WO2007125041A1

WO2007125041A1 - Hyperbranched polyesters with a low acid number and use thereof

Info

Publication number: WO2007125041A1
Application number: PCT/EP2007/053772
Authority: WO
Inventors: Jean-Francois Stumbe; Bernd Bruchmann; Harald Schäfer; Marta Martin-Portugues
Original assignee: Basf Se
Priority date: 2006-04-28
Filing date: 2007-04-18
Publication date: 2007-11-08

Abstract

The invention relates to hyperbranched polyesters with a low acid number in the region of 0.1 to 15 mg KOH/g, obtained (a1) by polycondensing at least one dicarboxylic acid or at least one derivative thereof with at least one at least trifunctional alcohol or, (a2) by polycondensing at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof with at least one diol or, (a3) by polycondensing at least one dicarboxylic acid or at least one derivative thereof with a mixture of at least one diol and at least trifunctional alcohol or, (a4) by polycondensing at least one diol with a mixture of at least one dicarboxylic acid or at least one derivative thereof and at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof and (b) by reacting with at least one mono-, di-, or polyol (b1), at least one epoxide (b2) or at least one carbodiimide (b3).

Description

Hyperbranched low acid polyesters and their use

description

The present invention relates to hyperbranched polyesters having an acid number in the range of 0.1 to 15 mg KOH / g

(a1) by polycondensation of at least one dicarboxylic acid or at least one derivative thereof with at least one at least trifunctional alcohol or

(a2) by polycondensation of at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof with at least one diol or

(a3) by polycondensation of at least one dicarboxylic acid or at least one derivative thereof with a mixture of at least one diol and at least one at least trifunctional alcohol or

(a4) by polycondensation of at least one diol with a mixture of at least one dicarboxylic acid or at least one derivative thereof and at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof

and (b) reaction with at least one mono-, di- or polyol (b1), at least one epoxide (b2) or at least one carbodiimide (b3).

Furthermore, the present invention relates to a process for the preparation of hyperbranched polyesters according to the invention. Finally, the present invention relates to the use of hyperbranched polyesters according to the invention.

Modified polyester-based dendrimers are known per se, see, for example, WO 96/19537, and are already used in some applications, such as impact modifiers. However, dendrimers are too expensive for general use, because the syntheses make high demands on yields of the construction reactions and purity of the intermediate and end products and require for large-scale use too expensive reagents. The preparation of hyperbranched high-functionality polyesters prepared by conventional esterification reactions usually requires rather drastic conditions, cf. WO 96/19537, for example high temperatures. This can lead to side reactions such as dehydration reactions, Decarboxylationen and as a result of side reactions to unwanted Verharzungen and discoloration. Hyperbranched polyurethanes have gained importance in recent years as an additive to printing inks, see, for example, WO 02/36695. Hyperbranched polyesters have found increased interest in recent years, for example as impact modifiers (impact modifiers) of polymers, see, for example, WO 03/54204 and WO 03/93343. In contrast to the symmetrical and molecularly structured so-called dendrimers (or dendritic polymers or dendritic polyesters), hyperbranched polymers and in particular hyperbranched polyesters are in many cases easy to synthesize. However, the impact modifier effect can be improved in some cases.

Highly branched and in particular dendritic polyesters are also known in modified form as a nanotransport system, see, for example, DE 10 2004 039 875. However, the systems disclosed in DE 10 2004 039 875 can still be improved. In particular, it can be observed that gel formation occurs when it is desired to store the disclosed nanotransport systems as a powder and then attempts to redisperse them in water.

It was therefore the object to provide polyesters which do not have the disadvantages known from the prior art.

Accordingly, the hyperbranched polyesters defined above were found.

Hyperbranched polyesters (a) and thus also the hyperbranched polyesters according to the invention having an acid number in the range from 0.1 to 15 mg KOH / g, which are also referred to below as hyperbranched polyesters according to the invention with low acid number or as hyperbranched polyesters according to the invention (c ) are molecularly and structurally nonuniform. They differ, for example, by their molecular non-uniformity of dendrimers and are produced with considerably less effort. An example of the molecular structure of a hyperbranched polymer based on an AB 2 molecule can be found, for example, in WO 04/20503 on page 2. For the structure (distribution of the branches, etc.) applies to the hyperbranched polyester (c) according to the invention, the A2 + B _x strategy are based (with x> 3), essentially analogous, see for example J.-F. Stumbe et al., Macromol. Rapid Commun. 2004, 25, 921.

In one embodiment of the present invention, hyperbranched polyester (c) according to the invention has a branching in from 20 to 80 mol%, preferably from 30 to 60 mol% of each AaB _x monomer unit. In one embodiment of the present invention, the polydispersity of hyperbranched polyester (c) according to the invention is from 1, 2 to 50, preferably 1, 4 to 40, more preferably 1, 5 to 30 and most preferably to 10.

In one embodiment of the present invention, hyperbranched polyesters (c) according to the invention are selected from hyperbranched polyesters having a molecular weight M _n in the range from 500 to 50,000 g / mol, preferably up to 3,000 g / mol, determinable, for example, by gel permeation chromatography.

In one embodiment of the present invention, hyperbranched polyesters (c) according to the invention are selected from those hyperbranched polyesters which have an OH number in the range from 100 to 700 mg KOH / g.

In one embodiment of the present invention, at least one diol used for the synthesis of polyester according to the invention or at least one at least trifunctional alcohol or at least one diester polycaboxylic acid used for its synthesis is cycloaliphatic, for example cyclohexane-1, 2-diol, cyclohexane-1, 4- diol, cyclohexane-1, 4-dimethanol (1, 4-dimethylolcyclohexane) each as a pure isomer or preferably as a mixture of isomers.

Hyper-branched polyesters (a) and hyperbranched polyesters (c) according to the invention are usually very soluble, i. You can clear-looking solutions with up to 50 wt .-%, in some cases even up to 80 wt .-%, hyperbranched polyester (a) or inventive hyperbranched polyester (c) in tetrahydrofuran (THF), n-butyl acetate , Ethanol and many other solvents without the naked eye detectable gel particles.

Hyperbranched polyesters (a) are carboxy group- and hydroxyl-terminated and preferably predominantly hydroxyl-terminated. Hyperbranched polyesters (c) according to the invention are essentially hydroxyl-terminated.

In one embodiment of the present invention, hyperbranched polyester (a) is a hyperbranched polyester having an acid number in the range from 1 to 100 mg KOH / g, preferably from 20 to 100 mg KOH / g, determinable, for example, according to DIN 53402.

Hyperbranched polyesters (c) according to the invention are hyperbranched polyesters having an acid number in the range from 0.1 to 15 mg KOH / g, preferably from 1 to 10 mg KOH / g, determinable, for example, according to DIN 53402.

Examples of dicarboxylic acids which can be reacted according to variant (a1) include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, Suberic acid, azelaic acid, sebacic acid, undecane-α, ω-dicarboxylic acid, dodecane-α, ω-dicarboxylic acid, cis- and trans-cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans -cyclohexane-1,4-dicarboxylic acid, cis-cyclohexene-3,4-dicarboxylic acid, norbornenedicarboxylic acid, norbornanedicarboxylic acid, cis- and trans-cyclopentane-1,2-dicarboxylic acid and also cis- and trans-cyclopentane-1 , 3-dicarboxylic acid,

wherein the above-mentioned dicarboxylic acids may be substituted with at least one radical selected from

C 1 -C 10 -alkyl groups, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethyl-hexyl, n-nonyl or n-decyl,

C 3 -C 12 -cycloalkyl groups, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl;

Alkylene groups such as methylene or ethylidene or

C 6 -C 14 aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl Phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

Examples of substituted dicarboxylic acids which may be mentioned are: 2-methyl malonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-E-methylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid.

Furthermore, the dicarboxylic acids which can be reacted according to variant (a1) include ethylenically unsaturated acids, such as, for example, maleic acid and fumaric acid, and aromatic dicarboxylic acids, for example phthalic acid, isophthalic acid or terephthalic acid.

Furthermore, mixtures of two or more of the aforementioned dicarboxylic acids can be used.

Succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, cis- and trans -cyclohexane-1,2-dicarboxylic acid, cis- and trans-cyclohexane-1,3-dicarboxylic acid, cis- and trans-cyclohexane are particularly preferably used 1, 4-dicarboxylic acid, cis-cyclohexene-3,4-dicarboxylic acid, norbornenedicarboxylic acid, norbornanedicarboxylic acid, bonsäure or their mono- or dimethyl esters or anhydrides. Most preferably, adipic acid is used. If it is desired to use hyperbranched polyesters (c) according to the invention as or in coating compositions, very particular preference is given to using at least one of the abovementioned cyclohexanedicarboxylic acids or one of their derivatives.

The aforementioned dicarboxylic acids can be used either as such or in the form of derivatives.

Derivatives are preferably understood to mean the respective anhydrides in monomeric or else polymeric form, mono- or dialkyl esters, preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols such as, for example, n-propanol, isopropanol, n Butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol-derived mono- and dialkyl esters,

Acid halides, in particular acid chlorides, furthermore mono- and divinyl esters and mixed esters, preferably methyl ethyl ester.

In the context of the present invention, it is also possible to use a mixture of a dicarboxylic acid and at least one of its derivatives. Likewise, it is within the scope of the present invention possible to use a mixture of several different derivatives of one or more dicarboxylic acids.

As at least trifunctional alcohols, for example, can be implemented: glycerol, butane-1, 2,4-triol, n-pentane-1, 2,5-triol, n-pentane-1, 3,5-triol, n-hexane-1 , 2,6-triol, n-hexane-1, 2,5-triol, n-hexane-1, 3,6-triol, 1,1,1-trimethylolbutane (trimethylolbutane), 1, 1, 1 Trimethylolpropane (trimethylolpropane) or di-trimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; Sugar alcohols such as mesoerythritol, threoti, sorbitol, mannitol or mixtures of the above at least trifunctional alcohols. Preference is given to choosing at least trifunctional alcohols from glycerol, 1,1,1-trimethylolpropane, 1,1,1-trimethylolethane and pentaerythritol.

In one embodiment of the present invention, at least trifunctional alcohols are monosubstituted or polysubstituted, for example 1 to 100 times alcoxylated, preferably 3 to 100 times ethoxylated glycerol, butane-1, 2,4-triol, n-pentane-1, 2,5-triol, n-pentane-1, 3,5-triol, n-hexane-1, 2,6-triol, n-hexane-1, 2,5-triol, n- Hexane-1, 3,6-triol, 1,1,1-trimethylolbutane, 1,1,1-trimethylolpropane, di-trimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol, in particular with molecular weights M _n in the range from 300 to 5,000 g / mol , According to variant (a2) convertible tricarboxylic acids or polycarboxylic acids are, for example, 1, 2,4-benzenetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1, 2,4,5-benzenetetracarboxylic acid and mellitic acid, furthermore 1, 2,3,4- butane tetracarboxylic acid.

Tricarboxylic acids or polycarboxylic acids can be used in the reaction according to the invention either as such or in the form of derivatives.

Derivatives are preferably understood to mean the respective anhydrides in monomeric or else polymeric form, mono-, di- or trialkyl esters, preferably mono-, di- or trimethyl esters or the corresponding mono-, di- or triethyl esters, but also those of higher alcohols such as For example, n-propanol, iso-propanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol derived mono- di- and triesters, acid halides, especially acid chlorides, - mono-, di- or Trivinylester and mixed methyl ethyl esters.

In the context of the present invention, it is also possible to use a mixture of a triester of polycarboxylic acid and at least one of its derivatives. Likewise, it is within the scope of the present invention possible to use a mixture of several different derivatives of one or more tri- or polycarboxylic acids.

