WO2013041436A1 - Polyesters de polysulfoxydes hyper-ramifiés destinés à la solubilisation de substances actives difficilement solubles - Google Patents

Polyesters de polysulfoxydes hyper-ramifiés destinés à la solubilisation de substances actives difficilement solubles Download PDF

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WO2013041436A1
WO2013041436A1 PCT/EP2012/067922 EP2012067922W WO2013041436A1 WO 2013041436 A1 WO2013041436 A1 WO 2013041436A1 EP 2012067922 W EP2012067922 W EP 2012067922W WO 2013041436 A1 WO2013041436 A1 WO 2013041436A1
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hyperbranched
polysulfoxide
thio
aliphatic
group
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PCT/EP2012/067922
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German (de)
English (en)
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Daniel STADLER
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Basf Se
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • 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
    • A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0225—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen
    • C08G64/025—Aliphatic polycarbonates saturated containing atoms other than carbon, hydrogen or oxygen containing sulfur

Definitions

  • the present invention relates to hyperbranched Polysulfoxidpolyester as described below.
  • the invention further relates to a process for the preparation of the hyperbranched polysulfoxide polyesters according to the invention and to compositions comprising hyperbranched polysulfoxide polyesters according to the invention and a sparingly soluble active substance in water. Furthermore, it relates to the use of the hyperbranched polysulfoxide polyesters according to the invention for solubilizing a sparingly soluble in water active substance in aqueous solutions.
  • the invention also relates to the use of the hyperbranched polysulfoxide polyesters according to the invention in an agrochemical formulation comprising the hyperbranched polysulfoxide polyesters and a pesticide and finally plant propagation material containing the hyperbranched polysulfoxide polyesters.
  • the invention relates to the use of the hyperbranched Polysulfoxidpolyester invention in a pharmaceutical formulation containing the hyperbranched Polysulfoxidpolyester and a pharmaceutical agent. Combinations of preferred features with other preferred features are encompassed by the present invention.
  • Hyperbranched polymers are known (P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499).
  • Pu et al. (Chinese Chemical Letters 18 (2007), 758-761) report the synthesis of hyperbranched polyglycerol grafted with thiol-functionalized polyethylene oxide monomethyl ether. The synthesis is carried out by radical addition of long-chain ethylene oxide thiols containing allyl polyglycerol. Corresponding compounds with S-oxide-containing groups are not described.
  • WO 2009/047210 discloses hyperbranched polyesters comprising dicarboxylic acid units and trifunctional alcohols, wherein succinic acid units substituted as dicarboxylic acid units with C 3 -C 40 alkyl radicals or alkenyl radicals are described.
  • Various trifunctional alcohols are mentioned, such as glycerol, trimethylolpropane, pentaerythritol and their alkoxylated derivatives.
  • WO 2007/068632 discloses hyperbranched polyesters obtainable by reaction of dicarboxylic acids containing polyisobutene groups and trifunctional alcohols, such as glycerol, trimethylolpropane, pentaerythritol and their alkoxylated derivatives.
  • WO 201 1/073220 describes hyperbranched polyesters based on a hydrophobic dicarboxylic acid and a trifunctional alcohol and their use for solubilizing a substance which is sparingly soluble in water.
  • the hydrophobic dicarboxylic acid is an aliphatic Ci 0 -C 3 2-dicarboxylic acid, a polyisobutylene group-containing dicarboxylic acid and / or a C 3 -C 40 -group containing succinic acid unit, and the trifunctional alcohol is glycerol, trimethylolethane, trimethylolpropane, bis (trimethylolpropane) , Pentaerythritol, or an alkoxylated derivative thereof.
  • the object of the present invention was to provide an alternative compound which is readily prepared from commercially available chemicals and industrially reliable and which is suitable for the solubilization of sparingly soluble active substances, especially in aqueous medium. Another task was to provide a compound that can solubilize the highest possible amounts of active ingredient.
  • trifunctional aliphatic polyols selected from the group consisting of glycerol, trimethylolethane, trimethylolpropane, bis (trimethylolpropane) and pentaerythritol and also their alkoxylated derivatives,
  • p and q are the same or different and are an integer from 1 to 6; at least trifunctional aliphatic polyols (a32) selected from the group consisting of glycerol, trimethylolethane, trimethylolpropane, bis (trimethylolpropane) and pentaerythritol and their alkoxylated derivatives, and carbonate coupling reagents (a33) selected from dialkyl carbonates, diaryl carbonates, chloroformates and phosgene derivatives, wherein the hyperbranched Polysulfoxidpolyester (a) optionally linked to at least one polyalkylene oxide group is.
  • Hyperbranched polysulfoxide polyesters (a) which are linked to at least one polyalkylene oxide group are preferred according to the invention.
  • di- or tricarboxylic acid also includes their derivatives, such as halides, esters or anhydrides, and the term diols or polyols also encompasses their alkoxylated derivatives.
  • q and p are preferably the same, q and p are preferably an integer of 2 to 4.
  • the aliphatic sulfoxide-group-containing dicarboxylic acid (a11) is preferably 3,3'-thiopropionic acid sulfoxide and / or 2,2'-thiodiacetic acid sulfoxide.
  • the aliphatic sulfoxide group-containing diol (a22) or (a31) is preferably thiodiethylene glycol sulfoxide.
  • the tricarboxylic acid (a21) is preferably a (C 3 -C 6 ) -alkyl group functionalized with 3 carboxylic acid groups, which may also be substituted by OH or NH 2 .
  • aromatic tricarboxylic acids (a21) mention may be made in particular of tricarboxylic acids of benzene, for example trimesic acid and / or trimellitic acid.
  • Aliphatic tricarboxylic acids (a21) are preferred. Particularly preferred is citric acid.
  • hyperbranched polysulfoxide polyesters (a) which have a weight-average molecular weight in the range from about 500 to 100,000, particularly preferably from 1,000 to 50,000.
  • the determination is carried out by gel permeation chromatography with a refractometer as detector. Preferably, the determination is carried out as described in the examples.
