1%.

[0097] Therefore, the above-mentioned pesticide polymer synergist of the present invention has a very significant effect on improving the herbicidal effect of glyphosate formulations and reducing the regrowth rate of weeds after application.

[0098] Example 4: Efficacy test of glyphosate formulation containing pesticide polymer synergist

[0099] The pesticide polymer synergist obtained in the embodiments of the present invention is applied to glyphosate aqueous solution. The glyphosate technical is glyphosate technical powder, various forms of glyphosate salts, or a compound with glyphosate as the main herbicide component and other herbicides. In the following examples, 62% glyphosate isopropylamine salt and glyphosate technical powder are selected as raw materials to prepare glyphosate aqueous solution.

[0100] I. Preparation of glyphosate formulations

[0101] Glyphosate aqueous solution 1

[0102] Add 10g of pesticide polymer synergist A1 obtained in Example 1, 50g of alkyl glycoside, 660g of 62% glyphosate isopropylamine salt mother liquor and 280g of water to a mixing pot, stir for about 30 minutes, and adjust the pH of the system to 4.8 to obtain glyphosate aqueous solution 1 of the present invention.

[0103] Glyphosate aqueous solution 2

[0104] Add 12g of pesticide polymer synergist A5 obtained in Example 1, 40g of alkyl glycoside, 660g of 62% glyphosate isopropylamine salt mother liquor and 245g of water to a mixing pot and stir for about 30 minutes. Then add 40g of ammonium sulfate and stir for 10 minutes. Adjust the pH of the system to 4.5 to obtain glyphosate aqueous solution 2 of the present invention.

[0105] Glyphosate aqueous solution 3

[0106] Add 10g of pesticide polymer synergist A6 obtained in Example 1, 60g of imidazoline amphoteric surfactant, 500g of 62% glyphosate isopropylamine salt mother liquor and 430g of water to a mixing pot, stir for about 30 minutes, and adjust the pH of the system to 4.6 to obtain glyphosate aqueous solution 3 of the present invention.

[0107] Glyphosate aqueous solution 4

[0108] 316 g of 95% glyphosate technical powder, 404 g of water, and 220 g of 25% ammonia water were added to a mixing pot in sequence and stirred for 15 minutes. Then, 10 g of pesticide polymer synergist A4 obtained in Example 1 and 50 g of alkyl glycoside were added to the mixing pot and stirred for about 30 minutes. The pH value of the system was adjusted to 4.7 to obtain glyphosate aqueous solution 4 of the present invention.

[0109] Glyphosate aqueous solution 5

[0110] 316 g of 95% glyphosate technical powder, 527 g of water, and 87 g of 98% potassium hydroxide were added to a mixing pot in sequence and stirred for 15 min. Then, 20 g of pesticide polymer synergist A2 obtained in Example 1 and 50 g of alkyl glycoside were added to the mixing pot and stirred for about 30 min. The pH value of the system was adjusted to 4.9 to obtain glyphosate aqueous solution 5 of the present invention.

[0111] II. Glyphosate herbicidal efficacy test

[0112] According to the following national standards, the stability, sustained foaming properties, low-temperature stability, and thermal storage stability of the above-mentioned glyphosate aqueous solution at 1-5 dilutions were determined, and the measurement standards are shown below:

[0113] Dilution stability: HG / T2467.5-2003 / 4.9

[0114] Persistent foaming properties: HG / T2467.5-2003 / 4.11

[0115] Low temperature stability: GB / T19137-2003

[0116] Thermal storage stability: GB / T19136-2003

[0117] The performance test results for glyphosate aqueous solutions 1-5 are shown in Table 4 below:

[0118] Table 4. Performance of glyphosate formulations prepared using pesticide polymer synergists

[0119]

[0120] The above test results show that all indicators of the glyphosate aqueous solution with the pesticide synergist of this invention are qualified. In other words, in the process of preparing glyphosate formulations, using the pesticide polymer synergist of this invention as a raw material can ensure the various formulation requirements of glyphosate formulations.

[0121] Field trials were conducted on the above glyphosate aqueous solutions 1-5. The test methods are described in Example 3. The specific results are shown in Table 5 below.

