DE19933832A1 - Scatter granules - Google Patents

Abstract

The invention relates to novel granulates to be strewn which are comprised of: A) styrene-copolymerizate consisting of a) 30 to 93 wt. % of styrene, b) 5 to 40 wt. % of (meth)acrylnitrile, c) 2 to 50 wt. % of (meth)acrylic-acid ester with 4 to 18 carbon atoms in the ester part, and d) 0 to 30 wt. % of other vinyl monomers, and of; B) at least one agrochemical active substance, as well as of; C) optional additives. The inventive granulates have an average particle size ranging from 100 to 1000 mu m, whereby the content of agrochemical active substance ranges from 0.5 to 75 wt. % with regard to the granulates to be strewn. The invention also relates to a method for producing these granulates to be strewn and to their use for applying agrochemical active substances.

Description

The present invention relates to new granules, the agrochemical effect contain substances and an average particle size between 100 and 1000 microns have, a method for producing these granules and their use for the application of agrochemical agents.

From EP-A 0 201 214 are already from ethylenically unsaturated monomers adjustable microparticles known that contain pesticidal agents and a Have particle diameters between about 0.01 and 250 microns. Disadvantageous These preparations, however, is that the active components especially when it is substances with a relatively high vapor pressure, not always about released for a sufficiently long period of time and in the desired amount become.

Furthermore, formulations have been described that are easily washable agro Chemical agents in microencapsulated form in unsaturated polyester resins included (cf. EP-A 0 517 669). It is unfavorable, however, that the release of the micro encapsulated active ingredients do not always meet the practical requirements.

Furthermore, EP-A 0 281 918 shows that macroporous, crosslinked polystyrene Pearl polymers are suitable as carriers for agrochemicals and in crop protection are reversible. Even when using these preparations, however, the speed remains and the amount in which the agrochemicals are released often increase wish left.

Finally, it can be seen from US Pat. No. 4,269,959 that weakly crosslinked polystyrene Bead polymers can absorb liquid active ingredients, such as agrochemicals, and the products loaded in this way can be used as slow release formulations. However, the duration of action of such preparations is not always sufficient.  

New scattering granules have now been found, which consist of

• A) styrene copolymer
  • a) 30 to 93% by weight of styrene,
  • b) 5 to 40% by weight of (meth) acrylonitrile,
  • c) 2 to 50 wt .-% (meth) acrylic acid ester with 4 to 18 carbon atoms in the ester part and
  • d) 0 to 30% by weight of further vinyl monomers,
  and
• B) at least one agrochemical active ingredient
  such as
• C) optional additives

exist and an average particle size between 100 and 1000 microns have, the content of agrochemical active ingredient between 0.5 and 75 wt .-% based on the scattering granules.

Furthermore, it was found that scatter granules according to the invention can be produced by

• A) an organic phase
  • - 25 to 99.5 wt .-% of a monomer mixture
    • a) 30 to 93% by weight of styrene,
    • b) 5 to 40% by weight of (meth) acrylonitrile,
    • c) 2 to 50 wt .-% (meth) acrylic acid ester with 4 to 18 carbon atoms in the ester part and
    • d) 0 to 30% by weight of further vinyl monomers,
    and
    0.5 to 75% by weight of at least one agrochemical active ingredient,
  • - at least one initiator,
  • - if necessary additives
    and
  • optionally an organic solvent which is not very miscible with water,
• B) in an aqueous phase
  • - Water,
  • - at least one dispersant,
  • and optionally a seed polymer with stirring at temperatures between 0 ° C. and 60 ° C., finely divided,
• C) then polymerized while increasing the temperature and with stirring and
• D) then separates any volatile organic substances that may be present and the resulting granules are isolated, washed and dried.

Finally, it was found that the granules according to the invention are very good for Application of agrochemical active ingredients are suitable. The scatter granules be sit excellent flowability and are particularly good as spreading material can be used, with a very even distribution on the treated surfaces is enough.

