WO2020094823A1 - Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques - Google Patents

Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques Download PDF

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Publication number
WO2020094823A1
WO2020094823A1 PCT/EP2019/080634 EP2019080634W WO2020094823A1 WO 2020094823 A1 WO2020094823 A1 WO 2020094823A1 EP 2019080634 W EP2019080634 W EP 2019080634W WO 2020094823 A1 WO2020094823 A1 WO 2020094823A1
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poly
lysine
range
mol
plants
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PCT/EP2019/080634
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English (en)
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Markus KALT
Peter Eck
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Basf Se
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    • 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
    • A01N37/44—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 nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives

Definitions

  • the present invention relates to a compound selected from the group of poly-lysine and poly-lysine derivative to increase the effectiveness of agrochemically active compounds in agrochemical formulations; the use of at least one poly-lysine or poly-lysine derivative as adjuvant in an agrochemical formulation; method for preparation of an agrochemical formulation by mixing at least an agrochemically active compound, at least one compound selected from the group of poly-lysine and poly-lysine derivative and at least one compound selected from formulation auxiliaries; a method for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein an agrochemical formulation comprising at least one agrochemically active compound and at least one adjuvant selected from poly-lysine and poly-lysine derivative is allowed to act on the respective pests, their environment or on the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or
  • agrochemical formulations comprising at least one agrochemically active compound which allows the best result achievable for the agrochemical application, such as controlling phytopathogenic fungi and/or undesired vegetation and/or undesired insect or mite attack and/or for regulating the growth of plants.
  • the effect of agrochemically active compounds may be controlled by addition of adjuvants to agrochemical formulations.
  • Adjuvants usually increase the effectiveness of an agrochemical formulation.
  • An object of the invention at hand was to find an adjuvant for agrochemical formulations allowing controlling phytopathogenic fungi and/or undesired vegetation and/or undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical formulation comprises at least one agrochemically active compound in reduced amounts but with at least maintained effectivity when compared to agrochemical formulations comprising higher amounts of the same agrochemically active compound (s) but lacking any adjuvant.
  • the object was achieved by providing a compound selected from the group of poly-lysine and derivatives thereof to increases the effectiveness of an agrochemical active compound comprised in an agrochemical formulation.
  • Said compound increasing the effectiveness of an agrochemical active compound may be called adjuvant herein.
  • said compound is poly-lysine characterized in being a non- crosslinked, water-soluble molecule having a K-value in the range of 10-14 and/or a weight-average molecular weight in the range of about 6,000 g/mol to about 20,000 g/mol and/or a polydispersity index in the range of 2.0 to 4.0.
  • said compound is a poly-lysine derivative, preferably a poly-lysine oleate or poly-lysine laurate, characterized in having a K-value of in the range of 13-16 and/or a molecular weight in the range of about 35,000 g/mol to about 55,000 g/mol, and/or a polydispersity index in the range of about 5.0 to about 7.0.
  • the invention provides a process for the preparation of an in-can agrochemical formulation comprising the steps of mixing in any order in one or more steps
  • formulation auxiliaries selected from surface-active substances (such as dispersants, emulsifiers, surfactants, solubilizers, protective colloids, wetters and stickers), solvents, solid carriers, defoamers, preservatives, antifreeze agents, rheology modifiers, colorants, antioxidants, retention enhancers, penetration enhancers, tackifiers or binders oils, and compatibilizers.
  • the invention provides a process for the preparation of a tank-mix comprising the steps of mixing in any order in one or more steps
  • formulation auxiliaries selected from surface-active substances (such as dispersants, emulsifiers, surfactants, solubilizers, protective colloids, wetters and stickers), solvents, solid carriers, defoamers, preservatives, antifreeze agents, rheology modifiers, colorants, antioxidants, retention enhancers, penetration enhancers, tackifiers or binders oils, and compatibilizers, and
  • the invention provides a method to increase the effectiveness of agrochemically active compounds in agrochemical formulations by adding at least one compound selected from the group of poly-lysine and a derivative thereof according to the invention to the agrochemical formulation.
  • the invention provides a method to increase control phytopathogenic fungi and/or undesired plant growth and/or u ndesired insect or mite attack and/or for regulating the growth of plants comprising the steps of applying an agrochemical formulation comprising at least one compound selected from poly-lysine and a derivative thereof according to the invention onto pests and/or their environment and/or the plants to be protected from the respective pest and/or the soil and/or undesired plants, when compared to application of an agrochemical formulation lacking at least one compound selected from poly-lysine and derivatives thereof.
  • the invention provides the use or method of use of an agrochemical formulation comprising a compound selected from the group of poly-lysine and a derivative thereof according to the invention to the increase improvement of health of crop plants by applying the agrochemical formulation comprising a compound selected from the group of poly-lysine and a derivative thereof according to the invention onto plants, preferably crop plants, when compared to application of an agrochemical formulation lacking at least one compound selected from poly-lysine and poly-lysine derivative.
  • the invention provides the use of a compound selected from the group of poly-lysine and a derivative thereof according to the invention as an adjuvant in agrochemical formulations.
  • the invention provides the use of at least one compound selected from poly-lysine and a derivative thereof according to the invention as an additive to agrochemical formulations to increase effectiveness of an agrochemical formulation.
  • the invention provides a method to prepare an agrochemical formulation with increased effectiveness when applied onto plants comprising the step of adding at least one compound selected from poly-lysine and derivatives thereof according to the invention to an agrochemical formulation.
  • the invention provides a method to reduce the amount of agrochemically active compound(s) in agrochemical formulations necessary for controlling phytopathogenic fungi and/or undesired vegetation and/or undesired insect or mite attack and/or for regulating the growth of plants by adding at least one compound selected the group of poly-lysine and a derivative thereof according to the invention to an agrochemical formulation and applying the resulting mixture to the respective pests, their environment or on the plants to be protected from the respective pest, on the soil and/or on undesired plants and/or on the crop plants and/or on their environment.
  • Adjuvants usually modify the effect of active compounds such as agrochemically active compounds comprised in agrochemical formulations.
  • An adjuvant usually increases the effectiveness of an agrochemical formulation.
  • I ncrease of effectiveness of an agrochemical formulation of the invention may mean that the agrochemical formulation is more effective in controlling phytopathogenic fungi and/or plant growth and/or undesired insect or mite attack when compared to agrochemical formulations lacking an adjuvant.
  • I ncrease of effectiveness of an agrochemical formulation may mean that the agrochemical formulation is more effective in improving the health of crop plants when compared to agrochemical formulations lacking an adjuvant.
  • I ncrease in effectiveness of an agrochemical formulation may mean that an agrochemical formulation comprising less amounts of an agrochemically active compound ( ⁇ 100%) and an adjuvant exhibits at least maintained effectiveness when compared to a reference agrochemical formulation lacking the adjuvant but comprising higher amounts of agrochemically active compound (i.e. 100% agrochemically active compound).
  • the effectiveness of an agrochemical formulation may be maintained when the effectiveness of agrochemical formulation of the invention in controlling phytopathogenic fungi and/or plant growth and/or undesired insect or mite attack is essentially maintained.
