EP2222716A1 - Use of highly-branched polymers for producing polymer dispersions with improved freeze/thaw stability - Google Patents

Abstract

The invention relates to producing polymer dispersions with improved freeze/thaw stability by adding a highly-branched polymer thereto and the use of highly-branched polymers for the above.

Description

 Use of highly branched polymers to produce polymer dispersions with improved freeze / thaw stability

description

The present invention relates to a process for the preparation of polymer dispersions having improved freeze-thaw stability, in which a highly branched polymer is added thereto, and to the use of highly branched polymers for this purpose.

Aqueous polymer dispersions and paints based on such dispersions tend to lose desirable application properties when exposed to temperatures at which the contained water freezes. The ice crystals formed thereby lead to a concentration of the latex particles, first in the still remaining liquid and finally between the ice crystals. This can lead to undesirable formation of larger polymer particles through association or agglomeration and is usually associated with a significant increase in viscosity. Often thawing does not restore the original application properties. This leads to problems during storage, transport and processing of aqueous polymer dispersions and paints based thereon.

It is known to add antifreeze to polymer dispersions and latex paints to improve their tolerance to low temperatures. Suitable antifreeze are z. In Ullmann ^'s Encyclopedia of Industrial Chemistry, 5 ^th ed., Vol. A3, pp. 23-31. These are, among other things, higher-quality ones

Alcohols and alcohol ethers, such as ethylene glycol, diethylene glycol and propylene glycol. However, the use of such volatile organic hydrocarbons (VOC) that are slowly released from the paints to the environment is becoming increasingly undesirable. There is therefore a need for nonvolatile additives for polymer dispersions to improve freeze / thaw stability.

WO 2005/054384 describes a resin composition for aqueous paints which have a low content of volatile organic compounds (VOC content) and good freeze / thaw stability. These coating compositions contain an aqueous dispersion based on a multistage polymer which contains in copolymerized form a polymerizable alkoxylated surface-active compound.

It is not yet known to use highly branched polymers for the preparation of polymer dispersions with improved freeze / thaw stability. Such highly branched polymers are known as such and are also used in some cases as additives in the preparation of aqueous polymer dispersions. WO 00/29495 describes a coating composition containing a solvent, an alkyd resin (polyester resin) and a star polymer. The star polymers serve as modifiers to improve the application properties of the coating agent, for. B. to achieve a lower viscosity. They are derived from polyfunctional thiols which have at least three vinylically unsaturated side chains.

WO 01/9641 1 describes amphiphilic star polymers which have a mercaptan-based core and at least three polymer arms emanating therefrom, and the use of these star polymers for the stabilization of aqueous polymer dispersions.

WO 2004/016700 describes a water-based copolymer dispersion obtainable by copolymerization using at least one dendritic polymer functionalized with alkylene groups. The copolymer dispersions obtained in this way are characterized by improved "blocking properties." This document does not teach how to add a highly branched polymer to an aqueous polymer dispersion following emulsion polymerization, thus improving the freeze / thaw properties ,

WO 2005/003186 describes a process for the preparation of aqueous polymer dispersions based on copolymers which contain at least one hydrophilic allyl, vinyl, maleic or diene monomer in copolymerized form, the polymerization taking place in the presence of at least one dendritic polymer. The dendritic polymer also makes it possible to use highly hydrophobic monomers having a water solubility of less than 0.001 g / l for emulsion polymerization. The use of such dendritic polymers as an additive to polymer dispersions to improve their freeze / thaw stability has not been described.

Z. Xu and W.T. Ford describe in the Journal of Polymer Science: Part A: Polymer

Chemistry, Vol. 41, 597-605 (2003) and in Macromolecules 2002, 35, 7662-7668, polystyrene latexes obtained by aqueous emulsion polymerization in the presence of a dodecanamide derivative of a poly (propylene imine) dendrimer and of sodium dodecyl sulfate getting produced. C. Yi, Z. Xu and W. T. Fort describe in colloid. Polym. Be. (2004), 282, pp. 1054-1058, the preparation of poly (amidoamine) dendrimer / polystyrene composite latexes by emulsion polymerization according to the seed method.

The present invention is based on the object to provide aqueous polymer dispersions with improved freeze / thaw stability available. These should preferably have substantially unchanged application properties after a freeze / thaw load, such as a substantially unchanged viscosity, essentially unchanged particle sizes and / or particle size distributions. Preferably, it should preferably be dispensed with additives that increase the VOC content of the dispersions.

Surprisingly, it has been found that this object is achieved by the use of highly branched polymers.

A first subject of the invention is therefore a process for preparing an aqueous polymer dispersion PD) with improved freeze / thaw stability by free-radical emulsion polymerization of at least one α, ß-ethylenically unsaturated monomer M) and at least one highly branched polymer.

Another object of the invention is a binder composition consisting of or containing an aqueous polymer dispersion PD), at least one highly branched polymer and optionally at least one further film-forming polymer.

Another object of the invention is a coating composition in the form of an aqueous composition containing

a binder composition consisting of or containing an aqueous polymer dispersion PD), a highly branched polymer and optionally at least one further film-forming polymer,

optionally at least one inorganic filler and / or at least one inorganic pigment,

optionally further aids, and

Water.

Another object of the invention is the use of highly branched polymers as an additive for aqueous polymer dispersions to improve the freezing / thawing stability.

Another object of the invention is a method for improving the

Freeze / thaw stability of an aqueous polymer dispersion PD) obtainable by free-radical emulsion polymerization of at least one o-ethylenically unsaturated monomer M) by adding at least one highly branched polymer.

The addition of the highly branched polymer to the polymer dispersion PD) can be carried out before and / or during and / or after the emulsion polymerization for the preparation of PD). Preferably, the addition of the highly branched polymer takes place in the Conclusion of the emulsion polymerization. An addition after the emulsion polymerization also includes an addition in the context of the formulation of a product which contains an emulsion polymer based on at least one α, ß-ethylenically unsaturated monomer M). For this purpose, at least one highly branched polymer, as defined below, may be added as an additive, for example, to a paint. Another object of the invention is therefore the use of at least one hyperbranched polymer as an additive for a product containing an emulsion polymer based on at least one α, ß-ethylenically unsaturated monomer M), as defined below, to improve the freeze / thaw Stability of the product. Specifically, it is the use as an additive for a paint.

Another object of the invention is the use of an aqueous polymer dispersion PD), which contains at least one highly branched polymer as additive, as a component in paints.

Freeze / thaw stability is a parameter well known to those skilled in the art. The principle of the determination of the freeze-thaw stability can be taken from the standard ISO 1147. The determination of the freeze-thaw stability of aqueous polymer dispersions can be carried out according to ASTM D 2243-95 (reapproved 2003). Thereafter, the dispersion is placed for 17 hours in a cooling chamber at -18 ⁰ C and then allowed to stand for 7 hours at room temperature (23 ⁰ C), so that a freeze-thaw cycle of 24 hours results. Subsequently, one checks whether coagulation has occurred or not. If this is not the case, that is, the latex dispersion against coagulation was stable, the cycle described (cooling and thawing) is repeated and rechecked for coagulation. This freeze-thaw cycle is repeated until either coagulum formation is observed or a maximum of 5 cycles without coagulation is achieved.

The highly branched polymer is preferably added to the polymer dispersion PD) in an amount of from 0.1 to 20% by weight, more preferably from 0.2 to 15% by weight, in particular from 0.5 to 10% by weight, based on the total weight of hyperbranched polymer and polymer dispersion.

The use according to the invention of the highly branched polymers brings at least one of the following advantages:

substantially unchanged viscosity of the freeze / thaw loaded dispersion,

substantially unchanged particle sizes, particle size distribution of the freeze / thaw loaded dispersion, no or little coagulum formation in the freeze / thaw loaded dispersion,

Possibility of processing the dispersions also near freezing point,

good compatibility of the highly branched polymers used with a large number of dispersions,

an at least partial or complete elimination of antifreeze, associated with a reduction in the VOC content of the dispersions.

The determination of the viscosity may, for. B. according to DIN EN ISO 3219 at a temperature of 23 ⁰ C with a rotational viscometer, z. B. with a Brookfield viscometer model RVT performed, wherein z. For example, spindle # 5 is used at a revolution speed of 10 rpm, or spindle # 4 is used at a speed of 20 rpm.

The determination of the coagulum amount can, for. B. by filtration of the polymer dispersion after the freeze / thaw exposure through a sieve of certain mesh size (eg., 125 microns) take place.

According to the invention, at least one highly branched polymer is used to prepare the polymer dispersion PD). The term "highly branched polymers" in the context of this invention generally refers to polymers which are distinguished by a highly branched structure and a high functionality. For general definition of highly branched polymers, reference is also made to P. J. Flory, J. Am. Chem. Soc. 1952, 74, 2718, and H. Frey et al., Chem. Eur. J. 2000, 6, No. 14, 2499, incorporated herein by reference (as defined by the definition herein, as "hyperbranched polymers").

Among the highly branched polymers in the sense of the invention are star polymers, dendrimers, arborols and various highly branched polymers such as especially hyperbranched polymers.

Star polymers are polymers in which three or more chains originate from one center. The center can be a single atom or an atomic group.

Dendrimers are derived structurally from the star polymers, but the individual chains are in turn branched star-shaped. They arise from small molecules through a repetitive sequence of reactions, resulting in ever higher branches, at the ends of which functional groups are located, which in turn are the starting point for further branching. So grow along For each reaction step, the number of monomer end groups exponentially, resulting in an end, ideally spherical, tree structure at the end. A characteristic feature of dendrimers is the number of reaction stages (generations) carried out for their construction. Due to their uniform structure (ideally all branches contain exactly the same number of monomer units), dendrimers are essentially monodisperse, ie they generally have a defined molar mass.

Molecular, such as structurally uniform hyperbranched polymers are also referred to below as uniformly dendrimers.

"Hyperbranched polymers" in the context of this invention are highly branched polymers which, in contrast to the abovementioned dendrimers, are both molecularly and structurally nonuniform. They have side chains and / or side branches of different length and branching as well as a molecular weight distribution (polydispersity).

The highly branched polymers used according to the invention preferably have a degree of branching (DB) per molecule of from 10 to 100%, preferably from 10 to 90% and in particular from 10 to 80%. The degree of branching DB is defined as DB (%) = (T + Z) / (T + Z + L) × 100, with

T is the average number of terminal monomer units, Z is the mean number of branching monomer units, L is the average number of linearly bound monomer units.

Dendrimers generally have a degree of branching DB of at least 99%, especially 99.9 to 100%.

Hyperbranched polymers preferably have a degree of branching DB of 10 to 95%, preferably 25 to 90% and in particular 30 to 80%.

To achieve advantageous freeze / thaw properties, both the structurally and molecularly uniform dendrimers and also hyperbranched polymers can be used. Hyperbranched polymers, however, are generally simpler and thus more economical to produce than dendrimers. So z. For example, the preparation of the monodisperse dendrimers is complicated by the need to introduce and remove protecting groups at each linking step and to require intensive purification operations prior to the commencement of each new growth stage, which is why dendrimers can usually only be produced on a laboratory scale. Hyperbranched polymers with their molecular weight distribution can also have an advantageous effect on the viscosity properties of the dispersions modified with them. Hyperbranched polymers also have a more flexible structure than dendrimers.

Highly branched polymers are in principle suitable for those which are obtainable by polycondensation, polyaddition or by polymerization of ethylenically unsaturated compounds. Preference is given to polycondensates and polyaddition products. By polycondensation is meant the repeated chemical reaction of functional compounds with suitable reactive compounds with elimination of low molecular weight compounds such as water, alcohol, HCl, etc. By polyaddition is meant the repeated chemical reaction of functional compounds with suitable reactive compounds without cleavage of low molecular weight compounds.

Suitable polymers are those which have functional groups which are preferably selected from ether groups, ester groups, carbonate groups, amino groups, amide groups, urethane groups and urea groups.

In particular, as polymers polycarbonates, polyesters, polyethers, polyurethanes, polyureas, polyamines, polyamides, and their mixed forms, such as poly (urea urethanes), poly (etheramines), poly (esteramine), poly (etheramides), poly (esteramides), poly (amidoamines), poly (ester carbonates), poly (ether carbonates), poly (ether esters), poly (ether ester carbonates), etc. may be used.

Preferred hyperbranched polymers are those based on ethers, amines, esters, carbonates, amides and their mixed forms, such as, for example, ester amides, amidoamines, ester carbonates, ether carbonates, ether esters, ether ester carbonates, urea-urethanes, etc.

Hyperbranched polycarbonates, hyperbranched poly (ether carbonates), hyperbranched poly (ether esters), hyperbranched poly (ether ester carbonates), hyperbranched polyesters, hyperbranched polyethers, hyperbranched polyurethanes, hyperbranched poly (urea-urethanes), hyperbranched polyureas, hyperbranched polyamines, hyperbranched polyamides, hyperbranched polymers, hyperbranched poly (ether amines), hyperbranched poly (ester amines), hyperbranched poly (ether amides), hyperbranched poly (esteramides), and mixtures thereof. A specific embodiment of hyperbranched polymers are hyperbranched polycarbonates. Another specific embodiment of hyperbranched polymers are hyperbranched nitrogen atom-containing polymers, especially polyurethanes, polyureas, polyamides, poly (esteramide) s and poly (esteramine) s.

The hyperbranched polymer used is preferably a hyperbranched polycarbonate, poly (ether carbonate), poly (ester carbonate) or poly (etherester carbonate) or a mixture hyperbranched polymers containing at least one hyperbranched polycarbonate, poly (ether carbonate), poly (ester carbonate) or poly (etherestercarbonat) used.

Hyperbranched polymers suitable for use according to the invention and processes for their preparation are described in the following documents, to which reference is made in full:

highly branched and especially hyperbranched polycarbonates according to WO 2005/026234, hyperbranched polyesters according to WO 01/46296, DE 101 63 163, DE 102 19 508 or DE 102 40 817, hyperbranched polyethers according to WO 03/062306, WO 00/56802, DE 102 1 1 664 or DE 199 47 631, - hyperbranched nitrogen-containing polymers (especially polyurethanes, polyureas, polyamides, poly (esteramides), poly (esteramines)), as in

WO 2006/087227, hyperbranched polyurethanes according to WO 97/02304 or DE 199 04 444, hyperbranched poly (urea-urethanes) according to WO97 / 02304 or DE 199 04 444, hyperbranched polyureas as described in WO 03/066702, WO 2005/044897 and US Pat

WO 2005/075541, hyperbranched amino group-containing polymers, especially polyesteramines according to WO 2005/007726, - hyperbranched poly (esteramides) according to WO 99/16810 or EP 1 036 106, hyperbranched polyamides as described in WO 2006/018125, hyperbranched poly ( estercarbonates) as described in WO 2006/089940.

Preference is given to polymers which have a weight-average molecular weight M _w in the range from about 500 to 500,000, preferably 750 to 200,000, in particular 1,000 to

100 000 g / mol. The molar mass determination can be carried out by gel permeation chromatography with a standard such. As polymethyl methacrylate, take place.