Examples of diols for variant (a2) of the present invention are ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1 , 4-diol, butane-2,3-diol, pentane-1, 2-diol, pentane-1, 3-diol, pentane-1, 4-diol, pentane-1, 5-diol, pentane-2,3 -diol, pentane-2,4-diol, neopentyl glycol (2,2-dimethylpropane-1,3-diol), hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, Hexane-1, 5-diol, hexane-1, 6-diol, hexane-2,5-diol, heptane-1,2-diol 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 1 , 9-nonanediol, 1, 10-decanediol, 1, 2-decanediol, 1, 12-dodecanediol, 1, 2-dodecanediol, 1, 5-hexadiene-3,4-diol, cyclopentanediols, cyclohexanediols, cyclohexanedimethanoles, in particular 1, 4-cyclohexanedimethanol (1,4-dimethylolcyclohexane), inositol and derivatives, (2) -methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 2 , 5-dimethyl-2,5-hexanediol, 2,2,4-trimethyl-1, 3-pentanediol, pinacol, diethylene glycol, triethylene glycol, dipropylene glycol, triprop Ylenglykol, polyethylene glycols HO (CH2CH2θ) _n -H or polypropylene glycols HO (CH [CHa] CHaO) _n -H or mixtures of two or more representatives of the above compounds, wherein n is an integer and n> 4. Here, a or both hydroxyl groups in the abovementioned diols are also substituted by SH groups. Preference is given to ethylene glycol, propane-1,2-diol and diethylene glycol, triethylene glycol, dipropylene glycol and tripropylene glycol.

In one embodiment of the present invention, in step (a1) or (a2) or (a3) or (a4) OH component and carboxylic acid component are added in a sol A ratio that the molar ratio of OH groups and COOH groups, free or derivatized, in the range of 2: 1 to 1: 2, preferably 1: 1, 8 to 1, 8: 1.

The according to variant (a1) reacted at least trifunctional alcohols may each have hydroxyl groups of the same reactivity.

However, the at least trifunctional alcohols reacted according to variant (a1) can also have hydroxyl groups with at least two chemically different reactivities.

For carrying out variant (a3) suitable dicarboxylic acids or their derivatives are mentioned above. Diols which are suitable for carrying out variant (a3) and at least trifunctional alcohols are likewise mentioned above.

Diols suitable for carrying out variant (a4) are mentioned above. Dicarboxylic acids and their derivatives suitable for carrying out variant (a4) and also tricarboxylic acids or higher polycarboxylic acids and their derivatives are likewise mentioned above.

In one embodiment of the present invention, to carry out variant (a3), diol and at least trifunctional alcohol are employed in a molar ratio in the range from 5: 1 to 1: 100, preferably 4: 1 to 1: 10, and more preferably 3: 1 to 1 to 10.

In one embodiment of the present invention, to carry out variant (a4), dicarboxylic acid or derivative of dicarboxylic acid and tricarboxylic acid or higher polycarboxylic acid or derivative of tricarboxylic acid or higher polycarboxylic acid is used in a molar ratio in the range from 5: 1 to 1: 100, preferably 4 to 1 to 1 to 10, and more preferably 3 to 1 to 1 to 10.

The different reactivity of the functional groups, such as, for example, hydroxyl groups, can be based either on chemical (eg primary / secondary / tertiary OH group) or on steric causes. Preference is given here also to acid groups reactive compounds whose OH groups are initially the same reactive, in which, however, by reacting with at least one acid group, a drop in reactivity due to steric or electronic influences in the remaining OH groups can be induced. This is the case, for example, when using 1,1,1-trimethylolpropane or pentaerythritol.

For example, the triol may be a triol having primary and secondary hydroxyl groups, preferred example being glycerin. When carrying out the reaction according to variant (a1), preference is given to working in the absence of diols.

In a specific embodiment of the present invention, in the preparation, preferably towards the end of the production of hyperbranched polyester (a), one or more stoppers can be added selected from monocarboxylic acids such as, for example, fatty acids or their anhydrides or methyl or ethyl esters, monoalcohols , Carboxylic acids having one (or more) further functional group or corresponding derivatives.

Examples of monofunctional monocarboxylic acids are acetic acid, propionic acid, trimethylacetic acid, heptanoic acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, montanic acid, isostearic acid, stearic acid, isononanoic acid and 2-ethylhexanoic acid.

In one embodiment of the present invention, after step (a), the hyperbranched polyester is reacted with one or more lactones, e.g. with ε-caprolactone, implemented. This reaction can be e.g. perform under Lewis acid catalysis at temperatures ranging from 170 to 180 ° C.

After the preparation of hyperbranched polyester (a), it is possible to purify hyperbranched polyester (a). However, preference is given to purifying and reacting with at least one mono-, di- or polyol (b1), at least one epoxide (b2) or at least one carbodiimide (b3), particularly preferably in the sense of a one-pot reaction.

Suitable monools (b1), also referred to below as monoalcohols (b1), are in particular fatty alcohols, saturated or monounsaturated or polyunsaturated, in particular C 10 -C 30 fatty alcohols, for example glycerol monolaurate, glycerol monostearate, ethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, benzyl alcohol, n-decanol , Cetyl alcohol (n-dodecanol), n-tetradecanol, n-hexadecanol, n-octadecanol and n-eicosanol.

Suitable diols (b1) are in particular the abovementioned diols. Suitable triols (b1) as examples of polyols (b1) are in particular the abovementioned triols. Very particularly suitable triols are glycerol and 1,1,1-trimethylolpropane.

In one embodiment of the present invention, diol (b1) or polyol (b1) is identical to the diol or trifunctional alcohol (triol) already used for the synthesis of hyperbranched polyester (a). In another embodiment of the present invention, diol (b1) or polyol (b1) is different from the diol or trifunctional alcohol (triol) already used for the synthesis of hyperbranched polyester (a).

In another embodiment of the present invention, in step (b) hyperbranched polyester (a) is reacted with at least one epoxide (b2). Preferably, these are monoepoxides, e.g. epoxidized (cyclo) olefins, glycidyl esters (e.g., glycidyl (meth) acrylate) of saturated or unsaturated carboxylic acids or glycidyl ethers, aliphatic or aromatic alcohols. Examples of monofunctional epoxides are ethylene oxide, propylene oxide, 1, 2-butene oxide, cis / trans-2,3-butene oxide, isobutylene oxide, 1, 2-pentenoxide, 2,3-pentenoxide, cyclopentene oxide, cyclohexene oxide, epichlorohydrin, epoxidized fatty acid derivatives and mixtures thereof ,

In one embodiment of the present invention, in step (b) the hyperbranched polyester (a) is reacted with a preferably monofunctionalized carboxylic acid-reactive compound, such as reacted with at least one carbodiimide (b3), for example dicyclohexylcarbodiimide and di-isopropylcarbo diimide. Preference is given to carbodiimides, which may be monomeric or polymeric.

For the purposes of the present invention, polymeric carbodiimides are understood as meaning those compounds which carry in the range from 2 to 50, preferably up to 20, -N = C = N groups per mole. For the purposes of the present invention, polymeric carbodiimides advantageously have no free isocyanate groups.

Polymeric carbodiimides are known per se and can be prepared by methods known per se, for example by condensation or polycondensation of diisocyanate in the presence of a catalyst, for example trialkylphosphoxide, acyclic or preferably cyclic, also as phospholene oxide, triarylphosphine oxide, alkali metal alkoxide For example, sodium ethoxide, alkali metal carbonate, for example sodium carbonate or potassium carbonate, or tertiary amine, for example triethylamine. Particularly suitable catalysts are phospholene oxides and phospholene oxides, e.g. 1-phenyl-2-methylphospholenoxide-2, 1-phenyl-2-methylphospholene oxide-3, 1-methylphospholenoxide-2 and 1-methylphospholenoxide-3. See, for example, US 2,853,473. In the condensation or polycondensation to polymeric Carbodiimid carbon dioxide is split off. Following the condensation reaction is carried out with a compound which is capable of reacting with isocyanate, for example with alcohol, preferably ethanol, methanol, or with polyethylene glycol.

Examples of polymeric carbodiimides are obtainable by condensation or polycondensation of at least one aromatic diisocyanate, for example 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate or 1,7-naphthylene diisocyanate or at least one aliphatic or cycloaliphatic diisocyanate, such as Isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-hexahydrotoluylene diisocyanate, 2,6-hexahydrotoluylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. Following the condensation or polycondensation is reacted with a compound which is capable of reacting with isocyanate, for example with alcohol, preferably ethanol, methanol, or with polyethylene glycol.

Preferred polymeric carbodiimides are copolycarbodiimides obtainable by condensation or polycondensation of at least one aromatic diisocyanate, for example 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or 1,7-naphthylene diisocyanate, with at least one aliphatic or cycloaliphatic diisocyanate such as for example, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-hexahydrotoluylene diisocyanate, 2,6-hexahydrotoluylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. Following the condensation or polycondensation is reacted with a compound which is capable of reacting with isocyanate, for example with alcohol, preferably ethanol, methanol, or with polyethylene glycol.

Carbodiimide (b3) is very particularly preferably a polymeric carbodiimide obtainable by polycondensation of m-TMXDI or p-TMXDI

m-TMXDI ^{P "TMXDI}

or mixtures of m-TMXDI and p-TMXDI having from 2 to 20, preferably to 15 and more preferably to 5 -N = C = N groups per mole, and then reacting with alcohol.

In one embodiment of the present invention, in step (b) about 0.7 to 3 mol, preferably 0.8 to 2 mol monoalcohol (b1), diol (b1), polyol (b1), epoxide (b2) or carbodiimide (b3), based on carboxylic acid groups in hyperbranched polyester (a).

In one embodiment of the present invention, step (b) is repeated at least once. Hyperbranched polyesters (c) according to the invention are particularly suitable, for example, as impact modifiers for thermoplastic polymers such as, for example, polyesters, in particular polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene, polypropylene and copolymers of ethylene and propylene with one another or with one or more comonomers such as, for example, Olefins or (meth) acrylic acid, homo- and copolymers of styrene, for example polystyrene, ABS (terpolymers of acrylonitrile, 1, 3-butadiene and styrene), SAN, polyoxymethylene (POM), polyamides and polymethyl methacrylate. Furthermore, hyperbranched polyesters (c) according to the invention are suitable as or for the preparation of binders for coating compositions.

Further objects of the present invention are therefore impact modifiers for thermoplastic polymers containing or consisting of one or more hyperbranched polyesters.

Further objects of the present invention are coating compositions comprising one or more hyperbranched polyesters (c) according to the invention, for example as binders.

Hyperbranched polyesters (c) according to the invention can be used as binder component, for example in coating compositions, optionally together with other hydroxyl- or amino-containing binders, for example with hydroxy (meth) acrylates, hydroxystyryl (meth) acrylates, linear or branched polyesters, polyethers, polycarbonates , Polyurethanes, melamine resins or urea-formaldehyde resins or hybrids of the binders containing hydroxyl or amino groups, together with carboxy- and / or hydroxy-functional compounds, for example with isocyanates, capped isocyanates, epoxides, carbonates and / or aminoplasts, preferably isocyanates, epoxides or aminoplasts, more preferably with isocyanates or epoxides, and most preferably with isocyanates.

Examples of isocyanates are aliphatic, aromatic and cycloaliphatic di- and polyisocyanates having an average NCO functionality of at least 1, 8, preferably 1, 8 to 5 and particularly preferably 2 to 4, and also their isocyanurates, oxadiazinetrions, iminooxadiazinediones, ureas, biurets, Amides, urethanes, allophanates, carbodiimides, uretonimines and uretdiones.

The diisocyanates are preferably isocyanates having 4 to 20 C atoms. Examples of customary diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate, trimethylhexane diisocyanate or Tetramethylhexane diisocyanate, cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-iso-cyanato-3,3,5- trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-diisocyanato-1-methylcyclohexane and also aromatic diisocyanates such as 2, 4- or 2,6-tolylene diisocyanate and their mixtures of isomers, m- or p-xylylene diisocyanate, 2,4'- or 4,4'-diisocyanatodiphenylmethane and their isomer mixtures, 1,3- or 1,4-phenylene diisocyanate, 1 - Chloro-2,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate cyanate, tetramethylxylylene diisocyanate, 1,4-diisocyanatobenzene or diphenyl ether-4,4'-diisocyanate.

It is also possible to use mixtures of the abovementioned diisocyanates.

Suitable polyisocyanates are polyisocyanates containing isocyanurate groups, uretdione diisocyanates, biisocyanate-containing polyisocyanates, polyisocyanates containing urethane or allophanate groups, oxadiazinetrione groups or iminooxadiazinedione-containing polyisocyanates, carbodiimide- or uretonimine-modified polyisocyanates of straight-chain or branched C 4 -C 20 -alkylene diisocyanates , Cycloaliphatic diisocyanates having a total of 6 to 20 carbon atoms or aromatic diisocyanates having a total of 8 to 20 carbon atoms or mixtures thereof.