It can be described as extremely surprising that the scattering grains according to the invention nulate better for the application of agrochemical active substances, in particular of active components with a relatively high vapor pressure, are suitable as the consti the most similar, known preparations.

The scattering granules according to the invention are notable for a number of advantages out. So they are able to keep the active components for quite a long time to release space in an even quantity. It is also beneficial that even then none Odor nuisance occur when it comes to the agrochemical active ingredients are substances with a relatively high vapor pressure. For the rest is with A locally narrowly limited application with the aid of the scattering granules according to the invention possible. The risk that untreated neighboring stocks by volatile Be components are contaminated in an undesirable manner, is against conventional preparations significantly reduced.

The styrene copolymers present in the scattering granules according to the invention are characterized by the components listed under (a) to (d).  

The term (meth) acrylonitrile (b) in the present case is both acrylic to understand nitrile as well as methacrylonitrile.

Likewise under the name (meth) acrylic acid ester (c) are both esters of To understand acrylic acid as well as methacrylic acid. Preferably in question come esters, which are of optionally substituted, aliphatic, cyclo aliphatic, aromatic or mixed aromatic-aliphatic alcohols with 4 derive up to 18 carbon atoms. The aliphatic radicals can be either straight-chain or also be branched and interrupted by oxygen.

Examples of particularly preferred (meth) acrylic acid esters are:
n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, n-octyl acrylate, n-octyl methacrylate, decyl acrylate, decyl methacrylate, dodecyl methacrylate, dodecyl methacrylate, dodecyl methacrylate, dodecyl methacrylate , cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenylethyl acrylate, phenylethyl methacrylate, phenylpropyl acrylate, phenylpropyl methacrylate, Phenylnonylacrylat, Phenylnonylmethacrylat, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, di glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, Triethylene glycol monomethacrylate, tetraethylene glycol monoacrylate, tetraethylene glycol monomethacrylate, furfury acrylate, furfuryl methacrylate, tetrahydrofurury acrylate and tetrahydrofurfuryl methacrylate.

Other suitable vinyl monomers (d) are preferably (meth) acrylic acid esters with 1 to 3 carbon atoms in the alcohol radical, such as methyl methacrylate, ethyl acrylate and hydroxylethyl methacrylate, furthermore acrylic acid, Methacrylic acid, acrylamide, methacrylamide, vinyl pyrrolidone, vinyl chloride, vinyli denchloride, vinyl acetate, vinyl propionate, vinyl laurate and vinyl adipate.  

In addition, other vinyl monomers (d) can also be used, at least in part multifunctional vinyl monomers that act as crosslinkers in the styrene copoly merisat included. Examples include allyl methacrylate and ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, butanediol dimethacrylate, Hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimetha crylate, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate and divinyl benzene.

The proportion of multifunctional vinyl in the styrene copolymer can monomers can be varied within a certain range. The content of multifunctional vinyl monomers (d) is generally between 0 and 30% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.5 and 10% by weight.

In a particular embodiment of the present invention, the styrene-Co polymer is a so-called seed-feed polymer (seed-feed polymer).

Suitable seed polymers are swellable styrene polymers in pearl form, ins special cross-linked styrene polymers. They come up as crosslinkers above questioned multifunctional vinyl monomers (d). Divinyl is preferred benzene. The content of multifunctional vinyl monomers (d) is 0.1 to 10, preferably 0.2 to 5 wt .-% based on the seed. The used as seeds Styrene polymers can be copolymerized in amounts of up to 50% by weight Units of the compounds (b), (c) and (d) listed above.

The perfect styrene polymers suitable as seed polymers are known or can be made in a simple manner by known processes using suspension poly Generate merization from the above monomers. Particularly preferred Seed polymers are those styrene polymers which are known from DE-A 196 34 393 EP-A 0 870 772 and DE-A 198 26 049 are known, including those there mentioned monodisperse styrene polymers come into question.  

In the present context, agrochemical active ingredients are all for To understand plant treatment usual substances. May be mentioned Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plants growth regulators, plant nutrients and repellents.

