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EP1056337A1 - Pearl polymerizate formulations - Google Patents

Pearl polymerizate formulations

Info

Publication number
EP1056337A1
EP1056337A1 EP99908866A EP99908866A EP1056337A1 EP 1056337 A1 EP1056337 A1 EP 1056337A1 EP 99908866 A EP99908866 A EP 99908866A EP 99908866 A EP99908866 A EP 99908866A EP 1056337 A1 EP1056337 A1 EP 1056337A1
Authority
EP
European Patent Office
Prior art keywords
weight
water
bead polymer
agrochemical active
active ingredient
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP99908866A
Other languages
German (de)
French (fr)
Inventor
Wolfgang Podszun
Hilmar Wolf
Rafel Israels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Publication of EP1056337A1 publication Critical patent/EP1056337A1/en
Ceased legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • the present invention relates to new bead polymer formulations of agrochemical active substances, a process for the preparation of these preparations and their use for the application of agrochemical active substances.
  • EP-A 0 201 214 already discloses microparticles which can be prepared from ethylenically unsaturated monomers and which contain pesticidal active ingredients and have a particle diameter of between approximately 0.01 and 250 ⁇ m.
  • a disadvantage of these preparations is that the active components are not always released at the rate necessary for the biological action.
  • formulations which contain easily washable agrochemical active ingredients in microencapsulated form in unsaturated polyester resins (cf. EP-A 0 517 669).
  • release kinetics of the microencapsulated active ingredients do not always meet the practical requirements. Hydrophobic active ingredients are released very slowly from these formulations.
  • EP-A 0 281 918 shows that macroporous, crosslinked polystyrene bead polymers are suitable as carriers for agricultural chemicals and can be used in crop protection. Even when these preparations are used, however, the speed and the amount in which the agricultural chemicals are released often leave something to be desired.
  • agrochemical active ingredient is between 5 and 75% by weight and the solid phase having an average particle size between 1 and 100 ⁇ m
  • bead polymer formulations according to the invention can be produced by:
  • the bead polymer formulations according to the invention are notable for a number of advantages. This enables them to release the active components in a uniform amount over a fairly long period of time. It is particularly favorable that the release rate of the active ingredient can be controlled within wide limits by the content of water-soluble monomer.
  • copolymers present in the bead polymer formulations according to the invention are characterized by the constituents listed under (a) to (c).
  • water-insoluble monomers (a) is to be understood as meaning monoethylenically unsaturated compounds which dissolve in water at less than 5% by weight 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 and vinyl derivatives.
  • Examples include: 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, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate 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,
  • water-soluble monomers (b) are monoethylenically unsaturated compounds which dissolve in water at 20 ° C. to more than 5% by weight.
  • examples include: acrylic acid and its alkali metal and ammonium salts, methacrylic acid and its alkali metal and ammonium salts, hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol tetramonomethyl methacrylate, triethylene glycol tetramonomethacrylate, methacrylate methacrylate, triethylene glycol tetramonomethyl methacrylate, , Acrylamide, methacrylamide, vinyl pyrolidone and vinyl imidazole. Hydroxyethyl methacrylate is preferred.
  • the proportion of water-soluble monomer (b) is essential for the active ingredient release.
  • the release rate of the agrochemical active substance can be controlled within wide limits via the proportion of (b).
  • the proportion of (b) is in the range from 5 to 35% by weight. In many cases, particularly good effects are achieved with a proportion of (b) in the range from 7.5 to 20% by weight.
  • Crosslinkers (c) are compounds having at least two ethylenically unsaturated groups in the molecule. Examples include: allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, - 6 -
  • the proportion of crosslinking agent (c) in the copolymer can be varied within a certain range.
  • the (crosslinker (c) content is generally between 0 and 25% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.5 and 10% by weight.
  • agrochemical active substances are understood to mean all substances customary for plant treatment. Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, plant nutrients and repellents may preferably be mentioned.
  • fungicides are:
  • Imazalil Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutan
  • Nickel dimethyldithiocarbamate Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,
  • Tebuconazole Tebuconazole, tecloftalam, Techazen, tetraconazole, thiabendazole, Thicyofen, thio Phanat-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,
  • bactericides are:
  • insecticides examples include acaricides and nematicides.
  • Cadusafos Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N - [(6-Chloro-
  • Fipronil fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron,
  • Flufenprox Fluvahnate, Fonophos, Formothion, Fosthiazat, Fubfenprox,
  • Mecarbam Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
  • Parathion A Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrach
  • Tebufenozide Tebufenpyrad
  • Tebupirimiphos Teflubenzuron
  • Tefluthrin Temefos
  • Terbam Terbufos
  • Tetrachlorvinphos Thiafenox, Thiodicarb, Thiofanox
  • Triazophos triazuron, trichlorfon, triflumuron, trimethacarb,
  • herbicides examples are:
  • Anilides e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, e.g. Chloridazon and norflurazon;
  • Carbamates such as, for example, chloropropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroaniline such as Oryzalin, Pendimethalin and Trifl uralin; Diphenyl ethers such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz - 10 -
  • Hydroxylamines e.g. Alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim
  • Imidazolinones e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin
  • Nitriles e.g. Bromoxynil, dichlobenil and ioxynil
  • Oxyacetamides e.g. Mefenacet
  • Sulfonylureas e.g.
  • Amidosulfuron bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g.
  • Atrazin cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, 4-amino-N- (l, l-dimetylethyl) -4,5-dihydro-3- (l-methylethyl) -5-oxo-lH-l, 2,4-triazole-l-carboxamide, benfuresate, Bentazone, Cin- methylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
  • Triazinones e.g. Hexazinone, metami
  • Chlorcholine chloride and ethephon are examples of plant growth regulators.
  • plant nutrients are customary inorganic or organic
  • Fertilizer for supplying plants with macro and / or micronutrients called.
  • repellents are diethyltolylamide, ethylhexanediol and butopyronoxyl.
  • Suitable additives which can be present in the solid phase in the bead polymer formulations according to the invention are all those substances which are customarily usable as additives in plant treatment compositions. These include plasticizers, dyes, antioxidants, cold stabilizers and fillers. - 11 -
  • Suitable plasticizers in the present case are liquid or solid indifferent substances with a low vapor pressure and a molecular weight between 150 and 1000, which interact without a chemical reaction, preferably through their solvent or swelling capacity, with highly polymeric substances and thereby a homogeneous physical system with them form.
  • Colorants which are soluble or sparingly soluble are pigments, such as, for example, titanium dioxide, carbon black or zinc oxide.
  • Suitable antioxidants are all substances which can normally be used for this purpose in plant treatment products. Sterically hindered phenols and alkyl-substituted hydroxyanisoles and hydroxytoluenes are preferred.
  • Suitable cold stabilizers are all substances which can normally be used for this purpose in plant treatment products. Urea, glycerol or propylene glycol are preferred.
  • fillers come primarily inorganic particles, such as. B. carbonates, silicates and oxides with an average particle size of 0.005 to 5 microns, preferably 0.02 to 2 microns into consideration. Silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates and aluminosilicates are particularly suitable.
  • the content of the individual components can be varied within a substantial range in the bead polymer formulations according to the invention.
  • the concentrations are in the solid phase
  • copolymer (A) generally between 25 and 95% by weight, preferably between 40 and 90% by weight, - 12 -
  • agrochemical active ingredients (B) in general between 5 and 75% by weight, preferably between 10 and 60% by weight and
  • additives (C) generally between 0 and 30% by weight, preferably between 0 and 15% by weight.
  • the particle size of the solid particles can be varied within a certain range. It is generally between 1 and 100 ⁇ m, preferably between 5 and 50 ⁇ m.
  • the bead polymer formulations according to the invention can be present either as a particulate solid phase or as a dispersion of solid particles in a liquid phase.
  • liquid phase If a liquid phase is present, it essentially consists of water.
  • It can also contain components which are used in the preparation of the bead polymer formulations according to the invention and remain in the liquid phase. Possible components of this type are water-immiscible organic solvents, dispersants (protective colloids) and buffer reagents.
  • Suitable organic solvents are all customary organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the agrochemical active ingredients well.
  • aromatic hydrocarbons such as toluene and xylene
  • halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and dichloroethane
  • esters such as ethyl acetate.
  • loose esters and cellulose ethers also polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (meth) acrylic acid esters, and also also copolymers of methacrylic acid and methacrylic acid ester neutralized with alkali metal hydroxide.
  • the amounts of the additional substances mentioned in the aqueous phase can be varied within a substantial range.
  • the concentration depends on the amounts in which these substances are used in the preparation of the bead polymer formulations according to the invention, and on the manner in which they are worked up after the polymerization.
  • the bead polymer formulations according to the invention are prepared by the suspension polymerization procedure.
  • suspension polymerization is understood to mean a process in which a monomer or a monomer-containing mixture which contains an initiator which is soluble in the monomer (s) in the form in a phase which is essentially immiscible with the monomer (s) and which contains a dispersant of droplets, optionally in a mixture with small, solid particles, is distributed and cured by increasing the temperature with stirring. Further details of the suspension polymerization are, for example, in the publication "Polymer Processes", edited by C.E. Schildknecht, published in 1956 by Interscience
  • the monomer mixtures required as starting materials when carrying out the process according to the invention are those listed under (a) to (c)
  • initiators When carrying out the process according to the invention, all substances which can usually be used for initiating polymerizations can be used as initiators. Oil-soluble initiators are preferred.
  • Peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxidicarbonate, tert.-butyl peroctoate, 2,5-bis (2-ethylhexanoyl peroxi) -2,5-dimethylhexane and tert.-amylhexoxane-2-may be mentioned as examples , further azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-methylisobutyronitrile).
  • organic solvents which are not very miscible with water can be used as auxiliary solvents. All those organic diluents which have already been mentioned in connection with the description of the aqueous phase of the bead polymer formulations according to the invention are suitable.
  • the procedure is generally such that a homogeneous mixture of monomer mixture (a - c), one or more agrochemical active ingredients and optionally additives is first prepared.
  • This homogeneous mixture can be a solution or a finely divided dispersion.
  • an agrochemical active ingredient is insoluble or insufficiently soluble in the monomer mixture, it can be in finely divided form.
  • finely divided means that the active substance particles or active substance droplets have an average particle size of less than 2 ⁇ m, preferably less than 1 ⁇ m.
  • a finely divided dispersion can be produced with the aid of high-speed stirrers (preferably in the case of liquid active ingredients) or bead mills / ball mills (preferably in the case of solid active ingredients).
  • the process according to the invention can be carried out by using the mixture of monomer mixture, agrochemical active ingredient and optionally additives in the form of a solution, with the
  • auxiliary solvent is used to improve the solubility of the agrochemical active ingredient.