The usable di- and polyisocyanates preferably have a content of isocyanate groups (calculated as NCO, molecular weight = 42) of 1 to 60 wt .-% based on the respective di- and polyisocyanate (mixture), preferably 2 to 60 wt. %, and more preferably 10 to 55% by weight.

Preferred are aliphatic or cycloaliphatic di- and polyisocyanates, e.g. the abovementioned aliphatic or cycloaliphatic diisocyanates, or mixtures thereof.

Particularly preferred are hexamethylene diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and di (isocyanatocyclohexyl) methane, very particular preference is given to isophorone diisocyanate and hexamethylene diisocyanate, particularly preferably hexamethylene diisocyanate.

Further preferred

1) isocyanurate-containing polyisocyanates of aromatic, aliphatic and / or cycloaliphatic diisocyanates. Particular preference is given here to the corresponding aliphatic and / or cycloaliphatic isocyanuric to isocyanurates and in particular those based on hexamethylene diisocyanate and isophorone diisocyanate. The isocyanurates present are, in particular, trisisocyanatoalkyl or trisisocyanatocycloalkyl isocyanurates, which are cyclic trimers of the diisocyanates, or mixtures with their higher homologs having more than one isocyanurate ring. The isocyanato-isocyanurates generally have an NCO content of 10 to 30 wt .-%, in particular 15 to 25 wt .-% and an average NCO functionality of 2.6 to 4.5.

2) uretdione diisocyanates having aromatic, aliphatic and / or cycloaliphatic bound isocyanate groups, preferably aliphatically and / or cycloaliphatically bonded and in particular those derived from hexamethylene diisocyanate or isophorone diisocyanate. Uretdione diisocyanates are cyclic dimerization products of diisocyanates.

The uretdione diisocyanates can be used in coating compositions according to the invention as in addition to inventive hyperbranched polyester (c) only further component or in admixture with other polyisocyanates, especially those mentioned under 1).

3) biuret polyisocyanates having aromatic, cycloaliphatic or aliphatic bound, preferably cycloaliphatic or aliphatic bound isocyanate groups, in particular tris (6-isocyanatohexyl) biuret or mixtures thereof with its higher homologues. These biuret-containing polyisocyanates generally have an NCO content of 18 to 23 wt .-% and an average NCO functionality of 2.8 to 4.5.

4) containing urethane and / or allophanate polyisocyanates having aromatically, aliphatically or cycloaliphatically bonded, preferably aliphatically or cycloaliphatically bound isocyanate groups, as for example by

Reaction of excess amounts of hexamethylene diisocyanate or of isophorone diisocyanate with monohydric or polyhydric alcohols, such as, for example, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol , n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol), 2-ethylhexanol, stearyl alcohol, cetyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 1,3-propanediol monomethyl ether, cyclopentanol, Cyclohexanol, cyclooctanol, cyclododecanol or polyhydric alcohols, as listed above as diols for variant (a2) on page 6, or mixtures thereof can be obtained. The polyisocyanates containing urethane and / or allophanate groups listed above generally have an NCO content of 12 to 20% by weight and an average NCO functionality of 2.5 to 4.5. 5) oxadiazinetrione-containing polyisocyanates, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such oxadiazinetrione-containing polyisocyanates can be prepared from diisocyanate and carbon dioxide.

6) polyisocyanates containing iminooxadiazinedione groups, preferably derived from hexamethylene diisocyanate or isophorone diisocyanate. Such polyisocyanates containing iminooxadiazinedione groups can be prepared from diisocyanates by means of special catalysts.

7) carbodiimide and / or uretonimine-modified polyisocyanates.

Polyisocyanates 1) to 7) can be used in a mixture, if appropriate also in a mixture with diisocyanates.

The isocyanate groups of the di- or polyisocyanates may also be present in capped form. Suitable capping agents for NCO groups are e.g. Oximes, phenols, imidazoles, pyrazoles, pyrazolinones, triazoles, diketopiperazines, caprolactam, malonic acid esters or compounds as mentioned in the publications of Z.W. Wicks, Prog. Org. Coat. 1975, 3, 73 and Prog. Org. Coat 1981, 9, 3, by DA Wicks et al. Prog. Org. Coat. 1999, 36, 148 and Prog. Org. Coat. 2001, 41, 1 and in Houben-Weyl, Methods of Organic Chemistry, Vol. XIV / 2, 61 ff. Georg Thieme Verlag, Stuttgart 1963.

By blocking or blocking agents are meant compounds which convert isocyanate groups into blocked (capped or protected) isocyanate groups, which then do not exhibit the usual reactions of a free isocyanate group below the so-called deblocking temperature. Such compounds having blocked isocyanate groups are commonly used in dual-cure or powder coatings which are finally cured by isocyanate group cure.

The reaction of inventive hyperbranched polyester (c) with isocyanate groups used according to the invention as a binder can be accelerated by catalysts. Examples of catalysts are in particular tin compounds such as tin (II) n-octanoate, tin (II) 2-ethylhexanoate, tin (II) laurate, dibutyltin oxide, diphenyltin oxide, di-n-butyltin dichloride, di-n-butyltin diacetate , Di-n-butyltin dilaurate, di-n-butyltin dimaleate or di-n-octyltin diacetate.

Particularly preferred representatives of acidic organometallic catalysts are di-n-butyltin oxide, diphenyltin oxide and di-n-butyltin dilaurate. Furthermore, zinc compounds; Compounds of the metals of IV., V. or VI. Subgroup of the periodic table (in particular compounds of zirconium, vanadium, molybdenum or tungsten), aluminum, or bismuth compounds are used as catalysts.

Epoxy compounds are those having at least one, preferably having at least two, particularly preferably two to ten epoxide groups in the molecule.

Suitable examples include epoxidized olefins, glycidyl esters (eg glycidyl (meth) acrylate) of saturated or unsaturated carboxylic acids or glycidyl ethers of aliphatic or aromatic polyols. Such products are commercially available in large numbers. Polyglycidyl compounds of the bisphenol A, F or B type and glycidyl ethers of polyhydric alcohols, for example of butanediol, of 1,6-hexanediol, of glycerol and of pentaerythritol, are particularly preferred. Gene are examples of such polyepoxide compounds of Epikote ^® 812 (epoxide value: about 0.67 mol / 100g) and Epikote ^® 828 (epoxide value: about 0.53 mol / 100g), Epikote ^® 1001, Epikote ^® 1007, and Epikote ^® 162 (epoxide value: about 0.61 mol / 100 g) from resolution, Rutapox® 0162 (epoxide value: about 0.58 mol / 100g), Rütapox ^® 0164 (epoxide value: about 0.53 mol / 100g) and Rüta- pox ^® 0165 (epoxide value: about 0.48 mol / 100g) Bakelite AG, Araldite ^® DY 0397 (epoxide value: about 0.83 mol / 100g) from Vantico AG.

Carbonate compounds are those with at least one, preferably with at least two, preferably two or three carbonate groups in the molecule, which preferably contain terminal C 1 -C 20 -alkyl carbonate groups, particularly preferably terminal C 1 -C 4 -alkyl carbonate groups, very particularly preferably terminal methyl carbonate, ethyl carbonate or n -Butylcarbonat.

Also suitable are compounds having active methylol or alkylalkoxy groups, in particular methylalkoxy groups, such as, for example, etherified reaction products of formaldehyde with amines, such as melamine, urea, etc., phenol / formaldehyde adducts, siloxane or silane groups and anhydrides, as described, for example, in US Pat. in US 5,770,650 are described.

Among the technically widespread and known, preferred aminoplasts are particularly preferred urea resins and melamine resins, such. Urea-formaldehyde resins, melamine-formaldehyde resins, melamine-phenol-formaldehyde resins or melamine-urea-formaldehyde resins, usable.

Suitable urea resins are those which are obtainable by reacting ureas with aldehydes and can be modified if appropriate.

As ureas, urea, N-substituted or N, N'-disubstituted ureas are suitable, such as N-methyl urea, N-phenylurea, N, N'-dimethylurea, hexa methylene diurea, N, N'-diphenylurea, 1,2-ethylene diurea, 1,3-propylene diurea, diethylene triurea, dipropylene triurea, 2-hydroxypropylene diurea, 2-imidazolidinone (ethylene urea), 2-oxohexahydropyrimidine (propylene urea) or 2-oxo-5 -Hydroxyhexahydropyrimidine (5-hydroxypropyleneurea).

Urea resins may optionally be partially or fully modified, e.g. by reaction with mono- od. Polyfunctional alcohols, ammonia or amines (cationically modified urea resins) or with (hydrogen) sulfites (anionic modified urea resins), particularly suitable are the alcohol-modified urea resins.

Possible alcohols for the modification are C 1 -C 6 -alcohols, preferably C 1 -C 4 -alkyl alcohol and in particular methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol and sec-butanol.

Suitable melamine resins are those which are obtainable by reacting melamine with aldehydes and which may optionally be partially or completely modified.

Particularly suitable aldehydes are formaldehyde, acetaldehyde, isobutyraldehyde and glyoxal.

Melamine-formaldehyde resins are reaction products of the reaction of melamine with aldehydes, e.g. the o.g. Aldehydes, especially formaldehyde. Optionally, the resulting methylol groups are modified by etherification with the abovementioned monohydric or polyhydric alcohols. Furthermore, the melamine-formaldehyde resins can also be modified as described above by reaction with amines, aminocarboxylic acids or sulfites.

By the action of formaldehyde on mixtures of melamine and urea or on mixtures of melamine and phenol, melamine-urea-formaldehyde resins or melamine-phenol-formaldehyde resins which can also be used according to the invention are also produced according to the invention.

The preparation of the above-mentioned aminoplasts is carried out according to known methods.

Particularly cited examples are melamine-formaldehyde resins, including monomeric or polymeric melamine resins and partially or fully alkylated methylamine resins, urea resins, for example methylolureas such as formaldehyde-urea resins, alkoxyureas such as butylated formaldehyde-urea resins, but also N- Methylol acrylamide emulsions, isobutoxy methyl acrylamide emulsions, polyanhydrides, such as for example, polysuccinic anhydride, and siloxanes or silanes, for example dimethyldimethoxysilanes.

Particularly preferred are aminoplast resins such as melamine-formaldehyde resins or formaldehyde-urea resins.

The paints in which the polyesters according to the invention can be used may be conventional basecoats, water-based paints, essentially solvent-free and water-free liquid basecoats (100% systems), essentially solvent-free and water-free solid basecoats (powder coatings and pigmented powder coatings ) or substantially solvent-free, possibly pigmented powder coating dispersions (powder slurry basecoats) act. They can be thermal, radiation or DuaICure-curable, and self-crosslinking or externally crosslinking.

With the coating composition according to the invention, it is possible to coat any surfaces, for example those made of paper, cardboard, stone, concrete, or preferably of metal, plastic, wood, another lacquer layer, or another not yet cured lacquer layer.

Coating compositions according to the invention and in particular paints can be used, for example, in automotive applications such as OEM and refinish, for large and special vehicles, aircraft, industrial, wood or architectural coatings, leather, textiles or building materials. Paints are, for example, clearcoats, basecoats, topcoats, fillers or primers. Lacquers of the invention may be solvent or water based.

Coating compositions of the invention may contain conventional solvents and auxiliaries and additives.

These include, for example, catalysts, flow control agents, defoamers, wetting agents, pigments, fillers, silicone oils, plasticizers, viscosity modifiers, matting agents, antioxidants and / or peroxide decomposers, light stabilizers, such as e.g. UV absorbers and HALS derivatives, etc.

Hyperbranched polyesters (c) according to the invention lead in paints to excellent mechanical properties and resistances.

Further objects of the present invention are printing inks, inks, pigment and tinting pastes, masterbatches, ballpoint pen pastes, polishes, adhesives, sealants and insulating materials containing one or more polyesters according to the invention (c).

A further subject matter of the present invention is a process for the preparation of coating compositions according to the invention using at least one a hyperbranched polyester (c) according to the invention. For carrying out the process according to the invention, it is possible for example to proceed by mixing one or more hyperbranched polyesters (c) according to the invention with at least one other of the abovementioned components. With coating composition according to the invention, it is possible to coat any surface, for example of metal, plastic, stone, concrete, wood. A further subject of the present invention are surfaces coated according to the invention with coating material, in particular with lacquer according to the invention. Surfaces coated in accordance with the invention are characterized by good hardness combined with high elasticity of the coating. Furthermore, surfaces coated according to the invention show good solvent resistance, for example against acetone, and good acid resistance.

