WO2016087270A1 - Composition agrochimique solide pour libération prolongée de dioxyde de carbone - Google Patents

Composition agrochimique solide pour libération prolongée de dioxyde de carbone Download PDF

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Publication number
WO2016087270A1
WO2016087270A1 PCT/EP2015/077529 EP2015077529W WO2016087270A1 WO 2016087270 A1 WO2016087270 A1 WO 2016087270A1 EP 2015077529 W EP2015077529 W EP 2015077529W WO 2016087270 A1 WO2016087270 A1 WO 2016087270A1
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Prior art keywords
agrochemical composition
acid
carbon dioxide
dioxide source
composition according
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PCT/EP2015/077529
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English (en)
Inventor
Christian Sowa
Holger Kreusch
Ronald Wilhelm
Fabian Niedermair
Thomas Lichtenegger
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Basf Se
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Publication of WO2016087270A1 publication Critical patent/WO2016087270A1/fr

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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
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/04—Carbon disulfide; Carbon monoxide; Carbon dioxide

Definitions

  • the present invention relates to a solid agrochemical composition
  • a solid agrochemical composition comprising a binder and a carbon dioxide source, containing a solid acid and a C03 2_ -salt; or a salt of a cationic acid with a CC"3 2" -anion, and an insecticide.
  • the invention relates to a method for preparing said agrochemical composition by contacting the binder, the carbon dioxide source, the insecticide and optionally an organic carbon dioxide source.
  • Further subject matter is a method for controlling undesired insect or mite attack and/or for regulating the growth of plants, wherein said agrochemical composition is allowed to act on the respective pests, their environment or the crop 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.
  • the present invention comprises combinations of preferred features with other preferred features. Bernklau et al.
  • the object of the present invention was therefore to find a means of delivering carbon dioxide in a controlled and elongated manner by agrochemical compositions, whose characteristics should include high storage and temperature stability, as well as a high degree of adaptability to a given environment of application. Finally, these agrochemical compositions were aimed to be biodegradable to allow for repeated applications. This object was achieved by a solid agrochemical composition comprising
  • An agrochemical composition comprises a pesticidally effective amount of active ingredients, such as insecticides.
  • active ingredients such as insecticides.
  • effective amount denotes an amount of the composition or of the active ingredients, which is sufficient for controlling harmful insects on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the insect species to be controlled, the treated cultivated plant or material, the climatic condi- tions and the specific active ingredient used.
  • active ingredient herein denotes biologically active substances that are usually toxic to a given target organism.
  • the agrochemical composition is solid.
  • the expert clearly differentiates between a solid and a non-solid agrochemical composition, such as a liquid, a gel, a paste or putty.
  • solid state of matter is characterized by a distinct structural rigidity and virtual resistance to deformation (that is changes of shape and/or volume).
  • solids have high values both of Young's modulus (e.g. at least 0.1 GPa) and of the shear modulus of elasticity (e.g. at least 0.01 GPa).
  • the binder may be a thermoplastic and may be selected from biopolymers or synthetic poly- mers. It may be solid at room temperature and may further exhibit a suitable melting temperature.
  • Thermoplastics are usually polymers that are pliable and moldable above a specific temperature and return to a solid state upon cooling.
  • the polymer chains in thermoplastics are usually not covalently interconnected and the attracting forces between them are therefore often confined to non-covalent interactions.
  • the melting temperature of the binder may be from 40 to 150 °C, preferably from 50 to 120 °C, and most preferably from 60 to 100 °C.
  • melting temperature refers to polymers with a stochastic contribution of oligomers and also to biopolymers with a mixture of different chemical substances, and therefore melting may occur over a vast temperature range.
  • melting temperature designates the glass transition temperature of the substance, which is a parameter known to the skilled person.
  • the melting temperature may be measured by methods of common knowledge, such as differential scanning calorimetry (DSC) or differential thermal analysis (DTA), which have been described, for example, in ASTM E1356-08(2014) and DIN51007:1994-06.
  • DSC differential scanning calorimetry
  • DTA differential thermal analysis
  • the kinematic viscosity of the binder within the temperature range from 50 to 120 °C may be from 10 2 to 10 15 mPa-s, preferably from 10 3 to 10 12 mPa-s and most preferably from 10 3 to 10 10 mPa-s.
  • the binder may be selected from different chemical classes, such as waxes, polyketones, poly- amides, polyesters, polysaccharides, polyethers, polyamines, terpenes, as well as their chemical derivatives, their physical mixtures and compounds composed of at least two of these class members.
  • waxes usually refers, but is not limited to, petroleum derived waxes, such as paraffin waxes, montan wax or polyethylene waxes, to silicon waxes, as well as to plant and animal waxes, such as lipids, fatty acids, fatty alcohols, esters of carboxylic acids with fatty alcohols and steroids and mixtures of these compounds.