  • Suitable auxiliary solvents are organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the respective agrochemical active ingredient well.
  • the organic diluents already mentioned can preferably be used.
  • the process according to the invention can be carried out by adding a buffer reagent to the aqueous phase (B) so that the pH of the aqueous phase at the start of the polymerization is between 12 and 5, preferably between 10 and 6. - 16 -
  • the amounts of monomer mixture and agrochemical active ingredient are generally chosen so that in the homogeneous mixture used between 25 and 95% by weight of monomer mixture and between 5 and 75% by weight agrochemical active ingredient, preferably between 40 and 90% by weight. % of monomer mixture and between 10 and 60% by weight of agrochemical active ingredient are present.
  • 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 monomer mixture.
  • the amount of auxiliary solvent is generally between 30 and 300% by weight, based on the sum of the monomer mixture and agrochemical active ingredient.
  • the amount of aqueous phase is generally between 75 and
  • the amount of dispersant is generally between 0.05 and 2% by weight, preferably between 0.1 and 1% by weight, based on the aqueous phase.
  • the organic phase is added to the aqueous phase with stirring.
  • the temperature can be varied within a certain range. In general, temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 50 ° C. - 17 -
  • 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.
  • the mean particle size of the bead polymer decreases with increasing stirring speed.
  • the exact stirring speed for setting a certain predetermined bead size depends in individual cases on the reactor size, the reactor geometry and the stirrer geometry. It has proven to be expedient to determine the necessary stirring speed experimentally.
  • bead sizes are generally between 6 and 30 ⁇ m at speeds between 300 and 500 revolutions reached per minute.
  • the polymerization temperature can be varied within a wide range. It depends on the decomposition temperature of the initiator used. Generally 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.
  • 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. 70 ° C is started and the reaction temperature is increased as the polymerization conversion progresses.
  • the bead polymer can be isolated, for example by filtration or decanting, and, if appropriate, dried after washing. If it is desired to prepare a suspension of bead polymer in the aqueous phase, in most cases a further work-up is unnecessary. Any auxiliary solvent contained can be removed by distillation from the resulting mixture, optionally together with part of the water. - 18 -
  • the bead polymer formulations according to the invention are outstandingly suitable for applying agrochemical active ingredients to plants and / or their habitat. They ensure the release of the active components in the desired amount over a longer period of time.
  • bead polymer formulations according to the invention can be used as such either in solid form or as suspensions, if appropriate after prior dilution with water.
  • the application is carried out according to conventional methods, for example by pouring, spraying, spraying or
  • the application rate of the bead polymer formulations according to the invention can be varied within a substantial range. It is based on the respective agrochemical active ingredients and their content in the bead polymers.
  • the mixture is transferred to a stirred reactor which has previously been treated with 1.5 liters of a 1% by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted with sodium hydroxide solution to pH 8 50 wt .-% methyl methacrylate was filled.
  • the stirring speed is set to 700 revolutions per minute, and the temperature is kept at 60 ° C. for 3 hours, then at 78 ° C. for 10 hours and then at 85 ° C. for 2 hours.
  • the mixture is then cooled to room temperature within 2 hours. Dispersions of active ingredient-containing pearl polymers are obtained.
  • BeiX y z content of middle game no. (in g) (in g) (in g) Hydroxyethyl particle diameter methacrylate in the bead polymer copolymer particles
  • 3 different bead polymers with different copolymer compositions are produced.
  • x g of methyl methacrylate, y g of hydroxyethyl methacrylate, z g of ethylene glycol dimethacrylate, 100 g of imidachlopride and 30 g of finely divided silicon dioxide (HDK H2000 from Wacker) are mixed in a ball mill for 2 hours and then mixed with 3 g of dibenzoyl peroxide at room temperature with stirring.
  • the mixture is transferred to a stirred reactor which has previously been treated with 1.5 liters of a 1% strength by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted to pH 8 with sodium hydroxide solution .-% methyl methacrylate was filled.
  • the stirring speed is set to 500 revolutions per minute and the temperature is kept at 78 ° C. for 8 hours and then at 85 ° C. for 2 hours.
  • the mixture is then cooled to room temperature within 2 hours.
  • the bead polymer is isolated by settling and decanting, washed with cold water and dried at 50 ° C. in a drying cabinet.

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  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention relates to novel pearl polymerizate formulations, comprising I) a particle-shaped solid phase and II) an optional liquid phase. The solid phase contains: A) a copolymerizate consisting of a) 40 to 95 wt. % of a water-insoluble monomer; b) 5 to 35 wt. % of a water-soluble monomer and c) 0 to 25 wt. % of a cross-linking agent; B) at least one agrochemical active agent and C) optionally additives. The agrochemical active agent content ranges from 5 to 75 wt. % and the solid phase has a mean particle size ranging between 1 and 100 νm. The invention also relates to a method for the production of the novel formulations and their use in the application of agrochemical active agents.

Description

Perlpolymerisat-FormuiierungenBead polymer formulations
Die vorliegende Erfindung betrifft neue Perlpolymerisat-Formulierungen von agro- chemischen Wirkstoffen, ein Verfahren zur Herstellung dieser Zubereitungen und deren Verwendung zur Applikation von agrochemischen Wirkstoffen.The present invention relates to new bead polymer formulations of agrochemical active substances, a process for the preparation of these preparations and their use for the application of agrochemical active substances.
Aus der EP-A 0 201 214 sind bereits aus ethylenisch ungesättigten Monomeren herstellbare Mikropartikel bekannt, die pestizide Wirkstoffe enthalten und einen Teilchendurchmesser zwischen etwa 0,01 und 250 μm aufweisen. Nachteilig an diesen Zubereitungen ist jedoch, daß die aktiven Komponenten nicht immer mit der für die biologische Wirkung notwendigen Rate freigesetzt werden.EP-A 0 201 214 already discloses microparticles which can be prepared from ethylenically unsaturated monomers and which contain pesticidal active ingredients and have a particle diameter of between approximately 0.01 and 250 μm. However, a disadvantage of these preparations is that the active components are not always released at the rate necessary for the biological action.
Weiterhin wurden schon Formulierungen beschrieben, die leicht auswaschbare agro- chemische Wirkstoffe in mikroverkapselter Form in ungesättigten Polyesterharzen enthalten (vgl. EP-A 0 517 669). Auch in diesem Falle genügt die Freisetzungskinetik der mikroverkapselten Wirkstoffe nicht in allen Fällen den praktischen Anforderungen. Hydrophobe Wirkstoffe werden aus diesen Formulierungen nur sehr langsam freigesetzt.Furthermore, formulations have been described which contain easily washable agrochemical active ingredients in microencapsulated form in unsaturated polyester resins (cf. EP-A 0 517 669). In this case too, the release kinetics of the microencapsulated active ingredients do not always meet the practical requirements. Hydrophobic active ingredients are released very slowly from these formulations.
Ferner geht aus der EP-A 0 281 918 hervor, daß makroporöse, vernetzte Polystyrol- Perlpolymerisate als Träger für Agrochemikalien geeignet und im Pflanzenschutz anwendbar sind. Auch beim Einsatz dieser Präparate läßt allerdings die Geschwindigkeit und die Menge, in welcher die Agrochemikalien freigesetzt werden, häufig zu wünschen übrig.Furthermore, EP-A 0 281 918 shows that macroporous, crosslinked polystyrene bead polymers are suitable as carriers for agricultural chemicals and can be used in crop protection. Even when these preparations are used, however, the speed and the amount in which the agricultural chemicals are released often leave something to be desired.
Schließlich ist der US-A 4 269 959 zu entnehmen, daß schwach vernetzte Polystyrol- Perlpolymerisate flüssige Wirkstoffe, wie Agrochemikalien, aufsaugen können und die so beladenen Produkte sich als Slow-Release-Formulierungen einsetzen lassen. Die Wirkungsdauer derartiger Zubereitungen ist aber nicht immer ausreichend. - 2 -Finally, US Pat. No. 4,269,959 shows 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. - 2 -
Es wurden nun neue Perlpolymerisat-Formuiierungen gefunden, die ausNew bead polymer formulations have now been found, which consist of
I) einer teilchenförmigen, festen Phase, welcheI) a particulate solid phase which
A) Copolymerisat ausA) copolymer from
a) 40 bis 95 Gew.-% wasserunlöslichem Monomera) 40 to 95 wt .-% water-insoluble monomer
b) 5 bis 35 Gew.-% wasserlöslichem Monomerb) 5 to 35% by weight of water-soluble monomer
c) 0 bis 25 Gew.-% Vernetzer,c) 0 to 25% by weight of crosslinking agent,
undand
B) mindestens einen agrochemischen WirkstoffB) at least one agrochemical active ingredient
sowiesuch as
C) gegebenenfalls ZusatzstoffeC) optionally additives
enthält, wobei der Gehalt an agrochemischem Wirkstoff zwischen 5 und 75 Gew.-% liegt und die feste Phase eine mittlere Teilchengröße zwischen 1 und 100 μm aufweist,contains, the content of agrochemical active ingredient being between 5 and 75% by weight and the solid phase having an average particle size between 1 and 100 μm,
undand
II) gegebenenfalls einer flüssigen PhaseII) optionally a liquid phase
bestehen. - 3 -consist. - 3 -
Weiterhin wurde gefunden, daß sich erfindungsgemäße Perlpolymerisat-Formuiierungen herstellen lassen, indem manFurthermore, it has been found that bead polymer formulations according to the invention can be produced by:
A) eine organische Phase ausA) an organic phase
25 bis 95 Gew.-% eines Monomeren-Gemisches aus25 to 95 wt .-% of a monomer mixture
a) 40 bis 95 Gew.-% wasserunlöslichem Monomera) 40 to 95 wt .-% water-insoluble monomer
b) 5 bis 35 Gew.-% wasserlöslichem Monomerb) 5 to 35% by weight of water-soluble monomer
c) 0 bis 25 Gew.-% Vernetzer,c) 0 to 25% by weight of crosslinking agent,
5 bis 75 Gew.-% an mindestens einem agrochemischen Wirkstoff,5 to 75% by weight of at least one agrochemical active ingredient,
mindestens einem Initiator,at least one initiator,
gegebenenfalls Zusatzstoffenoptional additives
undand
gegebenenfalls einem mit Wasser wenig mischbaren organischen Solvens,optionally an organic solvent which is not very miscible with water,
B) in einer wäßrigen Phase ausB) in an aqueous phase
Wasser,Water,
mindestens einem Dispergiermittel undat least one dispersant and
gegebenenfalls einem Pufferreagenz - 4 -optionally a buffer reagent - 4 -
unter Rühren bei Temperaturen zwischen 0°C und 60°C fein verteilt,finely distributed with stirring at temperatures between 0 ° C and 60 ° C,
C) dann unter Temperaturerhöhung und unter Rühren polymerisiertC) then polymerized while raising the temperature and with stirring
D) und gegebenenfalls danach entwederD) and optionally afterwards either
α) das entstandene Perlpolymerisat isoliert, wäscht und trocknetα) isolates, washes and dries the resulting bead polymer
oderor
ß) gegebenenfalls enthaltene flüchtige, organische Substanzen abtrennt und so das Perlpolymerisat in wäßriger Suspension erhält.ß) any volatile organic substances present are separated off and the bead polymer is thus obtained in aqueous suspension.
