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WO2011069931A1 - Formulation de pesticides sensibles à la lumière et de polymères en peigne à teneur en absorbeur d'uv - Google Patents

Formulation de pesticides sensibles à la lumière et de polymères en peigne à teneur en absorbeur d'uv Download PDF

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Publication number
WO2011069931A1
WO2011069931A1 PCT/EP2010/068909 EP2010068909W WO2011069931A1 WO 2011069931 A1 WO2011069931 A1 WO 2011069931A1 EP 2010068909 W EP2010068909 W EP 2010068909W WO 2011069931 A1 WO2011069931 A1 WO 2011069931A1
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Prior art keywords
absorber
monomer
polymeric
composition according
pesticide
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German (de)
English (en)
Inventor
Richard Riggs
Oliver Labisch
Paola Uribe Arocha
Michael Ishaque
Christian Bittner
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate

Definitions

  • the present invention relates to a composition comprising a pesticide and a polymeric UV absorber comprising as monomeric units a) a UV absorber containing an ethylenically unsaturated group (UV monomer), and b) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer). Furthermore, the invention relates to a process for the preparation of said polymeric UV absorber, wherein the UV monomer and the PEG monomer are radically polymerized, and a composition comprising a pesticide and the aforementioned polymeric UV absorber.
  • WO 89/03386 discloses UV-absorbing copolymers composed of UV absorbers with ethylenically unsaturated groups and various comonomers. The copolymers are suitable for the production of contact lenses.
  • EP 0123368 discloses polymers comprising an olefinic p-aminobenzoate, N-vinylpyrrolidone, and (meth) acrylic acid.
  • the polymers are suitable for the production of sunscreen.
  • No. 3,992,356 discloses polymers for cosmetic applications comprising in the macromolecular chain an acrylic ester-containing UV absorber, and optionally comonomers, such as vinyl stearate or stearyl (meth) acrylate.
  • EP 0 896 006 discloses polymeric UV absorbers based on acrylic ester-containing UV absorbers, alkyl vinyl ethers and optionally alkyl acrylates.
  • WO08134674 discloses UV absorbers for ophthalmic lenses.
  • WO 2008/085682 discloses a composition comprising photolabile pesticide and a UV protecting agent, which may be, for example, Uvinul® P25 (PEG-25 para-aminobenzoic acid).
  • EP 0 376 888 A1 discloses agents for controlling harmful insects containing a behavior-altering substance and a pesticidally active compound, both of which are contained in a flowable matrix which protects the behavior-modifying substance from UV radiation.
  • compositions and UV absorbers of the prior art had various disadvantages: UV-sensitive pesticides were not sufficiently stabilized; high levels of surfactants had to be added to the agrochemical formulation to achieve high stability of drug dispersions; the interfacial activity of the UV absorbers was low, poorly soluble or poorly tolerated in agrochemical formulations.
  • the object was therefore to find a UV absorber that overcomes the disadvantages of the prior art.
  • composition comprising a pesticide and a polymeric UV absorber comprising as monomeric units
  • UV absorber containing an ethylenically unsaturated group (UV monomer)
  • UV absorbers containing an ethylenically unsaturated group are well known.
  • UV monomers are the compounds shown in EP 0 896 006, Formula I, Unit b (wherein there is shown the ethylenically unsaturated group in the form of the polymerized, i.e., saturated, form), which are hereby incorporated by reference.
  • Further examples of UV monomers are the compounds shown in US 5,620,838, formula (I), which are hereby incorporated by reference. Preference is given to UV monomers which contain a benzotriazole groups.
  • the UV monomers are the compounds 1 to 27 shown in FIGS. 1A, 1B and 1C.
  • UV absorber 2 is particularly preferred in FIG. 1A (2- (2'-hydroxy-5'-sulfonic acid) methacrylic oxyethylphenyl) -2H-benzotriazole). Mixtures of different UV monomers can also be present in the polymeric UV absorber.