Examples of fungicides are:
2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-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; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy) phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole, benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol, blasticidin-S. Bromuconazole, bupirimate, buthiobate, calcium polysulfide, captafol, captan, carbendazim; Carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram, dichlorophen, diclobutrazole, dichlofluanid, diclomezin, dicloranocomidazole, diethofenol , Dithianon, Dodine, Drazoxolon, Edifenphos, Epoxyconazole, Ethirimol, Etridiazol, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpro pimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Flimazole, Fluonilole, Fluonilole, Fluonilole, Fluquinil, Fluazinil Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminum, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox, Guazatine, Hexachlorobenzol, Hexaconazole, Hymexazol, Imazalil, Imibenconazole, Iminoctadine, Iprobefos (IBP), Iopiol, copper, isoprodione, copper prodrug, Ioprozione, copper prodrug, Ipriolanid, copper prodrug , Copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and board eaux-mix, Mancopper, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Metrifuroxam, Metiram, Metsulfovax, Myclobutanil, Nickeldimethyldithiocarbamat, Nitrothal-isopropyl, Oxarimadol, Oxurimolarbox, Ofurace Phosdiphene, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozen (PCNB), quinoxyfen, sulfur and sulfur preparations, teclazolazamol, teblazolazazetra, teblazolazazetra , Thicyofen, Thio phanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triform, Triticonazol, Validamycin A, Vinclozolin, Zineb, Butamyl, 8-tert, 2- (N-ethyl-Nn-propylamino) methyl-1,4-dioxa-spiro- [4,5] decane, N- (R) - (1- (4-chlorophenyl) ethyl) -2 , 2-dichloro-1-ethyl-3t-methyl-1r-cyclopropancar bonsäureamid (Diastereome mixture or individual isomers), [2-methyl-1 - ([[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl] carbamic acid 1-methyl ethyl ester, 1-methyl-cyclohexyl-1- carboxylic acid (2,3-dichloro-4-hydroxy) anilide, 2- [2- (1-chloro-cyclopropyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2,4-dihydro- [1 , 2,4] - triazol-3-thione and 1- (3,5-dimethyl-isoxazole-4-sulfonyl) -2-chloro-6,6-difluoro- [1,3] -dioxolo- [4,5 -f] - benzimidazole.

Examples of bactericides are:
Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofta lam, copper sulfate and other copper preparations.

Examples of insecticides, acaricides and nematicides are:
Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, 4-Bromo-2- (4-chlorophenyl) -1- (ethoxymethyl 5- (trifluorome thyl) -1H-pyrrole-3-carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox, bromophos A, bufencarb, buprofezin, butocarb oxin, butylpyridaben, cadusafosurion, carbaryl, carbanophenofos, carbaryl, carbanophenofos, carbaryl , Cartap, Chloetho carb, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro- 3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide, Chlorpyrifos, Chlorpyri fos M, Cis-Resmethrin , Clocythrin, Clofentezin, Cyanophos, Cycloprothrin, Cyflu thrin, Cyhalothrin, Cyhexatin, Cypermethrin, Cyromazin, Deltamethrin, Demeton-M, Demeton-S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthicion, Dichlorosophosophosphos Diflu benzuron, dimethoate, dimethylvinphos, dioxathione, disulfoton, E difenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho prophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximonuronuron, Fluon fonoxuron, Fluon fonoxuron, Fluon fonoxuron, Fluon fonoxuron, Fluon fonoxuron, Fluon fonoxuron, Fluon fontronuron, Fluon fonium, Fluon fontronium, Fluon fonate , flufenoxuron, flufenprox, fluvalinate, fonophos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH, heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos, isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos , Mesulfenphos, Metaldehyd, Methacrifos, Metha midophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Mono crotophos, Moxidectin, Naled, NC 184, Nitenpyram, Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos, Parathion Ahrin, Permathion A, Parathion A, , Phorat, Phosalon, Phosmet, Phos phamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Pro mecarb, Propaphos, Propox ur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos, Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen, Quinalphos, Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos, Tebufenozide, Tebufenefirimonur, Tebufenefyrimuron , Tetrachlorvinphos, Thiacloprid, Thiafenox, Thiamethoxan, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Transfluthrin, Triarathen, Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimothyethramethramethramethramethramethramethramethamethramethramethramethramethrate, Trimethyethrin, X