  • the effectiveness of an agrochemical formulation may be maintained when the effectiveness of agrochemical formulation of the invention in improving the health of crop plants is essentially maintained.
  • “Essentially maintained” in this context may mean that the effectiveness of an agrochemical formulation comprising less amounts of an agrochemically active compound ( ⁇ 100%) and an adjuvant in terms of control of phytopathogenic fungi and/or plant growth and/or undesired insect or mite attack, or in terms of improvement of the health of crop plants is not reduced by more than 10% when compared to a reference agrochemical formulation lacking the adjuvant but comprising higher amounts of agrochemically active compound (i.e. 100% agrochemically active compound).
  • “Essentially maintained” may mean that the effectiveness of an agrochemical formulation comprising less amounts of an agrochemically active compound ( ⁇ 100%) and an adjuvant in terms of control of phytopathogenic fungi and/or plant growth and/or undesired insect or mite attack, or in terms of improvement of the health of crop plants is not reduced by more than 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% when compared to a reference agrochemical formulation lacking the adjuvant but comprising higher amounts of agrochemically active compound (i.e. 100% agrochemically active compound).
  • An agrochemically active compound comprised in an agrochemical formulation may be selected from“pesticides” and“fertilizers”.
  • Pesticides may be selected from synthetic pesticides and biopesticides. The skilled worker is familiar with pesticides, which can be found, for example, in the Pesticide Manual, 17th Ed. (2015), The British Crop Protection Council, London.
  • Non-limiting examples of pesticides include, but are not limited to fungicides, insecticides, nematicides, herbicides (algicides, arboricides, graminicides), akaricides, molluskicides, ovicides, rodenticides, safeners and growth regulators.
  • component (a) comprises at least one fungicide and/or at least one insecticide and/or at least one nematicide and/or at least one herbicide and/or at least one akaricide and/or at least one molluskicide and/or at least one ovicide and/or at least one rodenticide and/or at least one safener and/or at least one growth regulator.
  • Non-limiting examples of suitable insecticides include compounds from the class of the carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, milbemycins, juvenile hormone analogs, alkyl halides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI acaricides, and insecticides such as chloropicrin, pymetrozine, flonicamid, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorfenapyr, DNOC, buprofezin, cyromazine, amitraz, hydramethylnon, acequinocyl, fluacrypyrim, rotenon, or their derivatives.
  • insecticides are selected from the group of organo-phosphates and neonicotinoids. I n one embodiment, insecticides are selected from dimethoate and imididachloprid.
  • Non-limiting examples of suitable fungicides include compounds from the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzoisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxylic acid amides, chloronitriles, cyanoacetamide oximes, cyanoimidazoles, cyclopropanecarboxamides, dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy(2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones,
  • fungicides are selected from the group of methoxyacrylates, morpholines, triazoles, and carboxamides.
  • fungicides may be selected from azoxystrobin, pyraclostrobin, fenpropimorph, epoxiconacole, mefentrifluconazole, tebuconazole, and fluxapyroxad.
  • fungicides are selected from azoxystrobin, pyraclostrobin, epoxiconacole, and tebuconazole.
  • Non-limiting examples of suitable herbicides include compounds from 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, phthal
  • herbicides are selected from the group of benzoic acids, sulfonyl ureas, and diphenyl ethers. I n one embodiment, herbicides are selected from dicamba, rimsulfuron, and oxyfluorofen.
  • Non-limiting examples of suitable growth regulators include abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6- dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate
  • Fertilizer includes organic and synthetic fertilizers that may be applied to soils or plant tissue such as leaves to supply plant nutrients which usually enhance growth of plants. Fertilizers typically provide in varying proportions nitrogen and/or phosphorus and/or potassium and/or calcium and/or magnesium and/or sulfur and/or copper and/or iron and/or manganese and/or molybdenum and/or zinc and/or boron and/or other nutrients.
  • An agrochemical formulation may comprise at least one water-insoluble agrochemically active compound.
  • Water-insoluble in this context means that ⁇ 50 g of the respective agrochemically active compound is soluble in 1000 g water at 20° C and 101.3 kPa.
  • Water-insoluble may mean that ⁇ 30 g, ⁇ 25 g, ⁇ 20 g, ⁇ 15 g, ⁇ 10 g, ⁇ 9 g, ⁇ 8 g, ⁇ 7 g, ⁇ 6 g, ⁇ 5 g, ⁇ 2.5 g, ⁇ 1 g, ⁇ 0.5 g, ⁇ 0.1 g, ⁇ 0.05 g, ⁇ 0.025 g, ⁇ 0.01 g, or ⁇ 0,005 g of the respective agrochemically active compound is solu ble in 1000 g water at 20° C and 101.3 kPa without phase separation.
  • an agrochemical formulation comprises at least one water-insoluble fungicide and/or at least one water-insoluble insecticide and/or at least one water- insoluble nematicide and/or at least one water-insoluble herbicide and/or at least one water-insoluble akaricide and/or at least one water-insoluble molluskicide and/or at least one water-insoluble ovicide and/or at least one water-insoluble rodenticide and/or at least one water-insoluble safener and/or at least one water-insoluble growth regulator.
  • an agrochemical formulation comprises at least one water-insoluble agrochemically active compound and at least one water-soluble agrochemically active compound.
  • At least one water-soluble agrochemically active compound may be selected from at least one water-soluble pesticide, at least one water-soluble fertilizer, and combinations thereof.
  • an agrochemical formulation usually comprises one or more formulation auxiliaries, which means any suitable ingredient for designing agrochemical formulations of various types.
  • formulation auxiliaries are known to those skilled in the art and may be selected from surface-active substances (such as dispersants, emulsifiers, surfactants, solubilizers, protective colloids, wetters and stickers), solvents, solid carriers, defoamers, preservatives, antifreeze agents, rheology modifiers, colorants, antioxidants, retention enhancers (e.g. Lutensol ® ON 60), penetration enhancers, adjuvants, tackifiers or binders (for example for the treatment of seeds) oils, and compatibilizer.
  • the function of a specific formulation auxiliary in the final application of an agrochemical formulation may depend on its amount within the agrochemical formulation, i.e. the effective amount of a formulation auxiliary.
  • At least one agrochemically active compound as described above may or may not (fully) be dissolved in at least one solvent comprised in an agrochemical formulation.
  • At least one solvent may be selected from water.
  • At least one solvent may be selected from the group of organic solvents, such as mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, alicyclic and aromatic hydrocarbons, for example paraffins, tetrahydronaphthalene, alkylated naphthalenes and their derivatives, 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 strongly polar solvents, for example amines such as N-methylpyrrolidone.
  • organic solvents such as mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, furthermore coal tar oils and oils of vegetable or
  • At least one solvent is selected from the group of polar aprotic solvents such as sulfoxides, amides, hydrocarbyl- or hydrohydrocarbylene carbonates.
  • polar aprotic solvents such as sulfoxides, amides, hydrocarbyl- or hydrohydrocarbylene carbonates.
  • An example of a suitable sulfoxide is but is not limited to dimethyl sulfoxide.
