EP2964019A1 - Neue formulierungshilfstoffe, deren herstellung und verwendung - Google Patents

Neue formulierungshilfstoffe, deren herstellung und verwendung

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Publication number
EP2964019A1
EP2964019A1 EP14714183.2A EP14714183A EP2964019A1 EP 2964019 A1 EP2964019 A1 EP 2964019A1 EP 14714183 A EP14714183 A EP 14714183A EP 2964019 A1 EP2964019 A1 EP 2964019A1
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EP
European Patent Office
Prior art keywords
surfactants
formula
surfactant
formulations
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP14714183.2A
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German (de)
English (en)
French (fr)
Inventor
Gerhard Schnabel
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Bayer Intellectual Property GmbH
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Bayer Intellectual Property GmbH
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Publication date
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Publication of EP2964019A1 publication Critical patent/EP2964019A1/de
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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals

Definitions

  • the invention relates to the technical field of the formulation, in particular the formulation of agrochemicals.
  • Pesticides improved by compounds of formula 1.2 are based on the fact that the substances 1.2 represent new surfactants with improved properties.
  • Agrochemical formulation technologies as well as necessary auxiliaries are well known to the person skilled in the art. Recent research in these areas is often aimed at an increased effect or an improved safety profile.
  • Formulation aids well known.
  • the alkyl chain of these surfactants may be branched or linear or of synthetic or natural origin. Frequently, these surfactants are used as wetting agents or adjuvants, such as in the product Biopower from Bayer CS.
  • Formulation preparation and finally, it may happen that the content of active ingredients and surfactants is relatively low.
  • the aim of the present invention was to find new surfactants that do not have these disadvantages.
  • the present invention relates to surfactants of formula 1, whose
  • Surfactants of formula 1 are new. They can be prepared by, for example, first alkoxylating alcohols of the formula 2. The resulting compounds of the formula 3 are known from the literature and for the most part are commercially available. They are then converted into corresponding sulfates (equation 1).
  • Surfactants by reaction with, for example, sulfur trioxide or Cl-S0 3 H with subsequent neutralization are well known to the expert industrial chemical transformations and as such.
  • Suitable bases for the neutralization are, for example, KOH,
  • Alkoxylations e.g. Ethoxylation or
  • surfactants of formula 1 may be prepared by nucleophilic substitution according to equation 2 from an alcohol of formula 2 and a sulfate of formula 4
  • Surfactants of the formula 1 are characterized in that
  • R is an aliphatic (C 8 -C 8 ) radical which may be linear or branched or saturated or mono- or polyunsaturated,
  • A is a polyalkoxylene group which is composed of alkoxylene oxides, where the monomers may be different and the oligo- or
  • M + is a cation from the group potassium, quaternary ammonium ion, sulfonium, phosphonium or sulfoxonium ion,
  • X is Nuclefug such as Cl, Br, I or tosyl and x is a number between 1 and 100.
  • Preferred surfactants of the formula 1 are characterized in that
  • R is an aliphatic (Ce-Ci 6 ) radical which may be linear or branched or saturated or mono- or polyunsaturated,
  • A is a polyalkoxylene group consisting of ethylene oxide, propylene oxide and / or
  • Butylene oxide is built up, it being possible for the monomers to be different and for the oligo- or polyalkoxylene units to be formed from the monomers in blockwise or randomly mixed form,
  • M is a cation from the group potassium, quaternary (or quaternary)
  • Particularly preferred surfactants of formula 1 are wherein R is an aliphatic (C8-Ci 4) radical, which may be unsaturated, linear or branched and saturated or mono- or polysubstituted,
  • A is a polyalkoxylene group consisting of ethylene oxide, propylene oxide and / or
  • Butylene oxide is built up, it being possible for the monomers to be different and for the oligo- or polyalkoxylene units to be formed from the monomers in blockwise or randomly mixed form,
  • M is a cation from the group potassium, quaternary (or quaternary)
  • Ammonium ion which contains no hydrogen-nitrogen bond and x is a number between 1 and 10 mean.
  • surfactants of the formula 1 show advantages known and z.T. do not have commercially available surfactants.
  • the surfactants of formula 1 are, in many cases, better adjuvants for agrochemical active ingredients or pesticides.
  • the surfactants of the structure 1 generally have advantageous properties, can be recognized by the targeted variation of the individual structural elements preferred embodiments.
  • a preferred embodiment is characterized in that the radical R is a mixture of C 12 and C 4 radicals.