Examples of herbicides are:
Anilides such as B. Diflufenican and Propanil; Arylcarboxylic acids, such as. B. dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, such as. B. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkane acid esters, such as. B. diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, such as B. Chloridazon and Norflurazon; Carbamates, e.g. B. Chlorpropham, Desmedipham, Phenmedipham and Propham; Chloroacetanilides such as e.g. B. alachlor, acetochlor, butachlor, metazachlor, metola chlorine, pretilachlor and propachlor; Dinitroanilines such as e.g. B. Oryzalin, Pendimethalin and Trifluralin; Diphenyl ether, such as. B. acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as B. chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; Hydroxyl amines, such as. B. Alloxydim, Clethodim, Cycloxydim, Sethoxydim and Tralkoxydim; Imidazolinones, e.g. B. Imazethapyr, Imazamethabenz, Imazapyr and Imazaquin; Nitriles such as B. bromoxynil, dichlobenil and ioxynil; Oxyacetamides such as e.g. B. Mefenacet; Sulfonylureas, such as. B. amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulflxron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates such as e.g. B. butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g. B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne and Terbutylazin; Triazinones such as e.g. B. hexazinone, metamitron and metribuzin; Others, such as B. aminotriazole, benfuresate, bentazone, cinmethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethofumesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.

Chlorcholine chloride and ethephon are examples of plant growth regulators called.

Examples of plant nutrients are customary inorganic or organic Fertilizer for supplying plants with macro and / or micronutrients called.

Examples of repellents are diethyl tolylamide, ethylhexanediol and buto called pyronoxyl.

The scatter granules according to the invention contain one or more agrochemical active substances. Agrochemical active ingredients are preferably present which have a vapor pressure between 5 and 10 ⁶ mPa, particularly preferably between 50 and 10 ⁵ mPa at 20 ° C. Examples of such active substances are the substances listed in the following tables.

Table 1

insecticides

Table 2

Fungicides

Table 3

Herbicides

As additives that are present in the granules according to the invention all substances that are usually found in plants can be used treatment agents can be used as additives. These include, for example Plasticizers, dyes, and antioxidants.  

Liquid or solid plasticizers come into consideration in the present case indifferent substances with a low vapor pressure and a molecular weight between 150 and 1000, preferably without chemical reaction their solvent or swelling properties interact with high polymer substances and form a homogeneous physical system with them.

Derivatives of organic and inorganic acids are particularly suitable as plasticizers, in particular esters, amides and imides of organic acids. Be particularly preferred are esters and imides with C ₄ -C ₁₂ alkyl units.

Examples include:
Abietic acid esters, adipic acid esters, azelaic acid esters, benzoic acid esters, butteric acid esters, higher fatty acid esters, epoxidized fatty acid esters, glycolic acid esters, phthalic acid esters, isophthalic acid esters, terephthalic acid esters, propionic acid esters, sebacic acid esters, trimellitic acid esters, citric acid esters, phosphoric acid ester and sulphonic acid esters.

Also suitable as plasticizers are alkyl and aryl esters of hydroxy acids, such as hydroxybenzoic acid and salicylic acid and N-alkylphthalimides.

Examples include:
Di-2-ethylhexyl adipate, diisooctyl adipate, diisodecyl adipate, benzyl octyl adipate, di-2-ethyl hexyl azelate, dibutyl phthalate, dicapryl phthalate, dioctyl phthalate, di-2-ethyl hexophthalate, diisooctyl phthalate, butyl benzyl phthalate, di-isononyl phthalate, di-isononyl phthalate Di-2-ethylhexyl terephthalate, diisooctyl sebacate, triisooctyl trimellitate, salicylic acid methyl ester, salicylic acid phenyl ester, butyl phthalimide, 4-hydroxybenzoic acid-n-propyl ester, tri-2-ethylhexyl phosphate, triphenyl phosphate, diphenyloctyl phosphate, tri-phenyl phosphate, tri-phenyl phosphate, tri-phenyl phosphate, di-phenyl phosphate, tri-phenyl phosphate, di-phenyl phosphate, and phenyl phosphate, di-phenyl phosphate, tri-phenyl phosphate, and di-phenyl phosphate, as well