  • Paraffin waxes are usually hydrocarbons, which may be linear or branched, saturated or aro- matic.
  • paraffin waxes are linear and saturated, and usually comply with the general formula CnHbn+n, wherein n is from 15 to 45 and are solid at 25 °C.
  • the index n is usually from 50 to 100 in polyethylene waxes.
  • Montan waxes are usually mixtures of non-glyceride long-chain carboxylic acid esters, free long-chain organic acids, long-chain alcohols, ketones and hydrocarbons and resins, such as resin acid.
  • long-chain may refer to a range from C24 to C30.
  • Silicone waxes are typically alkylpolysiloxanes or arylpolysiloxanes or alkylarylpolysiloxanes.
  • alkyl usually refers to a linear or branched alkyl moiety containing from 1 to 8 carbon atoms, preferably from 1 to 6.
  • aryl refers to aromatic and cyclic moieties and their derivatives, containing from 5 to 10 carbon atoms in the cyclic aromatic.
  • the siloxane scaffold may be branched or linear, preferably branched, and contain from 100 to 10,000 silicon atoms per molecule, preferably from 100 to 1000.
  • plant and animal waxes examples include bee wax, lanolin, spermaceti, sugar cane wax, jojoba wax, carnauba wax, candelilla wax, Japan wax, soy wax, and saturated and unsaturated fatty alcohols or acids, esters of fatty alcohols with fatty acids and esters of fatty acids with steroids.
  • fatty usually refers to chain lengths of the respective compound from 8 to 40 carbon atoms, preferably from 12 to 30, and most preferably from 14 to 25 carbon atoms.
  • Examples of saturated and unsaturated fatty alcohols or acids, esters of fatty alcohols with fatty acids and esters of fatty acids with steroids are myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, lignoceric acid, melissic acid, icosanoic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linolaidic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, docosahexaenoic acid, as well as the cholesterol, di- hydrocholesterol, lanosterol, dihydrolanosterol, agnosterol, dihydroagnosterol esters of the aforementioned fatty acids, and myricyl palmitate, cetyl palmitate, myricyl cerotate Preferred waxes are plant wax
  • Preferred plant and animal waxes are soy wax, carnauba wax and jojoba wax, more preferably carnauba wax.
  • Polyesters are well-known polymers. They may comprise monomers in polymerized form, such as diols and diacids (or diesters), or hydroxyacids (or hydroxyesters). Preferably, the polyester is an aliphatic or a semiaromatic polyester.
  • Aliphatic polyesters typically include homopolymers of aliphatic hydroxycarboxylic acids or lac- tones, and also copolymers or block copolymers of different hydroxycarboxylic acids or lactones or mixtures of these. These aliphatic polyesters may also contain units of diols and/or of isocya- nates. The aliphatic polyesters may also contain units which derive from tri- or polyfunctional compounds, for example from epoxides, from acids or from triols. The aliphatic polyesters may contain the latter units as individual units, or a number of these, possibly together with the diols and/or isocyanates. Processes for preparing aliphatic polyesters are known to the skilled worker.
  • aliphatic polyesters In preparing the aliphatic polyesters it is, of course, also possible to use mixtures made from two or more co-monomers and/or from other units, for example from epoxides or from polyfunctional aliphatic or aromatic acids, or from polyfunctional alcohols.
  • aliphatic polyesters are polymeric reaction products of lactic acid, 3- hydroxybutyrate, 4-hydroxybutyrate, caprolactone, or polyesters built up from aliphatic or cyclo- aliphatic dicarboxylic acids and from aliphatic or cycloaliphatic diols, such as polybutylene succinate.
  • the aliphatic polyesters may also be random or block copolyesters which contain other monomers. The proportion of the other monomers is generally up to 10 percent by weight.
  • Pre- ferred monomers are hydroxycarboxylic acids or lactones or mixtures of these.
  • Polymeric reaction products of lactic acid, 3-hydroxybutyrate, 4-hydroxybutyrate and caprolactone are known per se or may be prepared by processes known per se.
  • the polyester may comprise 3-hydroxyvaleric acid, in particular with a proportion by weight of up to 30 percent, preferably up to 20 percent.
  • Suitable polymers of this type also include those with R-stereospecific configuration.
  • Polyhy- droxybutyrates or copolymers of these can be prepared microbially. Processes for the preparation from various bacteria and fungi are known as well as a process for preparing stereospecific polymers. It is also possible to use block copolymers of the above-mentioned hydroxycarboxylic acids or lactones, or of their mixtures, oligomers or polymers.
  • Suitable co-polyesters built up from aliphatic or cycloaliphatic dicarboxylic acids and from aliphatic or cycloaliphatic diols are those built up from aliphatic or cycloaliphatic dicarboxylic acids or from mixtures of these, and from aliphatic or cycloaliphatic diols, or from mixtures of these. According to the invention either random or block copolymers may be used.