A special subject matter of the present invention is the use of polyester (c) according to the invention for the solubilization of hydrophobic active substances, in particular selected from fluorescence agents, pharmaceutically active substances and crop protection agents.

By solubilization is meant that in an aqueous medium hydrophobic, that is insoluble or poorly soluble as such, drug can be distributed molecularly dispersed. This can be done, for example, by complexing or coating the relevant hydrophobic active ingredient.

For the purposes of the present invention, aqueous medium is understood as meaning, for example, water, solvent mixtures of water and at least one organic solvent such as, for example, methanol, ethanol, ethylene glycol, propylene glycol, polyethylene glycol, isopropanol, 1,4-dioxane, N, N-. Dimethylformamide, aqueous sugar solutions such as aqueous glucose solution, aqueous salt solutions such as aqueous saline or aqueous potassium chloride solutions, aqueous buffer solutions such as phosphate buffer, or especially plant cages or human or animal water-containing body fluids such as blood, urine and spleen fluid.

Preferably, aqueous medium is understood as meaning pure (distilled) water, aqueous saline solution, in particular physiological saline solution, or mixtures of solvents of water with at least one of the abovementioned organic solvents, the proportion of organic solvent not being 10% by weight of the relevant aqueous medium exceeds.

Active substances in the context of the present invention may also be referred to as effect substances and are substances which, for example, have an activity as crop protection agents, for example as insecticides, herbicides or fungicides, or as fluorescent agents or pharmaceutical agents, for example as Cardiovascular or cytostatic. Pigments are not active substances in the sense of the present invention.

Examples of suitable cardiovascular agents are those of the formula I.

The variables or residues are defined as follows:

Y is NO ₂ , CN or COOR ¹ , where

R ^{1 is} C ¹ -C ⁴ -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, unsubstituted or monosubstituted or polysubstituted with C ¹ -C ³ -alkyl Alkoxy, for example methoxy, ethoxy, n-propoxy, iso -propoxy; Examples of substituted radicals R ¹ are, for example, methoxymethyl, ethoxymethyl, 2-methoxyethyl.

W is CO-NH-C ₃ -C ₇ -cycloalkyl or COOR ² , where

R ^{2 is} selected from C 1 -C 10 -alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec Pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl ; particularly preferably C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl-unsubstituted or mono- or polysubstituted with C 1 -C 3 -alkyl Alkoxy, trifluoromethyl, N-methyl-N-benzylamino or CH 2 -C 6 H 5. Examples of substituted radicals R ² are, for example, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2,2,2-trifluoroethyl.

R ^{3 is} selected from CN, ω-hydroxyalkyl, preferably ω-hydroxy-C 1 -C ₄ -alkyl, in particular hydroxymethyl and 2-hydroxyethyl, or C 1 -C ₄ -alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl and tert-butyl.

X ^{1 is the} same or different and selected from NO 2, halogen, in particular fluorine, chlorine or bromine, C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert. Butyl, C 1 -C ₄ -alkoxy, for example methoxy, Ethoxy, n-propoxy, iso -propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy; Benzoyl, acetyl, O-CO-CH3, trifluoromethyl or 2- (4-methylbenzyloxy).

m is selected from integers in the range of zero to two, preferably one or two.

Particularly suitable pharmaceutical active compounds are, for example, nifedipine, nimodipine (1,4-dihydro-2,6-dimethyl-4- (3'-nitrophenyl) -pyridine-3-β-methoxyethyl ester-5-isopropyl ester, known from DE 28 15 278), nisoldipine, nitrendipine, felodipine and amlodipine.

Hydrophobic in connection with active ingredients is understood to mean that the solubility in distilled water at 20 ° C. is preferably below 0.1 g / l, more preferably below 0.01 g / l.

Examples of suitable cytostatic agents are doxorubicin and paclitaxel.

Examples of suitable fungicidal active ingredients, which are obtained after the inventive

Solubilize process include:

Acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl;

Amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin,

Guazatine, iminoctadine, spiroxamine, tridemorph;

Anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl; Antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin and

streptomycin;

Azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole,

Epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochlorazole, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimol, triflumizole, triticonazole;

2-Methoxybenzophenone, as described in EP-A 897,904 by the general formula I, z. Eg metrafenone;

Dicarboximides such as iprodione, myclozoline, procymidone, vinclozolin; Dithiocarbamates such as Ferbam, Nabam, Maneb, Mancozeb, Metam, Metiram, Propineb,

Polycarbamate, thiram, zircon, zineb;

Heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboximine, oxycarboxine, cyazofamide, dazomet, dithianone, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolanes, mepronil, nuarimol, picosamide, probenazoles, proquinazide , Pyrifenox, Pyroquilon, Quinoxyfen, Silthiofam;

Thiabendazoles, thifluzamide, thiophanate-methyl, tiadinil, tricyclazoles, triforins;

Nitrophenyl derivatives such as binapacryl, dinocap, dinobutone, nitrophthalic-isopropyl; Phenylpyrroles such as fenpiclonil and fludioxonil; unclassified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamid, cymoxanil, diclomethine, diclocymet, diethofencarb, edfenphos, ethaboxam, fenhexamide, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, Iprovalicarb, hexachlorobenzene, metrafenone, pencycuron, propamocarb, phthalides, toloclofos-methyl, quintozene, zoxamide; Strobilurins as described in WO 03/075663 by the general formula I, for example azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin; Sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid; Cinnamic acid amides and analogs such as dimethomorph, flumetover, Flumorp; 6-Aryl- [1,2,4] triazolo [1,5-a] pyrimidines as described, for. In WO 98/46608, WO 99/41255 or WO 03/004465 are each described by the general formula I; Amide fungicides such as cyclofenamide and (Z) -N- [α- (cyclopropylmethoxyimino) -2,3-difluoro-6- (difluoromethoxy) benzyl] -2-phenylacetamide.

Examples of herbicides that can be formulated as the aqueous active ingredient composition of the present invention include:

1, 3,4-thiadiazoles such as buthidazole and cyprazole;

Amides such as allidochlor, benzoylpropyl, bromobutide, chlorthiamide, dimepiperate,

Dimethenamid, Diphenamid, Etobenzanid, Flampropmethyl, Fosamin, Isoxaben,

Metazachlor, monalides, naptalams, pronamide, propanil;

Aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate, sulfosates;

Aminotriazoles such as amitrole, anilides such as anilofos, mefenacet;

Aryloxyalkanoic acid such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop-P, dichloroprop-P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide,

Napropanilide, triclopyr; Benzoic acids such as Chloramben, Dicamba;

Benzothiadiazinones such as bentazone;

Bleachers such as Clomazone, Diflufenican, Fluorochloridone, Flupoxam, Fluridone, Pyrazoate, Sulcotrione;

Carbamates such as carbetamide, chlorobufam, chlorpropham, desmedipham, pheneadipham, vernolates;

Quinolinic acids such as Quinclorac, Quinmerac;

Dichloropropionic acids such as Dalapon;

Dihydrobenzofurans such as ethofumesates;

Dihydrofuran-3-one such as flurtamone; Dinitroanilines such as Benefin, Butraline, Dinitramine, Ethalfluralin, Fluchloralin, Isopropalin,

Nitralin, Oryzalin, Pendimethalin, Prodiamine, Profluralin, Trifluralin, Dinitrophenole like

Bromofenoxime, Dinoseb, Dinosebacetate, Dinoterb, DNOC, Minoterbacetate; Diphenyl ethers such as acifluorfensodium, aclonifen, bifenox, chloronitrofen, difenoxuron, ethoxyfen, fluorodifen, fluoroglycofenethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen, oxyfluorfen;

Dipyridyls such as cyperquat, difenzoquat methyl sulfate, diquat, paraquat dichloride; Imidazoles such as isocarbamide;

Imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazethabenzmethyl, imazethapyr, imazapic, imazamox;

Oxadiazoles such as methazoles, oxadiargyl, oxadiazon;

Oxiranes such as tridiphanes; Phenols such as bromoxynil, loxynil;

Phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofopbutyl, diclofopmethyl, fenoxapropethyl, fenoxaprop-p-ethyl, fenthiapropethyl, fluazifopbutyl, fluazifop-p-butyl, haloxyfopethoxyethyl, haloxyfopmethyl, haloxyfop-p-methyl, isoxapyrifop, propaquizafop, quizalofopethyl, quizalofop-p-ethyl, Quizalofoptefuryl; Phenylacetic acids such as chlorfenac;

Phenylpropionic acids such as chlorophenprophe-methyl; ppi agents (ppi = preplant incorporated) such as benzofenap, flumicloracpentyl, flumi- oxazine, flumipropyne, flupropacil, pyrazoxyfen, sulfentrazone, thidiazimine; Pyrazoles such as Nipyraclofen; Pyridazines such as Chloridazon, Maleic hydrazide, Norflurazon, Pyridate; Pyridinecarboxylic acids such as clopyralid, dithiopyr, picloram, thiazopyr; Pyrimidyl ethers such as pyrithiobacic acid, pyrithiobacsodium, KIH-2023, KIH-6127; Sulfonamides such as flumetsulam, metosulam; Triazole carboxamides such as triazofenamide; Uracils such as bromacil, lenacil, terbacil; Benazoline, Benfuresate, Bensulide, Benzofluor, Bentazone, Butamifos, Cafenstrole, Chlorthaldimethyl, Cinmethylin, Dichlobenil, Endothall, Fluorbentranil, Mefluidide, Perfluidone, Piperophos, Topramezone and Prohexandione-Calcium; Sulfonylureas such as amidosulfuron, azimsulfuron, bensulfuronmethyl, chlorimuronethyl, chlorosulfuron, cinosulfuron, cyclosulfamuron,

Ethametsulfuron-methyl, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron methyl, nicosulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, thifensulfuron-methyl, triasulfuron, IPF I t3BEiθnc3tαhn £ tl ± ¥ yK (i rTrsflliαSθ ItυσnπnΘi ^ hi ^ ß ^ rdihπsuTr ^ pDtn ^ ie alloxydim, Clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim.

Very particularly preferred cyclohexenone-type herbicidally active compounds are: tepraloxydim (compare AGROW, No. 243, 3.1.195, page 21, caloxydim) and 2- (1- [2- {4-chlorophenoxy} propyloxyimino] butyl) -3- hydroxy-5- (2H-tetrahydrothiopyran-3-yl) -2-cyclohexene-1-one and of the sulfonylurea type: N - (((4-methoxy-6- [trifluoromethyl] -1,3,5-triazine) 2-yl) - amino) carbonyl) -2- (trifluoromethyl) benzenesulfonamide. Examples of suitable insecticides include:

Organophosphates, such as acephates, azinphos-methyl, chlorpyrifos, chlorfenvinphos, diazinone, dichlorvos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoates, disulfonate, ethion, EPN, fenitrothion, fenthione, isoxathione, malathion, methamidophos, methidathion, methyl parathion, Mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidone, phorates, phoxim, pirimiphos-methyl, profenofos, prothiofos, primiphos-ethyl, pyraclofos, pyridaphenthione, sulprophos, triazophos, trichlorofon; Tetrachlorin-phosphine, vamidothion

Carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamates;

Pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, fenvalerate, ethofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, tralomethrin, alpha-cypermethrin, zeta-cypermethrin, permethrin;

Arthropod growth regulators: a) chitin synthesis inhibitors e.g. Benzoylureas such as chlorofluorazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, fluenuron, novaluron, teflubenzuron, triflumuron; Buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b) ecdysone antagonists such as halofenozides, methoxyfenocides, tebufenozides; c) juvenoids such as pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors such as spirodiclofen;

Neonicotinoids such as flonicamid, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nithiazine, acetamiprid, thiacloprid;

Other unclassified insecticides such as abamectin, acequinocyl, acetamiprid, amitraz, azadirachtin, bensultap, bifenazate, cartap, chlorfenapyr, chlordimeform, cyromacines, diafenthiuron, dinetofuran, diofenolan, emamectin, endosulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochloride , gamma-HCH-hydramethyl-non, imidacloprid, indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, XMC and xylylcarb. N-phenylsemicarbazones, as described in EP-A 462 456 by the general formula I, in particular compounds of the general formula II

wherein R ⁵ and R ⁶ independently of one another are hydrogen, halogen, CN, C 1 -C ₄ -alkyl, C 1 -C ₄ -alkoxy, C 1 -C ₄ -haloalkyl or C 1 -C ₄ -haloalkoxy and R ^{4 is} C 1 -C ⁴ ₄ -alkoxy, Ci-C ₄ haloalkyl or Ci-C ₄ haloalkoxy, z. B. Compound IV wherein R ^{5 is} 3-CF ₃ and R ^{6 is} 4-CN and R ^{4 is} 4-OCF ₃ .

