• 专利附录
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    • 专利摘要:
    The present invention relates to agrochemical formulations comprising a copolymer obtainable by copolymerizing glycerin (a), at least one dicarboxylic acid (b) and at least one monocarboxylic acid (c) of formula (I). Formula I In Formula I above, R 1 is (C 5 -C 29 ) -alkyl; (C 7 -C 29 ) -alkenyl; Phenyl or naphthyl. The copolymer increases the bioactivity of the pesticide. The pesticide is preferably a herbicide.
    公开号:KR20030088495A
    申请号:KR10-2003-7013249
    申请日:2002-04-06
    公开日:2003-11-19
    发明作者:체를러랄프；마이어게르트롤란트；쉐를프란츠싸버
    申请人:클라리언트 게엠베하；
    IPC主号:
    专利说明:

    Pesticide preparations comprising copolymers
    [1] The present invention relates to agrochemical formulations comprising copolymers obtainable by copolymerizing glycerol, dicarboxylic acids and monocarboxylic acids. Copolymers improve the bioavailability of pesticides (herbicides, insecticides, fungicides, fungicides, mollusc control agents, nematode killers and insecticides).
    [2] Crop protection agents are chemical or natural substances in which plant cells, plant tissues, or parasitic organisms penetrate into or damage plants and / or destroy them. Most of the pesticides are herbicides, followed by insecticides and fungicides.
    [3] The most important herbicides are chemicals that act on the transport system of plants by inhibiting photosynthesis, fatty acid biosynthesis or amino acid biosynthesis, for example, to inhibit germination and growth or to kill plants.
    [4] The bioactivity of the pesticide can be measured in relation to plant growth as a function of active time and active concentration, or damage to the plant caused by the effect of the active ingredient on the leaves.
    [5] To develop optimal pesticide performance, the pesticide must wet the chlorophyll, keep it sufficiently for a long time, or penetrate the active substance throughout the leaf surface. The general problem of the present invention is that only a part of the active substance can exhibit the desired activity, ie it can be sprayed on harmful plants and grasses and adhered to them for a sufficiently long time to penetrate into plant cells. A very important part is lost without developing its effect.
    [6] As described in most of this patent specification, to overcome its ecological and economic disadvantages, additives are added to most aqueous pesticide formulations to improve the wettability, solubility, emulsification capacity or adsorption behavior of the active substance. In addition, the additive promotes penetration of the active substance into the plant through the leaf surface.
    [7] International Patent Publication No. 98/06259 discloses a method for assisting in the bioactivity of a crop protection agent by spraying an aqueous solution of a surfactant as an adjuvant with or after spraying the active substance with the adjuvant. This is described. Wetting agents used are aqueous organosilicon and / or organofluorine compounds.
    [8] In EP-A-379 852 and U.S. Patent No. 4 853 026, oil is added to the herbicide N-phosphonomethylglycine (glyphosate) as a water-in-oil emulsion, so that the hydrophilic active ingredient and the lipophilic surface of the plant Improves contact. The disadvantage is the insufficient stability of the emulsion.
    [9] According to International Publication No. 99/05914, the action of anionic pesticides can be improved by formulating anionic actives as aqueous colloidal dispersions with protonated polyamines or derivatives thereof.
    [10] US Pat. No. 5,858,921 teaches that the addition of water soluble long chain alkyldimethylamine oxides and water soluble quaternary ammonium halides can reduce the concentration of glyphosate without reducing bioactivity.
    [11] U.S. Patent 5 750 468 describes glyphosate formulations comprising tertiary or quaternary ether amines as adjuvants.
    [12] All the methods described so far to improve the biocidal properties have been successful to a limited extent. Accordingly, it is an object of the present invention to provide a novel preparation of pesticides, in particular pesticides of the N-phosphonomethylglycine (glyphosate) class, which is an improved potency, which is at the same time cost effective, easy to handle and sufficient for humans and the environment. To develop a composition or formulation. Glyphosate, a high-efficiency pesticide that is extremely resistant to the environment and can be used extensively, is used in large quantities in agriculture. Preferably, together with a humectant, a water-soluble salt (e.g., alkali metal salt, ammonium salt, alkylamine salt, alkylsulfonium salt, alkylphosphonium salt, sulfonylamine salt or aminoguanidine salt), or in an aqueous formulation or solid form Spraying other free acids on leaves and grasses acts on the plant's delivery system and destroys it.