  • a further preferred embodiment is characterized in that it is an isotridecyl radical the radical R ( '3 radical Ci) is.
  • a further preferred embodiment is characterized in that the radical R is a 2-ethylhexyl radical.
  • a further preferred embodiment is characterized in that the radical R is a 2-propylheptyl radical.
  • a further preferred embodiment is characterized in that the alkoxylate block A is a polymeric or oligomeric unit which is base-catalyzed from the monomers ethylene oxide, propylene oxide and butylene oxide, it being possible for the various monomers to be linked in blocks or randomly mixed , acts.
  • alkoxylate block A is a polymeric or oligomeric unit which is constructed blockwise from the units ethyleneoxy (EO), propyleneoxy (PO) and butyleneoxy (BO) according to the following scheme:
  • PO propyleneoxy unit (propoxylene unit): -CH 2 -CHMe-0- or -CHMe-CH 2 -0- BO butyleneoxy unit (butoxylene unit): -CH 2 -CHEt-0 or -CHEt-CH 2 -0- or -CHMe-CHMe-O-, preferably -CH 2 -CHEt-0 or -CHEt-CH 2 - 0-
  • a further preferred embodiment is characterized in that the alkoxylate block A is a polyethoxylene unit - (CH 2 -CH 2 -O) z .
  • a further preferred embodiment is characterized in that "z" is a number between 0.5 and 10, preferably a number between 1, 5 and 4.5.
  • a further preferred embodiment is characterized in that the cation M is the potassium cation.
  • a further preferred embodiment is characterized in that it is a quaternized ammonium ion, such as Me3N-CH 2 wherein the cation M - CH 2 -OH is, NMe 4, NEt 4 NPr 4 and NBu. 4
  • Surfactants of the formula 1 can be used as formulation auxiliaries for crop protection agents or as adjuvants. Both applications are also new and are covered by this application.
  • surfactants of formula 1 in liquid form or as solid, free-flowing products, so they can be used directly as formulation adjuvants or adjuvants.
  • surfactants of the formula 1 are combined with at least one further adjuvant to form a solid, pasty or liquid mixture.
  • surfactants of Formal 1 as a formulation adjunct such as e.g. as wetting agent, is characterized in that between 0.1 weight percent and 80 weight percent of one or more surfactants of formula 1 are contained in an agrochemical formulation.
  • adjuvants are characterized in that as a rule between 20 g and 1000 g of surfactant 1 or a mixture of surfactants of formula 1 are applied per hectare. Surfactants of the formula 1 can also be mixed with other non-inventive adjuvants.
  • surfactants of formula 1 are used as adjuvants for agrochemicals, e.g. Pesticides used
  • these drug-free can be used as "adjuvants", or they can be formulated together with one or more agrochemical active ingredients, so that the corresponding pesticides already include an adjuvant.
  • adjuvants based on surfactants of formula 1 are prepared, these are generally liquid formulations which are generally distinguished by the highest possible content of surfactant or surfactants of formula 1. In such cases, other surfactants and other excipients may be present in the formulation.
  • surfactants 1 as adjuvants constitutes a further preferred embodiment.
  • liquid adjuvants containing 5 percent by weight, preferably at least 10 Percent by weight and more particularly of at least 20% by weight of surfactant (s) 1 represent a preferred embodiment.
  • Surfactants of formula 1 are usually incorporated into suitable formulations before they are used.
  • Adjuvants, formulation adjuvants, formulation types and technologies such as those described in e.g. in agrochemical
  • Formulations are well known to those skilled in the art and e.g.
  • Suitable formulations containing one or more surfactants 1 according to the invention are solid and liquid formulations. These formulations can be monophase or polyphase. In the case of liquid formulations, they can be aqueous or non-aqueous solutions, oil-in-water or water-in-oil (micro) emulsions, suspensions, capsule suspensions, suspoemulsions or mixed forms of these formulations. In the case of solid formulations may be, for example, dusts, powders, granules or compacts such as tablets.
  • Suitable formulation adjuvants are e.g. Solvents, stabilizers such as pH stabilizers (buffers, acids, bases), antioxidants and UV stabilizers, surfactants such as emulsifiers, dispersants or wetting agents, colorants such as dyes or pigments, thickeners, in particular thickeners, which impart thixotropic properties to a liquid mixture, polymers, the eg increase the viscosity of a solution, increase the adhesion of a solution, or increase the solubility of active ingredients in a liquid phase (solubilizers), or combine several of said properties, defoamers, adsorptive carriers, absorptive carriers, biocides, e.g.