Useful growth regulators are z. As chlormoquat chloride, mepiquat chloride, prohexadione calcium or the group of gibberellins. These include z. Gibberellins GAi, GA ₃ , GA ₄ , GA ₅ and GA ₇ etc. and the corresponding exo-16,17-dihydrogibberellins as well as the derivatives thereof, eg. As the esters with Ci-C ₄ -carboxylic acids. Preferably according to the invention is the exo-16,17-dihydro-GA ₅ -13-acetate.

Preferred fungicides are, in particular, strobilurins, azoles and 6-aryltriazolo [1, 5a] pyrimidines, as described, for example, in US Pat. In WO 98/46608, WO 99/41255 or WO 03/004465 are described by the general formula I there, in particular for active compounds of the general formula IM,

wherein:

R ^{x is} a group NR ⁷ R ⁸ , or linear or branched C ₁ -C 8 -alkyl which is optionally substituted by halogen, OH, C 1 -C ₄ -alkoxy, phenyl or C ₃ -C 6 -cycloalkyl, C ₂ -C 6 -alkyl Alkenyl, C ₃ -C 6 -cycloalkyl, C ₃ -C 6 -cycloalkenyl, phenyl or naphthyl, where the four last-mentioned radicals 1, 2, 3 or 4 substituents selected from halogen, OH, Ci-C ₄ alkyl, Ci-C ₄ -Halogenalkoxy, Ci-C ₄ alkoxy and Ci-C ₄ -Halogenalkyl may have; R ⁷ , R ⁸ independently of one another are hydrogen, C 1 -C 8 -alkyl, C 1 -C 5 -haloalkyl, C 3 -C 10 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 2 -C 8 -alkenyl, C 4 -C 10 -alkadienyl, C 1 -C 5 -synyl Haloalkenyl, C3-C6-cycloalkenyl, C2-C8-halocycloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl or C3-C6-cycloalkynyl, or

R ⁷ and R ⁸ together with the nitrogen atom to which they are attached, five- to eight-membered heterocyclyl which is bonded via N and contain one, two or three further heteroatoms from the group O, N and S as ring member and / or one or a plurality of substituents from the group halogen, C ₁ -C ₆ -alkyl, C ₁ -C ₆ -haloalkyl, C ₂ -C ₆ -alkenyl, C ₂ -C ₆ -haloalkenyl, C ₁ -C ₆ -alkoxy, C ₁ -C ₆ -haloalkoxy, C ₃ -C 3 -alkyl C6-alkenyloxy, C3-C6-haloalkenyloxy, (exo) -Ci-C6-alkylene and oxy-Ci-C3-alkyleneoxy can carry;

L is selected from halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 4 -haloalkoxy and C 1 -C 6 -alkoxycarbonyl;

L ^{1 is} halogen, C ¹ -C 6 -alkyl or C ¹ -C 6 -halogenoalkyl and in particular fluorine or chlorine;

X ^{2 is} halogen, C 1 -C ₄ -alkyl, cyano, C 1 -C ₄ -alkoxy or C 1 -C ₄ -haloalkyl and is preferably halogen or methyl and in particular chlorine.

Examples of compounds of formula IM are

5-Chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 - (4-methylpiperazin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (morpholine-1 -yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (piperidin-1-yl) -6- ( 2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl ) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (isopropylamino) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [ 1, 5-a] pyrimidine, 5-chloro-7- (cyclopentylamino) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-chloro -7- (2,2,2-trifluoroethylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- ( 1, 1, 1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (3,3-dimethylbutan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5- Chloro-7- (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (cyclohexyl) -6- ( 2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (2-methylbutan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 - (3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7- (4-methylcyclohexan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7- (hexan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Chloro-7- (2-methylbut-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-chloro-7 - (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-chloro-7- (1-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (4-methylpiperazin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (morpholin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (isopropylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (cyclopentylamino) -6 - (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (2,2,2-trifluoroethylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (1,1-trifluoropropan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7- (3,3-dimethylbutan-2-ylamino) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (cyclohexylmethyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (cyclohexyl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (2-methylbutan-3-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methylpropan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (4-methylcyclohexan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-methyl-7- (hexan-3-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine,

5-Methyl-7- (2-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine, 5-methyl-7 - (3-methylbutan-1-yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine and 5-methyl-7- (1-methylpropane 1 -yl) -6- (2,4,6-trifluorophenyl) - [1,2,4] triazolo [1,5-a] pyrimidine.

Suitable insecticides are, in particular, arylpyrroles such as chlorfenapyr, pyrethroids such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltamethrin, esfenvalerates, ethofenprox, fenpropathrin, fenvalerates, cyhalothrin, lambda-cyhalothrin, permethrin, silafluofen, tau-fluvalinate, tefluthrin, Tralomethrin, α-cypermethrin, zeta-cypermethrin and permethrin, - neonicotinoids and

Semicarbazone of formula II. Suitable fluorescers are, for example, pyrene, uranine, rhodamine, fluorescein, coumarin, allophycocyanin, naphthalene, anthracene.

In one embodiment of the present invention, it is possible to solubilize by means of the process according to the invention in the range from 0.01 to 1% by weight of hydrophobic active ingredient in an aqueous medium, preferably at least 0.1% by weight, based on total inventively prepared aqueous formulation.

For the solubilization of hydrophobic active substance, it is possible to use hyperbranched polyester (c) according to the invention or else one or more so-called modified hyperbranched polyesters (d), in the context of the present invention also referred to as modified polyesters (d) according to the invention. Modified polyesters (d) according to the invention can be obtained by reacting one or more hyperbranched polyesters (d) according to the invention with at least one isocyanate (s) or chloroformate (s) bonded to at least one group bonded via a carbonate, urea or urethane group Polyalkylene oxide unit carries reacted. Modified polyesters (d) according to the invention have a molecular core, which is therefore also hyperbranched, and a hydrophilic shell.

The preparation of chloroformates (e) and isocyanates (e) is known per se. For the preparation of chlorocarbonic acid esters (e), preference is given to using a diol, for example one of the abovementioned diols, with two equivalents of phosgene, diphosgene or preferably triphosgene to form a bis-chlorocarbonic acid ester and then with a preferably C 1 -C 4 -ester. Alkyl group capped polyalkylene glycol.

The preparation of isocyanates (e) is preferably carried out by reacting a diisocyanate, preferably one of the diisocyanates mentioned below, with one equivalent of polyalkylene glycol, preferably capped with a C 1 -C 4 -alkyl group, or a corresponding polyalkylene glycolamine.

Suitable capped polyalkylene glycols are, in particular, polypropylene glycol capped with a C 1 -C 4 -alkyl group and polyethylene glycol capped with a C 1 -C 4 -alkyl group, for example having a molecular weight M _n in the range from 150 to 5,000 g / mol, preferably 350 to 2,000 g / mol, more preferably 350 to 1,000 g / mol.

Suitable diisocyanates are aromatic, cycloaliphatic and in particular aliphatic diisocyanates. Examples which may be mentioned are: 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,7-naphthylene diisocyanate, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, cyclohexane-1,4-diisocyanate, 2,4 Hexahydrotoluylene diisocyanate, 2,6-hexahydrotoluylene diisocyanate and 4,4'-dicyclohexylmethane diisocyanate. The preparation of chloroformate (e) succeeds particularly well in the presence of base, for example pyridine or trimethylamine or triethylamine.

The preparation of isocyanate (e) can be carried out in the presence of catalysts such as, for example, tin compounds, preferably di-n-butyltin oxide, di-n-butyltin diacetate or di-n-butyltin dilaurate, or in the absence of catalyst.

The preparation of isocyanates (e) can be carried out, for example, according to or in analogy to H. Petersen et al., Macromolecules 2002, 35, 6867 et seq.

For reacting hyperbranched polyester (c) according to the invention with chloroformate (e), it is possible, for example, to initially charge hyperbranched polyester (c) according to the invention and to add one or more bases, for example pyridine or triethylamine, and chloroformate (e).

For the reaction of hyperbranched polyester (c) according to the invention with isocyanate (e), it is possible, for example, to initially charge hyperbranched polyester (c) according to the invention and to add isocyanate (e) and optionally one or more catalysts, for example one or more organic tin compounds , in particular one of the abovementioned tin compounds.

The reaction of hyperbranched polyester (c) according to the invention with chloroformate (e) or isocyanate (e) can be carried out without solvent or preferably in one or more organic solvents. Suitable solvents are, for example, N, N-dimethylformamide (DMF), tetrahydrofuran (THF),

1, 4-dioxane, ethylene glycol dimethyl ether, dimethyl sulfoxide, chloroform, dichloromethane, acetonitrile, dimethylacetamide, N-methylpyrrolidone, xylene, toluene and acetone.

In one embodiment of the present invention, the reaction of hyperbranched polyester (c) according to the invention with chloroformate (e) or isocyanate (e) is carried out at room temperature or preferably at elevated temperature. The reaction of inventive hyperbranched polyester (c) with chloroformate (e) or isocyanate (e) is particularly preferably carried out at temperatures in the range from 40 to 120 ° C., especially when no catalyst is used.

In one embodiment of the present invention, the proportions of hyperbranched polyester (c) and chloroformate (s) or isocyanate (s) according to the invention are chosen such that at least 90 .mu.mol% of the functional groups, preferably at least 90 mol% of the hydroxyl groups and especially preferably 90 to 99 mol% of the functional groups of inventive hyperbranched polyester (c) are reacted with chloroformate (s) or isocyanate (e). In one embodiment of the present invention, hyperbranched polyester (c) according to the invention is brought into contact with one or more hydrophobic active substances and aqueous medium, for example by mixing. In a preferred embodiment of the present invention, modified polyester (d) according to the invention is brought into contact with one or more hydrophobic active substances and aqueous medium, for example by mixing. The mixing can be done, for example, by stirring with conventional stirrers or with high-speed stirrers. Other suitable methods are the use of ultrasound or intense shaking.

In one embodiment of the present invention, hyperbranched polyester (c) and hydrophobic active ingredient according to the invention are used in a mass ratio in the range from 1: 1 to 1000: 1, preferably 1: 1 to 100: 1.

In one embodiment of the present invention, modified polyester (d) and hydrophobic active ingredient according to the invention are used in a mass ratio in the range from 1: 1 to 1000: 1, preferably 100: 1 to 1: 1.

In one embodiment, hyperbranched polyester (c) according to the invention and preferably modified polyester (d) according to the invention are stirred with aqueous medium and subsequently with one or more active substances.

The mixing can be carried out at temperatures in the range of 0 ° C to 100 ° C and - if one wants to apply increased pressure - even at temperatures up to 150 ° C. The reaction is preferably carried out under atmospheric pressure and at temperatures in the range from 20 to 70 ^° C.

In one embodiment of the present invention, after completion of the mixing, unsolubilized hydrophobic drug is separated, for example, by filtration or centrifugation.

Another object of the present invention are modified polyester (d), obtainable by

(a) Preparation of at least one hyperbranched polyester available

(a1) by polycondensation of at least one dicarboxylic acid or at least one derivative thereof with at least one at least trifunctional alcohol or (a2) by polycondensation of at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof with at least one diol, or

(a4) by polycondensation of at least one diol with a mixture of at least one dicarboxylic acid or at least one derivative thereof and at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof,

one subsequently

with at least one monool (b1), diol (b1) or polyol (b1), at least one epoxide (b2) or at least one carbodiimide (b3) until the acid number is at most 15 mg KOH / g, and then

Reaction with at least one isocyanate (e) or a chloroformate

(e) which carries at least one polyalkylene oxide unit bonded via a carbonate, urea or urethane group.

In one embodiment of the present invention, modified polyester (c) according to the invention are those polyesters in which hyperbranched polyesters (c) according to the invention are

(d1) with at least one reaction product of at least one diisocyanate with a capped with a Ci-C4-alkyl group polyalkylene glycol.

In one embodiment of the present invention, at least 90 mol% of the functional groups, preferably at least 90 mol% of the hydroxyl groups and preferably 90 to 99 mol% of the functional groups of hyperbranched polyester (c) according to the invention with isocyanate (e) or chloroformate ( e) implemented.