In the context of the present invention, the term alkyl includes straight-chain and branched alkyl groups. Suitable short-chain alkyl groups are, for. B. straight-chain or branched Ci-Cz-alkyl, preferably d-Cε-alkyl and particularly preferably Ci-C4-alkyl groups. These include in particular methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl , 1, 1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2 , 3-dimethylbutyl, 1, 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, 1-ethyl-2-methylpropyl, n-heptyl, 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, etc.

Suitable longer-chain Cs-Cso-alkyl groups are straight-chain and branched alkyl groups. These are preferably predominantly linear alkyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include z. N-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, etc The term alkyl includes unsubstituted and substituted alkyl radicals.

The above comments on alkyl also apply to the alkyl moieties in arylalkyl. Preferred arylalkyl radicals are benzyl and phenylethyl.

C 8 -C 32 -alkenyl in the context of the present invention represents straight-chain and branched alkenyl groups which may be mono-, di- or polyunsaturated. Preferably, it is Cio-C2o-alkenyl. The term alkenyl includes unsubstituted and substituted alkenyl radicals. Specifically, these are predominantly linear alkenyl radicals, as they also occur in natural or synthetic fatty acids and fatty alcohols and oxo alcohols. These include, in particular, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, linolyl, linolenyl, eleostearyl and oleyl (9-octadecenyl).

The term alkylene in the context of the present invention stands for straight-chain or branched alkanediyl groups having 1 to 7 carbon atoms, eg. As methylene, 1, 2-ethylene, 1, 3-propylene, etc.

Cycloalkyl is preferably C4-C6-cycloalkyl, such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

The term aryl in the context of the present invention comprises mononuclear or polynuclear aromatic hydrocarbon radicals which may be unsubstituted or substituted. The term aryl is preferably phenyl, ToIyI, XyIyI, mesityl, Duryl, naphthyl, fluorenyl, anthracenyl, phenanthrenyl or naphthyl, particularly preferably phenyl or naphthyl, said aryl groups in the case of a substitution generally 1, 2, 3, 4 or 5, preferably 1, 2 or 3 substituents can carry.

For the synthesis of hyperbranched polymers suitable for use in the process according to the invention, in particular so-called AB _X monomers are suitable. These have two different functional groups A and B, which can react with each other to form a linkage. The functional group A is included only once per molecule and the functional group B two or more times (eg AB2 or AB3 monomers). On the one hand, the AB _X monomers can be incorporated completely in the form of branches into the hyperbranched polymer, they can be incorporated as terminal groups, thus still have x free B groups, and they can be linear groups with (x-1) free B groups are incorporated. Depending on the degree of polymerization, the hyperbranched polymers obtained have a greater or lesser number of B groups, either terminal or as side groups. For details, see, for example, Journal of Molecular Science, Rev. Macromol. Chem. Phys., C37 (3), 555-579 (1997).

The hyperbranched polymers used according to the invention preferably have carbonate groups in the case of hyperbranched polycarbonates, hyperbranched polyurethanes urethane and / or urea groups or further groups resulting from the reaction of isocyanate groups, hyperbranched polyamides Amide groups, etc.) at least four further functional groups. The maximum number of these functional groups is usually not critical. However, it is often not more than 100. Preferably, the proportion of functional groups is 4 to 100, especially 5 to 80, and more particularly 6 to 50.

The other terminal functional groups which have the hyperbranched polymers used according to the invention are, for. B. independently selected from -OC (= O) OR, -COOH, -COOR, -CONH ₂ , -CONHR, -OH, -NH ₂ , -NHR or -SO ₃ H. With OH, COOH and / or -OC (= O) OR-terminated hyperbranched polymers have been found to be particularly advantageous.

Hyperbranched polycarbonates

For example, hyperbranched polycarbonates suitable for use in improving freeze / thaw stability can be prepared by

a) reacting at least one organic carbonate (A) of the general formula R ^a OC (= O) OR ^b with at least one aliphatic alcohol (B) which has at least three OH groups, with elimination of alcohols R ³ OH or R ^b OH to one or more condensation products (K), wherein R ^a and R ^{b are} each independently selected from among straight-chain or branched alkyl, arylalkyl, cycloalkyl and aryl radicals, where R ^a and R ^{b are} also taken together with the group -OC ( = O) O- to which they are attached may represent a cyclic carbonate,

b) intermolecular conversion of the condensation products (K) into a highly functional, hyperbranched polycarbonate, wherein the quantitative ratio of the OH groups to the carbonates in the reaction mixture is selected so that the condensation products (K) have on average either a carbonate group and more than one OH group or one OH group and more than one carbonate group. The radicals R ^a and R ^b may have the same or different meanings. In a specific embodiment, R ^a and R ^{b have the} same meanings. Preferably, R ^a and R ^{b are} selected from C 1 -C 20 -alkyl, C 5 -C 7 -cycloalkyl, Cβ-do-Aryl and C 6 -C 10 -aryl-C 1 -C 20 -alkyl, as defined above. R ^a and R ^b may also together represent a C 2 -C 6 -alkylene group. R ^a and R ^b are particularly preferably selected from straight-chain and branched C 1 -C 5 -alkyl, as defined above.

Dialkyl or diaryl carbonates may, for. Example, be prepared from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalko- get with phosgene. Furthermore, they can also be prepared via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO _x . For preparation methods of diaryl or dialkyl carbonates, see also "Ullmann's Encyclopedia of Industrial Chemistry", 6 ^th Edition, 2000 Electronic Release, Verlag Wiley-VCH.

Examples of suitable carbonates include aliphatic or aromatic carbonates, such as ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, Dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, diheptyl carbonate, di-octyl carbonate, didecylacarbonate and didodecyl carbonate.

Aliphatic carbonates are preferably used, in particular those in which the radicals comprise 1 to 5 carbon atoms, such as. For example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.

The organic carbonates are reacted with at least one aliphatic alcohol (B) which has at least three OH groups or mixtures of two or more different alcohols.

Examples of compounds having at least three OH groups are glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, Bis (trimethylolpropane), di (pentaerythritol), di-tri- or oligoglycerols, or sugars, such as. As glucose, tri- or higher functional polyetherols based on tri- or higher functional alcohols and ethylene oxide, propylene oxide or butylene oxide, or polyesterols. Glycerol, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, pentaerythritol, as their polyethers based on ethylene oxide or propylene oxide is particularly preferred.

These polyhydric alcohols can also be used in mixture with difunctional alcohols (B '), with the proviso that the average OH functionality of all the alcohols used together is greater than 2. Examples of suitable compounds having two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2 and 1, 3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol, 1, 2-, 1, 3- and 1, 5-pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, difunctional polyether or polyesterols.

The reaction of the carbonate with the alcohol or alcohol mixture to the highly functional hyperbranched polycarbonate used according to the invention takes place with elimination of the monofunctional alcohol or phenol from the carbonate molecule.

The highly functional hyperbranched polycarbonates formed by the process described are terminated after the reaction, ie without further modification, with hydroxyl groups and / or with carbonate groups. They dissolve well in various solvents, eg. Example in water, alcohols, such as methanol, ethanol, butanol, alcohol / - water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, Methoxypropylace- tat, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate ,

In the context of this invention, a highly functional polycarbonate is to be understood as meaning a product which, in addition to the carbonate groups which form the polymer backbone, also has at least four, preferably at least eight, functional groups at the end or at the side. The functional groups are carbonate groups and / or OH groups. In principle, the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility. The high-functionality polycarbonates of the present invention generally have not more than 500 terminal or pendant functional groups, preferably not more than 100, in particular not more than 50 terminal or pendant functional groups.

In the preparation of the high-functionality polycarbonates, it is necessary to adjust the ratio of the compounds containing OH groups to the carbonate so that the resulting simplest condensation product (referred to hereinafter as condensation product (K)) has on average either one carbonate group and more than one OH group. Contains group or an OH group and more than one carbonate group. The simplest structure of the condensation product (K) from a carbonate (A) and a di- or polyalcohol (B) results in the arrangement XY _n or YX _n , where X is a carbene Y is a hydroxyl group and n is generally a number between 1 and 6, preferably between 1 and 4, particularly preferably between 1 and 3. The reactive group, which thereby results as a single group, is generally referred to below as the "focal group".

If, for example, in the preparation of the simplest condensation product (K) from a carbonate and a dihydric alcohol, the reaction ratio is 1: 1, the average results in a molecule of the type XY, illustrated by the general formula 1.

In the preparation of the condensation product (K) from a carbonate and a trihydric alcohol at a conversion ratio of 1: 1 results in the average molecule of the type XY2, illustrated by the general formula 2. Focal group here is a carbonate group.

In the preparation of the condensation product (K) from a carbonate and a tetrahydric alcohol also with the conversion ratio 1: 1 results in the average, a molecule of the type XY3, illustrated by the general formula 3. Focal group here is a carbonate group.

In the formulas 1 to 3, R has the meaning defined above and R ¹ is an aliphatic radical.

Furthermore, the preparation of the condensation product (K) z. B. also from a carbonate and a trihydric alcohol, illustrated by the general formula 4, take place, wherein the molar conversion ratio is 2: 1. This results in the average molecule of type X2Y, focal group here is an OH group. In the formula 4, R and R ^{1 have} the same meaning as in the formulas 1 to 3.

Are the components additionally difunctional compounds, eg. For example, given a dicarbonate or a diol, this causes an extension of the chains, as illustrated for example in the general formula 5. The result is again on average a molecule of the type XY2, focal group is a carbonate group.

In formula 5, R ^{2 is} an organic, preferably aliphatic radical, R and R ¹ are defined as described above.

The simple condensation products (K) described by way of example in the formulas 1 to 5 preferably react according to the invention intermolecularly to form highly functional polycondensation products, referred to below as polycondensation products (P). The reaction to give the condensate (K) and the polycondensation densationsprodukt (P) is usually carried out at a temperature of 0 to 250 ^° C, preferably at 60 to 160 ⁰ C in bulk or in solution. In general, all solvents can be used which are inert to the respective starting materials. Preference is given to using organic solvents, such as. As decane, dodecane, benzene, toluene, chlorobenzene, XyIoI, dimethylformamide, dimethylacetamide or solvent naphtha.

In a preferred embodiment, the condensation reaction is carried out in bulk. The monofunctional alcohol ROH or phenol liberated in the reaction can be removed from the reaction equilibrium by distillation, optionally under reduced pressure, to accelerate the reaction.

If removal by distillation is intended, it is generally advisable to use those carbonates te, which during the implementation of alcohols ROH with a boiling point of less than 140 ⁰ C. To accelerate the reaction, it is also possible to add catalysts or catalyst mixtures. Suitable catalysts are compounds which catalyze esterification or transesterification reactions, e.g. For example, alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, preferably of sodium, potassium or cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, titanium, zirconium or bismuth organic compounds, continue so called double metal cyanide (DMC) catalysts, such as. B. in DE 10138216 or DE 10147712 described.

Preference is given to potassium hydroxide, potassium carbonate, potassium bicarbonate, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles, such as imidazole, 1-methylimidazole or 1,2-dimethylimidazole, titanium tetrabutylate, titanium tetraisopropylate, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, Zirconium acetylacetonate or mixtures thereof.

The addition of the catalyst is generally carried out in an amount of 50 to 10,000, preferably from 100 to 5000 ppm by weight, based on the amount of the alcohol or alcohol mixture used.

Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, the average molecular weight of the polymer (P) can be adjusted via the composition of the starting components and over the residence time.

The condensation products (K) or the polycondensation products (P), which were prepared at elevated temperature, are usually stable at room temperature for a longer period.

Due to the nature of the condensation products (K), it is possible that the condensation reaction may result in polycondensation products (P) having different structures that have branches but no crosslinks. Furthermore, the polycondensation products (P) ideally have either a carbonate group as a focal group and more than two OH groups or an OH group as a focal group and more than two carbonate groups. The number of reactive groups results from the nature of the condensation products used (K) and the degree of polycondensation.

For example, a condensation product (K) according to the general formula 2 by three-fold intermolecular condensation to two different polycondensation onsprodukten (P), which are represented in the general formulas 6 and 7, react.

In formulas 6 and 7, R and R ^{1 are} as defined above.

There are various possibilities for stopping the intermolecular polycondensation reaction. For example, the temperature can be lowered to a range in which the reaction comes to a standstill and the product (K) or the polycondensation product (P) is storage-stable.

In a further embodiment, as soon as a polycondensation product (P) with the desired degree of polycondensation is present due to the intermolecular reaction of the condensation product (K), the product (P) to terminate the reaction is added to a product having groups which are reactive towards the focal group of (P) - the. Thus, in a carbonate group as a focal group z. As a mono-, di- or polyamine are added. In the case of a hydroxyl group as the focal group, the product (P) may be added with, for example, a mono-, di- or polyisocyanate, an epoxy group-containing compound or an OH group-reactive acid derivative.

The preparation of the high-functionality polycarbonates according to the invention is usually carried out in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades which are operated batchwise, semicontinuously or continuously.

By the aforementioned adjustment of the reaction conditions and optionally by the choice of the appropriate solvent, the products can be further processed after preparation without further purification. In a further preferred embodiment, the polycarbonates, in addition to the functional groups already obtained by the reaction, can be given further functional groups. The functionalization can take place during the molecular weight build-up or else subsequently, ie after the end of the actual polycondensation.

If, before or during the molecular weight build-up, components which have other functional groups or functional groups in addition to hydroxyl or carbonate groups are obtained, a polycarbonate polymer having randomly distributed functionalities other than the carbonate or hydroxyl groups is obtained.

Such effects can be z. B. by addition of compounds during the polycondensation, in addition to hydroxyl or carbonate groups further functional groups or functional elements, such as mercapto, primary, secondary or tertiary amino groups, ether groups, derivatives of carboxylic acids, derivatives of sulfonic acids, derivatives of phosphonic acids , Aryl radicals or long-chain alkyl radicals. For modification by means of carbamate groups, for example, ethanolamine, propanolamine, isopropanolamine, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2-amino-1-butanol, 2- (2'-aminoethoxy) ethanol or higher can be used Alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine,

Diethanolamine, dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane, tris (hydroxyethyl) aminomethane, ethylenediamine, propylenediamine, hexamethylenediamine or isophoronediamine.

For the modification with mercapto groups can be z. As mercaptoethanol or thioglycerol. Tertiary amino groups can be z. B. by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine produce. Ether groups may, for. B. by condensation of di- or higher-functional polyetherols are generated. Long-chain alkyl radicals can be introduced by reaction with long-chain alkanediols, the reaction with alkyl or aryl diisocyanates generates polycarbonates having alkyl, aryl and urethane groups.

Subsequent functionalization can be obtained by reacting the resulting highly functional, hyperbranched polycarbonate with a suitable functionalizing reagent which can react with the OH and / or carbonate groups of the polycarbonate.

Hydroxyl-containing high-functionality, hyperbranched polycarbonates may, for. B. be modified by the addition of molecules containing acid groups or isocyanate groups. For example, polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups. Furthermore, hydroxyl-containing high-functionality polycarbonates by reaction with alkylene oxides, for. For example, ethylene oxide, propylene oxide or butylene oxide are converted into highly functional polycarbonate polyether polyols.

A great advantage of the method according to the invention lies in its economy. Both the conversion to a condensation product (K) or polycondensation product (P) and the reaction of (K) or (P) to polycarbonates with other functional groups or elements can be carried out in a reaction apparatus, which is technically and economically advantageous.