  • Suitable aliphatic dicarboxylic acids according to the invention generally have from 2 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. They may be either linear or branched.
  • cycloaliphatic dicarboxylic acids which may be used are generally those having from 7 to 10 carbon atoms, and in particular those having 8 carbon atoms. However, in principle use may also be made of dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • malonic acid succinic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1 ,3-cyclopentanedicarboxylic acid, 1 ,4- cyclohexanedicarboxylic acid, 1 ,3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornanedicarboxylic acid, preferably adipic acid.
  • ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which may likewise be used, in particular the di-C1-C6-alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl, di-tert-butyl, di-n- pentyl, diisopentyl and di-n-hexyl esters.
  • Anhydrides of the dicarboxylic acids may likewise be used.
  • the dicarboxylic acids or ester forming derivatives of these may be used individually or as a mixture of two or more of these.
  • Suitable aliphatic or cycloaliphatic diols generally have from 2 to 10 carbon atoms, preferably from 4 to 6 carbon atoms. They may be either linear or branched. Examples are 1 ,4-butanediol, ethylene glycol, 1 ,2- or 1 ,3-propanediol, 1 ,6-hexanediol, 1 ,2- or 1 ,4-cyclohexanediol or mixtures of these.
  • aliphatic polyesters which may be used are aliphatic co-polyesters as described in WO 94/14870, in particular aliphatic co-polyesters made from succinic acid, from its diesters, or from mixtures with other aliphatic acids or, respectively, diesters, for example glutaric acid and butanediol, or mixtures made from this diol with ethylene glycol, propanediol or hexanediol or mixtures of these.
  • semiaromatic polyesters may refer to polyester, which comprises aliphatic and aromatic monomers in polymerized form, such as polybutylenadipatterephthalate.
  • semiaromatic polyesters is also intended to include derivatives of semiaromatic polyesters, such as semiaromatic polyetheresters, semiaromatic polyesteramides, or semiaromatic polyetherester- amides.
  • suitable semiaromatic polyesters are linear non-chain-extended polyesters (WO 92/09654). Preference is given to chain-extended and/or branched semiaromatic polyesters.
  • Preferred polyesters are polylactic acid, polycaprolactone, polybutylene succinate and poly- butylenadipat-terephthalate, more preferably polylactic acid, polycaprolactone and polybutylenadipatterephthalate and especially preferably polycaprolactone and polybutylenadipatterephthalate.
  • a particularly preferred polyester is polycaprolcatone.
  • polycaprolactone may refer either to homopolymers of caprolactone in polymerized form or to a polymer comprising caprolactone and a polyol, such as glycerol, butane-1 ,4-diol, neopentyl glycol or 1 1 1-trimethylolpropane, in polymerized form.
  • a polyol such as glycerol, butane-1 ,4-diol, neopentyl glycol or 1 1 1-trimethylolpropane
  • the polycaprolactone is either a homopolymer of caprolactone in polymerized form or a polymer comprising caprolactone and neopentyl glycol in polymerized form. More preferably, the polycaprolactone is a homopolymer of caprolactone.
  • the polyester has a mass average molar mass of 2,000 to 100,000 g/mol, preferably from 2,000 to 60,000 and more preferably from 2,000 to 50,000 g/mol.
  • the binder is selected from waxes and polyesters, preferably from animal and plant waxes and polyesters, more preferably from animal and plant waxes and polyester selected from polylactic acid, polycaprolactone, polybutylene succinate and polybutylenadipatterephthalate.
  • the binder is selected from plant and animal waxes and polyesters selected from polycaprolactone and polybutylenadipatterephthalate, and in particular the binder is selected from plant waxes and polycaprolactone.
  • the binder may be selected from soy wax, carnauba wax, jojoba wax and a polyester selected from polylactic acid, polycaprolactone, polybutylene succinate and polybutylenadipatterephthalate; preferably the binder may be selected from carnauba wax and a polyester selected from polycaprolactone and polybutylenadipatterephthalate, more preferably from carnauba wax and polycaprolactone.
  • binder used herein may also refer to a mixture of two or more different binders.
  • the concentration of the binder (a) in the agrochemical composition may be in the range from 20 to 99 wt% with regard to the total mass of the agrochemical composition, preferably from 30 to 99 wt% and especially preferably from 40 to 95 wt% of the agrochemical composition.
  • the carbon dioxide source is a mixture of a solid acid and a C03 2_ -salt; or a salt of a cationic acid with a C03 2_ -anion.
  • solid acid usually refers to acids that are solid at room temperature and whose melting temperature may be in the range from 40 to 150 °C, preferably from 50 to 120 °C, and most preferably from 60 to 100 °C.
