WO2011069931A1

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

Info

Publication number: WO2011069931A1
Application number: PCT/EP2010/068909
Authority: WO
Inventors: Richard Riggs; Oliver Labisch; Paola Uribe Arocha; Michael Ishaque; Christian Bittner
Original assignee: Basf Se
Priority date: 2009-12-09
Filing date: 2010-12-06
Publication date: 2011-06-16

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

Formulation of light-sensitive pesticides and comb polymers containing UV absorbers

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 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.

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.

The object has been achieved by 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). 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.

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.

Very particularly preferred PEG monomers are those of the formula A.

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 or WO 2008/068213. Mixtures of different PEG monomers can also be present in the polymeric UV absorber

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 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-

Ethylhexyl acrylate, cyclohexyl acrylate and the corresponding methacrylic acid esters,

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 monoethylenically unsaturated nitriles such as acrylonitrile,

C5 vinylaromatic monomers such as styrene and vinyltoluenes,

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.

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%. 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%.

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.

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 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.

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.

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.

In 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 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.

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.

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,

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.

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.

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.

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 .-%.

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) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer), wherein the PEG monomer corresponds to the formula A,

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.

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.

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.

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 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.

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.

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).

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.

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.

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.

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.

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.

Examples of composition types are:

1 . Compositions for dilution in water

i) Water-soluble concentrates (SL, LS)

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 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) Emulsifiable Concentrates (EC)

15 parts by weight of the pesticide are in 75 parts by weight of xylene with the addition of

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) Emulsions (EW, EO, ES)

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

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) suspensions (SC, OD, FS)

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) Water-dispersible and water-soluble granules (WG, SG)

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) Water-dispersible and water-soluble powders (WP, SP, SS, WS)

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) gels (GF)

In a ball mill 20 parts by weight of the pesticide, 10 parts 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.

2. Composition types for direct application

ix) dusts (DP, DS)

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) Granules (GR, FG, GG, MG)

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 solutions (UL)

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.

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.

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. 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.

The following examples illustrate the invention without limiting it.

Examples

UV absorber A: 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole (CAS no.

96478-09-0), commercially available as CIBA® Tinuvin® R796 from CIBA Specialty Chemicals.

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.

example 1

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

27,900 g / mol, determined by gel permeation chromatography) with a pH of 7.3.

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.

Example 3

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.

Example 4

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.

Overview of the polymers from Example 1 to 4

Table 1

Example 5

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.

Table 2

a) not according to the invention

Claims

claims

A composition containing a pesticide and a polymeric UV absorber acting as monomeric units

b) a polyalkylene oxide containing an ethylenically unsaturated group (PEG monomer)

includes.

The composition of claim 1, wherein the PEG monomer contains at least three alkylene oxide groups.

A composition according to claim 1 or 2, wherein the PEG monomer contains five to 50 alkylene oxide groups.

A composition according to any one of claims 1 to 3, wherein the polymeric UV absorber contains as monomeric unit c) (meth) acrylic acid.

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.

A composition according to any one of claims 1 to 5, wherein the UV monomer contains a benzotriazole group.

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.

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%.

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.

A composition according to any one of claims 1 to 9, wherein the pesticide is UV sensitive.

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.

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. Polymeric UV absorber comprising as monomeric units

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. A process for producing the polymeric UV absorber according to claim 13, wherein the UV monomer and the PEG monomer are radically polymerized.

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.