The preparation of hyperbranched polyesters (c) according to the invention and also modified polyesters (d) according to the invention can be carried out, for example, as described above.

A further subject of the present invention is a process for the preparation of the hyperbranched polyesters (c) according to the invention. In particular, the present invention provides a process for the preparation of hyperbranched polyesters (c) according to the invention by reacting (a) at least one hyperbranched polyester available

(a2) by polycondensation of at least one tricarboxylic acid or higher polycarboxylic acid or at least one derivative thereof with at least one diol, or

one subsequently

Reaction with at least one isocyanate (e) or a chloroformate (s), which carries at least one bonded via a carbonate, urea or urethane group polyalkylene oxide.

The modified polyesters (d) according to the invention can be prepared, for example, as described above.

In one embodiment of the present invention, the preparation of hyperbranched polyester (c) according to the invention is carried out in the presence of a solvent. Suitable are, for example, hydrocarbons such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene. Furthermore, suitable solvents in the absence of acidic catalysts are very particularly suitable: chloroform, methylene chloride and N, N-dimethylformamide, ethers such as dioxane or tetrahydrofuran and ketones such as, for example, methyl ethyl ketone and methyl isobutyl ketone. According to the invention, the amount of solvent added is at least 0.1% by weight, based on the mass of the starting materials to be reacted, preferably at least 1% by weight and more preferably at least 10% by weight. It is also possible to use excesses of solvent, based on the mass of reacted starting materials to be reacted, for example 1:01 to 10 times. Solvent amounts of more than that

100 times, based on the mass of reacted starting materials to be reacted, are not advantageous because at significantly lower concentrations of the reactants, the reaction rate decreases significantly, resulting in uneconomical long reaction times.

For carrying out the process according to the invention, it is possible to work as an additive in the presence of a water-removing agent which is added at the beginning of the reaction. Suitable examples are molecular sieves, in particular molecular sieve 4A, MgSO ₄ and Na ₂ SO ₄ . It is also possible during the reaction to add further de-watering agent or to replace de-watering agent with fresh de-watering agent. It is also possible to distill off water or alcohol formed during the reaction and to use, for example, a water separator or water separator.

In another embodiment of the present invention, the preparation of hyperbranched polyester (c) according to the invention is carried out without the use of solvents.

In one embodiment of the present invention, the preparation of hyperbranched polyester (a) and preferably also hyperbranched polyester (c) according to the invention is carried out in the absence of acidic catalysts.

In one embodiment of the present invention, the reaction is carried out in the presence of an acidic inorganic, organometallic or organic catalyst or mixtures of several acidic inorganic, organometallic or organic catalysts.

Examples of acidic inorganic catalysts for the purposes of the present invention are sulfuric acid, phosphoric acid, phosphonic acid, hypophosphorous acid, aluminum sulfate hydrate, alum, acidic silica gel (pH <6, in particular <5) and acidic aluminum oxide. Furthermore, for example, aluminum compounds of the general formula AI (OR ⁹ ) 3 and titanates of the general formula Ti (OR ⁹ ) ₄ can be used as acidic inorganic catalysts, wherein the radicals R ^{9 may be} the same or different and are independently selected from each other C 1 -C 10 -alkyl radicals, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethyl-propyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethyl-hexyl, n-nonyl or n-decyl,

C 3 -C 12 -cycloalkyl radicals, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.

The radicals R ⁹ in Al (OR ⁹ ) 3 or Ti (OR ⁹ ) 4 are preferably identical and selected from isopropyl or 2-ethylhexyl.

Particularly suitable acidic catalysts are compounds of antimony (e.g., Sb2Ü3 or antimony triacetate); Germanium (e.g., Ge2) or titanium, for example, bis-taloxetoxoxalate.

Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides (R ⁹⁾ SnO, where R ^{9 is} as defined above. Preference is given to tin (II) n-octanoate, tin (II) 2-ethylhexanoate, tin (II ) laurate, dibutyltin oxide, diphenyltin oxide, di-n-butyltin dichloride, di-n-butyltin diacetate, di-n-butyltin dilaurate,

Di-n-butyltin dimaleate or di-n-octyltin diacetate. A particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin.

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. It is also possible to use such organic or organometallic or else inorganic catalysts which are present in the form of discrete molecules in immobilized form.

If it is desired to use acidic inorganic, organometallic or organic catalysts, according to the invention 0.1 to 10% by weight, preferably 0.2 to 2% by weight of catalyst, based on the sum of the respective reaction partners in variant (a1) or (a2) or (a3) or (a4). In another embodiment of the present invention, the preparation of hyperbranched polyester (a) and optionally hyperbranched polyester (c) according to the invention is carried out in the presence of one or more enzymes. Preference is given to the use of lipases and esterases. Highly suitable lipases and esterases are Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucorjavanicus, Mucor mihei, pig pancreas, Pseudomonas spp., Pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus , Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or Esterase from Bacillus spp. and Bacillus thermoglucosidase. Particularly preferred is Candida antarctica lipase B. The enzymes listed are commercially available, for example from Novozymes Biotech Inc., Denmark.

Preferably, enzyme is used in immobilized form, for example on silica gel or Lewatit®. Processes for the immobilization of enzymes are known per se, for example from Kurt Faber, "Biotransformations in Organic Chemistry", 3rd edition 1997, Springer Verlag, Chapter 3.2 "Immobilization" page 345-356. Immobilized enzymes are commercially available, for example from Novozymes Biotech Inc., Denmark.

The amount of enzyme used is 1 to 20 wt .-%, in particular 10-15 wt .-%, based on the mass of the total starting materials to be reacted.

If it is desired to use ethylenically unsaturated monocarboxylic or dicarboxylic acids in the preparation of hyperbranched polyester (a), it may be useful to work at temperatures below 120.degree. C., preferably below 100.degree. Furthermore, it may be useful to use one or more radical scavengers (inhibitors). Examples of suitable radical scavengers are phenolic compounds such as MEHQ (hydroquinone monomethyl ether), 2,6-di-tert-butyl-4-hydroxytoluene, aromatic or aliphatic phosphites, phenothiazine, nitroxyl compounds such as TEMPO (2,2,6,6-tetramethylpiperidinyl 1-oxy), OH-TEMPO, methoxy-TEMPO and alkoxamine initiators such as N-tert-butyl-N- (1-diethylphosphono-2,2-dimethylpropyl) nitroxides or mixtures thereof.

In one embodiment of the present invention, the preparation of hyperbranched polyester (c) according to the invention is carried out at a temperature in the range from 100 to 220 ° C., preferably from 120 to 200 ° C. This embodiment is preferred when working without catalyst or with nonenzymatic catalyst. In another embodiment of the present invention, the preparation of hyperbranched polyester (c) according to the invention is carried out at a temperature in the range from 40 to 120.degree. C., preferably from 50 to 100.degree. C. and particularly preferably from 65 to 90.degree. This embodiment is preferred when operating as a catalyst without catalyst or with one or more enzymes.

The preparation of hyperbranched polyester (c) according to the invention can be carried out at atmospheric pressure. However, it is preferred to produce hyperbranched polyesters (c) according to the invention at reduced pressure, for example in the range from 1 mbar to 500 mbar, preferably from 5 mbar to 400 mbar.

After completion of the reaction to produce inventive hyperbranched polymer (c) can be dispensed in many cases to a purification.

In another embodiment of the present invention, cleaning is carried out after the end of the chemical reaction to produce hyperbranched polymer (c) according to the invention. Such a purification can, for example, if chlorocarbonic acid ester (b) has been used, comprise a separation of salts formed and / or optionally used catalyst or decomposition products of optionally used catalyst. Furthermore, it may be useful to separate off by-products which are formed, for example, in the preparation of chloroformate (b) or isocyanate (b).

It is possible to work up by methods known per se, for example by chromatography, reprecipitation, filtration, particle size-dependent separation processes such as, for example, ultrafiltration or by dialysis.

A further subject of the present invention are complexes comprising at least one hyperbranched polyester (c) according to the invention and at least one hydrophobic active substance or at least one modified polyester (d) according to the invention and a hydrophobic active substance. Complexes should be understood to mean not only complexes in the sense of complex theories, but also inclusion compounds or other aggregates of hydrophobic active ingredient and inventive hyperbranched polyester (c) or modified polyester (d) according to the invention and hydrophobic active ingredient, without any theory of the invention Preference should be given.

Complexes according to the invention can comprise, for example, one or more molecules of hydrophobic active ingredient and one or more hyperbranched polyester (c) or modified polyester (d) according to the invention, ie they do not have to contain exactly one molecule of hydrophobic active ingredient and exactly one hyperbranched polyester of the invention (c) or modifi- encapsulated polyester (d). Furthermore, complexes according to the invention may also contain incorporated water.

Another object of the present invention is a process for the preparation of complexes of the invention. For the preparation of complexes according to the invention, it is possible to proceed by mixing at least one hydrophobic active ingredient and at least one hyperbranched polyester (c) or at least one modified polyester (d) according to the invention, for example by one of the abovementioned processes, preferably in the presence of water ,

Another object of the present invention are aqueous formulations containing at least one complex according to the invention, for example in concentrations of 0.01 to 400 g / l, particularly preferably from 0.015 to 100 g / l.

Depending on the hydrophobic active ingredient used, complexes according to the invention and thus aqueous formulations according to the invention can be used, for example, as crop protection agents or as or for the production of medicaments. The invention will be explained by working examples.

General Preliminary Remarks: The acid number was always determined according to DIN 53402. Figures in ppm are always ppm by weight.

The viscosity measurements were always carried out with a cone-plate viscometer. A rapid addition means that the reagent in question is not added over several minutes or hours, but in one portion.

I. Synthesis of Hyperbranched Polyesters of the Invention (c)

1.1 Synthesis of Hyperbranched Polyester (c.1) According to the Invention (ADS + Gly)

92 g (0.63 mol) of adipic acid and 48 g (0.521 mol) of glycerol were placed in a 250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 0.15 ml of a 0.02 M solution of sulfuric acid was added and the mixture was heated to 135.degree. A reduced pressure of 60 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 8.5 hours at 135 ° C and 60 mbar. The progress of the reaction was monitored by viscosity measurements and by determining the acid number. At a dynamic viscosity of 4.2 Pa s at 75 ° C. and an acid number of 116 mg KOH / g, 26.24 g (0.285 mol) of glycerol were added rapidly to the reaction mixture (1 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). , The mixture was stirred for a further 25 hours at 140 ° C, of which 18 hours at a pressure of 20 mbar and another 7 hours at 5 mbar. Than the value for the Acid number 1, 2 mg KOH / g, the reaction was stopped by cooling to room temperature and aerated.

This gave 143 g of hyperbranched polyester (c.1) according to the invention in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.2 Synthesis of Hyperbranched Polyester According to the Invention (c.2) (ADS + Gly)

92 g (0.63 mol) of adipic acid and 48 g (0.521 mol) of glycerol were in a

250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 0.15 ml of a 0.02 M solution of sulfuric acid was added and the mixture was heated to 135.degree. A reduced pressure of 20 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 9.5 hours at 135 ° C and 20 mbar. The progress of the reaction was monitored by viscosity measurements and by determining the acid number. At a dynamic viscosity of 4.8 Pa s at 75 ° C and an acid number of 1 10 mg KOH / g was added 26.4 g (0.287 mol) of glycerol over a period of 4 hours to the reaction mixture (1, 1 molar, based to the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 16 hours at 135 ° C, then the temperature was raised to 170 ° C and stirred for a further 6.5 hours, each at a pressure of 20 mbar. When the acid value reached 1.9 mg KOH / g, the reaction was quenched by cooling to room temperature and venting. This gave 158 g of hyperbranched polyester (c.2) in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.3 Synthesis of Hyperbranched Polyester (c.3) According to the Invention (ADS + Gly)

92 g (0.63 mol) of adipic acid and 48 g (0.521 mol) of glycerol were in a

250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 200 ppm of di-n-butyltin oxide, based on the reaction mixture, were added, commercially available as Fascat® 4201, and heated to 135.degree. A reduced pressure of 20 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 7.5 hours at 135 ° C and 20 mbar. The progress of the reaction was monitored by viscosity measurements and by the determination of the acid number. With a dynamic viscosity of 4.4 Pa s at 75 ° C and an acid number of 112 mg KOH / g was quickly added 25.8 g (0.28 mol) of glycerol to the reaction mixture (1 molar, based on the equivalents of the carboxylic acid groups of reaction mixture). The mixture was stirred for a further 27 hours at 135 ° C at a pressure of 10 mbar. When When the acid number value reached 4.6 mg KOH / g, the reaction was stopped by cooling to room temperature and venting.

