EP2482802A1 - Nouvelles formulations de pesticides - Google Patents

Nouvelles formulations de pesticides

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Publication number
EP2482802A1
EP2482802A1 EP10820940A EP10820940A EP2482802A1 EP 2482802 A1 EP2482802 A1 EP 2482802A1 EP 10820940 A EP10820940 A EP 10820940A EP 10820940 A EP10820940 A EP 10820940A EP 2482802 A1 EP2482802 A1 EP 2482802A1
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EP
European Patent Office
Prior art keywords
formulation
matrix
acid
mixture
bioactive substance
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EP10820940A
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German (de)
English (en)
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EP2482802A4 (fr
Inventor
Michael Burnet
Jan-Hinrich Guse
Martin Reisser
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Individual
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Individual
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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
    • 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
    • A01N25/08—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 containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds

Definitions

  • This invention relates to formulations of biologically active agents and more specifically to formulation with a particular focus on optimizing the matrices needed for its application. It builds on integrating principles of agronomy, soil science, and polymer chemistry in addition to agrochemistry, plant protection, and plant physiology. Background of the invention
  • pesticides The challenge in agrochemistry or other large scale field applications of chemicals such as herbicides, bacteriocides, rodenticides, nematicide and fungicides (together defined as pesticides) is to find ways of achieving control of the target organism while limiting the amount of the xenobiotic substance that is loaded into and is free-moving in the ecosystem by leaching or by aerosol drift.
  • the amount of such chemicals that is required is a function of their potency, the ability to place the compound selectively and their susceptibility to removal either via destruction in the environment (metabolism, photolysis, etc.) or loss (leaching, drift).
  • environmentally desirable properties such as facile biodegradation or other loss may result in a need for frequent re-application and thus an increase in the load on
  • herbicides used in annual crops should retain activity at or near the soil surface to ensure that germinating weeds are exposed to the compound. These same compounds should not enter the subsoil where they may be taken up by trees or other deep-rooted species resulting in off- target effects. This presents the agrochemist with a paradox in that the properties of many successful herbicides are also those that result in effects on non-target species.
  • systemic insecticides or fungicides would ideally be applied at seeding in small quantities that would remain with and protect the crop plant throughout its life cycle, however, for reasons of persistence, stability and economy, it is not generally feasible with
  • a common goal of formulation is to prevent aggregation of the active ingredient following dilution; another is to ensure that during mixing and packaging, the product remains uniform, flowable and non-accretive. Yet another goal of formulation is to govern droplet size such that small droplets will not drift off target. Formulation to enhance performance once applied to the target in the field is, however, less common (see US 2007/0149409).
  • formulation for enhanced field performance include, amongst others, use of encapsulation, granulation, surfactants, stickers, control of droplet size and rheology, as well as humectants.
  • encapsulation granulation
  • surfactants stickers
  • control of droplet size and rheology as well as humectants.
  • humectants very rarely does a single compound perform more than one function: there are commercially available, separate sticking agents, separate humectants, separate compounds that control droplet size and again, separate slow release formulations.
  • Most available slow release formulations are bulky; the ratio of formulant to agent on a dry weight basis is over 4 and often 10 to 50 times more.
  • a hitherto poorly explored area in pesticide chemistry (meaning the fields of agronomy, soil science and polymer chemistry in addition to agrochemistry, plant protection and plant physiology) is, however, that of mixed-function substituted matrices that have the capacity to retain and/or reversibly trap active ingredients to form water-insoluble solid complexes.
  • Such matrices can be selected to suit the properties and the applications of the associated compound and thus extend its range of uses consistent with the current need described above. Many can simultaneously perform many of the requirements of a formulant described above.
  • the problems of achieving season-long control provide another example of the benefits of using tuned matrix-formulations.
  • Certain herbicides for example, are anions or cations and thus highly water-soluble. This means that they may not be used in residual control applications because they are readily washed off leaves or leached into soil beyond the desired activity zone by rainfall.
  • This problem is typically solved by either applying a larger amount of herbicide to compensate for losses (expensive and potentially toxic to a crop and environmentally hazardous), applying a mixture (difficult to find combinations that have the same spectrum and crop safety) or making analogs with greater stability or soil binding (expensive to register and non-availability may reduce early season control).
  • fungicides especially those where residual systemic activity is required.
  • the matrix-formulations of fungicides can be incorporated into seed dressings or applied in furrow during seeding. Here properties of tuned slow release can be used to ensure that the fungicide has a longer duration of availability with equal or less active fungicide.
  • use of a matrix that unloads its active ingredient in the presence of hydrogen ions will make the compound only selectively available in the soil, either in the immediate environment of the root, or of fungal hyphae.
  • the instant invention provides solution to the problems encountered by the known technology.
  • broadly applicable matrices that allow the preparation of chemical agents in such a way that their availability to the environment may be controlled by a range of factors including particle size, melting point, degree of cross-linking and proportion of alkaline and acidic functions.
  • Chemical agents are dissolved in the matrices and the resulting mixture may be formed, extruded, sprayed as a melt, ground, emulsified, or otherwise prepared for application.
  • the matrix is biologically degradable, sparingly soluble in water, amenable to disagregation by organisms (notably roots of plants) and other sources of protons, and able to promote the retention of chemical agents against concentration gradients in water.
  • the present invention provides for the use of a matrix explicitly functionalized depending on needs as formulation agents in preparations of pesticidal ingredients (herbicides, fungicides, insecticides, nematicides, acaricides and rodenticides as well as other chemicals used in the wider environment) and/or pharmaceutical agents.
  • pesticidal ingredients herebicides, fungicides, insecticides, nematicides, acaricides and rodenticides as well as other chemicals used in the wider environment
  • the matrices may be comprised of a monomeric, oligomeric or
  • polymeric backbones are of synthetic or semi-synthetic origin.
  • the polymers may vary widely in length (for example, 50, 100, 200, 2000, 10000, 20000 units to greater than 50000) and may be formed of a range of repeat structures and linking arrangements including but not limited to those we have described as a "polymeric backbone” and esters, amides, ethers, glycols, alkanes, thiols, sulfones, lignins, and sugars (e.g. substituted polymers of glucose, chitin or chitosan), their derivatives and co-polymers and mixed polymers.
  • the polymers are, by economic necessity, generally derived from bulk commodities and include but are not limited to: substituted celluloses, dextrans, polyimines, oligo- and polypeptides, styrenes, vinyls, hydroxybutyrates, starches, fructans, carbonates, paraffin derived, and lignins.
  • the monomeric or oligomeric backbones are defined as reaction products of either a fatty acid or carboxylic acid with primary or secondary amino functions of an amine, polyamine, and/or an amino alcohol compound.
  • the matrix formulation contains modifiers and or additives that assist the ease of the preparation of the end product and to obtain optimal controlled release and anti-leaching properties.
