MXPA00008102A - Pearl polymerizate formulations - Google Patents

Abstract

Novel polymer polymer formulations, which are composed of I) a particulate solid phase comprising, A) copolymer of, a) 40 to 95% by weight of monomer insoluble in, b) 5 to 35% by weight of monomer soluble in, c) 0 to 25% by weight of crosslinker, and B) at least one active agrochemical compound and, C) if appropriate, additives, the active agrochemical compound content is between 5 and 75% by weight and the solid phase has an average particle size of between 1 and 100 μm, and II) if appropriate, a liquid phase a process for the preparation of novel formulations, and its use for the application in active agrochemicals.

Description

FORMULATIONS OF POLYMERS IN THE FORM OF PEARLS DESCRIPTION OF THE INVENTION The present invention relates to polymer formulations in the form of pearls, novel, active agrochemical compounds, with a process to produce these preparations, and with its use to apply active agrochemical compounds. EP-A 0 201 214 has already described microparticles which can be prepared from ethylenically unsaturated monomers and which comprise active pesticidal compounds and having a particle diameter of between about 0.01 and 250 μm. However, the disadvantage of these preparations is that the active components are not always released at the speed that is required for the biological effect. In addition, formulations comprising active agrochemical compounds easily filterable or leachable in microencapsulated form in unsaturated polyester resins have already been described (see EP-A 0 517 669). Again, the kinetics of release of the microencapsulated active compounds does not always meet the practical requirements in this case. The compounds Ref .: 12S068 Active hydrophobes are only released at a very slow rate of those formulations. Furthermore, it can be seen from EP-A 0 281 918 that macroporous, crosslinked polystyrene bead polymers are suitable as carriers for agrochemicals and that they can be applied in crop protection. When these products are used, again, the speed at which agrochemicals are released and their quantity often leaves something to be desired. Finally, it can be seen from US-A 4 269 959 that the polymer polymers of weakly cross-linked polystyrenes are capable of absorbing active liquid compounds, such as agrochemicals, and the products thus loaded can be used as slow release formulations. However, the duration of the action of such preparations is not always sufficient. Now new polymer formulations have been found in the form of beads which are composed of I) a particulate solid phase comprising A) a copolymer of a) 40 to 95% by weight of water insoluble monomer; b) 5 to 35% by weight of water-soluble monomer c) 0 to 25% by weight of crosslinking agent; and B) at least one active agrochemical compound Y, C) if appropriate, additives, the content of active agrochemical compound is between 5 and 75% by weight and the solid phase has an average particle size of between 1 and 100 μm, and II) if appropriate, a liquid phase. Furthermore, it has been found that the polymer formulations in the form of beads according to the invention can be produced by finely dividing, at a temperature of between 0 ° C and 60 ° C and with stirring, A) an organic phase of -25 to 95% by weight of a monomer mixture of 40 to 95% by weight of water-insoluble monomer; 5 to 35% by weight of water-soluble monomer c) 0 to 25% by weight of crosslinking agent; 5 and 75% by weight of at least one active agrochemical compound, at least one initiator, - if appropriate, additives, Y. if appropriate, an organic solvent which is moderately miscible with water, B) in an aqueous water phase, at least one dispersant and, if appropriate, a buffering agent, C) then polimetizing the mixture with agitation until the temperature increases, D) and, if appropriate, after this either a) isolating, washing and drying the polymer in the form of resultant beads or ß) removing any organic substances volatiles that may be present and thereby retaining the polymer in the form of beads in aqueous suspension. Finally, it has been found that the polymer formulations in the form of beads according to the invention are very suitable for application to active agrochemical compounds. The polymer formulations in the form of beads according to the invention are distinguished by a series of advantage. In this way, they are able to release a uniform amount of the active components over a substantial period. What is especially convenient is that the rate of release of the active compound can be controlled within wide limits by the content of water-soluble monomer. The copolymers of the present invention in the polymer formulations in the form of beads according to the invention are characterized by the components listed under (a) to (c). The term water-insoluble monomers (a) means monoethylenically unsaturated compounds of which less than 5% is dissolved in water at 20 ° C. Preferred water-insoluble monomers (a) are the alkyl esters of acrylic acid and methacrylic acid, styrene, styrene derivatives and mixtures of styrene and acrylonitrile, or also vinyl derivatives. Examples that may be mentioned are: styrene, alpha-methylstyrene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl propionate, vinyl laurate, vinyl adipate, methyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl methacrylate, n-propyl methacrylate, b-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate , n-octyl acrylate, n-octyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate. Another possibility is acrylonitrile, which is slightly more readily soluble in water, as part of a mixture with other monomers (a), preferably a mixture with styrene.

