WO2011069931A1 - Formulation of light-sensitive pesticides and comb polymers containing a uv absorber - Google Patents

Formulation of light-sensitive pesticides and comb polymers containing a uv absorber 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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PCT/EP2010/068909
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German (de)
French (fr)
Inventor
Richard Riggs
Oliver Labisch
Paola Uribe Arocha
Michael Ishaque
Christian Bittner
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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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Abstract

The invention relates to a compound containing 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). The invention further relates to a method for producing said polymeric UV absorber, wherein the UV monomer and the PEG monomer are radically polymerized, and to a compound containing a pesticide and said polymeric UV absorber. Finally, the invention also relates to a method for combating phytopathogenic fungi and/or undesirable plant growth and/or undesirable insect or mite infestation and/or for regulating the growth of plants, wherein said compound is allowed to act on the respective pests, the habitat thereof or the plants to be protected from the respective pest, the ground and/or undesirable plants and/or the useful plants and/or the habitat thereof.

Description

Formulierung von lichtempfindlichen Pestiziden und UV-Absorber haltigen Kammpolymeren  Formulation of light-sensitive pesticides and comb polymers containing UV absorbers
Die vorliegende Erfindung betrifft eine Zusammensetzung enthaltend ein Pestizid und einen polymeren UV-Absorber umfassend als monomere Einheiten a) ein UV-Absorber enthaltend eine ethylenisch ungesättigte Gruppe (UV-Monomer), und b) ein Polyalky- lenoxid enthaltend eine ethylenisch ungesättigte Gruppe (PEG-Monomer). Weiterhin betrifft die Erfindung ein Verfahren zur Herstellung des genannten polymeren UV- Absorbers, wobei das UV-Monomer und das PEG-Monomer radikalisch polymerisiert werden, sowie eine Zusammensetzung enthaltend ein Pestizid und den vorgenannten polymeren UV-Absorber. Schließlich betrifft sie auch ein Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die vorgenannte Zusammensetzung auf die jeweiligen Schädlin- ge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. Kombinationen bevorzugter Merkmale mit anderen bevorzugten Merkmalen werden von der vorliegenden Erfindung umfasst. Verschiedenen polymere UV-Absorber sind bekannt: 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. Finally, it also 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 aforementioned composition on the respective Schädlin- ge, 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. Combinations of preferred features with other preferred features are encompassed by the present invention. Various polymeric UV absorbers are known:
WO 89/03386 offenbart UV-absorbierende Copolymere aufgebaut aus UV-Absorbern mit ethylenisch ungesättigte Gruppen sowie verschiedenen Comonomeren. Die Copolymere eigene sich zur Herstellung von Kontaktlinsen. 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 offenbart Polymere umfassend ein olefinisches p-Aminobenzoat, N- Vinylpyrrolidon, und (Meth)acrylsäure. Die Polymere eigene sich zur Herstellung von Sonnencreme. US 3,992,356 offenbart Polymere für kosmetische Anwendungen umfassend in der makromoleklaren Kette eine Acrylester-haltigen UV-Absorber, und optional Comono- mere, wie Vinylstearat oder Stearyl(meth)acrylat. 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 offenbart polymere UV-Absorber auf Basis von Acrylester-haltigen UV- Absorbern, Alkylvinyethern und optional Alkylacrylaten. EP 0 896 006 discloses polymeric UV absorbers based on acrylic ester-containing UV absorbers, alkyl vinyl ethers and optionally alkyl acrylates.
WO08134674 offenbart UV-Absorber für ophthalmologische Linsen. WO08134674 discloses UV absorbers for ophthalmic lenses.
Agrochemische Formulierungen enthaltend ein Pestizid und einen UV-Absorber sind ebenfalls bekannt: WO 2008/085682 offenbart eine Zusammensetzung umfassend photolabiles Pestizid und ein UV-Schutzmittel, welches beispielsweise Uvinul® P25 (PEG-25 Para- Aminobenzoesäure) sein kann. EP 0 376 888 A1 offenbart Mittel zur Bekämpfung schädlicher Insekten enthaltend eine das Verhalten der Schädliche verändernde Substanz und eine pestizid wirksame Verbindung, welche beide in einer fließfähigen Matrix enthalten sind, die die verhaltensverändernde Substanz vor UV-Strahlung schützt. Die Zusammensetzungen und UV-Absorber aus dem Stand der Technik hatten verschiedenen Nachteile: UV-sensitive Pestizide wurden nicht ausreichend stabilisiert; hohe Mengen an Tensiden mussten der agrochemischen Formulierung zugesetzt werden um eine hohe Stabilität von Wirkstoff-Dispersionen zu erreichen; die Grenzflächenaktivität der UV-Absorber war gering, sie waren schlecht löslich oder schlecht ver- träglich in agrochemischen Formulierungen. Aufgabe war daher, eine UV-Absorber zu finden, der die Nachteile des Standes der Technik überwindet. Agrochemical formulations containing a pesticide and a UV absorber are also known: 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. The 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.
Die Aufgabe wurde gelöst durch eine Zusammensetzung enthaltend ein Pestizid und einen polymeren UV-Absorber umfassend als monomere Einheiten The object has been achieved by a composition comprising a pesticide and a polymeric UV absorber comprising as monomeric units
a) ein UV-Absorber enthaltend eine ethylenisch ungesättigte Gruppe (UV-Monomer), und a) a UV absorber containing an ethylenically unsaturated group (UV monomer), and
b) ein Polyalkylenoxid enthaltend eine ethylenisch ungesättigte Gruppe (PEG- Monomer). UV-Absorber enthaltend eine ethylenisch ungesättigte Gruppe (im folgenden auch UV- Monomer genannt) sind allgemein bekannt. Beispiele für UV-Monomere sind die in EP 0 896 006, Formel I, Einheit b dargestellten Verbindungen (wobei dort die ethylenisch ungesättigte Gruppe in Form der polymerisierten, d.h. gesättigten Form dargestellt wird), die hiermit durch Verweis mit einbezogen werden. Weitere Beispiele für UV- Monomere sind die in US 5,620,838, Formel (I) dargestellten Verbindungen, die hiermit durch Verweis mit einbezogen werden. Bevorzugt sind UV-Monomere, die eine Ben- zotriazol-Gruppen enthalten. In einer weiteren bevorzugten Ausführungsform sind die UV-Monomere die in Figur 1A, 1 B und 1 C dargestellten Verbindungen 1 bis 27. Besonders bevorzugt ist der UV-Absorber 2 in Fig. 1A (2-(2'-Hydroxy-5'-methacryl- oxyethylphenyl)-2H-benzotriazol). Auch Mischungen von verschiedenen UV- Monomeren können im polymeren UV-Absorber enthalten sein. b) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer). UV absorbers containing an ethylenically unsaturated group (hereinafter also called UV monomer) are well known. Examples of 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. In a further preferred embodiment, 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.
Polyalkylenoxide enthaltend eine ethylenisch ungesättigte Gruppe (im folgenden auch PEG-Monomer genannt) sind allgemein bekannt. Das PEG-Monomer enthält bevorzugt mindestens drei Alkylenoxid-Gruppen, besonders bevorzugt enthält es fünf bis 50 Alky- lenoxid-Gruppen. Geeignete Alkylenoxid-Gruppen sind beispielsweise Ethylenoxid, Propylenoxid, Butylenoxid, bevorzugt Ethylenoxid. Beispiele für ethylenisch ungesättigte Gruppen sind Vinyl- , Acrylat- oder Methacrlyat-Gruppen. Polyalkylene oxides containing an ethylenically unsaturated group (hereinafter also called PEG monomer) are well known. 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.
Ganz besonders bevorzugte PEG-Monomere sind die der Formel A
Figure imgf000004_0001
Very particularly preferred PEG monomers are those of the formula A.