  • the mixture of the pesticidal ingredients and the matrices are maintained in a solvent as a solution or suspension.
  • the substituted matrices may be positively or negatively charged or with strong hydrophobic binding groups.
  • the backbone may have side chains that are composed of but not limited to amines, variable length carbon chains, alcohols, aromatic groups, sulfides, sulfonates, carboxy acids, halogens, chelating functions, glycols and hydrophobic binding domains.
  • the backbone may be further grafted at their termini to introduce additional functions different from those of the repeat unit.
  • the bioactive substance forms hydrophobic interactions with the matrix.
  • the matrix has humectant properties; in another embodiment the matrix is an ion exchanger.
  • the exchanger is a high capacity anion exchanger and is composed of naturally occurring functions such as primary, secondary, tertiary and quaternary amines. These include but are not limited to substituted polymers containing imines, imidazoles, dimethylamines, diethylamines, betaines and guanidines.
  • the exchanger is a high capacity cation exchanger and includes functions such as sulfides, sulfonates, sulphoxyethyls, phosphates, carboxyalkanes, and carboxyls.
  • the matrix may be used as products applied in water as dispersible formulations co-administered with water.
  • the same types of matrices may be incorporated into solid formulations for use in broadcast application, seed dressings or other point applications.
  • the matrix may assist in improving the solubility or packaging of the active ingredient in the concentrated form or assist in the re-suspension of the dry form of a formulation, in water.
  • the substituted matrices may be soluble or remain as solid carriers, as pellets or as water-dispersible, micronized small particles and may used alone or in combination with other ingredients such as lipids or fatty acids to form microemulsions or microspheres.
  • the pesticidal ingredients of formulations may be loaded onto the matrices during manufacture. In another embodiment, they may be loaded by the end user.
  • the matrices may incorporate coding via size distribution that can be used, in addition to improved efficacy, to identify source of product and counterfeit products.
  • the matrices can be attached to solid supports, or themselves form insoluble beads or small fibers. These beads or fibers may be derivatized as for other polymers.
  • the beads may be selected for positive buoyancy in which case they are of potentially enhanced utility in the control of floating aquatic weeds in the case of herbicides, or of surface borne larvae or disease pathogens in the case of insecticides and fungicides, respectively.
  • the beads/supports may also be negatively buoyant for use in paddy rice where preferential distribution of the active ingredient to the upper water or lower sediment layer may improve efficacy.
  • the various matrix-based formulations may be used as seed coats for the control of pathogens and parasites including weeds.
  • the formulation comprising of a matrix, pesticide, and/or modifier may be melted at a specific temperature to render a liquid mixture which may be strategically sprayed in melted form to the target application, wherein the mixture solidifies at certain environmental temperature and forms a coating directly at the target point.
  • This methodology offers a slow and controlled release of the pesticide thus ensuring long-term application scheme.
  • the possible applications for this methodology include but are not limited to field application, wood and stone handling, textile treatment, and seed coating.
  • the various matrices may be incorporated into a kit for research use to assist chemical developers in finding optimal formulations for either a new active ingredient, or a new formulation for a specific condition or use.
  • Fig. 1 Effect of various formulations of dicamba applied to the cotyledons of sunflower seedlings and determined by subsequent growth as measured by internode extension.
  • Fig. 2 Effect of various formulations of sulfentrazone applied to the cotyledons of sunflower seedlings and determined by subsequent growth as measured by internode extension.
  • Fig. 4. Elution of mesotrione from soil columns when applied in three different formulations. Data are log concentration in relative units.
  • Fig. 5. Elution of terbuthylazine from soil columns when applied in three different formulations. Data are concentration in relative units.
  • Fig. 7 Elution of quinclorac from soil columns when applied in four different formulations. Data are concentration in relative units.
  • Fig. 8 Elution of sulfentrazone from soil columns when applied in a formulation ground to different size ranges. Data are concentration in ng/mL following application of the same amount of sulfentrazone.
  • the general objective of formulation is to make a biologically active substance (bioactive substance) readily packagable as a concentrate, which may, in turn, be easily diluted and applied, typically via water.
  • bioactive substance biologically active substance
  • a typical example is the use of excipients, surfactants and polymers to carry a hydrophobic substance into solution or emulsion for intravenous injection in an aqueous medium.
  • small molecules are also typically slightly hydrophobic in nature and not always readily soluble in spray solutions.
  • the goal of formulation is to allow intrinsically insoluble materials to be dispersed and applied via water vehicles.
  • bioactive substance in such a way that it is available for a sustained period of time through a physical separation from the biological system.
  • the material is, thereby protected from losses to the environment or from rapid elimination by a non-saturable process (pH mediated hydrolysis).
  • Granules are distributed by spreaders and generally have the disadvantage of low loading of active ingredient and correspondingly high costs of excipients and application.
  • Encapsulation formulations are made by means of interfacial polymerization of emulsions containing the active ingredient. They are effective but are limited in the concentration of the species that they may carry, and are correspondingly expensive to produce.
  • the present invention is an efficient means to formulate substances in which highly functionalized polymers comprise a matrix in which the substance is retained with high affinity and which in combination with properties of particle size, cross-linking and material stability, provide for a sustained release process leading to more stable concentrations of the formulated substance over time.
  • the matrices are made in a separate process (see examples 1-40) involving condensation and similar reactions that give rise to a solid that can be immediately mixed with the substance or substances to be formulated either as a molten material, or as a concentrate in a volatile solvent.
  • the matrix may also be formed by mixing a free base of a fatty substance, and the free acid of a polymer, or oligomeric acid or divalent acid or fatty acid; or mixing a free organic acid with a the free base of a polymer, or oligomeric base or divalent base or aliphatic base.
  • Appropriately derivatized matrices are mixed with bioactive substances (i.e. pesticides) to form water-resistant solid complexes that exhibit desirable properties including sustained release, resistance to leaching through the soil, improved retention on leaf surfaces (rainfastness), selective unloading of compounds into the root environment and more convenient packaging and application.
  • bioactive substances i.e. pesticides
  • the matrices are generally bio-degradable, inexpensive, and regarded as safe with respect to toxicity.
  • the matrices are composed mainly of a backbone derivatized with chemical groups that exhibit ionic interactions, hydrophobic interactions, complexing interactions (e.g. metal chelating) and ligand binding interactions.
  • the matrix/bioactive substance mixtures may be mixed with additives or modifiers, grafted, or fused to obtain optimal controlled release and anti-leaching properties.
  • the matrices exert their beneficial effects through binding to both the bioactive substance to be delivered and interaction with the leaf, soil or organic matter to modify pesticide exposure to the environment.
  • pesticides with which the invention may be useful include herbicides, insecticides, bacteriocides, rodenticides, nematicides and fungicides.