The water-soluble monomers (b) for the purposes of the invention are monoethylenically unsaturated compounds of which more than 5% by weight is dissolved in water at 20 ° C. Examples which may be mentioned are: acrylic acid and its alkali metal and ammonium salts, methacrylic acid and its alkali metal and ammonium salts, hydroxyethyl methacrylate, hydroxyethyl acrylate, ethylene glycol monoacrylate, diethylene glycol monomethacrylate, monoacrylate triethylene glycol, triethylene glycol monomethacrylate, tetraethylene glycol monoacetate, tetraethylene glycol monomethacrylate, glycerol monoacrylate, aminoethyl methacrylate, dimethylammoethyl methacrylate, acplamide, methacrylamide, vmylpyrrolidone and vinylimidazole. The preferred one is hydroxyethyl methacrylate. The amount of water soluble monomer (b) is essential for the release of the active compound. The release rate of the active agrochemical compound can be controlled within wide limits via the amount of (b). The greater the amount of (b), the greater the rate of release of the active compound. For more practical applications, the amount of (b) is in the range of 5 to 35% by weight. In many cases, an amount of (b) in the range of 7.5 to 20% by weight results in particularly good effects. Suitable crosslinkers (c) are compounds with at least two ethylenically unsaturated groups in the molecule. Examples that may be mentioned are: allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, tetramethyl methacrylate, pentaeptritol and divinylbenzene. Preferred are ethylene glycol dimethacrylate and divinylbenzene. The amount of crosslinker (c) in the polymer may vary within a certain range. In general, the amount of crosslinking agent (c) is between 0 and 25% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.5 and 10% by weight. It should be understood that active agrochemical compounds means in the context of the present all substances customary in the treatment of plants. The Addddltfl_.