Figure imgf000004_0001
wobei R1 = H oder CH3, R2 = H oder Ci-Ci2-Alkyl, R3 = H oder Ci-Ci2-Alkyl, R4 = H oder Ci-Ci2-Alkyl, und n= 3 - 50. R1 ist bevorzugt CH3. R2 ist bevorzugt CH3. R3 ist bevorzugt H oder CH3, insbesondere H. R4 ist bevorzugt H oder CH3, insbesondere H. n ist bevorzugt 5 - 35, insbesondere 7 - 30. PEG-Monomere, insbesondere die der Formel A, sind erhältlich nach bekannten Verfahren, beispielsweise aus WO wherein 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, and 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
2006/024538 oder WO 2008/068213. Auch Mischungen von verschiedenen PEG- Monomeren können im polymeren UV-Absorber enthalten sein  2006/024538 or WO 2008/068213. Mixtures of different PEG monomers can also be present in the polymeric UV absorber
Der polymere UV-Absorber kann mindestens eine weitere monomere Einheit c) enthal- ten, die üblicherweise mit den UV-Monomeren und den PEG-Monomer polymerierbar sind. Hierzu zählen insbesondere monoethylenisch ungesättigte Monomere (Monomere C). Beispiele hierfür sind: 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. These include in particular monoethylenically unsaturated monomers (monomers C). Examples for this are:
C1 monoethylenisch ungesättigte Mono- und Dicarbonsäuren mit 3 bis 8 C-Atomen wie Acrylsäure, Methacrylsäure, Crotonsäure, Isocrotonsäure, Maleinsäure, Fumarsäure und Itaconsäure, 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 Alkylester monoethylenisch ungesättigter Mono- und Di-C3-Cs-carbonsäuren, insbesondere der Acrylsäure und der Methacrylsäure mit Ci-Cio-Alkanolen oder C3-Cio-Cycloalkanolen wie Methylacrylat, Ethylacrylat, n-Propylacrylat, iso- Propylacrylat, n-Butylacrylat, iso-Butylacrylat tert.-Butylacrylat, n-Hexylacrylat, 2-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-
Ethylhexylacrylat, Cyclohexylacrylat und die entsprechenden Methacrylsäu- reester, Ethylhexyl acrylate, cyclohexyl acrylate and the corresponding methacrylic acid esters,
C3 Hydroxyalkylester monoethylenisch ungesättigter Mono- und Di-Cs-Cs-carbonsäuren, insbesondere der Acrylsäure und der Methacrylsäure wie 2-Hydroxy- ethylacrylat, 3-Hydroxypropylacrylat, 4-Hydroxybutylacrylat, 2-Hydroxyethylmeth- acrylat, 3-Hydroxypropylmethacrylat und 4-Hydroxybutylmethacrylat,  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,
C4 monoethylenisch ungesättigte Nitrile wie Acrylnitril,  C4 monoethylenically unsaturated nitriles such as acrylonitrile,
C5 vinylaromatische Monomere wie Styrol und Vinyltoluole,  C5 vinylaromatic monomers such as styrene and vinyltoluenes,
C6 monoethylenisch ungesättigte Sulfonsäuren und Phosphonsäuren und deren Salze, insbesondere deren Alkalimetallsalze wie Vinylsulfonsäure, Allylsulfonsäu- re, Methallylsulfonsäure, Styrolsulfonsäure, 2-Acryloxyethansulfonsäure, 2-Acryl- amido-2-methylpropansulfonsäure, Vinylphosphonsäure, Allylphosphonsäure, 2- Acryloxyethanphosphonsäure, 2-Acrylamido-2-methylpropanphosphonsäure, sowie C7 Aminogruppen-tragende Monomere und deren Protonierungs- und deren Qua- ternierungsprodukte wie [2-(N,N-Dimethylamino)ethyl]acrylat, [2-(N,N- Dimethylamino)ethyl]methacrylat, [3-(N,N-Dimethylamino)propyl]acrylat, [2-(N,N- Dimethylamino)propyl]methacrylat, [2-(N,N,N-Trimethylammonium)ethyl]acrylat, [2-(N,N,N-Trimethylammonium)ethyl]methacrylat, [3-(N,N,N-Trimethyl- ammonium)propyl]acrylat, [2-(N,N,N-Trimethylammonium)propyl]methacrylat in Form ihrer Chloride, Sulfate und Methosulfate. C6 monoethylenically unsaturated sulfonic acids and phosphonic acids and their salts, in particular their alkali metal salts such as vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-acryloxyethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, vinylphosphonic acid, allylphosphonic acid, 2-acryloxyethanephosphonic acid, 2-acrylamido 2-methylpropanephosphonic acid, as well C7 amino-carrying monomers and their protonation and their quaternization products such as [2- (N, N-dimethylamino) ethyl] acrylate, [2- (N, N-dimethylamino) ethyl] methacrylate, [3- (N, N -Dimethylamino) propyl] acrylate, [2- (N, N-dimethylamino) propyl] methacrylate, [2- (N, N, N-trimethylammonium) ethyl] acrylate, [2- (N, N, N-trimethylammonium) ethyl ] methacrylate, [3- (N, N, N-trimethylammonium) propyl] acrylate, [2- (N, N, N-trimethylammonium) propyl] methacrylate in the form of its chlorides, sulfates and methosulfates.
Bevorzugte monomere Einheit c) ist sind die Monomere der Gruppe C1 , insbesondere Methacrylsäure und Acrylsäure, speziell Methacrylsäure. Preferred monomeric unit c) are the monomers of group C1, in particular methacrylic acid and acrylic acid, especially methacrylic acid.
Das molare Verhältnis von UV-Monomer zu PEG-Monomer liegt meist im Bereich von 1 : 9 bis 9 : 1 , bevorzugt im Bereich von 1 : 5 bis 5 : 1 , und insbesondere im Bereich von 1 : 2 bis 2 : 1 . 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.
Das molare Verhältnis von monomerer Einheit c) (speziell von (Meth)Acrylsäure) zu UV-Monomer liegt meist im Bereich von 1 : 9 bis 9 : 1 , bevorzugt im Bereich von 1 : 5 bis 5 : 1 , und insbesondere im Bereich von 1 : 2 bis 2 : 1. Der polymere UV-Absorber hat meist einen Anteil von UV-Monomer an allen monomeren Einheiten von 5 bis 70 mol%, bevorzugt von 10 bis 60 mol%. In einer weiteren bevorzugten Ausführungsform hat das UV-Monomer einen Anteil an allen monomeren Einheiten von 20 bis 70 mol%, bevorzugt 30 bis 70 mol%, und insbesondere 40 bis 60 mol%. 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%. In a further preferred embodiment, 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%.
Außerdem kann es zur Erhöhung des Molekulargewichts der polymeren UV-Absorber zweckmäßig sein, die Copolymerisation in Gegenwart von geringen Mengen an mehrfach ethylenisch ungesättigten Monomeren mit z. B. 2, 3 oder 4 polymerisierbaren Doppelbindungen durchzuführen (Vernetzer). Beispiele hierfür sind Diester und Tries- ter ethylenisch ungesättigter Carbonsäuren, insbesondere die Bis- und Trisacrylate von Diolen oder Polyolen mit 3 oder mehr OH-Gruppen, z. B. die Bisacrylate und die Bis- meth-acrylate von Ethylenglykol, Diethylenglykol, Trietylenglykol, Neopentylglykol oder Polyethylenglykolen. Derartige Vernetzer werden, sofern erwünscht, in einer Menge von in der Regel 0,01 bis 5 Gew.-% bezogen auf die Gesamtmenge der zu polymeri- sierenden Monomere eingesetzt. Vorzugsweise werden weniger als 0,01 Gew.-% und insbesondere keine Vernetzermonomere eingesetzt. 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). 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. 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.
Die Copolymerisation von UV-Monomeren mit PEG-Monomeren und gegebenenfalls weiteren Monomeren erfolgt üblicherweise in Gegenwart von Radikale bildenden Ver- bindungen, sogenannten Initiatoren. Derartige Verbindungen werden üblicherweise in Mengen bis zu 30 Gew.-%, vorzugsweise 0,05 bis 15 Gew.-%, insbesondere 0,2 bis 8 Gew.-%, bezogen auf die zu polymerisierenden Monomere eingesetzt. Bei aus mehre- ren Bestandteilen bestehenden Initiatoren (Initiatorsysteme z. B. bei Redox- Initiatorsystemen) beziehen sich die vorstehenden Gewichtsangaben auf die Summe der Komponenten. Geeignete Initiatoren sind beispielsweise organische Peroxide und Hydroperoxide, weiterhin Peroxodisulfate, Percarbonate, Peroxidester, Wasserstoffperoxid und Azo- verbindungen. Beispiele für Initiatoren sind Wasserstoffperoxid, Dicyclohexylperoxidi- carbonat, Diacetylperoxid, Di-tert.-butylperoxid, Diamylperoxid, Dioctanoylperoxid, Di- decanoylperoxid, Dilauroylperoxid, Dibenzoylperoxid, Bis(o-toluyl)peroxid, Succinylpe- roxid, Methylethylketonperoxid, Di-tert.-Butylhydroperoxid, Acetylacetonperoxid, Butyl- peracetat, tert.-Butylpermaleinat, tert.-Butylperisobutyrat, tert.-Butylperpivalat, tert- Butylperoctoat, tert.-Butylperneodecanoat, tert.-Butylperbenzoat, tert.-Butylhydro- peroxid, Cumolhydroperoxid, tert.-Butylperneodecanoat, tert.-Amylperpivalat, tert.- Butylperpivalat, tert.-Butyl-perbenzoat, tert.-Butylperoxi-2-ethylhexanoat und Diisopro- pylperoxidicarbamat; weiterhin Lithium-, Natrium-, Kalium- und Ammoniumperoxodisul- fat, Azoinitiatoren 2,2'-Azobis-isobutyronitril, 2,2'-Azobis(2-methylbutyronitril), 2,2'- Azobis[2-methyl-N-(-2-hydroxyethyl)propionamid, 1 ,1 '-Azobis(1 -cyclohexancarbonitril), 2,2'-Azobis(2,4-dimethylvaleronitril), 2,2'-Azobis(N,N'-dimethylenisobutyroamidin)- dihydrochlorid, und 2,2'-Azobis(2-amidinopropan)dihydrochlorid sowie die im folgenden beschriebenen Redox-Initiatorsysteme. 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. 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. For several In the case of existing initiators (initiator systems, for example, in the case of redox initiator systems), 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. Butyl hydroperoxide, acetylacetone peroxide, butyl peracetate, tert-butyl per- malate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl pernodecanoate, tert-butyl perbenzoate, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl pernodecanoate tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate; furthermore lithium, sodium, potassium and ammonium peroxodisulfate, azo initiators 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- ( 2-hydroxyethyl) propionamide, 1,1'-azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) dihydrochloride, and 2,2'-azobis (2-amidinopropane) dihydrochloride and the redox initiator systems described below.
Redox-Initiatorsysteme enthalten mindestens eine peroxidhaltige Verbindung in Kombination mit einem Redox-Coinitiator, z.B. ein reduzierend wirkende Schwefelverbindung, z. B. Bisulfite, Sulfite, Thiosulfate, Dithionite und Tetrathionate von Alkalimetallen oder von Ammoniumverbindungen. So kann man Kombinationen von Peroxodisulfaten mit Alkalimetall- oder Ammoniumhydrogensulfiten einsetzen, z. B. Ammoniumperoxo- disulfat und Ammoniumdisulfit. Die Menge der peroxidhaltigen Verbindung zum Redox- Coinitiator beträgt 30 : 1 bis 0,05 : 1. Die Initiatoren können allein oder in Mischung untereinander angewendet werden, z. B. Mischungen aus Wasserstoffperoxid und Natriumperoxodisulfat. 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.