  • the polydispersity of the polysulfoxide polyesters (a) according to the invention is generally from 1.2 to 50, preferably from 1.4 to 40, particularly preferably from 1.5 to 30 and very particularly preferably from 2 to 30.
  • the details on polydispersity and on the number average and weight average Molecular weight M n and M w here refer to gelper- methylation chromatography measurements using polymethylmethacrylate as standard and tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol as eluent. The method is described in the Analyst Taschenbuch Vol. 4, pages 433 to 442, Berlin 1984.
  • the nature of the terminal groups can be influenced by the ratio of the monomers used. If predominantly OH-terminated polymers are to be obtained, then the alcohols should be used in excess. If predominantly COOH-terminated polymers are to be obtained, then the carboxylic acids should be used in excess.
  • the number of free OH groups (hydroxyl number) of the hyperbranched polysulfoxide polyester (a) is generally from 10 to 500, preferably from 20 to 450 mg KOH per gram of polymer and may be e.g. be determined by titration according to DIN 53240-2.
  • the number of free COOH groups (acid number) of the hyperbranched Polysulfoxid- polyester (a) is usually 0 to 400, preferably 25 to 300, most preferably 50 to 250, and in particular 120 to 250 mg KOH per gram of polymer and can by Titration to DIN 53402 be determined.
  • the hyperbranched polysulfoxide polyesters (a) according to the invention have at least 4 functional groups.
  • the number of functional groups is in principle not limited to the top.
  • products with too many functional groups often have undesirable properties, such as poor solubility or very high viscosity.
  • the hyperbranched polysulfoxide polyesters (a) according to the invention generally have no more than 100 functional groups.
  • the hyperbranched polysulfoxide polyesters (a) preferably have 6 to 50 and particularly preferably 6 to 30 functional groups.
  • the hyperbranched polysulfoxide polyester (a) is preferably linked to a polyalkylene oxide group. This is particularly advantageous if the water solubility of the Polysulfoxidpolyester (a) is not sufficient. As a result, nonionic, amphiphilic solubilizers can be obtained since (partial) neutralization of the carboxylic acid groups to achieve water solubility / water dispersibility is no longer necessary. These nonionic solubilizers are particularly well suited for the production of long-term stable drug formulations.
  • Examples of a polyalkylene oxide group are polyethylene glycol or polyethylene glycol monoalkyl ethers having a molecular weight Mn of 200 to 10,000 g / mol, preferably 300 to 2000 g / mol. It is preferable that the polyethylene glycol is a po- lyethyleneglycol mono-C 1 -C 8 -alkyl ethers, in particular a polyethylene glycol monomethyl ether.
  • the hyperbranched polysulfoxide polyester (a) is preferably linked to the polyalkylene oxide group by means of a polyisocyanate linker.
  • Dendrimers and hyperbranched polymers are names for polymers that are characterized by a highly branched structure and a high functionality. However, there are distinct differences in structure between dendrimers and hyperbranched polymers: dendrimers are molecularly uniform macromolecules with a highly symmetrical structure. Dendrimers can be prepared starting from a central molecule by controlled, stepwise linking of two or more di- or polyfunctional monomers with each already bound monomer. With each linking step, the number of monomer end groups (and thus the linkages) multiplied by a factor of 2 or higher, and obtained generationally constructed, monodisperse polymers with tree-like structures, ideally spherical, whose branches each contain exactly the same number of monomer units.
  • the polymer properties are advantageous, for example, one observes a surprisingly low viscosity and high reactivity due to the high number of functional groups on the spherical surface.
  • the preparation of the monodisperse dendrimers is complicated by the need to introduce and remove protecting groups at each linking step and to require intensive purification operations prior to the commencement of each new growth stage, which is why dendrimers are usually only produced on a laboratory scale.
  • hyperbranched polymers are both molecularly and structurally non-uniform, i. the molecules of the polymer have both a distribution in terms of molecular weight and in terms of the structure of the molecules. They are obtained by a non-generational construction. It is therefore not necessary to isolate and purify intermediates.
  • Hyperbranched polymers can be obtained by simply mixing the components required for construction and their reaction in a so-called one-pot reaction. Hyperbranched polymers can have dendrimeric substructures. In addition, they also have linear polymer chains and unequal polymer branches.
  • AB x monomers are suitable for the synthesis of hyperbranched polymers. These have two different functional groups A and B in one molecule, which can intermolecularly react with each other to form a linkage. The functional group A is contained only once per molecule and the functional group B twice or more times. Due to the reaction of the Together, AB x monomers form uncrosslinked polymers with a high number of branch points. The polymers have almost exclusively B groups at the chain ends. Furthermore, hyperbranched polymers can be prepared via the A x + B y synthesis route as in the process according to the invention.
  • a x and B y represent at least two different monomers with the functional groups A and B and the indices x and y represent the number of functional groups per monomer.
  • a x + B y synthesis shown here using the example of an A 2 + B 3 synthesis, a difunctional monomer A 2 is reacted with a trifunctional monomer B 3 .
  • the hyperbranched polymers thus obtained also have predominantly B groups as end groups.
  • the non-dendrimeric, hyperbranched polymers according to the invention differ significantly from dendrimers in the degree of branching.
  • degree of branching see also H. Frey et al., Acta Polym. 1997, 48, 30.
  • the term "hyperbranched" in connection with the polymers means that the degree of branching DB 10 to 95%, preferably 25 to 90% and particularly preferably 30 to 80%.
  • a dendrimer has the maximum possible number of branching points which can only be achieved by a highly symmetrical structure.
  • the polysulfoxide polyesters (a) according to the invention have ester linkages in a known manner.
  • the polymers comprise as building blocks in each case at least one sulfoxide-containing dicarboxylic acid unit and at least one trifunctional alcohol or at least one sulfoxide-containing diol and at least one tricarboxylic acid.
  • Further polysulfoxide polyesters (a) according to the invention have carbonate linkages, the polymers comprising building blocks of at least one sulfoxide-group-containing aliphatic diol, at least one at least trifunctional alcohol and a carbonate coupling reagent.