Preferred substances that can be mentioned preferably are fungicides, bactericides, insecticides, caresses, nematicides, herbicides, plant growth regulators, plant nutrients and repellents. Examples of fungicides that may be mentioned are: 2-aminobutane; 2-anilino-4-methyl-6-cyclopro? Il-pyrimidine; 2 ', 6' -dibromo-2-methyl-4 '-trifluoromethoxy-4' -trifluoromethyl-1,3-thiazole-5-carboxanilide; 2,6-dichloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoximino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; (E) -2- (2- [6- (2-Cyanophenoxy) pyrimidin-4-yloxy] phenyl) -3-methoxy-acrylate methyl ester; (E) -methoximino [alpha- (o-tolyloxy) -o-tolyl] methyl acetate; 2-Phenylphenol (OPP), aldimorf, ampropylphos, anilazin, azaconazole, banalaxyl, benodanil, benomyl, binapacril, bion, biphenyl, bitertanol, blasticidin-S, bromoconazole, bupirimate, butiobate, calcium polysulfide, captafol, captan, carbensazim, carboxin , quinomethionate chloroneb, chloropicrin, chlorothalonil, clozolinate, cufraneb, cymoxanil, ciproconazole, ciprofuram, dichlororene, dichlorobutrazol, dichlorofuanide, diclomezin, dichloran, dietofercab, difenoconazole, dimetirimol, dimetomorph, diniconazole, dinocarp, diphenylamine, dipyrition, ditalimphos, dithianon, dodin, drazoxolon, edifenfos, epoxiconazole, etirimol, etridazole, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorf, fentin acetate, fentin hydroxide, ferbam, fermzone, fluazinam, fluidioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanil, flutriafol, folpet, fosetil-aluminum, phthalide, fuberidazole, furalaxyl, furmeciclox, guazatine, hexachlorobenzene, hexaconazole, himexazole, imazalil, imibenconazole, iminoctadin, iprobenfos ( PPI), iprodion, isoprothiolan, asugamycin, mancozeb, maneb, mepaniprim, mepronil, metalaxyl, metconazole, metasulfocarb, metfuroxam, metiram, metsulfovax, myclobutanil, nickel dimethylthiocarbamate, nitrotalisopropyl, nuarimol, ofurace, oxadixil, oxamocarb, oxycarboxin, pefurazoate, penconazole , pencicuron, fosdifen, pimaricim, piperalin, polioxin, probenazol, porchloraz, procymidone, propamicarb, pripio conazole, propineb, pyrazophos, pirifenox, pyrimethanil, pyroquilon, quintozene (PCNB), tebuconazole, tecloftalam, techacen, tetraconazole, thiabendazole, tichophore, thiophanate-methyl, thiram, tolcoflos-methyl, tolylfuanid, triadimefon, triadimenol, triazoxide, triclamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, valimadicin A, vinclozolin, Zineb, Ziram, 8-tert-butyl-2- (N-ethyl-Nn-propyl-amino) -methyl-1,4-dioxa-spiro - [4, 5] decane, N- (R) - [1- (-chlorophenyl) -ethyl] -2,2-dichloro-l-ethyl-3-t-methyl-lr-c-clopropanecarboxamide (diastereomeric mixture or individual isomers ), [2-methyl-l- [[[1- (4-methylphenyl) -ethyl] -amino] -carbonyl] -propyl] -carbamic acid-1-methylethyl ester (2, 3-dichloro-4-hydroxy) - 1-methyl-cyclohexane-l-carboxanilide, 2- [2-1-chloro-cyclopropyl] -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1,2,4] -triazol-3-thione and 1- (3,5-dimet? l-isoxazole-4-sulfonyl) -2-chloro-6,6-d? fluoro- [1,3] -dioxolo- [4,5- f] -benzimidazole. Examples of bactericides that may be mentioned are: Bronopol, dichlorophen, nitrapyrin, nickel dimethylditicarbonate, kasugamycin, octylinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations. Examples of insecticides, acaricides and nematicides that may be mentioned are: abamectin, acefate, acrinatrin, alanicarba, aldicarb, alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinfos A, azinfos M, azociclotin, Bacillus thuringiensis, 4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betaciflutrin, bifenthrin, BFMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben, cadusafos, carbaryl, carbofuran, carbofenotion, carbosulfan, cartap, cloetocarb, chloretoxyphos, chlorfenvinphos, chlorofluazuron, chloromides, N- [(6-chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide, chlorpyrifos, chlorpyrifos M, cis -resmethrin, clocitrin, clofentezin, cyanophos, cycloprotrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton-M, demeton-S, demeton-S-methyl, diafentiuron, diacinon, diclofention, dichlorvos, diclifos, dicrotophos, dietion , diflubenzuron, dimethatoate, dimethylvinfos, dioxation, disulfoton, edifenfos, emamectin, efenvalerate, etiofencarb, etion, etofenprox, ethoprofos, etrimfos, fenamifos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb, phenothiocarb, fenoxicarb, fenpropatrin, fenpirad, fenpyroximate, fention , fenvalerate, fipronil, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fostiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexylthiazox, imidacloprid, iprobenfos, isazofos, isofenfos, isoprocarb, isoxation, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinfos, mesulfenfos, metaldehyde, metacrofos, methamidophos, metidation, methiocarb, methomil, metolcarb, milbemectin, monocrotrophs, moxidectin, naled, NC 184, nitenpyram , ometoat, oxamyl, oxidemeton M, oxideprofos, paration A, paration M, permethrin, pentoate, phorate, fosalone, fosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A, profenofos, promecarb, propafos, propoxur, protiofos, protoate, pymetrozin, pyraclorophos, pyridafention, piresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalfos, salition, sebufos, silafluofen, sulfotep, sulprofos, tebufenozido, tebufenpyrad, tebupirimiphos, teflubenzuron, tefluthrin, temephos, terbam, terbufos, tetrachlorovinfos, thiafenox, thiodicarb, thiofanox, thiometon, thiocincin, turingiensin, tralometrin, transflutrin, triaratene, trisophos, triazuron, trichlorfon, triflumuron, trimetacarb, vamidothion XMC, xilicarb, zetamethrin.