[0122] Table 5. Herbicidal effect of glyphosate aqueous solution

[0123]

[0124] Note: The commercially available formulations in Table 5 are 30% glyphosate aqueous solutions. These commercially available formulations do not contain pesticide polymer synergists.

[0125] The test results above show that the glyphosate aqueous solution prepared with the pesticide polymer synergist of this invention has a very good weed control effect, which is better than that of similar excellent products in the industry and has a relatively outstanding effect.

[0126] Example 5: Efficacy test of formulations containing other active ingredients of pesticide polymer synergists

[0127] The efficacy of fungicides such as pyraclostrobin, insecticides such as spinosad, acaricides such as pyridaben, and plant growth regulators such as brassinolide was verified. The existing formulations were supplemented with synergist A4 at a rate of 0.5% wt, and the effects were compared with those of formulations without synergist. The enhancement index was measured, and the details are shown in Table 6 below.

[0128] Table 6. Enhancement of the effect of synergists on pesticide active ingredients.

[0129]

[0130] In addition to the pesticide active ingredients listed in Table 6, efficacy tests were conducted on other components of the present invention, and it was found that the synergists of the present invention can enhance the corresponding effects of the pesticide active ingredients.

[0131] The above is merely a specific description of the pesticide polymer synergist and pesticide active ingredient formulation of the present invention. These embodiments are not intended to limit the scope of protection of the present invention. Any equivalent implementation or modification that does not depart from the technical solution of the present invention, such as the replacement of commonly used reagents in the polymerization process of pesticide polymer synergists or the replacement of commonly used adjuvants in glyphosate aqueous solutions, should be included in the scope of protection of the present invention.

Claims

1. A pesticide polymeric synergist, wherein the synergist comprises a high molecular weight polymer, the synergist is water-soluble, has a solid content of 5-75%, and when diluted with water to a 1% solid content aqueous solution, the pH value is 5-8; when diluted with water to a 200 ppm solid content solution, the conductivity of the aqueous solution is 100-250 μS / cm; and when diluted with water or concentrated to a 25% solid content, the apparent viscosity of the synergist at 25°C is 3000-30000 centipoise. The polymer is obtained by solution polymerization of raw materials comprising anionic monomers and cationic monomers, and / or nonionic monomers, wherein the weight ratio of anionic monomers, cationic monomers, and nonionic monomers is 5-95:5-95:0-30. The anionic monomers are selected from one or two of acryloyldimethyl taurate and itaconic acid; the cationic monomers are selected from one or two of methacryloylpropyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride; and the nonionic monomers are selected from one or two of methacrylamide and acrylamide. The solution polymerization method includes the following steps: (1) Add water and neutralizing agent to the reactor. Under stirring, slowly pump the anionic monomer into the reactor. Control the temperature of the reactor to not exceed 60°C, the stirring speed to be within 60 rpm, and the pH value of the system to be controlled between 5 and 9. (2) Add cationic monomers and nonionic monomers, and stir until homogeneous; (3) Control the system temperature at 55-65℃, add 2 / 3 of the initiator, stir evenly, control the stirring speed to within 30 rpm, and keep the reaction slow. (4) When the system temperature reaches 90℃, add the remaining initiator, keep the reactor temperature between 90℃ and 98℃, keep it at that temperature for 2-4 hours, and then lower the reactor temperature to 50-70℃. (5) Add a chain terminator to terminate the reaction and obtain the pesticide polymer synergist of the present invention.

2. The pesticide polymer synergist according to claim 1, characterized in that... The neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, ethanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and ammonia. The initiator is an inorganic peroxide or an organic peroxide. The chain terminator is selected from one or more of hydroquinone, p-tert-butylcatechol, sodium dimethyl dithiocarbamate, sodium polysulfide, sodium nitrite, and sodium sulfite.

3. The pesticide polymer synergist according to claim 2, characterized in that... The inorganic peroxide is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate, and the organic peroxide is benzoyl peroxide.