Die Initiatoren können sowohl wasserlöslich als auch in Wasser nicht oder nur geringfügig löslich sein. Für die Polymerisation in wässrigem Medium werden bevorzugt was- serlösliche Initiatoren eingesetzt, d. h. Initiatoren, die in der zur Polymerisation üblicherweise eingesetzten Konzentration im wässrigen Polymerisationsmedium löslich sind. Hierzu zählen Peroxodisulfate, Azoinitiatoren mit ionischen Gruppen, organische Hydroperoxide mit bis zu 6 C-Atomen, Acetonhydroperoxid, Methylethylketonhydrope- roxid und Wasserstoffperoxid, sowie die vorgenannten Redoxinitiatoren. 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.
In Kombination mit den Initiatoren bzw. den Redoxinitiatorsystemen können zusätzlich Übergangsmetallkatalysatoren eingesetzt werden, z. B. Salze von Eisen, Kobalt, Ni- ekel, Kupfer, Vanadium und Mangan. Geeignete Salze sind z. B. Eisen (ll).sulfat, Kobalt (ll)chlorid, Nickel(ll)sulfat, oder Kupfer(l)chlorid. Bezogen auf die Monomeren wird das reduzierend wirkende Übergansmetallsalz in einer Konzentration von 0,1 ppm bis 1000 ppm eingesetzt. So kann man Kombinationen von Wasserstoffperoxid mit Ei- sen(ll)-Salzen einsetzen, wie beispielsweise 0,5 bis 30 % Wasserstoffperoxid und 0,1 bis 500 ppm Mohrsches Salz. In combination with the initiators or the Redoxinitiatorsystemen 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.
Auch bei der erfindungsgemäßen Copolymerisation in organischen Lösungsmitteln können in Kombination mit den oben genannten Initiatoren Redox-Coinitiatoren und/oder Übergangsmetallkatalysatoren mitverwendet werden, z. B. Benzoin, Dime- thylanilin, Ascorbinsäure sowie in organischen Lösungsmitteln lösliche Komplexe von Schwermetallen, wie Kupfer, Cobalt, Eisen, Mangan, Nickel und Chrom. Die üblicherweise verwendeten Mengen an Redox-Coinitiatoren bzw. Übergansmetallkatalysatoren betragen etwa 0,1 bis 1000 ppm, bezogen auf die eingesetzten Mengen an Monome- ren. In the copolymerization according to the invention in organic solvents, 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. 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.
Um das mittlere Molekulargewicht der erfindungsgemäß erhältlichen Polymerisate zu kontrollieren, ist es oft zweckmäßig, die erfindungsgemäße Copolymerisation in Gegenwart von Reglern durchzuführen. Hierfür können übliche Regler verwendet werden, insbesondere organische SH-Gruppen enthaltende Verbindungen, insbesondere wasserlösliche SH-Gruppen enthaltende Verbindungen wie 2-Mercaptoethanol, 2- Mercaptopropanol, 3-Mercaptopropionsäure, Cystein, N-Acetylcystein, weiterhin Phos- phor(lll)- oder Phosphor(l)-Verbindungen wie Alkalimetall- oder Erdalkalimetallhy- pophosphite, z. B. Natriumhypophosphit, sowie Hydrogensulfite wie Natriumhydrogen- sulfit. Die Polymerisationsregler werden im Allgemeinen in Mengen von 0,05 bisIn order to control the average molecular weight of the polymers obtainable according to the invention, it is often expedient to carry out the copolymerization according to the invention in the presence of regulators. Conventional 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
10 Gew.-%, insbesondere 0,1 bis 2 Gew.-%, bezogen auf die Monomere, eingesetzt. Bevorzugte Regler sind die vorgenannten SH-Gruppen tragenden Verbindungen, insbesondere wasserlösliche SH-Gruppen tragende Verbindungen wie 2-Mercaptoethanol, 2-Mercaptopropanol, 3-Mercaptopropionsäure, Cystein und N-Acetylcystein. 10 wt .-%, in particular 0.1 to 2 wt .-%, based on the monomers used. 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.
Die Polymerisation kann nach den üblichen Polymerisationsverfahren erfolgen, einschließlich Lösungs-, Fällungs-, Suspensions- oder Substanzpolymerisation erfolgen. Bevorzugt ist die Methode der Lösungspolymerisation, d. h. die Polymerisation in Lösungs- oder Verdünnungsmitteln. The polymerization can be carried out by customary polymerization processes, including solution, precipitation, suspension or bulk polymerization. Preferably, the method of solution polymerization, d. H. the polymerization in solvents or diluents.
Zu den geeigneten Lösungs- oder Verdünnungsmitteln zählen sowohl aprotische Lösungsmittel, z. B. die vorgenannten Aromaten wie Toluol, o-Xylol, p-Xylol, Cumol, Chlorbenzol, Ethylbenzol, technischen Mischungen von Alkylaromaten, Aliphaten und Cycloaliphaten wie Cyclohexan und technischen Aliphatenmischungen, Ketone wie Aceton, Cyclohexanon und Methylethylketon, Ether wie Tetrahydrofuran, Dioxan,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 Aliphatenmischungen, ketones such as acetone, cyclohexanone and methyl ethyl ketone, ethers such as tetrahydrofuran, dioxane,
Diethylether, tert.-Butylmethylether, und Ci-C4-Alkylester aliphatischer Ci-C4-Carbon- säuren wie Essigsäuremethylester und Essigsäureethylester, weiterhin protische Lösungsmittel wie Glykole und Glykolderivate, Polyalkylenglykole und deren Derivate, Ci-C4-Alkanole, z. B. n-Propanol, n-Butanol, Isopropanol, Ethanol oder Methanol, sowie Wasser und Mischungen von Wasser mit Ci-C4-Alkanolen wie z. B. Isopropa- nol/Wasser-Mischungen. Vorzugsweise erfolgt das erfindungsgemäße Copolymerisati- onsverfahren in Wasser oder einer Mischung aus Wasser mit bis zu 60 Gew.-% an Ci-C4-Alkanolen oder Glykolen als Lösungs- oder Verdünnungsmittel. Besonders bevorzugt wird Wasser als alleiniges Lösungsmittel eingesetzt. Diethyl ether, tert-butyl methyl ether, and C 1 -C 4 -alkyl esters of aliphatic C 1 -C 4 -carboxylic acids such as methyl acetate and ethyl acetate, furthermore protic Solvents such as glycols and glycol derivatives, polyalkylene glycols and their derivatives, C 1 -C 4 alkanols, eg. For example, n-propanol, n-butanol, isopropanol, ethanol or methanol, and water and mixtures of water with Ci-C4-alkanols such. B. isopropanol / water mixtures. 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.
Die Polymerisation wird bevorzugt unter weitgehendem oder vollständigem Ausschluss von Sauerstoff, vorzugsweise in einem Inertgas-strom, z. B. einem Stickstoffstrom durchgeführt. 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.
Die Polymerisation kann in den für Polymerisationsmethoden üblichen Apparaturen durchgeführt werden. Hierzu zählen Rührkessel, Rührkesselkaskaden, Autoklaven, Rohrreaktoren und Kneter. 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.
Die Polymerisation erfolgt üblicherweise bei Temperaturen im Bereich von 0 bis 300°C, vorzugsweise im Bereich von 40 bis 120°C. Die Polymerisationsdauer liegt üblicherweise im Bereich von 0,5 h bis 15 h und insbesondere im Bereich von 2 bis 6 h. Der bei der Polymerisation herrschende Druck ist für den Erfolg der Polymerisation von untergeordneter Bedeutung und liegt in der Regel im Bereich von 800 mbar bis 2 bar und häufig bei Umgebungsdruck. 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.
Je nach Wahl der Polymerisationsbedingungen weisen die polymeren UV-Absorber in der Regel gewichtsmittlere Molekulargewichte (Mw) im Bereich von 10.000 bis 500.000 g/mol auf, bevorzugt von 12.000 bis 300.000 g/mol, insbesondere von 15.000 bis 100.000 g/mol. Das gewichtsmittlere Molekulargewicht Mw kann in üblicher weise durch Gelpermeations-chromatographie, wie in den Beispielen erläutert, bestimmt werden. Depending on the choice of polymerization conditions, 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. The weight-average molecular weight M w can be determined in the usual way by gel permeation chromatography, as explained in the examples.
Wird die Polymerisation als Lösungspolymerisation in Wasser durchgeführt, so ist für viele Anwendungszwecke eine Entfernung des Wassers nicht erforderlich. Im übrigen kann eine Isolierung des polymeren UV-Absorbers in an sich üblicher Weise durchgeführt werden, z. B. durch Sprühtrocknung des Polymerisationsgemischs. Wird die Po- lymerisation in einem wasserdampfflüchtigen Lösungsmittel oder Lösungsmittelgemisch durchgeführt, so kann man das Lösungsmittel durch Einleiten von Wasserdampf entfernen. Bevorzugt werden die polymeren UV-Absorber in Form einer wässrigen Dispersion oder Lösung gewonnen. Der Feststoffgehalt beträgt vorzugsweise 10 bis 80 Gew.-%, insbesondere 30 bis 65 Gew.-%. When the polymerization is carried out as a solution polymerization in water, removal of the water is not required for many applications. Moreover, an isolation of the polymeric UV absorber can be carried out in a conventional manner, for. B. by spray drying of the polymerization mixture. If the polymerization is carried out in a steam-volatile solvent or solvent mixture, the solvent can be removed by passing in steam. 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 .-%.