  • Herbicides include but are not restricted to: imidazolinone herbicides, amitrole, glyphosate, glufosinate, carbetamide indole acetic acids, allidochlor, beflubutamid, benzadox, benzipram, bromobutide, cafenstrole, CDEA, chlorthiamid, cyprazole, dimethenamid, dimethenamid-P, diphenamid, epronaz, etnipromid, fentrazamide, flupoxam, fomesafen, halosafen, isocarbamid, isoxaben, napropamide, naptalam, pethoxamid, propyzamide, quinonamid, tebutam, anilide, herbicides
  • monisouron, noruron, phenylurea herbicides anisuron, buturon, chlorbromuron, chloreturon, chlorotoluron, chloroxuron, daimuron, difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluothiuron, isoproturon, linuron, methiuron, methyldymron, metobenzuron, metobromuron, metoxuron, monolinuron, monuron, neburon, parafluron, phenobenzuron, siduron, tetrafluron, thidiazuron, sulfonylurea herbicides, pyrimidinylsulfonylurea herbicides, amidosulfuron, azimsulfuron, bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron, fla
  • Fungicides include but are not limited to pyridine, carbamate and benzimidazole type fungicides (respectively cyprodinil, propamocarb, and carbendazim) penconazole, validamycin, kasugamycin, butylamine, azoxystrobin, aliphatic nitrogen fungicides, butylamine, cymoxanil, dodicin, dodine, guazatine, iminoctadine, amide fungicides, carpropamid, chloraniformethan, cyflufenamid, diclocymet, ethaboxam, fenoxanil, flumetover, furametpyr, mandipropamid, penthiopyrad, prochloraz, quinazamid, silthiofam, triforine, acylamino acid fungicides, benalaxyl, benalaxyl-M, furalaxyl, metalax
  • Insecticides include thiocyclam, nicotine, CGA50439, cartap, allosamidin, thuringiensin, macrocyclic lactone insecticides, spinosad, avermectin insecticides, abamectin, doramectin, emamectin, eprinomectin, ivermectin, selamectin, milbemycin insecticides, lepimectin, milbemectin, milbemycin oxime, moxidectin, arsenical insecticides, calcium arsenate, copper acetoarsenite, copper arsenate, lead arsenate, potassium arsenite, sodium arsenite, botanical insecticides, anabasine, azadirachtin, d-limonene, nicotine, pyrethrins, cinerins, cinerin I, cinerin II, jasmolin I, acetamiprid, ja
  • Matrices useful for the formulation and complexation of pesticides can be considered as twofold: the main backbone which may be primarily either a monomer, oligomer or (co)polymer and the specific functionalities attached to them based on the pesticide employed.
  • polymeric backbone includes but is not limited to polyamides, polyimines, polyamines, glycols, vinyls, styrenes, polyacrylates examples of which may include: acrylonitrile butadiene styrene (ABS), polyamide (PA), polybutadiene, poly(butylene terephthalate) (PBT), polycarbonate, poly(ether sulphone) (PES, PES/PEES), poly(ether ether ketone)s (PEEK, PES/PEEK), polyethylene (PE), polyethylene glycol) (PEG), polyethyleneimine (PEI), poly(ethylene terephthalate) (PET), polyimide, polypropylene (PP), polystyrene (PS), styrene acrylonitrile (SAN), poly(trimethylene terephthalate) (PTT), polyurethane (PU), polyvinylchloride (PVC), polyvinyldifluorine (PVDF),
  • the polymer itself does not interact strongly with a pesticide, it may be derivatized with functions that do make interaction possible. These derivatization processes are widely known in the art and are cited or described herein.
  • matrices having a monomelic or oligomeric backbone are defined as salts or reaction products of either an aliphatic amine and a carboxylate oligomer; or a fatty acid or carboxylic acid with a primary or secondary amino functions of an amine, polyamine, and/or an amino alcohol compound which include but are not limited to the following: N- Butyldiethanolamine, 2-(Butylamino)ethanol, N-(2-Hydroxyethyl)ethylene-diamine, Triethanolamine, Diethanolamine, 2-(Methylamino)ethanol, Diethylenetriamine, N-(2- Aminoethyl)- 1 ,3-propane-diamine, 1 ,2-Bis(3-aminopropylamino)ethane, Bis(3- aminopropyl)-amine, 3,3'-Diamino-N-methyldipropylamine, Bis(hexamethylene)tri-amine, l,4-Bis(3--N
  • Matrices with a monomeric backbone may also be comprised of aliphatic amines with one to five amine or amide functions and a linear carbon chain of at least 12 carbon atomes. This includes amines derived from fatty acids, like for example tallowamine or products like Noram 42 or Dinoram 42 ( ® of Ceca).
  • Formulations of pesticides are made by forming a slurry or solution of the pesticide and matrix in an appropriate solvent followed by addition of the additive or modifier, where needed.
  • the matrix and the pesticide can be melted together with or without the additive in such a way as to form a homogenous mixture.
  • the procedure is performed, depending on the reagents, at room temperature or elevated temperature with vigorous stirring to assure homogeneity, and then by drying or concentration if the final product is not dry.
  • the dry product may be ground at a temperature where it is brittle, or left ageing in a moist atmosphere and/or at elevated temperature to harden.
  • the formulation blend comprising of a matrix, pesticide, and/or modifier may be melted at a specific temperature to render a liquid mixture which can be strategically applied/sprayed to the target objects, examples of which are, but not limited to field application, wood and stone handling, textile treatment, and seed coating.
  • the liquid mixtures solidify at ambient temperature and forms a coating directly at the target point, or results in the formation of solid particles through cooling in ambient air that are then slow- release repositories of the substance. This methodology offers a slow and controlled release of the pesticide thus ensuring a long-term application scheme.
  • the matrices are prepared from common materials.
  • the backbones are derivatized to form functions that interact with the selected pesticides via hydrophobic, ionic, stacking or chelation means.
  • Derivatizations include the addition of acid groups, basic groups, rings and alkyl chains. Derivatizations may be also used to cross-link polymers to form gels or more stable particles.
  • Formulations of pesticides are made by forming a slurry (or solution) of the pesticide and matrix in an appropriate solvent followed by addition of the additive or modifier, where needed.
  • the matrix and the pesticide can be melted together with or without the additive in such a way as to form a homogenous mixture.
  • the procedure is performed, depending on the reagents, at room temperature or elevated temperature with vigorous stirring to assure homogeneity, and then by drying or concentration if the final product is not dry.
  • the dry product may be ground with aid of liquid nitrogen, or left ageing in a moist atmosphere and/or at elevated temperature to harden.
  • Bioactive substance A chemical composition that exerts an effect on an organism such as regulating growth, behaviour or homeostasis.