4. A white to slightly yellow powdery or granular pesticide polymer synergist, characterized in that... The pesticide polymer synergist according to any one of claims 1-3 is obtained by drying and pulverizing.

5. A method for preparing the pesticide polymer synergist according to any one of claims 1-3, the method comprising the following steps: polymerizing raw materials containing anionic monomers and cationic monomers, and / or nonionic monomers by solution polymerization, controlling the solid content of the product to be 5-75%, diluting the product with water to an aqueous solution with a solid content of 1% at a pH of 5-8, and when the product is diluted with water to a solution with a solid content of 200ppm, the conductivity of the aqueous solution is 100-250μs / cm, thereby obtaining the pesticide polymer synergist.

6. The preparation method according to claim 5, characterized in that... The anionic monomer is selected from one or two of acryloyldimethyl taurate and itaconic acid; the cationic monomer is selected from one or two of methacryloylpropyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride; and the nonionic monomer is selected from one or two of methacrylamide and acrylamide.

7. The preparation method according to claim 5, characterized in that... The method further includes drying and pulverizing the obtained pesticide polymer synergist to obtain white to slightly yellow powder particles.

8. The preparation method according to claim 6, characterized in that... The preparation method includes the following steps in sequence: (1) Add water and neutralizing agent to the reactor. Under stirring, slowly pump the anionic monomer into the reactor. Control the temperature of the reactor to not exceed 60°C, the stirring speed to be within 60 rpm, and the pH value of the system to be controlled between 5 and 9. (2) Add cationic monomers and nonionic monomers, and stir until homogeneous; (3) Control the system temperature at 55-65℃, add 2 / 3 of the initiator, stir evenly, control the stirring speed to within 30 rpm, and keep the reaction slow. (4) When the system temperature reaches 90℃, add the remaining initiator, keep the reactor temperature between 90℃ and 98℃, keep it at that temperature for 2-4 hours, and then lower the reactor temperature to 50-70℃. (5) Add a chain terminator to terminate the reaction and obtain the pesticide polymer synergist of the present invention.

9. The preparation method according to claim 8, characterized in that... The neutralizing agent is selected from one or more of sodium hydroxide, potassium hydroxide, ethanolamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and ammonia. The initiator is an inorganic peroxide or an organic peroxide. The chain terminator is selected from one or more of hydroquinone, p-tert-butylcatechol, sodium dimethyl dithiocarbamate, sodium polysulfide, sodium nitrite, and sodium sulfite.

10. The preparation method according to claim 9, characterized in that... The inorganic peroxide is selected from one or more of ammonium persulfate, sodium persulfate, and potassium persulfate, and the organic peroxide is benzoyl peroxide.

11. A pesticide formulation comprising a pesticide polymeric synergist as described in any one of claims 1-3 and an active ingredient, wherein the pesticide polymeric synergist accounts for 0.01-5.0% of the pesticide formulation by weight, and the weight percentage of the pesticide polymeric synergist is calculated based on the percentage of solids.

12. The pesticide formulation according to claim 11, characterized in that... The active ingredient is one or more of the following: herbicide, insecticide, acaricide, nematicide, fungicide, and plant growth regulator.

13. The pesticide formulation according to claim 12, characterized in that... The herbicide is one or more of a cytotoxic herbicide or a selective herbicide, or the herbicide is at least two of a cytotoxic herbicide and a selective herbicide, wherein the cytotoxic herbicide is one or more of glyphosate, glyphosate isopropylamine salt, glyphosate diammonium salt, glyphosate ammonium salt, glyphosate dimethylamine salt, glyphosate sodium salt, glyphosate potassium salt, and paraquat.

14. The pesticide formulation according to claim 11, characterized in that... The pesticide formulation is in the form of granules, powders, or liquids.

15. The pesticide formulation according to claim 14, characterized in that... The pesticide formulation is an aqueous solution, a wettable powder, or a soluble granule.

16. The use of the pesticide polymer synergist according to any one of claims 1-3, wherein the pesticide polymer synergist is used to enhance the effect of the active ingredient of the pesticide, wherein the active ingredient is one or more of herbicides, insecticides, acaricides, nematicides, fungicides, and plant growth regulators.

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