Die Erfindung betrifft weiterhin polymere UV-Absorber umfassend als monomere Einheiten a) ein UV-Absorber enthaltend eine ethylenisch ungesättigte Gruppe (UV-Monomer), und The invention further relates to polymeric UV absorbers comprising as monomeric units a) a UV absorber containing an ethylenically unsaturated group (UV monomer), and
b) ein Polyalkylenoxid enthaltend eine ethylenisch ungesättigte Gruppe (PEG- Monomer), wobei das PEG Monomer der Formel A entspricht,
Figure imgf000009_0001
b) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer), wherein the PEG monomer corresponds to the formula A,
Figure imgf000009_0001
wobei R1 = H oder CH3, R2 = H oder Ci-Ci2-Alkyl, R3 = H oder Ci-Ci2-Alkyl, R4 = H oder Ci-Ci2-Alkyl, und n= 3 - 50. Bevorzugte Ausführungsformen des polymeren UV- Absorbers sind wie oben beschrieben. Die Erfindung betrifft auch ein Verfahren zur Herstellung des erfindungsgemäßen polymeren UV-Absorbers, wobei das UV-Monomer und das PEG-Monomer radikalisch polymerisiert werden. Geeignete und bevorzugte Ausführungsformen sind wie vorstehend beschrieben. Die erfindungsgemäßen polymeren UV-Absorber eignen sich hervorragend als Zusatzmittel für agrochemische Formulierungen. Daher betrifft die Erfindung auch eine Zusammensetzung enthaltend ein Pestizid und einen erfindungsgemäßen polymeren UV-Absorber. Die erfindungsgemäße agrochemische Zusammensetzung umfasst im allgemeinen 0,1 bis 50 Gew.-%, bevorzugt 0,5 bis 30 Gew.-%, besonders bevorzugt 1 ,0 bis 15 Gew.-% polymeren UV-Absorber, jeweils bezogen auf die Zusammensetzung. wherein 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, and n = 3 - 50. Preferred embodiments of the polymeric UV absorbers are as described above. 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.
Die erfindungsgemäße agrochemische Zusammensetzung umfasst im allgemeinen 0,01 bis 95 Gew.-%, vorzugsweise 0,5 bis 80 Gew.-%, besonders bevorzugt 2 bis 50 Gew.-% und speziell 5 bis 20 Gew.% Pestizid, jeweils bezogen auf die Zusammensetzung. 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.
Das Gewichtsverhältnis von Pestizid zu polymerem UV-Absorber beträgt meist von 30 : 1 bis 1 : 3, bevorzugt 15 : 1 bis 1 : 2, besonders bevorzugt 8 : 1 bis 1 : 1 . 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.
Der Begriff Pestizid bezeichnet mindestens einen Wirkstoff ausgewählt aus der Gruppe der Fungizide, Insektizide, Nematizide, Herbizide, Safener und/oder Wachstumsregulatoren. Bevorzugte Pestizide sind Fungizide, Insektizide und Herbizide, insbesondere Insektizide. Auch Mischungen von Pestiziden aus zwei oder mehr der vorgenannten Klassen können verwendet werden. Der Fachmann ist vertraut mit solchen Pestiziden, die beispielsweise in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London, gefunden werden können. Geeignete Insektizide sind Insektizide der Klasse der Carbamate, Organophosphate, Organochlor-Insektizide, Phenylpyrazole, Pyrethroide, Neonicotinoide, Spinosine, Avermectine, Milbemycine, Juvenil Hormon Analoga, Alkylhalide, Organozinn-Verbindungen, Nereistoxin-Analoga, Benzoyl- harnstoffe, Diacylhydrazine, METI Akarizide, sowie Insektizide wie Chloropicrin, Py- metrozin, Flonicamid, Clofentezin, Hexythiazox, Etoxazol, Diafenthiuron, Propargit, Tetradifon, Chlorfenapyr, DNOC, Buprofezin, Cyromazin, Amitraz, Hydramethylnon, Acequinocyl, Fluacrypyrim, Rotenon, oder deren Derivate. Geeignete Fungizide sind Fungizide der Klassen Dinitroaniline, Allylamine, Anilinopyrimidine, Antibiotica, aromatische Kohlenwasserstoffe, Benzenesulfonamide, Benzimidazole, Benzisothiazole, Benzophenone, Benzothiadiazole, Benzotriazine, Benzylcarbamate, Carbamates, Car- boxamide, Carbonsäureamdide, Chloronitrile, Cyanoacetamideoxime, Cyanoimidazole, Cyclopropanecarboxamide, Dicarboximide, Dihydrodioxazine, Dinitrophenylcrotonate, Dithiocarbamate, Dithiolane, Ethylphosphonate, Ethylaminothiazolcarboxamide, Gua- nidines, Hydroxy-(2-amino-)pyrimidine, Hydroxyanilides, Imidazole, Imidazolinone, A- norganika, Isobenzofuranone, Methoxyacrylate, Methoxycarbamates, Morpholines, N- Phenylcarbamate, Oxazolidinedione, Oximinoacetate, Oximinoacetamide, Peptidylpy- rimidinnucleoside, Phenylacetamide, Phenylamide, Phenylpyrrole, Phenylharnstoffe, Phosphonate, Phosphorothiolate, Phthalamsäuren, Phthalimide, Piperazine, Piperidi- ne, Propionamide, Pyridazinone, Pyridine, Pyridinylmethylbenzamide, Pyrimidinamine, Pyrimidine, Pyrimidinonehydrazone, Pyrroloquinolinone, Quinazolinone, Chinoline, Chinone, Sulfamide, Sulfamoyltriazole, Thiazolecarboxamide, Thiocarbamate, Thiocar- bamate, Thiophanate, Thiophenecarboxamide, Tolua-mide, Triphenylzinn Verbindungen, Triazine, Triazole. Geeignete Herbizide sind Herbizide der Klassen der Acetami- de, Amide, Aryloxyphenoxypropionate, Benzamide, Benzofuran, Benzoesäuren, Ben- zothiadiazinone, Bipyridylium, Carbamate, Chloroacetamide, Chlorcarbonsäuren, Cyc- lohexanedione, Dinitroaniline, Dinitrophenol, Diphenylether, Glycine, Imidazolinone, Isoxazole, Isoxazolidinone, Nitrile, N-phenylphthalimide, Oxadiazole, Oxazolidinedione, Oxyacetamide, Phenoxycarbonsäuren, Phenylcarbamate, Phenylpyrazole, Phenylpy- razoline, Phenylpyridazine, Phosphinsäuren, Phosphoroamidate, Phosphorodithioate, Phthalamate, Pyrazole, Pyridazinone, Pyridine, Pyridincarbonsäuren, Pyridinecarbo- xamide, Pyrimidindione, Pyrimidinyl(thio)benzoate, Chinolincarbonsäuren, Semicarba- zone, Sulfonylaminocarbonyltriazolinone, Sulfonylharnstoffe, Tetrazolinone, Thiadiazo- le, Thiocarbamate, Triazine, Triazinone, Triazole, Triazolinone, Triazolinone, Triazolo- carboxamide, Triazolopyrimidine, Triketone, Uracile, Harnstoffe. The term 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. Also, 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, organometallics, isobenzofuranones, methoxyacrylates, methoxycarbamates, morpholines, N-phenylcarbamates, oxazolidinediones, oximinoacetates , Oximinoacetamides, peptidyl-pyrimidine nucleosides, phenylacetamides, phenylamides, phenylpyrroles, phenylureas, phosphonates, phosphorothiolates, phthalamic acids, phthalimides, piperazines, piperidines, propionamides, pyridazinones, pyridines, pyridinylmethylbenzamides, P yrimidinamines, pyrimidines, pyrimidinonehydrazones, pyrroloquinolinones, quinazolinones, quinolines, quinones, sulphamides, sulphamoyltriazoles, thiazolecarboxamides, thiocarbamates, thiocarbamates, thiophanates, thiophenecarboxamides, toluenemides, triphenyltin compounds, triazines, triazoles. 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, pyrazoles, pyridazinones, pyridines, pyridinecarboxylic acids, pyridinecarboxamides, pyrimidinediones, pyrimidinyl (thio ) benzoates, quinolinecarboxylic acids, semicarbazone, sulfonylaminocarbonyltriazolinones, sulfonylureas, tetrazolinones, thiadiazoles, thiocarbamates, triazines, triazinones, triazoles, triazolinones, triazolinones, triazolocarboxamides, triazolopyrimidines, triketones, uracils, ureas.
Bevorzugte Herbizide sind Napropamid, Proparnil, Bentazone, Paraquatdichlorid, Cyc- loxydim, Sethoxydim, Ethalfluralin, Oryzalin, Pendimethalin, Trifluralin, Acifluren, Aclo- nifen, Fomesafen, oxyfluoren, loxynil, Imazetapyr, Imazaquin, chloridazon, norflurazon, Thiazopyr, Triclopyr, dithiopyr, Diflufenican, picolinafen, amidosulfuron, Molinate, ver- nolate, Promethon , Metribuzin, azafenidin, Carfentrazone-ethyl, sulfentrazone, meto- xuron, monolinuron, Fluchloralin and Flurenol. Bevorzugte Fungizide sind Cyprodinil, Fuberidazol, Dimethomorph, Procloraz, Triflumizol, Tridemorph, Edifenfos, Fenarimol, Nuarimol, ethirimol, Quinoxylen, Dithianon, Metominostrobin,Trifloxystrobin, Dichloflu- amid, Bromuconnazol and myclobutanil. Bevorzugte Insektizide sind Acephate, A- zinphos-Ethyl, Azinphos-Methyl, Isofenphos, Chlorpyriphos-Methyl, Dimethylvinphos, Phorate, Phoxim, Prothiofos, cyhexatin, alanycarb, Ethiofencarb, pirimicarb, Thiodi- carb, Fipronil, bioallethrin, bioresmethin, Deltamethrin, fenpropathin, Flucythrinate, Taufluvalinate, alphacypermethrin, metaflumizon, Zetacypermethrin, resmethin, tefluthrin, Lambda cyhalothrin and hydramethylnon. In einer weiteren Ausführungsform sind bevorzugte Pestizide Pyrethroide oder Metaflumizon, insbesondere Pyrethroide. Besonders bevorzugte Pestizide sind Alphacypermethrin und Metaflumizon. 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. In another embodiment, preferred pesticides are pyrethroids or metaflumizone, especially pyrethroids. Particularly preferred pesticides are alphacypermethrin and metaflumizone.