Examples of herbicides that may be mentioned are: anuides such as, for example, diflufenican and propanil; aryl carboxylic acids such as, for example, dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids such as, for example, 2-D, 2,4-DB, 2, 4-D, 2,4-DB, 2,4-DP, fluroxypir, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoates such as, for example, diclofop-methyl, phenoxapropi-ethyl, fluazifop-butyl, haloxifop-methyl and quizalofop-ethyl; azinones such as, for example, chloridazon and norflurazon; carbamates such as, for example, chlorprofam, desmedipham, fenmedifam and profam; chloroacetanilides such as, for example, alachlor, acetochlor, butachlor, metazachlor, metolachlor, pentylchlor and propachlor; dinitroanilines such as, for example, orizalin, pendimethalin and trifluralin; diphenyl ethers such as, for example, acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas such as, for example, chlortoluron, diuron, fluometuron, isoproturon, linuron and metabenzthiazuron; hydroxylamines such as, for example, alloxydim, clethodim, cycloxydim, sethoxydim and traxoxidim; irnidazolms such as, for example, imazetrapyr, imazametabenz, imazapyr and imazaquin; nitriles such as, for example, bromoxynil, diclobenyl and ioxynil; oxyacetamides such as, for example, mefenacet; sulfonylureas such as, for example, amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cmosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, tifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiolcarbamates such as, for example, butylate, cycloate, di-alato, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and trialate; triazines such as, for example, atrazine, cyanazine, simazine, symmetry, terbutpn and terbutylazine; triacinones such as, for example, hexazinone, metamitron and metribuzin; others such as, for example, aminotriazole, 4-amino-N- (1,1-dimethylethyl) -4,5-dihydro-3- (1-methylethyl) -5-oxo-lH-1, 2, 4 -triazol-l-carboxamide, benfuresate, bentazone, cinmetilin clomazone, clopyralid, difenzocuat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, qumclorac, qummerac, sulfosate and tridifone. Examples of plant growth regulators that may be mentioned are chlorochlor chloride and ethephon. Examples of plant nutrients that may be mentioned are the usual inorganic and organic fertilizers to provide the plants with macro and / or micronutrients. Examples of repellents that may be mentioned are diethylthyl amide, ethylhexandiol and butopironoxil. Suitable additives which may be present in the solid phase in the polymer formulations in the form of beads according to the invention are those substances which can be conventionally used as additives in products for the treatment of plants. These include, for example, plasticizers, colors, antioxidants, antifreeze agents and fillers or fillers. The plasticizers which are suitable in the present case are indifferently liquid or solid materials with a low vapor pressure and a molecular weight of between 150 and 1000 which interact with highly polymeric materials without chemical reaction, preferably by virtue of their dissolving power or its swelling capacity or volume increase, thus forming a homogeneous physical system with the former. Suitable colors are soluble or sparingly soluble color pigments such as, for example, titanium dioxide, black color or zinc oxide. Suitable antioxidants are all substances that can be used conventionally for this purpose in compositions for the treatment of plants. Sterically hindered phenols and alkyl substituted hydroxyanizoles and hydroxytoluenes are preferred. Suitable antifreeze agents are all materials that can be used conventionally for this purpose in the compositions for the treatment of plants. Urea, glycerol or propylene glycol are preferably suitable. Fillers or fillers that are mainly suitable are organic particles such as, for example, carbonates, silicates and oxides with an average particle size of 0.005 to 5 μm, preferably 0.2 to 2 μm. Especially suitable are silicon dioxide, also known as highly dispersed silica, silica gels, and natural and synthetic aluminosilicates. The amount of the individual components in the polymer formulations in the form of beads according to the invention can be varied within a substantial range. In the solid phase, the concentrations of copolymer (A) are thus generally between 25 and 95% by weight, preferably between 40 and 90% by weight, of active agrochemical compounds (B) are generally between 5 and 10% by weight. 75% by weight, preferably between 10 and 60% by weight, and - of the additives (C) are generally between 0 and 30% by weight, preferably between 0 and 15% by weight . The particle size of the solid particles in the polymer formulations in the form of beads according to the invention can be varied within a certain interval. This is generally between 1 and 100 μm, preferably between 5 and 50 μm. The polymer formulations in the form of beads according to the present invention can be present as a particulate solid phase or as a dispersion of solid particles in a liquid phase. If a liquid phase is present, it consists essentially of water. In addition, the components which are used in the preparation of the polymer formulations in the form of beads according to the invention and which remain in the liquid phase can be present. The substances that are suitable as such components are organic solvents which are poorly miscible with water, dispersants (protective colloids) and absorbing reagents. The organic solvents suitable in this context are all those customary organic solvents which, on the one hand, are not very miscible with water but, on the other hand, effectively dissolve the active agrochemical compounds used. Examples of such solvents that may be mentioned are aromatic hydrocarbons such as toluene and xylene, in addition to halogenated hydrocarbons such as tetrachloromethane, chloroform, methylene chloride and dichloroethane, and also also esters such as ethyl acetate. The substances that are suitable as dispersants are all those conventionally used for this purpose. The following may be mentioned as preferred: natural and synthetic water-soluble polymers such as gelatin, starch and cellulose derivatives, in particular cellulose esters and cellulose ethers, in addition to polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and copolymers of (meth) acrylic acid and (meth) acrylates, and also copolymers of methacrylic acid and methacrylate which have been neutralized with alkali metal hydroxide. The substances that are suitable as damping reagents are all those conventionally used for this purpose. The phosphate and borate salts can be mentioned as preferred. The amounts of additional substances in the aqueous phase that have been mentioned can be varied within a substantial range. The concentration depends on the amounts in which these substances are used during the preparation of the polymer formulations in the form of beads according to the invention and the type of work after the polymer.