    [13] Surprisingly, it has been found by the present invention that the pesticide performance of the crop protection agents is significantly improved by adding a copolymer obtainable by copolymerizing glycerol, dicarboxylic acid (s) and monocarboxylic acid (s).
    [14] By using dicarboxylic acid (s) the polyglycerols are crosslinked to produce a network condensation product. Surprisingly, crosslinked polyglycerols exhibit significantly higher efficacy than uncrosslinked polyglycerols.
    [15] Efficacy can be influenced in a targeted manner by the degree of crosslinking.
    [16] Crosslinking also advantageously affects the increased electrolyte stability of the formulation. In addition, the viscosity of a formulation can be set by the degree of crosslinking.
    [17] The present invention provides pesticide preparations comprising at least one copolymer obtainable by copolymerizing glycerol (a), at least one dicarboxylic acid (b) and at least one monocarboxylic acid (c) of formula (I).
    [18]
    [19] In Formula I above,
    [20] R 1 is (C 5 -C 29 ) -alkyl; (C 7 -C 29 ) -alkenyl; Phenyl or naphthyl.
    [21] Alkyl or alkenyl radicals R 1 may be linear or branched. Phenyl or naphthyl radicals may be substituted and include substituents (C 1 -C 6 ) -alkyl, (C 1 -C 6 ) -alkenyl, (C 1 -C 6 ) -alkoxy, -CHO, -CO (( Preference is given to C 1 -C 6 ) -alkyl) or halogen.
    [22] Preferred dicarboxylic acids (b) are oxalic acid, dicarboxylic acid of formula II and / or dicarboxylic acid of formula III.
    [23]
    [24]
    [25] In the above formulas II and III,
    [26] R 2 is a (C 1 -C 40 ) -alkylene bridge, preferably (C 1 -C 10 ) -alkylene, particularly preferably (C 1 -C 4 ) -alkylene, or (C 2 -C 20 ) -alkenylene bridge, preferably (C 2 -C 6 ) -alkenylene, particularly preferably C 2 -alkenylene,
    [27] R is H; (C 1 -C 20 ) -alkyl, preferably (C 1 -C 6 ) -alkyl, particularly preferably (C 1 -C 2 ) -alkyl; (C 2 -C 20 ) -alkenyl, preferably (C 2 -C 6 ) -alkenyl; Phenyl; benzyl; halogen; -NO 2 ; (C 1 -C 6 ) -alkoxy; At least one radical selected from the group consisting of —CHO and —CO ((C 1 -C 6 ) -alkyl).
    [28] R 2 in formula (II) may be linear or branched.
    [29] Formula II may also include dimer fatty acids such as, for example, Pripol acid.
    [30] Particularly preferred dicarboxylic acids (b) are oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suveric acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid and / or terephthalic acid.
    [31] Particularly preferred dicarboxylic acids (b) are phthalic acid, isophthalic acid and / or terephthalic acid.
    [32] Very particularly preferred dicarboxylic acid (b) is phthalic acid.
    [33] Preferred monocarboxylic acids (c) are compounds wherein R 1 is (C 7 -C 22 ) -alkyl or (C 7 -C 22 ) -alkenyl.
    [34] Particularly preferred monocarboxylic acids (c) include saturated or unsaturated fatty acids or mixtures thereof, such as coconut acid, oleic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, margaric acid, Stearic acid, nonadecanoic acid, arachidic acid, behenic acid, linoleic acid, linolenic acid, palmitic acid and tallow fatty acids.
    [35] Particularly preferred monocarboxylic acids (c) are coconut acids and tallow fatty acids.
    [36] Very particularly preferred monocarboxylic acid (c) is coconut acid.
    [37] Particularly advantageous copolymers are compounds obtainable by copolymerizing glycerol, phthalic acid and coconut acid.
    [38] Preferably, the copolymer is from 19.9 to 99% by weight of the structural unit attributable to component (a), from 0.1 to 30% by weight of the structural unit attributable to component (b) and from 0.9 to 80% by weight of structural unit attributable to component (c). Contains%
    [39] The copolymer comprises 50 to 90% by weight of the structural unit attributable to component (a), 1 to 25% by weight of the structural unit attributable to component (b) and 2 to 49% by weight of the structural unit attributable to component (c). .