In addition to the low-molecular compounds mentioned come as plasticizers in the present case also oligomers with no more than 4 recurring ones units, e.g. B. oligomers of aliphatic or aromatic polyesters based on, for example, adipic acid, succinic acid, sebacic acid, phthal acid and hexahydrophthalic acid as an acid component and, for example, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and cyclo hexanedimethanol as a hydroxy component. Oligomers from Hy are also suitable droxycarboxylic acids such as B. polycaprolactone, polyhydroxystearic acid and polyhy droxybutyric acid and polyols such as. B. polyethylene oxide, polypropylene oxide, poly butylene oxide and its cooligomers.

Soluble dyes or sparingly soluble color pigments come in as dyes Consider, such as titanium dioxide, carbon black or zinc oxide.

Antioxidants are all commonly used in plants for this purpose substances that can be used in agents. Sterically hindered are preferred Phenols and alkyl-substituted hydroxyanisoles and hydroxytoluenes.

The content of the individual components can be varied within a substantial range in the scattering granules according to the invention. So the concentrations are

• Styrene copolymer (A) generally between 25 and 99.5% by weight, preferably between 50 and 99% by weight,
• - Agrochemically active substances (B) generally between 0.5 and 75% by weight, preferably between 1 and 50% by weight and
• - Additives (C) generally between 0 and 30 wt .-%, preferably as between 0 and 15 wt .-%.

In the scattering granules according to the invention, the particle size can be within a certain range can be varied. It is generally between 100 and 1000 microns, preferably between 150 and 1000 microns. Also the width of the particles size distribution can be varied. Monodisperse particle size distributions can be obtained using monodisperse seeds. For determination the average particle size (∅) and the particle size distribution are common Methods such as sieve analysis or image analysis are suitable. As a measure of the width of the Particle size distribution of the scattering granules produced is the ratio of the 90% value (∅ (90)) and the 10% value (∅ (10)) of the volume distribution. Narrow particle size distributions mean ∅ (90) / ∅ (10) ≦ 2.0, preferred ∅ (90) / ∅ (10) ≦ 1.5, particularly preferably ∅ (90) / ∅ (10) ≦ 1.2.

The granules according to the invention are produced by the process as the suspension polymerization or by a seed feed process.

The term suspension polymerization is understood to mean a process in which which is a monomer or a monomer-containing mixture which contains one in the monomer (s) contains soluble initiator in one with the monomer (s) essentially not miscible phase, which contains a dispersant, in the form of droplets, ge if necessary in a mixture with small, solid particles, is broken up and through Temperature increase is cured with stirring. More details of the Suspension polymerization is described, for example, in H. Greens "Polymerization Processes ", in: Ullmanns Encyclopedia of Industrial Chemistry, Vol. A21, p. Ed. (B. Elvers, S. Hawkins, G. Schulz, ed.), VCH, Weinheim 1992, pp. 363-373 be wrote.

In this context, a process is referred to as a seed feed process were in which a monomer or a monomer-containing mixture that one in Contains monomer (s) soluble initiator, to an aqueous dispersion of a poly merisates is given, the monomer or the monomer-containing mixture in the seeds swell and are cured by increasing the temperature while stirring. There  at the addition of the monomer or the monomer-containing mixture can both before the polymerization as well as during the polymerization.

In a preferred variant, one proceeds when carrying out the seed feed Process in such a way that the organic phase (A) before the polymerization in contact with a swellable styrene polymer (seed). More appropriate the seed is added to the aqueous phase (B). The organic phase (A) then swells in the seed and is cured there by polymerization. The be Special advantage of seed feed polymers is that the particle size of the scattering granules formed can easily be checked over the particle size of the seeds can be lated. For example, when using a monodisperse Seed obtained a monodisperse granules.