The polymer formulations in the form of beads according to the invention are prepared by the suspension polymerization method. It should be understood that the term "suspension polymerization" means a process in which a monomer or mixture comprising monomers comprising an initiator which is soluble in the monomers is distributed in the form of droplets, if appropriate in a mixture with small solid particles. , in a phase comprising a dispersant and essentially immiscible with the onomers, and the mixture is cured, with stirring, by increasing the temperature. Further details on suspension polymerization are described, for example, in the publication "Processes of Polymers "edited by CE Schildknecht, published in 1956 by Interscience Publishers Inc., New York, in the chapter" Suspension Polymerization "on pages 69 a 109. The monomer mixtures required as starting materials for carrying out the process according to the invention are characterized by the components listed under (a) to (c). Preferred components are those which have already been mentioned in connection with the description of the copolymers. The active agrochemical compounds that can be used to carry out the process according to the invention are all those substances which can be used to treat plants and which have already been mentioned as active agrochemical compounds in connection with the description with the polymer formulations in the form of beads according to the invention. The initiators that can be used to carry out the process according to the invention are all substances that can be conventionally used to initiate polymerizations. Initiators that are soluble in oil are preferably suitable. Examples that may be mentioned are peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (food processor peroxide-chlorobenzoyl), dicyclohexyl peroxydicarbonate, tert-butyl peroctoate, 2,5-bis (2-ethylhexanoylperoxy) ) -2,5-dimethylhexane and tert-amylperoxy-2-ethylhexane, and further azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-methylisobutyronitrile). The additives that can be used to carry out the process according to the invention are all those substances that have already been mentioned as additives in relation to the description of the polymer formulations in the form of beads according to the invention. When the process of the invention is carried out, organic solvents that are low in water are irascible They can be employees or solvents. Suitable cosolvents are all those organic diluents which have already been mentioned in connection with the description of the aqueous phase of the polymer formulations in the form of beads according to the invention. Substances which are suitable as dispersants or damping reagents for carrying out the process according to the invention, have also already been mentioned in connection with the description of the aqueous phase of the polymer formulations in the form of beads according to the invention. When the process according to the invention is carried out, a process is generally followed in which a homogeneous mixture or monomer mixture (a-c) of one or more active agrochemical compounds and, if appropriate, additives is prepared first. This homogeneous mixture can be a solution or also a fine dispersion. If an active agrochemical compound is not, or is insufficiently soluble in the monomer mixture, it can exist in a finely dispersed form. It should be understood that the term "fine" in the present context means that the active compound particles, or drops of active compound, have an average particle size of less than 2 μm, preferably less than 1 μm. A fine dispersion can .H ^ prepare with the aid of high performance agitators (preferred in the case of liquid active compounds) or bead mills / ball mills (preferred in the case of solid active compounds). In a preferred variant, the processes according to the invention can be carried out in such a way that the mixture of the monomer mixture, active agrochemical compound and, if appropriate, additives are used in the form of a solution, a cosolvent being used to improve the solubility of the active agrochemical compound. Suitable cosolvents are organic solvents which, although they are not very irascible with water, dissolve the respective active agrochemical compound well. The materials that can be preferably used are the organic diluents that have already been mentioned. In an additional preferred variant, the process according to the invention can be carried out in such a way that the absorbing reagent is added to the aqueous phase (B) so that the pH of the aqueous phase has a value of between 12 and 5, preferably between 10 and 6, at the beginning of the polymerization. When carrying out the process according to the invention, the ratio is quantitative of the components used can be varied within a substantial range.