Schließlich wurde gefunden, daß die erfindungsgemäßen Perlpolymerisat-Formuiierungen sehr gut zur Applikation von agrochemischen Wirkstoffen geeignet sind.Finally, it was found that the bead polymer formulations according to the invention are very well suited for the application of active agrochemicals.
Die erfindungsgemäßen Perlpolymerisat-Formuiierungen zeichnen sich durch eine Reihe von Vorteilen aus. So sind sie in der Lage, die aktiven Komponenten über einen recht langen Zeitraum in gleichmäßiger Menge freizusetzen. Besonders günstig ist, daß die Freisetzungsrate des Wirkstoffs in weiten Grenzen durch den Gehalt an wasserlöslichem Monomer gesteuert werden kann.The bead polymer formulations according to the invention are notable for a number of advantages. This enables them to release the active components in a uniform amount over a fairly long period of time. It is particularly favorable that the release rate of the active ingredient can be controlled within wide limits by the content of water-soluble monomer.
Die in den erfindungsgemäßen Perlpolymerisat-Formuiierungen vorhandenen Co- polymerisate sind durch die unter (a) bis (c) aufgeführten Bestandteile charakterisiert.The copolymers present in the bead polymer formulations according to the invention are characterized by the constituents listed under (a) to (c).
Unter der Bezeichnung wasserunlösliche Monomere (a) sind monoethylenisch ungesättigte Verbindungen zu verstehen, die sich bei 20 °C zu weniger als 5 Gew.-% in Wasser lösen. Bevorzugte wasserunlösliche Monomere (a) sind die Alkylester der Acrylsäure und Methacrylsäure, Styrol, Styrolderivate und Mischungen von Styrol und Acrylnitril sowie Vinyl-Derivate. Beispielhaft seien genannt: Styrol, alpha- Methylstyrol, Vinylchlorid, Vinylidenchlorid, Vinylacetat, Vinylpropionat, Vinyl- laurat, Vinyladipat, Methylmethacrylat, Methylacrylat, Ethylacrylat, Isopropyl- methacrylat, n-Propylmethacrylat, n-Butylacrylat, n-Butylmethacrylat, iso-Butyl- acrylat, iso-Butylmethacrylat, n-Hexylacrylat, n-Hexylmethacrylat, Ethylhexyl- acrylat, Ethylhexylmethacrylat, n-Octylacrylat, n-Octylmethacrylat, Decylacrylat, Decylmethacrylat, Dodecylacrylat, Dodecylmethacrylat, Stearylacrylat, Stearyl- methacrylat, Cyclohexylacrylat, und Cyclohexylmethacrylat. Auch das etwas besser wasserlösliche Acrylnitril kommt im Gemisch mit anderen Monomeren (a) anteilig in Betracht, vorzugsweise im Gemisch mit Styrol.The term water-insoluble monomers (a) is to be understood as meaning monoethylenically unsaturated compounds which dissolve in water at less than 5% by weight 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 and vinyl derivatives. Examples include: 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, n-butyl acrylate, n-butyl methacrylate, iso-butyl acrylate, iso-butyl methacrylate 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 hexyl acrylate, cyclohexyl acrylate. The somewhat more water-soluble acrylonitrile may also be used proportionately in a mixture with other monomers (a), preferably in a mixture with styrene.
Wasserlösliche Monomere (b) im Sinne der Erfindung sind monoethylenisch ungesättigte Verbindungen, die sich bei 20°C zu mehr als 5 Gew.-% in Wasser lösen. Als Beispiele seien genannt: Acrylsäure und ihre Alkalimetall- und Ammoniumsalze, Methacrylsäure und ihre Alkalimetall- und Ammoniumsalze, Hydroxyethylmeth- acrylat, Hydroxyethylacrylat, Diethylenglykolmonoacrylat, Diethylenglykolmono- methacrylat, Triethylenglykolmonoacrylat, Triethylenglykolmonomethacrylat, Tetra- ethylenglykolmonoacrylat, Tetraethylenglykolmonomethacrylat, Glycerinmono- acrylat, Aminoethylmethacrylat, Dimethylaminoethylmethacrylat, Acrylamid, Meth- acrylamid, Vinylpyrolidon und Vinylimidazol. Bevorzugt ist Hydroxyethyl- methacrylat.For the purposes of the invention, water-soluble monomers (b) are monoethylenically unsaturated compounds which dissolve in water at 20 ° C. to more than 5% by weight. Examples include: acrylic acid and its alkali metal and ammonium salts, methacrylic acid and its alkali metal and ammonium salts, hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, triethylene glycol monoacrylate, triethylene glycol tetramonomethyl methacrylate, triethylene glycol tetramonomethacrylate, methacrylate methacrylate, triethylene glycol tetramonomethyl methacrylate, , Acrylamide, methacrylamide, vinyl pyrolidone and vinyl imidazole. Hydroxyethyl methacrylate is preferred.
Der Anteil an wasserlöslichem Monomer (b) ist für die Wirkstofffreisetzung wesentlich. Über den Anteil an (b) läßt sich die Freisetzungsrate des agrochemischen Wirkstoffs in weiten Grenzen steuern. Je höher der Anteil an (b) ist, um so schneller wird der Wirkstoff abgegeben. Für die meisten praktischen Anwendungen liegt der Anteil von (b) im Bereich von 5 bis 35 Gew.-%. In vielen Fällen werden mit einem Anteil von (b) im Bereich von 7,5 bis 20 Gew.-% besonders gute Wirkungen erzielt.The proportion of water-soluble monomer (b) is essential for the active ingredient release. The release rate of the agrochemical active substance can be controlled within wide limits via the proportion of (b). The higher the proportion of (b), the faster the active ingredient is released. For most practical applications, the proportion of (b) is in the range from 5 to 35% by weight. In many cases, particularly good effects are achieved with a proportion of (b) in the range from 7.5 to 20% by weight.
Als Vernetzer (c) kommen Verbindungen mit mindestens zwei ethylenisch unge- sättigten Gruppen im Molekül in Betracht. Als Beispiele genannt seien: Allyl- methacrylat, Ethylenglykoldimethacrylat, Ethylenglykoldiacrylat, Butandioldiacrylat, - 6 -Crosslinkers (c) are compounds having at least two ethylenically unsaturated groups in the molecule. Examples include: allyl methacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, butanediol diacrylate, - 6 -
Butandioldimethacrylat, Hexandioldimethacrylat, Triethylenglykoldimethacrylat, Te- traethylenglykoldimethacrylat, Trimethylolpropantriacrylat, Pentaerythritoltetrameth- acrylat und Divinylbenzol. Bevorzugt sind Ethylenglycoldimethacrylat und Divinyl- benzol.Butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol tetramethacrylate and divinylbenzene. Ethylene glycol dimethacrylate and divinyl benzene are preferred.
Im Copolymerisat kann der Anteil an Vernetzer (c) innerhalb eines bestimmten Bereiches variiert werden. Der Gehalt an (Vernetzer (c) liegt im allgemeinen zwischen 0 und 25 Gew.-%, vorzugsweise zwischen 0,1 und 15 Gew.-%, besonders bevorzugt zwischen 0,5 und 10 Gew.-%.The proportion of crosslinking agent (c) in the copolymer can be varied within a certain range. The (crosslinker (c) content is generally between 0 and 25% by weight, preferably between 0.1 and 15% by weight, particularly preferably between 0.5 and 10% by weight.
Unter agrochemischen Wirkstoffen sind im vorliegenden Zusammenhang alle zur Pflanzenbehandlung üblichen Substanzen zu verstehen. Vorzugsweise genannt seien Fungizide, Bakterizide, Insektizide, Akarizide, Nematizide, Herbizide, Pflanzen- wuchsregulatoren, Pflanzennährstoffe und Repellents.In the present context, agrochemical active substances are understood to mean all substances customary for plant treatment. Fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, plant growth regulators, plant nutrients and repellents may preferably be mentioned.