Hyperbranched polyester

Preferably, as hyperbranched polyesters such by A2B _X type. Particularly preferred are hyperbranched polyesters from A2B3-TVP. These have a less rigid structure than hyperbranched AB2-type polyesters. Therefore, hyperbranched AB2-type polyesters are less preferred. Hyperbranched polyesters suitable for use in improving freeze-thaw stability are obtainable by reacting at least one aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid (A2) or derivatives thereof

a) at least one at least trifunctional aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (B3), or

b) with at least one divalent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (B2) having at least one x-valent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (C _x ) having more than two OH groups, where x is a number greater 2, preferably 3 to 8, particularly preferably 3 to 6, very particularly preferably 3 to 4 and in particular 3,

or by reacting at least one aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid (D _y ) or derivatives thereof which has more than two acid groups, where y is a number greater than 2, preferably 3 to 8, particularly preferably 3 to 6, very particularly preferably 3 to 4 and in particular 3 is, with

c) at least one at least difunctional aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (B2), or

d) with at least one divalent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (B2) with at least one x-valent aliphatic, cycloaliphatic, araliphatic or aromatic alcohol (C _x ), the has more than two OH groups, where x is a number greater than 2, preferably 3 to 8, particularly preferably 3 to 6, very particularly preferably 3 to 4 and in particular 3,

e) optionally in the presence of further functionalized units E and

f) optionally subsequent reaction with a monocarboxylic acid F,

wherein the ratio of the reactive groups in the reaction mixture is selected so that a molar ratio of OH groups to carboxyl groups or derivatives thereof of 5: 1 to 1: 5, preferably from 4: 1 to 1: 4, particularly preferably from 3: 1 to 1: 3 and most preferably from 2: 1 to 1: 2 sets.

Hyperbranched polyesters in the context of this invention are understood as meaning uncrosslinked polyesters having hydroxyl and carboxyl groups which are structurally as well as molecularly nonuniform. Uncrosslinked in the context of this document means that a degree of crosslinking of less than 15% by weight, preferably less than 10% by weight, determined by the insoluble fraction of the polymer, is present. The insoluble portion of the polymer was determined by extraction for four hours with the same solvent as used for gel permeation chromatography, ie, tetrahydrofuran or hexafluoroisopropanol, depending on the solvent in which the polymer is more soluble, in a Soxhlet apparatus and drying the residue until to constant weight and weighing the residue.

The dicarboxylic acids (A2) include, for example, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 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- and trans-cyclopentane-1,2-dicarboxylic acid, cis- and trans-cyclopentane-1,3-dicarboxylic acid. Furthermore, aromatic dicarboxylic acids, such as. For example, phthalic acid, isophthalic acid or terephthalic acid. It is also possible to use unsaturated dicarboxylic acids, such as maleic acid or fumaric acid.

The dicarboxylic acids mentioned can also be substituted by one or more radicals selected from C 1 -C 10 -alkyl groups, C 3 -C 12 -cycloalkyl groups, alkylene groups such as methylene or ethylidene or C 6 -C 14 -aryl groups. Examples which may be mentioned of substituted dicarboxylic acids are: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid, 3,3-dimethylglutaric acid. Furthermore, mixtures of two or more of the aforementioned dicarboxylic acids can be used.

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

In particular, C 1 -C 4 -alkyl is methyl, ethyl, isopropyl, n-propyl, n-butyl, isobutyl, sec-butyl and tert-butyl, preferably methyl, ethyl and n-butyl, particularly preferably methyl and ethyl, and most preferably methyl.

It is also possible to use a mixture of a dicarboxylic acid and one or more of its derivatives. Likewise, it is possible to use a mixture of several different derivatives of one or more dicarboxylic acids.

Particular preference is given to using malonic acid, succinic acid, glutaric acid, adipic acid, 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid (hexahydrophthalic acids), phthalic acid, isophthalic acid, terephthalic acid or their mono- or dialkyl esters.

Examples of convertible tricarboxylic acids or polycarboxylic acids (D _y ) are aconitic acid, 1,3,5-cyclohexanetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid ( Pyromellitic acid) as well as mellitic acid and low molecular weight polyacrylic acids.

Tricarboxylic acids or polycarboxylic acids (D _y ) can be used either as such or in the form of derivatives.

Derivatives are the relevant anhydrides in monomeric or else polymeric form, mono- or dialkyl esters, preferably mono- or di-C 1 -C 4 -alkyl esters, particularly preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, also mono- and divinyl esters and mixed esters, preferably mixed esters with different C 1 -C 4 -alkyl components, particularly preferably mixed methyl ethyl esters.

It is also possible to use a mixture of a tri- or polycarboxylic acid and one or more of their derivatives, for. B. a mixture of pyromellitic acid and pyromellitic dianhydride. Likewise, it is possible to use a mixture of several different derivatives of one or more tri- or polycarboxylic acids, for. Example, a mixture of 1, 3,5-cyclohexane tricarboxylic acid and pyromellitic dianhydride.

The diols (B2) used are, for example, 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, 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, 2-decanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1, 12th -Dodecandiol, 1, 5-hexadiene-3,4-diol, 1, 2 and 1, 3-cyclopentanediols, 1, 2, 1, 3 and 1, 4-cyclohexanediols, 1, 1, 1, 2 -, 1, 3 and 1, 4-bis (hydroxymethyl) cyclohexanes, 1, 1, 1, 2, 1, 3 and

1, 4-bis (hydroxyethyl) cyclohexanes, neopentyl glycol, (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, tripropylene glycol, polyethylene glycols HO (CH 2 CH 2 O) _n -H or polypropylene glycols HO (CI) I [CI-I ₃ ] CI-I ₂ O) _n -II, where n is an integer and n> 4, polyethylene glycols, where the sequence of the ethylene oxide or propylene oxide units can be blockwise or random, polytetramethylene glycols, preferably up to a molecular weight of up to 5000 g / mol, poly-1,3-propanediols, preferably having a molecular weight of up to 5000 g / mol, polycaprolactones or mixtures of two or more representatives of the above compounds. It can be one or both

Hydroxyl groups in the aforementioned diols are substituted by SH groups. Preferably used diols are ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2, 1, 3 - And 1, 4-cyclohexanediol, 1, 3- and 1, 4-bis (hydroxymethyl) cyclohexane, and diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol polyethylene glycols

HO (CH ₂ CH ₂ O) _n -H or polypropylene glycols HO (CH [CH ₃ ] CH ₂ O) _n -H, where n is an integer and n> 4, polyethylene-polypropylene glycols, the sequence being ethylene oxide and propylene oxide Units may be blockwise or random, or polytetramethylene glycols. The molecular weight of the polyalkylene glycols is preferably up to 5000 g / mol.

The dihydric alcohols B ₂ may optionally contain other functionalities such as carbonyl, carboxy, alkoxycarbonyl or sulfonyl functions, such as dimethylolpropionic acid or dimethylol butyric acid, and their Ci-C4-alkyl esters, glycerol monostearate or glycerol monooleate.

At least trifunctional alcohols (C _x ) include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, diglycerol, triglycerol or higher condensation products of glycerol, di (trimethylolpropane),

Di (pentaerythritol), trishydroxymethylisocyanurate, tris (hydroxyethyl) isocyanurate (THEIC), tris (hydroxypropyl) isocyanurate, inositols or sugars, such as e.g. As glucose, fructose or sucrose, sugar alcohols such. B. sorbitol, mannitol, threitol, erythritol, adonite (ribitol), arabitol (Lyxit), XyNt, Dulcit (galactitol), maltitol, isomalt, tri- or higher polyethers based on tri- or higher functional alcohols and ethylene oxide, propylene oxide and / or butylene oxide. In this case, glycerol, diglycerol, triglycerol, trimethylolethane, trimethylolpropane, bis (trimetylolpropane), 1, 2,4-butanetriol, pentaerythritol, di (penterythrit), tris (hydroxyethyl) isocyanurate and their polyetherols based on ethylene oxide and / or propylene oxide are particularly preferred ,

The reaction can be carried out in the presence or absence of a solvent. Suitable solvents are, for example, hydrocarbons such as paraffins, aromatics, ethers and ketones. Preferably, the reaction is carried out free of solvent. The reaction can be carried out in the presence of a dehydrating agent as an additive, which is added at the beginning of the reaction. Suitable examples are molecular sieves, in particular 4 Å molecular sieve, and also MgSO ₄ and Na ₂ SO ₄ . It is also possible to distill off water or alcohol formed during the reaction and, for example, to use a water separator in which the water is removed by means of an entraining agent.

You can carry out the reaction in the absence of catalysts. However, it is preferable to work in the presence of at least one catalyst. These are preferably acidic inorganic, organometallic or organic catalysts or mixtures of several acidic inorganic, organometallic or organic catalysts.

Examples of acidic inorganic catalysts for the purposes of the present invention include sulfuric acid, sulfates and hydrogen sulfates, such as sodium hydrogensulfate, 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 Al (OR ¹ ) 3 and titanates can be used. Preferred acidic organometallic catalysts are, for example, dialkyltin oxides or dialkyltin esters. Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. It is also possible to use acidic ion exchangers as acidic organic catalysts.

The reaction is carried out at temperatures of 60 to 250 ⁰ C.

The hyperbranched polyesters used according to the invention have a molecular weight M w of at least 500, preferably at least 600 and particularly preferably 1000 g / mol. The upper limit of the molecular weight M _w is preferably 500,000 g / mol, more preferably not more than 200,000 and most preferably not more than 100,000 g / mol.

The information on the polydispersity and the number average and weight average molecular weight M _n and M w relate here to gel permeation chromatography Measurements using polymethylmethacrylate as standard and tetrahydrofuran, dimethylformamide, dimethylacetamide or hexafluoroisopropanol as eluent. The method is described in the Analyst Taschenbuch Vol. 4, pages 433 to 442, Berlin 1984.

The polydispersity of the polyesters used according to the invention is generally from 1.2 to 50, preferably from 1.4 to 40, particularly preferably from 1.5 to 30 and very particularly preferably from 2 to 30.

Hyperbranched polyurethanes

The term "polyurethanes" in the context of this invention includes, beyond the usual understanding, polymers which can be obtained by reacting di- or polyisocyanates with compounds having active hydrogen, and which are prepared by urethane but also, for example, by urea, allophanate , Biuret, carbodiimide, amide, uretonimine, uretdione, isocyanurate or oxazolidone structures.

For the synthesis of the hyperbranched polyurethanes used according to the invention, it is possible to use AB _X monomers which have both isocyanate groups and groups which can react with isocyanate groups to form a linkage. To synthesize the hyperbranched polyurethanes used according to the invention, it is also possible to use monomer combinations which initially form intermediate ABχ building blocks, where x is a natural number between 2 and 8, preferably 2 or 3. Such hyperbranched polyurethanes and processes for their preparation are described in WO 97/02304, which is incorporated herein by reference. Suitable hyperbranched polyurethanes can also be obtained by reacting diisocyanates and / or polyisocyanates with compounds having at least two isocyanate-reactive groups, wherein at least one of the reactants has functional groups with different reactivity with respect to the other reactant and the reaction conditions are selected such that At each reaction step, only certain reactive groups react with each other. Such hyperbranched polyurethanes and processes for their preparation are described in EP 1026185, which is incorporated herein by reference.

The groups reactive with the isocyanate groups are preferably OH, NH ₂ , NHR or SH groups.

The ABχ monomers can be prepared in a known manner. For example, AB _X monomers can be synthesized according to the method described in WO 97/02304 using protective group techniques. An example of this technique is the preparation of an AB 2 monomer from 2,4-tolylene diisocyanate (TDI) and triamine. methylolpropane explained. First, one of the isocyanate groups of the TDI is capped in a known manner, for example by reaction with an oxime. The remaining free NCO group is reacted with trimethylolpropane, wherein only one of the three OH groups reacts with the isocyanate group, while two OH groups are blocked by acetalization. After cleavage of the protecting group, a molecule having an isocyanate group and 2 OH groups is obtained.

Particularly advantageously, the AB _X molecules can be synthesized by the method described in DE-A 199 04 444, in which no protective groups are required. In this method di- or polyisocyanates are used and reacted with compounds having at least two isocyanate-reactive groups. At least one of the reactants in this case has groups with respect to the other reactants of different reactivity. Preferably, both reactants have groups with different reactivity than the other reactant. The reaction conditions are chosen so that only certain reactive groups can react with each other.

Suitable di- and polyisocyanates are the aliphatic, cycloaliphatic and aromatic isocyanates known from the prior art. Preferred di- or polyisocyanates are 4,4'-diphenylmethane diisocyanate, the mixtures of monomeric diphenylmethane diisocyanates and oligomeric diphenylmethane diisocyanates (polymer-MDI), tetramethylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis (cyclohexyl) diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate , Dodecyl diisocyanate, lysine alkyl ester diisocyanate, where alkyl is C 1 -C 10 -alkyl, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1,4-diisocyanatocyclohexane or 4-isocyanatomethyl-1, 8-octamethylene diisocyanate.

Particularly preferred are di- or polyisocyanates with NCO groups of different reactivity, such as 2,4-tolylene diisocyanate (2,4-TDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), triisocyanatotoluene, isophorone diisocyanate (IPDI), 2-butyl-2-ethylpentamethylene diisocyanate, 2-isocyanatopropylcyclohexyl isocyanate, 3 (4) isocyanatomethyl-1-methylcyclohexylisocyanate, 1,4-diisocyanato-4-methylpentane, 2,4'-methylenebis (cyclohexyl) diisocyanate and Methylcyclohexane-1,3-diisocyanate (H-TDI). Furthermore, particular preference is given to isocyanates (b) whose NCO groups are initially identically reactive, but in which a drop in reactivity in the second NCO group can be induced by initial addition of an alcohol or amine to an NCO group. Examples are isocyanates whose NCO groups are coupled via a delocalized electron system, e.g. B. 1, 3- and 1, 4-phenylene diisocyanate, 1, 5-naphthylene diisocyanate, diphenyl diisocyanate, tolidine diisocyanate or 2,6-toluene diisocyanate.

It is also possible, for example, to use oligoisocyanates or polyisocyanates which are obtained from the diisocyanates or polyisocyanates mentioned or mixtures thereof by urethane, allophanate, urea, biuret, uretdione, amide, isocyanurate, carbodiimide, uretonimine, oxadiazinetrione or iminooxadiazinedione structures.

As compounds having at least two isocyanate-reactive groups it is preferred to use di-, tri- or tetra-functional compounds whose functional groups have a different reactivity with respect to NCO groups. Preference is given to compounds having at least one primary and at least one secondary hydroxyl group, at least one hydroxyl group and at least one mercapto group, particularly preferably having at least one hydroxyl group and at least one amino group in the molecule, in particular amino alcohols, amino diols and aminotrioles, since the reactivity of the amino group relative to the hydroxyl group at the reaction with isocyanate is significantly higher.

Examples of the stated compounds having at least two isocyanate-reactive groups are propylene glycol, glycerol, mercaptoethanol, ethanolamine, N-methylethanolamine, diethanolamine, ethanolpropanolamine, dipropanolamine, diisopropanolamine, 2-amino-1,3-propanediol, 2-amino-2 -methyl-1,3-propanediol or tris (hydroxymethyl) aminomethane. Furthermore, mixtures of the compounds mentioned can be used.