In general, the amounts of monomepca mixture and active agrochemical compound are chosen in such a way that it is between 25 and 95% by weight of monomeric mixture and between 5 and 75% by weight of active agrochemical compound, preferably between 40 and 90% by weight of monomeric mixture and between 10 and 60% by weight of agrochemical compound are present in the homogeneous mixture used.

The initiators are generally used in amounts between 0.05 and 2.5% by weight, preferably between 0.2 and 1.5% by weight, based on the monomeric mixture. The amounts of cosolvent are generally between 30 and 300% by weight, based on the total of the monomeric mixture and the active agrochemical compound. The amounts of aqueous phase are between 75 and 1200% by weight, preferably between 100 and 500%, on the basis and total of the monomepca mixture and the active agrochemical compound. The amounts of dispersants are generally between 0.05 and 2% by weight, preferably between 0.1 and 1% by weight, based on the aqueous phase. In the first step of the process according to the invention, the organic phase is added to the aqueous phase with stirring. During this process, the temperature can be varied within a certain range. In general, the process it is carried out at temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 50 ° C. The polymerization is carried out during the second step of the process according to the invention. Agitation speed is important to establish the particle size. In this way, the average particle size of the pearl-shaped polymers decreases with the increase in the stirring speed. The exact agitation speed for establishing a predetermined, particular bead size depends to a great extent on each individual case of the reactor size, the geometry of the reactor and the geometry of the agitator. It has proved to be appropriate to determine the agitation speed required by experimentation. If copolymers of (meth) acrylic acid and (meth) acrylates are used as dispersants, particle sizes between 6 and 30 μm are generally achieved at speeds between 300 and 500 revolutions per minute in the case of laboratory reactors which have a 3 liter reaction volume and equipped with paddle agitators. The polymerization temperature can be varied within a substantial range. This depends on the disintegration temperature of the initiator used. In general, the process is carried out at temperatures between 50 ° C and 150 ° C, preferably between 55 ° C and 100 ° C.

The polymerization time depends on the reactivity of the compounds used. In general, polymerization takes between 30 minutes and several hours. It has proven to be suitable to use a temperature program in which the polymerization starts at a low temperature, for example 70 ° C, and the reaction time increases as the polymerization progresses. The work during the last step of the process according to the invention is carried out by the usual methods. If it is desired to remove the finely divided solid phase, the polymer in the form of beads can be isolated, for example by filtration or decantation, and then dried, if appropriate after washing. If it is desired to produce a suspension of polymer in the form of beads in the aqueous phase, additional work may be dispensed in most cases. Any remaining cosolvent can be removed from the resulting mixture by distillation, if appropriate along with some of the water. The polymer formulations in the form of beads according to the invention are remarkably suitable for applying active agrochemical compounds to plants and / or their environment. They allow in each case that the desired quantity of active components is released over a prolonged period.

The formulations of polymers in the form of beads according to the invention can therefore be used in practice either in solid form or as suspensions, if appropriate after the previous dilution with water. They are applied by the usual methods, for example, irrigation, spray, atomization or dispersion. The application speed of the polymer formulations in the form of beads according to the invention can be varied within a substantial range. This depends on the respective active agrochemical compounds and their content in the polymers in the form of beads. The invention is illustrated by the following examples.

Preparation Examples Example 1 Polymers in the form of beads comprising 4-amino-N- (1,1-dimethyl-ethyl) -4,5-d? ? -3- (1-met? lo-et? l) -5-oxo-lH-1, 2, -tr? azole-l-carboxamide, of the formula Three polymers were prepared in the form of different beads with different copolymer compositions. In each case xg of methyl methacrylate, and g of hydroxyethyl methacrylate, zg of ethylene glycol dimethyl acrylate and 97 g of 4-amino-N- (1,1-dimethylethyl) -4,5-di-h? dro-3- (1-methylethyl) -5-oxo-lH-l, 2,4-triazole-l-carboxamide for two hours in a ball mill, and subsequently 3.9 g of dibenzoyl peroxide was added to the mix, with stirring, at room temperature. The mixture was transferred to a stirred reactor which had previously been charged with 1.5 liters of a 1% by weight aqueous alkaline solution of a copolymer of 50% by weight of methacrylate and 50% by weight of methyl meta-plate solution which It had been brought to pH 8 with sodium hydroxide solution. The stirring speed was set at 700 revolutions per minute and the temperature was maintained for 3 hours at 60 ° C, then for 10 hours at 78 ° C, and then for 2 hours at 85 ° C. The mixture was then cooled to room temperature over the course of 2 hours. This gives dispersions of polymers in the form of beads containing active compound.