  • Pesticide or Pesticidal ingredient A chemical composition that exerts a desirable effect on a pest species, said composition may, depending on its activity, be considered by those skilled in the art to be any of: herbicides, insecticides (including compounds controlling non- insect arthropods and nematodes), bacteriocides, rodenticides, and fungicides
  • Polymer A chemical composition composed of repeating units covalently bound in a linear or networked (cross-linked) array.
  • Polymers may be homo- (one repeating unit/monomers) or co-polymers (composed of multiple repeat units/monomers).
  • Monomer A substance that possesses functionalities capable of being chemically bonded to itself or other monomers to form a polymer.
  • Oligomer A chemical composition, which consists of a limited number of monomer units.
  • Matrix The substance which is often a major component in a formulation which may be defined as being either a monomelic, oligomeric- or (co)polymeric backbone which may be acidic or basic in nature, branched or linear, crosslinked or non-crosslinked and may exist in the free form or covalently linked to, mixed with and/or grafted with neutral components which include but are not limited to polyethylene glycol, propylene glycol, or fatty acid condensates, or a as reaction products of either a fatty acid or carboxylic acid with a primary or secondary amino functions of an amine, polyamine, and/or an amino alcohol compound.
  • the matrix may be composed of a single substance or a mixture of substances.
  • the matrix may be composed of alkyl acids or alkylamines alone or mixed.
  • Modiflers or Additives A substance added during the formulation process to improve or modify the chemical, physical or biological properties of the end product, thus to obtain optimal controlled release and anti-leaching properties.
  • Modifiers may be waxes, surfactants, ions, colourants, odours and neutral polymers.
  • Formulations of pesticides Mixtures of a pesticidal ingredient and other chemical compositions with the effect of permitting preparation, storage and application of the ingredient.
  • Alkylamines are the same as fatty amines and the terms are used herein to mean primary, secondary or tertiary amines with at least one carbon chain longer than twelve units.
  • Alkylacids are substances with an acidic function and at least one carbon chain longer than eight units.
  • Packaging The means of containment by which formulations are weighed, stored, sold, transported, prepared for use and applied.
  • Beads and solid supports Particles from 1 to 10000 microns that are water insoluble at pH
  • Rainfastness The ability of a pesticidal ingredient to be held on a surface such that more than 5% of an amount deposited in a thin film on a leaf may be recovered from the leaf when said leaf is subject to simulated rainfall equivalent to 10 mm in an hour, said simulated rain commencing 120 minutes after application of the substance in conditions of relative humidity of 50% or less.
  • the invention described herein is a matrix system that may be easily adapted to incorporate a wide variety of chemical compounds and mediate their release to the environment over a sustained period.
  • the Matrices have a very high capacity for compounds that allows practical formulations in which the compound may be a high proportion of the total weight of the preparation including ranges from 66% down to 5% or less.
  • Example 1 Formulation to retard non-polar pesticide for a longer activity (F001).
  • Example 2 Preparation of a slow release formulation of sulfentrazone to a solid cationic exchange resin based on polyethylenimine (F002).
  • Example 3 Preparation of slow release formulations with a solid ion exchange resin based on polyethylenimine and silica (F003).
  • Dicamba (100 mg) was dissolved in 1 mL of a solution of 10 % polyethylenimine and 10 % water in methanol. Dissolution was sluggish and was accelerated by gentle warming and vigorous agitation. Tetraethyl orthosilicate (TEOS) (3$5 ⁇ , of a 13 % solution) in ethanol were added, and the mixture was homogenized by shaking or stirring. After 45 min in a closed vessel, the mixture was transferred into an open container and left to air-dry for 12 h. The flexible, solid product can be milled when cooled i.e. with liquid nitrogen, or left for ageing in a moist atmosphere and/or at elevated temperature to harden. The same procedure can be applied to other active ingredient. Examples of which are, but not limited to bromacil, sulfentrazone, quinclorac, or imazamox. In addition, fungicides, insecticides, nematicides and other pest controlling agents can be treated the same way.
  • Example 4 Preparation of a non-crystalline formulation with high load of active ingredient specifically herbicides (F004).
  • the flexible solid product can be milled when cooled i.e. with liquid nitrogen, 'or left for ageing in a moist atmosphere or/and at elevated temperature to harden.
  • Iron-(III)-chloride (1.6 g) was dissolved in 140 mL of dry THF. Mesotrione (9.33 g) was added and the mixture was shaken to produce a homogenous solution. Powdered iron (1.5 g) were added and the mixture was agitated in a closed vessel for 5 days. The precipitate was filtered off, washed with THF and ether, air-dried, and ground to a fine powder. Residual elemental iron was removed with the aid of a magnet. The product was obtained as a brown powder (5 g).
  • Example 6 Preparation of slow release formulations with a solid cationic exchange resin based on poly(diallyldimethylammonium chloride) and silica (F006).
  • Glyphosate 100 mg, dissolved in 1 mL of dilute ammonia
  • 385 ⁇ , of a 2.1 M solution of TEOS in ethanol were mixed and left standing in a closed vessel for 45 min until a clear viscosity increase could be seen.
  • the mixture was air dried in an open vessel for 12 h.
  • the product was pulverized with the aid of liquid nitrogen or left ageing in a moist atmosphere or/and at elevated temperature.
  • Example 7 Preparation of a slow release formulation of sulfentrazone with a fatty amine (F007).
  • Stearylamine (500 mg) and sulfentrazone (500 mg) were dissolved in approximately 10 mL of ethanol by slight heating. To this mixture was added 180 ⁇ , of a 20 % solution of polyacrylic acid in ethanol (ca. 36 mg). A flocculent precipitation occurs. The reaction mixture is air-dried in an open vessel and left to harden for 4 to 7 days. The resulting slightly brittle white material can be carefully milled to a particle size of less then 50 ⁇ and then be applied as such.
  • Example 8 Preparation of a slow release formulation of various herbicides to a solid cationic exchange resin based on polyethylenimine (F008).
  • Example 9 Preparation of a slow release formulation of clomazone with a urethane matrix (F009).
  • Clomazone (167 mg) and matrix (example 29, M019, 1.4 g) were dissolved in ethanol and concentrated by evaporation. After vacuum-drying (ca. 2 h at 3 mbar), a white rubbery foam remains, that was pulverized with the aid of liquid nitrogen.
  • Quantification of the active ingredient showed 10.8 % content.
  • Example 10 Preparation of a slow release formulation of Metribuzin with colophony in an acidic matrix (F010).
  • Metribuzin 45 mg were dissolved in 360 iL of a 25 % solution of colophony in ethanol. To the resulting solution were added triethoxy(octadecyl)silane (35 mg), and 530 of a 2.1 M solution of tetraethoxysilane in ethanol. After a homogenous mixture formed, the mixture was air-dried overnight. The resulting product was exposed to water (ca. 4 mL), and left to dry once again. The product, which was brittle and hard, was pulverized to a particle size of 100 ⁇ or smaller. Analysis with HPLC UV gives an active ingredient content of 16%.