Man received 146 g of hyperbranched polyester (c.3) in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.4 Synthesis of hyperbranched polyester (c.4) according to the invention (ADS + Gly)

92 g (0.63 mol) of adipic acid and 48 g (0.521 mol) of glycerol were placed in a 250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. One gave

200 ppm of di-n-butyltin dilaurate (DBTL), based on the reaction mixture, and heated to 150 ° C. A reduced pressure of 100 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 7 hours at 150 ° C and 100 mbar. The progress of the reaction was monitored by viscosity measurements and by the determination of the acid number. At a dynamic viscosity of 10 Pa s at 75 ° C and an acid number of 93 mg KOH / g was quickly added 26.4 g (0.287 mol) of glycerol to the reaction mixture (1, 8 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture) , The mixture was stirred for a further 18 hours at 150 ° C at a pressure of 15 mbar. When the acid value reached 4.2 mg KOH / g, the reaction was quenched by cooling to room temperature and venting.

146 g of hyperbranched polyester (c.4) were obtained in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.5 Synthesis of hyperbranched polyester (c.5) according to the invention (ADS + Gly)

200 ppm tetra-n-butoxytitanium (TBOT), based on the reaction mixture, and heated to 150 ° C. A reduced pressure of 100 mbar was applied to separate water formed during the reaction. The reaction mixture was held for 6.5 hours at 150 ° C and 100 mbar. The progress of the reaction was monitored by viscosity measurements and by the determination of the acid number. At a dynamic viscosity of 10 Pa s at 75 ° C and an acid number of 107.3 mg KOH / g were quickly added 25.8 g (0.28 mol) of glycerol to the reaction mixture (1, 07 molar, based on the equivalents of Carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 18 hours at 150 ° C at a pressure of 10 mbar. When the value for the acid value reached 5.2 mg KOH / g, the reaction was stopped by cooling to room temperature and venting. 145 g of hyperbranched polyester (c.5) were obtained in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.6 Synthesis of Hyperbranched Polyester (c.6) According to the Invention (ADS + Gly)

92 g (0.63 mol) of adipic acid and 48 g (0.521 mol) of glycerol were placed in a 250 mL glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 200 ppm of p-toluenesulfonic acid was added, based on the reaction mixture, and heated to 150 ° C. A reduced pressure of 100 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 7 hours at 150 ° C and 100 mbar. The progress of the reaction was monitored by viscosity measurements and by determining the acid number. At a dynamic viscosity of 5.5 Pa s at 100 ° C and an acid number of 93.5 mg KOH / g was quickly added 26.4 g (0.287 mol) of glycerol to the reaction mixture (1, 8 molar, based on the equivalents of Carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 18 hours at 150 ° C at a pressure of 15 mbar. When the acid value reached 12.3 mg KOH / g, the reaction was quenched by cooling to room temperature and venting.

146 g of hyperbranched polyester (c.6) were obtained in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.7 Synthesis of Hyperbranched Polyester According to the Invention (c.7) (ADS + Gly)

1713 g (1 1, 72 mol) of adipic acid and 900 g (9.77 mol) of glycerol were placed in a 4 l glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 2.6 ml of a 0.02 M solution of sulfuric acid were added and the mixture was heated to 140.degree. A reduced pressure of 600 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 12.5 hours at 150 ° C and 100 mbar. The progress of the reaction was monitored by viscosity measurements and by determining the acid number. At a dynamic viscosity of 1 Pa.s at 75 ° C. and an acid number of 101 mg KOH / g, 350 g (3.8 mol) of glycerol were rapidly added to the reaction mixture (0.8 molar, based on the equivalents of the carboxylic acid groups of reaction mixture). The mixture was stirred for a further 6 hours at 140 ° C at a pressure of 5 mbar. At a dynamic viscosity of 1 Pa.s at 75 ° C. and an acid number of 31 mg KOH / g, 150 g (1.63 mol) of glycerol were rapidly added to the reaction mixture (1 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 6 hours at 140 ° C at a pressure of 5 mbar. At an acid number of 15 mg KOH / g, an additional 77 g (0.84 mol) of glycerol were added to the reaction mixture (1 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). research). The mixture was stirred for a further 10 hours at 140 ° C at a pressure of 5 mbar. When the acid value reached 9 mg KOH / g, the reaction was quenched by cooling to room temperature and venting.

2950 g of hyperbranched polyester (c.7) were obtained in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.8 Synthesis of Hyperbranched Polyester According to the Invention (c.8) (BS + Gly)

73.6 g (0.62 mol) of succinic acid and 48 g (0.52 mol) of glycerol were placed in a 250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 0.15 ml of 0.02 M sulfuric acid was added and heated to 135 ° C. A reduced pressure of 20 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 4 hours at 135 ° C and 20 mbar. The progress of the reaction was monitored by viscosity measurements and by determining the acid number. At a dynamic viscosity of 6.4 Pa s at 75 ° C and an acid number of 166 mg KOH / g was added rapidly 28 g (0.3 mol) of glycerol to the reaction mixture (0.84 molar, based on the equivalents of the carboxylic acid groups of reaction mixture). The mixture was stirred for a further 25 hours at 140 ° C at a pressure of 15 mbar. When the acid value reached 4.5 mg KOH / g, the reaction was stopped by cooling to room temperature and venting.

This gave 121 g of hyperbranched polyester (c.8) in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.9 Synthesis of Hyperbranched Polyester According to the Invention (c.9) (BS + Gly)

2001 g (16.95 mol) of succinic acid and 1300 g (14.1 mol) of glycerol were placed in a 4 l glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 3.3 ml of 0.02 M sulfuric acid were added and the mixture was heated to 140.degree. A reduced pressure of 500 mbar was applied to separate water formed during the reaction. The reaction mixture was held at 140 ° C and 500 mbar for 13 hours. The progress of the reaction was monitored by viscosity measurements and by determining the acid number. At a dynamic viscosity of 1 Pa.s at 75 ° C. and an acid number of 126 mg KOH / g, 550 g (6 moles) of glycerol were rapidly added to the reaction mixture (1.86 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 15 hours at 150 ° C at a pressure of 400 mbar. When the acid value reached 15 mg KOH / g, another 100 g (1.10 mol) of glycerin (1 molar, based on the equivalents of carboxylic acid groups in the reaction mixture) were added and stirring was continued for a further 5 hours 150 ° C and a pressure of 400 mbar. When the acid value reached 7 mg KOH / g, the reaction was stopped by cooling to room temperature and venting. 3780 g of hyperbranched polyester (c.9) were obtained in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.10 Synthesis of Hyperbranched Polyester According to the Invention (c.10)

92 g (0.63 mol) of adipic acid and 70.3 g (0.52 mol) of 1,1,1-trimethylolpropane were placed in a 250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap was equipped. 0.15 ml of 0.02 M sulfuric acid were added and the mixture was heated to 135.degree. A reduced pressure of 20 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 4.5 hours at 135 ° C and 20 mbar. The progress of the reaction was monitored by determining the dynamic viscosity and the acid number. At a dynamic viscosity of 5.1 Pa s at 75 ° C and an acid number of 82.9 mg KOH / g was quickly added 38 g (0.28 mol) of 1,1,1-trimethylolpropane to the reaction mixture (1, 7 molar , based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 52 hours at 135 ° C at a pressure of 15 mbar and a further 16 hours at 145 ° C and 15 mbar. When the acid value reached 4.9 mg KOH / g, the reaction was quenched by cooling to room temperature and venting. This gave 153 g of hyperbranched polyester (c.10) in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.1 1 Synthesis of Hyperbranched Polyester According to the Invention (c.11)

500 g (3.4 mol) of adipic acid and 1910 g (2.85 mol) of 1, 1, 1-trimethylolpropane (1,1,1-tris (hydroxymethyl) propane) ethoxylated with 12 mol of ethylene oxide were dissolved in a 4- 1 glass stirrer, which was equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 2.4 ml of 0.02 M sulfuric acid were added and the mixture was heated to 150.degree. A reduced pressure of 300 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 25 hours at 150 ° C and 300 mbar. The progress of the reaction was monitored by determining the dynamic viscosity and the acid number. At a dynamic viscosity of 1 Pa s at 25 ° C and an acid number of 36 mg KOH / g was rapidly 830 g (1, 24 mol) with 12 mol of ethylene oxide ethoxylated 1,1,1-trimethylolpropane to the reaction mixture (1, 24 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 9 hours at 150 ° C at a pressure of 5 mbar. When the dynamic viscosity value reached 0.78 Pa s (25 ° C) and the acid number reached 14 mg KOH / g, an additional 540 g (0.8 mol) of 12 mol ethylene oxide ethoxylated 1, 1, 1 - Trimethylolpropane and stirred for a further 8 hours at 150 ° C and 5 mbar. As the acid number has a value of

8 mg KOH / g, the reaction was stopped by cooling to room temperature and venting. This gave 3630 g of hyperbranched polyester (c.1 1) in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.12 Synthesis of Hyperbranched Polyester According to the Invention (c.12)

160 g (1, 04 mol) of hexahydrophthalic anhydride and 146.2 g (1, 09 mol) of 1,1,1-tris-hydroxymethylpropane were placed in a 500 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection equipped with cold trap. 200 ppm of di-n-butyltin dilaurate (DBTL) was added, based on the reaction mixture, and heated to an internal temperature of 200 ° C. with the aid of an oil bath. A reduced pressure of 500 mbar was applied to separate water formed during the reaction. The reaction mixture was held for 10 hours at said temperature and pressure. The progress of the reaction was monitored by determining the acid number. At an acid number of 21 mg KOH / g was quickly added 15.4 g (0.11 mol) of 1,1,1-trishydroxymethylpropane to the reaction mixture (0.8 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 7 hours at 200 ° C at a pressure of 400 mbar. When the acid value reached 8 mg KOH / g, the reaction was quenched by cooling to room temperature and venting. This gave 282 g of hyperbranched polyester (c.12) in the form of a colorless clear solid. The analytical data are summarized in Table 1.

1.13 Synthesis of Hyperbranched Polyester According to the Invention (c.13)

1000 g (6.49 mol) of hexahydrophthalic anhydride, 265 g (1.84 mol) of 1,4-cyclohexanedimethanol and 479 g (3.57 mol) of 1,1,1-tris (hydroxymethyl) propane were dissolved in a 4 I glass flask presented, which was equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 400 ppm of di-n-butyltin dilaurate (DBTL) was added, based on the total reaction mixture, and heated to 180.degree. A reduced pressure of 400 mbar was applied to separate water formed during the reaction. The reaction mixture was kept at said temperature and pressure for 6 hours. The progress of the reaction was monitored by determining the acid number. At an acid number of 69 mg KOH / g was quickly added 230 g (1, 72 mol) of 1,1,1-trishydroxymethylpropane to the reaction mixture (0.8 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 12 hours at 180 ° C, of which 4 hours at a pressure of 300 mbar and 8 hours at a pressure of 10 mbar. When the acid value reached 8 mg KOH / g, the reaction was quenched by cooling to room temperature and venting. This gave 1835 g of hyperbranched polyester (c.13) in the form of a colorless clear solid. The analytical data are summarized in Table 1. 1.14 Synthesis of Hyperbranched Polyester According to the Invention (c.14)

1000 g (6.49 mol) of hexahydrophthalic anhydride, 265 g (1.84 mol) of 1,4-cyclohexanedimethanol and 479 g (3.57 mol) of 1,1,1-tris (hydroxymethyl) propane were dissolved in a 4 l glass flask presented, which was equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 400 ppm of di-n-butyltin dilaurate (DBTL) were added, based on the total reaction mixture, and heated to 180.degree. A reduced pressure of 400 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 8 hours at 180 ° C and 400 mbar. The progress of the reaction was monitored by determining the dynamic viscosity and the acid number. At a dynamic viscosity of 1 Pa s at 150 ° C and an acid number of 66 mg KOH / g was added quickly 220 g (1, 64 mol) of 1,1,1-trimethylolpropane to the reaction mixture (0.8 molar, based on the Equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 7 hours at 180 ° C, of which 4 hours at a pressure of 300 mbar and 3 hours at a pressure of 10 mbar. When the dynamic viscosity value reached 1 Pa · s (150 ° C) and the acid value reached 28 mg KOH / g, an additional 116.8 g (0.87 mol) of 1,1,1-trimethylolpropane (1 molar, based on the carboxylic acid groups in the reaction mixture) and stirred for a further 17.5 hours at 150 ° C and 10 mbar. When the acid number reached 6 mg KOH / g, the reaction was stopped by cooling to room temperature and venting. This gave 1820 g of hyperbranched polyester (c.14) in the form of a colorless clear solid. The analytical data are summarized in Table 1.