In particular, the granules according to the invention can be produced in which is an organic phase consisting of the components of the monomer mix (a), (b), (c) and (d), at least one agrochemical active ingredient, at least one initiator, optionally additives and optionally one organic solvent which is not very miscible with water in an aqueous phase Water, at least one dispersant and optionally a seed polymer finely divided with stirring at temperatures between 0 ° C and 60 ° C, if necessary the organic phase swells in the seed polymer, then under temperature increase and polymerized with stirring and then optionally contained volatile, organic substances are separated and the resulting granules are isolated and if necessary washes and dries.

The starting material in carrying out the method according to the invention Rialien required monomer mixtures are those listed under (a) to (d) Components characterized. Those components are preferred, the ge already in connection with the description of the styrene copolymers were named.  

As agrochemical active ingredients in the implementation of the invention Process all those substances usable for the treatment of plants are used, which already in connection with the description of the inventions scattering granules according to the invention were mentioned as agrochemical active ingredients. Before the use of agrochemical active substances with a relatively high vapor pressure is increasing.

All can be initiators when carrying out the process according to the invention Substances usually usable for the initiation of polymerizations be used. Oil-soluble initiators are preferred. At Peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, Bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxidicarbonate, tert-butyl peroctoate, 2,5- Bis- (2-ethylhexanoylperoxy) -2,5-dimethylhexane and tert.-amylperoxy-2-ethylhexane, further azo compounds, such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2- methyl isobutyronitrile).

Additives can be used when carrying out the process according to the invention all those substances are used that are already in connection with the Description of the granules according to the invention mentioned as additives were. Auxiliary solvents are also suitable.

All sub that are usually used for this purpose come as dispersants punch into consideration. Natural and synthetic water are preferred soluble polymers such as gelatin, starch and cellulose derivatives, especially Cellu loose esters and cellulose ethers, also polyvinyl alcohol, polyvinyl pyrrolidone, poly acrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (Meth) acrylic acid esters, and also neutralized with alkali metal hydroxide Copolymers of methacrylic acid and methacrylic acid ester To adjust the Conventional buffering reagents can be used for the pH of the aqueous phase.

The process according to the invention is generally carried out so that you first have a homogeneous mixture of monomer mixture, one  or several agrochemical active ingredients and optionally additives poses. This homogeneous mixture can be a solution or else act a finely divided dispersion.

If an agrochemical active ingredient in the monomer mixture is not or insufficiently is soluble, it can be in finely divided form. Finely divided means in this connection that the drug particles or drug droplets average particle size of less than 5 microns, preferably less than 2 microns point. The production of a fine dispersion can be done with the help of Schnell stirrers (preferably for liquid active ingredients) or pearl mills / ball mills (before moves with solid active substances).

In a preferred variant, the process according to the invention can be carried out in the Carry out that the mixture of monomer mixture, agrochemical Active ingredient and optionally additives in the form of a solution, wherein for An auxiliary solvent to improve the solubility of the agrochemical active ingredient is used. Suitable auxiliary solvents are organic solvents on the one hand are not very miscible with water, but on the other hand the respective agrochemicals Dissolve the active ingredient well. The organi already mentioned can preferably be used diluent. Examples of such solvents are mentioned aromatic hydrocarbons such as toluene and xylene continue to be halogenated Hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and Dichloroethane, and also esters, such as ethyl acetate.

In a further preferred variant, the method according to the invention can do so be carried out by adding a seed polymer to the aqueous phase (B). There with all those substances are suitable as seeds that are already related to the description of the granules according to the invention were mentioned. The Particle size of the seed depends on the desired particle size of the he Scattering granules according to the invention, with those occurring in the seed feed process  Volume increase in a simple manner from the ratio of feed and seed and the density of the polymerized feed can be calculated.

The proportions of the components used can be in the through implementation of the method according to the invention within a larger range be.