  • Suitable hydrocarbyl carbonates include but are not limited to dialkyl-carbonates such as those with Cx-C 8 alkyl chains.
  • Suitable hydrocarbylene carbonates include but are not limited to alkylene carbonates such as C 2 -C 6 alkylene-carbonates (ethylene carbonate; 1,2- propylene carbonate; 1,3-propylene carbonate; 1,2-butylene carbonate; 1,3-butylene carbonate; 2,3-butylene carbonate; 1,2-pentylene carbonate; 1,3-pentylene carbonate;
  • alkylene carbonates such as C 2 -C 6 alkylene-carbonates (ethylene carbonate; 1,2- propylene carbonate; 1,3-propylene carbonate; 1,2-butylene carbonate; 1,3-butylene carbonate; 2,3-butylene carbonate; 1,2-pentylene carbonate; 1,3-pentylene carbonate;
  • At least one solvent comprised in the agrochemical formulation is miscible with at least one compound selected from poly-lysine and poly lysine derivative at 20° C and 101.3 kPa.“Miscible” in this context means, that that no visible phase separation takes place between the mixed components.
  • the solvent is water and at least one compound selected from poly lysine and poly-lysine derivative is provided as an aqueous solution.
  • the agrochemical formulation of the invention is liquid.
  • the liquid agrochemical formulation may be an emulsifiable concentrates (EC) or emulsions (EW, EO, ES, ME) or soluble liquids (SL).
  • At least one agrochemically active compound is soluble
  • Solubility is related to the amount soluble in a liquid phase until the saturation point is achieved.
  • the agrochemical formulation of the invention comprises solid particles and may be called solid-based agrochemical formulation since at least one agrochemically active compound is insoluble
  • An agrochemically active compound insoluble remains solid in the liquid phase at 20° C and 101.3 kPa.
  • a solid agrochemically active compound herein includes any kind of particles of a size which are dispersible.
  • a solid agrochemically active compound may be insoluble, when ⁇ 10 g of the respective solid agrochemically active compound is soluble in 1000 g of the liquid phase at 20° C and 101.3 kPa. At least one solid agrochemically active compound may be insoluble, when ⁇ 5 g, ⁇ 3 g, ⁇ 1 g, or ⁇ 0.5 g of the respective solid agrochemically active compound is soluble in 1000 g of the liquid phase at 20° C and 101.3 kPa.
  • a solid-based agrochemical formulation may be a suspension concentrate (SC) or suspo- emulsions (SE) or oil dispersions (OD) or liquid formulations comprising microencapsulated particles (CS).
  • SC suspension concentrate
  • SE suspo- emulsions
  • OD oil dispersions
  • CS microencapsulated particles
  • the invention provides a compound selected from poly-lysine and derivatives thereof to increase effectiveness of agrochemical formulations.
  • the compound increasing the effectiveness of an agrochemical active compound comprised in an agrochemical formulation is poly-lysine selected from poly-lysines having a K-value of 10-14, 10-13, 10-12, 11-13, or 11-12.
  • the K-values are those determined by measurement of kinematic viscosity via Ubbelohde-viscosimeter (DI N 51562-3) at 20° C and 101.3 kPa.
  • poly-lysine is non-crosslinked and water-soluble.
  • N on -crossl inked herein means that that there is no deliberate cross-linking in the sense of formation of covalent bounds between single poly-lysine derivative molecules or modified poly-lysine derivative molecules introduced. Therefore, essentially no cross links are introduced by the process of production as such. Essentially no cross-links may mean that the degree of cross-linking is low, such as below 5%, which might be due to cross-linking substances being present in the reaction mixture as impurities of the aqueous lysine solution, such as arginine.
  • Water soluble herein means that a compound is soluble in water till its saturation point is achieved.
  • the saturation point usually means the concentration where water cannot dissolve more than a maximum concentration of a substance at 20° C and 101.3 kPa. Adding more than this maximum concentration will result in phase separation (precipitation, flocculation, gelling turbitity).
  • the poly-lysine molecule has a weight-average molecular weight in the range of about 6,000 g/mol to about 20,000 g/mol, or in the range of about 6,500 g/mol to about 20,000 g/mol, or in the range of about 6,500 g/mol to about 18,000 g/mol.
  • Weight-average molecular weight for the purposes of this invention is to be determined by size exclusion chromatography (SEC or GPC) using hexafluoro iso-propanol with 0.055% of trifluoro acetic acid potassium salt as an eluent at 35° C. Signal detection is performed by UV/Vis and refractive index sensors.
  • the poly-lysine molecule may have a polydispersity index of ⁇ 4, of ⁇ 3.5, or ⁇ 3.
  • the poly-lysine molecule may have a polydispersity index in the range of 2.0 to 4.0, or in the range of in the range of 2.5 to 3.5.
  • the poly-lysine molecule has a K-Value of 10-13, a weight-average molecular weight in the range of about 6,500 g/mol to about 18,000 g/mol and a polydispersity index in the range of 2.5 to 3.5.
  • the poly-lysine increasing the effectiveness of an agrochemical active compound comprised in an agrochemical formulation is selected from a poly-lysine obtained by a process comprising the steps of
  • melt viscosity of the reaction mixture in the range of about 350 mPa*s to about 6,500 mPa*s when measured at 160° C and
  • poly-lysine may be modified prior to step (e) by alkoxylation such as ethoxylation and/or reaction with monofunctional molecules such as amines, isocyanate, carboxylic acids, alcohols such as mPEG, thiols, esters, acid chlorides, anhydrides, and carbonates.
  • alkoxylation such as ethoxylation and/or reaction with monofunctional molecules such as amines, isocyanate, carboxylic acids, alcohols such as mPEG, thiols, esters, acid chlorides, anhydrides, and carbonates.
  • reaction temperature refers to the internal temperature of the reaction mixture in a reaction vessel.
  • the temperature of an external heat source used for heating the reaction vessel may be higher or lower than the reaction temperature.
  • the aqueous lysine solution and/or the reaction mixture of the invention are part of the “reaction system” which also includes a reaction vessel.
  • the process may be carried out in a continuously or batchwise working reaction system.
  • the process may be carried out in what is called a one-pot mode, in which the lysine is furnished in its entirety in the initial charge and the polycondensation reaction is carried out in a reactor with backmixing.
  • Polycondensation may also be started with only a part of the amount of lysine desired to be furnished in the whole process, wherein the rest of the lysine may be fed during the polycondensation process batchwise or continuously.
  • Any suitable reaction system may be used such as multistage reactor, a stirred-tank reactor, or a tube reactor.
  • the type of reaction vessel or reactor used, its volume, its isolation measures and other characteristics as well as the actual volume of the reaction mixture in the vessel, have to be recognized during operation accordingly. The one skilled in the art is familiar with the handling of different
  • reaction mixture herein comprises the aqueous lysine solution and/or possible impurities of the same and/or poly-lysine and/or poly-lysine derivative and/or water and/or non-reacted compounds including but not limited to alkenyl-carboxyl acid and/or by-products of the reactions taking place and/or one or more catalysts.
  • Aqueous lysine solution herein means any aqueous lysine-comprising solution such as fermentation broth comprising lysine.