  • the polysulfoxide polyesters of the invention may further comprise further building blocks.
  • the invention further provides a process for the preparation of the hyperbranched polysulfoxide polyesters (a) according to the invention.
  • polycondensates (a1) it is possible to use aliphatic sulfoxide-group-containing dicarboxylic acids (a11) or aliphatic thio-group-containing dicarboxylic acids (a11-thio).
  • the aliphatic thio groups-containing dicarboxylic acids (a1 1 -thio) also contain the structural unit of the formula (I), wherein -S (O) - is replaced by -S-.
  • the dicarboxylic acids (a1 1) or (a1 1-thio) can also be used in the form of activated derivatives, in particular in the form of halides, esters or anhydrides.
  • Derivatives are, in particular, the relevant anhydrides in monomeric or else polymeric form, mono- or dialkyl esters, preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, furthermore mono- and divinyl esters and mixed ones ester.
  • the dicarboxylic acids (a1 1) or (a1 1-thio) are preferably used as such as starting material. It is also possible to use mixtures of different dicarboxylic acids (a1 1) or (a1 1-thio). Some thio-containing dicarboxylic acids (a1 1 thio) are commercially available. For example, 3,3'-thiodipropionic acid is commercially available from ABCR.
  • the preparation of the sulfoxide-containing dicarboxylic acids (a1 1) used according to the invention can advantageously be carried out by treating a thio-containing dicarboxylic acid (a1 1-thio) with hydrogen peroxide (30%) in glacial acetic acid. After removing the glacial acetic acid and recrystallization from acetone, the corresponding sulfoxide-containing dicarboxylic acids (a11) can be obtained in good yield and high purity.
  • the hyperbranched polysulfoxide polyester (a) based on polycondensate (a1) at least one dicarboxylic acid (a1 1) or (a1 1 thio) are reacted with at least one trifunctional alcohol (a12), wherein the ratio of the reactive groups in the reaction mixture so chooses that a molar ratio of OH groups to carboxyl groups or their derivatives of 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, more preferably from 3: 1 to 1: 3 and most preferably from 2: 1 to 1: 2 sets.
  • the stoichiometry of OH groups to carboxyl groups is usually complied with as described above.
  • Trifunctional alcohols are understood as meaning aliphatic alcohols having at least three alcohol groups.
  • Glycerol, trimethylolethane, trimethylolpropane, bis (trimethylolpropane), pentaerythritol, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof are suitable as the trifunctional alcohol.
  • Preferred trifunctional alcohols are glycerol, trimethylolpropane and pentaerythritol and their alkoxylated derivatives. Very particular preference is given to glycerol and trimethylolpropane and also their alkoxylated derivatives.
  • Alkoxylated derivatives of glycerol, trimethylolethane, trimethylolpropane, bis (trimethylolpropane), pentaerythritol can be obtained in a manner known in principle by alkoxylation of the alcohols with alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, and / or pentylene oxide.
  • alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, and / or pentylene oxide.
  • the mixed alkoxylated polyetherols can be copolymers in which, for example, different alkylene oxide units are randomly distributed in the chain or they can be block copolymers.
  • the alkoxylated derivative of glycerol, trimethylolethane, trimethylolpropane, bis (trimethylolpropane) or pentaerythritol with 1, 1 to 20 alkylene oxide units, preferably ethylene oxide and / or propylene oxide units, is preferably alkoxylated.
  • the alkoxylated derivative of glycerol, trimethylolpropane or pentaerythritol is alkoxylated with 1, 1 to 20 propylene oxide units.
  • the aliphatic thio-containing diols (a22-thio) also contain the structural unit of the formula (II), wherein -S (O) - is replaced by -S-.
  • the diols (a22) or (a22-thio) are preferably used as such as starting material. It is also possible to use mixtures of different diols (a22) or (a22-thio) or derivatives thereof.
  • thio-containing diols are commercially available.
  • thiodiethylene glycol is commercially available from BASF as Thiodiglycol Ultra.
  • the preparation of the sulfoxide-containing diols (a22) used according to the invention can advantageously be carried out by treating a thio-containing, containing diol (a22-thio) with hydrogen peroxide (30%) in aqueous solution. After removal of the water and recrystallization from hot isopropanol, the corresponding sulfoxide-containing diols (a22) can be obtained in good yield and high purity.
  • the ratio of the reactive groups in the reaction mixture so chooses that a molar ratio of OH groups to carboxyl groups or derivatives thereof from 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, more preferably from 3: 1 to 1: 3 and most preferably from 2: 1 to 1: 2 sets.
  • the stoichiometry of OH groups to carboxyl groups is usually maintained as described above.
  • a thio-containing diol (a22-thio) was used to prepare the polycondensates (a2), the polycondensation is followed by oxidation of the hyperbranched polythioether polyester formed to give the hyperbranched polysulfoxide polyester (a).
  • thio-group-containing aliphatic diols (a31-thio).
  • the diols (a31) and (a31 thio) correspond to the diols (a22) and (a22-thio), respectively, to the above description and preparation of which reference is expressly made.
  • At least one aliphatic thio group-containing diol (a31-thio) is reacted with at least one trifunctional aliphatic polyol (a32) and at least one carbonate coupling reagent (a33), the ratio of the reactive groups in the reaction mixture such that a molar ratio of from 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, particularly preferably from 3: 1 to 1: 3 and very particularly preferably from 2: 1 to 1: 2 sets.
  • the trifunctional polyols (a32) correspond to the trifunctional alcohols (a12), the above description of which is expressly referred to.
  • the dialkyl carbonates used as carbonate coupling reagents (a33) are in particular di-C 1 -C 4 -alkyl carbonates, for example dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate and / or diisobutyl carbonate. Especially preferred is diethyl carbonate.
  • the carbonate coupling reagents (a33) may also be aromatic diaryl carbonates, of which typical representatives are diphenyl carbonate and carbonyldiimidazole. Further suitable carbonate coupling reagents (a33) are alkyl or aryl chloroformates.