1.15 Synthesis of Hyperbranched Polyester According to the Invention (c.15)

68.4 g (0.47 mol) of adipic acid, 261.4 g (0.39 mol) of 12 mol of ethylene oxide ethoxylated 1,1,1-trimethylolpropane and 1.7 g (7 mmol) of cetyl alcohol were dissolved in a 500 ml Glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 0.5 g of di-n-butyl tin oxide was added, commercially available as Fascat® 4201, and heated to 150 ° C. A reduced pressure of 400 mbar was applied to separate water formed during the reaction. The reaction mixture was stirred for 3.5 hours at 150 ° C and 400 mbar. The progress of the reaction was monitored by determining the acid number. At an acid number of 78 mg KOH / g was quickly added 247 g (0.37 mol) with 12 mol of ethylene oxide ethoxylated 1, 1, 1-Trishydroxymethylpropan to the reaction mixture (0.8 molar, based on the equivalents of the carboxylic acid groups of the reaction mixture). The mixture was stirred for a further 9 hours at 150 ° C at a pressure of 20 mbar. When the value for the acid number had reached 12 mg KOH / g, a further 29.7 g (0.044 mol) of 1,1-trimethylolpropane ethoxylated with 12 mol of ethylene oxide (1 molar, based on the carboxylic acid groups in the reaction mixture) were added and stirred more 3 hours at 150 ° C and 10 mbar. When the acid value reached 4.7 mg KOH / g, the reaction was quenched by cooling to room temperature and venting.

This gave 3630 g of hyperbranched polyester (c.15) in the form of a colorless clear viscous resin. The analytical data are summarized in Table 1.

1.16 Synthesis of Hyperbranched Polyester According to the Invention (c.16)

200 g (1.297 mol) of hexahydrophthalic anhydride, 53.0 g (0.368 mol) of 1,4-cyclohexanedimethanol and 95.7 g (0.713 mol) of 1,1,1-tris (hydroxymethyl) propane were dissolved in a 1 l glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 400 ppm of di-n-butyltin dilaurate (DBTL) was added, based on the total reaction mixture, and heated to 150 ° C. A reduced pressure of 100 mbar and 15 h of 6 mbar were applied for 4 hours in order to separate off water formed during the reaction. The progress of the reaction was monitored by determining the dynamic viscosity and the acid number. At a dynamic viscosity of 10 Pa s- at 150 ° C and an acid number of 82 mg KOH / g was added 54.7 g (0.408 mol) of 1,1,1-trimethylolpropane at once to the reaction mixture. The mixture was stirred for a further 18 hours at 155 ° C at a pressure of 7 mbar. When the dynamic viscosity value reached 9 Pa s (150 ° C) and the acid number reached 27 mg KOH / g, another 22.5 g (0.168 mol) of 1,1,1-trimethylolpropane was added and stirring was continued for a further 21 hours at 170 ° C and 7 mbar. When the acid value reached 7 mg KOH / g, the reaction was stopped by cooling to room temperature and venting. Hyperbranched polyester (c.16) was obtained in the form of a colorless clear solid. The analytical data are summarized in Table 1.

1.17 Synthesis of Hyperbranched Polyester According to the Invention (c.17)

70 g (0.407 mol) of cyclohexanedicarboxylic acid, 32.2 g (0.224 mol) of 1,4-cyclohexanedimethanol and 15.0 g (0.1 12 mol) of 1,1,1-tris (hydroxymethyl) propane were dissolved in a 250 ml glass flask equipped with stirrer, internal thermometer, gas inlet tube, reflux condenser and vacuum connection with cold trap. 2000 ppm of di-n-butyltin dilaurate (DBTL) were added, based on the total reaction mixture, and heated to 150.degree. The mixture was stirred for 8 hours at a pressure of 6 mbar and separated from the water formed in the reaction. The progress of the reaction was monitored by determining the dynamic viscosity and the acid number. At a dynamic viscosity of 89 mPa.s at 150 ° C. and an acid number of 88 mg KOH / g, 24.7 g (0.184 mol) of 1,1,1-trimethylolpropane were added to the reaction mixture. The mixture was stirred for a further 13 hours at 153 ° C at a pressure of 6 mbar. When the acid number reached 14.5 mg KOH / g, the reaction was quenched by cooling to room temperature and venting. Hyperbranched polyester (c.17) was obtained in the form of a colorless clear solid. The analytical data are summarized in Table 1.

Table 1: Data on the hyperbranched polyesters (c.1) to (c.17) according to the invention

The OH number was determined according to DIN 53240, n.b .: not determined.

The molecular weight determination was performed by SEC (size exclusion chromatography) using an apparatus comprising a Merck / Hitachi pump (L-6200A) and four PSS-S DV-Styragel columns (10 ⁴ , 10 ³ , 500 and 100 Å) with THF as a mobile phase and a flow rate of 0.8 ml / min. The refractive index was determined using a Hewlett Packard HP1047A differential refractometer. To calibrate the columns in terms of molecular weights and molecular weight distribution polymethyl methacrylate standard samples (PMMA) was used (PSS, Mainz, Germany).

II. Preparation of Inventive Coating Materials (Varnishes) Using Hyperbranched Polyesters According to the Invention The ingredients (KL-1), (KL-2), (KL-3), hyperbranched polyester and solvent according to the invention were stirred together at room temperature according to Table 2. The paints (L-1), (L-2) according to the invention were obtained. and (L-3).

Preparation of the paints according to the invention:

(KL-1): isocyanurate of hexamethylene diisocyanate; 100%

(KL-2): isocyanurate of isophorone diisocyanate; 70% by weight in n-butyl acetate / solvesso

100 = 1: 2 (Degussa AG), solvesso: mixture of alkylaromatic Cs-Cio-hydrocarbons, for example ethylbenzene, isopropylbenzene, ethyltoluene (isomers),

naphthalene

(KL-3): biuret of hexamethylene diisocyanate; 100%

Table 2: Composition of the paints of the invention

The viscosity was adjusted to a flow time of approx. 20 s according to ISO 2431 and EN 535 in the DIN 4 cup.

Non-volatile components: 1 g of the paint mixture was dried for one hour at 125 ° C. in a circulating air oven and the residual weight was determined based on the initial value (= 100%).

To check the performance properties of the coatings of the invention were at room temperature in each case with a box doctor blade 180 microns wet doctored onto a plate as a substrate. The paint layer thickness after drying was about 40 microns. Then allowed to cure over a period of thirty minutes, each at room temperature, at 80 ° C or at 130 ° C. Test Methods:

The investigations of the coating properties were carried out after 24 hours of storage of the painted sheets in a climate chamber at 23 ° C and 50% relative humidity.

The paints according to the invention were clear and transparent after curing for 30 minutes at room temperature, at 80 ° C. and at 130 ° C.

Flow time: Measured based on ISO 2431 and EN 535 in DIN 4 cup at room temperature. Indicated is the period of time from the beginning of the outflow to the tearing of the liquid thread in seconds.

Table 3: Application tests on paints (L-1) to (L-3) according to the invention in the cured state

Acetone double-stroke test: Using an acetone-soaked cotton swab was rubbed by hand with double strokes until the varnish layer had rubbed through to the metal plate. The number of double strokes necessary for this is indicated. At one hundred strokes the experiment was stopped.

Erichsen cupping: cupping test according to DIN EN ISO 1520 in mm cupping.

Etching test with sulfuric acid: 25 .mu.l drops of 1% by weight aqueous sulfuric acid were placed on a gradient oven plate with a pipette and this was heated in a gradient oven at 30 to 75.degree. C. for 30 minutes. The sheet was then washed off with water and dried. Given is the lowest temperature at which the unaided eye was still an etching was observed. Adhesion with cross-hatching according to DIN 53151. The grade 0 denotes the top grade, the grade 5 the worst grade. See also Goldberg and Streitberger, BASF manual coating technology, Vincentz-Verlag Hannover, 2002, page 395.

Pendulum hardness according to König in number of vibrations based on DIN EN ISO 1522.

Scrub test, scratch resistance in the Scotch-Brite test: a nonwoven (Scotchbrite®, 7448 type S ultrafine) was attached to the top of a 500 g fitters hammer with double-sided adhesive tape. The hammer was held with two fingers on the end of the handle and moved with uniform double strokes without tilting and without additional pressure application on a line on the paint film back and forth. After 50 double strokes and after subsequent annealing for 60 minutes in a convection oven at 60 ° C (reflow) and storage for 4 h at ~ 23 ° C and -50% relative humidity, the gloss was determined across the scrub direction. The nonwoven fabric was replaced after each test with a new nonwoven fabric.

Gloss measurement: gloss meter Mikro TRI-Gloss at 60 ° angle of incidence.

Result of the application-technical investigations on lacquers according to the invention at a curing temperature of 80 ° C. or 130 ° C. (Table 3):

The coatings according to the invention (paints) showed in the cured state high hardness values (pendulum hardness) while at the same time having high elasticity (Erichsen depression).

These two paint properties are usually in opposite directions. In addition, excellent solvent resistance was already evident at temperatures above 80 ° C

Acetone test.

Claims

claims

1. Hyperbranched polyesters having an acid number in the range of 0.1 to 15 mg KOH / g

(a1) by polycondensation of at least one dicarboxylic acid or at least one derivative thereof with at least one at least trifunctional alcohol (s) or

(a3) by polycondensation of at least one dicarboxylic acid or at least one derivative thereof with a mixture of at least one

Diol and at least one at least trifunctional alcohol or

2. Hyperbranched polyesters according to claim 1, characterized in that they have a molecular weight M _n in the range of 500 to 50,000 g / mol.

3. Hyperbranched polyesters according to claim 1 or 2, characterized in that in variant (a1) at least trifunctional alcohols selected from glycerol,

1, 1, 1-trimethylolpropane, 1, 1, 1-trimethylolethane and pentaerythritol.

4. Hyperbranched polyesters according to any one of claims 1 to 3, characterized in that they have an OH number in the range of 100 to 700 mg KOH / g.

5. Hyperbranched polyesters according to any one of claims 1 to 4, characterized in that at least one used for its synthesis diol or at least one used for its synthesis at least trifunctional alcohol or at least one di- or polycabonic acid is cycloaliphatic.

6. A process for the preparation of hyperbranched polyesters according to any one of claims 1 to 5, characterized in that initially

(a3) by polycondensation of at least one dicarboxylic acid or one or more derivatives thereof with a mixture of at least one diol and at least one at least trifunctional alcohol or

produces a hyperbranched polyester (a) and then

(b) reacting with at least one mono-, di- or polyol (b1), at least one epoxide (b2) or at least one carbodiimide (b3),

until the acid number is a maximum of 15 mg KOH / g.

7. The method according to claim 6, characterized in that one uses as enzyme an enzyme.

8. The method according to claim 6, characterized in that the catalyst used is an acidic inorganic, organic or organometallic compound.

9. The method according to claim 6, characterized in that one works without catalyst sator.

10. The method according to any one of claims 6 to 9, characterized in that one uses in step (a1) or (a2) or (a3) or (a4) OH component and carboxyl component in such a ratio that the molar ratio of OH groups and COOH groups, free or derivatized, is in the range of 2: 1 to 1: 2.

1 1. Use of hyperbranched polyesters according to any one of claims 1 to 5 as or for the preparation of binders for coating compositions.

12. A process for the preparation of coating compositions using at least one hyperbranched polyester according to any one of claims 1 to 5.

13. Coating composition comprising at least one hyperbranched polyester according to any one of claims 1 to 5.

14. Use of hyperbranched polyesters according to any one of claims 1 to 5 as impact modifiers for thermoplastic polymers.

15. Modified hyperbranched polyester, obtainable by reacting a hyperbranched polyester according to any one of claims 1 to 5 with at least one isocyanate or a chloroformate, which carries at least one attached via a carbonate, urea or urethane group Polyalkylenoxidein- unit.