  • Aqueous lysine solution may also mean that lysine in its solid state has been dissolved in a liquid medium comprising water.
  • Aqueous lysine solutions of the invention may comprise lysine in amounts of at least 5% by weight, at least 10% by weight, at least 20% by weight, at least 30% by weight, at least 40% by weight, at least 50% by weight, at least 60% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, or at least 95% by weight, all relative to the total weight of the aqueous lysine solution.
  • the aqueous lysine solution may comprise L-lysine, D-lysine, or any mixture of L-lysine and D-lysine, e.g. a racemic mixture.
  • Aqueous lysine solution of the invention comprises water in amounts of about 5% by weight, about 10% by weight, about 15% by weight, about 20%, about 25% by weight, about 30% by weight, about 40% by weight, about 50% by weight, about 60% by weight, about 70% by weight, about 80% by weight, about 90% by weight, or about 95% by weight, all relative to the total weight of the aqueous lysine solution.
  • Aqueous lysine solution of the invention may comprise impurities such as salts originating from the fermentation medium, cell debris originating from the production host cells, metabolites produced by the production host cells during fermentation.
  • impurities are comprised in aqueous lysine solution in amounts less than about 20% by weight, less than about 15% by weight, less than about 10% by weight, or less than about 5% by weight, all relative to the total weight of the aqueous lysine solution.
  • Heating to boiling means increase of the internal temperature of the aqueous lysine solution to at least about 100° C. I n one embodiment heating to boiling includes heating to internal temperatures within the aqueous lysine solution in the range of about 100 to about 110° C, or in the range of about 100° C to about 105° C.
  • the pressure within the reaction system may be reduced to about 90 kPa, to about 80 kPa, to about 75 kPa, to about 73 kPa, to about 70 kPa, to about 65 kPa, or to about 60 kPa.
  • the reduction of pressure within a reaction system is usually synonymous with “vacuum is applied”.
  • the boiling temperature usually depends on the actual vacuum applied.
  • At least one catalyst may be added to the aqueous lysine solution in step (a) in amounts up to 1% by weight relative the total weight of the reaction mixture.
  • catalyst sodium hypophosphite may be employed in amounts up to 1% by weight relative the total weight of the reaction mixture.
  • the internal temperature of the reaction mixture is increased to a temperature above boiling temperature, which ranges from about 105° C to about 180° C.
  • the internal temperature of the reaction mixture may be increased to a temperature in the range of 105° C to 180° C, in the range of about 135° C to about 180° C, or in the range of 140° C to 175° C.
  • the internal temperature of the reaction mixture is increased to 160° C.
  • vacuum is applied in step (b).
  • pressure within the reaction system has been reduced to a certain extent in step (a) and is further reduced in step (b).
  • the pressure may be reduced as much as for the given reaction system feasible by taking into account that foaming of the reaction mixture has to be avoided.
  • Pressure within the reaction system may be reduced to about 90 kPa, to about 80 kPa, to about 75 kPa, to about 73 kPa, to about 70 kPa, to about 65 kPa, or to about 60 kPa.
  • vacuum is applied within short time.
  • the increase of the internal temperature of the reaction mixture is achieved within short time.
  • “Within short time” in the context of applying vacuum and/or increase of internal temperature means that the desired pressure reduction and/or increase of the internal temperature of the reaction mixture is achieved within a time-span that is reasonably short for the given reaction system.“Within short time” may mean within ⁇ 1.5 hours, within ⁇ 1 hour, within ⁇ 35 minutes, or within ⁇ 15 minutes.
  • pressure within the reaction system is reduced to about 78 kPa within 35 minutes.
  • vacuum may be applied in step (c).
  • pressure within the reaction system has been reduced to a certain extent in step (a) and/or step (b) and is further reduced in step (b).
  • the pressure may be reduced as much as for the given reaction system feasible by taking into account that foaming of the reaction mixture has to be avoided.
  • Pressure within the reaction system may be reduced to about 90 kPa, to about 80 kPa, to about 75 kPa, to about 73 kPa, to about 70 kPa, to about 65 kPa, or to about 60 kPa.
  • vacuum is applied within short time.
  • pressure has already been reduced in step (b) and is further reduced in step (c).
  • pressure may have been reduced within the reaction system in step (b) to 78 kPa within short time and may be further reduced to 73 kPa in step (c) within short time such as 35 minutes.
  • the desired internal temperature of the reaction mixture once achieved, is kept until i. melt viscosity of the reaction mixture in the range of about 350 mPa*s to about 6,500 mPa*s is achieved when measured at 160° C, and
  • an amine number in the range of about 100 mg KOH/g to about 500 mg KOH/g is achieved.
  • the melt viscosity to be achieved may be in the range of about 350 mPa*s to about 6,500 mPa*s, in the range of 500 to 5,000 mPa*s, or in the range of about 1,000 mPa*s to about 3,000 mPa*s when measured at 160° C.
  • the melt viscosity to be achieved may be in the range of 1000 mPa*s to 6,500 mPa*s, in the range of about 3,000 mPa*s to about 6,500 mPa*s, in the range of about 3,200 mPa*s to about 6,500 mPa*s, when measured at 140° C.
  • the melt viscosity values are determined by melt rheology measurement (plate-plate) using an I.C.I. Cone Plate Viscosimeter from Epprecht GmbH (now Brookfield GmbH). Said melt rheology measurement is to be performed according to DI N 53018.
  • the amine number to be achieved may be in the range of 100 KOH/g to 500 mg KOH/g, in the range of 150 KOH/g to 450 mg KOH/g, in the range of 200 KOH/g to 450 mg KOH/g, in the range of 300 KOH/g to 450 mg KOH/g, or in the range of 350 KOH/g to 430 mg KOH/g.
  • the amine number is determined by potentiometric titration of the reaction mixture at 20° C and 101.3 kPa with trifluoromethanesulfonic acid: amount of KOH in mg equals lg amine-comprising substance.
  • the desired internal temperature of the reaction mixture once achieved is kept until
  • melt viscosity of the reaction mixture in the range of about 350 mPa*s to about 6,500 mPa*s is achieved, and
  • an amine number in the range of about 150 mg KOH/g to about 500 mg KOH/g is achieved.
  • the reaction mixture is kept at its internal temperature until a K-value of 10-14, 10-13, 10-12.5, 11-13, or 11-12.5 is achieved.
  • the K-values are those determined by measurement of kinematic viscosity via Ubbelohde-viscosimeter (DI N 51562-3) at 20° C and 101.3 kPa.
  • the end point of the condensation reaction may also be determined via N I R (near infrared) measurement.
  • N I R near infrared
  • the amine number which may be determined according to DIN 53176 or the viscosity measurement which may be determined according to DIN 51562-3 is correlated with N I R spectrum followed by subsequent statistical analysis.
  • the poly-lysine obtained by the process has
  • polydispersity index of ⁇ 4 preferably ⁇ 3.5, and more preferably ⁇ 3; the poly lysine molecule may have a polydispersity index in the range of 2.0 to 4.0, or in the range of in the range of 2.5 to 3.5.
