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WO2013017388A1 - Granulat d'amidon poreux contenant un pesticide anionique ou cationique et une matrice cationique ou anionique - Google Patents

Granulat d'amidon poreux contenant un pesticide anionique ou cationique et une matrice cationique ou anionique Download PDF

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Publication number
WO2013017388A1
WO2013017388A1 PCT/EP2012/063634 EP2012063634W WO2013017388A1 WO 2013017388 A1 WO2013017388 A1 WO 2013017388A1 EP 2012063634 W EP2012063634 W EP 2012063634W WO 2013017388 A1 WO2013017388 A1 WO 2013017388A1
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WO
WIPO (PCT)
Prior art keywords
anionic
cationic
starch granules
pesticide
matrix
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Ceased
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PCT/EP2012/063634
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German (de)
English (en)
Inventor
Ralph Rieger
Harald Keller
Robert Reinhard
Tina SCHRÖDER-GRIMONPONT
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BASF SE
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BASF SE
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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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles

Definitions

  • Porous starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix The present invention relates to a porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged.
  • Further objects are a process for producing the starch granules by bringing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix in contact with each other; and methods for controlling phytopathogenic fungi and / or undesired plant growth and / or unwanted insect or mite infestation and / or for regulating the growth of plants, wherein the composition of the respective pests, their habitat or the plants to be protected from the respective pest , the soil and / or on unwanted plants and / or the crops and / or their habitat act. Combinations of preferred features with other preferred features are encompassed by the present invention.
  • US 2007/0160637 discloses a composition comprising a partially hydrolyzed porous granular starch in which a pesticide is absorbed and a binder or filler.
  • WO 1995/19376 discloses a porous starch granule which is combined with a binder and which can act as a carrier for insecticides or herbicides.
  • WO 1989/04842 discloses a partially hydrolyzed starch matrix containing a releasable absorptive such as insecticides or herbicides.
  • a disadvantage of the known starch granules is that they allow only a very rapid release of active ingredients.
  • the object of the present invention was to provide a composition comprising pesticide which overcomes these disadvantages.
  • the object has been achieved by a porous, partially hydrolyzed starch granules containing an anionic or cationic pesticide and a cationic or anionic matrix, wherein the pesticide and the matrix are oppositely charged.
  • the invention relates to porous, partially hydrolyzed starch granules containing an anionic pesticide and a cationic matrix. In another In preferred form, the invention relates to porous, partially hydrolyzed starch granules containing a cationic pesticide and an anionic matrix.
  • Porous, partially hydrolyzed starch granules are well known, for example from WO 1989/04842.
  • the starch granules may be prepared by treating starch granules in an aqueous medium (e.g., in aqueous suspension), with a glucoamylase, alpha-amylase, or mixtures thereof.
  • the temperature will usually be below the gel point of the starch.
  • Suitable alpha-amylases or glucoamylases are those of Rhizopus niveus, Aspergillus niger, Rhizopus oryzae, Bacillus subtilis.
  • the starch granules are used without further work-up, for example in an aqueous medium.
  • the starch granules are isolated in powder form, for example by drying. Suitable drying methods are freeze drying, spray drying, belt drying or drum drying. Suitable starch granules are based, for example, on corn starch, wheat, tapioca, potato. Preferred starch granules are based on corn starch.
  • the pore volume of the porous starch granules may range from 0.05 to 1 ml / g, preferably from 0.2 to 0.8 ml / g, more preferably from 0.35 to 0.65 ml / g.
  • the pore volume can be determined by the absorption of hexadecane compared to the hexadecane absorption of a non-porous starch granule.
  • the starch granules usually have a particle size of 1 to 300 ⁇ , preferably from 5 to 100 ⁇ , particularly preferably from 8 to 30 ⁇ .
  • the particle size can be measured by means of laser diffraction.
  • the matrix can be in the form of a continuous or discontinuous matrix.