The amounts of monomer mixture and agrochemical active ingredient are in all generally chosen so that in the homogeneous mixture used between 25 and 99.5% by weight of monomer mixture and between 0.5 and 75% by weight of agroche mixed active ingredient, preferably between 50 and 99 wt .-% of monomer mixed and between 1 and 50 wt .-% of agrochemical active ingredient are.

Initiators are generally present in amounts between 0.05 and 2.5% by weight preferably between 0.2 and 1.5% by weight, based on the monomer mixture set.

The amount of auxiliary solvent is generally between 30 and 300 wt .-%, based on the sum of the monomer mixture and agrochemical Active ingredient.

The amount of seed polymer is generally between 10 and 200 wt .-%, preferably between 20 and 100 wt .-%, based on the sum from monomer mixture and agrochemical active ingredient.

The amount of aqueous phase is generally between 75 and 1200 wt .-%, preferably between 100 and 500 wt .-%, based on the Sum of the monomer mixture and agrochemical active ingredient.  

The amount of dispersant is generally between 0.05 and 2% by weight, preferably between 0.1 and 1 wt .-%, based on the aqueous phase.

In the first step of the method according to the invention, the organic phase is under Stir in the aqueous phase. The temperature can be within one certain range can be varied. Generally one works at Tempera structures between 0 ° C and 60 ° C, preferably between 10 ° C and 50 ° C.

The polymerization takes place in the second step of the process according to the invention. The stirring speed is important for setting the particle size. So takes the mean particle size of the scattering granules with increasing stirring speed from. The exact stirring speed for setting a certain specified pearl Size depends strongly on the reactor size, the reactor geometry and the Stirrer geometry.

The polymerization temperature can be varied within a wide range the. It depends on the decomposition temperature of the initiator used. Generally I think one works at temperatures between 50 ° C and 150 ° C, preferably between 55 ° C and 100 ° C.

The duration of the polymerization depends on the reactivity of the components involved from. The polymerization generally lasts between 30 minutes and several Hours. It has proven useful to use a temperature program in which the Low temperature polymerization, e.g. B. 70 ° C is started and continues progressing polymerization conversion, the reaction temperature is increased.

Working up in the last step of the method according to the invention is carried out after usual methods. For example, the scattering granules can be filtered or Decant isolated and, if necessary, dried after washing. Any auxiliary solvent contained can be obtained from the resulting mixture, ge if necessary, be removed by distillation together with part of the water.  

The scattering granules according to the invention are outstandingly suitable for application of agrochemical agents. They are particularly suitable for use as litter and because of their good flow properties, they allow a particularly uniform flow Distribution of the active ingredient on the area to be treated. Will be a special value placed on an extraordinarily high flowability, so according to the invention Scatter granules with a monodisperse particle size distribution are used. Especially the granules according to the invention can advantageously be used to agro to apply chemical agents with a relatively high vapor pressure. You grant perform the release of the active components in the desired amount over an extended timespan.

The application rate of the scattering granules according to the invention can be within one larger range can be varied. It depends on the respective agro chemical agents and their content in the granules.

The invention is illustrated by the following examples.  

Manufacturing examples

example 1

Scatter granules containing dichlobenil of the formula

483 g styrene, 70 g acrylonitrile, 140 g ethylhexyl acrylate, 7 g technical divinyl benzene (81% in vinyl ethyl styrene) and 37 g dichlobenil become one homogeneous solution mixed and then at room temperature with stirring 3.5 g of tert-butyl peroctanoate were added. The solution is transferred to a stirrer reactor that previously with 2 liters of a 0.4 wt.% aqueous solution of Hy droxyethyl cellulose (Tylose® H200, Clariant) was filled. The stirring speed speed is set to 180 revolutions per minute and the temperature becomes 9 Hours at 63 ° C and then held at 95 ° C for 2 hours. After cooling down The resulting granules are filtered off at room temperature, three times with deionized water and dried at 60 ° C in a drying cabinet. Man receives 720 g of a scattering granulate; the average particle size is 480 µm; the Active ingredient content is 5.0% by weight.