  • the K-values are those determined by measurement of kinematic viscosity via Ubbelohde-viscosimeter (DI N 51562-3) at 20° C and 101.3 kPa.
  • Weight-average molecular weight for the purposes of this invention is to be determined by size exclusion chromatography (SEC or GPC) using hexafluoro iso-propanol with 0.055% of trifluoro acetic acid potassium salt as an eluent at 35° C.
  • Signal detection is performed by UV/Vis and refractive index sensors.
  • the compound increasing the effectiveness of an agrochemical active compound comprised in an agrochemical formulation is a derivative of the poly-lysine obtained by the process as disclosed above.
  • the invention provides at least one compound selected from poly-lysine derivatives to increase effectiveness of agrochemical formulations, wherein the derivative has a K- value of 13-16, or 14-15.
  • the derivative has a K- value of 13-16, or 14-15.
  • said poly-lysine derivatives are non-crosslinked and water-soluble.
  • the poly-lysine derivative according to the invention is a non-crosslinked molecule preferably selected from poly-lysine oleate and poly-lysine laurate, more preferably from poly-lysine oleate.
  • the poly-lysine derivative according to the invention has
  • a poly dispersity index in the range of about 5.0 to about 7.0, preferably in the range of about 6.0 to about 7.0, and more preferably in the range of 6.5 to 7.0.
  • the poly-lysine derivative increasing the effectiveness of an agrochemical active compound comprised in an agrochemical formulation is selected from a poly-lysine derivative obtained by a process comprising the steps of
  • melt viscosity of the reaction mixture in the range of about 350 mPa*s to about 6,500 mPa*s when measured at 160° C and
  • poly-lysine may be modified prior to step (e) and/or may be modified in step (g) by alkoxylation such as ethoxylation and/or reaction with monofunctional molecules such as amines, isocyanate, carboxylic acids, alcohols such as mPEG, thiols, esters, acid chlorides, anhydrides, and carbonates.
  • alkoxylation such as ethoxylation and/or reaction with monofunctional molecules
  • monofunctional molecules such as amines, isocyanate, carboxylic acids, alcohols such as mPEG, thiols, esters, acid chlorides, anhydrides, and carbonates.
  • Steps (a) to (c) in the process obtaining poly-lysine derivative are the same as steps (a) to (c) in the process obtaining the poly-lysine as disclosed above.
  • release of the vacuum applied in steps (a), (b), or (c) may be necessary due to adding further reactants such as alkyl-carboxylic acid or alkenyl-carboxylic acid as described in step (e).
  • Release of vacuum may mean that pressure is increased to about 101.3 kPa.
  • the poly-lysine obtained is non-modified poly-lysine which is further processed in step (e).
  • the melt viscosity of non-modified poly-lysine may be in the range of 500 mPa*s to 3,000 mPa*s, or in the range of about 1,000 mPa*s to about 2,300 mPa*s when measured at 160° C.
  • the melt viscosity of non-modified poly-lysine may be in the range of 3,000 mPa*s to 6,500 mPa*s, or in the range of about 3,200 mPa*s to about 6,400 mPa*s when measured at 140° C.
  • the poly-lysine obtained is modified prior to step (e) by alkoxylation such as ethoxylation (resulting in ethoxylated amine groups) and/or reaction with monofunctional molecules such as amines, isocyanate, carboxylic acids, alcohols such as mPEG, thiols, esters, acid chlorides, anhydrides, and carbonates.
  • alkoxylation such as ethoxylation (resulting in ethoxylated amine groups)
  • monofunctional molecules such as amines, isocyanate, carboxylic acids, alcohols such as mPEG, thiols, esters, acid chlorides, anhydrides, and carbonates.
  • the poly-lysine obtained is modified prior to step (e) may be called modified poly-lysine herein.
  • the melt viscosity of modified poly-lysine, e.g. poly-lysine-mPEG may be in the range of about 350 mPa*s to about 6,500 mPa*s, or in the range of about 350 mPa*s to about 1,000 mPa*s when measured at 160° C.
  • the melt viscosity of modified poly-lysine, e.g. poly-lysine-mPEG may be in the range of about 1,000 mPa*s to about 6,500 mPa*s, or in the range of about 1,000 mPa*s to about 2,000 mPa*s when measured at 140° C.
  • Alkyl-carboxylic acid or alkenyl-carboxylic acid is added in amounts in the range of 2.5 mol% to 10 mol%, relative to the theoretical amount of non-modified poly-lysine and/or modified poly-lysine.
  • the amount of alkyl-carboxylic acid or alkenyl-carboxylic acid added may be in the range of 3 mol% to 8 mol%, or about 5 mol%, all relative to the theoretical amount of non-modified poly-lysine and/or modified poly-lysine comprised in the reaction mixture.
  • reaction water means the amount of water that evolves from the polymerization reaction.
  • alkyl-carboxylic acid or alkenyl-carboxylic acid is to be conducted“within short time”. In any case this relates to avoidance of reduction of the internal temperature of the reaction mixture as far as possible.“Within short time” in the context of adding alkyl-carboxylic acid or alkenyl-carboxylic acid may mean, that the time-span of supplementation should be kept reasonably short for the given reaction system, e.g.
  • “Within short time” in the context of adding alkyl-carboxylic acid or alkenyl-carboxylic acid may also mean, that the time-span during which vacuum is released for the purposes of addition of alkyl-carboxylic acid or alkenyl-carboxylic acid is kept reasonably short for the given reaction system.“Within short time” may mean within about 30 minutes, within about 20 minutes, or within about 10 minutes or less.
  • Alkyl-carboxylic acid may be C 8 -C 22 or C 12 -C 18 saturated carboxylic acids.
  • Alkenyl-carboxylic acid may be selected from C 16 -C 22 mono-, and poly-unsaturated fatty acids.
  • Alkyl-carboxylic acid or alkenyl-carboxylic acid may be oxidized to a certain extent, meaning that this oxidation is naturally occurring by exposure to air. These oxidations may be initiated by e.g. oxygen, ozone and nitrous oxide. Oxidized to a certain extent in this context means, that ⁇ 75% of the oleic acid is oxidized. Oxidized to a certain extent may mean, that ⁇ 70%, ⁇ 65%, ⁇ 60%, ⁇ 55%, ⁇ 50%, ⁇ 45%, or ⁇ 40% oleic acid is oxidized.
  • the alkyl-carboxylic acid is lauric acid.
  • Laurac acid for supplementation can be derived from animal or plant origin and constitutes a variety of carbon chain lengths, the predominant being the C 12 saturated carboxylic acid.
  • Lauric acid is a major component of coconut oil and palm kernel oil.
  • Lauric acid may be oxidized to a certain extent.
  • Oxidized to a certain extent in this context means, that ⁇ 75% of the lauric acid is oxidized.
  • Oxidized to a certain extent may mean, that ⁇ 70%, ⁇ 65%, ⁇ 60%, ⁇ 55%, ⁇ 50%, ⁇ 45%, or ⁇ 40% lauric acid is oxidized.
  • the alkenyl-carboxylic acid is oleic acid.
  • Oleic acid for supplementation can be derived from animal or plant origin and constitutes a variety of carbon chain lengths, the predominant being the C 18 mono- and poly-unsaturated oleic acid.