  • suitable carbonate coupling reagents are phosgene and its derivatives such as diphosgene and triphosgene.
  • further di- or polyfunctional carboxylic acids can be used.
  • further carboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, 1, 2-, 1, 3- or 1, 4-cyclohexanedicarboxylic acid (hexahydrophthalic acids), phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, in particular their anhydrides or esters .
  • the amount of such further carboxylic acids should as a rule not exceed 50 mol% with respect to the amount of all the carboxylic acids used (that is to say the sum of hydrophobic dicarboxylic acids and further di- or polyfunctional carboxylic acids) together.
  • the amount of further di- or polyfunctional carboxylic acids is preferably not more than 30 mol%, particularly preferably not more than 20 mol%.
  • polycondensates (a1) and (a2) can also be used in the polycondensates (a1) and (a2).
  • dihydric alcohols By suitable choice of dihydric alcohols, the properties of the Polysulfoxidpolyester can be influenced.
  • diols examples include ethyleneglycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1, 2, 1, 3- and 1, 4-cyclohexanediol, 1, 3- and 1, 4-bis (hydroxymethyl) cyclohexane, and diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycols HO (CH 2 CH 2 O) n - H or polypropylene glycols HO (CH [CH 3 ] CH 2 O) n -H, where n is an integer and n> 4, polyethylene glycols, where the sequence of the ethylene oxide or propylene oxide units may be blockwise or random, or polytetramethylene glycols, preferably up to a molecular weight of 5000 g /
  • Suitable aromatic diols are, for example, resorcinol, catechol and hydroquinone.
  • the dihydric alcohols may optionally contain further functionalities such as, for example, carbonyl, carboxy, alkoxycarbonyl or sulfonyl functions, for example dimethylolpropionic acid or dimethylolbutyric acid, and also their C 1 -C 4 -alkyl esters, glycerol monostearate or glycerol monooleate.
  • the amount of such other dihydric alcohols should, however, generally not exceed 50 mol% with respect to the amount of all the alcohols used (ie the sum of trifunctional alcohol and difunctional diol).
  • the amount of dihydric alcohols is preferably not more than 30 mol%, particularly preferably not more than 20 mol%. Very particular preference is given to using only the trifunctional alcohols for the polycondensates (a1).
  • the reaction of all components in the preparation of the hyperbranched polysulfoxide polyester (a) or of the corresponding polythioether polyester can be carried out in the presence or absence of a solvent.
  • Suitable solvents are, for example, hydrocarbons such as paraffins, aromatics, ethers and ketones.
  • the reaction is carried out in xylene or solvent-free.
  • the reaction is generally carried out at elevated temperatures, for example 30 to 250 ° C, in particular 80 to 220 ° C and particularly preferably 80 to 180 ° C.
  • the water or the alcohols formed during the polycondensation should be removed from the reaction medium by means of suitable measures.
  • the reaction can be carried out, for example, in the presence of a dehydrating agent as an additive, which is added at the beginning of the reaction.
  • a dehydrating agent as an additive, which is added at the beginning of the reaction.
  • Suitable examples are molecular sieves, especially molecular sieve 4A, anhydrous MgS0 4 or anhydrous Na 2 S0. 4
  • water or alcohols formed during the reaction can be distilled off. This can also be done by means of a suitable entraining agent using a water separator.
  • the distilling off can preferably be carried out under reduced pressure, for example at a pressure of from 1 mbar to 500 mbar.
  • catalysts You can carry out the reaction in the absence of catalysts. However, it is preferable to work in the presence of at least one catalyst. These are preferably acidic inorganic, organometallic or organic catalysts or mixtures of several acidic inorganic, organometallic or organic catalysts. It is also possible according to the invention to use enzymes as catalysts, if their use is also less preferred.
  • acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, sulfates and hydrogen sulfates, such as sodium hydrogen sulfate, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH ⁇ 6, in particular ⁇ 5) and acidic aluminum oxide.
  • radicals R 1 may be the same or different and are independently selected from CrC 2 o-alkyl radicals, for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec-pentyl, neo -Pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n Dode
  • Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R 1 2 SnO or dialkyltin diesters R 1 2 Sn (OR 2 ) 2 where R 1 is as defined above and may be identical or different.
  • R 2 may have the same meanings as R 1 and additionally C 6 -C 2 -aryl, for example phenyl, o-, m- or p-tolyl, xylyl or naphthyl. Each R 2 may be the same or different.
  • organotin catalysts examples include tin (II) n-octanoate, tin (II) 2-ethylhexanoate, tin (II) laurate, dibutyltin oxide, diphenyltin oxide, dibutyltin dichloride, di-butyltin diacetate, dibutyltin dilaurate, dibutyltin dimaleate or dioctyltin diacetate , Also conceivable are antimony, bismuth or organoaluminum catalysts. Particularly preferred representatives of acidic organometallic catalysts are dibutyltin oxide, diphenyltin oxide and dibutyltin dilaurate.
  • Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as para-toluene sulfonic acid. It is also possible to use acidic ion exchangers as acidic organic catalysts, for example polystyrene resins containing sulfonic acid groups, which are crosslinked with about 2 mol% of divinylbenzene. It is also possible to use combinations of two or more of the aforementioned catalysts.
  • the reaction time is usually 5 minutes to 48 hours, preferably 30 minutes to 24 hours and more preferably 1 hour to 10 hours.
  • the end of the reaction can often be recognized by the fact that the viscosity of the reaction mixture suddenly begins to increase rapidly.
  • the reaction can be stopped, for example by cooling.
  • the number of carboxyl groups in the (pre) polymer can be determined on a sample of the mixture, for example by titration of the acid number according to DIN 53402-2.
  • the insoluble portion of the polymer was determined by extraction for 4 hours with the same solvent as used for gel permeation chromatography, that is, tetrahydrofuran, dimethylacetamide or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble, in a Soxhiet apparatus and after drying of the residue to constant weight Weighing the remaining residue.