    [40] The content of 1 to 10% by weight of the structural unit attributable to component (b) is particularly advantageous for the properties of the copolymer.
    [41] The OH number of the copolymer is advantageously between 400 and 1,000 mg KOH per gram (measured according to DIN 53240).
    [42] The viscosity of 100% pure copolymers measured at 60 ° C. using a rotational viscometer is advantageously in the range of 1,500 to 35,000 mPas. High viscosity is possible but interferes with handling of the material. The copolymer is advantageous to handle in an aqueous solution of 75 to 90% by weight.
    [43] Copolymers can be obtained by copolymerizing glycerol (a), at least one dicarboxylic acid (b) and at least one monocarboxylic acid (c) of formula (I).
    [44] It is preferable to first polymerize the glycerol component (a) to obtain a polyglycerol, and then to copolymerize the mixture of the polyglycerol and the dicarboxylic acid component (b) and the monocarboxylic acid component (c).
    [45] In another preferred variant process, the glycerol component (a) is first polymerized to produce a polyglycerol, followed by copolymerization of the dicarboxylic acid component (b) followed by copolymerization of the monocarboxylic acid component (c).
    [46] In a further preferred variant process, the glycerol component (a) is first polymerized to produce a polyglycerol, and then the monocarboxylic acid component (c) is copolymerized and then the dicarboxylic acid component (b) is copolymerized.
    [47] However, copolymerization is not limited to this modification process.
    [48] For example, a modification process may also be advantageous in which a portion of glycerol (a) is polymerized with an oligomer and then copolymerized with the dicarboxylic acid component (b), the monocarboxylic acid component (c) and the remaining glycerol (a).
    [49] Advantageous embodiments of the copolymerization reaction are described in the examples below.
    [50] A) Polymerization of Glycerol to Oligoglycerol or Polyglycerol:
    [51] The polymerization of glycerol to oligoglycerol or polyglycerol can occur as standard in a stirrer with a water separator and a nitrogen introducer at 240 to 270 ° C. The catalyst used is a sodium hydroxide solution at a concentration of 50% in the concentration range 0.1 to 0.4% by weight. After 5 to 20 hours, the polymerization reaction is terminated according to the desired degree of polymerization. A sample is taken and the OH number is measured. The average molar mass of oligoglycerol or polyglycerol can be calculated from OH number.
    [52] B) one-pot process using prepolymerized polyglycerol:
    [53] The polyglycerol is mixed in a molten state with dicarboxylic acid and monocarboxylic acid in a desired molar ratio in a stirrer equipped with a water separator, and then heated with stirring at 200 to 240 ° C. for 7 hours. The acid value of the final product is less than 1 mg KOH per gram.
    [54] C) First copolymerize polyglycerol with dicarboxylic acid (crosslink) and then copolymerize with monocarboxylic acid:
    [55] The polyglycerol is mixed in the molten state with the dicarboxylic acid in the desired molar ratio in a stirrer with a water separator and then heated with stirring at 200 to 240 ° C. for 2 hours. The resulting product is transparent and uniform. Monocarboxylic acid is then added and esterified at 200-240 ° C. for 5 hours. The acid value of the final product is less than 1 mg KOH per gram.
    [56] D) First copolymerize polyglycerol with monocarboxylic acid and then copolymerize (crosslink) with dicarboxylic acid:
    [57] The polyglycerol is mixed in the molten state with the monocarboxylic acid in the desired molar ratio in a stirrer with a water separator and then heated with stirring at 200 to 240 ° C. for 5 hours. The acid value of the resulting product is less than 1 mg KOH per gram. Dicarboxylic acid is then added in the desired molar ratio and esterified at 200-240 ° C. for 2 hours. The acid value of the final product is less than 1 mg KOH per gram.
    [58] The copolymers are suitable for agrochemical formulations to improve the biocidal properties of herbicides, insecticides, fungicides, acaricides, fungicides, mollusk control agents, nematode insecticides and killicides as adjuvants.
    [59] The copolymer is preferably used in the formulation of the preparation.