  • Pentaethylenehexamine (23.2 g, 0.1 mol) and stearic acid (56.8 g, 0.2 mol) were mixed together.
  • Sodium hypophosphite (0.1 g) was added. The mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • the resulting product was a waxy, slightly yellow substance.
  • Pentaethylenehexamine (23.2 g, 0.1 mol), stearic acid (28.4 g, 0.1 mol) and oleic acid (28.2 g, 0.1 mol) were mixed together.
  • Sodium hypophosphite (0.1 g) was added. The mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased. The resulting product was a pale yellow paste.
  • Example 13 Preparation of a Matrix (M003). Pentaethylenehexamine (23.2 g, 0.1 mol) and stearic acid (56.8 g, 0.2 mol) were mixed together. Sodium hypophosphite (0.1 g) was added. The mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased. Then adipic acid (7.3 g, 0.05 mol) was added. The mixture was heated to 175 °C for an additional 5 h at reduced pressure (0.1 mbar). The resulting product was a waxy, light brown substance.
  • M003 Matrix
  • Tetraethylenepentamine (18.9 g, 0.1 mol), stearic acid (28.4 g, 0.1 mol) and oleic acid (28.2 g, 0.1 mol) were mixed together.
  • Sodium hypophosphite (0.1 g) was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • sebacic acid 10.1 g, 0.05 mol
  • the mixture was heated to 175 °C for an additional 5 h at reduced pressure (0.1 mbar).
  • the resulting product was a light brown paste.
  • Example 16 Preparation of a Matrix (M006).
  • Pentaethylenehexamine (23.2 g, 0.1 mol), tetradecanoic acid (45.6 g, 0.2 mol) and oleic acid (56.4 g, 0.2 mol) were mixed together.
  • Sodium hypophosphite (0.1 g) was added. The mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased. The resulting product was a light brown paste.
  • Tetraethylenepentamine 37.8 g, 0.2 mol
  • stearic acid 113.6 g, 0.4 mol
  • Sodium hypophosphite 0.5 g was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • sebacic acid 10.1 g
  • Example 19 Preparation of a Matrix (M009) Triethylenetetramine 60% (24 g, 0.1 mol) and stearic acid (56.8 g, 0.2 mol). Sodium hypophosphite (0.2 g) was added. The mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased. The resulting product was a waxy, yellow solid. Nitrogen number: 3.79 mmoles/g
  • N-(2-Hydroxyethyl)ethylendiamine (20.8 g, 0.2 mol) and stearic acid (1 13.6 g, 0.4 mol) were mixed together.
  • Sodium hypophosphite (0.5 g) was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • the mixture was heated to 175 °C for an additional 5 h at reduced pressure (0.1 mbar).
  • the resulting product was a waxy, light brown solid.
  • N-(2-Hydroxyethyl)ethylendiamine (10.4 g, 0.1 mol), stearic acid (28.4 g, 0.1 mol) and oleic acid (28.2 g, 0.1 mol) were mixed together.
  • Sodium hypophosphite (0.5 g) was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • the mixture was heated to 175 °C for an additional 5 h at reduced pressure (0.1 mbar).
  • the resulting product was a light brown paste.
  • N-(2-Hydroxyethyl)ethylendiamine (20.8 g, 0.2 mol) and stearic acid (101.4 g, 0.357 mol) were mixed together.
  • Sodium hypophosphite (0.5 g) was added. The mixture was heated to
  • Tetraethylenepentamine (37.8 g, 0.2 mol), stearic acid (56.8 g, 0.2 mol) and oleic acid (56.4 g, 0.2 mol) were mixed together.
  • Sodium hypophosphite (0.5 g) was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • the mixture was heated to 175 °C for an additional 5 h at reduced pressure (0.1 mbar).
  • the resulting product was a light yellow paste.
  • Tetraethylenepentamine (37.8 g, 0.2 mol) and stearic acid (113.6 g, 0.4 mol) were mixed together.
  • Sodium hypophosphite (0.5 g) was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • the mixture was heated to 175 °C for an additional 5 h at reduced pressure (0.1 mbar).
  • sebacic acid (10.1 g, 0.05 mol) was added.
  • the mixture was heated to 175 °C for an additional 5 h at reduced pressure
  • Nitrogen number 2.8 mmoles/g
  • Tertiary Nitrogen 2.61 mmoles/g
  • Matrix (15.24 g) from example 12 (M002) was melted at 50 °C and mixed with Hexamethylene diisocyanate (1.68 g). The mixture was kept at 50 °C for another 30 min. The resulting product was a honey-like yellow paste.
  • Example 31 Preparation of a Matrix (M021 )
  • Matrix (16.9 g) from example 14 (M004) was melted at 50 °C and mixed with Hexamethylene diisocyanate (1.68 g). The mixture was kept at 50 °C for another 30 min. The resulting product was a resin-like yellow paste.
  • Matrix (14.4 g) from example 18 (M008) was melted at 50 °C and mixed with Hexamethylene diisocyanate (1.68 g). The mixture was kept at 50° C for another 30 min. The resulting product was a waxy, yellow solid.
  • Pentaethylenehexamine (46.5 g, 0.2 moles) was mixed with oleic acid (1 12.8 g; 0.4 moles).
  • Sodium hypophosphite (0.5g) was added. The mixture was kept at 135° C for 1 hour and at 175° C for an additional 5h until no more water is formed. Heating was continued at 0.1 mbar for another 2h.
  • Tetraethylenepentamine (28.4 g, 0.15 moles) is mixed with stearic acid (127.8 g, 0.45 moles). 0.5g Sodium hypophosphite is added. The mixture is kept at 135° C for 1 hour and at 175° C for an additional 5h until no more water is formed. Heating is continued for another 5h at 0.1 mbar. Waxy, yellow solid.
  • Stearylamine (6500 mg) and sulfentrazone (3900 mg) were dissolved in approximately 150 mL of ethanol by slight heating. To this mixture was added 4000 ⁇ . of a 20 % solution of polyacrylic acid in ethanol (800 mg). A flocculant precipitation occurs. The reaction mixture is dried in an open vessel at 50°C for 6h and left to harden at room temperature for 3 days. The resulting slightly brittle white material is milled to a particle size of less then 100 ⁇ ⁇ ⁇ and then be applied as such.
  • Example 43 Formulation (F013) Matrix (example 24, MO 14, 15 g) was finely ground and dissolved in hot ethanol (approximately 200 mL). To this solution was added mesotrione (6.78 g). Upon dissolution, stirring is continued without heating. The product precipitates as faint yellow powder. AI: 28.9%
  • Matrix (example 39, M029, 1.6 g) was finely ground and dissolved in hot ethanol ( ⁇ 20 ml). To this solution mesotrione (0.7 g) was added. Upon dissolution, stirring was continued without heating. The product precipitates as faint yellow powder. AI: 30 %.