  • the matrix mostly has ionic interactions with the pesticide. The ionic interactions can lead to reduced migration of the pesticide in the matrix.
  • the matrix can form salts with the pesticide.
  • the anionic matrix usually comprises at least one anionic compound.
  • the anionic matrix may contain at least 70% by weight, preferably at least 85% by weight and in particular at least 95% by weight of anionic compounds.
  • the anionic matrix preferably comprises an inorganic acid, an organic acid, and / or a polymeric acid, organic acid, in particular aliphatic C 2-30 carboxylic acids, and especially oxalic acid being preferred.
  • the inorganic, organic and / or polymeric acids may comprise one or more acid groups (eg carboxylic acid groups).
  • Suitable inorganic acids are sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, metaphosphoric acid, and boric acid, with phosphonic acid and phosphorous acid being preferred.
  • Suitable organic acids are aliphatic C 2-30 carboxylic acids (such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, citric acid, malic acid, tartaric acid) or aromatic C 7-30 carboxylic acids (such as terephthalic acid, phthalic acid, isophthalic acid).
  • Preferred organic acids are aliphatic C 2-20 carboxylic acids, more preferably C 2-8 aliphatic carboxylic acids such as oxalic acid.
  • the anionic matrix comprises a C2-3o-dicarboxylic acid.
  • the anionic matrix comprises organic acids having at least two deprotonation steps and a pKa value for the first deprotonation step of less than 2.5.
  • Suitable polymeric acids are organic polymeric acids, such as polymers obtainable from ethylenically unsaturated anionic monomers (for example, from mono- ethylenically unsaturated C3-5-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, sulfonic acids, such as vinylsulfonic acid , Styrenesulfonic acid and acrylamidomethylpropanesulfonic acid; and phosphonic acids, such as vinylphosphonic acid, and / or in each case the alkali metal, alkaline earth metal and / or ammonium salts of these acids), preferably poly (meth) acrylic acid.
  • anionic monomers for example, from mono- ethylenically unsaturated C3-5-carboxylic acids, such as acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid
  • acidic biopolymers such as alginic acid, gum arabic, nucleic acids, pectins, proteins, and chemically modified biopolymers, such as ionic or ionizable polysaccharides, eg. Carboxymethylcellulose, chitosan, chitosan sulfate, and lignosulfonate.
  • anionic resins such as phenolsulfonic acid resins, or sulfonated melamine-formaldehyde resin.
  • the cationic matrix usually comprises at least one cationic compound.
  • the cationic matrix may contain at least 70% by weight, preferably at least 85% by weight and in particular at least 95% by weight of cationic compounds.
  • the cationic matrix preferably comprises an amine, in particular an alkylamine or an amine-containing polymer. Most preferably, the cationic matrix comprises a C8-3o primary alkylamine, such as octadecylamine.
  • the alkylamine or the amine-containing polymer preferably has a melting point of at least 30 ° C., particularly preferably of at least 40 ° C., and in particular of at least 50 ° C.
  • Suitable amines are aliphatic or aromatic amines which optionally carry further functional groups, such as hydroxyl or ether groups.
  • Suitable alkylamines are amines which contain a linear, branched and / or cyclic alkyl group.
  • the alkylamines may optionally carry further functional groups, such as hydroxy or ether groups.
  • Preferred alkylamines are linear or branched, primary alkylamines having 4-36 C atoms, preferably 10-24, and particularly preferably 14-22 C atoms.
  • Examples of these primary alkylamines are octadecylamine, laurylamine, olamine, palmitylamine, of which octadecylamine is especially preferred.
  • Further preferred alkylamines are linear or branched, secondary alkylamines having 2-24 C atoms, preferably 4-22, particularly preferably 6-18 C atoms. Examples of these secondary alkylamines are dioctylamine, di (ethylhexyl) amine. Further preferred alkylamines are linear or branched, tertiary alkylamines having 3-24 C atoms, preferably 6-22, particularly preferably 8-18 C atoms. Examples of these tertiary alkylamines are tributylamine.