    [60] Particularly suitable herbicides are glyphosate (N-phosphonomethylglycine) and salts and / or derivatives thereof. Examples of suitable water soluble salts are alkali metal salts, ammonium salts, alkylamine salts, alkylsulfonium salts, alkylphosphonium salts, sulfonylamine salts or aminoguanidine salts. Examples of further suitable herbicides include acifluorfen, asulam, bennazoline, bentazone, villanafos, bromasil, bromoxynil, chlorambene, clopyralde, 2,4-D, 2,4-DB , Dalfon, Dicamba, Dichlorprop, Diclopov, Endortal, Penac, Phenoxprop, Flamprop, Fluazifop, Flumichlorak, Fluoroglycopene, Pomesafen, Posamine, Glufosinate, Haloxypope, Imazapic, Imazamabenz, Imazomax, Imazafir, Imazaquin, Imazetapyr, Roxynyl, MCPA, MCPB, Mecoprop, Methylargeneic Acid / MSMA, Naph Talam, picloram, quinclorac, quizarope, 2,3,6-TBA and TCA.
    [61] The pesticide preparation according to the invention may comprise a copolymer of substantially any concentration.
    [62] Particularly preferred formulations are "tank-mixtures" comprising from 0.001 to 10% by weight of pesticides, from 0.05 to 2% by weight and from 0.01 to 10% by weight of copolymers, preferably from 0.1 to 2% by weight, particularly preferably from 0.2 to 1% by weight. (tank-mix) "and" immediately available compositions ". The weight ratio of copolymer to pesticide in the present invention is preferably 1:10 to 500: 1, particularly preferably 1: 4 to 4: 1.
    [63] Concentrated formulations diluted prior to use may comprise 5 to 60% by weight of pesticides, preferably 20 to 40% by weight, and may include copolymers in an amount of 3 to 50% by weight. The weight ratio of copolymer to pesticide in the present invention is 1:20 to 1: 1, preferably 1:10 to 1: 2. Alternatively, the formulations according to the invention can be prepared in solid form as powders, pellets, tablets or granules, which are dissolved in water before use. The solid preparation comprises 20 to 80% by weight of pesticides, preferably 50 to 75% by weight, particularly preferably 60 to 70% by weight, and 5 to 50% by weight of copolymer, preferably 10 to 30% by weight. It can be included in an amount of%.
    [64] Agrochemical formulations may also include conventional thickeners, antigelling agents, antifreezes, solvents, dispersants, emulsifiers, preservatives, additional auxiliaries, binders, antifoams, diluents, disintegrants and wetting agents.
    [65] Thickeners that can be used are xanthine gum and / or cellulose, such as carboxycellulose, methylcellulose, ethylcellulose or propylcellulose. The final composition preferably contains 0.01 to 5% by weight thickener.
    [66] Suitable solvents are monopropylene glycol, animal fats and oils.
    [67] Suitable dispersants and emulsifiers include nonionic, amphoteric, cationic and anionic surfactants.
    [68] Preservatives which can be used include organic acids and esters thereof such as ascorbic acid, ascorbyl palmitate, sorbate, benzoic acid, methyl and propyl 4-hydroxybenzoate, propionate, phenol, for example 2 -Phenyl phenate, 1,2-benzisothiazolin-3-one, formaldehyde, sulfurous acid and salts thereof.
    [69] Suitable antifoams include polysilicon.
    [70] Other auxiliaries that can be used include alcohol ethoxylates, alkyl polysaccharides, fatty amine ethoxylates, sorbitan and sorbitol ethoxylate derivatives, and alkyl (alkenyl) succinic anhydrides.
    [71] The mixing ratio of the adjuvant to the copolymer is preferably in the range of 1:10 to 10: 1.
    [72] Suitable binders for solid formulations are polyvinylpyrrolidone, polyvinyl alcohol, carboxymethylcellulose, sugars such as sucrose, sorbitol or starch.
    [73] Suitable diluents, absorbents or carriers are carbon black, talc, kaolin, aluminum stearate, calcium stearate, magnesium stearate, sodium tripolyphosphate, sodium tetraborate, sodium sulfate, silicate and sodium benzoate.