  • the solid acid is a solid organic acid.
  • solid organic acids are tartaric acid, citric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, succinic acid, lactic acid, malic acid, oketoglutaric acid, oxaloacetic acid, phthalic acid, terephthalic acid, fumaric acid, aspartic acid, glutamic acid, benzoic acid, nicotinic acid, abietic acid and salicylic acid.
  • Preferred solid organic acids are tartaric acid, citric acid, malic acid, and oxalic acid, more preferably tartaric acid and citric acid and especially preferably tartaric acid.
  • the Lewis acidity of the solid acid refers to a value below 14, preferably below 10 and most preferably below 6.
  • C0 3 2 -salts are LiCOs, LiHCOs, Na 2 C0 3 , NaHCOs, K 2 C0 3 , KHCOs MgCOs, CaCOs, SrCOs, MnCOs and FeCOs.
  • C0 3 2 --salts are Na 2 C0 3 , NaHCOs, K 2 C0 3 , KHCOs, and CaCOs, more preferred
  • cationic acid usually refers to positively charged ions displaying Lewis acidity, such as NH4 + -, methylammonium- or pyridinium-ions.
  • Lewis acidity of the cationic acid refers to a pK s value below 14, more preferably below 12 and most preferably below 10.
  • the carbon dioxide source is a mixture of a solid organic acid and a C03 2 "-salt.
  • the carbon dioxide source is a salt of a cationic acid with a C03 2" -ion, such as NH4CO3 and NH4(HC03).
  • the carbon dioxide source is a mixture of a solid organic acid selected from tartaric acid, citric acid, malic acid and oxalic acid with a C03 2" -salt selected from Na2C03, NaHC03, K2CO3, KHCO3, and CaCOs; or of a salt of a cationic acid with a C03 2" -ion, such as NH4CO3 and NH4(HC03).
  • the carbon dioxide source is a mixture of a solid or- ganic acid selected from tartaric acid and citric acid with a CC"3 2" -salt selected from Na2C03, K2CO3, and CaCOs; or NH4CO3.
  • the carbon dioxide source does not comprise NH4CO3.
  • the carbon dioxide source is a mixture of a solid organic acid selected from tartaric acid or citric acid, and a C03 2_ -salt; more preferably a mixture of a solid organic acid selected from tartaric acid or citric acid, and a C03 2" -salt selected from Na2C03, NaHC03, K2CO3, KHCO3, and CaCOs; most preferably a mixture of a solid organic acid selected from tartaric acid and citric acid with CaCC"3.
  • the carbon dioxide source is a mixture of tartaric
  • the concentration of the carbon dioxide source (b) in the agrochemical composition may be in the range from 1 to 80 wt% with regard to the total mass of the agrochemical composition, preferably from 5 to 70 wt% and especially preferably from 5 to 50 wt% of the agrochemical composition.
  • the molar ratio of the solid acid and CO3 2 - may be from 10 1 to 1/10, preferably from 5/1 to 1/2 and most preferably from 3/1 to 1/1.
  • Suitable insecticides for the present application are known to the skilled person and can be found, for example, in the Pesticide Manual, 16th Ed. (2013), The British Crop Protection Council, London. They may be selected from the class of carbamates, organophosphates, organo- chlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosins, avermectins, mil- bemycins, juvenile hormone analogs, alkyl halides, organotin compounds nereistoxin analogs, benzoylureas, diacylhydrazines, METI acarizides, and insecticides such as chloropicrin, pymet- rozin, flonicamid, clofentezin, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, chlorofenapyr, DNOC, buprofezine, cyromazine, amit
  • the insecticide is selected from neonicotinoides, such as acetamiprid, thia- methoxam, clothianidin, imidacloprid, thiacloprid, dinotefuran, and netenpyram.
  • the insecticide is selected from fiproles, such as fipronil, ethiprole, flufiprole, pyra- fluprole, and pyriprole.
  • the insecticide is selected from compounds with unknown or uncertain mode of action, such as afidopyropen, afoxolaner, azadirachtin, ami- doflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, di- cloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradi- furone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, and triflumezopyrim, preferably broflanilide.
  • compounds with unknown or uncertain mode of action such as afidopyropen, afoxolaner, azadirachtin,
  • the insecticide is selected from pyrethroids, such as cyhalothrin, lambda-cyhalothrin, gamma- cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, permethrin, phenothrin, and pyrethrin (pyrethrum).
  • the insecticide is not boric acid, metaboric acid, their salts, or boron triox- ide.
  • the insecticide is an organic compound.
  • the insecticide is typically solid and may have a melting temperature of at least 30 °C, preferably of at least 50 °C and more preferably of at least 60 °C.
  • the concentration of the insecticide (c) in the agrochemical composition may be in the range from 0,001 to 90 wt% with regard to the total mass of the agrochemical composition, preferably from 0,01 to 10 wt% and especially preferably from 0,1 to 5 wt% of the agrochemical composition.