EXAMPLE 2 Polymers in the form of beads, comprising idiocloprid, of the formula Three polymers were prepared in the form of different beads with different copolymer compositions. In each case, xg of methyl methacrylate, and g of hydroxyethyl methacrylate, zg of dimethyl acyl acetate of ethylene glycol and 100 g of midacloppd and 30 g of finely divided silicon dioxide (HDK H2000, from Wacker) were mixed for 2 hours in a ball mill, and subsequently 3 g of dibenzoyl peroxide was added to the mixture with stirring to room temperature. The mixture was transferred to a stirred reactor which had previously been charged with 1.5 liters of a 1% by weight aqueous alkaline solution of a 50% by weight copolymer of metacrate and 50% by weight of methyl methacrylate, solution which had been taken to pH 8 with sodium hydroxide solution. The stirring speed was set at 500 revolutions per minute and the temperature was maintained for 8 hours at 78 ° C and then for 2 hours at 85 ° C. The mixture was then cooled to room temperature over the course of 2 hours. The polymer in the form of a pearl was isolated allowing it to sediment and decant, washed with cold water and dried in the drying oven at 50 ° C Release test A In order to verify the release rate of the active compound, homogenous samples were diluted in each case of 4 ml in the dispersions of Examples 1 A-C with 950 ml of water. The mixture was stored for 35 days with agitation. After the times shown in Table 1, the content of active compound in the aqueous phase was determined by means of CLAP. The numerical value in the following table indicates the percentage of the active compound that has been released into the water, based on the amount of active compound that has been added.

Table 1 The experimental series clearly demonstrates that the release rate of the active compound is governed for the content of hydroxyethyl meta-plate in the copolymer.

Release test B In order to verify the release rate of the active compound, in each case 1 g of the pearl-shaped polymers of Examples 2 A-C in 1 liter of water was dispersed. The dispersion was stored for 240 hours, with stirring. After the times indicated in Table 2, the content of active compound in the aqueous phase was determined. The numerical value indicates the percentage of active compound released into water, based on the amount of active compound that has been added.

Table 2 Again, the experimental series clearly demonstrates that the release rate of the active compound is governed by the content of hydroxyethyl methacrylate in the copolymer. It is noted that with respect to this date, the best method known to the applicant to carry out the present invention is that which is clear from the present description of the invention.

Claims (5)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property.

1. Formulations of polymers in the form of beads, characterized in that they are composed of I) a particulate solid phase comprising A) copolymer of a) 40 to 95% by weight of monomer soluble in water, b) 5 to 35% by weight of soluble monomer in water c) 0 to 25% by weight of crosslinking agent; and B) at least one active agrochemical compound and, C) if appropriate, additives, the content of active agrochemical compound is between 5 and 75% by weight and the solid phase has an average particle size of between 1 and 100 μm, and II) if appropriate, a liquid phase.

2. The process for the preparation of polymer formulations in the form of beads according to claim 1, characterized in that A) an organic phase of from -25 to 95% by weight of a monomeca mixture of a) 40 to 95% by weight of monomer more soluble in water; b) 5 to 35% by weight of water-soluble monomer c) 0 to 25% by weight of crosslinker; 5 and 75% by weight of at least one active agrochemical compound, at least one initiator, - if appropriate, additives, and, if appropriate, an organic solvent which is moderately miscible with water, B) is finely divided into an aqueous phase of water, at least one dispersant and, if appropriate, a buffering agent, at temperatures between 0 ° C and 60 ° C and with stirring, C) then polymerizing the mixture with agitation until the temperature increases, D) and, if appropriate, after this either a) isolating, washing and drying the polymer in the form of resultant beads or ß) removing any organic substances volatiles that may be present and thereby retaining the polymer in the form of beads in aqueous suspension.

3. The use of polymer formulations in the form of beads according to claim 1 for applying active agrochemical compounds to plants and / or their environment.

4. The polymer formulations in the form of beads according to claim 1, characterized in that they comprise 4-ammo-N- (1,1-d? Methylethyl) -4,5-dihydro-3- (1-meth? -et? l) -5-oxo-lH-l, 2,4-triazole-l-carboxamide as active agrochemical compound.

5. The polymer formulations in the form of beads according to claim 1, characterized in that they comprise imidaclopnd as an active agrochemical compound.