Example 2 Scatter granules containing dichlobenil

787.7 g styrene, 202.5 g acrylonitrile, 56.3 g ethylhexyl acrylate, 78.8 g technical Divinylbenzene (81% in vinylethylstyrene) and 79.6 g dichlobenil become one homogeneous solution mixed and then at room temperature with stirring with 9 g of dibenzoyl peroxide (75%). The solution is transferred to a stirrer reactor, previously with a mixture of 1600 g of deionized water, 3 g of Hy  droxyethyl cellulose (Tylose® H200, Clariant) 1.2 g sodium hydroxide, 4.5 g boron acid and 375 g of bead polymer [poly (styrene-co-divinylbenzene) -99 / 1-w / w, particles size 295 µm, monodispers] when seed was filled. The stirring speed will set at 220 revolutions per minute and the temperature becomes 10 hours kept at 65 ° C and then at 95 ° C for 2 hours. After cooling to room the resulting scattering granulate is filtered off, three times with deionized Washed water and dried at 50 ° C in a drying cabinet. 1540 g are obtained a monodisperse, active ingredient-containing scattering granules; the average particle size is 500 µm; the active ingredient content is 5.0% by weight.

Example 3 Scatter granules containing dichlobenil

Example 2 was repeated, using only 38.5 g of dichlobenil instead of 79.6 g were set. 1515 g of a monodisperse, active substance-containing litter are obtained granules; the average particle size is 500 µm; the active substance content is 2.5% by weight.

Comparative example Pumice granules, covered with dichlobenil

95 g of pumice granules with an average particle size of 0.5 mm were in 100 ml Slurried dichloromethane. A solution was made to this slurry 5 g of dichlobenil, 1 g of polyvinyl acetate and 94 g of dichloromethane. The dichlor methane was removed in vacuo at 20 ° C. 100 g of one with dichlo were obtained benil coated granules.

Claims (6)

1. Scatter granules that come from

• A) styrene copolymer
  • a) 30 to 93% by weight of styrene,
  • b) 5 to 40% by weight of (meth) acrylonitrile,
  • c) 2 to 50 wt .-% (meth) acrylic acid ester with 4 to 18 carbon atoms in the ester part and
  • d) 0 to 30% by weight of further vinyl monomers,
  and
• B) at least one agrochemical active ingredient and
• C) optional additives

exist and have an average particle size between 100 and 1000 microns, the content of agrochemical active ingredient between 0.5 and 75 wt .-% based on the scattering granules. 2. Scatter granules according to claim 1, characterized in that as agro chemical agent a fungicide, bactericide, insecticide, acaricide, Nematicide, herbicide, plant growth regulator, plant nutrient or a Repellent is included.   3. scattering granules according to claim 1, characterized in that an agrochemical active ingredient is an active ingredient which has a vapor pressure between 5 and 10 ⁶ mPa at 20 ° C. 4. scattering granules according to claim 1, characterized in that as agro chemical agent dichlobenil is included. 5. A method for producing scattering granules according to claim 1, characterized in that

• A) an organic phase
  • - 25 to 99.5 wt .-% of a monomer mixture
    • a) 30 to 93% by weight of styrene,
    • b) 5 to 40% by weight of (meth) acrylonitrile,
    • c) 2 to 50 wt .-% (meth) acrylic acid ester with 4 to 18 carbon atoms in the ester part and
    • d) 0 to 30% by weight of further vinyl monomers,
      and
      5 to 75% by weight of at least one agrochemical active ingredient,
  • - at least one initiator,
  • - optionally additives and
  • optionally an organic solvent which is not very miscible with water,
• B) in an aqueous phase
  • - Water,
  • - At least one dispersant and
  • - optionally a seed polymer
  finely distributed with stirring at temperatures between 0 ° C and 60 ° C,
• C) then polymerized while raising the temperature and with stirring
  and
• D) any volatile organic substances that may be present are then separated off and the resulting granules are isolated, washed and dried.

6. Use of scattering granules according to claim 1 for the application of agrochemical active substances on plants and / or their habitat.