  • oleic acid comprises C 18 mono-unsaturated oleic acid in amounts of at least 50%.
  • Oleic acid may comprise C 18 mono-unsaturated oleic acid in amounts of at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, or at least 80%.
  • Oleic acid may be oxidized to a certain extent. Oxidized to a certain extent in this context means, that ⁇ 75% of the oleic acid is oxidized. Oxidized to a certain extent may mean, that ⁇ 70%, ⁇ 65%, ⁇ 60%, ⁇ 55%, ⁇ 50%, ⁇ 45%, or ⁇ 40% oleic acid is oxidized.
  • the reaction mixture needs again to be increased to the desired internal temperature of the reaction mixture. I n one embodiment, this increase is done within short time.
  • vacuum may again be applied, meaning that pressure may be reduced to about 90 kPa, to about 80 kPa, to about 75 kPa, to about 73 kPa, to about 70 kPa, to about 65 kPa, or to about 60 kPa.
  • vacuum is applied within short time.
  • “Within short time” in the context of applying vacuum and/or increase of internal temperature means that the desired pressure reduction and/or increase of the internal temperature of the reaction mixture is achieved within a time-span that is reasonably short for the given reaction system.“Within short time” may mean within ⁇ 1.5 hours, within ⁇ 1 hour, within ⁇ 30 minutes, or within ⁇ 15 minutes.
  • the desired internal temperature is kept until the number of free alkyl-carboxylic acid or alkenyl-carboxylic acid is ⁇ 9% by weight, relative to the total weight of poly-lysine derivative.
  • the desired internal temperature may be kept until the number of free acid is less ⁇ 8% by weight, ⁇ 5% by weight, ⁇ 2.7% by weight, or ⁇ 2.5% by weight, all relative to the total weight of the reaction mixture.
  • free acid is determined by reacting free alkyl-carboxylic acid or alkenyl-carboxylic acid with MSTFA (N-Methyl-N- (trimethy lsilyl)trif I uoroaceta mide) and detecting the resulting alkyl-carboxylic acid or alkenyl-carboxylic acid silyl ester by gaschromatography.
  • MSTFA N-Methyl-N- (trimethy lsilyl)trif I uoroaceta mide
  • the total amount of free alkyl- carboxylic acid or alkenyl-carboxylic acid is determined by adding commercially available standards and by supplementation of alkyl-carboxylic acid or alkenyl-carboxylic acid.
  • the amount of free alkyl-carboxylic acid or alkenyl-carboxylic acid is calculated based on the amount of non-reacted C 12 - saturated fatty acid or non-reacted C 18 -mono-unsaturated fatty acid.
  • free lauric acid is determined by this method, wherein the number of free lauric acid is calculated based on the amount of non-reacted C 12 -saturated lauric acid.
  • free oleic acid is determined by this method, wherein the number of free oleic acid is calculated based on the amount of non-reacted C 18 -mono- unsaturated oleic acid.
  • the poly-lysine derivative obtained by the process has
  • the invention provides a process for the preparation of an in-can agrochemical formulation by mixing in any order in one or more steps an agrochemical formulation comprising at least one agrochemical active compound, with at least one compound selected from the group of poly-lysine and poly-lysine derivative of the invention, and one or more formulation auxiliaries, selected from surface-active substances (such as dispersants, emulsifiers, surfactants, solubilizers, protective colloids, wetters and stickers), solvents, solid carriers, defoamers, preservatives, antifreeze agents, rheology modifiers, colorants, antioxidants, retention enhancers, penetration enhancers, tackifiers or binders oils, and compatibilizer.
  • surface-active substances such as dispersants, emulsifiers, surfactants, solubilizers, protective colloids, wetters and stickers
  • solvents solid carriers, defoamers, preservatives, antifreeze agents, rheology modifiers, colorants, antioxidant
  • Mixing may be carried out by customary mixing processes, such as stirring, shaking or any other energy input.
  • At least one compound selected from poly-lysine and poly-lysine oleate is comprised in the in-can agrochemical formulation in amounts effective to increase effectiveness of an agrochemically active compound in the actual application. Effective amount may range from about 1 to about 500 ml per ha, from about 5 to about 300 ml per ha, or from about 10 to 200 ml per ha when applied onto plants, preferably crop plants “ml per ha” in this context relates to the amount of 100% active polymer content.
  • Active polymer content may mean the actual poly-lysine or poly-lysine derivative obtained by the process as described above water is added before step (e) or step (h) in poly-lysine and poly-lysine derivative production respectively.
  • the in-can agrochemical formulation is liquid at 20° C and 101.3 kPa.
  • the in-can agrochemical formulation is a solid-based agrochemical formulation at 20° C and 101.3 kPa, which may have been prepared by the process of comminution.
  • comminution processes divide a solid into fine particles in the dispersing medium or in a dry state before mixing with a dispersing medium.
  • the one skilled in the art is familiar with the specifics of wet and dry comminution.
  • the effectiveness of comminution depends on the shape and crystal form of particles. Usually, wet comminution is more effective than dry comminution and reduces particle size better.
  • wet comminution is often operated by using impeller mills, ball mills, small-media mills (such as sand mills and bead mills), vibratory mills, roll mills or ultrasonic dispersers.
  • mills useful include but are not limited to agitator ball mills, circulating mills (agitator ball mills with pin grinding system), disk mills, annular chamber mills, double cone mills, triple roll mills, batch mills, and colloid mills.
  • the comminution chambers may be fitted with cooling systems.
  • the particle size within 50% of the total amount of solid compound (dx 50 ) comprised in the solid-based composition of the invention may be about ⁇ 50 pm, about ⁇ 30 pm, about ⁇ 20 pm, or about ⁇ 10 pm.
  • the particle size within 90% of the total amount of solid compound (dx 90 ) is less than 100 pm, less than 50 pm, less than 30 pm, or less than 20 pm.
  • Size particle distributions may be measured by any suitable method known to those skilled in the art. Suitable methods include but are not limited to methods using laser diffraction. Descriptions for the use of laser diffraction methods are provided e.g. in ISO 13320-1, CI PAC MT184 (Handbook K).
  • the in-can agrochemical formulation comprises at least one agrochemically active compound selected from methoxyacrylates, and triazoles, preferably in amounts of 1-10 g/ha when applied, more preferably in amounts of about 5 g/ha. At least one agrochemically active compound selected from azoxystrobine and epoxiconazole.
  • the in-can agrochemical formulation may be diluted with water prior to application in order to prepare the so-called tank-mix.
  • the present invention provides the use or method of use of a compound selected from poly-lysine and poly-lysine derivates according to the invention as additive in agrochemical formulation for the treatment of plants, preferably crop plants, wherein said additive increases the effectiveness of the agrochemical formulation.
  • the invention provides a process for the preparation of a tank-mix by mixing in any order in one or more steps
  • formulation auxiliaries selected from surface-active substances (such as dispersants, emulsifiers, surfactants, solubilizers, protective colloids, wetters and stickers), solvents, solid carriers, defoamers, preservatives, antifreeze agents, rheology modifiers, colorants, antioxidants, retention enhancers, penetration enhancers, tackifiers or binders oils, and compatibilizer, and
  • the tank-mix is prepared by mixing in one or more steps in any order individual formulation ingredient, wherein at least one of the ingredients is selected from poly-lysine and poly-lysine derivative of the invention.