  • PEG monomer Polyalkylene oxides containing an ethylenically unsaturated group
  • the PEG monomer preferably contains at least three alkylene oxide groups, more preferably it contains five to 50 alkylene oxide groups.
  • Suitable alkylene oxide groups are, for example, ethylene oxide, Propylene oxide, butylene oxide, preferably ethylene oxide.
  • Examples of ethylenically unsaturated groups are vinyl, acrylate or methacrylate groups.
  • Very particularly preferred PEG monomers are those of the formula A.
  • R1 H or CH 3
  • R2 H or Ci-Ci 2 -alkyl
  • R 3 H or Ci-Ci 2 -alkyl
  • R4 H or Ci-Ci2-alkyl
  • n 3 - 50.
  • R1 is preferably CH 3 .
  • R 2 is preferably CH 3 .
  • R 3 is preferably H or CH 3, in particular H.
  • R 4 is preferably H or CH 3, in particular H.
  • n is preferably 5-35, in particular 7-30.
  • PEG monomers, in particular those of the formula A, are obtainable by known processes, for example from WHERE
  • the polymeric UV absorber may contain at least one further monomeric unit c), which is usually polymerizable with the UV monomers and the PEG monomer.
  • monomeric units c which is usually polymerizable with the UV monomers and the PEG monomer.
  • monomers C monoethylenically unsaturated monomers
  • C1 monoethylenically unsaturated mono- and dicarboxylic acids having 3 to 8 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid and itaconic acid,
  • C2 alkyl esters of monoethylenically unsaturated mono- and di-C3-Cs-carboxylic acids in particular of acrylic acid and of methacrylic acid with C 1 -C 10 -alkanols or C 3 -C 10 -cycloalkanols, such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, iso-butyl acrylate tert-butyl acrylate, n-hexyl acrylate, 2-
  • C3 hydroxyalkyl esters of monoethylenically unsaturated mono- and di-Cs-Cs-carboxylic acids in particular of acrylic acid and of methacrylic acid such as 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate and 4-hydroxybutyl methacrylate,
  • Preferred monomeric unit c) are the monomers of group C1, in particular methacrylic acid and acrylic acid, especially methacrylic acid.
  • the molar ratio of UV monomer to PEG monomer is usually in the range of 1: 9 to 9: 1, preferably in the range of 1: 5 to 5: 1, and in particular in the range of 1: 2 to 2: 1.
  • the molar ratio of monomeric unit c) (especially of (meth) acrylic acid) to UV monomer is usually in the range from 1: 9 to 9: 1, preferably in the range from 1: 5 to 5: 1, and in particular in the range of 1: 2 to 2: 1.
  • the polymeric UV absorber usually has a proportion of UV monomer at all monomeric units of from 5 to 70 mol%, preferably from 10 to 60 mol%.
  • the UV monomer has a proportion of all monomeric units of 20 to 70 mol%, preferably 30 to 70 mol%, and in particular 40 to 60 mol%.
  • polymeric UV absorber it may also be useful to increase the molecular weight of the polymeric UV absorber, the copolymerization in the presence of small amounts of polyethylenically unsaturated monomers with z. B. 2, 3 or 4 polymerizable double bonds perform (crosslinker).
  • crosslinker examples thereof are diesters and triesters of ethylenically unsaturated carboxylic acids, in particular the bis- and tris-acrylates of diols or polyols having 3 or more OH groups, eg.
  • bisacrylates and the bis meth-acrylates of ethylene glycol, diethylene glycol, trietylene glycol, neopentyl glycol or polyethylene glycols As the bisacrylates and the bis meth-acrylates of ethylene glycol, diethylene glycol, trietylene glycol, neopentyl glycol or polyethylene glycols.
  • Such crosslinkers are used, if desired, in an amount of generally 0.01 to 5 wt .-% based on the total amount of monomers to be polymerized. Preferably, less than 0.01 wt .-% and in particular no Vernetzermonomere be used.