  • the agrochemical composition contains
  • the binder selected from animal or plant waxes and polyesters;
  • the agrochemical composition contains a) the binder; the carbon dioxide source containing a solid acid selected from citric or tartaric acid and
  • the agrochemical composition contains a the binder selected from animal or plant waxes and polyesters;
  • the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0 3 2 --salt;
  • the agrochemical composition contains a the binder selected from carnauba wax and polycaprolactone;
  • the agrochemical composition contains a the binder selected from carnauba wax and polycaprolactone;
  • the carbon dioxide source containing a solid acid selected from citric or tartaric acid and
  • the agrochemical composition contains a the binder selected from carnauba wax and polycaprolactone;
  • the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0 3 2 --salt selected from Na 2 C0 3 , NaHCOs, K 2 C0 3 , KHCOs, and CaC0 3 ; and c the insecticide.
  • the agrochemical composition contains the binder selected from carnauba wax and polycaprolactone;
  • the agrochemical composition may further contain an organic carbon dioxide source (d), which may be selected from mono-, oligo- and polysaccharides.
  • organic carbon dioxide source (d) may be selected from mono-, oligo- and polysaccharides.
  • Chemical derivatives e.g. obtainable by alkylation, oxidation, etherfication, esterification, sulfatation, nitration, amination and ami- dation
  • Examples of mono-, oligo- and polysaccharides are glucose, fructose, arabinose, mannose, galactose, cellobiose, saccharose, maltose, lactose, trehalose, amylose, amylopectin, starch, glycogen, pectin, chitin, callose, agarose, sinistrin, cellulose, dextrane or xanthane, potato flour and cereal flours.
  • Starch comprises preferably one or more of corn, potato, wheat, rice, sago, tapioca, waxy maize, sorghum, and cassava starch.
  • Typical examples of cereal flours are flours produced from maize, rice, wheat, barley, sorghum, millet, oats, rye, triticale, buckwheat, fonio, quinoa, amaranth, einkorn, spelt, durum and emmer.
  • Preferred organic carbon dioxide sources are saccharose, maltose, lactose, starch, cellulose, potato flour and cereal flours. More preferred organic carbon dioxide sources are saccharose, lactose, cellulose, potato flour and cereal flours. Most preferred as organic carbon dioxide sources are saccharose, cellulose and cereal flour, especially preferred saccharose and cereal flour, and in particular saccharose and wheat flour.
  • the agrochemical composition comprises from 1 to 70% by weight of the organic carbon dioxide source, preferably from 5 to 50% and especially preferably from 5 to 30% of the carbon dioxide source, in each case based on the total weight of the agrochemical composition.
  • the components (a), (b), (c), and optionally (d) are usually homogeneously distributed in the agrochemical composition.
  • the term "homogeneous” relates to a thorough mixture of the components, e.g. obtainable by extrusion.
  • homogeneous typically does not only relate to a even distribution on a molecular level, but also to heterogenic mixtures with a statistically even spatial distribution.
  • the agrochemical composition contains
  • the binder selected from animal or plant waxes and polyesters;
  • the organic carbon dioxide source selected from saccharose, maltose, lactose, starch, cellulose, potato flour and cereal flour.
  • the agrochemical composition contains
  • the binder selected from carnauba wax or polycaprolactone;
  • the agrochemical composition contains a) the binder selected from carnauba wax or polycaprolactone;
  • the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0 3 2 --salt selected from Na 2 C0 3 , NaHCOs, K 2 C0 3 , KHCOs, and CaC0 3 ;
  • the organic carbon dioxide source selected from saccharose, lactose, cellulose, potato flour and cereal flours.
  • the agrochemical composition contains a) the binder
  • the organic carbon dioxide source selected from saccharose, cellulose and cereal flours.
  • the agrochemical composition contains a) the binder selected from carnauba wax or polycaprolactone;
  • the carbon dioxide source containing a solid acid selected from citric or tartaric acid and a C0 3 2 --salt selected from Na 2 C0 3 , NaHCOs, K 2 C0 3 , KHCOs, and CaC0 3 ;
  • the organic carbon dioxide source selected from saccharose, cellulose and cereal flours.
  • the agrochemical composition contains a) the binder selected from carnauba wax or polycaprolactone;
  • the organic carbon dioxide source selected from saccharose and wheat flour.
  • the concentration of the components (a), (b), (c) and (d) in the agrochemical composition may comprise from 20 to 99 wt% of the binder (a), from 5 to 70 wt% of the carbon dioxide source (b), from 0,001 to 90 wt% of the insecticide (c), and optionally from 1 to 70 wt% of the organic carbon dioxide source (d).