Als Beispiele für Fungizide seien genannt:Examples of fungicides are:
2-Aminobutan; 2-Anilino-4-methyl-6-cyclopropyl-pyrimidin; 2',6'-Dibromo-2-me- thyl-4'-trifluoromethoxy-4'-trifluoromethyl- 1 ,3-thiazol-5-carboxanilid; 2,6-Dichloro-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)-benzamid; (E)-2-Methoximino-N-methyl-2-(2-phenoxy- phenyl) acetamid; 8-Hydroxychinolinsulfat; Methyl-(E)-2-{2-[6-(2-cyanophenoxy)- pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylat; Methyl-(E)-methoximino[alpha-(o- tolyloxy)-o-tolyl]-acetat; 2-Phenylphenol (OPP),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, Anilazin, Azaconazol,Aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Bion, Biphenyl, Bitertanol, Blasticidin- S, Bromuconazole, Bupirimate, Buthiobate,Benalaxyl, Benodanil, Benomyl, Binapacryl, Bion, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calciumpolysulfid, Captafol, Captan, Carbendazim, Carboxin, ChinomethionatCalcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate
(Quinomethionat), Chloroneb, Chloropicrin, Chlorothalonil, Chlozolinat, Cufraneb,(Quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb,
Cymoxanil, Cyproconazole, Cyprofuram,Cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, Diclobutrazol, Dichlofluanid, Diclomezin, Dicloran, Diethofencarb, Difenoconazol, Dimethirimol, Dimethomorph, Diniconazol, Dinocap, Diphenylamin,Dichlorophen, diclobutrazole, dichlofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine,
Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon, - 7 -Dipyrithion, Ditalimfos, Dithianon, Dodine, Drazoxolon, - 7 -
Edifenphos, Epoxyconazole, Ethirimol, Etridiazol,Edifenphos, epoxyconazole, ethirimol, etridiazole,
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpro- pimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanil, Flutriafol, Folpet, Fosetyl-Aluminium, Fthalide, Fuberidazol, Furalaxyl, Furmecyclox,Fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole, flusilazole, flusulfamide, flutolanol, futrianol, flutrianol, flutrianol Furalaxyl, furmecyclox,
Guazatine,Guazatine,
Hexachlorobenzol, Hexaconazol, Hymexazol,Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobenfos (IBP), Iprodion, Isoprothiolan, Kasugamycin, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil,Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, Mancozeb, Maneb, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutan
Nickeldimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,Nickel dimethyldithiocarbamate, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadixyl, Oxamocarb, Oxycarboxin,
Pefurazoat, Penconazol, Pencycuron, Phosdiphen, Pimaricin, Piperalin, Polyoxin, Probenazol, Prochloraz, Procymidon, Propamocarb, Propiconazole, Propineb, Pyrazophos, Pyrifenox, Pyrimethanil, Pyroquilon,Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),Quintozen (PCNB),
Tebuconazol, Tecloftalam, Techazen, Tetraconazol, Thiabendazol, Thicyofen, Thio- phanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflumizol, Triforin, Triticonazol, Validamycin A, Vinclozolin,Tebuconazole, tecloftalam, Techazen, tetraconazole, thiabendazole, Thicyofen, thio Phanat-methyl, thiram, Tolclophos-methyl, tolylfluanid, triadimefon, triadimenol, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole, validamycin A, vinclozolin,
Zineb, Ziram,Zineb, Ziram,
8-tert.-Butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-l,4-dioxa-spiro-[4,5]decan, N-(R)-[ 1 -(4-Chlorphenyl)-ethyl]-2,2-dichlor- 1 -ethyl-3t-methyl- 1 r-cyclopropancar- bonsäureamid (Diastereomerengemisch oder einzelne Isomere), [2-Methyl-l-[[[l-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl]-carbaminsäure-8-tert-butyl-2- (N-ethyl-Nn-propyl-amino) -methyl-l, 4-dioxa-spiro- [4,5] decane, N- (R) - [1 - (4- Chlorophenyl) ethyl] -2,2-dichloro-1-ethyl-3t-methyl-1 r-cyclopropanecarboxamide (mixture of diastereomers or individual isomers), [2-methyl-l - [[[l- (4-methylphenyl) -ethyl] -amino] -carbonyl] -propyl] -carbamic acid-
1 -methylethylester,1 -methylethyl ester,
1 -Methyl-cyclohexyl- 1 -carbonsäure-(2,3 -dichlor-4-hydroxy)-anilid, 2-[2-(l-Chlor-cyclopropyl)-3-(2-chlo henyl)-2-hydroxypropyl]-2,4-dihydro-[l,2,4]- triazol-3-thion und l-(3,5-Dimethyl-isoxazol-4-sulfonyl)-2-chlor-6,6-difluor-[l ,3]-dioxolo-[4,5-f]- benzimidazol. - 8 -1-methyl-cyclohexyl-1-carboxylic acid- (2,3-dichloro-4-hydroxy) -anilide, 2- [2- (l-chloro-cyclopropyl) -3- (2-chloro-henyl) -2-hydroxypropyl] -2,4-dihydro- [l, 2,4] - triazol-3-thione and l- (3,5-dimethyl-isoxazole-4-sulfonyl) -2-chloro-6,6-difluoro- [l, 3] -dioxolo- [4,5-f] - benzimidazole. - 8th -
Als Beispiele für Bakterizide seien genannt:Examples of bactericides are:
Bronopol, Dichlorophen, Nitrapyrin, Nickel-Dimethyldithiocarbamat, Kasugamycin, Octhilinon, Furancarbonsäure, Oxytetracyclin, Probenazol, Streptomycin, Teclofta- lam, Kupfersulfat und andere Kupfer-Zubereitungen.Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, teclofalam, copper sulfate and other copper preparations.
Als Beispiele für Insektizide, Akarizide und Nematizide seien genannt:Examples of insecticides, acaricides and nematicides are:
Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz,Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz,
Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, 4-Bromo-2-(4-chloφhenyl)-l-(ethoxymethyl)-5-(trifluorome- thyl)-lH-pyrrole-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, Betacyfluthrin,Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, 4-Bromo-2- (4-chloφhenyl) -l- (ethoxymethyl) -5- (trifluoromethyl) -lH-pyrrole-3- carbonitrile, bendiocarb, benfuracarb, bensultap, betacyfluthrin,
Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarb- oxin, Butylpyridaben,Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Butocarboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho- carb, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlormephos, N-[(6-Chloro-Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, 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,3-pyridinyl) -methyl] -N'-cyano-N-methyl-ethanimidamide, chlorpyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine
Deltamethrin, Demeton-M, Demeton-S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat,Deltamethrin, Demeton-M, Demeton-S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlofenthion, Dichlorvos, Dicliphos, Dicrotophos, Diethion, Diflu- benzuron, Dimethoat,
Dimethylvinphos, Dioxathion, Disulfoton,Dimethylvinphos, dioxathione, disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Etho- prophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb,Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethoprophos, Etrimphos, Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb,
Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate,Fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate, fenthion, fenvalerate,
Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxuron,Fipronil, fluazinam, fluazuron, flucycloxuron, flucythrinate, flufenoxuron,
Flufenprox, Fluvahnate, Fonophos, Formothion, Fosthiazat, Fubfenprox,Flufenprox, Fluvahnate, Fonophos, Formothion, Fosthiazat, Fubfenprox,
Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox, - 9 -Furathiocarb, HCH, Heptenophos, Hexaflumuron, Hexythiazox, - 9 -
Imidacloprid, Iprobenfos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda-cyhalothrin, Lufenuron,Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyd, Methacrifos, Metha- midophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Mono- crotophos, Moxidectin,Malathion, Mecarbam, Mevinphos, Mesulfenphos, Metaldehyde, Methacrifos, Methamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, Nitenpyram,Naled, NC 184, Nitenpyram,
Omethoat, Oxamyl, Oxydemethon M, Oxydeprofos,Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phos- phamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Pro- mecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrachlophos,Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenophos, Promecarb, Propaphos, Propoxur, Prothiophos, Prothoat, Pymetrozin, Pyrach
Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,Pyridaphenthion, Pyresmethrin, Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,Quinalphos,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Teme- phos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox,Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Temefos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox,
Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Transfluthrin, Triarathen,Thiomethon, Thionazin, Thuringiensin, Tralomethrin, Transfluthrin, Triarathen,
Triazophos, Triazuron, Trichlorfon, Triflumuron, Trimethacarb,Triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,
Vamidothion, XMC, Xylylcarb, Zetamethrin.Vamidothione, XMC, xylylcarb, zetamethrin.
Als Beispiele für Herbizide seien genannt:Examples of herbicides are:
Anilide, wie z.B. Diflufenican und Propanil; Arylcarbonsäuren, wie z.B. Dichlor- picolinsäure, Dicamba und Picloram; Aryloxyalkansäuren, wie z.B. 2,4-D, 2,4-DB, 2,4-DP, Fluroxypyr, MCPA, MCPP und Triclopyr; Aryloxy-phenoxy-alkan- säureester, wie z.B. Diclofop-methyl, Fenoxaprop-ethyl, Fluazifop-butyl, Haloxyfop- methyl und Quizalofop-ethyl; Azinone, wie z.B. Chloridazon und Norflurazon;Anilides, e.g. Diflufenican and Propanil; Aryl carboxylic acids, e.g. Dichloropicolinic acid, dicamba and picloram; Aryloxyalkanoic acids, e.g. 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; Aryloxy-phenoxy-alkanoic acid esters, e.g. Diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; Azinones, e.g. Chloridazon and norflurazon;
Carbamate, wie z.B. Chloφropham, Desmedipham, Phenmedipham und Propham; Chloracetanilide, wie z.B. Alachlor, Acetochlor, Butachlor, Metazachlor, Metolachlor, Pretilachlor und Propachlor; Dinitroaniline, wie z.B. Oryzalin, Pendimethalin und Trifl uralin; Dipheny lether, wie z.B. Acifluorfen, Bifenox, Fluoroglycofen, Fomesafen, Halosafen, Lactofen und Oxyfluorfen; Harnstoffe, wie z.B. Chlortoluron, Diuron, Fluometuron, Isoproturon, Linuron und Methabenz- - 10 -Carbamates, such as, for example, chloropropham, desmedipham, phenmedipham and propham; Chloroacetanilides such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; Dinitroaniline such as Oryzalin, Pendimethalin and Trifl uralin; Diphenyl ethers such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; Ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenz - 10 -
thiazuron; Hydroxylamine, wie z.B. Alloxydim, Clethodim, Cycloxydim, Sethoxydim und Tralkoxydim; Imidazolinone, wie z.B. Imazethapyr, Imazametha- benz, Imazapyr und Imazaquin; Nitrile, wie z.B. Bromoxynil, Dichlobenil und Ioxynil; Oxyacetamide, wie z.B. Mefenacet; Sulfonylharnstoffe, wie z.B. Amidosul- furon, Bensulfuron-methyl, Chlorimuron-ethyl, Chlorsulfuron, Cinosulfuron, Metsul- furon-methyl, Nicosulfuron, Primisulfuron, Pyrazosulfuron-ethyl, Thifensulfuron- methyl, Triasulfuron und Tribenuron-methyl; Thiolcarbamate, wie z.B. Butylate, Cycloate, Diallate, EPTC, Esprocarb, Molinate, Prosulfocarb, Thiobencarb und Triallate; Triazine, wie z.B. Atrazin, Cyanazin, Simazin, Simetryne, Terbutryne und Terbutylazin; Triazinone, wie z.B. Hexazinon, Metamitron und Metribuzin; Sonstige, wie z.B. Aminotriazol, 4-Amino-N-(l,l-dimetylethyl)-4,5-dihydro-3-(l- methylethyl)-5-oxo-lH-l,2,4-triazole-l-carboxamid, Benfuresate, Bentazone, Cin- methylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluoro- chloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate und Tridiphane.thiazuron; Hydroxylamines, e.g. Alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; Imidazolinones, e.g. Imazethapyr, imazamethabenz, imazapyr and imazaquin; Nitriles, e.g. Bromoxynil, dichlobenil and ioxynil; Oxyacetamides, e.g. Mefenacet; Sulfonylureas, e.g. Amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; Thiol carbamates, e.g. Butylates, cycloates, dialallates, EPTC, esprocarb, molinates, prosulfocarb, thiobencarb and triallates; Triazines, e.g. Atrazin, cyanazin, simazin, simetryne, terbutryne and terbutylazin; Triazinones, e.g. Hexazinone, metamitron and metribuzin; Others, such as Aminotriazole, 4-amino-N- (l, l-dimetylethyl) -4,5-dihydro-3- (l-methylethyl) -5-oxo-lH-l, 2,4-triazole-l-carboxamide, benfuresate, Bentazone, Cin- methylin, Clomazone, Clopyralid, Difenzoquat, Dithiopyr, Ethofumesate, Fluorochloridone, Glufosinate, Glyphosate, Isoxaben, Pyridate, Quinchlorac, Quinmerac, Sulphosate and Tridiphane.