  • the tank-mix comprises at least one agrochemically active compound selected from methoxyacrylates, and triazoles, preferably in amounts of 1-10 g/ha when applied, more preferably in amounts of about 5 g/ha. At least one agrochemically active compound selected from azoxystrobine and epoxiconazole.
  • a tank-mix is usually applied by spraying or fogging onto plants, preferably crop plants.
  • At least one compound selected from poly-lysine and poly-lysine oleate is comprised in the tank-mix in amounts effective to increase effectiveness of an agrochemically active compound. Effective amount may range from about 1 to about 500 ml per ha, from about 5 to about 300 ml per ha, or from about 10 to 200 ml per ha.“ml per ha” in this context relates to the amount of 100% active polymer content.
  • Active polymer content may mean the actual poly-lysine or poly-lysine derivative obtained by the process as described above water is added before step (e) or step (h) in poly-lysine and poly-lysine derivative production respectively.
  • crop plant is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http: //www. bio. org/speeches/pubs/er/agri products asp).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein (s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • the invention relates to the use or method of use of a compound selected from poly lysine and poly-lysine derivates according to the invention as additive in agrochemical formulation for the treatment of plants, preferably crop plants, to control phytopathogenic fungi and/or plant growth and/or undesired insect or mite attack, wherein said additive increases the effectiveness of the agrochemical formulation on the respective pests, their environment or in terms of plants to be protected from the respective pest, the soil and/or on undesired plants and/or the useful plants and/or their environment.
  • Control of plant growth includes the inhibition of growth of weed and favor or increase of growth of crop plants.
  • the invention relates to the use or method of use of a compound selected from poly lysine and poly-lysine derivates according to the invention as additive in agrochemical formulation for the treatment of plants, preferably crop plants, wherein said additive increases the effectiveness of the agrochemical formulation in terms of improvement of health of “crop plants” which may be determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves (“greening effect”)), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves (“greening effect”)
  • quality e. g. improved content or composition of certain ingredients
  • the invention relates to the use or method of use of the agrochemical formulation according to the invention for controlling undesired insect or mite attack on plants and/or for controlling phytopathogenic fungi and/or for controlling undesired plant growth, wherein plant propagation material is treated with an agrochemical formulation comprising at least one compound selected from poly-lysine and poly-lysine derivative of the invention.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil. These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring. I n one embodiment, treatment of plant propagation materials with the agrochemical formulation of the invention is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • the invention relates to seed which has been treated with the agrochemical formulation of the invention.
  • the seed may be dressed with the agrochemical formulation of the invention.
  • Dressing means that the seed is treated with the agrochemical formulation and the agrochemical formulation remains on the seed.
  • This agrochemical formulation may be applied to the seed in undiluted or, preferably, diluted form.
  • the agrochemical formulation in question can be diluted 2- to 10-fold, so that from 0.01% to 60% by weight, or from 0.1% to 40% by weight, of agrochemically active compound are present in the agrochemical formulation to be used for dressing the seed.
  • the application can take place before sowing.
  • the treatment of plant propagation material such as the treatment of seed
  • the treatment of plant propagation material is known to the skilled worker and is carried out by dusting, coating, pelleting, dipping or soaking the plant propagation material, the treatment may be effected by pelleting, coating and dusting, so that, for example, premature germination of the seed is prevented.
  • the treatment of seed one may use amounts of agrochemically active compound in the range of 1 to 1000 g/100 kg, or in the range of 5 to 100 g/100 kg propagation material or seed.
  • Adjuvants used in the examples are those provided in the Table ExAdjuv below.
  • Pesticides used in examples are those listed in the following Table ExPest:
  • the K-value was determined by measurement of kinematic viscosity via Ubbelohde-viscosimeter (DIN 51562-3).
  • the amine number was determined by potentiometric titration of the reaction mixture at 20° C and 101.3 kPa with trifluoromethanesulfonic acid: amount of KOH in mg equals lg amine-comprising substance.
  • the weight-average molecular weight of the resulting poly-lysine derivative was determined by size exclusion chromatography (SEC or GPC) using hexafluoro iso propanol with 0.055% of trifluoro acetic acid potassium salt as an eluent at 35° C.
  • SEC or GPC size exclusion chromatography
  • GPC hexafluoro iso propanol with 0.055% of trifluoro acetic acid potassium salt as an eluent at 35° C.
  • Signal calibration is done using a PMMA standard from the company PSS with molecular weights from 800 g/mol to 2,200,000 g/mol.
  • Signal detection was performed by UV/Vis and refractive index sensors.
  • sample having a concentration of 1.5 mg/mL were injected onto the column setup (1 st precolumn 8 mm inner diameter, 5 cm length; separation column one 7.5 mm inner diameter, 30 cm length; separation column two 7.5 mm inner diameter, 30 cm length) with a flow rate of 0.85 mL/min.
  • An initial charge was started to be heated. At an internal temperature of 100° C, feed 1 was started to be added to the boiling initial charge. After 45 minutes the internal temperature of 160° C has been achieved. The internal temperature of the reaction mixture (i.e reaction temperature) was to be kept at this temperature at the following. Feed 1 was added within 5 hours to the reaction mixture.
  • the pressure within the reaction system was reduced to 780 mbar within 35 minutes. Within further 35 minutes, the pressure within the reaction system was further reduced to 725 mbar. The reaction mixture has been kept at 160° C and 725 mbar for additional 45 minutes.
  • the amine number was determined after achieving the target K-value by potentiometric titration as described above being 422.
  • the molecular weight, viscosity and PDI were determined: the poly-lysine had a Mw of 6,990 g/mol, Mn of 2,720 g/mol, and a PDI of 2.6; melt viscosity: 3,280 mPa*s at 140° C, and 1,000 mPa*s 160° C.
  • the product obtained was diluted with water to give a solution with an active polymer content of about 23.7% w/w.
  • An initial charge was started to be heated. At an internal temperature of 100° C, feed 1 was started to be added to the boiling initial charge. After 45 minutes the internal temperature of 160° C has been achieved. The internal temperature of the reaction mixture (i.e reaction temperature) was to be kept at this temperature at the following. Feed 1 was added within 5 hours to the reaction mixture.
  • the pressure within the reaction system was reduced to 780 mbar within 35 minutes. Within further 35 minutes, the pressure within the reaction system was further reduced to 725 mbar. The reaction mixture has been kept at 160° C and 725 mbar for additional 45 minutes.
  • the poly- lysine had a Mw of 17,100 g/mol, Mn of 4,910 g/mol, and a PDI of 3.5.
  • the amine number was 391; melt viscosity: 6,320 mPa*s at 140° C, and 2,240 mPa*s at 160° C.
  • the product obtained was diluted with water to give a solution with an active polymer content of about 24.6% w/w.