  • solvent used for gel permeation chromatography
  • the synthesis is characterized by its great simplicity and makes it possible to produce hyperbranched polysulfoxide polyesters (a) or corresponding polyether ether polyesters in a simple one-pot reaction. Isolation or purification of intermediates or protecting groups for intermediates is not required.
  • the hyperbranched polysulfoxide polyesters (a) or corresponding polythioether polyesters are usually prepared in a pressure range from 2 mbar to 20 bar, preferably at atmospheric pressure, in reactors or reactor cascades which are operated batchwise, semicontinuously or continuously.
  • the oxidation of the polythioether polyester can be carried out with customary oxidizing agents, for example catalytically or particularly advantageously by treatment with aqueous hydrogen peroxide solution. If the hyperbranched polythioether polyester is poorly soluble in water, it is previously dissolved in a common organic solvent (e.g., methanol), preferably in a mixture of water and the organic solvent.
  • a common organic solvent e.g., methanol
  • the linking of the hyperbranched polysulfoxide polyester (a) with a polyalkylene oxide group is preferably carried out by means of a polyisocyanate linker.
  • a linker-reactive group a hydroxy group may be used at the chain end of the polyalkylene oxide group. Preference is given to polyethylene glycol monoalkyl ethers having exactly one linker-reactive group at the chain end.
  • Suitable polyisocyanate linkers are polyisocyanates having a functionality with respect to the isocyanate groups of at least 1, 5, in particular 1, 5 to 4.5 and especially 1, 8 to 3.5 comprising aliphatic, cycloaliphatic and aromatic di- and polyisocyanates and the isocyanurates, allophanates , Uretdiones and biurets of aliphatic, cycloaliphatic and aromatic diisocyanates.
  • the polyisocyanates have on average from 1.8 to 3.5 isocyanate groups per molecule.
  • suitable polyisocyanates are aromatic diisocyanates such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, commercially available mixtures of toluene-2,4 and 2,6-diisocyanate (TDI), n-phenylene diisocyanate, 3, 3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, cumene 2,4-diisocyanate, 1,5-naphthalene diisocyanate, p-xylylene diisocyanate, p-phenylene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-
  • Preferred polyisocyanates are those whose isocyanate groups differ in their reactivity, such as toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 4'-diphenylmethane diisocyanate, cis and trans isophorone diisocyanate, or mixtures of these compounds.
  • the reaction with the polyisocyanate linker takes place in melt or in an organic solvent, preferably in an aprotic-polar organic solvent or in mixtures of such solvents.
  • organic solvent preferably in an aprotic-polar organic solvent or in mixtures of such solvents.
  • ketones for example acetone
  • butyl acetate tetrahydrofuran
  • xylene xylene
  • chlorobenzene dimethyl sulfoxide (DMSO) or dimethylformamide (DMF).
  • Preferred solvents are tetrahydrofuran, butyl acetate, xylene and acetone.
  • the reaction usually takes place at elevated temperatures, wherein the temperature also depends on the boiling point of the selected solvent.
  • the reaction of the polyisocyanate linker with the first component can be carried out at 20 to 80 ° C, but optionally also up to 100 ° C.
  • the reaction of the further isocyanate group can be carried out at temperatures of 50 to 100 ° C.
  • the solvent can then be removed by distillation.
  • the reaction can be carried out in an equimolar manner, which means that the quantitative ratio is selected so that 1 mol of diisocyanate is used per mole of hydroxyl groups of the functionalizing reagent or of the linear polyalkylene oxide to be reacted.
  • light e.g., 0 to 15 mol
  • excess of the hydroxyl groups is used to reduce the amount of unreacted diisocyanate.
  • symmetrical diisocyanates such as HDI
  • the reaction is carried out in the presence of a catalyst.
  • Suitable catalysts are, for example, tertiary amines, for example triethylamine, tri-n-propylamine, N-methylpyrrolidine, N-methylpiperidine and diazabicyclooctane (DABCO), zinc carboxylates, bismuth carboxylates, titanium alkoxides, organotin compounds, in particular dialkyltin (IV) salts of aliphatic carboxylic acids such as di-butyltin dilaurate and dibutyltin dioctoate, tin (II) dialkanoates such as tin dioctoate, and cesium salts such as cesium acetate.
  • tertiary amines for example triethylamine, tri-n-propylamine, N-methylpyrrolidine, N-methylpiperidine and diazabicyclooctane (DABCO)
  • DABCO diaza
  • zinc carboxylates, bismuth carboxylates, titanium alcoholates are particularly suitable, the carboxylates preferably being C1-C20 carboxylates (such as formate, acetate, propionate, hexanoate, octanoate or neodecanoate).
  • the catalyst can be used in amounts of 50 to 50,000 ppm, preferably 100 to 5,000 ppm, based on total solids.
  • the reaction is usually carried out in such a way that first the component which is to be isocyanate-functionalized (for example the polyalkylene oxide) is reacted with the diisocyanate in the presence of the catalyst and a solvent until the isocyanate value in the reaction mixture has fallen to half.
  • the reaction is continued until the theoretical final value corresponds to the complete conversion of the hydroxyl groups. This can be determined in a known manner, for example titrimetrically.
  • the molar ratio of hyperbranched Polysulfoxidpolyester (a) to the polyalkylene oxide is from 1: 1 to 1: 25, preferably 1: 2 to 1: 15.
  • the reaction is continued until the isocyanate value has dropped to zero, optionally for the destruction of a Residual isocyanate content also a small amount of an amine can be added.
  • the invention furthermore relates to the use of the hyperbranched polysulfoxide polyester (a) according to the invention linked to at least one polyalkylene oxide group for solubilizing an active substance which is soluble in water at 20 ° C. to not more than 10 g / l in aqueous solutions.
  • Solubilization means that in the presence of the hyperbranched polysulfoxide polyester (a) linked to polyalkylene oxide groups, more active ingredient can be solubilized than in its absence under otherwise identical conditions.
  • at least twice the amount, more preferably at least five times and in particular ten times the amount, can be brought into solution.