  • Fungicides or bactericides auxiliaries for improving the resistance to rain, separating or flow agents, anti-drift agents, corrosion inhibitors, propellants such as dimethyl ether, butane, propane, carbon dioxide, nitrogen or mixtures of various propellants such as butane and propane.
  • Preferred formulation auxiliaries are organic solvents, water, thickeners, stabilizers, antioxidants, surfactants, biocides, dyes, pigments and
  • Suitable solvents are organic solvents and water.
  • Suitable organic solvents of the formulations according to the invention are selected from saturated, mono- or polyunsaturated, cyclic or acyclic, branched or unbranched, unsubstituted or mono- or polysubstituted hydrocarbons, including aromatic and heteroaromatic compounds and combinations thereof.
  • Suitable organic solvents are unsubstituted or monosubstituted or polysubstituted, where the substituents are one or more representatives from the following group: oxo, oxy, hydroxy, carboxy, carboxamido, Alkoxy, alkoxycarbonyl, carbamoyl, amino, imido, imino, thioyl, sulfonyl, sulfinyl, sulfo, sulfanyl, disulfanyl, ether group, ester group, keto group, aldehyde group, acetal group, carbonate group, nitrile group, sulfide group, sulfoxide group,
  • Sulfone group or halogen selected from fluorine, chlorine, bromine, iodine.
  • Preferred organic solvents are aliphatic (C 1 -C 18) -alcohols, where the aliphatic radical can be linear or branched or else cyclic or saturated or unsaturated, e.g. Methanol, ethanol, isopropanol, n-propanol, butanol, pentanol, 1-, 2- or 3-hexanol, allyl alcohol, amyl alcohol, glycol, propylene glycol, glycerol or sugar syrup, Preferred organic solvents and / or
  • Dispersants are also aromatic alcohols such as e.g. Benzyl alcohol or 4-methoxybenzyl alcohol
  • Preferred organic solvents are also ether compounds, e.g. Tertiary butyl methyl ether, diethyl ether, anisole, alkoxylates such as polyglycols,
  • polyalkoxylated alcohols and polyglycerols are polyalkoxylated alcohols and polyglycerols.
  • Preferred organic solvents are also esters, e.g. Ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, C8-18 fatty acid methyl ester, C8-18 fatty acid ethyl ester, substituted or unsubstituted benzoic acid esters, e.g. Methyl benzoate, ethyl benzoate, methyl p-methoxybenzoate.
  • esters e.g. Ethyl acetate, isopropyl acetate, propyl acetate, butyl acetate, C8-18 fatty acid methyl ester, C8-18 fatty acid ethyl ester, substituted or unsubstituted benzoic acid esters, e.g. Methyl benzoate, ethyl benzoate, methyl p-methoxybenzoate.
  • Preferred organic solvents are also aldehydes, e.g. Hexanal, decanal, benzaldehyde, 4-methoxybenzaldehyde.
  • Preferred organic solvents are still ketones such as e.g. Cyclohexanone, 4-methoxy-acetophenone, acetophenone, acetone, butanone (methyl ethyl ketone).
  • Preferred organic solvents are further nitriles, e.g. Acetonitrile, benzonitrile.
  • Preferred organic solvents are also amides, e.g. N-octylpyrrolidone, octanoic acid dimethylamide, decanecarboxylic acid dimethylamide or dodecanoic acid dimethylamide
  • Preferred organic solvents are also acetals such as benzaldehyde dimethyl acetal, 4-methoxy-benzaldehyde dimethyl acetal, benzaldehyde diethyl acetal.
  • Preferred organic solvents are also orthoesters such as 1, 1, 1-triethoxyethane
  • Preferred organic solvents are also sulfones and sulfoxides, e.g. Dimethylsulfone, sulfolane, dimethylsulfoxide.
  • Preferred organic solvents are furthermore carbonates, e.g.
  • Formulations of the invention may be up to 95 percent by weight, preferably up to 75 percent by weight, especially up to 50 percent by weight.