Als Beispiele für Pflanzenwuchsregulatoren seien Chlorcholinchlorid und Ethephon genannt.Chlorcholine chloride and ethephon are examples of plant growth regulators.
Als Beispiele für Pflanzennährstoffe seien übliche anorganische oder organischeExamples of plant nutrients are customary inorganic or organic
Dünger zur Versorgung von Pflanzen mit Makro- und/oder Mikronährstoffen genannt.Fertilizer for supplying plants with macro and / or micronutrients called.
Als Beispiele für Repellents seien Diethyltolylamid, Ethylhexandiol und Buto- pyronoxyl genannt.Examples of repellents are diethyltolylamide, ethylhexanediol and butopyronoxyl.
Als Zusatzstoffe, die in den erfindungsgemäßen Perlpolymerisat-Formuiierungen in der festen Phase vorhanden sein können, kommen alle diejenigen Substanzen in Frage, die üblicherweise in Pflanzenbehandlungsmitteln als Additive einsetzbar sind. Hierzu gehören zum Beispiel Weichmacher, Farbstoffe, Antioxidantien, Kältestabilisatoren und Füllstoffe. - 11 -Suitable additives which can be present in the solid phase in the bead polymer formulations according to the invention are all those substances which are customarily usable as additives in plant treatment compositions. These include plasticizers, dyes, antioxidants, cold stabilizers and fillers. - 11 -
Als Weichmacher in Betracht kommen im vorliegenden Fall flüssige oder feste indifferente Substanzen mit einem geringen Dampfdruck und einem Molekulargewicht zwischen 150 und 1000, die ohne chemische Reaktion vorzugsweise durch ihr Löse- oder Quellvermögen mit hochpolymeren Stoffen in Wechselwirkung treten und dabei ein homogenes physikalisches System mit diesen bilden.Suitable plasticizers in the present case are liquid or solid indifferent substances with a low vapor pressure and a molecular weight between 150 and 1000, which interact without a chemical reaction, preferably through their solvent or swelling capacity, with highly polymeric substances and thereby a homogeneous physical system with them form.
Als Farbstoffe kommen lösliche oder wenig lösliche Farbpigmente in Betracht, wie beispielsweise Titandioxid, Farbruss oder Zinkoxid.Colorants which are soluble or sparingly soluble are pigments, such as, for example, titanium dioxide, carbon black or zinc oxide.
Als Antioxidantien kommen alle üblicherweise für diesen Zweck in Pflanzenbehandlungsmitteln einsetzbaren Stoffe in Frage. Bevorzugt sind sterisch gehinderte Phenole und alkylsubstituierte Hydroxyanisole und Hydroxytoluole.Suitable antioxidants are all substances which can normally be used for this purpose in plant treatment products. Sterically hindered phenols and alkyl-substituted hydroxyanisoles and hydroxytoluenes are preferred.
Als Kältestabilisatoren kommen alle üblicherweise für diesen Zweck in Pflanzenbehandlungsmitteln einsetzbaren Stoffe in Betracht. Vorzugsweise in Frage kommen Harnstoff, Glycerin oder Propylenglykol.Suitable cold stabilizers are all substances which can normally be used for this purpose in plant treatment products. Urea, glycerol or propylene glycol are preferred.
Als Füllstoffe kommen in erster Linie anorganische Partikel, wie z. B. Carbonate, Silikate und Oxide mit einer mittleren Teilchengröße von 0,005 bis 5 μm, vorzugsweise, 0,02 bis 2 μm in Betracht. Besonders gut geeignet sind Siliziumdioxid, sogenannte hochdisperse Kieselsäure, Kieselgele, sowie natürliche und synthetische Silikate und Alumosilikate.As fillers come primarily inorganic particles, such as. B. carbonates, silicates and oxides with an average particle size of 0.005 to 5 microns, preferably 0.02 to 2 microns into consideration. Silicon dioxide, so-called highly disperse silica, silica gels, and natural and synthetic silicates and aluminosilicates are particularly suitable.
Der Gehalt an den einzelnen Komponenten kann in den erfindungsgemäßen Perlpolymerisat-Formuiierungen innerhalb eines größeren Bereiches variiert werden. So liegen in der festen Phase die KonzentrationenThe content of the individual components can be varied within a substantial range in the bead polymer formulations according to the invention. The concentrations are in the solid phase
an Copolymerisat (A) im allgemeinen zwischen 25 und 95 Gew.-%, vorzugs- weise zwischen 40 und 90 Gew.-%, - 12 -of copolymer (A) generally between 25 and 95% by weight, preferably between 40 and 90% by weight, - 12 -
an agrochemischen Wirkstoffen (B) im allgemeinen zwischen 5 und 75 Gew.-%, vorzugsweise zwischen 10 und 60 Gew.-% undof agrochemical active ingredients (B) in general between 5 and 75% by weight, preferably between 10 and 60% by weight and
an Zusatzstoffen (C) im allgemeinen zwischen 0 und 30 Gew.-%, vorzugsweise zwischen 0 und 15 Gew.-%.of additives (C) generally between 0 and 30% by weight, preferably between 0 and 15% by weight.
In den erfindungsgemäßen Perlpolymerisat-Formuiierungen kann die Teilchengröße der festen Partikel innerhalb eines bestimmten Bereiches variiert werden. Sie liegt im allgemeinen zwischen 1 und 100 μm, vorzugsweise zwischen 5 und 50 μm.In the bead polymer formulations according to the invention, the particle size of the solid particles can be varied within a certain range. It is generally between 1 and 100 μm, preferably between 5 and 50 μm.
Die erfindungsgemäßen Perlpolymerisat-Formuiierungen können entweder als teil- chenförmige feste Phase oder als Dispersion fester Teilchen in einer flüssigen Phase vorliegen.The bead polymer formulations according to the invention can be present either as a particulate solid phase or as a dispersion of solid particles in a liquid phase.
Ist eine flüssige Phase vorhanden, so besteht diese im wesentlichen aus Wasser.If a liquid phase is present, it essentially consists of water.
Zusätzlich können Komponenten enthalten sein, die bei der Herstellung der erfindungsgemäßen Perlpolymerisat-Formuiierungen eingesetzt werden und in der flüssigen Phase verbleiben. Als solche Komponenten in Betracht kommen mit Wasser wenig mischbare, organische Solventien, Dispergiermittel (Schutzkolloide) und Pufferreagenzien.It can also contain components which are used in the preparation of the bead polymer formulations according to the invention and remain in the liquid phase. Possible components of this type are water-immiscible organic solvents, dispersants (protective colloids) and buffer reagents.
Als organische Solventien kommen dabei alle üblichen organischen Lösungsmittel in Frage, die einerseits mit Wasser wenig mischbar sind, andererseits aber die eingesetzten agrochemischen Wirkstoffe gut lösen. Als Beispiele für derartige Solventien genannt seien aromatische Kohlenwasserstoffe, wie Toluol und Xylol, weiterhin halogenierte Kohlenwasserstoffe, wie Tetrachlormethan, Chloroform, Methylenchlorid und Dichlorethan, und außerdem auch Ester, wie Ethylacetat.Suitable organic solvents here are all customary organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the agrochemical active ingredients well. Examples of such solvents are aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride and dichloroethane, and also esters such as ethyl acetate.
Als Dispergiermittel kommen alle üblicherweise für diesen Zweck eingesetzten Sub- stanzen in Betracht. Vorzugsweise genannt seien natürliche und synthetische wasserlösliche Polymere, wie Gelatine, Stärke und Cellulosederivate, insbesondere Cellu- - 13 -All substances customarily used for this purpose can be considered as dispersants. Natural and synthetic water-soluble polymers such as gelatin, starch and cellulose derivatives, in particular cellulose - 13 -
loseester und Celluloseether, ferner Polyvinylalkohol, Polyvinylpyrrolidon, Poly- acrylsäure, Polymethacrylsäure und Copolymerisate aus (Meth)acrylsäure und (Meth)acrylsäureestern, und außerdem auch mit Alkalimetallhydroxid neutralisierte Copolymerisate aus Methacrylsäure und Methacrylsäureester.loose esters and cellulose ethers, also polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid and copolymers of (meth) acrylic acid and (meth) acrylic acid esters, and also also copolymers of methacrylic acid and methacrylic acid ester neutralized with alkali metal hydroxide.
Als Pufferreagenzien in Frage kommen alle üblicherweise für diesen Zweck eingesetzten Substanzen. Vorzugsweise genannt seien Phosphat- und Borat-Salze.All substances normally used for this purpose can be used as buffer reagents. Phosphate and borate salts are preferred.
Die Mengen an den erwähnten zusätzlichen Substanzen in der wäßrigen Phase können innerhalb eines größeren Bereiches variiert werden. Die Konzentration ist abhängig von den Mengen, in denen diese Substanzen bei der Herstellung der erfindungsgemäßen Perlpolymerisat-Formuiierungen eingesetzt werden, sowie von der Art, in der nach der Polymerisation aufgearbeitet wird.The amounts of the additional substances mentioned in the aqueous phase can be varied within a substantial range. The concentration depends on the amounts in which these substances are used in the preparation of the bead polymer formulations according to the invention, and on the manner in which they are worked up after the polymerization.
Die Herstellung der erfindungsgemäßen Perlpolymerisat-Formuiierungen erfolgt nach der Verfahrensweise der Suspensionspolymerisation.The bead polymer formulations according to the invention are prepared by the suspension polymerization procedure.
Unter dem Begriff Suspensionspolymerisation wird ein Verfahren verstanden, bei dem ein Monomer oder ein monomerhaltiges Gemisch, das einen im Monomer(en) löslichen Initiator enthält, in einer mit dem Monomer(en) im wesentlichen nicht mischbaren Phase, die ein Dispergiermittel enthält, in Form von Tröpfchen, gegebenenfalls im Gemisch mit kleinen, festen Partikeln, verteilt wird und durch Temperaturerhöhung unter Rühren ausgehärtet wird. Weitere Einzelheiten der Suspensionspolymerisation werden beispielsweise in der Publikation "Polymer Processes", herausgegeben von C.E.Schildknecht, publiziert 1956 durch InterscienceThe term suspension polymerization is understood to mean a process in which a monomer or a monomer-containing mixture which contains an initiator which is soluble in the monomer (s) in the form in a phase which is essentially immiscible with the monomer (s) and which contains a dispersant of droplets, optionally in a mixture with small, solid particles, is distributed and cured by increasing the temperature with stirring. Further details of the suspension polymerization are, for example, in the publication "Polymer Processes", edited by C.E. Schildknecht, published in 1956 by Interscience
Publishers, Inc. New York, im Kapitel "Polymerization in Suspension" auf den Seiten 69 bis 109 beschrieben.Publishers, Inc. New York, in the chapter "Polymerization in Suspension" on pages 69 to 109.