    [74] Suitable disintegrants are celluloses such as carboxymethylcellulose, polyvinylpyrrolidone, sodium acetate, potassium acetate, carbonates, bicarbonates, carbonates, ammonium sulfate or potassium hydrogen phosphate.
    [75] Wetting agents that can be used include alcohol ethoxylates / propoxylates.
    [76] The pesticide preparation preferably has a pH of 4 to 8, particularly preferably 6 to 7.
    [77] The formulations according to the invention can be used according to conventional methods.
    [78] Aqueous concentrates and solid formulations are diluted with a significant amount of water before sparging. Preferably, 0.1 to 5 kg, preferably 0.3 to 2.5 kg of pesticides are sparged per ha. The amount of the copolymer is preferably 0.1 to 3.0 kg per ha. The amount of preparation formulation for spray spraying is preferably 50 to 1,000 L per ha.
    [79] For example, the properties of a copolymer or agrochemical formulation, such as water solubility, electrolyte stability, viscosity, and miscibility with the crop protection formulation active ingredient, can be advantageously determined very easily by the degree of crosslinking. In the degree of crosslinking, the properties and content of the dicarboxylic acid component (b) are important and the content is particularly important.
    [80] Surprisingly, it has been found that anionic pesticides in high concentrations of aqueous formulations, in particular glyphosate and copolymers in salt form, are phase stable. Even if the storage period is extended, no crystallization of the ionic component is observed.
    [81] In addition to high stability, the copolymers according to the invention improve the miscibility and contact of the hydrophilic active ingredient with the lipophilic epidermis of the plant.
    [82] The good wettability and absorption of the pesticide formulations according to the invention aids the bioactivity of the active ingredients of the plant.
    [83] The present invention also provides the use of a pesticide in the form of a pesticide formulation comprising a copolymer obtainable by copolymerizing glycerol (a), at least one dicarboxylic acid (b) and at least one monocarboxylic acid of formula (I). Provides ways to increase life.
    [84] The method is preferably suitable for herbicides, in particular glyphosate, and salts and / or derivatives thereof.
    [85] Example
    [86] The following example illustrates the effect of the copolymer on the bioactivity of the herbicide glyphosate.
    [87] 1) Method for Preparing Copolymers I to V
    [88] Process for preparing polyglycerol with n of 9.7:
    [89] 2,000 g of glycerol and 6.0 g of NaOH (50%) are heated to 270 ° C. in a stirring apparatus equipped with a nitrogen introducer and a water separator. After 9 hours of reaction time and release of 444 g of water, a sample is taken to determine the OH number. The measured OH number is 891 mg of KOH per 1 g. This corresponds to glycerol units having an average degree of condensation n of 9.7. In addition, the degree of condensation can be measured approximately by the viscosity or refractive index of the reaction mixture. To do this, you need to create a test curve in advance.
    [90] Preparation of Copolymer I:
    [91] 180.00 g (0.243 mol) of polyglycerol with n of 9.7 was added to a stirrer equipped with an N 2 introducer and a water separator, to 24.70 g (0.121 mol) of coconut fatty acid (C 8 / C 18 ) and 10.13 g (0.061 mol) of phthalic acid. Process. The reaction mixture is then heated with stirring at 220 ° C. for 7 hours. The acid value of the copolymer is 0.40 mg of KOH per gram.
    [92] Preparation of Copolymer II:
    [93] 190.00 g (0.256 mol) of polyglycerol with n = 9.7 was added to a stirrer equipped with an N 2 introducer and a water separator, and 26.11 g (0.128 mol) of coconut fatty acid (C 8 / C 18 ) and 4.32 g (0.026 mol) of phthalic acid were added. Process. The reaction mixture is then heated with stirring at 220 ° C. for 7 hours. The acid value of the copolymer is 0.46 mg of KOH per gram.
    [94] Preparation of Copolymer III:
    [95] 185.00 g (0.256 mol) of polyglycerol n with 9.7 are added to a stirrer with N 2 introducer and water separator and treated with 4.25 g (0.026 mol) of phthalic acid at 215 ° C. for 2 hours. The reaction mixture is transparent and uniform. 25.50 g (0.125 mol) of coconut fatty acid (C 8 / C 18 ) is added to the stirrer and reacted at 215 ° C. for 5 hours. The acid value of the copolymer is 0.38 mg of KOH per gram.