  • the copolymerization of UV monomers with PEG monomers and optionally other monomers usually takes place in the presence of free-radical forming compounds, so-called initiators.
  • initiators Such compounds are usually used in amounts of up to 30 wt .-%, preferably 0.05 to 15 wt .-%, in particular 0.2 to 8 wt .-%, based on the monomers to be polymerized.
  • the above weights are based on the sum of the components.
  • Suitable initiators are, for example, organic peroxides and hydroperoxides, furthermore peroxodisulfates, percarbonates, peroxide esters, hydrogen peroxide and azo compounds.
  • Examples of initiators are hydrogen peroxide, dicyclohexyl peroxydicarbonate, diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, dicanoanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toluyl) peroxide, succinyl peroxide, methyl ethyl ketone peroxide, di-tert.
  • Redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator, e.g. a reducing sulfur compound, e.g. Bisulfites, sulfites, thiosulfates, dithionites and tetrathionates of alkali metals or of ammonium compounds. So you can use combinations of peroxodisulfates with alkali metal or ammonium hydrogen sulfites, z. For example, ammonium peroxodisulfate and ammonium disulfite.
  • the amount of the peroxide-containing compound to the redox coinitiator is 30: 1 to 0.05: 1.
  • the initiators may be used alone or in admixture with each other, for. B. mixtures of hydrogen peroxide and sodium peroxodisulfate.
  • the initiators can be either water-soluble or not soluble in water or only slightly soluble.
  • Water-soluble initiators are preferably used for the polymerization in aqueous medium, ie. H. Initiators which are soluble in the aqueous polymerization medium in the concentration commonly used for the polymerization. These include peroxodisulfates, azo initiators with ionic groups, organic hydroperoxides having up to 6 C atoms, acetone hydroperoxide, methyl ethyl ketone hydroperoxide and hydrogen peroxide, as well as the abovementioned redox initiators.
  • transition metal catalysts may additionally be used, for. Salts of iron, cobalt, nickel, disgust, copper, vanadium and manganese. Suitable salts are, for. Ferrous sulfate, cobaltous chloride, nickel (II) sulfate, or copper (I) chloride. Based on the monomers, the reducing transition metal salt is used in a concentration of 0.1 ppm to 1000 ppm. So you can use combinations of hydrogen peroxide with iron (II) salts, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt.
  • redox coinitiators and / or transition metal catalysts may also be used in combination with the abovementioned initiators, eg. B. benzoin, dimethylaniline, ascorbic acid and soluble in organic solvents complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium.
  • initiators eg. B. benzoin, dimethylaniline, ascorbic acid and soluble in organic solvents complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium.
  • the amounts of redox coinitiators or transition metal catalysts usually used are about 0.1 to 1000 ppm, based on the amounts of monomers used.
  • regulators can be used for this purpose, in particular organic compounds containing SH groups, in particular water-soluble compounds containing SH groups such as 2-mercaptoethanol, 2-mercaptopropanol, 3-mercaptopropionic acid, cysteine, N-acetylcysteine, furthermore phosphorus (III) or Phosphorus (I) compounds such as alkali metal or alkaline earth metal hypophosphites, eg. For example, sodium hypophosphite, as well as hydrogen sulfites such as sodium hydrogen sulfite.
  • the polymerization regulators are generally used in amounts of 0.05 to
  • Preferred regulators are the abovementioned SH-group-carrying compounds, in particular water-soluble compounds bearing SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, 3-mercaptopropionic acid, cysteine and N-acetylcysteine.
  • the polymerization can be carried out by customary polymerization processes, including solution, precipitation, suspension or bulk polymerization.
  • the method of solution polymerization d. H. the polymerization in solvents or diluents.