  • UV absorbers examples include inorganic UV absorbers such as e.g. Titanium dioxide, zinc dioxide and organic UV absorbers such as e.g. Compounds commercially available under the trade name Uvinul, e.g. Benzophenone-9, diethylamino-hydroxybenzoyl-hexylbenzoate, ethylhexyltriazone, oxybenzone, octyl-methoxycinnamate, octocrylene, polyethylene glycol 25-4-aminobenzoic acid,
  • UV absorbers can be up to 100,000 ppm
  • antioxidants examples include tocopherols (vitamin E), e.g. D, L-alpha-tocopherol, ascorbic acid, t-butyl hydroquinones (TBHQ), butylated hydroxytoluenes and butylated hydroxyanisoles.
  • vitamin E tocopherols
  • TBHQ t-butyl hydroquinones
  • attractant composition of the invention is up to 100,000 ppm
  • surfactants are salts, such as alkali metal, alkaline earth metal or ammonium salts of lignosulfonic acids, naphthalenesulfonic acids, phenolsulfonic acids,
  • Dibutylnaphthalenesulfonic acids alkylarylsulfonic acids, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, sulfated fatty alcohol glycol ethers, and the like
  • propylene oxide instead of propylene oxide and butylene oxide can be used.
  • the terminal OH group of (alkyl) glycol moieties may be further modified by standard reactions.
  • sulfation or phosphation acidic surfactants are obtained, which can be neutralized partially or completely.
  • the resulting salts - e.g. Alkali or ammonium salts - are also suitable surfactants.
  • alkylation such as methylation or acylation, e.g.
  • Preferred nonionic surfactants are alkylpolyglycosides and fatty acid alkoxylates, such as: Lutensol XP 30, Lutensol TO 6, Lutensol TO 8, Lutensol TO 10, Lutensol TO 15, Genapol X-060, Genapol X-080, Genapol X-150.
  • the terminal OH group of these surfactants may also be occluded, e.g. through a methyl group.
  • alkyl polyglucosides are Lutensol GD 70, Agnique PG 8105-G, Agnique PG 8107-G.
  • the surfactants of the brands Lutensol and Agnique are commercially available from BASF AG.
  • Genapol brand surfactants are commercially available from Clariant AG.
  • the content of surfactants in formulations according to the invention can be up to 50% by weight, preferably up to 30% by weight and in particular up to 15% by weight.
  • defoamers examples include silicone defoamers such as e.g. Silicone emulsions (suitable compounds are marketed, for example, under the brand names Silikon® SRE from Wacker or Rhodorsil® from Rhodia), long-chain alcohols or fatty acids which may also be alkoxylated, in particular propoxylated.
  • silicone defoamers such as e.g. Silicone emulsions (suitable compounds are marketed, for example, under the brand names Silikon® SRE from Wacker or Rhodorsil® from Rhodia), long-chain alcohols or fatty acids which may also be alkoxylated, in particular propoxylated.
  • the content of defoamers in formulations according to the invention can be up to 5 percent by weight, preferably up to 3 percent by weight.
  • thickeners i.e., adjuvants which impart a pseudo-plastic rheology to the product, i.e., impart a high-viscosity, low-viscosity fluid to the fluid and a low viscosity in the agitated state
  • thickeners i.e., adjuvants which impart a pseudo-plastic rheology to the product, i.e., impart a high-viscosity, low-viscosity fluid to the fluid and a low viscosity in the agitated state
  • Polysaccharides or organically modified minerals or phyllosilicates such as Xanthan gum (eg Kelzan® from Kelco), Rhodopol® 23 (Rhone Poulenc) or Veegum® (from RT Vanderbilt) or Attaclay® (from Engelhardt) or Bentonite or Byk D-410 or Byk D-420.
  • Xanthan gum eg Kelzan® from Kelco
  • Rhodopol® 23 Rhone Poulenc
  • Veegum® from RT Vanderbilt
  • Attaclay® from Engelhardt
  • Bentonite Byk D-410 or Byk D-420.
  • the content of thickeners in formulations according to the invention can be up to 5% by weight, preferably up to 3% by weight.
  • Suitable colorants are, for example, pigments and dyes. Both pigments which are sparingly soluble in water and dyes which are soluble in solvents such as e.g. Water soluble, can be used. Examples are the compounds available under the following brand names: Rhodamine B, C.I. Pigment Red 112 and C.I.
  • Solvent Red 1 and Pigment Blue 15 4, Pigment Blue 15: 3, Pigment Blue 15: 2, Pigment Blue 15: 2, Pigment Blue 15: 1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 1 12, Pigment Red 48: 2, Pigment Red 48: 1, Pigment Red 57: 1, Pigment Red 53: 1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10, Basic Red 108 and their dyes such as Disperse Blue 69-0007. These products are commercially available.