  • the agrochemical composition comprises from 40 to 95 wt% of the binder (a), from 5 to 70 wt% of the carbon dioxide source (b), from 0,01 to 10 wt% of the insecticide (c), and optionally from 1 to 70 wt% of the organic carbon dioxide source (d). More preferably, the agrochemical composition comprises from 40 to 95 wt% of the binder (a), from 5 to 50 wt% of the carbon dioxide source (b), from 0,1 to 5 wt% of the insecticide (c), and optionally from 1 to 70 wt% of the organic carbon dioxide source (d).
  • the agrochemical composition according to the invention comprises from 40 to 95 wt% of the binder (a), from 5 to 50 wt% of the carbon dioxide source (b), from 0,1 to 5 wt% of the insecticide (c), and optionally from 5 to 50 wt% of the organic carbon dioxide source (d).
  • the agrochemical composition comprises from 5 to 70 wt% of the carbon dioxide source (b), and from 5 to 50 wt% of the organic carbon dioxide source (d).
  • the agrochemical composition comprises from 5 to 50 wt% of the carbon dioxide source (b), and from 5 to 50 wt% of the organic carbon dioxide source (d). In yet another form of the invention, the agrochemical composition comprises from 5 to 50 wt% of the carbon dioxide source (b), and from 5 to 30 wt% of the organic carbon dioxide source (d)
  • the agrochemical composition may be biodegradable.
  • a substance or a mixture of substances complies with the feature termed "biodegradable”, if this substance or the mixture of substances has a percentage degree of biodegradation of at least 90 wt% within 6 months under aerobic conditions according to the processes defined in DIN EN 13432:2000 and DIN EN ISO 14855:1999.
  • the result of the biodegradability is generally that the agrochemical composition breaks down within an appropriate and demonstrable period.
  • the degradation may be brought about enzy- matically, hydrolytically, oxidatively, and/or via exposure to electromagnetic radiation, such as UV-radiation, and is most predominantly caused by exposure to microorganisms, such as bac- teria, yeasts, fungi, and algae.
  • An example of a method of quantifying the biodegradability mixes a sample with soil and stores it for a particular time.
  • the release of CO2 as a measure of biodegradation of the sample can be analyzed according to Guideline OECD 301 :1992 (301 F Manometric Respiratory Test).
  • a sample is mingled with soil and inserted into a bottle that is subsequently hermetically closed.
  • the bottle further contains a CO2 ab- sorbing reservoir, such as sodium hydroxide, to remove evolved CO2 from the internal atmosphere.
  • the head of the bottle further contains a valve for inserting oxygen in order to maintain the pressure and oxygen concentration in the bottle.
  • the amount of consumed oxygen can be quantitatively measured over a given time period to calculate the degree of biodegradation of the sample. Alternatively, no further oxygen is supplied during the experiment and the partial vacuum in the bottle is measured in the bottle head.
  • the agrochemical composition may further be prepared as a granulate containing components (a), (b), (c) and optionally (d).
  • the granulate may be of any shape, preferably of tubular shape.
  • the granules may have a granule diameter up to 20 mm, more preferably up to 10 mm and es- pecially preferably up to 5 mm.
  • the granule diameter may be at least 0.01 mm, preferably at least 0.1 mm and more preferably at least 1 mm.
  • the term granule diameter refers either to the length or the width of the granulate, whatever dimension is longer.
  • the amount of insecticides applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.05 to 0.5 kg per ha.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 to 2 kg, preferably 0.005 to 1 kg, of active substance per cubic meter of treated material.
  • the amount of granulate applied is usually from 1 to 500 kg per ha, more preferably from 1 to 200 kg per ha, and most preferably from 1 to 10 kg per ha.
  • agrochemical composition Various types of further attractants, fertilizers, bittering agents, or solid carriers may be added to said agrochemical composition. These agents can be admixed with the agrochemical composition according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • Suitable further attractants are non-pesticidal materials which may act in one or several of the following ways: a) entice the insect to approach the agrochemical composition or the material treated with the agrochemical composition; b) entice the insect to touch the agrochemical composition or the material treated with the agrochemical composition; c) entice the insect to consume the agrochemical composition or the material treated with the agrochemical composition; and d) entice the insect to return to the agrochemical composition or the material treated with the agrochemical composition.
  • Suitable attractants include non-food attractants and food at- tractants, also termed as feeding stimulants.
  • Non-food attractants are usually volatile material.
  • the volatile attractants act as a lure and their type will depend on the pest to be controlled in a known manner.
  • Non-food attractants include for example flavors of natural or synthetic origin. Suitable flavors include meat flavor, yeast flavor, seafood flavor, milk flavor, butter flavor, cheese flavor, onion flavor, and fruit flavors such as flavors of apple, apricot, banana, blackberry, cherry, currant, gooseberry, grape, grapefruit, raspberry and strawberry.