The preparation of an AB 2 molecule is illustrated by way of example for the case of a diisocyanate with an amino diol. Here, first, one mole of a diisocyanate with one mole of an aminodiol at low temperatures, preferably in the range between -10 to 30 ⁰ C, implemented. In this temperature range, a virtually complete suppression of the urethane formation reaction takes place and the more reactive NCO groups of the isocyanate react exclusively with the amino group of the aminodiol. The formed AB _X molecule has a free NCO group and two free OH groups and can be used for the synthesis of a hyperbranched polyurethane.

By heating and / or catalyst addition, this AB2 molecule can intermolecularly react to form a hyperbranched polyurethane. The synthesis of the hyperbranched polyurethane can be carried out advantageously without prior isolation of the AB _X molecule in a further reaction step at elevated temperature, preferably in the range between 30 and 80 ⁰ C. When using the described AB ² molecule with two OH groups and one NCO Group is a hyperbranched polymer, which per molecule has a free NCO group and - depending on the degree of polymerization - a more or less large number of OH groups. The reaction can be carried out to high conversions, resulting in very high molecular structures. However, it can also be prepared, for example, by adding suitable monofunctional compounds or by adding one of the starting compounds to the preparation. abort the AB2 molecule when reaching the desired molecular weight. Depending on the starting compound used for termination, either completely NCO-terminated or completely OH-terminated molecules are formed.

Alternatively, for example, an AB2 molecule can also be prepared from one mole of glycerol and two moles of 2,4-TDI. At low temperature, preferably the primary alcohol groups and the isocyanate group react in the 4-position and an adduct is formed which has one OH group and two isocyanate groups and which can be reacted as described at higher temperatures to form a hyperbranched polyurethane. The result is first a hyperbranched polymer which has a free OH group and - depending on the degree of polymerization - a more or less large number of NCO groups.

The preparation of the hyperbranched polyurethanes can in principle be carried out without solvents, but preferably in solution. All solvents which are liquid at the reaction temperature and inert to the monomers and polymers are suitable as solvents.

Other products are accessible through further synthetic variants. AB3 molecules can be obtained, for example, by reaction of diisocyanates with compounds having at least 4 isocyanate-reactive groups. By way of example, the reaction of 2,4-tolylene diisocyanate with tris (hydroxymethyl) aminomethane may be mentioned.

To terminate the polymerization, it is also possible to use polyfunctional compounds which can react with the respective A groups. In this way, several small hyperbranched molecules can be linked to form a large hyperbranched molecule.

Hyperbranched polyurethanes with chain-extended branches can be obtained, for example, by addition of a diisocyanate and a compound having two isocyanate-reactive groups in addition to the AB _X molecules in the molar ratio of 1: 1 to the polymerization reaction. These additional AA or BB compounds may also have other functional groups, but may not be reactive to the A or B groups under the selected reaction conditions. In this way, additional functionalities can be introduced into the hyperbranched polymer.

Further synthesis variants for hyperbranched polyurethanes can be found in DE 100 13 187 and DE 100 30 869.

The functional groups of the hyperbranched polyurethanes obtained by the synthesis reaction can, as described above, be rendered hydrophobic, hydrophilic or hydrophobic. be nationalized. Due to their reactivity, the hyperfunctional polyurethanes containing isocyanate groups are particularly suitable for re-functionalization. OH- or NH ₂ -terminated polyurethanes can also be functionalized by means of suitable reaction partners.

Preferred groups introduced into the hyperbranched polyurethanes are -COOH, -CONH ₂ , -OH, -NH ₂ , -NHR, -NR ₂ , -NR ₃ ⁺ , -SO ₃ H and their salts.

Groups which have sufficiently acidic H atoms can be converted into the corresponding salts by treatment with suitable bases. Analogously, basic groups can be converted with suitable acids into the corresponding salts. As a result, water-soluble hyperbranched polyurethanes can be obtained.

By reacting NCO-terminated products with saturated or unsaturated aliphatic alcohols and amines, in particular with Cs-C ₄ O-Al kylresten, hydrophobized products can be obtained.

Hydrophilic but nonionic products can be obtained by reaction of NCO-terminated polymers with polyether alcohols, such as, for example, di-, tri- or tetra- or polyethylene glycol.

Acid groups can be introduced, for example, by reaction with hydroxycarboxylic acids, hydroxysulfonic acids or amino acids. Examples of suitable reactants are 2-hydroxyacetic acid, 4-hydroxybenzoic acid, 12-hydroxydodecanoic acid, 2-hydroxyethanesulfonic acid, glycine or alanine.

It is also possible to produce hyperbranched polyurethanes which have various functionalities. This can be done, for example, by reaction with a mixture of different compounds, or else by reacting only one part of the originally present functional groups, for example only a part of the OH and / or NCO groups.

The re-functionalization of the hyperbranched polyurethane can advantageously be carried out immediately after the polymerization reaction, without the NCO-terminated polyurethane being previously isolated. The functionalization can also be done in a separate reaction.

The hyperbranched polyurethanes used according to the invention generally have on average at least 4 and not more than 100 functional groups. The hyperbranched polyurethanes preferably have 8 to 80 and particularly preferably 8 to 50 functional groups. Preferred hyperbranched polyurethanes have a weight-average molecular weight Mw of from 1000 to 500,000 g / mol, more preferably from 5000 to 200,000 g / mol, in particular from 10,000 to 100,000 g / mol.

Hyperbranched polyureas

Highly functional hyperbranched polyureas, which are used according to the invention as demulsifiers, can be z. B. obtained by reacting one or more carbonates with one or more amines having at least two primary and / or secondary amino groups, wherein at least one amine has at least three primary and / or secondary amino groups.

Suitable carbonates are aliphatic, aromatic or mixed aliphatic-aromatic carbonates, preferred are aliphatic carbonates such as dialkyl carbonates with Ci-Ci2-alkyl radicals. Examples are ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, diheptyl carbonate, dioctyl carbonate, didecyl carbonate or didodecyl carbonate , Particularly preferably used carbonates are dimethyl carbonate, diethyl carbonate, dibutyl carbonate and diisobutyl carbonate.

The carbonates are reacted with one or more amines having at least two primary and / or secondary amino groups, wherein at least one amine has at least three primary and / or secondary amino groups. Amines having two primary and / or secondary amino groups cause chain extension within the polyureas, while amines having three or more primary and / or secondary

Amino groups are the cause of the branching in the obtained high-functionality, hyperbranched polyureas.

Suitable amines having two primary or secondary amino groups which are reactive toward a carbonate or carbamate group are, for example, ethylenediamine, N-alkylethylenediamine, propylenediamine, 2,2-dimethyl-1,3-propylenediamine, N-alkylpropylenediamine, butylenediamine, N-alkylbutylenediamine, pentanediamine, Hexamethylenediamine, N-alkylhexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, dodecanediamine, hexadecanediamine, toluenediamine, xylylenediamine, diaminodiphenylmethane, diaminodicyclohexylmethane, phenylenediamine, cyclohexylenediamine, bis (aminomethyl) cyclohexane, diaminodiphenylsulfone, isophoronediamine, 2- Butyl 2-ethyl-1, 5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylenediamine, 2-aminopropylcyclohexylamine, 3 (4) -aminomethyl-1-methylcyclo- hexylamine, 1, 4-diamino-4-methylpentane, amine-terminated polyoxyalkylene polyols (so-called Jeffamine) or amine-terminated polytetramethylene glycols. Preferably, the amines have two primary amino groups, such as. Ethylenediamine, propylenediamine, 2,2-dimethyl-1,3-propanediamine, butylenediamine, pentanediamine, hexamethylenediamine, heptanediamine, octanediamine, nonanediamine, decanediamine, dodecanediamine, hexadecanediamine, tolylenediamine, xylylenediamine, diaminodiphenylmethane, diaminodicyclohexylmethane, phenylenediamine, Cyclohexylenediamine, diaminodiphenylsulfone, isophoronediamine, bis (aminomethyl) cyclohexane, 2-butyl-2-ethyl-1, 5-pentamethylenediamine, 2,2,4- or 2,4,4-trimethyl-1,6-hexamethylenediamine , 2-aminopropylcyclohexylamine, 3 (4) -aminomethyl-1-methylcyclohexylamine, 1, 4-diamino-4-methylpentane, amine-terminated polyoxyalkylene polyols (so-called Jeffamine) or amine-terminated polytetramethylene glycols.

Particularly preferred are butylenediamine, pentanediamine, hexamethylenediamine, toluenediamine, xylylenediamine, diaminodiphenylmethane, diaminodicyclohexylmethane, phenylenediamine, cyclohexylenediamine, diaminodiphenylsulfone, isophoronediamine, bis (aminomethyl) cyclohexane, amine-terminated polyoxyalkylene polyols (so-called Jeffamine) or amine-terminated polytetramethylene glycols.

Suitable amines having three or more relative to a carbonate or carbamate reactive primary and / or secondary amino groups are, for example, tris (aminoethyl) amine, tris (aminopropyl) amine, tris (aminohexyl) amine, trisaminohexane, 4-aminomethyl-1, 8-octamethylenediamine , Trisaminononane, bis (aminoethyl) amine, bis (aminopropyl) amine, bis (aminobutyl) amine, bis (aminopentyl) amine, bis (aminohexyl) amine, N- (2-aminoethyl) propanediamine, melamine, oligomeric diaminodiphenylmethanes , N, N'-bis (3-aminopropyl) ethylenediamine, N, N'-bis (3-aminopropyl) butanediamine, N, N, N ', N'-tetra (3-aminopropyl) ethylenediamine, N, N, N ', N'-Tetra (3-aminopropyl) butylenediamine, tri- or higher-functional amine-terminated polyoxyalkylene polyols (so-called Jeffamines), tri- or higher-functional polyethyleneimines or tri- or higher-functional polypropyleneimines.

Preferred amines having three or more reactive primary and / or secondary amino groups are tris (aminoethyl) amine, tris (aminopropyl) amine, tris (aminohexyl) amine, trisaminohexane, 4-aminomethyl-1,8-octamethylenediamine, trisaminononane, bis (aminoethyl) ethyl) amine, bis (aminopropyl) amine, bis (aminobutyl) amine, bis (aminopentyl) amine, bis (aminohexyl) amine, N- (2-aminoethyl) propanediamine, melamine or trifunctional or higher amine-terminated polyoxyalkylene polyols ( so-called Jeffamine).

Particular preference is given to amines having three or more primary amino groups, such as tris (aminoethyl) amine, tris (aminopropyl) amine, tris (aminohexyl) amine, trisaminohexane, 4-aminomethyl-1,8-octamethylenediamine, trisaminononane or trifunctional or higher-functional ones Amine-terminated polyoxyalkylene polyols (so-called Jeffamines).

Of course, mixtures of said amines can be used. In general, both amines having two primary or secondary amino groups are used in addition to amines having three or more primary or secondary amino groups. Such amine mixtures can also be characterized by the average amine functionality, with non-reactive tertiary amino groups being disregarded. For example, an equimolar mixture of a diamine and a triamine has an average functionality of 2.5. Preferably, such amine mixtures are implemented in which the average amine functionality of 2.1 to 10, in particular from 2.1 to 5.

The reaction of the carbonate with the di- or polyamine for the highly functional hyperbranched polyurea used according to the invention takes place with elimination of the alcohol or phenol bound in the carbonate. If one molecule of carbonyl reacts with two amino groups, two molecules of alcohol or phenol are eliminated and a urea group is formed. If a molecule reacts with only one amino group of carbonate, a carbamate group is formed by eliminating one molecule of alcohol or phenol.

The reaction of the carbonate or the carbonates with the amine or amines can be carried out in a solvent. In general, all solvents can be used which are inert to the respective starting materials. Preference is given to working in organic solvents, such as decane, dodecane, benzene, toluene, chlorobenzene, dichlorobenzene, xylene, dimethylformamide, dimethylacetamide or solvent naphtha.

In a preferred embodiment, the reaction is carried out in bulk, ie without an inert solvent. The alcohol or phenol liberated in the reaction between amine and carbonate or carbamate can be separated by distillation, if appropriate at reduced pressure, and thus removed from the reaction equilibrium. This also speeds up the implementation.

To accelerate the reaction between amine and carbonate or carbamate and catalysts or catalyst mixtures can be added. Suitable catalysts are generally compounds which catalyze the carbamate or urea formation, e.g. As alkali or alkaline earth metal hydroxides, alkali metal or Erdalkalihydrogen- carbonates, alkali metal or alkaline earth metal carbonates, tertiary amines, ammonium compounds, aluminum, tin, zinc, titanium, zirconium or bismuth organic compounds. For example, lithium, sodium, potassium or cesium hydroxide, lithium, sodium, potassium or cesium carbonate, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles, such as imidazole, 1-methylimidazole,

2-methylimidazole, 1, 2-dimethylimidazole, titanium tetrabutylate, dibutyltin oxide, dibutyltin dilaurate, tin dioctoate, zirconium acetylacetonate or mixtures thereof. The addition of the catalyst is generally carried out in an amount of 50 to 10,000, preferably from 100 to 5000 ppm by weight, based on the amount of amine used.

The high-functionality hyperbranched polyureas thus prepared are terminated after the reaction, ie without further modification, either with amino groups or with carbamate groups. They dissolve well in polar solvents, eg. In water, alcohols, such as methanol, ethanol, butanol, alcohol / water mixtures, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.

A highly functional hyperbranched polyurea within the meaning of the invention is understood as meaning a product which has urea groups and at least four, preferably at least six, in particular at least eight functional groups. In principle, the number of functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility. The high-functionality polyureas used according to the invention therefore generally have not more than 100 functional groups, preferably not more than 30 functional groups. By functional groups are meant primary, secondary or tertiary amino groups or carbamate groups. In addition, the highly functional hyperbranched polyurea may have other functional groups that do not participate in the construction of the hyperbranched polymer (see below). These further functional groups can be introduced by di- or polyamines which, in addition to primary and secondary amino groups, also have further functional groups.

The polyureas used according to the invention may contain further functional groups. The functionalization can be carried out during the reaction of the carbonates with the amine or amines, ie during the polycondensation reaction causing the formation of molecular weight, or else after the polycondensation reaction has ended, by subsequent functionalization of the resulting polyureas.

If, before or during the molecular weight build-up, components which have further functional groups in addition to amino or carbamate groups are obtained, a polyurea with randomly distributed further, ie. H. from the carbamate or amino groups different functional groups.

For example, it is possible to add components before or during the polycondensation which, in addition to amino groups or carbamate groups, contain hydroxyl groups, Mercapto groups, tertiary amino groups, ether groups, carboxyl groups, sulfonic acid groups, phosphonic acid groups, aryl radicals or long-chain alkyl radicals.

Hydroxyl-containing components which may be added for functionalization include, for example, ethanolamine, N-methylethanolamine, propanolamine, isopropanolamine, butanolamine, 2-amino-1-butanol, 2- (butylamino) ethanol, 2- (cyclohexylamino) ethanol, 2 - (2 ^' -Aminoethoxy) ethanol or higher alkoxylation products of ammonia, 4-hydroxypiperidine, 1-hydroxyethylpiperazine, diethanolamine, dipropanolamine, diisopropanolamine, tris (hydroxymethyl) aminomethane or tris (hydroxyethyl) aminomethane.