  • the content of colorants in formulations of the invention may be up to five percent by weight, preferably up to one percent by weight.
  • Suitable absorptive carriers are Sipernat 50 or Sipernat 50S.
  • the content of carriers in formulations according to the invention may be up to 50% by weight, preferably up to 30% by weight.
  • bactericides examples include Proxel® from ICI, Acticide® RS from Thor Chemie, Kathon® MK from Rohm & Haas and Dowicil® from Dow Elanco.
  • the content of bactericides in formulations according to the invention may be up to five percent by weight, preferably up to one percent by weight.
  • superplasticizers are minerals such as kaolin and aluminosilicates.
  • the content of flow agents in formulations according to the invention can be up to 50 percent by weight, preferably up to 30 percent by weight.
  • auxiliaries for improving rainfastness are tallow,
  • Paraffin waxes and plant waxes such as bee or carnauba wax.
  • Formulations of the invention may be up to 50 weight percent, preferably up to 30 weight percent.
  • Preferred formulation auxiliaries are organic solvents, water, biocides, surfactants, defoamers, thickeners, dyes, pigments and combinations thereof.
  • Formulations may be up to 95 percent by weight, preferably up to 75 percent by weight, especially up to 50 percent by weight.
  • one or more agrochemically active compounds may optionally be present, e.g. Herbicides, safeners, fungicides,
  • Insecticides molluscicides, nematicides, plant growth regulators, rodenticides. These are well known and described in The Pesticide Manual, 16 th edition (British Crop Protection Council). Particularly preferred are herbicides such as
  • Glyphosate and its salts in particular mono- and di-potassium salts, and the isopropylammonium salt
  • ALS inhibitors such as sulfonylureas and their salts, such as nicosulfuron, foramsulfuron, mesosulfuron, iodosulfuron, metsulfuron or rimsulfuron
  • ACC-Ase inhibitors e.g. Fenoxaprop-p-ethyl, glufosinates and its salts
  • HPPD inhibitors e.g. Sulcotrione, IFT or mesotrione
  • safeners such as isoxadiphene-ethyl or mefenpyr-diethyl
  • the content of agrochemically active compounds in formulations according to the invention can be up to 85% by weight, preferably up to 70% by weight, in particular up to 50% by weight.
  • agrochemicals that may optionally be included in the formulations of the present invention include: adjuvants such as wetting agents, penetration enhancers such as Mero or Hasten, Humectants such as e.g. Glycerin, fertilizer such as e.g. Ammonium sulfate, ammonium nitrate, potassium nitrate, ammonium phosphate, potassium salts of
  • Phosphoric acid potassium chloride, potassium sulfate, potassium carbonate or urea.
  • the content of further agrochemicals in formulations according to the invention can be up to 85% by weight, preferably up to 50% by weight.
  • the surfactants 1 of the invention are converted into suitable formulations, so that they are easy to use.
  • Formulations are liquid and solid formulations.
  • liquid, aqueous formulations in particular those in which surfactants of the formula 1 are dissolved, for example.
  • Solutions Very particular preference is given to liquid formulations which have a content of at least 50 g of compound 1 per liter, preferably of at least 100 g of surfactant 1 per liter, and in particular of at least 200 g of surfactant 1 per liter. Solutions according to the invention are readily available by adding surfactants 1 according to the invention
  • aqueous formulations Room temperature in a suitable solvent, such as water, stirred and dissolved.
  • auxiliaries such as biocides or other surfactants.
  • Other agrochemically active compounds which can be added to aqueous formulations are e.g. Glyphosate and its salts, in particular the mono- and di-potassium and the isopropyl salts.
  • Solid formulations can be prepared by, for example, subjecting surfactants 1 of the invention to a suitable carrier, e.g. Sipernat 50 S are absorbed and milled with a suitable dispersant and flow agent, e.g. by means of an air jet mill.
  • a suitable carrier e.g. Sipernat 50 S
  • the resulting powder can then be used as a powder directly for preparing spray liquors, but it can also be made into a paste with little water and converted by extrusion into a granulate.
  • the content of surfactants 1 according to the invention in solid formulations is preferably at least 5 percent by weight, particularly preferably at least 10 percent by weight.