  • alkylamines are linear or branched, quaternary alkylamines having 2-24 C atoms, preferably 4-22, particularly preferably 6-18 C atoms.
  • Suitable amine-containing polymers based on, for example, vinylimidazole units, vinylamine units, ethyleneimine units, dialkylaminoalkyl (meth) acrylates, dialkylaminoalkyl (meth) acrylamide, vinylpyridine units, preferably on ethyleneimine units.
  • Examples are polyethylenimine, polyvinylpyridine and copolymers of hydrophobic monomers with vinylpyridine, polyvinylimidazole and copolymers of hydrophobic monomers with vinylimidazole, poly-2- (N-dimethylamino) ethyl (meth) acrylate and copolymers of hydrophobic monomers with poly-2- ( N-dimethylamino) ethyl (meth) acrylate, poly-2- ⁇ - Morpholinoethyl (meth) acrylate and copolymers of hydrophobic monomers with poly-2-N-morpholinoethyl (meth) acrylate.
  • pesticide denotes at least one active ingredient selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators.
  • Preferred pesticides are fungicides, insecticides and herbicides, especially fungicides and herbicides. Also, mixtures of pesticides of two or more of the above classes may be used.
  • One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London.
  • Suitable insecticides are insecticides of the carbamate class, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloro-picrine, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargit, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenone, or derivatives thereof.
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxamides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides , Dihydrodioxazines, dinitrophenylcrotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganics
  • Suitable herbicides are herbicides of the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles , N-phenylphthalimides, oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamidates, phosphorodithioates, phthala
  • Suitable cationic pesticides comprise at least one amino group.
  • Preferred cationic pesticides are cationic fungicides, such as bupirimate, dimethirimol, ethirimol, cyprodinil, mepanipyrim, pyrimethanil, propamarocarb, prothiocarb, fuberidazole, carbendazim, diflumetorim, ametoctradine, iminoctadine, dodemorph, tridemorph, fenpropimoph, aldimorph, fenpropidin, piperanil, spiroxamine, prochloraz, pefurazoate, triflumizole, imazalil, pyrifenox. Particularly preferred is fenpropimorph.
  • Suitable anionic pesticides include at least one carboxyl, thiocarboxyl, sulfonyl, sulfinyl, thiosulfonyl or phosphoric acid group, with the carboxyl group being preferred.
  • carboxyl group is preferred.
  • One skilled in the art can easily select such anionic pesticides from the above list of pesticides.
  • anionic pesticides are anionic herbicides such as 2,4,5-T, 2,4-D, 2,4-DB, acifluorfen-sodium, amidosulfuron, aminopyralid, amitrole, asulam, azimsulfuron, benazolin, bensulfuron-methyl, bentazone, bispyribac-sodium, bromoxynil, butroxydim, chloramben, chlorimuron-ethyl, chlorosulfuron, cinosulfuron, clopyralid, cloransulam-methyl, cyclosulfamuron, cycloxy-dim, dalapon, dicamba, dichlorprop, dichlorprop-P, diclofop, diclosulam, diflufenzopyr, dinoseb, DNOC, endothal, ethametsulfuron-methyl, ethoxysulfuron, fenoprop, fenopurobutoty
  • the starch granules may include, in addition to the anionic or cationic pesticide, other pesticides, especially neutral pesticides (ie pesticides which are not anionic or cationic pesticides).
  • the molar ratio of ionic charges from pesticide to matrix may range from 5: 1 to 1: 3, with the range from 3: 1 to 1: 2, especially the range from 1, 5: 1 to 1: 1, 3, and in particular the range of 1, 1: 1 to 1: 1, 1 is preferred.
  • the invention further relates to a process for the preparation of starch granules according to the invention by bringing a porous, partially hydrolyzed starch granules with a salt matrix containing the anionic or cationic pesticide and the cationic or anionic matrix in contact with each other.