  • Suitable food attractants are proteins, including animal proteins and plant proteins, e. g.
  • dena- tonium benzoate which, in a suitable concentration (in general 1 to 200 ppm, in particular 5 to 20 ppm), has a most unpleasant taste for humans.
  • Colorants are frequently added, and the agrochemical composition is thereby clearly logged as not for consumption, in order to avoid ingestion by mistake by humans or non-targeted animals.
  • blue colorants serve to deter birds.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • fertilizers e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and mixtures thereof.
  • the present invention further relates to a method for preparing said agrochemical composition by contacting the binder (a), the carbon dioxide source (b), the insecticide (c) and optionally the organic carbon dioxide source (d).
  • the contacting may be achieved in a known manner, such as described by Mollet and Grube- mann, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • the contacting can be achieved by mixing, grinding or by use of an extruder.
  • the method for preparing the agrochemical composition may further comprise heating of the agrochemical composition to a temperature from 40 to 150 °C, preferably from 50 to 120 °C, and most preferably from 60 to 100 °C.
  • Mixing may be done by the use of a ribbon blender, a V-blender, a continuous processor, a cone screw blender, a screw blender, a double cone blender, a double planetary, a high viscosity mixer, a counter-rotating mixer, a double or a triple shaft mixer, a vacuum mixer, a high- shear-rotor-stator, a paddle mixer, a jet mixer, a drum blender, a banbury mixer, an interim mix- er or a planetary mixer.
  • the method for preparing the agrochemical composition may comprise extrusion, applied to a mixture, which contains the binder (a), the carbon dioxide source (b), the insecticide (c) and optionally the organic carbon dioxide source (d). Usually, the process further comprises cooling of the extruded or pelleted mixture.
  • Extrusion is usually performed by use of extruders, which are well known in the art. Examples of extruders are ram extruders, planetary-gear extruders, one screw and twin screw extruders. Typically, the extrusion is accomplished at a pressure (usually taken just before entering into the extrusion grid) from 1 to 80 bars, preferably from 1 to 60 bars, and more preferably from 1 to 40 bars. Typically, the extrusion is accomplished at a temperature from 40 to 150 °C, preferably from 50 to 120 °C, and more preferably from 60 to 100 °C. Said temperature refers to the paste during extrusion. When necessary, the temperature is maintained at the desired value by cooling.
  • An extrusion grid may be used with holes of any shape, preferably of circular shape. The diameter of the holes is usually up to 20 mm, preferably up to 10 mm and more preferably up to 5 mm.
  • the continuous extrudate may be collected on a moving cylinder or on a conveyor belt. Typically, it is subsequently cut, e.g. with a rotating knife, into shorter sticks before or after cooling, preferably after cooling.
  • the spaghetti-shaped extrudate may be cut into cylindrical shape.
  • polygonal holes e.g. triangular or rectangular
  • the extrudate may be cut into corresponding shapes.
  • the resulting pellets might be broken into shorter granules before or after drying, preferably after drying.
  • the present invention further relates to a method of controlling undesired insect or mite attack and/or for regulating the growth of plants, wherein the agrochemical composition is allowed to act on the respective pests, their environment or the crop 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.
  • the agrochemical composition is preferably allowed to act on the soil. More preferably, the agrochemical composition is mixed into the soil; most preferably the agrochemical composition is mixed into the soil before or concomitant to sowing. In particular the agrochemical composition is mixed into the soil concomitant to sowing.
  • suitable crop plants are cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar or fodder beet; pome fruit, stone fruit and soft fruit, for example apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, currants or goose- berries; legumes, for example beans, lentils, peas, lucerne or soybeans; oil crops, for example oilseed rape, mustard, olives, sunflowers, coconut, cacao, castor beans, oil palm, peanuts or soybeans; cucurbits, for example pumpkins/squash, cucumbers or melons; fiber crops, for example cotton, flax, hemp or jute; citrus fruit, for example oranges, lemons, grapefruit or tange- rines; vegetable plants, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, pumpkin/squash or capsicums; plants of the laurel family, for example avocados, cinnamon or cam
  • crop plants also includes those plants, which have been modified by breeding, mutagenesis or recombinant methods, including the biotechnological agricultural products, which are on the market or in the process of being developed.
  • Genetically modified plants are plants whose genetic material has been modified in a manner, which does not occur under natural conditions by hybridizing, mutations or natural recombination (i.e. recombination of the genetic material).
  • one or more genes will, as a rule, be integrated into the genetic material of the plant in order to improve the plant's properties.
  • Such recombinant modifications also comprise posttranslational modifications of proteins, oligo- or polypeptides, for example by means of gly- cosylation or binding polymers such as, for example, prenylated, acetylated or farnesylated residues or PEG residues.