  • Matrix (example 23, M013, 2 g) and 2,4-D (0.6 g) were dissolved with stirring in 20 ml of hot water. Once an emulsion has formed, the mixture was cooled down in an ice bath. Stable, white emulsion. AI: 2.65%
  • Matrix (example 23, M013, 2 g) and 2,4-D (1.2 g) were dissolved with stirring in 20 ml of hot water. Once an emulsion has formed, the mixture was cooled down in an ice bath. Stable, white emulsion. AI: 5.1%
  • Matrix (example 39, M029, 7.89 g) and dicamba (2.21 g) were heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ ⁇ ⁇ .
  • Matrix (example 20, M010, 4.65 g), paraffin (5 g), mp ⁇ 50° C, and dicamba (5 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 10.35 g talcum. White powder. AI: 20%.
  • Matrix (example 35, M025, 8.6 g) and dicamba (2.21 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ ⁇ 100 ⁇ .
  • Matrix (example 23, M013, 6 g) and dicamba (3.6 g) were mixed and heated until dissolved.
  • Triethyleneglycol (9.6 g) was added. Self-emulsifying brown oil. AI: 18.7%.
  • Matrix (example 39, M029, 6 g) and sulfentrazone (1.6 g) were heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Matrix (example 39, M029, 2 g) and bromacil (0.66 g) were heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Matrix (example 29, M019, 1.5 g) and bromacil (0.5 g) were heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Example 60 Formulation (F030) Matrix (example 20, MO 10, 10 g), ozokerit (10 g) and bromacil (10 g) were heated until a homogeneous melt was formed. The solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 6 g of ground talcum.
  • Matrix (example 20, M010, 5.2 g) and paraffin (5.2 g) mp. ⁇ 50° C, were heated until molten.
  • Bromacil (3.46 g) was added. The mixture was heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 3.5 g of ground talcum. White powder. AI: 19%.
  • Matrix (example 20, M010, 5.0 g) and dammar (5.0 g) were mixed and heated until molten. Bromacil (5.0 g) was added. The mixture was heated until a homogeneous melt was formed. The solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 5.0 g of ground talcum. White powder. AI: 25%.
  • Matrix (example 28, M018, 9.0 g) and bromacil (6.0 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 1.5 g of ground talcum. White powder. AI: 36%.
  • Matrix (example 38, M028, 2 g) and imazapyr (1 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Matrix (example 39, M029, 2 g) and imazapyr (0.66 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Example 68 Formulation (F038) Matrix (example 24, MO 14, 3 g), imazapyr (1.4 g) and stearic acid (1.52 g) were mixed and heated until a homogeneous melt of low viscosity was formed. To this melt paraffin (1.35 g), mp ⁇ 50° C, was added and stirred until homogeneous. The solid product was formulated as granules. Light brown granules. AI: 19%
  • Matrix (example 39, M029, 1.58 g) and Imazamox (0.66 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Matrix (example 39, M029, 3.16 g) was molten in hot water (40.3 g). Imazamox (1.32 g) was added with vigorous stirring. The hot emulsion was cooled in an ice bath. White paste. AI: 2.9%
  • Matrix (example 24, M014, 1.2 g) and azoxystrobin (0.2 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 0.3 g ground talcum. Emulsifiable white powder.
  • AI 1 1%.
  • Matrix (example 35, M025, 0.8 g) and azoxystrobin (0.2 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ .
  • Matrix (example 29, M019, 0.73 g) and azoxystrobin (0.25 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . Hydrophobic yellow powder. AI: 25.5%.
  • Matrix (example 26, M016, 2 g) and azoxystrobin (1.0 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 1 g of ground pumice. Emulsifiable white powder. AI: 25%.
  • Example 76 Formulation (F046) Matrix (example 24, MO 14, 2 g) and glyphosate (0.46 g) were mixed and heated until a homogeneous melt was formed. The solid product was ground to a powder with a particle size ⁇ 100 ⁇ . Hydrophobic white powder. AI: 18.7%.
  • Matrix (example 39, M029, 1.9 g), sulfomethuron (0.1 g) and beeswax (2.0 g) were mixed and heated until a homogeneous melt of low viscosity ws formed.
  • the solid product was formulated as granules. Light yellow granules. AI: 2.5%
  • Matrix (example 20, M010, 1 g) and colophony (1.0 g) were heated until molten.
  • Terbuthylazin (0.5 g) was added and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 0.5 g of ground talcum. Emulsifiable yellow powder. AI: 16%.
  • Matrix (example 35, M025, 2 g) and chlorothalonil (0.5 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 100 ⁇ . Dispersible powder.
  • AI 20%.
  • Example 82 Formulation of Metribuzine in a fluorosilicate (F052)
  • Metribuzine (l .Og) was dissolved in ethanol (15 mL). Water (5 mL) was added. Hydrofluoric acid (200 ⁇ 1 of a 50% solution of in water) was added with stirring. Tetraethylsilicate (7.62 mL) was added, and the mixture was heated until it starts gelling. Heating was continued overnight at 50°C in an open vessel to dry and age the material. The resulting product was ground to a fine powder.
  • Example 83 Formulation of Metribuzine in a Polyethyleneimine-fatty acid condensate (F053)
  • Lugalvan G35 (BASF) (70.4 g), behenic acid (17.6 g), and boric acid (500 mg) were combined and heated to 175 °C internal temperature with stirring and under a gentle stream of argon. After 3h of heating, additional 52.8 g of behenic acid was added, and heating was continued for 2 additional hours.
  • Metribuzine (680 mg) and boric acid (395 mg) were dissolved in 9 mL methanol, and 4.25 mL of tetraethylsilicate was added. Water (2.5 mL) was added, and the mixture was shaken, until the initially-occurring turbidity was cleared. The mixture was kept overnight at 37 °C and air dried.
  • Example 86 Formulation of sulfentrazone with a fatty amine (F056)
  • Stearylamine (3.23 g) and sulfentrazone (3.2 g) were dissolved in warm ethanol.
  • a solution of non crosslinked polyacrylic acid (230 mg) dissolved in 10 mL of ethanol was added.
  • the cloudy mixture was air-dried until a hard, malleable, white residue remains.
  • Glucose (17 g) and stearylamine (32 g) were suspended in 500 mL methanol and stirred overnight. The solids were filtered off and dried to yield 41g.
  • Example 88 Formulation of sulfentrazone in a polyethyleneimine phthalate (F058) a) Polyethyleneimine (50% in water, 1.5 g PEI, 3 g) was dried (35 mbar, 100 °C), and dissolved in 20 mL of methanol. Powdered phthalic anhydride (2.8 g) was suspended in 20 mL of THF and added batch wise with heavy agitation to the PEI. After evaporation of all volatiles, the residue was heated to 180 °C for 3h. Once cooled, the gel formed was broken to pieces in a mortar.