    [96] Preparation of Copolymer IV:
    [97] 185.00 g (0.256 mol) of polyglycerol with n of 9.7 are added to a stirrer equipped with an N 2 introducer and a water separator and treated with 10.38 g (0.0625 mol) of phthalic acid at 215 ° C. for 2 hours. The reaction mixture is transparent and uniform. 25.50 g (0.125 mol) of coconut fatty acid (C 8 / C 18 ) is added to the stirrer and reacted at 215 ° C. for 5 hours. The acid value of the copolymer is 0.53 mg of KOH per gram.
    [98] Preparation of Copolymer V:
    [99] 180.00 g (0.243 mol) of polyglycerol with n = 9.7 are added to a stirrer with an N 2 introducer and a water separator, esterified with 24.75 g (0.121 mol) of coconut fatty acid (C 8 / C 18 ), 215 after 5 hours. An acid value of 0.14 mg KOH per gram is achieved at an esterification temperature of ° C. 4.03 g of phthalic acid is then added and crosslinked at 215 ° C. for 2 hours. The reaction end product is transparent and uniform.
    [100] Process for the preparation of test formulations comprising copolymers I to V:
    [101] Test formulations are prepared in each case using 200 g, 300 g and 500 g of glyphosate and in each case 300 g of copolymers I to V in 300 L of water. Data by weight shows 100% active ingredient and 100% adjuvant. Formulations equivalent to a ratio of 300 L / ha in the greenhouse are plant species Abutylon Teoplasti (ABUTH), Sesbania Exaltata (SEBEX), Parbitis Perfurrea (PHBPU), Gallium Aparin (GALAP), Amaranthus retroplexers (AMARE) and Echinocloe croiss-Gali (ECHCG) were sprayed and plant growth was assessed according to% scale after 21 days at 20 ° C.
    [102] 0% means no effect, and 100% means that the plant form is completely destroyed.
    [103] The effects of copolymers I to V on the herbicidal action of glyphosate are shown in Table 1.
    [104]
    [105] It is clear that the copolymer significantly increases the herbicidal action of glyphosate.
    权利要求:
    Claims (19)
    [1" claim-type="Currently amended] Agrochemical formulations comprising at least one copolymer obtainable by copolymerizing glycerol (a), at least one dicarboxylic acid (b) and at least one monocarboxylic acid (c) of formula (I).
    Formula I

    In Formula I above,
    R 1 is (C 5 -C 29 ) -alkyl; (C 7 -C 29 ) -alkenyl; Phenyl or naphthyl.
    [2" claim-type="Currently amended] The pesticide preparation according to claim 1, wherein the dicarboxylic acid (b) is oxalic acid, dicarboxylic acid of formula II and / or dicarboxylic acid of formula III.
    Formula II

    Formula III

    In the above formulas II and III,
    R 2 is a (C 1 -C 40 ) -alkylene bridge or (C 2 -C 20 ) -alkenylene bridge,
    R is H, (C 1 -C 20 ) -alkyl, (C 2 -C 20 ) -alkenyl, phenyl, benzyl, halogen, -NO 2 , (C 1 -C 6 ) -alkoxy, -CHO and -CO is one or more radicals selected from the group consisting of - ((C 1 -C 6) alkyl).
    [3" claim-type="Currently amended] The pesticide preparation according to claim 2, wherein the dicarboxylic acid (b) is oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, fumaric acid, maleic acid, phthalic acid, isophthalic acid and / or terephthalic acid. .
    [4" claim-type="Currently amended] The pesticide preparation according to claim 3, wherein the dicarboxylic acid (b) is phthalic acid, isophthalic acid and / or terephthalic acid, preferably phthalic acid.
    [5" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 4, wherein the monocarboxylic acid (c) is a fatty acid or a mixture thereof.
    [6" claim-type="Currently amended] 6. The pesticide preparation according to claim 5, wherein the monocarboxylic acid (c) is coconut acid and / or tallow fatty acid, preferably coconut acid.
    [7" claim-type="Currently amended] The pesticide preparation according to claim 4 or 6, wherein the dicarboxylic acid (b) is phthalic acid and the monocarboxylic acid (c) is coconut fatty acid.