In einer Ausführungsform werden Pestizide verwendet, die UV-sensitiv sind. Diese UV- Sensitivität kann in einfachen Vortests bestimmt werden. Bevorzugt gelten Pestizide als UV-sensitiv, wenn sie bei Bestrahlung eines Pestizidfilms, der durch Trocknung einer 25 Gew.%igen Lösung des Pestizides in einem geeigneten Lösungsmittel, bevorzugt in Aceton, mit UVA/IS-Licht der Wellenlänge 300-800 nm innerhalb von 24 h bei 25 °C zu mindestens 20 Gew.% abgebaut werden. Üblicherweise wird dabei eine Beleuchtungsstärke von 10000 bis 100000 Lux, bevorzugt 50000 bis 80000 Lux verwendet. Die Pestizide gelten dabei als abgebaut, wenn die Konzentration des Pestizids (oder eine Pestizide Komponente in einer Mischung von mehreren Pestiziden Komponenten) entsprechend verringert wird. Es sind allgemein verschiedene Wege bekannt wie UV-sensitive Pestizide abgebaut werden. So können chemische Bindungen isomerisiert, radikalisiert oder gespalten werden, und gegebenenfalls danach wieder reagieren. Beispielsweise können E/Z- Isomere Doppelbindungen von Pestiziden (wie Metaflumizon) durch UV-Licht isomerisiert werden, so dass ein Isomer, das Pestizide Aktivität hat, in das andere Isomer um- gelagert wird, das weniger Aktivität hat. Mit der erfindungsgemäßen Zusammensetzung und den erfindungsgemäßen UV-Absorbern können alle oder einzelne dieser Abbauwege gehemmt werden. In one embodiment, 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. There are generally various ways known how UV-sensitive pesticides are degraded. Thus, chemical bonds can be isomerized, radicalized or cleaved, and optionally react again thereafter. For example, 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.
Die erfindungsgemäßen Zusammensetzung können in für agrochemische Formulie- rungen üblichen Zusammensetzungstypen vorliegen, z. B. Lösungen, Emulsionen, Suspensionen, Stäube, Pulver, Pasten und Granulate. Der Typ richtet sich nach dem jeweiligen Verwendungszweck; sie soll in jedem Fall eine feine und gleichmäßige Verteilung der erfindungsgemäßen Verbindung gewährleisten. Beispiele für Zusammensetzungstypen sind Suspensionen (SC, OD, FS), emulgierbare Konzentrate (EC), E- mulsionen (EW, EO, ES), Pasten, Pastillen, benetzbare Pulver oder Stäube (WP, SP, SS, WS, DP, DS) oder Granulate (GR, FG, GG, MG), die entweder in Wasser löslich oder dispergierbar sein können, sowie Gele für die Behandlung pflanzlicher Vermehrungsmaterialien wie Saatgut (GF). Köder für Tiere, wie Ameisen oder Ratten, können verschiedenen der vorgenannten Zusammensetzungtypen vorliegen, bevorzugt als Pulver, Pasten, Granulate oder Gele. Im Allgemeinen werden die Zusammensetzungstypen (z. B. SC, EC OD, FS, WG, SG, WP, SP, SS, WS, GF) verdünnt eingesetzt. Zu- sammensetzungstypen wie DP, DS, GR, FG, GG, MG oder Köder werden in der Regel unverdünnt eingesetzt. Bevorzugte Zusammensetzungstypen sind Suspensionen. The 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. Examples of 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. In general, the composition types (eg SC, EC OD, FS, WG, SG, WP, SP, SS, WS, GF) 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.
Die erfindungsgemäßen Zusammensetzungen können weiterhin auch für Pflanzen- Schutzmittel übliche Hilfsmittel enthalten, wobei sich die Wahl der Hilfsmittel nach der konkreten Anwendungsform bzw. dem Wirkstoff richtet. Beispiele für geeignete Hilfsmittel sind Lösungsmittel, feste Trägerstoffe, oberflächenaktive Stoffe (wie weitere So- lubilisatoren, Schutzkolloide, Netzmittel und Haftmittel), organische und anorganische Verdicker, Bakterizide, Frostschutzmittel, Entschäumer, ggf. Farbstoffe und Kleber (z. B. für Saatgutbehandlung) oder übliche Hilfsmittel für Köderformulierung (z. B. Lockstoffe, Futtermittel, Bitterstoffe). The 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. Examples of suitable 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).
Als Lösungsmittel kommen Wasser, organische Lösungsmittel wie Mineralölfraktionen von mittlerem bis hohem Siedepunkt wie Kerosin und Dieselöl, ferner Kohlenteeröle sowie Öle pflanzlichen oder tierischen Ursprungs, aliphatische, cyclische und aromatische Kohlenwasserstoffe, z.B. Paraffine, Tetrahydronaphthalin, alkylierte Naphthaline und deren Derivate, alkylierte Benzole und deren Derivate, Alkohole wie Methanol, Ethanol, Propanol, Butanol und Cyclohexanol, Gykole, Ketone wie Cyclohexanon, gamma-Butyrolacton, Dimethylfettsäureamide, Fettsäuren und Fettsäureester und stark polare Lösungsmittel, z.B. Amine wie N-Methylpyrrolidon, in Betracht. Grundsätzlich können auch Lösungsmittelgemische verwendet werden sowie Gemische aus den vorstehend genannten Lösungsmitteln und Wasser. 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. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, gycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters, and strong polar solvents, e.g. Amines such as N-methylpyrrolidone, into consideration. In principle, solvent mixtures and mixtures of the abovementioned solvents and water can also be used.
Feste Trägerstoffe sind Mineralerden wie Kieselsäuren, Kieselgele, Silikate, Talkum, Kaolin, Kalkstein, Kalk, Kreide, Bolus, Löß, Ton, Dolomit, Diatomeenerde, Calcium- und Magnesiumsulfat, Magnesiumoxid, gemahlene Kunststoffe, Düngemittel, wie Ammoniumsulfat, Ammoniumphosphat, Ammoniumnitrat, Harnstoffe und pflanzliche Produkte wie Getreidemehl, Baumrinden-, Holz- und Nußschalenmehl, Cellulosepulver oder andere feste Trägerstoffe. 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.
Als oberflächenaktive Stoffe (Adjuvantien, Netz-, Haft-, Dispergier- oder Emulgiermittel) kommen die Alkali-, Erdalkali-, Ammoniumsalze von aromatischen Sulfonsäuren, z. B. von Lignin-(Borresperse®-Typen, Borregaard, Norwegen), Phenol-, Naphthalin- (Morwet®-Typen, Akzo Nobel, USA) und Dibutylnaphthalinsulfonsäure (Nekal®-Typen, BASF, Deutschland), sowie von Fettsäuren, Alkyl- und Alkylarylsulfonaten, Alkyl-, Lau- rylether- und Fettalkoholsulfaten, sowie Salze sulfatierter Hexa-, Hepta- und Octade- canole sowie von Fettalkoholglykolethern, Kondensationsprodukte von sulfoniertem Naphthalin und seiner Derivate mit Formaldehyd, Kondensationsprodukte des Naphthalins bzw. der Naphthalinsulfonsäuren mit Phenol und Formaldehyd, Polyoxyethyle- noctylphenolether, ethoxyliertes Isooctyl-, Octyl- oder Nonylphenol, Alkylphenyl-, Tribu- tylphenylpolyglykolether, Alkylarylpolyetheralkohole, Isotridecylalkohol, Fettalkoholethy- lenoxid-Kondensate, ethoxyliertes Rizinusöl, Polyoxyethylen- oder Polyoxypropylenal- kylether, Laurylalkoholpolyglykoletheracetat, Sorbitester, Lignin-Sulfitablaugen sowie Proteine, denaturierte Proteine, Polysaccharide (z.B. Methylcellulose), hydrophob modifizierte Stärken, Polyvinylalkohol (Mowiol®-Typen, Clariant, Schweiz), Polycarboxyla- te (Sokalan®-Typen, BASF, Deutschland), Polyalkoxylate, Polyvinylamin (Lupamin®- Typen, BASF, Deutschland), Polyethylenimin (Lupasol®-Typen, BASF, Deutschland), Polyvinylpyrrolidon und deren Copolymere in Betracht. As surfactants (adjuvants, wetting agents, adhesives, dispersants or emulsifiers) 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 naphthalenesulfonic acids with phenol and Formaldehyde, polyoxyethyl toctylphenol ethers, ethoxylated isooctyl, octyl or nonylphenol, alkylphenyl, tributylphenyl polyglycol ethers, alkylarylpolyether alcohols, isotridecylalcohol, fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxypropylenealcaldehyde. 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.
Beispiele für Verdicker (d. h. Verbindungen, die der Zusammensetzung ein modifiziertes Fließverhalten verleihen, d. h. hohe Viskosität im Ruhezustand und niedrige Visko- sität im bewegten Zustand) sind Polysaccharide sowie organische und anorganische Schichtmineralien wie Xanthan Gum (Kelzan®, CP Kelco, USA), Rhodopol® 23 (Rho- dia, Frankreich) oder Veegum® (R.T. Vanderbilt, USA) oder Attaclay® (Engelhard Corp., NJ, USA). Bakterizide können zur Stabilisierung der Zusammensetzung zugesetzt werden. Beispiele für Bakterizide sind solche basierend auf Diclorophen und Benzylalkoholhemi- formal sowie Isothiazolinonderivaten wie Alkylisothiazolinonen und Benzisothiazolino- nen (Acticide® MBS der Fa. Thor Chemie). Beispiele für geeignete Frostschutzmittel sind Ethylenglycol, Propylenglycol, Harnstoff und Glycerin. Examples of thickeners (ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion) 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. Examples of bactericides are those based on dichlorophen and benzyl alcohol formal and isothiazolinone derivatives such as alkylisothiazolinones and Benzisothiazolino- nen (Acetide ® MBS from Thor Chemie).. Examples of suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
Beispiele für Entschäumer sind Silikonemulsionen (wie z. B. Silikon® SRE, Wacker, Deutschland oder Rhodorsil®, Rhodia, Frankreich), langkettige Alkohole, Fettsäuren, Salze von Fettsäuren, fluororganische Verbindungen und deren Gemische. Examples of defoamers are 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.