Mercapto-containing components that can be added for functionalization include, for example, cysteamine. With tertiary amino groups, the hyperbranched polyureas z. B. functionalized by the concomitant use of N-methyldiethylenetriamine or N, N-dimethylethylenediamine. Ether groups can be used to functionalize the hyperbranched polyureas by using amine-terminated polyetherols (so-called Jeffamines). With acid groups, the hyperbranched polyureas z. B. functionalized by co-use of aminocarboxylic acids, aminosulfonic acids or aminophosphonic acids. With long-chain alkyl radicals, the hyperbranched polyureas can be functionalized by the concomitant use of alkylamines or alkyl isocyanates with long-chain alkyl radicals.

Furthermore, the polyureas can also be functionalized by using small amounts of monomers which have functional groups which differ from amino groups or carbamate groups. Examples which may be mentioned here are di-, tri- or higher-functional alcohols which can be incorporated into the polyurea via carbonate or carbamate functions. So can be z. B. hydrophobic properties by addition of long-chain alkane, alkene or alkynediols, while Polyethy- lenoxiddiole or triols produce hydrophilic properties in the polyurea.

The abovementioned functional groups other than amine, carbonate or carbamate groups which are introduced before or during the polycondensation are generally used in amounts of from 0.1 to 80 mol%, preferably in amounts of from 1 to 50 mol%, based on the sum of the amino, carbamate and carbonate groups introduced.

Subsequent functionalization of amino-containing hyperfunctional hyperbranched polyureas may, for. B. can be achieved by adding acid groups, isocyanate groups, keto groups or molecules containing aldehydes or of activated double bonds, for. As acrylic double bonds, containing molecules. For example, polyisocyanuric acid-containing polyols can be ureas obtained by reaction with acrylic acid or maleic acid and derivatives thereof with optionally subsequent hydrolysis.

Furthermore, amino groups containing high-functionality hyperbranched polyureas by reaction with alkylene oxides, for. As ethylene oxide, propylene oxide or butylene oxide are converted into highly functional polyurea polyols.

By salt formation with protic acids or by quaternization of the amino functions with alkylating reagents, such as methyl halides or dialkyl sulfates, the highly functional, hyperbranched polyureas can be made water-soluble or water-dispersible.

In order to achieve hydrophobization, amine-terminated highly functional highly branched polyureas can be reacted with saturated or unsaturated long-chain carboxylic acids, their amine-reactive derivatives or else with aliphatic or aromatic isocyanates.

Carbamate-terminated polyureas can be rendered hydrophobic by reaction with long-chain alkylamines or long-chain aliphatic monoalcohols.

Hyperbranched polyamides

Suitable hyperbranched polyamides can be prepared by reacting a first monomer A2 having at least two functional groups A with a second monomer B3 having at least three functional groups B, wherein the functional groups A and B react with each other, and one of the monomers is an amine and the other of the monomers is a carboxylic acid or its derivative.

Suitable hyperbranched polyamides include hyperbranched polyamidoamines (see EP-A 802 215, US 2003/0069370 A1 and US 2002/0161 113 A1).

Although the first monomer A2 may also have more than two functional groups A, it will be referred to herein as A2 for the sake of simplicity, and although the second monomer B3 may also have more than three functional groups B, it will be referred to herein as B3 for the sake of simplicity , What is important is that the functionalities of A2 and B3 differ.

The functional groups A and B react with each other. The functional groups A and B are chosen such that A does not (or only to a negligible extent) react with A, and B does not (or only to a negligible extent) react with B. That's it one of the monomers A2 and B3 is an amine and the other of the monomers is a carboxylic acid, a derivative thereof.

Preferably, the monomer A2 is a carboxylic acid having at least two carboxyl groups, and the monomer B3 is an amine having at least three amino groups. Alternatively, the monomer A2 is an amine having at least two amino groups, and the monomer B3 is a carboxylic acid having at least three carboxyl groups.

Suitable carboxylic acids usually have 2 to 4, in particular 2 or 3, carboxyl groups, and an alkyl radical, aryl radical or arylalkyl radical having 1 to 30 C atoms.

As dicarboxylic acids come z. B. into consideration: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decane-α, ß-dicarboxylic acid, dodecane-α, ß-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- and trans-cyclopentane-1,2-dicarboxylic acid and also cis- and trans- Cyclopentane-1, 3-dicarboxylic acid, wherein the dicarboxylic acids may be substituted by one or more radicals selected from Ci-Cio-alkyl groups, C3-Ci2-cycloalkyl groups, alkylene groups and Cβ-Cu-aryl groups. Examples of substituted dicarboxylic acids include: 2-methylmalonic acid, 2-ethylmalonic acid, 2-phenylmalonic acid, 2-methylsuccinic acid, 2-ethylsuccinic acid, 2-phenylsuccinic acid, itaconic acid and 3,3-dimethylglutaric acid.

Likewise, ethylenically unsaturated dicarboxylic acids such as maleic acid and fumaric acid and aromatic dicarboxylic acids such as phthalic acid, isophthalic acid or terephthalic acid, are suitable.

Suitable tricarboxylic acids or tetracarboxylic acids are, for. Trimesic acid, trimellitic acid, pyromellitic acid, butanetricarboxylic acid, naphthalene-tricarboxylic acid and cyclohexane-1,3,5-tricarboxylic acid.

Furthermore, it is possible to use mixtures of two or more of the abovementioned carboxylic acids. The carboxylic acids can be used either as such or in the form of derivatives. Such derivatives are in particular

the anhydrides of said carboxylic acids, in monomeric or polymeric form;

- The esters of said carboxylic acids, eg. B.

Mono- or dialkyl esters, preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols. len such as n-propanol, iso-propanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n-hexanol derived mono- and dialkyl esters,

• mono and divinyl esters as well

Mixed esters, preferably methyl ethyl esters.

It is also possible to use a mixture of a carboxylic acid and one or more of its derivatives or a mixture of several different derivatives of one or more dicarboxylic acids.

Succinic acid, glutaric acid, adipic acid, cyclohexanedicarboxylic acids, phthalic acid, isophthalic acid, terephthalic acid or their mono- or dimethyl esters are particularly preferably used as the carboxylic acid. Very particular preference is given to succinic acid and adipic acid.

Suitable amines usually have 2 to 6, in particular 2 to 4, amino groups, and an alkyl radical, aryl radical or arylalkyl radical having 1 to 30 C atoms.

As diamines come z. B. those of the formula R ¹ -NH-R ² -NH-R ³ into consideration, wherein R ¹ , R ² and R ^{3 are} independently hydrogen or an alkyl radical, aryl or arylalkyl radical having 1 to 20 carbon atoms. The alkyl radical can also be cyclic, in particular linearly or in particular for R ² .

Suitable diamines are, for example, ethylenediamine, the propylenediamines (1, 2-diaminopropane and 1, 3-diaminopropane), N-methylethylenediamine, piperazine, tetramethylenediamine (1, 4-diaminobutane), N, N ^{'-dimethylethylenediamine,} N-ethylethylenediamine, 1, 5-diaminopentane, 1, 3-diamino-2,2-diethylpropane, 1, 3-bis (methylamino) propane, hexamethylenediamine (1,6-diaminohexane), 1, 5-diamino-2-methylpentane, 3- Propylamino) -propylamine, N, N'-bis (3-aminopropyl) piperazine, N, N'-bis (3-aminopropyl) piperazine and isophoronediamine (IPDA).

Suitable triamines, tetramines or higher-functional amines z. Tris (2-aminoethyl) amine, tris (2-aminopropyl) amine, diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), isopropyltriamine, dipropylenetriamine and N, N'-bis (3-aminopropyl- ethylenediamine).

Aminobenzylamines and aminohydrazides having two or more amino groups are also suitable.

Preferably used as amines DETA or tris (2-aminoethyl) amine or mixtures thereof. It is also possible to use mixtures of several carboxylic acids or carboxylic acid derivatives or mixtures of several amines. The functionality of the various carboxylic acids or amines may be the same or different.

In particular, when the monomer A2 is a diamine, it is possible to use as monomer B3 mixtures of dicarboxylic acids and tricarboxylic acids (or higher-functional carboxylic acids), the mixture B3 having an average functionality of at least 2.1. For example, a mixture of 50 mol% dicarboxylic acid and 50 mol% tricarboxylic acid has an average functionality of 2.5.

Similarly, when the monomer A2 is a dicarboxylic acid, as the monomer B3, mixtures of diamines and triamines (or higher functional amines) may be used, the mixture B3 having an average functionality of at least 2.1. This variant is particularly preferred. For example, a mixture of 50 mole% diamine and 50 mole% triamine has an average functionality of 2.5.

The reactivity of the functional groups A of the monomer A2 may be the same or different. Also, the reactivity of the functional groups B of the monomer B3 may be the same or different. In particular, the reactivity of the two amino groups of the monomer A2 or of the three amino groups of the monomer B3 can be the same or different.

In a preferred embodiment, the carboxylic acid is the difunctional monomer A2 and the amine is the trifunctional monomer B3, d. H. Preference is given to using dicarboxylic acids, and triamines or higher-functional amines.

Particular preference is given to using monomer A2 as a dicarboxylic acid and as monomer B3 as a triamine. Very particular preference is given to using adipic acid as monomer A2 and diethylenetriamine or tris (2-aminoethyl) amine as monomer B3.

During or after the polymerization of the monomers A2 and B3 to the hyperbranched polyamide, it is possible to use difunctional or higher-functional monomers C acting as chain extenders. As a result, the gel point of the polymer (time at which gel particles insoluble in crosslinking reactions are formed, see, for example, Flory, Principles of Polymer Chemistry, Cornell University Press, 1953, pages 387-398), and the architecture of the macromolecule, So the linkage of the monomer branches, change.

Accordingly, in a preferred embodiment, the process is characterized in that a monomer C acting as a chain extender is used during or after the reaction of the monomers A2 and B3. As a chain lengthening monomer C are suitable for. As the aforementioned diamines or higher-functional amines that react with the carboxyl groups of various polymer branches and connect them so. Isophoronediamine, ethylenediamine, 1, 2-diaminopropane, 1, 3-diaminopropane, N-methylethylenediamine, piperazine, tetramethylenediamine (1, 4-diaminobutane), N, N'-dimethylethylenediamine, N-ethylethylenediamine, 1 is particularly suitable , 5-diaminopentane, 1,3-diamino-2,2-diethylpropane, 1,3-bis (methylamino) propane, hexamethylenediamine (1,6-diaminohexane), 1, 5-diamino-2-methylpentane, 3- Propylamino) -propylamine, N, N'-bis (3-aminopropyl) piperazine, N, N'-bis (3-amino-propyl) -piperazine and isophoronediamine (IPDA).

Also, amino acids of the general formula H2N-R-COOH are suitable as chain extender C, wherein R is an organic radical.

The amount of chain extender C depends in the usual way on the desired gel point or the desired architecture of the macromolecule. In general, the amount of chain extender C is 0.1 to 50, preferably 0.5 to 40 and in particular 1 to 30 wt .-%, based on the sum of the monomers A2 used

For the preparation of functionalized polyamides monofunctional comonomers D are used with, which can be added before, during or after the reaction of the monomers A2 and B3. This gives a chemically modified polymer with the comonomer units and their functional groups.

Accordingly, in a preferred embodiment, the process is characterized in that a comonomer D having a functional group is used before, during or after the reaction of the monomers A 2 and B 3, resulting in a modified polyamide.

Such comonomers D are, for example, saturated or unsaturated monocarboxylic acids, including fatty acids, and their anhydrides or esters. Suitable z. Acetic acid, propionic acid, butyric acid, valeric acid, isobutyric acid, trimethylacetic acid, caproic acid, caprylic acid, heptanoic acid, capric acid, pelargonic acid, lauric acid, myristic acid, palmitic acid, montanic acid, stearic acid, isostearic acid, nonanoic acid, 2-ethylhexanoic acid, benzoic acid and unsaturated monocarboxylic acids such as meth - Acrylic acid, and the anhydrides and esters, for example acrylic acid esters or methacrylic acid esters of said monocarboxylic acids.

As unsaturated fatty acids D are z. As oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, fatty acids from soy, linseed, ricinus and sunflower. Suitable carboxylic acid esters D are, in particular, methyl methacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.

Suitable comonomers D are also alcohols, including fatty alcohols. These include z. As glycerol monolaurate, glycerol monostearate, ethylene glycol monomethyl ether, the polyethylene monomethyl ether, benzyl alcohol, 1-dodecanol, 1-tetradecanol, 1-hexadecanol and unsaturated fatty alcohols.

Suitable comonomers D are also acrylates, in particular alkyl acrylates such as n-, iso- and tert-butyl acrylate, lauryl acrylate, stearyl acrylate, or hydroxyalkyl acrylates such as hydroxyethyl acrylate, hydroxypropyl acrylate and hydroxybutyl acrylates. The acrylates can be introduced into the polymer in a particularly simple manner by Michael addition at the amino groups of the hyperbranched polyamide.

The amount of comonomers D depends in the usual way afterwards, in which

Extent the polymer is to be modified. In general, the amount of the monomers D is from 0.5 to 40, preferably from 1 to 35,% by weight, based on the sum of the monomers A2 and B3 used.

Depending on the type and amount of the monomers used and the reaction conditions, the hyperbranched polyamide may have terminal carboxyl groups (-COOH) or terminal amino groups (-NH, -NH 2) or both. The choice of the comonomer D added for functionalization depends in the usual way on the type and number of terminal groups with which D reacts. If carboxyl end groups are to be modified, preference is given to using from 0.5 to 2.5, preferably from 0.6 to 2, and particularly preferably from 0.7 to 1.5 molar equivalents of an amine, eg. Example, a mono- or diamine and in particular a triamine having primary or secondary amino groups, per one mol of carboxyl end groups.

If amino end groups are to be modified, preference is given to using from 0.5 to 2.5, preferably from 0.6 to 2, and particularly preferably from 0.7 to 1.5 molar equivalents of a monocarboxylic acid per one mol of amino end groups.

As mentioned, amino end groups can also be reacted with said acrylates in a Michael addition, preferably 0.5 to 2.5, in particular 0.6 to 2 and particularly preferably 0.7 to 1.5 molar equivalents of an acrylate per one moles of amino end groups.

The number of free COOH groups (acid number) of the final product polyamide is usually 0 to 400, preferably 0 to 200 mg KOH per gram of polymer and may, for. B. be determined by titration according to DIN 53240-2. The reaction of the monomers A2 with the monomers B3 is usually carried out at elevated temperature, for example 80 to 180 ⁰ C, in particular 90 to 160 ⁰ C. Preferably, it is carried out under inert gas, for. As nitrogen, or in vacuo, in the presence or absence of a solvent such as water, 1, 4-dioxane, dimethylformamide (DMF) or dimethylacetamide (DMAC). Are very suitable solvent mixtures z. B. from water and 1, 4-dioxane. However, a solvent is not required; For example, you can submit the carboxylic acid and melt, and add the amine to the melt. The water of reaction formed in the course of the polymerization (polycondensation) is removed, for example, in vacuo or removed by azeotropic distillation using suitable solvents, such as toluene.