  • Suitable solvents or diluents include both aprotic solvents, e.g. B. the aforementioned aromatics such as toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of alkylaromatics, aliphatic and cycloaliphatic compounds such as cyclohexane and technical Aliphatenmischept, ketones such as acetone, cyclohexanone and methyl ethyl ketone, ethers such as tetrahydrofuran, dioxane,
  • aprotic solvents e.g. B. the aforementioned aromatics such as toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of alkylaromatics, aliphatic and cycloaliphatic compounds such as cyclohex
  • the copolymerization process according to the invention is preferably carried out in water or a mixture of water with up to 60% by weight of C 1 -C 4 -alkanols or glycols as solvent or diluent. Particular preference is given to using water as the sole solvent.
  • the polymerization is preferably carried out with substantial or complete exclusion of oxygen, preferably in an inert gas stream, e.g. B. carried out a nitrogen stream.
  • the polymerization can be carried out in the apparatuses customary for polymerization methods. These include stirred tanks, stirred tank cascades, autoclaves, tube reactors and kneaders.
  • the polymerization is usually carried out at temperatures in the range of 0 to 300 ° C, preferably in the range of 40 to 120 ° C.
  • the polymerization time is usually in the range of 0.5 hours to 15 hours, and more preferably in the range of 2 to 6 hours.
  • the pressure prevailing in the polymerization is of minor importance for the success of the polymerization and is generally in the range from 800 mbar to 2 bar and often at ambient pressure.
  • the polymeric UV absorbers generally have weight-average molecular weights (M w ) in the range from 10,000 to 500,000 g / mol, preferably from 12,000 to 300,000 g / mol, in particular from 15,000 to 100,000 g / mol.
  • M w weight-average molecular weights
  • the weight-average molecular weight M w can be determined in the usual way by gel permeation chromatography, as explained in the examples.
  • the polymeric UV absorbers are preferably obtained in the form of an aqueous dispersion or solution.
  • the solids content is preferably 10 to 80 wt .-%, in particular 30 to 65 wt .-%.
  • the invention further relates to polymeric UV absorbers comprising as monomeric units a) a UV absorber containing an ethylenically unsaturated group (UV monomer), and
  • PEG monomer a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer), wherein the PEG monomer corresponds to the formula A,
  • the invention also relates to a process for the preparation of the polymeric UV absorber according to the invention, wherein the UV monomer and the PEG monomer are radically polymerized. Suitable and preferred embodiments are as described above.
  • the polymeric UV absorbers according to the invention are outstandingly suitable as additives for agrochemical formulations. Therefore, the invention also relates to a composition comprising a pesticide and a polymeric UV absorber according to the invention.
  • the agrochemical composition according to the invention generally comprises from 0.1 to 50% by weight, preferably from 0.5 to 30% by weight, particularly preferably from 0.1 to 15% by weight, of polymeric UV absorber, in each case based on the composition.
  • the agrochemical composition according to the invention generally comprises 0.01 to 95% by weight, preferably 0.5 to 80% by weight, more preferably 2 to 50% by weight and especially 5 to 20% by weight of pesticide, in each case based on the composition.
  • the weight ratio of pesticide to polymeric UV absorber is usually from 30: 1 to 1: 3, preferably 15: 1 to 1: 2, particularly preferably 8: 1 to 1: 1.
  • pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators.
  • Preferred pesticides are fungicides, insecticides and herbicides, especially insecticides.
  • mixtures of pesticides of two or more of the above classes may be used.
  • One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London.
  • Suitable insecticides are insecticides of the carbamate class, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone Analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozin, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, Cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines , Dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones,
  • Suitable herbicides are herbicides of the classes of the acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones , Nitriles, N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthalamates
  • Preferred herbicides are napropamide, proparnet, bentazone, paraquat dichloride, cyclopydim, sethoxydim, ethalfluralin, oryzalin, pendimethalin, trifluralin, aciflurene, acenifen, fomesafen, oxyfluorene, loxynil, imazetapyr, imazaquin, chloridazon, norflurazon, thiazopyr, triclopyr, dithiopyr , Diflufenican, picolinafen, amidosulfuron, molinates, enolates, promethone, metribuzin, azafenidine, carfentrazone-ethyl, sulfentrazone, metaxuron, monolinuron, fluchloralin and flurenol.