Beispiele für Zusammensetzungstypen sind: Examples of composition types are:
1 . Zusammensetzungstypen zur Verdünnung in Wasser  1 . Compositions for dilution in water
i) Wasserlösliche Konzentrate (SL, LS)  i) Water-soluble concentrates (SL, LS)
10 Gew.-Teile des Pestizids werden mit 90 Gew.-Teilen Wasser oder einem wasserlöslichen Lösungsmittel gelöst. Alternativ werden Netzmittel oder andere Hilfsmittel zugefügt. Bei der Verdünnung in Wasser löst sich das Pestizid. Man erhält auf diese Weise eine Zusammensetzung mit 10 Gew.-% Wirkstoffgehalt. ii) Dispergierbare Konzentrate (DC)  10 parts by weight of the pesticide are dissolved with 90 parts by weight of water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the pesticide dissolves. This gives a composition with 10 wt .-% active ingredient content. ii) Dispersible Concentrates (DC)
20 Gew.-Teile des Pestizids werden in 70 Gew.-Teilen Cyclohexanon unter Zusatz von 10 Gew.-Teilen eines Dispergiermittels z. B. Polyvinylpyrrolidon gelöst. Bei Verdünnung in Wasser ergibt sich eine Dispersion. Der Wirkstoffgehalt beträgt 20 Gew.-%  20 parts by weight of the pesticide are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant z. B. dissolved polyvinylpyrrolidone. Dilution in water gives a dispersion. The active ingredient content is 20% by weight
iii) Emulgierbare Konzentrate (EC)  iii) Emulsifiable Concentrates (EC)
15 Gew.-Teile des Pestizids werden in 75 Gew.-Teilen Xylol unter Zusatz von 15 parts by weight of the pesticide are in 75 parts by weight of xylene with the addition of
Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 Gew.-Teile) gelöst. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Zusammenset- zung hat 15 Gew.-% Wirkstoffgehalt. Ca-dodecylbenzenesulfonate and castor oil ethoxylate (each 5 parts by weight) were dissolved. Dilution in water results in an emulsion. The composition tion has 15 wt .-% active ingredient content.
iv) Emulsionen (EW, EO, ES)  iv) Emulsions (EW, EO, ES)
25 Gew.-Teile des Pestizids werden in 35 Gew.-Teile Xylol unter Zusatz von Ca-Dodecylbenzolsulfonat und Ricinusölethoxylat (jeweils 5 Gew.-Teile) gelöst. Diese Mischung wird mittels einer Emulgiermaschine (z. B. Ultra-Turrax) in 30 25 parts by weight of the pesticide are dissolved in 35 parts by weight of xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is prepared by means of an emulsifying machine (eg Ultra-Turrax) in 30
Gew.-Teile Wasser gegeben und zu einer homogenen Emulsion gebracht. Bei der Verdünnung in Wasser ergibt sich eine Emulsion. Die Zusammensetzung hat einen Wirkstoffgehalt von 25 Gew.-%. Parts by weight of water added and brought to a homogeneous emulsion. Dilution in water results in an emulsion. The composition has an active ingredient content of 25 wt .-%.
v) Suspensionen (SC, OD, FS)  v) suspensions (SC, OD, FS)
20 Gew.-Teile des Pestizids werden unter Zusatz von 10 Gew.-Teilen Disper- gier- und Netzmitteln und 70 Gew.-Teilen Wasser oder einem organischen Lösungsmittel in einer Rührwerkskugelmühle zu einer feinen Wirkstoffsuspension zerkleinert. Bei der Verdünnung in Wasser ergibt sich eine stabile Suspension des Wirkstoffs. Der Wirkstoffgehalt in der Zusammensetzung beträgt 20 Gew.- %.  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.
vi) Wasserdispergierbare und wasserlösliche Granulate (WG, SG)  vi) Water-dispersible and water-soluble granules (WG, SG)
50 Gew.-Teile des Pestizids werden unter Zusatz von 50 Gew.-Teilen Disper- gier- und Netzmitteln fein gemahlen und mittels technischer Geräte (z. B. Ex- trusion, Sprühturm, Wirbelschicht) als wasserdispergierbare oder wasserlösli- che Granulate hergestellt. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Die Zusammensetzung hat einen Wirkstoffgehalt von 50 Gew.-%.  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.
vii) Wasserdispergierbare und wasserlösliche Pulver (WP, SP, SS, WS)  vii) Water-dispersible and water-soluble powders (WP, SP, SS, WS)
75 Gew.-Teile des Pestizids werden unter Zusatz von 25 Gew.-Teilen Disper- gier- und Netzmitteln sowie Kieselsäuregel in einer Rotor-Strator Mühle vermählen. Bei der Verdünnung in Wasser ergibt sich eine stabile Dispersion oder Lösung des Wirkstoffs. Der Wirkstoffgehalt der Zusammensetzung beträgt 75 Gew.-%.  75 parts by weight of the pesticide are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the composition is 75% by weight.
viii) Gele (GF)  viii) gels (GF)
In einer Kugelmühle werden 20 Gew.-Teile des Pestizids, 10 Gew.-Teile In a ball mill 20 parts by weight of the pesticide, 10 parts by weight
Dispergiermittel, 1 Gew.-Teil Quellmittel („gelling agent") und 70 Gew.-Teile Wasser oder eines organischen Lösungsmittels zu einer feinen Suspension vermählen. Bei der Verdünnung mit Wasser ergibt sich eine stabile Suspension mit 20 Gew.-% Wirkstoffgehalt. 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.
2. Zusammensetzungstypen für die Direktapplikation 2. Composition types for direct application
ix) Stäube (DP, DS)  ix) dusts (DP, DS)
5 Gew.-Teile des Pestizids werden fein gemahlen und mit 95 Gew.-Teilen fein- teiligem Kaolin innig vermischt. Man erhält dadurch ein Stäubemittel mit 5 Gew.-% Wirkstoffgehalt.  5 parts by weight of the pesticide are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.
x) Granulate (GR, FG, GG, MG)  x) Granules (GR, FG, GG, MG)
0,5 Gew.-Teile des Pestizids werden fein gemahlen und mit 99,5 Gewichtsteilen Trägerstoffe verbunden. Gängige Verfahren sind dabei die Extrusion, die Sprühtrocknung oder die Wirbelschicht. Man erhält dadurch ein Granulat für die Direktapplikation mit 0,5 Gew.-% Wirkstoffgehalt, 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,
xi) ULV- Lösungen (UL)  xi) ULV solutions (UL)
10 Gew.-Teile des Pestizids werden in 90 Gew.-Teilen eines organischen Lö- sungsmittel z. B. Xylol gelöst. Dadurch erhält man eine Zusammensetzung für die Direktapplikation mit 10 Gew.-% Wirkstoffgehalt.  10 parts by weight of the pesticide are dissolved in 90 parts by weight of an organic solvent z. B. dissolved xylene. This gives a composition for direct application with 10 wt .-% active ingredient content.
Die Verbindungen können als solche oder in Form ihrer Zusammensetzungen, z. B. in Form von direkt versprühbaren Lösungen, Pulvern, Suspensionen, Dispersionen, E- mulsionen, Oldispersionen, Pasten, Stäubemitteln, Streumitteln oder Granulaten durch Versprühen, Vernebeln, Verstäuben, Verstreuen, Auslegen von Ködern, Einstreichen, Eintauchen oder Gießen angewendet werden. Wässrige Anwendungsformen können aus Emulsionskonzentraten, Pasten oder netzbaren Pulvern (Spritzpulver, Oldispersionen) durch Zusatz von Wasser bereitet werden. Zur Herstellung von Emulsionen, Pas- ten oder Oldispersionen können die Substanzen als solche oder in einem Öl oder Lösungsmittel gelöst, mittels Netz-, Haft-, Dispergier- oder Emulgiermitttel in Wasser homogenisiert werden. Es können aber auch aus wirksamer Substanz Netz-, Haft-, Dispergier- oder Emulgiermittel und eventuell Lösungsmittel oder Öl bestehende Konzentrate hergestellt werden, die zur Verdünnung mit Wasser geeignet sind. 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. To prepare emulsions, pastes or old dispersions, the substances, as such or dissolved in an oil or solvent, 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.
Die Wirkstoffkonzentrationen in den anwendungsfertigen Zubereitungen können in größeren Bereichen variiert werden. Im Allgemeinen liegen sie zwischen 0,0001 und 10%, vorzugsweise zwischen 0,01 und 1 %. Die Aufwandmengen liegen bei der Anwendung im Pflanzenschutz je nach Art des gewünschten Effektes zwischen 0,01 und 2,0 kg Wirkstoff pro ha. Bei der Behandlung von pflanzlichen Vermehrungsmaterialien, z. B. Staatgut, werden im allgemeinen Wirkstoffmengen von 1 bis 1000 g/100 kg, vorzugsweise 5 bis 100 g/100 kg Vermehrungsmaterial bzw. Saatgut verwendet. Bei der Anwendung im Material- bzw. Vorratsschutz richtet sich die Aufwandmenge an Wirkstoff nach der Art des Einsatzgebietes und des gewünschten Effekts. Übliche Auf- wandmengen sind im Materialschutz beispielsweise 0,001 g bis 2 kg, vorzugsweise 0,005 g bis 1 kg Wirkstoff pro Kubikmeter behandelten Materials. 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.