The pressure is usually not critical and is z. B. 1 mbar to 100 bar absolute. If you do not use a solvent, by working under vacuum, z. B. 1 to 500 mbar, the reaction water can be removed in a simple manner.

The reaction time is usually 5 minutes to 48 hours, preferably 30 minutes to 24 hours and more preferably 1 hour to 10 hours.

The reaction of carboxylic acid and amine can be carried out in the absence or presence of catalysts. Suitable catalysts are, for example, the amidation catalysts mentioned below.

If catalysts are used, their amount is usually 1 to 5000, preferably 10 to 1000 ppm by weight, based on the sum of the monomers A2 and B ₃ .

During or after the polymerization, if desired, the mentioned chain extenders C can be added. In addition, it is possible to add said comonomers D before, during or after the polymerization in order to chemically modify the hyperbranched polyamide.

The reaction of the comonomers D may, if required, be catalyzed by conventional amidation catalysts. Such catalysts are z. For example, ammonium phosphate, triphenyl phosphite or dicyclohexylcarbodiimide. Particularly in the case of temperature-loan comonomers D and methacrylates or fatty alcohols as comonomer D, the reaction can be also carried enzymes catalyze, usually being at 40 to 90 ⁰ C, preferably 50 to 85 ⁰ C and in particular 55 to 80 ⁰ C and in Presence of a radical inhibitor works.

The inhibitor and, if appropriate, working under inert gas prevents free-radical polymerization and also undesired crosslinking reactions of unsaturated functional groups. Such inhibitors are z. Hydroquinone, hydroquinone mono- methyl ether, phenothiazine, phenol derivatives such as 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol or N-oxyl compounds such as 4-hydroxy-2,2,6,6-tetramethyl-piperidine-N- oxyl (hydroxy-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), in amounts of from 50 to 2000 ppm by weight, based on the sum of the monomers A2 and B3 ,

The preparation is preferably batchwise, but can also be carried out continuously, for example in stirred tanks, tube reactors, tower reactors or other conventional reactors, which can be equipped with static or dynamic mixers and customary devices for pressure and temperature control and for working under inert gas ,

When working without solvent is usually obtained directly the final product, which can be cleaned if necessary by conventional cleaning operations. If a solvent has been used with, this can be removed after the reaction in a conventional manner from the reaction mixture, such as by vacuum distillation.

The process is characterized by its great simplicity. It allows the preparation of hyperbranched polyamides in a simple one-pot reaction. The isolation or purification of intermediates or the use of protective groups for intermediates are not required. The process is economically advantageous because the monomers are commercially available and inexpensive.

Hyperbranched polyesteramides

Suitable hyperbranched polyesteramides can be z. Example, by reacting a carboxylic acid having at least two carboxyl groups with an aminoalcohol having at least one amino group and at least two hydroxyl groups produce.

The process is based on a carboxylic acid having at least two carboxyl groups (dicarboxylic acid, tricarboxylic acid or higher functional carboxylic acid) and an aminoalcohol (alkanolamine) having at least one amino group and at least two hydroxyl groups.

Suitable carboxylic acids usually have 2 to 4, in particular 2 or 3, carboxyl groups, and an alkyl radical, aryl radical or arylalkyl radical having 1 to 30 C atoms. Suitable carboxylic acids are all di-, tri- and tetracarboxylic acids and derivatives thereof already mentioned in connection with the hyperbranched polyamides.

Succinic acid, glutaric acid, adipic acid, 1, 2, 1, 3 or 1, 4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, Rephthalic acid or its dimethyl ester. Very particular preference is given to succinic acid and adipic acid.

Suitable amino alcohols (alkanolamines) having at least one amino group and at least two hydroxyl groups are preferably dialkanolamines and trialkanolamines. As dialkanolamines come z. B. those of formula 1

(1 )

in which R1, R2, R3 and R4, independently of one another, denote hydrogen, C 1-6 -alkyl, C 3-12 -cycloalkyl or Cβ-M-aryl (including arylalkyl).

Suitable dialkanolamines are, for. B. diethanolamine, dipropanolamine, diisopropanolamine, 2-amino-1, 3-propanediol, 3-amino-1, 2-propanediol, 2-amino-1, 3-propanediol, dibutanolamine, diisobutanolamine, bis (2- hydroxy-1-butyl) amine, bis (2-hydroxy-1-propyl) amine and dicyclohexanolamine.

Suitable trialkanolamines are those of the formula 2

(2)

wherein R1, R2 and R3 have the meaning given in formula 1 and I, m and n are independently integers from 1 to 12. For example, tris (hydroxymethyl) aminomethane is suitable.

The amino alcohol used is preferably diethanolamine (DEA) or diisopropanolamine (DIPA). In a preferred process, the carboxylic acid used is a dicarboxylic acid and the amino alcohol is an alcohol having one amino group and two hydroxyl groups.

The process can also be used to produce functionalized polyesteramides. Comonomers C are used for this purpose, and these can be added before, during or after the reaction of carboxylic acid, aminoalcohol and optionally monomer M. This gives a chemically modified polymer with the comonomer units and their functional groups.

Accordingly, in a preferred embodiment, the process is characterized in that a comonomer C is used before, during or after the reaction of carboxylic acid, aminoalcohol and, if appropriate, monomer M, with the result that a modified polyesteramide is formed. The comonomer may contain one, two or more functional groups.

Suitable comonomers C are the saturated and unsaturated monocarboxylic acids already mentioned in connection with the hyperbranched polyamides, also fatty acids, their anhydrides and esters, alcohols, acrylates and the already mentioned mono- or higher-functional alcohols (also diols, polyols), amines (also diamines, Triamines) and amino alcohols (alkanolamines).

The amount of comonomer C depends in the usual way by how much the polymer is to be modified. In general, the amount of C monomers C is 0.5 to 40, preferably 1 to 35 wt .-%, based on the sum of the monomers used carboxylic acid and aminoalcohol.

The number of free OH groups (hydroxyl number) of the end product polyester amide is generally from 10 to 500, preferably from 20 to 450 mg KOH per gram of polymer and can, for. B. be determined by titration according to DIN 53240-2.

The number of free COOH groups (acid number) of the end product polyesteramide is generally 0 to 400, preferably 0 to 200 mg KOH per gram of polymer and can likewise be determined by titration to DIN 53240-2.

The reaction of the carboxylic acid with the amino alcohol is generally carried out at elevated temperature, for example 80 to 250 ⁰ C, in particular 90 to 220 ⁰ C and particularly preferably 95 to 180 ⁰ C. If the polymer for the purpose of modification with C monomers C and catalysts used for this purpose (see below), you can adjust the reaction temperature of the respective catalyst and usually operates at 90 to 200 ⁰ C, preferably 100 to 190 ⁰ C and in particular 1 10 to 180 ⁰ C. Preference is given to working under inert gas, for. As nitrogen, or in vacuo, in the presence or absence of a solvent such as 1, 4-dioxane, dimethylformamide (DMF) or dimethylacetamide (DMAc). However, a solvent is not required; For example, the carboxylic acid can be mixed with the aminoalcohol and, if appropriate in the presence of a catalyst, reacted at elevated temperature. The water of reaction formed in the course of the polymerization (polycondensation) is removed, for example, in vacuo or removed by the use of suitable solvents, such as toluene, by azeotropic distillation.

The end of the reaction of carboxylic acid and aminoalcohol can often be recognized by the fact that the viscosity of the reaction mixture suddenly begins to increase rapidly. At the onset of viscosity increase, the reaction can be stopped, for example by cooling. Thereafter, the carboxyl group number in the (pre) polymer can be determined on a sample of the mixture, for example by titration of the acid number according to DIN 53402-2, and then optionally the monomer M and / or comonomer C, add and react.

The pressure is usually not critical and is z. B. 1 mbar to 100 bar absolute. If you do not use a solvent, by working under vacuum, z. B. 1 to 500 mbar absolute, the reaction water can be easily removed. The reaction time is usually 5 minutes to 48 hours, preferably 30 minutes to 24 hours and more preferably 1 hour to 10 hours.

As mentioned, before, during or after the polymerization, the said monomers C can be added in order to chemically modify the hyperbranched polyesteramide.

In the method, a catalyst can be used, which catalyzes the reaction of the carboxylic acid with the amino alcohol (esterification).

Suitable catalysts are acidic, preferably inorganic catalysts, organometallic catalysts or enzymes.

Examples of acidic inorganic catalysts 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 Al (OR) 3 and titanates of the general formula Ti (OR) ₄ can be used as acidic inorganic catalysts. Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R2SnO, where R is as defined above. A particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin. Suitable examples are Fascat® 4201, a di-n-butyltin oxide from Fa. Atofina.

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-toluenesulfonic 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.

If a catalyst is used, its amount is usually 1 to 5,000 and preferably 10 to 1,000 ppm by weight, based on the sum of carboxylic acid and amino alcohol.

Specifically, the reaction of the comonomers C can also be catalysed by the above-mentioned amidation catalysts, which is usually at 40 to 90 ⁰ C, preferably 50 to 85 ⁰ C and especially 55 to 80 ⁰ C and in the presence of a radical inhibitor works.

The process may preferably be carried out batchwise, but also continuously, for example in stirred tanks, tubular reactors, tower reactors or other conventional reactors, which may be equipped with static or dynamic mixers, and conventional pressure and temperature control devices and with inert gas.

When working without solvent is usually obtained directly the final product, which can be cleaned if necessary by conventional cleaning operations. If a solvent was also used, this can be removed from the reaction mixture in a customary manner after the reaction, for example by vacuum distillation.

The hyperbranched polymers described above may additionally be subjected to a polymer-analogous reaction. This makes it possible, under certain circumstances, to adapt their properties even better to use in different dispersions. For the polymer-analogous reaction, functional groups originally present in the polymer (eg A or B groups) may be subjected to a reaction, so that the resulting polymers have at least one new functionality.

The polymer-analogous reaction of the hyperbranched polymers can take place during the preparation of the polymers, immediately after the polymerization reaction or in a separate reaction step. If, before or during the polymer synthesis, components are added which have further functional groups in addition to A and B groups, the result is a hyperbranched polymer in which these further functional groups are substantially randomly distributed.

Compounds used for re-functionalization may contain, on the one hand, the desired functional group to be introduced and a second group which is capable of reacting with the B groups of the hyperbranched polymer used as the starting material to form a bond. An example of this is the reaction of an isocyanate group with a hydroxycarboxylic acid or an aminocarboxylic acid to form an acid functionality or the reaction of an OH group with acrylic anhydride to form a reactive acrylic double bond.

Examples of suitable functional groups which can be introduced by means of suitable reactants include, in particular, acidic or basic groups containing H atoms, and derivatives thereof, such as -OC (O) OR, -COOH, -COOR, -CONHR, -CONH ₂ , -OH, -SH, -NH _2, -NHR, -NR _2, -SO ₃ H, - SO ₃ R, -NHCOOR, -NHCONH _2, -NHCONHR, etc. Optionally ionizable functional group-pen with the aid of suitable Acids or bases are converted into the corresponding salts. Furthermore, primary, secondary or tertiary amino groups also a quaternization, z. With alkyl halides or dialkyl sulfates. In this way, for example, water-soluble or water-dispersible hyperbranched polymers can be obtained.

The radicals R of the said groups are preferably straight-chain or branched, unsubstituted or substituted alkyl radicals. For example, they are C ₁ -C 30 -alkyl radicals or C 6 -C 14 -aryl radicals. Suitable functional groups are, for example, -CN or -OR ^a , with R ^a = H or alkyl.

For the use of the hyperbranched polymers in dispersions, it may be advantageous if hydrophilic and hydrophobic moieties are in a specific relationship to one another. A hydrophobing of a hyperbranched polymer can, for. Example, by using monofunctional hydrophobic compounds are modified with the existing reactive groups before, during or after the polymerization. Thus, the polymers of the invention z. B. be rendered hydrophobic by reaction with monofunctional, saturated or unsaturated aliphatic or aromatic amines, alcohols, carboxylic acids, epoxides or isocyanates.

Furthermore, z. B. di- or higher functional, hydrophobic group-containing monomers can be polymerized during the molecular weight build-up. For example, difunctional or higher-functional alcohols, di- or higher-functional alcohols can be used for this purpose. onelle amines, di- or higher functional isocyanates, di- or higher functional carboxylic acids, di- or higher functional epoxides, which additionally carry aromatic radicals or long-chain alkane, alkene or alkyne radicals to the reactive groups.

Examples of such monomers are alcohols, such as glycerol monostearate, glycerol monooleate, hexanediol, octanediol, decanediol, dodecanediol, octadecanediol, dimer fatty alcohols, amines, such as hexamethylenediamine, octanediamine, dodecanediamine, isocyanates, such as aromatic or aliphatic di- and polyisocyanates, eg. Diphenylmethane diisocyanate and its higher oligomeric species, tolylene diisocyanate, naphthylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate trimers, isophorone diisocyanate, bis (diisocyanatocyclohexyl) methane or bis (isocyanatomethyl) cyclohexane, acids such as adipic acid, octanedioic acid, dodecanedi acid, octadecanedioic acid or dimer fatty acids.

Furthermore, the hyperbranched polymers used according to the invention can be hydrophilized. These can z. As hydroxyl groups and / or primary or secondary amino groups containing hyperbranched polymers by reaction with Alky- lenoxiden, z. For example, ethylene oxide, propylene oxide, butylene oxide or mixtures thereof, be converted into highly functional polymer polyols. Preferably, ethylene oxide is used for the alkoxylation. As a further option, however, di- or higher-functional alkylene oxide alcohols or alkylene oxide amines can also be used as synthesis components in the preparation of the hyperbranched polymers.

It is also possible to produce hyperbranched polymers which have various functionalities. This can be done, for example, by reaction with a mixture of different compounds for re-functionalization, or also by reacting only a part of the originally present functional groups.

Furthermore, mixed functional compounds can be produced by using ABC or AB2C type monomers for the polymerization, where C represents a functional group which is unreactive with A or B under the chosen reaction conditions.

Polymer dispersion PD

At least one ethylenically unsaturated monomer (M) is used to prepare the polymer dispersion PD). The monomer (M) is α, β-ethylenically unsaturated monomers, which in the context of the invention are understood to mean monomers having a terminal double bond. The monomer (M) is preferably selected from esters of α, β-ethylenically unsaturated mono- and dicarboxylic acid. acids with C 1 -C 20 -alkanols, vinylaromatics, esters of vinyl alcohol with C 1 -C 30 -monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, monoethylenically unsaturated carboxylic and sulfonic acids, phosphorus-containing monomers, esters of α, β-ethylenically unsaturated mono - And dicarboxylic acids with C2-C3o-alkanediols, amides of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group, primary amides of α, ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl - and N, N-dialkyl derivatives, N-vinyl lactams, open-chain N-vinyl amide compounds, esters of allyl alcohol with Ci-C3o monocarboxylic acids, esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, amides α, ß-ethylenic unsaturated mono- and dicarboxylic acids with diamines having at least one primary or secondary amino group, N, N-diallylamines, N, ND iallyl-N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, C 2 -C 8 monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, polyether (meth) acrylates, monomers containing urea groups and mixtures thereof.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 20 -alkanols are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n Butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl ( meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl (meth) acrylate, tridecyl ( meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate, palmityl (meth) acrylate,

Heptadecyl (meth) acrylate, nonadecyl (meth) acrylate, arachinyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate, cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate, oleyl ( meth) acrylate, linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate and mixtures thereof.