  • insects or mites may be from the order of coleoptera, diptera, hemiptera, and homoptera, more preferably from the order coleoptera.
  • the agrochemical composition is used for combating corn root worm ⁇ Diabrotica virgifera).
  • agrochemical composition for combating undesired insects or mites.
  • the advantages of the agrochemical composition according to the invention are a high storage and temperature stability, a high adaptability towards the application, e.g. the soil, the temperature and the humidity.
  • the agrochemical composition does not degas toxic substances; and it can be easily prepared by extrusion.
  • Further advantages are an extended and constant carbon dioxide release over time (e.g. at least two months, preferably at least 3 months), the instant onset of CO2 production at the time of application, and the biodegradability of the agrochemical composition.
  • the following examples are intended for illustration and do not limit the scope of the invention.
  • Effervescent powder Ground mixture of tartaric acid and calcium carbonate with a molar ratio of 2/1.
  • Dispersant 1 Sodium salt of a water-soluble cross-linked phenol polymers containing sulfonic acid moieties
  • Dispersant 2 25% aqueous solution of sodium salt of an anionic copolymer of maleic acid and an olefin; pH 10.5; viscosity 50 mPas
  • Granulates G1 -G12 were prepared according to Table 1 .
  • the effervescent powder was premixed with the polysaccharides (wheat flour, saccharose or cellulose) to a macroscopi- cally homogeneous mixture.
  • an insecticide in form of a granulate or a powder could be added to the premix.
  • a Micro Compounder Haake MiniLab
  • the speed was again decreased to 25 rpm and the tubular product was obtained by conducting it through a circular bypass and collecting it on a plastic roll. After cooling and solidification of the material, it was granulated to pieces of approximately 3-5 mm diameter.
  • Example-2 Preparation of CQ2-releasing granulate containing Broflanilide
  • Granulates G13-G15 were prepared according to Table 2.
  • the effervescent powder was premixed with Broflanilid and the wheat flour to a macroscopically homogeneous mixture.
  • a Micro Compounder Haake MiniLab
  • both the PCL and the premix were inserted alternatingly by a funnel.
  • Homog- enization was achieved by circulation of the mixture at 100 rpm for 5 minutes.
  • the speed was again decreased to 25 rpm and the tubular product was obtained by conducting it through a circular bypass and collecting it on a plastic roll. After cooling and solidification of the material, it was granulated to pieces of approximately 3-5 mm diameter.
  • the experiments were performed according to Guideline OECD 301 :1992.
  • the carbon contents of granulates G1 , G2, G4, G5 and G10 were determined by standard quantitative elemental analysis.
  • a quantity of granulates equivalent to 45 mg of carbon content was thoroughly mixed with 56 g of soil (pH 6.8) and inserted into an Oxitop ® flask.
  • Such flasks are composed of a 250 ml GL45 bottle and a bottle head containing a C02-absorber reservoir and a pressure measuring device.
  • the C02-absorber reservoir was filled with one gram of sodium hydroxide, which absorbed any produced CO2 during the experiment, and the bottle heads were screwed onto the bottles.
  • Table 3 displays the partial vacuum of the samples in percent compared to a sample con- taining only soil and no granule, which corresponds to a value of 100%.
  • Table 3 demonstrated that all granulates decayed by releasing CO2 during the specified time period, depending on their respective compositions, e.g. their organic carbon dioxide source and the concentration of effervescent powder. Hence, the CO2 release pattern can be adapted to the application and environmental conditions.
  • Example-4 Measurement of controlled CO2 release and biodegradability after different time periods
  • Comparative granules G16 * were produced with the ingredients according to Table 5. The in- gredients were mixed and the mixture was submitted to extrusion according to Example 1. The granules did not contain a binder nor an effervescent powder. Table 5: Composition of granules G16 *
  • Example-6 Measurement of controlled CO2 release after different time periods

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Inorganic Chemistry (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

La présente invention concerne une composition agrochimique solide comprenant un liant et une source de dioxyde de carbone, contenant un acide solide et un sel CO3 2- ; ou un sel d'un acide cationique avec un anion CO3 2-, et un insecticide ; un procédé pour préparer ladite composition agrochimique ; un procédé pour lutter contre une attaque d'insecte ou d'acarien indésirable et/ou pour réguler la croissance de plantes, comprenant l'application de ladite composition agrochimique.
PCT/EP2015/077529 2014-12-04 2015-11-24 Composition agrochimique solide pour libération prolongée de dioxyde de carbone WO2016087270A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022165355A1 (fr) * 2021-01-29 2022-08-04 Provivi, Inc. Compositions agrochimiques et leurs procédés de fabrication et d'utilisation

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022165355A1 (fr) * 2021-01-29 2022-08-04 Provivi, Inc. Compositions agrochimiques et leurs procédés de fabrication et d'utilisation

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