  • Matrix (example 20, M010, 5.0 g), dammar (2.5 g) and beeswax (2.5 g) were heated until molten. Bromacil (5.0 g) was added. The mixture was heated until a homogeneous melt was formed. The solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 3.0 g of ground talcum. White powder. AI: 27%.
  • Matrix (example 20, M010, 5.0 g) and beeswax (5.0 g) mp. were heated until molten. Bromacil (5.0 g) was added. The mixture was heated until a homogeneous melt was formed. The solid product was ground to a powder with a particle size ⁇ 100 ⁇ . This powder was mixed thoroughly with 3.0 g of ground talcum. White powder.AI: 27%.
  • example 53a 120mg is dissolved together with imidacloprid (80mg) in 3ml of dichloromethane and 500 ⁇ 1 of methanol. C0 2 is bubbled through the solution, until all volatiles are evaporated and the mixture has reached room temperature. The whitish product is pistoned to achieve a powder.AI: 40%
  • Example 94 Formulation (F064) a) Lupasol G10 (BASF) (19.7g, lOg PEI), behenic acid (20g), and boric acid (250mg) are combined and heated to an inner temperature of 170°C under a gentle stream of Ar with stirring. After 90min, the mixture is left cooling, and 3.3g of 2-[2-(2- methoxyethoxy)ethoxy]acetic acid are added. The mixture is heated carefully, until a homogenous mixture is achieved, and then heated to 175°C (internally) for 4h. Then the reaction is left cooling, and dissolved in a boiling mixture of ethyl acetate and THF (1+1). Succinic acid anhydride (3.3g), dissolved in hot ethyl acetate, is added and all volatiles are evaporated to yield a brown, brittle wax.
  • BASF BASF
  • boric acid 250mg
  • the columns Prior to use, the columns were wetted with deionized water and allowed to drain until no further water leaves the column.
  • a suspension, emulsion, or solution of the sample was prepared in deionized water, and 100 ⁇ of this preparation, containing 200 ⁇ g of A.I. were applied on top of the column. Elution was achieved by addition of successive aliquots of 1 mL of deionized water. After each aliquot, the column was allowed to drain freely and the resulting eluate collected as fractions of approximately 1 mL. Each fraction was collected in a 1.5-mL centrifuge tube and to this 0.3 mL of methanol was added. The solution was mixed thoroughly, and centrifuged at 14,000 x g for 5 minutes.
  • the top 0.3 mL was transferred to an HPLC sample vial.
  • the A.I. in the fractions was quantified by HPLC-MS-MS: an ionics EP10+ triple quadrupole mass spectrometer was tuned to efficiently detect the analytes via MS-MS and specific non-interfering molecular and daughter ions were assigned for each analyte.
  • the instrument was calibrated using a mixed standard dilutions from 100 ⁇ to 10 nM.
  • the analytes were separated using a 50 x 2.5 mm reprosil CI 8 column (Dr. Maisch GmbH, Ammerbuch, Germany) using an isocratic elution at 75% methanol in water containing 0.1 % formic acid.
  • the elution time of the A.I. main peak was indicated by expressing the data as the % of total material eluted.
  • a mixture of sieved (0.5 mm) soil and sand was prepared. 50 mL were filled into a pot with an area of 20 cm 2 (5 cm diameter) and wetted with deionized water. A slurry or solution of the formulation in deionized water was applied on top of the pot. Rainfall was simulated by repeated addition of water in 20-mL portions, each portion representing approximately 10 mm/m 2 of rain. 0.15 mL of rape seed ⁇ Brassica napus) were applied to the soil surface and covered with a thin layer of sand.
  • Soil application premergent to canola 66 66 mm simulated rainfall, assessed 14 days after
  • Table 1 Pre-emergent, canola, 100 g/ha sulfentrazone, 84 mm simulated rainfall, assessed 18 days after planting
  • Example 97 Assay on foliar uptake Sunflowers or peas was seeded and left to germinate and emerge until the cotyledons were fully expanded, but the primary leaves have not appeared.
  • the formulation was suspended in deionized water to achieve an established concentration (ca. 0.01 to 2 % W/V), and an amount of this suspension (1 to 20 ⁇ ) is applied to one or two cotyledons of the seedlings.
  • an indicative parameter was observed, i.e. length of interaodes for hormone type herbicides, or leaf damage for photosystem inhibitors or other signs of phytotoxicity for fungicides and insecticides. Other parameters include survival, plant height or fresh weight.
  • Example 98 Rainfastness on leaves.
  • Established banana, rose, wheat or grape vine leaves were either obtained fresh from outdoor grown plants or from potted plants.
  • potted plants ere used the leaf was treated attached to the plant.
  • outdoor plants the leaf was cut under water and placed in water until used. Rose leaves were not kept longer than 8 h.
  • a suspension of the test formulation was applied to the leaf surface with an application density of 20 ⁇ 1, ⁇ ; ⁇ 2 . If a drying time was foreseen, the formulation was allowed to dry for up to 4 hours. On the other hand, if a drying time was not foreseen, the leaf as immediately subject to a water stream as follows. Rainfastness is determined by resistance to a water stream.
  • leaves were washed with a stream corresponding to greater than 100 mm/hour rainfall for ca. 120 s.
  • Leaves were allowed to dry for 4 h and the treated areas are visually assessed both in normal and UV light, and then swabbed with alcohol containing swabs to remove active ingredient attached to the leaves.
  • the treated areas of the leaf were then extracted using liquid phase extraction by grinding methanol 0.1 % formic acid. Active ingredient in the leaf extracts or swabs was quantified by LC-MS-MS according to the method provided for assessing column eluates.
  • Triethylenetetramine 60% (48.75 g, 0.2 mol) and behenic acid 85% (134.9 g, 0.4 mol) were mixed together.
  • Sodium hypophosphite (0.5 g) was added.
  • the mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased.
  • the mixture was heated to 175 °C for an additional 10 h at reduced pressure (0.1 mbar).
  • the resulting product was a yellow solid with a nitrogen number of 3.86 mmoles/g.
  • Example 101 Preparation of a Matrix (M033) Tetraethylenepentamine (47.2 g, 0.2 mol) and oleic acid (141 g, 0.5 mol) were mixed together. Sodium hypophosphite (0.5 g) was added. The mixture was heated to 135 °C for 1 h and at 175 °C for an additional 5 h until water formation ceased. The mixture was heated to 175 °C for an additional 8 h at reduced pressure (0.1 mbar). The resulting product was a light-brown oil. Nitrogen number: 3.61 mmoles/g
  • Matrix (example 37, M027, 8.5 g) and acetamprid (2.125 g) were mixed and dissolved in N- methylpyrrolidone (3.54 g).