  • the salt matrix contains the anionic or cationic pesticide and the cationic or anionic matrix, with the pesticide and matrix being oppositely charged.
  • the salt matrix also contains a liquid.
  • the salt matrix may contain from 1 to 90% by weight, preferably from 5 to 70% by weight, and in particular from 15 to 50% by weight, of anionic or cationic pesticide.
  • the starch granules are usually dispersed in a liquid.
  • Preferred liquid is water or an organic solvent which is at least 5% by weight soluble in water at 20 ° C.
  • the person skilled in the art depends on the solubility of the pesticide.
  • pesticides like Dicamba-Na, Dicamba-IPA, Imazapyr-Na
  • water is suitable.
  • Dicamba-H i.e., free acid
  • fenpropimorph organic solvents are suitable.
  • Preferred organic solvents are acetone, methyl ethyl ketone, methanol, ethanol, propanol, isopropanol, 1-butanol, isobutanol, THF. Particularly preferred are acetone, ethanol and isobutanol.
  • the temperature in the production process with aqueous pesticide solutions is usually from 10 to 80.degree. C., preferably from 15.degree. C. to 60.degree.
  • the temperature during filling with organic pesticide solutions is usually at least 10 ° C.
  • the temperature can rise to the boiling point of the organic solvent, preferably up to a maximum of 5 ° below the boiling point.
  • In order to bring the components into contact usually a period of 1 min to 24 h, preferably 0.5 h to 3 h. During this time, the components can be mixed.
  • the order of bringing the components into contact is arbitrary.
  • the organic solvent used can be removed, for example under vacuum.
  • the ratio of starch granules to pesticide may range from 1.2 to 5, preferably from 1.4 to 4.
  • the starch granules of the invention may also be contained in an agrochemical composition.
  • the composition may contain formulation auxiliaries, wherein the choice of the auxiliaries usually depends on the specific application form or the active substance.
  • suitable formulation auxiliaries are additional solvents, surfactants and other surface-active substances (such as solubilizers, protective colloids, wetting agents and adhesives), adjuvants, organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, dyes and adhesives (for example for seed treatment).
  • Suitable agrochemical compositions are water-soluble concentrates (SL, LS), redispersible concentrates (TLC), emulsifiable concentrates (EC), emulsions (EW, EO, ES, ME), suspensions (SC, OD, FS), suspoemulsions (SE) , and powders and granules (WP, WG).
  • Additional solvents include organic solvents such as medium to high boiling point mineral oil fractions such as kerosene and diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffins, tetrahydronaphthalene, alkylated naphthalenes and derivatives thereof, alkylated benzenes and their derivatives, alcohols such as ethanol, propanol, butanol, benzyl alcohol and cyclohexanol, glycols, ketones such as cyclohexanone, gamma-butyrolactone, dimethyl fatty acid amides, fatty acids and fatty acid esters and highly polar Solvent, eg Amines such as N-methylpyrrolidone, into consideration.
  • solvent mixtures can also be used.
  • Surfactants can be used individually or in a mixture.
  • Surfactants are compounds that reduce the surface tension of water.
  • Suitable surfactants are anionic, cationic, nonionic and amphoteric surfactants, block polymers and polyelectrolytes.
  • Suitable anionic surfactants are alkali metal, alkaline earth metal or ammonium salts of sulfonates, sulfates, phosphates or carboxylates.
  • sulfonates are alkyla- rylsulfonates, diphenylsulfonates, alpha-olefinsulfonates, lignosulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of ethoxylated arylphenols, sulfonates of condensed naphthalene, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates ,
  • sulfates are sulfates of fatty acid and
  • phosphates are phosphate esters.
  • carboxylates are alkylcarboxylates and carboxylated alcohol or alkylphenol ethoxylates.