    [8" claim-type="Currently amended] 8. The pesticide according to any one of claims 1 to 7, wherein the copolymer comprises 19.9 to 99% by weight of component (a), 0.1 to 30% by weight of component (b) and 0.9 to 80% by weight of component (c). Formulation.
    [9" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 8, wherein the copolymer comprises 1 to 10% by weight of component (b).
    [10" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 9, wherein the copolymer has an OH value of 400 to 1,000 mg KOH per gram.
    [11" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 10, wherein the copolymer has a viscosity range of 1,500 to 35,000 mPas at 60 ° C.
    [12" claim-type="Currently amended] The method according to any one of claims 1 to 11, wherein during the copolymerization, the glycerol component (a) is first polymerized into polyglycerol, and then the polyglycerol is formed from the dicarboxylic acid component (b) and the monocarboxylic acid component (c). Pesticide formulations copolymerized with the mixture.
    [13" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 11, wherein the glycerol component (a) is first polymerized with polyglycerol and then the dicarboxylic acid component (b) is copolymerized and then the monocarboxylic acid component (c) is copolymerized. .
    [14" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 11, wherein the glycerol component (a) is first polymerized with polyglycerol and then the monocarboxylic acid component (c) is copolymerized and then the dicarboxylic acid component (b) is copolymerized. .
    [15" claim-type="Currently amended] The pesticide preparation according to any one of claims 1 to 11, which is a herbicide, an insecticide, a fungicide, a fungicide, a mollusk control agent, an nematode insecticide or an insecticide.
    [16" claim-type="Currently amended] The pesticide preparation according to claim 15, which is a herbicide.
    [17" claim-type="Currently amended] The pesticide preparation according to claim 16, wherein the herbicide is glyphosate, and salts and / or derivatives thereof.
    [18" claim-type="Currently amended] 18. Agrochemical preparation according to any one of claims 1 to 17 in the form of a "tank-mix", "composition immediately available", concentrate, powder, pellet, tablet or granules.
    [19" claim-type="Currently amended] A method for increasing the bioactivity of a pesticide, characterized in that the pesticide is used in the form of a pesticide preparation according to any one of claims 1 to 18.
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    AU766395B2|2003-10-16|Enhanced method of killing weeds with glyphosate herbicide
    EP2425716B1|2016-05-04|Thickening glyphosate formulations
    同族专利:
    公开号 | 公开日
    DE10117993A1|2002-10-17|
    KR100862876B1|2008-10-15|
    HK1065220A1|2006-11-10|
    BR0208737A|2004-07-20|
    BR0208737B1|2013-04-30|
    IL158290A|2007-05-15|
    US7407667B2|2008-08-05|
    CN1250077C|2006-04-12|
    MY129826A|2007-05-31|
    WO2002089575A1|2002-11-14|
    IL158290D0|2004-05-12|
    CN1501772A|2004-06-02|
    AT292381T|2005-04-15|
    JP2004525189A|2004-08-19|
    CA2443817C|2008-09-16|
    DK1379129T3|2005-06-20|
    MXPA03009183A|2004-02-17|
    US20060166826A1|2006-07-27|
    DE50202717D1|2005-05-12|
    ES2240800T3|2005-10-16|
    CA2443817A1|2002-11-14|
    EP1379129A1|2004-01-14|
    EP1379129B1|2005-04-06|
    JP4298298B2|2009-07-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-04-10|Priority to DE10117993.6
    2001-04-10|Priority to DE2001117993
    2002-04-06|Application filed by 클라리언트 게엠베하
    2002-04-06|Priority to PCT/EP2002/003827
    2003-11-19|Publication of KR20030088495A
    2008-10-15|Application granted
    2008-10-15|Publication of KR100862876B1
    优先权:
    申请号 | 申请日 | 专利标题
    DE10117993.6|2001-04-10|
    DE2001117993|DE10117993A1|2001-04-10|2001-04-10|Pesticidal composition containing copolymer of glycerol and both di- and mono-carboxylic acids, useful for increasing biological activity, particularly of glyphosate|
    PCT/EP2002/003827|WO2002089575A1|2001-04-10|2002-04-06|Pesticidal preparations comprising copolymers|
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