  • Matrix (example 101 , M033, 6.75 g) and dicamba (4.5 g) were mixed together with triethyleneglycol (3.75 g) and heated until a homogeneous mixture was formed.
  • Matrix (example 100, M032, 1.6 g), beeswax (0.5 g), and acetamiprid (0.4 g) were mixed and heated until a homogeneous melt was formed.
  • the product was formulated as granules.
  • Matrix (example 99, M031, 3.0 g) and sulfentrazone (1.0 g) were mixed and heated until a homogeneous melt was formed.
  • the solid product was ground to a powder with a particle size ⁇ 50 ⁇ . Hydrophobic powder.
  • AI 25%.
  • Matrix (example 24, M014, 10.0 g) and polyacrylic acid 1800 (0.5 g) are mixed and molten until homogeneous.
  • Sulfentrazone (2.5 g) was stirred in and kept molten until homogeneous.
  • the solid product was ground to a powder with a particle size ⁇ 50 ⁇ ⁇ ⁇ . Hydrophobic powder.
  • Matrix (example 34, M024, 5.0 g) and polyacrylic acid 1800 (0.25 g) are mixed and molten until homogeneous. Sulfentrazone (1.25 g) was stirred in and kept molten until homogeneous. The solid product was ground to a powder with a particle size ⁇ 50 ⁇ . Hydrophobic yellow powder. AI: 25%.
  • Example 110 Formulation of sulfentrazone with a fatty amine (F011) and a polymeric acid
  • Example 113 Preparation of a formulation of a herbicide with a fatty amine.
  • Stearylamine (1.55 g) and 2,4-D (1.42 g) are melted together at 75-80°C until a homogenous solution is formed. After cooling over night, the resulting slightly brittle white material can be carefully milled to a particle size of less then 50 ⁇ and then be applied as such.
  • it may be sprayed in the molten state in a cooled tower to render particles defined by spray temperature and carrier gas pressure.
  • Example 114 Preparation of a formulation of 2,4-D with a fatty amine.
  • Stearylamine 145 g is melted, and 2,4-D (1 13.9 g) is dissolved, until a clear solution is formed.
  • the material is poured on a plate of room temperature and left cooling, then grinded and sieved through a 50 ⁇ sieve.
  • Example 115 Preparation of a formulation of a herbicide with a fatty amine.
  • Noram 42 ® (3.44 g is melted, and 2,4-D (2.45 g) is dissolved, until a clear solution is formed.
  • the material is poured on a plate of room temperature and left cooling, then grinded and sieved to the desired particle size.
  • 10.23 g of Noram 42® are melted and 9.06 g of sulfentrazone is dissolved in it.
  • the homogenous clear melt cooled, ground and sieved to the desired particle size. Alternatively, it may be sprayed in the molten state in a cooled tower to render particles defined by spray temperature and carrier gas pressure.
  • Example 116 Preparation of a formulation of Metazachlor with rosin
  • a) 99 g of colophonium ("rosin") and 29.7 g of polyethylenimine (50% solution in water, 14.85 g of polyethylenimine) are mixed and heated with stirring to 195°C under vacuum (1 mbar) for 90min. After cooling to RT, a glass is formed, that can be used for the next step.
  • b) 1.62 g of the product of a), and 0.59 g of rosin are mixed and melted at 160°C. 1.06 g of metazachlor are added with heavy stirring, and as soon as everything is dissolved (ca. 3- 4min), the mixture is poured on a cool plate. The brittle glassy product is powdered and sieved to the required particle size.
  • Example 117 Application of a formulation as a melted concentrate
  • a formulation such as that in examples 7, 45, 50 or 67 is formed into granules in the range of 2 mm in diameter that are loaded into a hopper.
  • the hopper is connected to an air stream and the hopper distributes the granules to the air stream using a metered archemedes screw.
  • the airstream forces the granules to a heated compartment where they melt and the molten material is atomized and sprayed in the air stream toward its target.
  • the molten formulation is contacted to a heated spinning disk, which uses centripetal force to create particles that leave the disk and which are then distributed to the target.
  • the matrices and formulations based on these are suitable for use in agriculture, industrial pest control, and as vehicles and excipients for biologically active substances such as pharmaceuticals, cosmetics and personal care products.

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Abstract

Selon l'invention, des substances bioactives sont noyées ou incorporées par mélange dans des matrices fonctionnalisées afin de former des complexes solides homogènes, insolubles dans l'eau, ayant des propriétés désirables sur le terrain, telles qu'une lixiviation réduite dans le sol, une rétention améliorée sur les feuilles, un déchargement sélectif vers les racines et des conditionnement et application facilités. Des substances bioactives de cette invention comprennent des agents pharmaceutiques et des pesticides comprenant des herbicides, des insecticides, des bactériocides, des rodenticides, des nématicides et des fongicides. Les matrices comprennent un squelette monomère, oligomère ou co(polymère) qui peut être transformé en dérivé avec des groupes chimiques présentant des interactions ioniques (amines, carboxyles), hydrophobes et de liaison à un ligand afin de former la matrice de la formulation. Les diverses matrices peuvent être mélangées avec des additifs ou des agents modifiants, greffées ou fusionnées pour obtenir des propriétés optimales. Les formulations peuvent être appliquées sous la forme de granulés, de suspensions, d'émulsions dans des pulvérisations, des mousses ou des enrobages pour des semences et des engrais. En variante, elles peuvent être fondues et pulvérisées sous la forme de concentrés. Les formulations peuvent être appliquées sur le feuillage, le sol, l'eau d'irrigation, les matériaux de construction, les matières d'ensemencement, les grains et les bâtiments.
EP10820940.4A 2009-09-29 2010-09-29 Nouvelles formulations de pesticides Withdrawn EP2482802A4 (fr)

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PCT/US2010/002633 WO2011040956A1 (fr) 2009-09-29 2010-09-29 Nouvelles formulations de pesticides

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US20130122766A1 (en) * 2010-07-30 2013-05-16 Dow Global Technologies Llc Curable compositions
CN106993617B (zh) 2011-08-16 2019-11-08 陶氏益农公司 除草羧酸和含胺聚合物或低聚物的配合物
BR102016019512B8 (pt) 2015-08-26 2022-10-11 Dow Agrosciences Llc Composição compreendendo complexo protetor compreendendo cloquintocet e polímeros ou oligômeros contendo amina, seu método de preparação, e método para controle da vegetação indesejável
CN114982774B (zh) * 2022-07-12 2023-09-22 河北八源生物制品有限公司 一种多功能复配型种子处理悬浮剂及其制备方法

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EP2482802A4 (fr) 2013-08-07
AU2010301135A1 (en) 2012-04-12

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