  • Preferred anionic surfactants are sulfonates of ethoxylated arylphenols, in particular phosphated or sulfated di- and / or Tristyrylphenylalkoxylate, as described for example in WO 2007/1 10355, page 3, line 30 to page 5, line 11.
  • Suitable nonionic surfactants are alkoxylates, N-alkylated fatty acid amides, amine oxides, esters or sugar-based surfactants.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated.
  • ethylene oxide and / or propylene oxide can be used, preferably ethylene oxide.
  • N-alkylated fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkyl polyglucosides.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds having one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkyl betaines and imidazoline.
  • Suitable block polymers are block polymers of A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali metal salts of polyacrylic acid. Examples of polybases are polyvinylamines or polyethyleneamines.
  • composition of the invention may comprise any amount of surfactant. It can comprise from 0.1 to 40% by weight, preferably from 1 to 30% by weight and in particular from 2 to 20% by weight, of the total amount of surfactants, based on the total amount of the composition.
  • adjuvants examples include organically modified polysiloxanes such as BreakThruS 240 ®; Alcohol alkoxylates such as Atplus ® 245 ® Atplus MBA 1303 ®, Plurafac LF and Lutensol ® ON; EO-PO block polymers, eg. B. Pluronic RPE 2035 ® and Genapol B ®; alcoholic Lethoxylates, z. B. Lutensol ® XP 80; and sodium dioctylsulfosuccinate, e.g. B. Leophen ® RA.
  • organically modified polysiloxanes such as BreakThruS 240 ®
  • Alcohol alkoxylates such as Atplus ® 245 ® Atplus MBA 1303 ®, Plurafac LF and Lutensol ® ON
  • EO-PO block polymers eg. B. Pluronic RPE 2035 ® and Genapol B ®
  • alcoholic Lethoxylates z.
  • thickeners ie, compounds that give the composition a modified flow properties, ie high viscosity at rest and low viscosity in motion
  • thickeners are polysaccharides and organic and inorganic sheet minerals, such as xanthan gum (Kelzan ®, CP Kelco), Rhodopol ® 23 (Rhodia) or Veegum ® (RT Vanderbilt) or attaclay ® (Engelhard Corp.).
  • Bactericides may be added to stabilize the composition.
  • bactericides are those based on dichlorophen and benzyl alcohol formal (Proxel ®. Fa. ICI or Acetide ® RS from Thor Chemie and Kathon ® MK from. Rohm & Haas), and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones (Acetide ® MBS from Thor Chemie).
  • suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerin.
  • defoamers are silicone emulsions (such as, for example, silicone ® SRE, Wacker, Germany or Rhodorsil ®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, organofluorine compounds and mixtures thereof.
  • adhesives are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ethers (Tylose ®, Shin-Etsu, Japan).
  • the agrochemical composition is usually diluted before use to produce the so-called tank mix.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, eg toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, Propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration.
  • the diluted composition is usually applied by spraying or atomizing.
  • wetting agents, adjuvants, herbicides, bactericides, fungicides can be added immediately before use (tank mix). These agents may be mixed into the agrochemical compositions in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • the pesticide concentration in the tank mix can be varied in larger areas. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
  • the present invention also relates to a method for controlling phytopathogenic fungi and / or undesired plant growth and / or undesired insect or mite infestation and / or for regulating the growth of plants, wherein the starch granule (as in an agrochemical composition) affecting the particular pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat.
  • Advantages of the invention are that a slow release of the pesticide is possible, that controllable release of the pesticide is possible, that only a lesser loss of volatile pesticides takes place (eg a reduction in the evaporation rate, such as fenpropimorph), that the pesticide is resistant to chemical degradation is protected and that hydrophobic pesticides are more dispersible in aqueous formulations.
  • the preparation of the porous starch particles was carried out from corn starch having an average particle size of 14 ⁇ m as described in WO89 / 04842.
  • the preparation of a fine powder was carried out by freeze-drying.