Preferred vinyl aromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene and particularly preferably styrene.

Suitable esters of vinyl alcohol with Ci-C3o-monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and mixtures thereof.

Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof. Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

Suitable ethylenically unsaturated carboxylic acids and sulfonic acids or their derivatives are acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, the half esters of monoethylenically unsaturated dicarboxylic acids with 4 to 10, preferably 4 to 6 C atoms, for. For example, maleic acid monomethyl ester, vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acids and 2-acrylamido-2-methylpropanesulfonic acid. Suitable styrenesulfonic acids and derivatives thereof are styrene-4-sulfonic acid and styrene-3-sulfonic acid and the alkaline earth or alkali metal salts thereof, e.g. Sodium styrene-3-sulfonate and sodium styrene-4-sulfonate. Particularly preferred are acrylic acid, methacrylic acid and mixtures thereof.

Examples of phosphorus-containing monomers are e.g. Vinylphosphonic acid and allylphosphonic acid. Also suitable are the mono- and diesters of phosphonic acid and phosphoric acid with hydroxyalkyl (meth) acrylates, especially the monoesters. Also suitable are diesters of phosphonic acid and phosphoric acid which are readily alkylated with a hydroxyalkyl (meth) and additionally simply with a different alcohol, eg. As an alkanol, are esterified. Suitable hydroxyalkyl (meth) acrylates for these esters are those mentioned below as separate monomers, in particular 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,

4-hydroxybutyl (meth) acrylate, etc. Corresponding dihydrogen phosphate ester monomers include phosphoalkyl (meth) acrylates such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and 3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are the esters of phosphonic acid and phosphoric acid with alkoxylated hydroxyalkyl (meth) acrylates, eg. As the ethylene oxide condensates of (meth) acrylates, such as H ₂ C = C (H ₁ CH ₃ ) COO (CH ₂ CH ₂ O) _n P (OH) ₂ and

H ₂ C = C (H, CH ₃ ) COO (CH ₂ CH ₂ O) _n P (= O) (OH) ₂ where n is 1 to 50. Also suitable are phosphoalkyl crotonates, phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth) acrylates, phosphodialkyl crotonates and allyl phosphates. Other suitable phosphorus group-containing monomers are described in WO 99/25780 and US 4,733,005, which is incorporated herein by reference.

Suitable esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with C ₂ -C 3o-alkanediols are, for. 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc.

Suitable primary amides of α, ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives are acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide , N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl ) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide,

N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide, N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide, N-arachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignoceryl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide,

N-palmitoleinyl (meth) acrylamide, N-oleyl (meth) acrylamide, N-linolyl (meth) acrylamide, N-linolenyl (meth) acrylamide, N-stearyl (meth) acrylamide, N-lauryl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, morpholinyl (meth) acrylamide.

Suitable N-vinyl lactams and derivatives thereof are, for. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc.

Suitable open-chain N-vinyl amide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.

Suitable esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.

Suitable amides of α, β-ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide, etc.

Suitable monomers M) are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products. Alkyl is preferably Ci-C24-alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides.

Suitable monomers M) are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.

Suitable C 2 -C 8 -monoolefins and non-aromatic hydrocarbons having at least two conjugated double bonds are, for example, For example, ethylene, propylene, isobutylene, isoprene, butadiene, etc.

Suitable polyether (meth) acrylates are compounds of the general formula (A)

R ^b O

H ₂ C = C - CY (CH ₂ CH ₂ O) _k (CH ₂ CH (CH ₃ ) O), Ra

(A)

wherein

the order of the alkylene oxide units is arbitrary,

k and I independently of one another represent an integer from 0 to 100, the sum of k and I being at least 3,

R ^{a is} hydrogen, C 1 -C ₆ -alkyl, C ₅ -C ₈ -cycloalkyl, Ce-Cu-aryl or (C ₆ -C ₄ ) -aryl (C ₁ -C ₄ ) -alkyl,

R ^{b is} hydrogen or C 1 -C ₈ -alkyl,

Y is O or NR ^C , wherein R ^{c is} hydrogen, C 1 -C ₈ -alkyl or C ₅ -C ₈ -cycloalkyl. Preferably k is an integer from 1 to 100, particularly preferably 3 to 50, in particular 4 to 25. Preferably I is an integer from 0 to 100, more preferably 3 to 50, in particular 4 to 25.

The sum of k and I is preferably 3 to 200, especially 4 to 100.

Preferably, R ^a in the formula (A) is hydrogen or C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2 Ethylhexyl, decyl, lauryl, palmityl or stearyl and benzyl.

R ^b is preferably hydrogen or C 1 -C 6 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular for hydrogen, Methyl or ethyl. R ^{b is} particularly preferably hydrogen or methyl.

Preferably, Y in the formula (A) is O or NH, especially O.

In a specific embodiment, at least one polyether (meth) acrylate is used in the free-radical emulsion polymerization for the preparation of PD). This is preferably used in an amount of up to 25 wt .-%, preferably up to 20 wt .-%, based on the total weight of the monomers M). It is particularly preferable to use 0.1 to 20% by weight, preferably 1 to 15% by weight, of at least one polyether (meth) acrylate for the emulsion polymerization. Suitable polyether (meth) acrylates are, for. As the polycondensation of the aforementioned α, ß-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with polyetherols. Suitable polyetherols can be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule such as water or a short-chain alcohol R ^a -OH. The alkylene oxides can be used individually, alternately successively or as a mixture. The polyether acrylates can be used alone or in mixtures for the preparation of the emulsion polymers used according to the invention.

The polymer dispersion PD) preferably contains at least one polyether (meth) acrylate in copolymerized form, which is selected from compounds of the general formulas I or II or mixtures thereof R ^b O

H ₂ C = CC O (CH ₂ CH ₂ O) _n - Ra

(I)

R ^b O

H ₂ C = C - CO (CH ₂ CH (CH ₃ ) O) _n - R ^a

(H) wherein

n is an integer from 3 to 15, preferably 4 to 12,

R ^{a is} hydrogen, C ₁ -C 20 -alkyl, C ₅ -C ₈ -cycloalkyl or Ce-Cu-aryl,

R ^{b is} hydrogen or methyl.

Suitable polyether (meth) acrylates are commercially available, for. In the form of various Bisomer® products from Laporte Performance Chemicals, UK. This includes z. Bisomer® MPEG 350 MA, a methoxypolyethylene glycol monomethacrylate.

In a further specific embodiment, at least one urea group-containing monomer is used in the free-radical emulsion polymerization for the preparation of PD). This is preferably used in an amount of up to 25% by weight, preferably up to 20% by weight, based on the total weight of the monomers M). With particular preference, 0.1 to 20% by weight, in particular 1 to 15% by weight, of at least one urea group-containing monomer is used for the emulsion polymerization. Suitable urea group-containing monomers are, for. N-vinyl or N-allyl urea or derivatives of imidazolidin-2-one. These include N-vinyl and N-allylimidazolidin-2-one, N-vinyloxyethylimidazolidin-2-one, N- (2- (meth) acrylamidoethyl) imidazolidin-2-one, N- (2- (meth) acryloxyethyl) imidazolidine 2-one (= 2-ureido (meth) acrylate), N- [2 - ((meth) acryloxyacetamido) ethyl] imidazolidin-2-one, etc.

Preferred urea group-containing monomers are

N- (2-Acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one. Particularly preferred is N- (2-methacryloxyethyl) imidazolidin-2-one (2-ureidomethacrylate, UMA). The abovementioned monomers M) can be used individually, in the form of mixtures within a monomer class or in the form of mixtures of different monomer classes.

At least 40% by weight, more preferably at least 60% by weight, in particular at least 80% by weight, based on the total weight of the monomers M), of at least one monomer M1) which is selected from esters α are preferably used for the emulsion polymerization , .beta.-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 20 -alkanols, vinylaromatics, esters of vinyl alcohol with C 1 -C 30 -monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides and mixtures thereof (main monomers). Preferably, the monomers M1) in an amount of up to 99.9 wt .-%, particularly preferably up to 99.5 wt .-%, in particular up to 99 wt .-%, based on the total weight of the monomers M), used for emulsion polymerization.

The main monomers M1) are preferably selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Styrene, 2-methylstyrene, vinyl acetate, acrylonitrile, methacrylonitrile and mixtures thereof.

In addition to at least one main monomer M1), in radical emulsion polymerization for the preparation of PD) at least one further monomer M2), which is generally present to a lesser extent (secondary monomer), can be used. Preferably, up to 60% by weight, particularly preferably up to 40% by weight, in particular up to 20% by weight, based on the total weight of the monomers M), of at least one monomer M2) which is selected are used for the emulsion polymerization among ethylenically unsaturated mono- and dicarboxylic acids and the anhydrides and semiesters of ethylenically unsaturated dicarboxylic acids, ethylenically unsaturated sulfonic acids, (meth) acrylamides, C 1 -C 10 -hydroxyalkyl (meth) acrylates, C 1 -C 10 -hydroxyalkyl (meth) acrylamides and mixtures thereof. Preferably, the monomers M2), if present, in an amount of at least 0.01 wt .-%, more preferably at least 0.05 wt .-%, in particular at least 0.1 wt .-%, especially at least 0.5 wt .-%, more particularly at least 1 wt .-%, based on the total weight of the monomers M), used for emulsion polymerization.

For the emulsion polymerization it is particularly preferred to use 0.1 to 60% by weight, preferably 0.5 to 40% by weight, in particular 0.1 to 20% by weight, of at least one monomer M2). In a first embodiment, the monomers M2) comprise at least one monomer bearing acid groups, which is preferably selected from monoethylenically unsaturated Cs-Cs-monocarboxylic acids, monoethylenically unsaturated. C4-C8 dicarboxylic acids, their anhydrides and half-esters, monoethylenically unsaturated sulfonic acids and mixtures thereof. The proportion of acid group-carrying monomers M2) (if present) is preferably from 0.05 to 15% by weight, particularly preferably from 0.1 to 10% by weight, based on the total weight of the monomers M). The monomers M2) comprise in a second embodiment at least one neutral monoethylenically unsaturated monomer, which is preferably selected from amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids, hydroxy-C 2 -C 4 -alkyl esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids and mixtures thereof. The proportion of neutral monomers M2) (if present) is preferably 0.01 to 15 wt .-%, particularly preferably 0.1 to 10 wt .-%, based on the total weight of the monomers M). In a third embodiment, the monomers M2) comprise a mixture of at least one acid group-carrying monomer and at least one neutral monoethylenically unsaturated monomer. The sum of these monomers M2) is preferably 0.1 to 20 wt .-%, particularly preferably 0.5 to 15 wt .-%, based on the total weight of the monomers M). The monomers M2) are specifically selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, acrylic acid amide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, and mixtures thereof.

Particularly suitable monomer combinations of main monomers M1) for the process according to the invention are, for example:

n-butyl acrylate, methyl methacrylate; n-butyl acrylate, styrene; n-butyl acrylate, methyl methacrylate, styrene; n-butyl acrylate, ethylhexyl acrylate, methyl methacrylate; n-butyl acrylate, ethylhexyl acrylate, styrene;

Ethylhexyl acrylate, styrene; Ethylhexyl acrylate, methyl methacrylate;

Ethylhexyl acrylate, methyl methacrylate, styrene.

The abovementioned particularly suitable combinations of main monomers M1) can be combined with particularly suitable monomers M2), which are preferably selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide and mixtures thereof.

In the preparation of the polymer dispersions of the invention, in addition to the aforementioned monomers M), at least one crosslinker can be used. Monomers having a crosslinking function are compounds having at least two polymerizable, ethylenically unsaturated, non-conjugated double bonds in the molecule. A networking can also z. B. by photochemical activation suc- For this purpose, for the preparation of PD) additionally at least one monomer with photoactivatable groups can be used. Photoinitiators can also be added separately. A networking can also z. For example, by functional groups which can enter into a chemical crosslinking reaction with complementary functional groups. In this case, the complementary groups can both be bound to the emulsion polymer for crosslinking, a crosslinker can be used, which is capable of being able to enter into a chemical crosslinking reaction with functional groups of the emulsion polymer.

Suitable crosslinkers are z. As acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.

Examples of the underlying alcohols are dihydric alcohols such as 1, 2-ethanediol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, 2,3-butanediol, 1, 4-butanediol , But-2-ene-1, 4-diol, 1, 2-pentanediol, 1, 5-pentanediol, 1, 2-hexanediol, 1, 6-hexanediol, 1, 10-decanediol, 1, 2-dodecanediol, 1 , 12-dodecanediol, neopentyl glycol, 3-methylpentane-1, 5-diol, 2,5-dimethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-cyclohexanediol, 1 , 4-cyclohexanediol,

1,4-bis (hydroxymethyl) cyclohexane, hydroxypivalic acid neopentyl glycol monoester, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis [4- (2-hydroxypropyl) phenyl] propane, diethylene glycol, triethylene glycol, Tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, 3-thiapentane-1, 5-diol, and polyethylene glycols, polypropylene glycols and polytetrahydrofurans having molecular weights of 200 to 10,000. In addition to the homopolymers of ethylene oxide or propylene oxide and block copolymers of ethylene oxide or propylene oxide or copolymers containing incorporated incorporated ethylene oxide and propylene oxide groups. Examples of underlying alcohols having more than two OH groups are trimethylolpropane, glycerol, pentaerythritol, 1, 2,5-pentanetriol, 1, 2,6-hexanetriol, cyanuric acid, sorbitan, sugars such as sucrose, glucose, mannose. Of course, the polyhydric alcohols can also be used after reaction with ethylene oxide or propylene oxide as the corresponding ethoxylates or propoxylates. The polyhydric alcohols can also be first converted by reaction with epichlorohydrin in the corresponding glycidyl ether.

Further suitable crosslinkers are the vinyl esters or the esters of monohydric, unsaturated alcohols with ethylenically unsaturated Cs-Cβ-carboxylic acids, for example acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid. Examples of such alcohols are allyl alcohol, 1-buten-3-ol, 5-hexen-1-ol, 1-octene-3-ol,

9-decene-1-ol, dicyclopentenyl alcohol, 10-undecene-1-ol, cinnamyl alcohol, citronellol, crotyl alcohol or cis-9-octadecen-1-ol. But one can also use the monovalent, saturated alcohols with polybasic carboxylic acids, for example malonic acid, tartaric acid, trimellitic acid, phthalic acid, terephthalic acid, citric acid or succinic acid.

Further suitable crosslinkers are esters of unsaturated carboxylic acids with the polyhydric alcohols described above, for example oleic acid, crotonic acid, cinnamic acid or 10-undecenoic acid.

Also suitable as crosslinking agents are straight-chain or branched, linear or cyclic, aliphatic or aromatic hydrocarbons which have at least two double bonds which must not be conjugated in aliphatic hydrocarbons, eg. B. divinylbenzene, divinyltoluene, 1, 7-octadiene, 1, 9-decadiene, 4-vinyl-1-cyclohexene, trivinylcyclohexane or polybutadienes having molecular weights of 200 to 20,000.