Die bei der Durchführung des erfindungsgemäßen Verfahrens als Ausgangsmateria- lien benötigten Monomeren-Gemische sind durch die unter (a) bis (c) aufgeführtenThe monomer mixtures required as starting materials when carrying out the process according to the invention are those listed under (a) to (c)
Bestandteile charakterisiert. Bevorzugt in Frage kommen diejenigen Komponenten, - 14 -Components characterized. Those components are preferred, - 14 -
die bereits im Zusammenhang mit der Beschreibung der Copolymerisate genannt wurden.which have already been mentioned in connection with the description of the copolymers.
Als agrochemische Wirkstoffe können bei der Durchführung des erfindungsgemäßen Verfahrens alle diejenigen zur Behandlung von Pflanzen verwendbaren Substanzen eingesetzt werden, die schon im Zusammenhang mit der Beschreibung der erfindungsgemäßen Perlpolymerisat-Formuiierungen als agrochemische Wirkstoffe genannt wurden.All those substances which can be used for the treatment of plants and which have already been mentioned as agrochemical active substances in connection with the description of the bead polymer formulations according to the invention can be used as agrochemical active substances when carrying out the process according to the invention.
Als Initiatoren können bei der Durchfuhrung des erfindungsgemäßen Verfahrens alle üblicherweise für die Einleitung von Polymerisationen verwendbaren Substanzen eingesetzt werden. Vorzugsweise in Betracht kommen öllösliche Initiatoren. Beispielhaft genannt seien Peroxiverbindungen, wie Dibenzoylperoxid, Dilaurylperoxid, Bis(p-chlorbenzoylperoxid), Dicyclohexylperoxidicarbonat, tert.-Butylperoctoat, 2,5- Bis-(2-ethylhexanoylperoxi)-2,5-dimethylhexan und tert.-Amylperoxi-2-ethylhexan, desweiteren Azoverbindungen, wie 2,2'-Azobis(isobutyronitril) und 2,2'-Azobis(2- methylisobutyronitril) .When carrying out the process according to the invention, all substances which can usually be used for initiating polymerizations can be used as initiators. Oil-soluble initiators are preferred. Peroxy compounds such as dibenzoyl peroxide, dilauryl peroxide, bis (p-chlorobenzoyl peroxide), dicyclohexyl peroxidicarbonate, tert.-butyl peroctoate, 2,5-bis (2-ethylhexanoyl peroxi) -2,5-dimethylhexane and tert.-amylhexoxane-2-may be mentioned as examples , further azo compounds such as 2,2'-azobis (isobutyronitrile) and 2,2'-azobis (2-methylisobutyronitrile).
Als Zusatzstoffe können bei der Durchführung des erfindungsgemäßen Verfahrens alle diejenigen Substanzen eingesetzt werden, die schon im Zusammenhang mit derWhen carrying out the method according to the invention, all those substances can be used as additives which are already in connection with the
Beschreibung der erfϊndungsgemäßen Perlpolymerisat-Formuiierungen als Zusatzstoffe genannt wurden.Description of the bead polymer formulations according to the invention were mentioned as additives.
Bei der Durchführung des erfindungsgemäßen Verfahrens können mit Wasser wenig mischbare, organische Solventien als Hilfslösungsmittel eingesetzt werden. In Betracht kommen dabei alle diejenigen organischen Verdünnungsmittel, die bereits im Zusammenhang mit der Beschreibung der wäßrigen Phase der erfindungsgemäßen Perlpolymerisat-Formuiierungen genannt wurden.When carrying out the process according to the invention, organic solvents which are not very miscible with water can be used as auxiliary solvents. All those organic diluents which have already been mentioned in connection with the description of the aqueous phase of the bead polymer formulations according to the invention are suitable.
Auch die bei der Durchführung des erfindungsgemäßen Verfahrens als Dispergiermittel bzw. Pufferreagenzien in Frage kommenden Substanzen wurden schon im Zu- - 15 -The substances which are suitable as dispersants or buffer reagents when carrying out the process according to the invention were also - 15 -
sammenhang mit der Beschreibung der wäßrigen Phase der erfindungsgemäßen Perlpolymerisat-Formuiierungen erwähnt.mentioned in connection with the description of the aqueous phase of the bead polymer formulations according to the invention.
Bei der Durchführung des erfindungsgemäßen Verfahrens geht man im allgemeinen so vor, daß man zunächst eine homogene Mischung aus Monomerengemisch (a - c), einem oder mehreren agrochemischen Wirkstoffen und gegebenenfalls Zusatzstoffen herstellt. Bei dieser homogenen Mischung kann es sich um eine Lösung oder auch um eine feinteilige Dispersion handeln.When carrying out the process according to the invention, the procedure is generally such that a homogeneous mixture of monomer mixture (a - c), one or more agrochemical active ingredients and optionally additives is first prepared. This homogeneous mixture can be a solution or a finely divided dispersion.
Wenn ein agrochemischer Wirkstoff in der Monomermischung nicht oder unzureichend löslich ist, kann er in feinteilig dispergierter Form vorliegen. Feinteilig heißt in diesem Zusammenhang, daß die Wirkstoffpartikel bzw. Wirkstofftröpfchen eine mittlere Teilchengröße von weniger als 2 μm, vorzugsweise weniger als 1 μm aufweisen. Die Herstellung einer feinteiligen Dispersion kann mit Hilfe von Schnell- rührern (bevorzugt bei flüssigen Wirkstoffen) oder Perlmühlen/Kugelmühlen (bevorzugt bei festen Wirkstoffen) durchgeführt werden.If an agrochemical active ingredient is insoluble or insufficiently soluble in the monomer mixture, it can be in finely divided form. In this context, finely divided means that the active substance particles or active substance droplets have an average particle size of less than 2 μm, preferably less than 1 μm. A finely divided dispersion can be produced with the aid of high-speed stirrers (preferably in the case of liquid active ingredients) or bead mills / ball mills (preferably in the case of solid active ingredients).
In einer bevorzugten Variante läßt sich das erfindungsgemäße Verfahren in der Weise durchführen, daß man das Gemisch aus Monomerengemisch, agrochemischem Wirkstoff und gegebenenfalls Zusatzstoffen in Form einer Lösung einsetzt, wobei zurIn a preferred variant, the process according to the invention can be carried out by using the mixture of monomer mixture, agrochemical active ingredient and optionally additives in the form of a solution, with the
Verbesserung der Löslichkeit des agrochemischen Wirkstoffes ein Hilfslösungsmittel eingesetzt wird. Geeignete Hilfslösungsmittel sind organische Solventien, die einerseits mit Wasser wenig mischbar sind, andererseits aber den jeweiligen agrochemischen Wirkstoff gut lösen. Bevorzugt verwendbar sind die bereits genannten organi- sehen Verdünnungsmittel.An auxiliary solvent is used to improve the solubility of the agrochemical active ingredient. Suitable auxiliary solvents are organic solvents which, on the one hand, are not very miscible with water, but on the other hand dissolve the respective agrochemical active ingredient well. The organic diluents already mentioned can preferably be used.
In einer weiteren bevorzugten Variante kann das erfindungsgemäße Verfahren so durchgeführt werden, daß man der wäßrigen Phase (B) ein Pufferreagenz zufügt, so daß der pH-Wert der wäßrigen Phase bei Beginn der Polymerisation einen Wert zwi- sehen 12 und 5, vorzugsweise zwischen 10 und 6 aufweist. - 16 -In a further preferred variant, the process according to the invention can be carried out by adding a buffer reagent to the aqueous phase (B) so that the pH of the aqueous phase at the start of the polymerization is between 12 and 5, preferably between 10 and 6. - 16 -
Die Mengenverhältnisse an den eingesetzten Komponenten können bei der Durchführung des erfindungsgemäßen Verfahrens innerhalb eines größeren Bereiches variiert werden.The proportions of the components used can be varied within a substantial range when carrying out the process according to the invention.
Die Mengen an Monomerengemisch und agrochemischem Wirkstoff werden im allgemeinen so gewählt, daß in dem eingesetzten homogenen Gemisch zwischen 25 und 95 Gew.-% an Monomerengemisch und zwischen 5 und 75 Gew.-% an agrochemischem Wirkstoff, vorzugsweise zwischen 40 und 90 Gew.-% an Monomerengemisch und zwischen 10 und 60 Gew.-% an agrochemischem Wirkstoff vorhanden sind.The amounts of monomer mixture and agrochemical active ingredient are generally chosen so that in the homogeneous mixture used between 25 and 95% by weight of monomer mixture and between 5 and 75% by weight agrochemical active ingredient, preferably between 40 and 90% by weight. % of monomer mixture and between 10 and 60% by weight of agrochemical active ingredient are present.
Initiatoren werden im allgemeinen in Mengen zwischen 0,05 und 2,5 Gew.-%, vorzugsweise zwischen 0,2 und 1,5 Gew.-%, bezogen auf die Monomerenmischung, eingesetzt.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 monomer mixture.
Die Menge an Hilfslösungsmittel beträgt im allgemeinen zwischen 30 und 300 Gew.-%, bezogen auf die Summe aus Monomerengemisch und agrochemischem Wirkstoff.The amount of auxiliary solvent is generally between 30 and 300% by weight, based on the sum of the monomer mixture and agrochemical active ingredient.
Die Menge an wäßriger Phase beträgt im allgemeinen zwischen 75 undThe amount of aqueous phase is generally between 75 and
1200 Gew.-%, vorzugsweise zwischen 100 und 500 Gew.-%, bezogen auf die Summe aus Monomerengemisch und agrochemischem Wirkstoff.1200 wt .-%, preferably between 100 and 500 wt .-%, based on the sum of the monomer mixture and agrochemical active ingredient.
Die Menge an Dispergiermittel beträgt im allgemeinen zwischen 0,05 und 2 Gew.-%, vorzugsweise zwischen 0,1 und 1 Gew.-%, bezogen auf die wäßrige Phase.The amount of dispersant is generally between 0.05 and 2% by weight, preferably between 0.1 and 1% by weight, based on the aqueous phase.