  • Preferred fungicides are cyprodinil, fuberidazole, dimethomorph, proclonaz, triflumizole, tridemorph, edifenfos, fenarimol, nuarimol, ethirimol, quinoxylene, dithianone, metominostrobin, trifloxystrobin, dichlofluamide, bromuconnazole and myclobutanil.
  • Preferred insecticides are acephates, A- zinphos-ethyl, azinphos-methyl, isofenphos, chlorpyriphos-methyl, dimethylvinphos, phorates, phoxim, prothiofos, cyhexatin, alanycarb, ethiofencarb, pirimicarb, thiodi-carb, fipronil, bioallethrin, bioresemethine, deltamethrin, fenpropathine, flucythrinates, baptismalvalinates, alphacypermethrin, metaflumizone, cetacypermethrin, resmethin, tefluthrin, lambda cyhalothrin and hydramethylnon.
  • preferred pesticides are pyrethroids or metaflumizone, especially pyrethroids. Particularly preferred pesticides are alphacypermethrin and metaflum
  • pesticides that are UV sensitive are used. This UV sensitivity can be determined in simple preliminary tests. Pesticides are preferably UV-sensitive when irradiated with a pesticidal film obtained by drying a 25% strength by weight solution of the pesticide in a suitable solvent, preferably in acetone, with UVA / IS light of wavelength 300-800 nm within 24 h at 25 ° C to at least 20 wt.% Degraded. Usually, an illuminance of 10,000 to 100,000 lux, preferably 50,000 to 80,000 lux, is used. The pesticides are considered to be degraded if the concentration of the pesticide (or a pesticide component in a mixture of several pesticide components) is correspondingly reduced.
  • UV-sensitive pesticides There are generally various ways known how UV-sensitive pesticides are degraded.
  • chemical bonds can be isomerized, radicalized or cleaved, and optionally react again thereafter.
  • E / Z isomers of double bonds of pesticides (such as metaflumizone) can be isomerized by UV light so that one isomer that has pesticidal activity is rearranged to the other isomer that has less activity. All or some of these degradation pathways can be inhibited with the composition according to the invention and the UV absorbers according to the invention.
  • compositions according to the invention can be present in the usual types of compositions for agrochemical formulations, eg. As solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the type depends on the respective purpose; It should in any case ensure a fine and uniform distribution of the compound according to the invention.
  • composition types are suspensions (SC, OD, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, DP, DS ) or granules (GR, FG, GG, MG), which may either be soluble or dispersible in water, as well as gels for the treatment of plant propagation materials such as seeds (GF). Baits for animals, such as ants or rats, may be of various of the aforementioned types of composition, preferably as powders, pastes, granules or gels.
  • composition types eg SC, EC OD, FS, WG, SG, WP, SP, SS, WS, GF
  • composition types are used diluted.
  • To- Types of compounds such as DP, DS, GR, FG, GG, MG or bait are generally used undiluted.
  • Preferred types of compositions are suspensions.
  • compositions according to the invention can furthermore also contain auxiliaries customary for plant protection agents, the choice of auxiliaries being directed to the specific application form or the active ingredient.
  • auxiliaries are solvents, solid carriers, surface-active substances (such as further solubilizers, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate dyes and adhesives (for example for seed treatment). or usual bait formulation aids (eg attractants, feeds, bittering agents).
  • Suitable solvents include water, organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g.
  • solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
  • Solid carriers are mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.