Die vorliegende Erfindung betrifft weiterhin ein Verfahren zur Bekämpfung von phyto- pathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die erfindungsgemäße Zusammensetzung auf die jeweiligen Schädlinge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. Unter Lebensraum wird überlicherweise die Anbau- fläche von Nutzpflanzen, die Nutzpflanzen oder deren Vermehrungsmaterial verstanden. Die erfindungsgemäße Zusammensetzung enthaltend ein Pestizid ist naturgemäß nicht für die Anwendung am Menschen geeignet und nicht zugelassen. Vorteile der vorliegenden Erfindung ist, dass die polymeren UVAbsorber UV-sensitive Pestizide stabilisieren, insbesondere schon bei niederen Konzentrationen an polyme- rem UV-Absorber. Weiterer Vorteil ist, dass weniger Tenside eingesetzt werden brau- chen um eine hohe Stabilität Wirkstoff-Dispersionen, insbesondere Wirkstoff- Suspensionen, zu erhalten. Außerdem ist von Vorteil, dass die erfindungsgemäßen UV-Absorber die Oberflächenspannung von Wasser stärker herabsetzen können, d.h. dass sie eine höhere Grenzflächenaktivität ausweisen. Die UV-Absorber sind leicht löslich in agrochemischen Formulierungen, oder sehr gut verträglich mit agrochemi- sehen Formulierungen, wie wässrige Emulsionen und wässrige Suspensionen. Beispielsweise ist auch kein zusätzlicher Emulgator notwendig um die UV-Absorber in die Formulierung einzuarbeiten. 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. Another advantage is that less surfactants are used in order to obtain a high stability of active substance dispersions, in particular active substance suspensions. In addition, it is advantageous that the 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.
Nachfolgende Beispiele erläutern die Erfindung ohne sie einzuschränken. The following examples illustrate the invention without limiting it.
Beispiele Examples
UV-Absorber A: 2-(2'-Hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazol (CAS Nr. UV absorber A: 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (CAS no.
96478-09-0), kommerziell erhältlich als CIBA® Tinuvin® R796 von CIBA Special- ty Chemicals.  96478-09-0), commercially available as CIBA® Tinuvin® R796 from CIBA Specialty Chemicals.
MPEGMA350 (Methylpolyethylenglykol-350-methylacrylat), MPEGMA475 (Methylpoly- ethylenglykol-475-methylacrylat), und MPEGMA1 100 (Methylpolyethylenglykol- 1 100-methylacrylat) sind durch Ver- bzw. Umesterung von Methacrylsäure bzw. Methylmethacrylat mit dem entsprechenden Methylpolyethylenglykol (mittlere Molmasse 375, 475 oder 1 100 g/mol) zugänglich. MPEGMA350 ist kommerziell erhältlich as Bisomer® MPEG350MA von Cognis.  MPEGMA350 (methyl polyethylene glycol-350-methyl acrylate), MPEGMA475 (methyl polyethylene glycol-475-methyl acrylate), and MPEGMA1 100 (methyl polyethylene glycol-1 100-methyl acrylate) are obtained by esterification or transesterification of methacrylic acid or methyl methacrylate with the corresponding methyl polyethylene glycol (average molecular weight 375, 475 or 1100 g / mol). MPEGMA350 is commercially available as Bisomer® MPEG350MA from Cognis.
Beispiel 1 example 1
Es wurden 76,2 g Toluol vorgelegt und unter Stickstoffeinleitung auf 75 °C erhitzt. An- schließend wurden über einen Zeitraum von 5 Stunden 105,6 g einer 65 %igen Lösung von MPEGMA1 100 in Toluol und 155,0 g einer 13 %igen Lösung von UV-Absorber A in Toluol zugegeben. Gleichzeitig wird über einen Zeitraum von 5,5 Stunden 0,65 g von t-Butylperoxopivalat in 28,3 g Toluol zugegeben. Anschließend wurde für eine Stunde nachpolymerisiert. Danach wurden 207,1 g Wasser zugegeben und das Toluol ausge- kreist. Man erhielt eine 19 Gew.-%ige klare, wässrige Lösung des Polymers 1 (Mw 76.2 g of toluene were initially charged and heated to 75 ° C. while introducing nitrogen. Subsequently, 105.6 g of a 65% solution of MPEGMA1 100 in toluene and 155.0 g of a 13% solution of UV absorber A in toluene were added over a period of 5 hours. At the same time, 0.65 g of t-butyl peroxypivalate in 28.3 g of toluene is added over a period of 5.5 hours. The mixture was then postpolymerized for one hour. Thereafter, 207.1 g of water were added and the toluene was circled out. This gave a 19 wt .-% pure, clear aqueous solution of the polymer 1 (Mw
27900 g/mol, bestimmt durch Gelpermeationschromatographie) mit einem pH-Wert von 7,3. 27,900 g / mol, determined by gel permeation chromatography) with a pH of 7.3.
Beispiel 2 Example 2
Analog zu Beispiel 1 wurde ein Polymer hergestellt, bei dem zusätzlich Methacrylsäure (MAS) copolymerisiert wurde. Das Molverhältnis UV-Absorber zu Methacrylsäure und die resulierenden Molgewichte der Polymere 2 und 3 sind in Tabelle 1 zusammenge- fasst. Die Polymere waren klar wasserlöslich. 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.
Beispiel 3 Example 3
Es wurden 77,9 g Toluol vorgelegt und unter Stickstoffeinleitung auf 75 °C erhitzt. Anschließend wurden über einen Zeitraum von 5 Stunden 200,7 g MPEGMA475 und 1049,8 g einer 13 %igen Lösung von UV-Absorber A in Toluol zugegeben. Gleichzeitig wurde über einen Zeitraum von 5,5 Stunden 4,4 g von t-Butylperoxopivalat in 44,7 g Toluol zugegeben. Anschließend wurde für eine Stunde nachpolymerisiert. Danach wurden 786,7 g Wasser zugegeben und das Toluol ausgekreist. Anschließend wurde mit 0,34 g Natronlauge (25 %ig) netraulisiert. Man erhielt eine 15% ige wässrige Lösung des Polymers 4 mit einem pH-Wert von 7,5.  77.9 g of toluene were initially charged and heated to 75 ° C. while introducing nitrogen. Subsequently, 200.7 g of MPEGMA475 and 1049.8 g of a 13% solution of UV absorber A in toluene were added over a period of 5 hours. At the same time, 4.4 g of t-butyl peroxypivalate in 44.7 g of toluene was added over a period of 5.5 hours. The mixture was then postpolymerized for one hour. Thereafter, 786.7 g of water were added and the toluene was removed. Subsequently, with 0.34 g sodium hydroxide solution (25%) was netraulisiert. A 15% aqueous solution of polymer 4 having a pH of 7.5 was obtained.
Beispiel 4 Example 4
Es wurden 150,7 g Toluol vorgelegt und unter Stickstoffeinleitung auf 75 °C erhitzt. Anschließend wurden über einen Zeitraum von 5 Stunden 147,9 g MPEGMA350 und 1050,0 g einer 13 %igen Lösung von UV-Absorber A in Toluol zugegeben. Gleichzeitig wurde über einen Zeitraum von 5,5 Stunden 4,41 g von t-Butylperoxopivalat in 45,6 g Toluol zugegeben. Anschließend wurde für eine Stunde nachpolymerisiert. Danach wurden 663,6 g Wasser zugegeben und das Toluol ausgekreist. Anschließend wurde mit 0,34 g Natronlauge (25 %ig) netraulisiert. Man erhiellt eine 1 1 % ige wässrige Lösung des Polymers 5 mit einem pH-Wert von 7,6.  150.7 g of toluene were initially charged and heated to 75 ° C. while introducing nitrogen. Subsequently, 147.9 g of MPEGMA350 and 1050.0 g of a 13% solution of UV absorber A in toluene were added over a period of 5 hours. At the same time, 4.41 g of t-butyl peroxypivalate in 45.6 g of toluene was added over a period of 5.5 hours. The mixture was then postpolymerized for one hour. Thereafter, 663.6 g of water were added and the toluene was removed. Subsequently, with 0.34 g sodium hydroxide solution (25%) was netraulisiert. A 1 1% aqueous solution of polymer 5 having a pH of 7.6 is obtained.
Übersicht der Polymere aus Beispiel 1 bis 4 Overview of the polymers from Example 1 to 4
Tabelle 1 Table 1
Figure imgf000017_0001
Figure imgf000017_0001
Beispiel 5 Example 5
Eine kommerzielle Formulierung von Metaflumizone (Alverde®) enthaltend 240 g/l Metaflumizone wurde mit 96 g/l Polymer Nr. 1 -5 versetzt und danach wurde wurde mit Wasser verdünnt, so dass ein Wirkstoffgehalt von 10 g/l erhalten wurde. Etwa 20 mg der so hergestellten Formulierung wurden auf einen Objektträger aufgebracht, 30 Minuten antrocknen gelassen und 24 h durchgehend belichtet (Atlas Suntest CRT plus, Einstellung„Outdoor", Belichtung entspricht die gleiche Spektrum und Intensität wie normale Sonnenlicht am Mittag in Sommer). Nach der Belichtungszeit wurden die Proben in Dimethylsulfoxid gelöst. Der Restgehalt an Metaflumizone wurde mittels quantitativer UPLC (Säule BEH C18 1 ,7 μηι 2,1x100; Elution mit einem Gradient von Aceto- nitril / 0,1 % H3P04 ansteigend von 5 / 95 zu 95 / 5) ermittelt. Zum Vergleich wurde in jeder Belichtungsreihe eine Probe ohne UV-Abosrber mitlaufen (Referenz) gelassen. Auswertung: 2 Proben wurden als Nullproben nach dem Antrocknen ohne Belichtung sofort wieder gelöst und der Gehalt an Metaflumizon bestimmt. Der resultierende Mittelwert wurde als 100% gesetzt und die restlichen Proben dagegen normiert. Die Er- gebnisse sind in Tabelle 2 zusammengefasst. A commercial formulation of 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. About 20 mg of the formulation thus prepared was applied to a slide, allowed to dry for 30 minutes and exposed continuously for 24 h (Atlas Suntest CRT plus, Setting "outdoor", exposure corresponds to the same spectrum and intensity as normal sunlight at noon in summer.) After the exposure time, the samples were dissolved in dimethyl sulfoxide The residual content of metaflumizone was determined by quantitative UPLC (column BEH C18 1, 7 μηι 2.1x100 Elution with a gradient of acetonitrile / 0.1% H3PO4 increasing from 5/95 to 95/5) For comparison, a sample without UV absorber was run (reference) in each exposure row Evaluation: 2 samples were obtained as zero samples immediately after exposure to light without exposure, and the content of metaflumizone was determined again, the resulting mean value being set to 100% and the remaining samples being normalized, the results being summarized in Table 2.