Im ersten Schritt des erfindungsgemäßen Verfahrens wird die organische Phase unter Rühren in die wäßrige Phase gegeben. Die Temperatur kann dabei innerhalb eines bestimmten Bereiches variiert werden. Im allgemeinen arbeitet man bei Temperaturen zwischen 0°C und 60°C, vorzugsweise zwischen 10°C und 50°C. - 17 -In the first step of the process according to the invention, the organic phase is added to the aqueous phase with stirring. The temperature can be varied within a certain range. In general, temperatures between 0 ° C and 60 ° C, preferably between 10 ° C and 50 ° C. - 17 -
Im zweiten Schritt des erfindungsgemäßen Verfahrens erfolgt die Polymerisation. Dabei ist die Rührgeschwindigkeit wichtig für die Einstellung der Teilchengröße. So nimmt die mittlere Teilchengröße der Perlpolymerisate mit zunehmender Rührdrehzahl ab. Die exakte Rührdrehzahl zur Einstellung einer bestimmten vorgegebenen Perlgröße hängt im Einzelfall stark von der Reaktorgröße, der Reaktorgeometrie und der Rührergeometrie ab. Es hat sich als zweckmäßig erwiesen, die notwendige Rührdrehzahl experimentell zu ermitteln. Für Laborreaktoren, die ein Reaktionsvolumen von 3 Litern aufweisen und mit Blattrührern ausgestattet sind, werden bei Verwendung von Copolymerisaten aus (Meth)acrylsäure und (Meth)acrylsäureestern als Dis- pergiermittel im allgemeinen Perlgrößen zwischen 6 und 30 μm bei Drehzahlen zwischen 300 und 500 Umdrehungen pro Minute erreicht.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. The mean particle size of the bead polymer decreases with increasing stirring speed. The exact stirring speed for setting a certain predetermined bead size depends in individual cases on the reactor size, the reactor geometry and the stirrer geometry. It has proven to be expedient to determine the necessary stirring speed experimentally. For laboratory reactors which have a reaction volume of 3 liters and are equipped with blade stirrers, when using copolymers of (meth) acrylic acid and (meth) acrylic acid esters as dispersants, bead sizes are generally between 6 and 30 μm at speeds between 300 and 500 revolutions reached per minute.
Die Polymerisationstemperatur kann innerhalb eines größeren Bereiches variiert werden. Sie hängt von der Zerfallstemperatur des eingesetzten Initiators ab. Im allge- meinen arbeitet man bei Temperaturen zwischen 50°C und 150°C, vorzugsweise zwischen 55°C und 100°C.The polymerization temperature can be varied within a wide range. It depends on the decomposition temperature of the initiator used. Generally one works at temperatures between 50 ° C and 150 ° C, preferably between 55 ° C and 100 ° C.
Die Dauer der Polymerisation hängt von der Reaktivität der beteiligten Komponenten ab. Im allgemeinen dauert die Polymerisation zwischen 30 Minuten und mehreren Stunden. Es hat sich bewährt, ein Temperatuφrogramm anzuwenden, bei dem dieThe duration of the polymerization depends on the reactivity of the components involved. The polymerization generally lasts between 30 minutes and several hours. It has proven useful to use a temperature program in which the
Polymerisation bei niedriger Temperatur, z.B. 70°C begonnen wird und mit fortschreitendem Polymerisationsumsatz die Reaktionstemperatur erhöht wird.Low temperature polymerization, e.g. 70 ° C is started and the reaction temperature is increased as the polymerization conversion progresses.
Die Aufarbeitung im letzten Schritt des erfindungsgemäßen Verfahrens erfolgt nach üblichen Methoden. Ist die Abtrennung der feinteiligen festen Phase erwünscht, so kann das Perlpolymerisat zum Beispiel durch Filtrieren oder Dekantieren isoliert und gegebenenfalls nach dem Waschen getrocknet werden. Ist die Herstellung einer Suspension von Perlpolymerisat in der wäßrigen Phase gewünscht, so erübrigt sich in den meisten Fällen eine weitere Aufarbeitung. Eventuell enthaltenes Hilfslösungs- mittel kann aus dem anfallenden Gemisch, gegebenenfalls zusammen mit einem Teil des Wassers, destillativ entfernt werden. - 18 -Working up in the last step of the method according to the invention is carried out using customary methods. If it is desired to separate the finely divided solid phase, the bead polymer can be isolated, for example by filtration or decanting, and, if appropriate, dried after washing. If it is desired to prepare a suspension of bead polymer in the aqueous phase, in most cases a further work-up is unnecessary. Any auxiliary solvent contained can be removed by distillation from the resulting mixture, optionally together with part of the water. - 18 -
Die erfindungsgemäßen Perlpolymerisat-Formuiierungen eignen sich hervorragend zur Applikation von agrochemischen Wirkstoffen auf Pflanzen und/oder deren Lebensraum. Sie gewährleisten die Freisetzung der aktiven Komponenten in der je- weils gewünschten Menge über einen längeren Zeitraum.The bead polymer formulations according to the invention are outstandingly suitable for applying agrochemical active ingredients to plants and / or their habitat. They ensure the release of the active components in the desired amount over a longer period of time.
Die erfindungsgemäßen Perlpolymerisat-Formuiierungen können als solche entweder in fester Form oder als Suspensionen, gegebenenfalls nach vorherigem Verdünnen mit Wasser, in der Praxis eingesetzt werden. Die Anwendung erfolgt dabei nach üb- liehen Methoden, also zum Beispiel durch Gießen, Verspritzen, Versprühen oderThe bead polymer formulations according to the invention can be used as such either in solid form or as suspensions, if appropriate after prior dilution with water. The application is carried out according to conventional methods, for example by pouring, spraying, spraying or
Verstreuen.Scatter.
Die Aufwandmenge an den erfindungsgemäßen Perlpolymerisat-Formuiierungen kann innerhalb eines größeren Bereiches variiert werden. Sie richtet sich nach den je- weiligen agrochemischen Wirkstoffen und nach deren Gehalt in den Perlpolymeri- saten.The application rate of the bead polymer formulations according to the invention can be varied within a substantial range. It is based on the respective agrochemical active ingredients and their content in the bead polymers.
Die Erfindung wird durch die folgenden Beispiele veranschaulicht.The invention is illustrated by the following examples.
HerstellungsbeispieleManufacturing examples
Beispiel 1example 1
Perlpolymerisate, enthaltend 4-Amino-N-( 1 , 1 -dimetylethyl)-4,5-dihydro-3-( 1 - methylethyl)-5-oxo-lH-l,2,4-triazol-l-carboxamid der FormelBead polymers containing 4-amino-N- (1,1-dimethylethyl) -4,5-dihydro-3- (1-methylethyl) -5-oxo-lH-l, 2,4-triazole-l-carboxamide of the formula
-N-N
" I " I
-N-N
H2 r. ,NH N' H 2 r. , NH N '
O ϊ O - 19O ϊ O - 19th
Es werden 3 verschiedene Perlpolymerisate mit unterschiedlicher Copolymerzu- sammensetzung hergestellt. Dabei werden jeweils x g Methylmethacrylat, y g Hy- droxyethylmethacrylat, z g Ethylenglycoldimethacrylat und 97 g 4-Amino-N-(l,l-di- metylethyl)-4,5-dihydro-3-( 1 -methylethyl)-5-oxo- 1 H- 1 ,2,4-triazol- 1 -carboxamid in einer Kugelmühle 2 Stunden lang gemischt und anschließend bei Raumtemperatur unter Rühren mit 3,9 g Dibenzoylperoxid versetzt. Man überführt die Mischung in einen Rührreaktor, der zuvor mit 1 ,5 Litern einer 1 gew.-%igen, wäßrig-alkalischen, mit Natronlauge auf einen pH- Wert von 8 eingestellten Lösung eines Copoly- merisates aus 50 Gew.-% Methacrylsäure und 50 Gew.-% Methylmethacrylat gefüllt wurde. Die Rührgeschwindigkeit wird auf 700 Umdrehungen pro Minute eingestellt, und die Temperatur 3 Stunden auf 60°C , anschließend 10 Stunden auf 78°C und dann 2 Stunden auf 85°C gehalten. Danach wird innerhalb von 2 Stunden auf Raumtemperatur abgekühlt. Man erhält Dispersionen von wirkstoffhaltigen Perlpoly- merisaten.3 different bead polymers with different copolymer compositions are produced. In each case xg methyl methacrylate, yg hydroxyethyl methacrylate, zg ethylene glycol dimethacrylate and 97 g 4-amino-N- (l, l-dimethylethyl) -4,5-dihydro-3- (1-methylethyl) -5-oxo 1 H-1, 2,4-triazole-1-carboxamide mixed in a ball mill for 2 hours and then mixed with 3.9 g of dibenzoyl peroxide at room temperature with stirring. The mixture is transferred to a stirred reactor which has previously been treated with 1.5 liters of a 1% by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted with sodium hydroxide solution to pH 8 50 wt .-% methyl methacrylate was filled. The stirring speed is set to 700 revolutions per minute, and the temperature is kept at 60 ° C. for 3 hours, then at 78 ° C. for 10 hours and then at 85 ° C. for 2 hours. The mixture is then cooled to room temperature within 2 hours. Dispersions of active ingredient-containing pearl polymers are obtained.