  • mineral earths such as silicic acids, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, Ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour
  • surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesul
  • aromatic sulfonic acids eg. B. of lignin (Borresper
  • alkyl ethers alkyl ethers, lauryl alcohol polyglycol ether, sorbitol esters, lignin-sulphite waste liquors and proteins, denatured proteins, polysaccharides (eg methylcellulose), hydrophobically modified starches, polyvinyl alcohol (Mowiol ® types, Clariant, Switzerland), Polycarboxyla- te (Sokalan ® types, BASF, Germany) , polyalkoxylates, polyvinylamine (Lupamin ® - types, BASF, Germany), polyethyleneimine (Lupasol ® types, BASF, Germany), polyvinylpyrrolidone and copolymers thereof.
  • thickeners ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion
  • thickeners are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ®, CP Kelco, U.S.A.), Rhodopol ® 23 (Rho dia, France) or Veegum ® (RT Vanderbilt, USA) or attaclay ® (Engelhard Corp., NJ, USA).
  • Bactericides may be added to stabilize the composition.
  • bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ® MBS from Thor Chemie).
  • suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
  • defoamers examples include silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • composition types are:
  • Emulsions (EW, EO, ES)
  • the composition has an active ingredient content of 25 wt .-%.
  • the pesticide 20 parts by weight of the pesticide are comminuted with the addition of 10 parts by weight dispersing and wetting agents and 70 parts by weight of water or an organic solvent in a stirred ball mill to a fine active substance suspension. Dilution in water results in a stable suspension of the active ingredient.
  • the active ingredient content in the composition is 20% by weight.
  • 50 parts by weight of the pesticide are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of technical equipment (eg extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient.
  • the composition has an active substance content of 50% by weight.
  • the active ingredient content of the composition is 75% by weight.
  • Dispersing agent 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight of water or an organic solvent to a fine suspension .. Dilution with water results in a stable suspension with 20 wt .-% active ingredient content.
  • 0.5 parts by weight of the pesticide are finely ground and combined with 99.5 parts by weight of carriers. Common methods are the extrusion, the Spray drying or the fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content,
  • the compounds may be used as such or in the form of their compositions, e.g. B. in the form of directly sprayable solutions, powders, suspensions, dispersions, e-mulsions, Oldispersionen, pastes, dusts, scattering agents or granules by spraying, misting, dusting, scattering, laying baits, painting, dipping or pouring are applied.
  • Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, old dispersions) by adding water.
  • the substances can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the application rates in the application in crop protection depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha. In the treatment of plant propagation materials, eg. B. State, are generally used amounts of active ingredient of 1 to 1000 g / 100 kg, preferably 5 to 100 g / 100 kg of propagating material or seed. When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates in material protection are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated.
  • the present invention further relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the composition according to the invention on the respective pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
  • Habitat is usually understood to mean the cultivation area of crops, the crops or their propagation material.
  • the composition according to the invention containing a pesticide is naturally not suitable for human use and not authorized.
  • Advantages of the present invention is that the polymeric UV absorbers stabilize UV-sensitive pesticides, in particular even at low concentrations of polymeric UV absorber.
  • UV absorbers according to the invention can reduce the surface tension of water more strongly, ie that they exhibit a higher interfacial activity.
  • the UV absorbers are readily soluble in agrochemical formulations, or very well tolerated with agrochemical formulations, such as aqueous emulsions and aqueous suspensions. For example, no additional emulsifier is necessary to incorporate the UV absorber in the formulation.
  • UV absorber A 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (CAS no.
  • MPEGMA350 methyl polyethylene glycol-350-methyl acrylate
  • MPEGMA475 methyl polyethylene glycol-475-methyl acrylate
  • MPEGMA1 100 methyl polyethylene glycol-1 100-methyl acrylate
  • MPEGMA350 is commercially available as Bisomer® MPEG350MA from Cognis.
  • Example 2 Analogously to Example 1, a polymer was prepared in which additionally methacrylic acid (MAS) was copolymerized. The molar ratio of UV absorber to methacrylic acid and the resulting molecular weights of polymers 2 and 3 are summarized in Table 1. The polymers were clearly water-soluble.