  • Example 1 (a) for production of A3 was not stopped when a K-value of 11 was achieved, but vacuum was released for adding 120.8 g oleic acid (feed 2) to the reaction mixture within 10 minutes. I mmediately after finishing the addition of feed 2, pressure within the reaction system was reduced to 725 mbar and the internal temperature of the reaction mixture was kept at 160° C for another 4 hours. During this time, evaporating water was distilled of.
  • the resulting poly-lysine oleate had a K-value of 14.9, an amine number of 315 mg KOH/g, Mw of 46,200 g/mol, Mn of 6,740 g/mol and a PDI of 6.9. Free acid was 2.1% relative to the total weight of the poly-lysine derivative (solid matter).
  • the product obtained was diluted with water to give a solution with an active polymer content of about 19.4% w/w.
  • the pH of the poly-lysine oleate solution was 8.3.; the pH was adjusted with lactic acid to a pH value of about 8.
  • Example 1 (b) for production of A4 was not stopped when a K-value of 12.3 was achieved, but vacuum was released for adding 120.8 g oleic acid (feed 2) to the reaction mixture within 10 minutes. I mmediately after finishing the addition of feed 2, pressure within the reaction system was reduced to 725 mbar and the internal temperature of the reaction mixture was kept at 160° C for another 4 hours. During this time, evaporating water was distilled of.
  • the resulting poly-lysine oleate the resulting poly-lysine oleate had a K-value of 15.1, an amine number of 321 mg KOH/g, Mw of 49,700 g/mol, Mn of 7,420 g/mol and a PDI of
  • the product obtained was diluted with water to a give a solution with an active polymer content of about 19.6% w/w.
  • the pH of the poly-lysine oleate solution was 8.5; the pH was adjusted with lactic acid to a pH value of about 8.
  • Example 1 (a) for production of A3 was run until a K-value of 11 was achieved: the poly-lysine had a Mw of 12,900 g/mol, Mn of 3,920 g/mol, and a PDI of 3.3.
  • the amine number was 422; melt viscosity: 3,280 mPa*s at 140° C, melt viscosity 1,000 mPa*s at 160° C. Vacuum was released for adding 362.4 g oleic acid (feed 2) to the reaction mixture within 10 minutes. I mmediately after finishing the addition of feed 2, pressure within the reaction system was reduced to 725 mbar and the internal temperature of the reaction mixture was kept at 160° C for another 4 hours. During this time, evaporating water was distilled of.
  • the resulting poly-lysine oleate had an amine number of 221 mg KOH/g, Mw of 44,000 g/mol, Mn of 6,500 g/mol and a PDI of 6.8. Free acid was 2.4% relative to the total weight of the poly-lysine derivative (solid matter).
  • the product obtained was diluted with water to give a solution with an active polymer content of about 12.4% w/w.
  • the pH of the poly-lysine-oleate solution was 8.0.
  • Plants tested barley (HORVX); cultivation of plants: three plants per pot were cultivated in fine Frustorfer soil for three weeks.
  • the plants were treated with the following SC formulation: fungicidal formulation - 25% by weight PI, 16.7% by weight Tamol ® N N 2901, 10% by weight propylene glycol, 48.3% by weight water.
  • the effect of an adjuvant was tested by adding the respective adjuvant (Table ExAdjuv) to the solid-based formulation prior to treatment of the plants. Dosing used was as indicated in Table Exla below.
  • the leaf segments on the agar plates were inoculated with fresh conidia of Blumeria graminis sp. hordei ⁇ type A6).
  • the agar plates (lOxlOcm) were then incubated at 18° C during night time and 23° C during day time at 60-70% air moisture in an incubator for a certain time.
  • the determination of the mildew infestation was carried out by determining the surface per leaf within 5 cm leaf length infested with mildew.
  • Table Exla PI with and without adjuvant in protective leaf-segment test on barley (HORVX) and the infestation of mildew after 2 WAT (weeks after treatment); “% leaf surface infested with mildew” corresponds to average value of 15 leaves
  • Plants tested barley (HORVX); cultivation of plants: three plants per pot were cultivated in fine Frustorfer soil for three weeks.
  • the plants were inoculated with fresh conidia of EHumeria graminis ⁇ . sp. hordei i type A6).
  • the determination of the mildew infestation was carried out by mildew pustules per leaf within 5 cm leaf length.

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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)
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Abstract

L'invention concerne un dérivé de poly-lysine possédant un ou plusieurs éléments parmi une valeur K définie, un poids moléculaire moyen et un indice de polydispersité capables d'augmenter l'efficacité de composés agrochimiquement actifs dans des formulations agrochimiques. L'invention concerne également des procédés de préparation de formulations agrochimiques en boîte et de mélange en cuve et l'utilisation de telles formulations pour améliorer la santé des cultures.
PCT/EP2019/080634 2018-11-09 2019-11-08 Dérivés de poly-lysine pour augmenter l'efficacité de formulations agrochimiques WO2020094823A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0254419A2 (fr) * 1986-06-24 1988-01-27 Chisso Corporation Agent pour prévenir les maladies à virus des plantes
WO2006108835A2 (fr) * 2005-04-15 2006-10-19 Basf Aktiengesellschaft Utilisation de polylysine dans des formulations biocides contenant du cuivre
US20080004177A1 (en) * 2003-10-17 2008-01-03 Thomas Pfeiffer Novel Copper-Containing Formulations
WO2010017075A1 (fr) * 2008-08-07 2010-02-11 Sigma-Aldrich Co. Préparation de polylysine et de polyornithine de faible masse moléculaire dans un rendement élevé
US20100249369A1 (en) * 2005-11-25 2010-09-30 Basf Se Production and use of highly functional, highly branched or hyperbranched polylysines
WO2016062578A1 (fr) * 2014-10-21 2016-04-28 Basf Se Procédé de préparation de polylysines

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0254419A2 (fr) * 1986-06-24 1988-01-27 Chisso Corporation Agent pour prévenir les maladies à virus des plantes
US20080004177A1 (en) * 2003-10-17 2008-01-03 Thomas Pfeiffer Novel Copper-Containing Formulations
WO2006108835A2 (fr) * 2005-04-15 2006-10-19 Basf Aktiengesellschaft Utilisation de polylysine dans des formulations biocides contenant du cuivre
US20100249369A1 (en) * 2005-11-25 2010-09-30 Basf Se Production and use of highly functional, highly branched or hyperbranched polylysines
WO2010017075A1 (fr) * 2008-08-07 2010-02-11 Sigma-Aldrich Co. Préparation de polylysine et de polyornithine de faible masse moléculaire dans un rendement élevé
WO2016062578A1 (fr) * 2014-10-21 2016-04-28 Basf Se Procédé de préparation de polylysines

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"the Pesticide Manual", 2015, THE BRITISH CROP PROTECTION COUNCIL
LAETITIA VIDAL ET AL: "Lauryl-poly-L-lysine: A New Antimicrobial Agent?", JOURNAL OF AMINO ACIDS, vol. 64, no. 9, 1 January 2014 (2014-01-01), pages 1442 - 10, XP055226199, ISSN: 2090-0104, DOI: 10.1155/2014/672367 *

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