BeiX y z Gehalt an Mittlerer spiel-Nr. (in g) (in g) (in g) Hydroxyethyl- Teilchendurchmesser methacrylat im der Perlpolymerisat- Copolymerisat TeilchenBeiX y z content of middle game no. (in g) (in g) (in g) Hydroxyethyl particle diameter methacrylate in the bead polymer copolymer particles
1A 232,8 29,1 29,1 10 % 7,9 μm1A 232.8 29.1 29.1 10% 7.9 µm
1B 203,7 58,2 29,1 20 % 7,6 μm1B 203.7 58.2 29.1 20% 7.6 µm
IC 174,6 87,3 29,1 30 % 6,5 μm IC 174.6 87.3 29.1 30% 6.5 µm
Beispiel 2Example 2
Perlpolymerisate, enthaltend Imidacloprid der FormelBead polymers containing imidacloprid of the formula
-NO,-NO,
NN
NHNH
Cl L - 20 -Cl L - 20 -
Es werden 3 verschiedene Perlpolymerisate mit unterschiedlicher Copolymerzu- sammensetzung hergestellt. Dabei werden jeweils x g Methylmethacrylat, y g Hy- droxyethylmethacrylat, z g Ethylenglycoldimethacrylat, 100 g Imidachloprid und 30 g feinteiliges Siliziumdioxid (HDK H2000 der Firma Wacker) in einer Kugelmühle 2 Stunden lang gemischt und anschließend bei Raumtemperatur unter Rühren mit 3 g Dibenzoylperoxid versetzt. Man überführt die Mischung in einen Rührreaktor, der zuvor mit 1,5 Litern einer 1 gew.-%igen, wäßrig-alkalischen, mit Natronlauge auf einen pH- Wert von 8 eingestellten Lösung eines Copolymerisates aus 50 Gew.-% Methacrylsäure und 50 Gew.-% Methylmethacrylat gefüllt wurde. Die Rührgeschwindigkeit wird auf 500 Umdrehungen pro Minute eingestellt, und die Temperatur 8 Stunden auf 78°C und dann 2 Stunden auf 85°C gehalten. Danach wird innerhalb von 2 Stunden auf Raumtemperatur abgekühlt. Das Perlpolymerisat wird durch Absetzen lassen und Dekantieren isoliert, mit kaltem Wasser gewaschen und bei 50°C im Trockenschrank getrocknet.3 different bead polymers with different copolymer compositions are produced. In each case, x g of methyl methacrylate, y g of hydroxyethyl methacrylate, z g of ethylene glycol dimethacrylate, 100 g of imidachlopride and 30 g of finely divided silicon dioxide (HDK H2000 from Wacker) are mixed in a ball mill for 2 hours and then mixed with 3 g of dibenzoyl peroxide at room temperature with stirring. The mixture is transferred to a stirred reactor which has previously been treated with 1.5 liters of a 1% strength by weight aqueous alkaline solution of a copolymer of 50% by weight methacrylic acid and 50% by weight adjusted to pH 8 with sodium hydroxide solution .-% methyl methacrylate was filled. The stirring speed is set to 500 revolutions per minute and the temperature is kept at 78 ° C. for 8 hours and then at 85 ° C. for 2 hours. The mixture is then cooled to room temperature within 2 hours. The bead polymer is isolated by settling and decanting, washed with cold water and dried at 50 ° C. in a drying cabinet.
Beispiel-Nr. X y z Gehalt an MittlererExample No. X y z mean content
(in g) (in g) (in g) Hydroxyethyl- Durchmesser der methacrylat im Perlpolymerisat- Copolymerisat Teilchen(in g) (in g) (in g) hydroxyethyl diameter of the methacrylate in the bead polymer copolymer particles
2A 255 30 15 10 % 42 μm2A 255 30 15 10% 42 μm
2B 225 60 15 20 % 50 μm 2C 195 90 15 30 % 45 μm 2B 225 60 15 20% 50 μm 2C 195 90 15 30% 45 μm
Freisetzungstest ARelease test A
Zur Übeφriifung der Freisetzungsrate für den Wirkstoff wurden homogene Proben von jeweils 4 ml der Dispersionen aus den Beispielen 1 A - C mit 950 ml Wasser verdünnt. Die Mischung wurde unter Schütteln 35 Tage gelagert. Nach den in der Tabelle 1 angegebenen Zeiten wurde der Wirkstoffgehalt in der Wasseφhase mittels HPLC bestimmt. Der Zahlenwert in nachfolgender Tabelle gibt den Anteil des an das Wasser abgegebenen Wirkstoffs bezogen auf die zugesetzte Wirkstoffmenge an. 21To check the release rate for the active ingredient, homogeneous samples of 4 ml each of the dispersions from Examples 1A-C were diluted with 950 ml of water. The mixture was stored with shaking for 35 days. After the times given in Table 1, the active substance content in the water phase was determined by means of HPLC. The numerical value in the table below indicates the proportion of the active ingredient released into the water based on the amount of active ingredient added. 21
Tabelle 1Table 1
Perlpolymerisat Menge an freigesetztem Wirkstoff nach gemäß.Bead polymer Amount of active ingredient released according to.
Beispiel-Nr ITag 3 Tagen 14 Tagen 21 Tagen 35 TagenExample No. ITag 3 days 14 days 21 days 35 days
1A 35% 48% 55% 60% 68%1A 35% 48% 55% 60% 68%
1B 46% 58% 66% 71 % 80%1B 46% 58% 66% 71% 80%
IC 76% 81 % 87% 92% 97% IC 76% 81% 87% 92% 97%
Die Versuchsreihe macht deutlich, daß die Freisetzungsrate des Wirkstoffs durch den Gehalt an Hydroxyethylmethacrylat im Copolymerisat gesteuert wird.The series of experiments makes it clear that the rate of release of the active ingredient is controlled by the content of hydroxyethyl methacrylate in the copolymer.
Freisetzungstest BRelease test B
Zur Überprüfung der Freisetzungsrate für den Wirkstoff wurde jeweils lg der Perlpolymerisate aus den Beispielen 2 A - C in 1 Liter Wasser dispergiert. Die Dispersion wurde unter Schütteln 240 Stunden gelagert. Nach den in der Tabelle 2 angegebenen Zeiten wurde der Wirkstoffgehalt in der Wasseφhase bestimmt. Der Zahlenwert gibt den Anteil des an das Wasser abgegebenen Wirkstoffs bezogen auf die zugesetzte Wirkstoffmenge anTo check the release rate for the active ingredient, 1 g of the bead polymers from Examples 2A-C was dispersed in 1 liter of water. The dispersion was stored with shaking for 240 hours. After the times given in Table 2, the active substance content in the water phase was determined. The numerical value indicates the proportion of the active ingredient released into the water based on the amount of active ingredient added
Tabelle 2Table 2
Perlpolymerisat Menge an freigesetztem Wirkstoff nach gemäßBead polymer Amount of active ingredient released according to
Beispiel-Nr. 4h 24 h 48 h 96 h 192 hExample No. 4h 24h 48h 96h 192h
2A 2% 5% 7% 10% 18%2A 2% 5% 7% 10% 18%
2B 8% 11% 13% 17% 32%2B 8% 11% 13% 17% 32%
2C 20% 38% 50% 62% 74% 2C 20% 38% 50% 62% 74%
Die Versuchsreihe macht wiederum deutlich, daß die Freisetzungsrate des Wirkstoffs durch den Gehalt an Hydroxyethylmethacrylat im Copolymerisat gesteuert wird. The series of experiments again shows that the release rate of the active ingredient is controlled by the content of hydroxyethyl methacrylate in the copolymer.

Claims

- 22 -Patentansprüche - 22 patent claims
1. Perlpolymerisat-Formuiierungen, die aus1. Bead polymer formulations that are made from
I) einer teilchenförmigen, festen Phase, welcheI) a particulate solid phase which
A) Copolymerisat ausA) copolymer from
a) 40 bis 95 Gew.-% wasserunlöslichem Monomera) 40 to 95 wt .-% water-insoluble monomer
b) 5 bis 35 Gew.-% wasserlöslichem Monomerb) 5 to 35% by weight of water-soluble monomer
c) 0 bis 25 Gew.-% Vernetzer,c) 0 to 25% by weight of crosslinking agent,
undand
B) mindestens einen agrochemischen WirkstoffB) at least one agrochemical active ingredient
sowiesuch as
C) gegebenenfalls ZusatzstoffeC) optionally additives
enthält, wobei der Gehalt an agrochemischem Wirkstoff zwischen 5 und 75 Gew.-% liegt und die feste Phase eine mittlere Teilchengröße zwischen 1 und 100 μm aufweist,contains, the content of agrochemical active ingredient being between 5 and 75% by weight and the solid phase having an average particle size between 1 and 100 μm,
undand
II) gegebenenfalls einer flüssigen PhaseII) optionally a liquid phase
bestehen. - 23 -consist. - 23 -
2. Verfahren zur Herstellung von Perlpolymerisat-Formuiierungen gemäß Anspruch 1 , dadurch gekennzeichnet, daß man2. A process for the preparation of bead polymer formulations according to claim 1, characterized in that
A) eine organische Phase ausA) an organic phase
25 bis 95 Gew.-% eines Monomeren-Gemisches aus25 to 95 wt .-% of a monomer mixture
a) 40 bis 95 Gew.-% wasserunlöslichem Monomera) 40 to 95 wt .-% water-insoluble monomer
b) 5 bis 35 Gew.-% wasserlöslichem Monomerb) 5 to 35% by weight of water-soluble monomer
c) 0 bis 25 Gew.-% Vernetzer,c) 0 to 25% by weight of crosslinking agent,
5 bis 75 Gew.-% an mindestens einem agrochemischen Wirkstoff,5 to 75% by weight of at least one agrochemical active ingredient,
mindestens einem Initiator,at least one initiator,
gegebenenfalls Zusatzstoffenoptional additives
undand
gegebenenfalls einem mit Wasser, wenig mischbaren organischen Solvens,optionally an organic solvent which is not very miscible with water,
B) in einer wäßrigen Phase ausB) in an aqueous phase
Wasser,Water,
- mindestens einem Dispergiermittel und - 24 -- At least one dispersant and - 24 -
gegebenenfalls einem Pufferreagenzoptionally a buffer reagent
unter Rühren bei Temperaturen zwischen 0°C und 60°C fein verteilt,finely distributed with stirring at temperatures between 0 ° C and 60 ° C,
C) dann unter Temperaturerhöhung und unter Rühren polymerisiertC) then polymerized while raising the temperature and with stirring
D) und gegebenenfalls danach entwederD) and optionally afterwards either
) das entstandene Perlpolymerisat isoliert, wäscht und trocknet) isolates, washes and dries the resulting bead polymer
oderor
ß) gegebenenfalls enthaltene flüchtige, organische Substanzen abtrennt und so das Perlpolymerisat in wäßriger Suspension er- hält.β) any volatile organic substances present are separated off and the bead polymer is thus obtained in aqueous suspension.
3. Verwendung von Perlpolymerisat-Formuiierungen gemäß Anspruch 1 zur Applikation von agrochemischen Wirkstoffen auf Pflanzen und/oder deren Lebensraum.3. Use of bead polymer formulations according to claim 1 for the application of agrochemical active ingredients to plants and / or their habitat.
4. Perlpolymerisat-Formuiierungen gemäß Anspruch 1, dadurch gekennzeichnet, daß sie 4-Amino-N-(l , 1 -dimethylethyl)-4,5-dihydro-3-(l -methyl-ethyl)-5- oxo-lH-l,2,4-triazol-l -carboxamid als agrochemischen Wirkstoff enthalten.4. bead polymer formulations according to claim 1, characterized in that they 4-amino-N- (l, 1-dimethylethyl) -4,5-dihydro-3- (l -methyl-ethyl) -5- oxo-lH- l, 2,4-triazole-l-carboxamide as an agrochemical active ingredient.
5. Perlpolymerisat-Formuiierungen gemäß Anspruch 1 , dadurch gekennzeichnet, daß sie Imidachloprid als agrochemischen Wirkstoff enthalten. 5. bead polymer formulations according to claim 1, characterized in that they contain imidachloprid as an agrochemical active ingredient.
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