  • MAS methacrylic acid
  • Metaflumizone (Alverde®) containing 240 g / l of metaflumizone was spiked with 96 g / l Polymer No. 1 -5 and thereafter was diluted with water to give an active ingredient content of 10 g / l.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne une composition contenant un pesticide et un absorbeur d'UV polymère comprenant comme unités monomères a) un absorbeur de rayonnement d'UV contenant un groupe éthyléniquement insaturé (monomère UV), et b) un poly(oxyde d'alkylène) contenant un groupe éthyléniquement insaturé (monomère PEG). L'invention concerne également un procédé de fabrication dudit absorbeur d'UV polymère, le monomère UV et le monomère PEG étant polymérisés par voie radicalaire, ainsi qu'une composition contenant un pesticide et ledit absorbeur d'UV polymère. L'invention concerne en outre un procédé pour lutter contre les champignons phytopathogènes et/ou la croissance indésirable de végétaux et/ou contre l'infestation inopportune par des insectes ou des acariens et/ou pour assurer la régulation de la croissance de végétaux, procédé selon lequel on fait agir ladite composition sur les parasites concernés, leur espace vital ou les plantes qui doivent être protégés du parasite concerné, le sol et/ou sur des plantes indésirables et/ou les plantes utiles et/ou leur espace vital.
PCT/EP2010/068909 2009-12-09 2010-12-06 Formulation de pesticides sensibles à la lumière et de polymères en peigne à teneur en absorbeur d'uv Ceased WO2011069931A1 (fr)

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EP09178511 2009-12-09

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Cited By (7)

* Cited by examiner, † Cited by third party
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CN102893967A (zh) * 2012-09-27 2013-01-30 华中农业大学 一种地下害虫诱杀方法
WO2013040449A1 (fr) * 2011-09-16 2013-03-21 Benz Research And Development Corp. Matériaux absorbant la lumière ultraviolette pour lentilles intraoculaires et utilisations associées
EP2863740A1 (fr) 2012-06-26 2015-04-29 Sumitomo Chemical Company, Limited Composition pesticide se présentant sous la forme d'une émulsion aqueuse
EP2863741A1 (fr) 2012-06-26 2015-04-29 Sumitomo Chemical Company, Limited Composition pesticide se présentant sous la forme d'une émulsion aqueuse
US9184057B2 (en) 2011-03-18 2015-11-10 Basf Se Method for manufacturing integrated circuit devices, optical devices, micromachines and mechanical precision devices having patterned material layers with line-space dimensions of 50 nm and less
CN111596048A (zh) * 2020-04-07 2020-08-28 浙江省农业科学院 两种杀虫剂的施用方法
CN119177002A (zh) * 2024-10-31 2024-12-24 东莞市凯柏塑胶科技有限公司 一种防紫外线的tpe热塑性弹性体材料的制备方法

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WO1989003386A1 (fr) 1987-10-15 1989-04-20 University Of Florida Monomeres et polymeres en vinyle absorbant les uv et implants oculaires prepares a partir de ceux-ci
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US5620838A (en) 1994-12-21 1997-04-15 Eastman Kodak Company Photographic elements containing directly dispersible UV absorbing polymers and method of making such elements and polymers
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WO2008085682A2 (fr) 2007-01-09 2008-07-17 Loveland Products, Inc. Composition pesticide et procédé d'utilisation de celle-ci