  • Agrochemical formulations of compounds 1 can be applied directly
  • Target organisms e.g. Harmful plants, applied to crops or target areas, in particular sprayed, become. They may be previously treated with a suitable carrier, e.g. Water or organic solvents diluted and then applied or sprayed.
  • a suitable carrier e.g. Water or organic solvents diluted and then applied or sprayed.
  • a preferred carrier is water.
  • the required application rates per hectare are usually diluted with water to a volume of from 5 L to 5000 L, preferably to a volume of from 50 L to 2000 L.
  • other products important for the agronomist can be added to the spray mixture, such as others Plant protection products, adjuvants, Additives for the attachment of spray mixtures such as defoamers, fertilizers or trace minerals.
  • Crop protection products usually include chemical agents that are either manufactured synthetically or agents that are of natural origin, or "biologicals", ie pesticides that are authorized in organic farming.An overview of these pesticides can be found in The Pesticide Manual, 16 edition (British Crop Protection Council) and The
  • Preferred crop protection agents are herbicides, fungicides, insecticides, accaricides, nematicides, plant growth regulators, safeners and rodenticides, in particular herbicides and safeners
  • Agrochemical formulations containing compounds of formula 1 are also new and subject of this invention.
  • the active compound formulations according to the invention are suitable with the surfactants 1 according to the invention and their formulations for the control of harmful organisms in non-genetically modified crops of useful plants, such as e.g. conventional corn, cereals such as oats, rye, rice, wheat, barley, triticale or spelled.
  • the active compounds 1 according to the invention and their formulations are also suitable for the control of harmful organisms in genetically modified plant crops, e.g. in insecticidal or herbicidal-resistant crop or ornamental crops.
  • Plant cultures which have a genetically engineered resistance to one or more active substances such as glyphosate, glufosinate, ALS inhibitors, HPPD inhibitors or towards auxins such as 2,4-D or dicamba.
  • active substances such as glyphosate, glufosinate, ALS inhibitors, HPPD inhibitors or towards auxins such as 2,4-D or dicamba.
  • foliar-active agrochemically active compounds i.e., active agents that exhibit activity when applied to green plant parts
  • Formula 1 surfactants are preferred and provide a preferred
  • Glyphosates and salts derived therefrom eg mono-, di- or tri-salts with the cations K, NH 4 , VrU 3
  • Glufosinates and salts derived therefrom eg mono- or di-salts with the cations NH 4 and K
  • ALS inhibitors such as sulfonylureas and salts derived therefrom such as e.g.
  • HPPD inhibitors e.g. Triketones such as sulcotrione, mesotrione and salts derived therefrom.
  • surfactant 1 + sulfonylureas such as nicosulfuron, rimsulfuron, mesosulfuron, lodosulfuron or foramsulfuron
  • the residue can either be further purified (for example by silica gel filtration with a polar, anhydrous solvent system such as tetrahydrofuran, ethyl acetate or ethanol and subsequent removal of the solvent in a high vacuum) or directly into
  • Adjuvantsstudien or formulation attempts are used. It can be prepared in this way surfactant 1.1 with a purity of at least 90%.
  • the surfactants of formula 1 of Table 1 can be prepared.
  • Ammonium salts, in particular quaternized ammonium salts, of the formula 1 are obtainable by using, instead of KOH, a dilute hydroxide solution of the corresponding ammonium ion for neutralizing the acid formed intermediately.
  • surfactant 1.1 10 g of surfactant 1.1 (purity> 90%) are dissolved together with 0.1 g of Aktizide MBS (bactericide, Thor chemistry) in 39.9 g of water. Depending on the purity of the surfactant 1.1, this may require an increased temperature and intensive mixing. This gives an adjuvant containing the surfactant 1.1 to 20 percent by weight, and can be used directly for biological tests.
  • Aktizide MBS bactericide, Thor chemistry
  • wheat is cultivated as a model plant for undesired plant growth. After the young plants have reached a height of about 20 cm, they are treated with glyphosate (Touchdown HiTech from Syngenta, di-potassium salt of glyphosate, without adjuvants) and an adjuvant.
  • glyphosate Touchdown HiTech from Syngenta, di-potassium salt of glyphosate, without adjuvants
  • Glyphosate (as Touchdown HiTech) with 300 g / ha of surfactant 1.1 (corresponds to 1, 5 kg of inventive adjuvant of inventive experiment 1) and water to a spray mixture of 400 L / ha and applied to about 20 cm high wheat plants.
  • the evaluation of the two experiments is carried out by measuring the height of green parts of plants 2 weeks after application.