  • the pore volume of the starch particles was calculated as follows:
  • Pore volume [(weight (weight) - weight (porous)) / density (strength)] x
  • the density of the starch was 1, 464 g / ml.
  • Example 1 Dicamba Na starch particles (not according to the invention)
  • porous starch particles 300 g were added to 399 g of aqueous solution of Dicamba isopropylammonium salt having a solids content of 50.1 wt.% And mixed with a mechanical stirrer at 20 ° C for 20h. Subsequently, the mixture was dried in a drying oven at 40 ° C and 100 mbar. This gave 513.3 g of colorless powder with a residual moisture content of 2.8%.
  • Example 3 Dicamba-H starch particles (not according to the invention)
  • Example 5 Dicamba H and Dicamba (Cationic Matrix) starch particles
  • Step A 10.0 g dicamba (free acid) and 1 1.33 g octadecylamine were mixed and heated to 120 ° C until a clear solution was obtained. After cooling to 20 ° C gave a waxy solid which has a melting point of 58 ° C.
  • Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g) and 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the iso-butanol was removed on a rotary evaporator at 60 ° C at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
  • Example 6 Dicamba-H and Dicamba-H (Cationic Matrix) Thickness Particles Step A) 10.0 g of dicamba (free acid) and 9.26 g of octadecylamine were mixed and heated to 120 ° C until a clear solution resulted. After cooling to 20 ° C to give a waxy solid.
  • Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g) and 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the iso-butanol was removed on a rotary evaporator at 60 ° C at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
  • Example 7 Starch particles with Dicamba-H and octadecylamine (cationic matrix) Step A) 10.0 g of dicamba (free acid) and 5.67 g of octadecylamine were mixed and heated to 120 ° C until a clear solution was formed. After cooling to 20 ° C gave a highly viscous liquid. Step B) 3.5 g of porous starch particles (pore volume 0.48 ml / g), 1, 5 g of the product of step A and 3.33 g of iso-butanol were heated to 50 ° C and stirred for 1 h at this temperature. Subsequently, the isobutanol was removed on a rotary evaporator at 60 ° C. at a pressure of 8 mbar. This gives 4.78 g of powdery solid.
  • the bottle was removed from the roller mixer and the sample allowed to sediment for 10 minutes. With a syringe 0.2 ml of the supernatant solution were removed and the pesticide content determined by HPLC.
  • Pesticide release was compared to a reference sample.
  • the reference sample was prepared under the same conditions and contained the same pesticide, but no retarding matrix.
  • the pesticide release of the reference sample was normalized to 100%.
  • the pesticide release of the matrix samples was reported relative to the reference sample (Table 1). By the starch granules according to the invention, the release could be slowed down.
  • Example 9 Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.42 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min.
  • Example 10 Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator.
  • Example 1 1-Starch particles with fenpropimorph and oxalic acid (anionic matrix) 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and mixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h , Then the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator. To the residue was added a solution of 0.14 g of oxalic acid in 3.6 g of water. The residue was stirred at 20 ° C for 15 min. Subsequently, the water was removed at 40 ° C on a rotary evaporator. 4.85 g of colorless powder were obtained.
  • Example 12 Fenpropimorph starch particles (not according to the invention)
  • fenpropimorph 1.0 g of fenpropimorph were dissolved in 3.3 g of acetone and admixed with 4 g of porous starch particles (pore volume 0.53 ml / g) and stirred at 20 ° C. for 1 h. Then, the acetone was removed at a pressure of 600 mbar and a bath temperature of 40 ° C on a rotary evaporator.