  • Another object of the invention is a composition
  • a composition comprising an active ingredient which is soluble in water at 20 ° C to at most 10 g / L, and at least one polyalkylene oxide-linked hyperbranched Polysulfoxidpolyester invention (a).
  • the active ingredient is soluble in water at 20 ° C to at most 10 g / L, preferably at most 2 g / l, more preferably at most 0.5 g / l and especially at most 0.1 g / l.
  • the composition may contain one or more different active ingredients.
  • active ingredients are agrochemical active ingredients, cosmetic active ingredients, pharmaceutical active ingredients or dietary supplements (such as vitamins and carotenoids).
  • Preferred active ingredients are agrochemical active ingredients.
  • cosmetic active ingredients are cosmetic oils, fragrances and flavorings, vitamins or UV absorbers.
  • Cosmetic oils include peanut oil, jojoba oil, coconut oil, almond oil, olive oil, palm oil, castor oil, soybean oil, wheat germ oil or essential oils such as mountain pine oil, lavender oil, rosemary oil, pine needle oil, pine needle oil, eucalyptus oil, peppermint oil, sage oil, bergamot oil, turpentine oil, lemon balm oil, Waxing oil, lemon oil, aniseed oil, cardamom oil, camphor oil etc. or mixtures thereof.
  • UV absorbers include 2-hydroxy-4-methoxybenzophenone, 2,2 ', 4,4'- Tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,4-dihydroxybenzophenone, 2-cyano-3,3-diphenylacrylic acid 2'-ethylhexyl ester, 2,4,6-trianilino-p- (carbo- 2'-ethylhexyl-1'-oxi) -1, 3,5-triazine, 3- (4-methoxybenzylidene) -camphor, N, N-dimethyl-4-aminobenzoic acid 2-ethylhexyl ester, salicylic acid-3,3 , 5-trimethylcyclohexyl ester, 4-isopropyl-dibenzoylmethane, 2-ethylhexyl p-methoxycinnamate and 2-isoamyl p-methoxycinnam
  • fragrances and flavorings are as described in WO 01/49817 or in "Flavors and Fragrances", Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, 2002, which is incorporated herein by reference.
  • vitamins examples include vitamins, provitamins and vitamin precursors from groups A, C, E and F, in particular 3,4-didehydroretinol, beta-carotene (provitamin of vitamin A), ascorbic acid (vitamin C), and the palmitic acid esters, glucosides or phosphates the ascorbic acid, tocopherols, especially alpha-tocopherol and its esters, eg the acetate, nicotinate, phosphate and succinate; vitamin F, which is understood as meaning essential fatty acids, especially linoleic acid, linolenic acid and arachidonic acid.
  • active pharmaceutical ingredients include: benzodiazepines, antihypertensives, vitamins, cytostatic drugs taxol, anesthetics, neuroleptics, antidepressants, antiviral agents such as anti-HIV agents, antibiotics, antimycotics, anti-dementia, fungicides, chemotherapeutics, urologics, platelet aggregation inhibitors, Sulfonamides, spasmolytics, hormones, immunoglobulins, serums, thyroid medicines, psychotropic drugs, antiparkinson drugs and other antihyperketics, ophthalmics, neuropathy preparations, calcium metabolism regulators, muscle relaxants, anesthetics, lipid lowering agents, liver therapeutics, coronary agents, cardiacs, immunotherapeutics, regulatory peptides and their inhibitors, hypnotics , Sedatives, gynecologics, gout, fibrinolytics, enzyme preparations and transport proteins, enzyme inhibitors, emetics, circulation-promoting agents
  • agrochemical active ingredients denotes at least one active substance selected from the group of fungicides, insecticides, nematicides, herbicides, safeners and / or growth regulators.
  • Preferred pesticides are fungicides, insecticides and herbicides, especially insecticides. Also mixtures pesticides from two or more of the above classes may be used.
  • One skilled in the art will be familiar with such pesticides as described, for example, in Pesticide Manual, 14th Ed. (2006), The British Crop Protection Council, London.
  • Suitable insecticides are insecticides of the class of carbamates, organophosphates, organochlorine insecticides, phenylpyrazoles, pyrethroids, neonicotinoids, spinosines, avermectins, milbemycins, juvenile hormone analogs, alkylhalides, organotin compounds, nereistoxin analogs, benzoylureas, diacylhydrazines, METI Acaricides, as well as insecticides such as chloropicrin, pymetrozine, flonicamide, clofentezine, hexythiazox, etoxazole, diafenthiuron, propargite, tetradifon, Chlorfenapyr, DNOC, burserocin, cyromazine, amitraz, hydramethylnone, acequinocyl, fluacrypyrim, rotenone, or their derivatives.
  • Suitable fungicides are fungicides of the classes dinitroanilines, allylamines, anilinopyrimidines, antibiotics, aromatic hydrocarbons, benzenesulfonamides, benzimidazoles, benzisothiazoles, benzophenones, benzothiadiazoles, benzotriazines, benzylcarbamates, carbamates, carboxamides, carboxamides, chloronitriles, cyanoacetamidoximes, cyanoimidazoles, cyclopropanecarboxamides , Dicarboximides, dihydrodioxazines, dinitrophenyl crotonates, dithiocarbamates, dithiolanes, ethylphosphonates, ethylaminothiazolecarboxamides, guanidines, hydroxy (2-amino) pyrimidines, hydroxyanilides, imidazoles, imidazolinones, inorganic
  • Suitable herbicides are herbicides of the classes of acetamides, amides, aryloxyphenoxypropionates, benzamides, benzofuran, benzoic acids, benzothiadiazinones, bipyridylium, carbamates, chloroacetamides, chlorocarboxylic acids, cyclohexanediones, dinitroanilines, dinitrophenol, diphenyl ethers, glycines, imidazolinones, isoxazoles, isoxazolidinones, nitriles, N-phenylphthalimides , O-oxadiazoles, oxazolidinediones, oxyacetamides, phenoxycarboxylic acids, phenylcarbamates, phenylpyrazoles, phenylpyrazolines, phenylpyridazines, phosphinic acids, phosphoroamides, phosphorodithioates, phthala
  • the pesticide contains an insecticide, preferably the pesticide is at least one insecticide.