  • the invention relates to the following items
  • R is an aliphatic (C 8 -C 8 ) radical which may be linear or branched or saturated or mono- or polyunsaturated,
  • A is a polyalkoxylene group which is composed of alkoxylene oxides, where the monomers may be different and the oligo- or Form polyalkoxylene unit from the monomers blockwise or randomly mixed,
  • M is a cation from the group consisting of potassium, quaternary ammonium ion, sulfonium, phosphonium or sulfoxonium ion, and x is a number between 1 and 100.
  • R is an aliphatic (C 8 -C 6 ) radical which may be linear or branched or saturated or mono- or polyunsaturated,
  • A is a polyalkoxylene group consisting of ethylene oxide, propylene oxide and / or
  • Butylene oxide is built up, it being possible for the monomers to be different and for the oligo- or polyalkoxylene units to be formed from the monomers in blockwise or randomly mixed form,
  • M is a cation from the group potassium, quaternary (or quaternary)
  • Ammonium ion containing no nitrogen-hydrogen bond and x is a number between 1 and 20, preferably between 1 and 10 mean.
  • alkoxylate block A is a polymeric or oligomeric unit which is constructed blockwise from the units ethyleneoxy (EO), propyleneoxy (PO) and butyleneoxy (BO) according to the following scheme,
  • PO propyleneoxy unit (propoxylene unit): -CH 2 -CHMe-0- or -CHMe-CH 2 -0-
  • BO butyleneoxy unit (butoxylene unit): -CH 2 -CHEt-0 or -CHEt-CH 2 -0- or -CHMe-CHMe-O-, preferably -CH 2 -CHEt-0 or -CHEt-CH 2 - 0-
  • Me methyl Et ethyl s 0-100 preferably 0-10, in particular 0-5 u 0-100, preferably 0-10, in particular 0-5 z 0-100, preferably 1-50, in particular 1, 5-20, especially 1, 7 to 10 w 0-50, preferably 0-10, in particular 0-5 and
  • v is 0-50, preferably 0-10, in particular 0-5 and x 1.
  • R is an aliphatic radical from the group 2-ethylhexyl; 2-propylhexyl; a mixture of n-dodecyl and n-tetradecyl; n-dodecyl; isotridecyl; a mixture of n-tetradecyl and n-hexadecyl; or n-hexadecyl.
  • Ethoxylene radical is.
  • surfactants of formula 1 or surfactants prepared in a process as described above as a formulation adjuvant.
  • surfactants of formula 1 or surfactants prepared in a process as previously described as an adjuvant for agrochemical products such as pesticides Liquid or solid formulations comprising or consisting of at least one surfactant of formula 1 or at least one surfactant prepared in a previously described process for use as adjuvants or as an adjuvant, wherein
  • Liquid formulations preferably solutions, with surfactants of the formula 1, wherein the content of one or more surfactants of the formula 1 is at least 5
  • formulations as described above in particular with surfactants of formula 1 or at least one surfactant prepared in a process as described above, wherein at least one surfactant of formula 1 is combined with at least one non-inventive formulation auxiliaries and optionally further components.
  • Liquid and solid agrochemical formulations or pesticides comprising or consisting of
  • Liquid and solid pesticides wherein the agrochemical formulations comprise one or more leaf-active active substances from the group: Glyphosates and salts derived therefrom (eg mono-, di- or tri-salts with the cations K, NH 4 , i PrNH 3 )
  • Glufosinates and salts derived therefrom eg mono- or di-salts with the cations NH 4 and K
  • ALS inhibitors such as sulfonylureas and salts derived therefrom, e.g.
  • HPPD inhibitors e.g. Triketones such as sulcotrione, mesotrione and salts derived therefrom. include.