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

Abstract

L'invention concerne un granulat d'amidon poreux partiellement hydrolysé contenant un pesticide anionique ou cationique et une matrice cationique ou anionique, le pesticide et la matrice étant chargés à l'opposé. L'invention a également pour objet entre autres : un procédé servant à fabriquer le granulat d'amidon consistant à mettre en contact un granulat d'amidon poreux partiellement hydrolysé avec une matrice saline contenant le pesticide anionique ou cationique et la matrice cationique ou anionique ; et un procédé servant à lutter contre les champignons phytopathogènes et/ou les mauvaises herbes et/ou contre l'invasion d'insectes ou d'acariens et/ou servant à réguler la croissance des plantes en laissant la composition agir sur les ravageurs respectifs, sur leur espace vital ou sur les plantes à protéger de ces ravageurs respectifs, sur le sol et/ou sur les mauvaises herbes et/ou sur les plantes utiles et/ou sur leur espace vital.
PCT/EP2012/063634 2011-07-29 2012-07-12 Granulat d'amidon poreux contenant un pesticide anionique ou cationique et une matrice cationique ou anionique Ceased WO2013017388A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110199988A (zh) * 2019-06-18 2019-09-06 罗宏生 一种复合除草剂

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004842A1 (fr) 1987-11-20 1989-06-01 Whistler Roy L Composition en amidon granulaire pour matrices microporeuses
WO1995019376A1 (fr) 1994-01-14 1995-07-20 Fuisz Technologies Ltd. Agregat particulaire poreux et son procede de preparation
DE10022987A1 (de) * 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Kombinationen von Pflanzenschutzmitteln mit kationischen Polymeren
DE10022986A1 (de) * 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Kombinationen von Pflanzenschutzmitteln mit anionischen Polymeren
US20070160637A1 (en) 2006-01-10 2007-07-12 Grain Processing Corporation Pest control agent, method for manufacture of pest control agent, and method for pest control
WO2007110355A2 (fr) 2006-03-24 2007-10-04 Basf Se Formulations agrochimiques
US20100105637A1 (en) * 2005-08-17 2010-04-29 Kim Cherng-Ju Drug-surfactant complexes for sustained release
US20100178358A1 (en) * 2006-03-28 2010-07-15 Louis Gastonguay Polysaccharide-based impregnated solid material with improved stability, processes for the preparation thereof and impregnating solutions used
DE102009017677A1 (de) * 2009-04-16 2010-10-21 Sarastro Gmbh Verfahren zum Herstellen eines Stoffs mit einstellbaren biologisch aktiven Gradienteneigenschaften und derartiger Stoff

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989004842A1 (fr) 1987-11-20 1989-06-01 Whistler Roy L Composition en amidon granulaire pour matrices microporeuses
WO1995019376A1 (fr) 1994-01-14 1995-07-20 Fuisz Technologies Ltd. Agregat particulaire poreux et son procede de preparation
DE10022987A1 (de) * 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Kombinationen von Pflanzenschutzmitteln mit kationischen Polymeren
DE10022986A1 (de) * 2000-05-11 2001-11-22 Aventis Cropscience Gmbh Kombinationen von Pflanzenschutzmitteln mit anionischen Polymeren
US20100105637A1 (en) * 2005-08-17 2010-04-29 Kim Cherng-Ju Drug-surfactant complexes for sustained release
US20070160637A1 (en) 2006-01-10 2007-07-12 Grain Processing Corporation Pest control agent, method for manufacture of pest control agent, and method for pest control
WO2007110355A2 (fr) 2006-03-24 2007-10-04 Basf Se Formulations agrochimiques
US20100178358A1 (en) * 2006-03-28 2010-07-15 Louis Gastonguay Polysaccharide-based impregnated solid material with improved stability, processes for the preparation thereof and impregnating solutions used
DE102009017677A1 (de) * 2009-04-16 2010-10-21 Sarastro Gmbh Verfahren zum Herstellen eines Stoffs mit einstellbaren biologisch aktiven Gradienteneigenschaften und derartiger Stoff

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Pesticide Manual", 2006, THE BRITISH CROP PROTECTION COUNCIL

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110199988A (zh) * 2019-06-18 2019-09-06 罗宏生 一种复合除草剂

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