  • Preferred insecticides are fipronil, alleth rin, alpha-cypermethrin, beta-cyfluthrin, bifenthrin, bioallethrin, 4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone ( CAS-RN: 120955-77-3), chlorfenapyr, chlorpyrifos, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, etofenprox, fenoxycarb, flufenoxuron, hydramethylnone, metaflumizone, permethrin, pyriproxifen, silafluofen, tebufenozide and tralomethrin.
  • insecticides are fipronil, alpha-cypermethrin, bifenthrin, chlorfenapyr, cyfluthrin, cypermethrin, deltamethrin, etofenprox, hydramethylnone, metaflumizone, permethrin.
  • very particularly preferred insecticides are fipronil, alpha-cypermethrin, deltamethrin, chlorfe-napyr, hydramethylnone and metaflumizone.
  • preferred insecticide is fipronil.
  • the pesticide contains a fungicide, preferably the pesticide consists of at least one fungicide.
  • Preferred fungicides are pyraclostrobin, metconazole, fluxapyroxad and epoxiconazole.
  • the pesticide contains a herbicide, preferably the pesticide consists of at least one herbicide.
  • the pesticide contains a growth regulator, preferably the pesticide consists of at least one growth regulator.
  • composition according to the invention usually comprises from 0.1 to 70% by weight of active compound, preferably from 1 to 60% by weight, in particular from 3 to 50% by weight, based on the composition.
  • composition according to the invention can be obtained by bringing into contact the hyperbranched polysulfoxide polyester (a) linked to at least one polyalkylene oxide group and the active substance which is soluble in water at 20 ° C. to not more than 10 g / l.
  • the components can be contacted by well-known methods such as mixing, emulsifying or suspending.
  • the weight ratio of hyperbranched polysulfoxide polyester (a) to active ingredient linked to polyalkylene oxide groups is usually in the range from 1:50 to 100: 1, preferably from 1: 5 to 50: 1, particularly preferably from 1: 2 to 25: 1.
  • the active ingredient may be in dissolved form or in solid, particulate form.
  • the drug particles may be crystalline or amorphous.
  • the particle size can be 1 nm to 10 ⁇ .
  • the composition may be present as a solid, solution, emulsion, suspension or suspension emulsion of the active ingredient.
  • the composition according to the invention is preferably an aqueous composition.
  • the composition according to the invention is a solid, wherein it is particularly preferably a solid solution (so-called solid solution).
  • the active ingredient is usually present in an amorphous form dispersed in a polymer matrix. It preferably contains at least 40% by weight, more preferably at least 60% by weight, and in particular at least 80% by weight of water. Usually, the composition contains at most 99% by weight of water.
  • the composition according to the invention may contain formulation auxiliaries, wherein the choice of auxiliaries usually depends on the specific application form or the active substance.
  • suitable formulation auxiliaries are solvents, solid carriers, surface-active substances (such as surfactants, protective colloids, wetting agents and adhesives), organic and inorganic thickeners, bactericides, antifreeze agents, defoamers, if appropriate dyes and adhesives (for example for seed treatment).
  • surfactants are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, eg. B. of lignin (Borresperse ® grades, Borregaard, Norway), phenol, naphthalene (Morwet ® types, Akzo Nobel, USA) and dibutyl (nekal ® types, BASF, Germany), and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octadecanols and of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or of naphthalenesul
  • aromatic sulfonic acids eg. B. of lignin (Borresper
  • the active ingredient is a pesticide and the compositions of the invention are in the form of an agrochemical formulation.
  • Suitable agrochemical formulations are water-soluble concentrates (SL, LS), redispersible concentrates (TLC), emulsifiable concentrates (EC), emulsions (EW, EO, ES, ME), suspensions (SC, OD, FS) or suspoemulsions (SE).
  • the composition is preferably in the form of an emulsifiable concentrate (EC), a suspension concentrate (SC), a water-soluble concentrate (SL), a solution for seed treatment (LS), or a redispersible concentrate (DC).
  • the agrochemical formulation is usually diluted before use to produce the so-called tank mix.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or its derivatives, methanol, Ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water into consideration. Preferably, water is used. It is also possible to add the polysulfoxide polyester (a) first to the tank mix.
  • the composition according to the invention is in the form of a tank mix.
  • the diluted composition is usually applied by spraying or atomizing.
  • Oils of various types, wetting agents, adjuvants, herbicides, bactericides, fungicides can be added to the tank mix immediately before use (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.
  • the pesticide concentration in the tank mix can be varied in larger areas. In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.
  • the application rates in the application in crop protection, depending on the nature of the desired effect between 0.01 and 2.0 kg of active ingredient per ha.
  • the use of the agrochemical formulations is possible for controlling phytopathogenic fungi and / or undesired plant growth and / or unwanted insect or mite infestation and / or for regulating the growth of plants, wherein the composition of the respective pests, their habitat or the plants to be protected from the respective pest, the soil and / or undesirable plants and / or the crops and / or their habitat. Furthermore, the use of the agrochemical formulations is possible for controlling unwanted insect or mite infestation on plants and / or for controlling phytopathogenic fungi and / or for controlling undesired plant growth, treating seeds of crop plants with the composition.
  • the preparation of the hyperbranched Polysulfoxidpolyesters invention is very simple and industrially possible; that a high concentration of active substance can be brought into solution with the aid of the hyperbranched polysulfoxide polyester (a) according to the invention linked to at least one polyalkylene oxide group and this amphiphilic hyperbranched polysulfoxide polyester itself is water-soluble or water-dispersible.
  • a further advantage of the invention is that the hyperbranched polysulfoxide polyesters (a) according to the invention which are linked to polyalkylene oxide groups are particularly stable to hydrolysis, the use of stable linker molecules which form urethane bonds, for example, being advantageous.
  • the abovementioned hyperbranched polysulfoxide polyesters (a) according to the invention can be used particularly well for the preparation of storage-stable agroformulations.