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Toxicology (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP14714183.2A 2013-03-05 2014-03-05 Neue formulierungshilfstoffe, deren herstellung und verwendung Withdrawn EP2964019A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102013003655.0A DE102013003655A1 (de) 2013-03-05 2013-03-05 Neue Formulierungshilfsstoffe, deren Herstellung und Verwendung
PCT/EP2014/054292 WO2014135606A1 (de) 2013-03-05 2014-03-05 Neue formulierungshilfstoffe, deren herstellung und verwendung

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CN (1) CN105188368B (es)
AU (1) AU2014224603B2 (es)
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104803888A (zh) * 2015-04-23 2015-07-29 中国日用化学工业研究院 一种异构醇衍生物硫酸盐及制备方法
DE102016100162B3 (de) * 2016-01-05 2016-11-03 Solvoluta GmbH Mittel zur Schnecken- und Schnegelabwehr
US20220015356A1 (en) * 2018-12-11 2022-01-20 Dow Global Technologies Llc Aqueous solutions of poorly soluble pesticides using polyalkyoxylated alcohols
AU2019410555B2 (en) 2018-12-21 2025-06-05 Battelle Uk Limited Agrochemical composition
EP3669653A1 (en) * 2018-12-21 2020-06-24 Battelle UK Limited Agrochemical composition
JP7682187B2 (ja) 2020-01-23 2025-05-23 ビーエーエスエフ ソシエタス・ヨーロピア 農薬製剤用の新規添加剤
US20230109972A1 (en) * 2020-04-24 2023-04-13 Dow Global Technologies Llc Solvent compositions with antioxidants
MX2023004876A (es) 2020-10-27 2023-05-11 Basf Se Composiciones de microemulsion de plaguicidas.
AU2022216834A1 (en) * 2021-02-05 2023-08-17 Basf Se Liquid herbicidal compositions
EP4338592A1 (en) * 2022-09-15 2024-03-20 Basf Se Use of compound for improving the efficacy of herbicides
CN115513465B (zh) * 2022-10-18 2025-08-12 深圳市皓飞实业有限公司 一种嵌段聚醚类锂电池正极浆料用分散剂

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2719087A (en) * 1953-05-25 1955-09-27 Eastman Kodak Co Light-sensitive photographic paper and composition
US3775349A (en) * 1970-06-29 1973-11-27 Ethyl Corp Detergent formulations containing alkyl polyethoxy sulfate mixtures
JPS59193803A (ja) * 1983-04-20 1984-11-02 Hokko Chem Ind Co Ltd 物理性の改良された顆粒状水和剤
US4592875A (en) 1984-06-25 1986-06-03 Atlantic Richfield Company Alkoxylated ether sulfate anionic surfactants from plasticizer alcohol mixtures
US4997641A (en) 1990-04-09 1991-03-05 Colgate-Palmolive Company Hair conditioning shampoo containing C6 -C10 alkyl sulfate or alkyl alkoxy sulfate
DE4343856A1 (de) 1993-12-22 1995-06-29 Hoechst Ag Öl-in-Wasser-Emulsionen
EG22088A (en) * 1996-04-16 2002-07-31 Procter & Gamble Alkoxylated sulfates
KR100913878B1 (ko) 1999-08-09 2009-08-26 바이엘 크롭사이언스 아게 발아후 살포용 제초제를 포함하는 토양 살포용 제초 제제
US7135437B2 (en) * 2000-05-19 2006-11-14 Monsanto Technology Llc Stable liquid pesticide compositions
JP4707254B2 (ja) * 2001-04-24 2011-06-22 クミアイ化学工業株式会社 粒状組成物及びその製造方法
WO2007079165A2 (en) * 2005-12-29 2007-07-12 Rhodia Inc. Agricultural pesticide compositions
EP2014169A1 (de) * 2007-07-09 2009-01-14 Bayer CropScience AG Wasserlösliche Konzentrate von 3-(2-Alkoxy-4-chlor-6-alkyl-phenyl)-substituierten Tetramaten und ihren korrespondierenden Enolen
MY157394A (en) * 2008-06-18 2016-06-15 Stepan Co Ultra-high loading glyphosate concentrate
JP5202497B2 (ja) * 2009-11-19 2013-06-05 株式会社Ａｄｅｋａ ポリカーボネート樹脂用帯電防止剤及びポリカーボネート樹脂組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2014135606A1 *

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CA2903644C (en) 2021-08-03
CN105188368B (zh) 2017-11-17
WO2014135606A1 (de) 2014-09-12
US20180368399A1 (en) 2018-12-27
AU2014224603B2 (en) 2017-08-10
BR112015021218A2 (pt) 2017-07-18
CA2903644A1 (en) 2014-09-12
DE102013003655A1 (de) 2014-09-11
BR112015021218B1 (pt) 2021-02-23
CN105188368A (zh) 2015-12-23
US20160015028A1 (en) 2016-01-21
MX2015011638A (es) 2016-06-21
US10091994B2 (en) 2018-10-09
MX367233B (es) 2019-08-09
AU2014224603A1 (en) 2015-10-15

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