Tabelle 2 Table 2
Figure imgf000018_0001
Figure imgf000018_0001
a) nicht erfindungsgemäß  a) not according to the invention

Claims

Ansprüche claims
Zusammensetzung enthaltend ein Pestizid und einen polymeren UV-Absorber, der als monomere Einheiten A composition containing a pesticide and a polymeric UV absorber acting as monomeric units
a) ein UV-Absorber enthaltend eine ethylenisch ungesättigte Gruppe (UV- Monomer), und  a) a UV absorber containing an ethylenically unsaturated group (UV monomer), and
b) ein Polyalkylenoxid enthaltend eine ethylenisch ungesättigte Gruppe (PEG- Monomer)  b) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer)
umfasst.  includes.
Zusammensetzung nach Anspruch 1 , wobei das PEG Monomer mindestens drei Alkylenoxid-Gruppen enthält. The composition of claim 1, wherein the PEG monomer contains at least three alkylene oxide groups.
Zusammensetzung nach Anspruch 1 oder 2, wobei das PEG Monomer fünf bis 50 Alkylenoxid-Gruppen enthält. A composition according to claim 1 or 2, wherein the PEG monomer contains five to 50 alkylene oxide groups.
Zusammensetzung nach einem der Ansprüche 1 bis 3, wobei der polymere UV- Absorber als monomere Einheit c) (Meth)Acrylsäure enthält. A composition according to any one of claims 1 to 3, wherein the polymeric UV absorber contains as monomeric unit c) (meth) acrylic acid.
Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei das molare Verhältnis von UV-Monomer zu PEG-Monomer im Bereich von 1 : 9 bis 9 : 1 liegt. A composition according to any one of claims 1 to 4, wherein the molar ratio of UV monomer to PEG monomer is in the range of 1: 9 to 9: 1.
Zusammensetzung nach einem der Ansprüche 1 bis 5, wobei das UV-Monomer eine Benzotriazol Gruppen enthält. A composition according to any one of claims 1 to 5, wherein the UV monomer contains a benzotriazole group.
Zusammensetzung nach einem der Ansprüche 1 bis 6, wobei das molare Verhältnis von (Meth)Acrylsäure zu UV-Monomer im Bereich von von 1 : 9 bis 9 : 1 liegt. A composition according to any one of claims 1 to 6, wherein the molar ratio of (meth) acrylic acid to UV-monomer is in the range of from 1: 9 to 9: 1.
Zusammensetzung nach einem der Ansprüche 1 bis 7, wobei der polymere UV- Absorber einen Anteil von UV-Monomer an allen monomeren Einheiten von 5 bis 70 mol% hat. A composition according to any one of claims 1 to 7, wherein the polymeric UV absorber has a proportion of UV monomer at all monomeric units of 5 to 70 mol%.
Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei das Molgewicht M des polymeren UV-Absorbers im Bereich von 10.000 bis 500.000 g/mol liegt. A composition according to any one of claims 1 to 8, wherein the molecular weight M of the polymeric UV absorber is in the range of 10,000 to 500,000 g / mol.
Zusammensetzung nach einem der Ansprüche 1 bis 9, wobei das Pestizid UV- sensitiv ist. A composition according to any one of claims 1 to 9, wherein the pesticide is UV sensitive.
Zusammensetzung nach einem der Ansprüche 1 bis 10, wobei das Gewichtsverhältnis von Pestizid zu polymerem UV-Absorber im Bereich von 30 : 1 bis 1 : 3 liegt. A composition according to any one of claims 1 to 10, wherein the weight ratio of pesticide to polymeric UV absorber is in the range of 30: 1 to 1: 3.
12. Zusammensetzung nach einem der Ansprüche 1 bis 1 1 , wobei das Pestizid Napropamid, Proparnil, Bentazone, Paraquatdichlorid, Cycloxydim, Sethoxydim, Ethalfluralin, Oryzalin, Pendimethalin, Trifluralin, Acifluren, Aclonifen, Fomesafen, oxyfluoren, loxynil, Imazetapyr, Imazaquin, chloridazon, norflurazon, Thiazopyr, Triclopyr, Dithiopyr, Diflufenican, picolinafen, amidosulfuron, Molinate, vernolate, Promethon , Metribuzin, azafenidin, Carfentrazone-ethyl, sulfentrazone, metoxu- ron, monolinuron, Fluchloralin, Flurenol, Cyprodinil, Fuberidazol, Dimethomorph, Procloraz, Triflumizol, Tridemorph, Edifenfos, Fenarimol, Nuarimol, ethirimol, Qui- noxylen, Dithianon, Metominostrobin,Trifloxystrobin, Dichlofluamid, Bromuconna- zol, myclobutanil, Acephate, Azinphos-Ethyl, Azinphos-Methyl, Isofenphos, Chlor- pyriphos-Methyl, Dimethylvinphos, Phorate, Phoxim, Prothiofos, cyhexatin, alany- carb, Ethiofencarb, pirimicarb, Thiodicarb, Fipronil, bioallethrin, bioresmethin, Del- tamethrin, fenpropathin, Flucythrinate, Taufluvalinate, Alphacypermethrin, Me- taflumizon, Zetacypermethrin, resmethin, tefluthrin, Lambda cyhalothrin oder Hydramethylnon ist. A composition according to any one of claims 1 to 11 wherein the pesticide is napropamide, proparnet, bentazone, paraquat dichloride, cycloxydim, sethoxydim, ethalfluralin, oryzalin, pendimethalin, trifluralin, aciflurene, aclonifen, fomesafen, oxyfluorene, loxynil, imazetapyr, imazaquin, chloridazon , norflurazon, thiazopyr, triclopyr, dithiopyr, diflufenican, picolinafen, amidosulfuron, molinates, vernolates, promethone, metribuzin, azafenidine, carfentrazone-ethyl, sulfentrazone, metoxuron, monolinuron, fluchloralin, flurenol, cyprodinil, fuberidazole, dimethomorph, procloraz, triflumizole , Tridemorph, edifenfos, fenarimol, nuarimol, ethirimol, quinoxylene, dithianon, metominostrobin, trifloxystrobin, dichlofluamide, bromucon- zole, myclobutanil, acephate, azinphos-ethyl, azinphos-methyl, isofenphos, chlorpyriphipho- methyl, dimethylvinphos, phorates , Phoxim, prothiofos, cyhexatin, alanycarb, ethiofencarb, pirimicarb, thiodicarb, fipronil, bioallethrin, bioresemethine, deltamethrin, fenpropat flucythrinates, baptized fluvalinates, alphacypermethrin, metaflumizone, cetacypermethrin, resmethin, tefluthrin, lambda cyhalothrin or hydramethylnon.
13. Polymere UV-Absorber umfassend als monomere Einheiten 13. Polymeric UV absorber comprising as monomeric units
a) ein UV-Absorber enthaltend eine ethylenisch ungesättigte Gruppe (UV- Monomer), und  a) a UV absorber containing an ethylenically unsaturated group (UV monomer), and
b) ein Polyalkylenoxid enthaltend eine ethylenisch ungesättigte Gruppe (PEG- Monomer), wobei das PEG Monomer der Formel A entspricht,
Figure imgf000020_0001
wobei R1 = H oder CH3, R2 = H oder Ci-Ci2-Alkyl, R3 = H oder Ci-Ci2-Alkyl, R4 = H oder Ci-Ci2-Alkyl, und n= 3 - 50. b) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer), wherein the PEG monomer corresponds to the formula A,
Figure imgf000020_0001
wherein R1 = H or CH 3, R2 = H or Ci-Ci 2 -alkyl, R 3 = H or Ci-Ci 2 -alkyl, R4 = H or Ci-Ci 2 alkyl, and n = 3-50.
14. Verfahren zur Herstellung des polymeren UV-Absorbers gemäß Anspruch 13, wobei das UV-Monomer und das PEG-Monomer radikalisch polymerisiert werden. 14. A process for producing the polymeric UV absorber according to claim 13, wherein the UV monomer and the PEG monomer are radically polymerized.
15. Verfahren zur Bekämpfung von phytopathogenen Pilzen und/oder unerwünschtem Pflanzenwuchs und/oder unerwünschtem Insekten- oder Milbenbefall und/oder zur Regulation des Wachstums von Pflanzen, wobei man die Zusammensetzung gemäß den Ansprüchen 1 1 bis 14 auf die jeweiligen Schädlinge, deren Lebensraum oder die vor dem jeweiligen Schädling zu schützenden Pflanzen, den Boden und/oder auf unerwünschte Pflanzen und/oder die Nutzpflanzen und/oder deren Lebensraum einwirken lässt. 15. 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 claims 1 1 to 14 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.
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