WO2008134674A1 (fr) 2007-04-30 2008-11-06 Alcon, Inc. Absorbeurs d'ultraviolets pour des matériaux de lentille ophtalmique
WO2009046243A1 (fr) * 2007-10-03 2009-04-09 Alcon, Inc. Matériaux pour dispositifs ophtalmiques et oto-rhino-laryngologiques

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EP0123368A1 (fr) 1983-04-22 1984-10-31 Gaf Corporation Polymères anti- solaires
WO1989003386A1 (fr) 1987-10-15 1989-04-20 University Of Florida Monomeres et polymeres en vinyle absorbant les uv et implants oculaires prepares a partir de ceux-ci
EP0376888A1 (fr) 1988-12-28 1990-07-04 Ciba-Geigy Ag Lutte contre les parasites
US5620838A (en) 1994-12-21 1997-04-15 Eastman Kodak Company Photographic elements containing directly dispersible UV absorbing polymers and method of making such elements and polymers
EP0896006A2 (fr) 1997-08-08 1999-02-10 Basf Aktiengesellschaft Polymères lipophiles absorbant les rayons UV
WO2006024538A1 (fr) 2004-09-03 2006-03-09 Basf Aktiengesellschaft Procede pour produire des esters d'acide (poly-c2-c4-alkyleneglycol)-mono(meth)acrylique
WO2007050395A2 (fr) * 2005-10-24 2007-05-03 Bausch & Lomb Incorporated Materiaux polymeres absorbant le rayonnement et dispositifs ophtalmiques les contenant
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WO2008085682A2 (fr) 2007-01-09 2008-07-17 Loveland Products, Inc. Composition pesticide et procédé d'utilisation de celle-ci
WO2008134674A1 (fr) 2007-04-30 2008-11-06 Alcon, Inc. Absorbeurs d'ultraviolets pour des matériaux de lentille ophtalmique
WO2009046243A1 (fr) * 2007-10-03 2009-04-09 Alcon, Inc. Matériaux pour dispositifs ophtalmiques et oto-rhino-laryngologiques

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9184057B2 (en) 2011-03-18 2015-11-10 Basf Se Method for manufacturing integrated circuit devices, optical devices, micromachines and mechanical precision devices having patterned material layers with line-space dimensions of 50 nm and less
WO2013040449A1 (fr) * 2011-09-16 2013-03-21 Benz Research And Development Corp. Matériaux absorbant la lumière ultraviolette pour lentilles intraoculaires et utilisations associées
CN103930455A (zh) * 2011-09-16 2014-07-16 宾视研发公司 人工晶状体用紫外线吸收材料及其用途
US10172705B2 (en) 2011-09-16 2019-01-08 Benz Research And Development Corp. Ultraviolet light absorbing materials for intraocular lens and uses thereof
US9561302B2 (en) 2011-09-16 2017-02-07 Benz Research & Development Corp. Ultraviolet light absorbing materials for intraocular lens and uses thereof
CN103930455B (zh) * 2011-09-16 2016-08-24 宾视研发公司 人工晶状体用紫外线吸收材料及其用途
EP2863740A1 (fr) 2012-06-26 2015-04-29 Sumitomo Chemical Company, Limited Composition pesticide se présentant sous la forme d'une émulsion aqueuse
JP2015525736A (ja) * 2012-06-26 2015-09-07 住友化学株式会社 水性乳濁状農薬組成物
JP2015521584A (ja) * 2012-06-26 2015-07-30 住友化学株式会社 水性乳濁状農薬組成物
EP2863741A1 (fr) 2012-06-26 2015-04-29 Sumitomo Chemical Company, Limited Composition pesticide se présentant sous la forme d'une émulsion aqueuse
US9572345B2 (en) 2012-06-26 2017-02-21 Sumitomo Chemical Company, Limited Pesticidal composition in the form of aqueous emulsion
CN102893967A (zh) * 2012-09-27 2013-01-30 华中农业大学 一种地下害虫诱杀方法
CN111596048A (zh) * 2020-04-07 2020-08-28 浙江省农业科学院 两种杀虫剂的施用方法
CN119177002A (zh) * 2024-10-31 2024-12-24 东莞市凯柏塑胶科技有限公司 一种防紫外线的tpe热塑性弹性体材料的制备方法

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