  • Further advantages are that the bioavailability of the active ingredients is increased, that the systemic effect of the agrochemical active ingredients is increased by foliar uptake, that even sparingly soluble agrochemical active substances can now be formulated dissolved, for example as SL (water-soluble concentrate) or LS (solution for seed treatment) in that the distribution of agrochemical active ingredients in the spray solution is improved and that the reusable packaging of the active substances and the application equipment (eg the pesticide sprayers) can be better cleaned with water.
  • SL water-soluble concentrate
  • LS solution for seed treatment
  • the hyperbranched polymers were analyzed by gel permeation chromatography with a refractometer as detector. THF was used as the mobile phase and polymethyl methacrylate (PMMA) was used as the standard for determining the molecular weight.
  • the acid number was determined in each case according to DIN 53402. The OH number (mg KOH / g) was determined on the basis of DIN 53240, Part 2.
  • Synthesis Example 1 Hyperbranched polysulfoxide Polvester polymer A.1 by reaction of thiodiethylene glycol sulfoxide
  • Mn 500 g / mol
  • Mn 500 g / mol
  • Mn 500 g / mol
  • Mn 500 g / mol
  • Step 2 Dissolve 32.5 g of the polymer A.6 in 97 g of tetrahydrofuran, then add 70.0 g of the product of Step 1 and another 0.2 g of zinc neodecanoate and raise the temperature to 80 ° C. After stirring for 42 hours, the remaining isocyanate groups (residual isocyanate content 0.12%) were destroyed with 0.6 g of diethanolamine, the solvent was removed at 80 ° C. under reduced pressure and then cooled.
  • Mn 500 g / mol
  • Stage 2 27.7 g of the polymer A.8 were dissolved in 83 g of acetone, then 89.2 g of the product from stage 1 and a further 0.2 g of zinc neodecanoate were added and the temperature was raised to 80.degree. After stirring for 72 hours, the solvent was removed at 80 ° C under vacuum and then cooled.
  • Table 1 demonstrates that the functionalized polysulfoxide polyesters according to the invention are well suited for the solubilization of poorly soluble active substances.

Abstract

L'invention concerne des polyesters de polysulfoxydes hyper-ramifiés, ainsi que des procédés pour les préparer, leur utilisation pour solubiliser des substances actives difficilement solubles, et des compositions contenant les polyesters de polysulfoxydes hyper-ramifiés et une substance active difficilement soluble.
PCT/EP2012/067922 2011-09-20 2012-09-13 Polyesters de polysulfoxydes hyper-ramifiés destinés à la solubilisation de substances actives difficilement solubles WO2013041436A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892701A (zh) * 2020-08-11 2020-11-06 广州德恒致远科技有限公司 一种生物可降解共聚酯及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4303963A1 (fr) 1992-02-10 1993-08-12 Toa Gosei Chem Ind
WO2001049817A2 (fr) 2000-01-05 2001-07-12 Basf Aktiengesellschaft Preparations de microcapsules et produits detergents et produits nettoyants contenant des microcapsules
WO2007068632A1 (fr) 2005-12-16 2007-06-21 Basf Se Polymeres hautement fonctionnels, hautement ramifies et hyper-ramifies, et leur procede de fabrication
WO2007078549A2 (fr) 2005-12-16 2007-07-12 Ppg Industries Ohio, Inc. Polyurethanes, polyurethanes-urees, polyurethanes contenant du soufre et polyurethanes-urees contenant du soufre et procedes de preparation
WO2009047210A1 (fr) 2007-10-08 2009-04-16 Basf Se Utilisation de polyesters et/ou de polyesters amides hyperramifiés pour séparer des émulsions huile dans l'eau
WO2011073220A1 (fr) 2009-12-18 2011-06-23 Basf Se Polyesters hyperramifiés à noyau hydrophobe pour la solubilisation d'agents actifs peu solubles

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4303963A1 (fr) 1992-02-10 1993-08-12 Toa Gosei Chem Ind
WO2001049817A2 (fr) 2000-01-05 2001-07-12 Basf Aktiengesellschaft Preparations de microcapsules et produits detergents et produits nettoyants contenant des microcapsules
WO2007068632A1 (fr) 2005-12-16 2007-06-21 Basf Se Polymeres hautement fonctionnels, hautement ramifies et hyper-ramifies, et leur procede de fabrication
WO2007078549A2 (fr) 2005-12-16 2007-07-12 Ppg Industries Ohio, Inc. Polyurethanes, polyurethanes-urees, polyurethanes contenant du soufre et polyurethanes-urees contenant du soufre et procedes de preparation
WO2009047210A1 (fr) 2007-10-08 2009-04-16 Basf Se Utilisation de polyesters et/ou de polyesters amides hyperramifiés pour séparer des émulsions huile dans l'eau
WO2011073220A1 (fr) 2009-12-18 2011-06-23 Basf Se Polyesters hyperramifiés à noyau hydrophobe pour la solubilisation d'agents actifs peu solubles

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
"Die Methode ist im Analytiker Taschenbuch", vol. 4, 1984, pages: 433 - 442
"Pesticide Manual", 2006, THE BRITISH CROP PROTECTION COUNCIL
"Ullmann's Encyclopedia of Industrial Chemistry", 2002, WILEY-VCH, article "Flavors and Fragrances"
CHOW ET AL., J. AM. CHEM. SOC., vol. 126, 2004, pages 12907 - 12915
H. FREY ET AL., CHEM. EUR. J., vol. 6, no. 14, 2000, pages 2499
H. FREY ET AL.: "Degree of Branching", ACTA POLYM., vol. 48, 1997, pages 30
MELLACE ET AL., CHEM. MATER., vol. 17, 2005, pages 1812 - 1817
P. J. FLORY, J. AM. CHEM. SOC., vol. 74, 1952, pages 2718
PU ET AL., CHINESE CHEMICAL LETTERS, vol. 18, 2007, pages 758 - 761

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111892701A (zh) * 2020-08-11 2020-11-06 广州德恒致远科技有限公司 一种生物可降解共聚酯及其制备方法

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