Other suitable crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines. Such amines are for. B. 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine. Also suitable are the amides of allylamine and unsaturated carboxylic acids, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.

Further, triallylamine and Triallylmonoalkylammoniumsalze, z. As triallylmethylammonium chloride or methyl sulfate, suitable as a crosslinker.

Also suitable are N-vinyl compounds of urea derivatives, at least divalent amides, cyanurates or urethanes, for example of urea, ethylene urea, propylene urea or tartaramide, for. N, N'-divinylethyleneurea or N, N'-divinylpropyleneurea.

Further suitable crosslinkers are divinyldioxane, tetraallylsilane or tetravinylsilane.

Of course, it is also possible to use mixtures of the abovementioned compounds. Preferably, water-soluble crosslinkers are used.

Furthermore, the crosslinking monomers also include those which, in addition to an ethylenically unsaturated double bond, a reactive functional group, eg. Example, an aldehyde group, a keto group or an oxirane group, which can react with an added crosslinker. Preferably, the functional groups are keto or aldehyde groups. The keto or aldehyde groups are preferably obtained by copolymerization of copolymerisable, ethylenically unsaturated bonded compounds with keto or aldehyde groups bonded to the polymer. Suitable such compounds are acrolein, methacrolein, vinyl alkyl ketones having 1 to 20, preferably 1 to 10 carbon atoms in the alkyl radical, formylstyrene, (meth) acrylic acid alkyl esters having one or two keto or aldehyde, or an aldehyde and a keto group in Alkyl radical, wherein the alkyl radical preferably comprises a total of 3 to 10 carbon atoms, for. B. (meth) acryloxyalkylpropanale, as described in DE-A-2722097. Furthermore, N-oxoalkyl (meth) acrylamides as described, for. From US-A-4226007, DE-A-2061213 or DE-A-2207209 are known. Particularly preferred are acetoacetyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate and especially diacetone acrylamide. The crosslinkers are preferably a compound having at least 2 functional groups, in particular 2 to 5 functional groups, which can undergo a crosslinking reaction with the functional groups of the polymer, especially the keto or aldehyde groups. These include z. For example, hydrazide, hydroxylamine or oxime ether or amino groups as functional groups for the crosslinking of the keto or aldehyde groups. Suitable compounds with hydrazide groups are, for. B. Polycarbonsäurehydrazide having a molecular weight of up to 500 g / mol. Particularly preferred hydrazide compounds are dicarboxylic acid dihydrazides having preferably 2 to 10 C atoms. These include z. For example, oxalic dihydrazide, malonic dihydrazide, succinic dihydrazide, glutaric dihydrazide, adipic dihydrazide, sebacic dihydrazide, maleic dihydrazide, fumaric dihydrazide, itaconic dihydrazide and / or isophthalic dihydrazide. Of particular interest are adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide. Suitable compounds with hydroxylamine or oxime ether groups are, for. As mentioned in WO 93/25588.

Also by a corresponding addition of the aqueous polymer dispersion PD), a surface crosslinking can be additionally produced. This includes z. B. addition of a photoinitiator or siccative. Suitable photoinitiators are those which are excited by sunlight, for example benzophenone or benzophenone derivatives. Sikkativierung are the recommended for aqueous alkyd resins metal compounds, for example based on Co or Mn (review in U. Poth, polyester and alkyd resins, Vincentz Network 2005, p 183 f).

The crosslinking component is preferably used in an amount of 0.0005 to 5 wt .-%, preferably 0.001 to 2.5 wt .-%, in particular 0.01 to 1, 5 wt .-%, based on the total weight of the polymerization used monomers (including the crosslinker) used. In a specific embodiment, at least 98% by weight, particularly preferably at least 99% by weight, in particular at least 99.5% by weight, especially 100% by weight, of monoethylenically unsaturated compounds, based on the total weight, are used for the emulsion polymerization the compounds capable of polymerization used. A special embodiment are polymer dispersions (PD) which contain no crosslinker in copolymerized form.

The radical polymerization of the monomer mixture M) can be carried out in the presence of at least one regulator. Regulators are preferably used in an amount of 0.0005 to 5 wt .-%, particularly preferably from 0.001 to 2.5 wt .-% and in particular from 0.01 to 1, 5 wt .-%, based on the total weight of the Polymerization used monomers used.

Regulators (polymerization regulators) are generally compounds with high transfer constants. Regulators accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers without affecting the gross reaction rate. In the case of the regulators, one can distinguish between mono-, bi- or polyfunctional regulators depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions. Suitable regulators are described in detail, for example, by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, pp. 11-81-11 / 141.

Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionic aldehyde, n-butyraldehyde, isobutyraldehyde.

It is also possible to use as regulators: formic acid, its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.

Other suitable regulators are halogen compounds, for. For example, alkyl halides, such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide and benzyl compounds, such as benzyl chloride or benzyl bromide.

Other suitable regulators are allyl compounds, such as. Allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers, or glycerol monoallyl ethers.

Preference is given to using compounds which contain sulfur in bound form as regulators.

Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones. These include di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, Dialkyl disulfide and / or diaryl sulfide. Also suitable as polymerization regulators are thiols (compounds which contain sulfur in the form of SH groups, also referred to as mercaptans). Preferred regulators are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids. Examples of these compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thio urea and Al kyl mercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.

Examples of bifunctional regulators containing two sulfur atoms in bonded form are bifunctional thiols such as. As dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropan, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol-bis-thioglycolate. Examples of polyfunctional regulators are compounds containing more than two sulfur in bound form. Examples of these are trifunctional and / or tetrafunctional mercaptans.

All mentioned controllers can be used individually or in combination with each other. A specific embodiment relates to polymer dispersions PD, which are prepared by free-radical emulsion polymerization without the addition of a regulator.

To prepare the polymers, the monomers can be polymerized with the aid of free-radical initiators.

As initiators for the radical polymerization, the peroxo and / or azo compounds customary for this purpose can be used, for example alkali metal or ammonium peroxydisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert. Butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, Diisopropylperoxidicarbamat, bis (o-toluoyl) peroxide, Didecanoylperoxid, Dioctanoylper- oxide, dilauroyl peroxide, tert-butyl perisobutyrate, tert-butyl peracetate, di-tert .-Amyl peroxide, tert-butyl hydroperoxide, azo-bis-isobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride or 2-2'-azobis (2-methyl-butyronitrile). Also suitable are mixtures of these initiators.

Reducing / oxidation (= Red-Ox) initiator systems can also be used as initiators. The redox initiator systems consist of at least one mostly inorganic reducing agent and one inorganic or organic oxidizing agent. The oxidation component is z. B. to the above-mentioned initiators for emulsion polymerization. In the reduction com- components are, for. B. to alkali metal salts of sulfurous acid, such as. For example, sodium sulfite, sodium hydrogen sulfite, alkali metal salts of the disulfurous acid such as sodium disulfite, bisulfite addition compounds aliphatic aldehydes and ketones such as acetone bisulfite or reducing agents such as hydroxymethanesulfinic acid and salts thereof, or ascorbic acid. The red-ox initiator systems can be used with the concomitant use of soluble metal compounds whose metallic component can occur in multiple valence states. Usual Red Ox initiator systems are z. As ascorbic acid / iron (II) sulfate / sodium peroxodisulfate, tert-butyl hydroperoxide / sodium disulfite, tert-butyl hydroperoxide / Na-hydroxymethanesulfinic acid. The individual components, eg. As the reduction component, mixtures may also be z. B. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.

The amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on all monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.

The preparation of the polymer dispersion PD) is usually carried out in the presence of at least one surface-active compound. A detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961,

41 to 420. Suitable emulsifiers can also be found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208.

Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers. Emulsifiers whose relative molecular weights are usually below those of protective colloids are preferably used as surface-active substances. In particular, it has proven useful to use exclusively anionic emulsifiers or a combination of at least one anionic emulsifier and at least one nonionic emulsifier.

Useful nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, examples being ethoxylated mono-, di- and trialkylphenols (EO units: 3 to 50, alkyl radical: C ₄ -C _0), ethoxylates of long-chain alcohols (EO units: 3 to 100, alkyl radical : Cs-Csβ) and polyethylene oxide / polypropylene oxide homo- and copolymers. These may contain randomly distributed alkylene oxide or polymerized in the form of blocks. Well suited z. B. EO / PO block copolymers. Ethoxylates of long-chain alkanols (alkyl C1-C30, average degree of ethoxylation from 5 to 100), and including particularly preferably those are preferably ₀ alkyl radical and a mean degree of ethoxylation of 10 to 50, and ethoxylated monoalkylphenols having a linear Ci2-C2. Suitable anionic emulsifiers are for example alkali metal and ammonium salts of alkyl sulfates (alkyl: C8-C22), nole of sulfuric monoesters of ethoxylated alkali (EO degree: from 2 to 50, alkyl radical: _Ci2-Ci8) and ethoxylated alkylphenols (EO units: 3 to 50, alkyl radical: C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: Cg-Cis). Further suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208). Also suitable as anionic emulsifiers are bis (phenylsulfonic acid) ethers or their alkali metal or ammonium salts which carry a C 4 -C 24 -alkyl group on one or both aromatic rings. These compounds are well known, for. From US-A-4,269,749, and commercially available, for example as Dowfax® 2A1 (Dow Chemical Company).

Suitable cationic emulsifiers are preferably quaternary ammonium halides, e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.

The amount of emulsifier is generally about 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the amount of monomers to be polymerized.

The polymer dispersions (PD) can also be added to customary auxiliaries and additives. These include, for example, the pH-adjusting substances, reduction and bleaching agents, such as. For example, the alkali metal salts of hydroxymethanesulfinic acid (eg Rongalit.RTM. C from BASF Aktiengesellschaft), complexing agents, deodorants, flavoring agents, odorous substances and viscosity modifiers, such as alcohols, eg. B. Glycerin, methanol, ethanol, tert-butanol, glycol, etc. These auxiliaries and additives can be added to the polymer dispersions in the template, one of the feeds or after completion of the polymerization.

The polymerization is generally carried out at temperatures in a range from 0 to 150 ⁰ C, preferably 20 to 100 ⁰ C, more preferably 30 to 95 ⁰ C. The polymerization is preferably carried out at atmospheric pressure, but is also possible a polymerization under elevated pressure, for example the autogenous pressure of the components used for the polymerization. In a suitable embodiment, the polymerization takes place in the presence of at least one inert gas, such as. As nitrogen or argon.

The polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used. The emulsion polymerization can be carried out both as a batch process and in the form of a feed process, including a stepwise or gradient procedure. Preference is given to the feed process in which a part of the polymerization batch or else a polymer seed is introduced, to which Polymerisation temperature heated, polymerized and then the remainder of the polymerization, usually via a plurality of spatially separate feeds, one or more of the monomers in pure or in emulsified form, continuously, stepwise or by superimposing a concentration gradient while maintaining the polymerization of the polymerization zone supplies.

The term ^" seed polymer ^" is understood by the person skilled in the art to mean a finely divided polymer in the form of an aqueous polymer dispersion. The weight average particle size of seed polymers (weight average, d.sub.50) is typically below 200 nm, often in the range of 10 to 150 nm. The monomer compositions of the seed polymers are generally of lesser importance. Both seed polymers, which are composed predominantly of vinylaromatic monomers and in particular of styrene (so-called styrene seed), as well as seed polymers which are predominantly composed of C 1 -C 10 -alkyl acrylates and / or C 1 -C 10 -alkyl methacrylates, eg. B. are composed of a mixture of butyl acrylate and methyl methacrylate. Beside these

Main monomers, which typically make up at least 80% by weight, and more preferably at least 90% by weight, of the seed polymer, the seed polymers can also contain various monomers, especially those having increased water solubility, e.g. B. monomers having at least one acid function and / or neutral monomers with increased water solubility in copolymerized form. The proportion of such monomers will usually not exceed 20% by weight and especially 10% by weight and, if present, is typically in the range of 0.1 to 10% by weight, based on the total amount of the seed polymer constituent monomers.

The manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced both completely into the polymerization vessel, or used continuously or in stages according to its consumption in the course of the free radical aqueous emulsion polymerization. Specifically, this depends in a manner known per se to those of ordinary skill in the art both on the chemical nature of the initiator system and on the polymerization temperature. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.

The dispersions formed during the polymerization can be subjected to a physical or chemical aftertreatment following the polymerization process. Such methods are, for example, the known methods for residual monomer reduction, such as. For example, the aftertreatment by addition of polymerization initiators or mixtures of several polymerization initiators at suitable temperatures, aftertreatment of the polymer solution by means of steam or ammonia vapor, or stripping with inert gas or treating the reaction mixture with oxidizing or reducing reagents, adsorption as the adsorption of impurity on selected media such. As activated carbon or ultrafiltration.

The aqueous polymer dispersion (PD) obtained usually has a solids content of from 20 to 70% by weight, preferably from 40 to 60% by weight, based on the polymer dispersion. The solids content is understood including added highly branched polymer. The glass transition temperature Tg of the emulsion polymer contained in the polymer dispersion is preferably in a range from -50 to 80 ^° C., more preferably from -10 to 50 ^° C.

The resulting aqueous polymer dispersion PD) can be used as such or mixed with further, generally film-forming, polymers as a binder composition in aqueous coating compositions, such as dye or lacquer mixtures.

A further subject of the invention is a binder composition which contains an aqueous polymer dispersion (PD) as described above or consists of such a polymer dispersion (PD). The binder composition also comprises the highly branched polymer (s) added to the polymer dispersion (PD)

In addition to the polymer dispersion (PD), the binder composition may comprise at least one further film-forming polymer. These include z. B. alkyd resins. Suitable alkyd resins are, for. B. water-soluble alkyd resins, which preferably have a weight-average molecular weight of 5000 to 40,000. Alkyd resins having a weight-average molecular weight of more than 40,000, especially more than 100,000, are also suitable. An alkyd resin is understood to mean a polyester which is esterified with a drying oil, a fatty acid or the like (U. Poth, Polyester and Alkyd resins, Vincentz Network 2005).

Suitable water-soluble alkyd resins are alkyd resins having a sufficiently high acid number, preferably in the range of 30 to 65 mg KOH / g. These may optionally be partially or completely neutralized. The weight-average molecular weight is preferably 8,000 to 35,000, and more preferably 10,000 to 35,000.

The use of such other film-forming polymers, especially alkyd resins, which increase the VOC content of the coating agents may not be preferred. A specific embodiment is therefore a coating composition comprising at least one dispersion PD) and at least one hyperbranched polymer, but no film-forming polymer other than the emulsion polymer contained in the polymer dispersion. The binder compositions according to the invention are preferably used in aqueous paints. These paints are for example in the form of an unpigmented system (clearcoat) or a pigmented system. The proportion of pigments can be described by the pigment volume concentration (PVK). The PVK describes the ratio of the volume of pigments (V _P ) and fillers (V _F ) to the total volume, consisting of the volumes of binder (VB), pigments and fillers of a dried coating film in percent: PVK = (VP + VF) x 100 / (V _P + V _F + V _B ). For example, paints can be classified using the PVK as follows:

high filled interior paint, washable, white / matt approx. 85

Interior paint, abrasion resistant, white / matt approx. 80

Semi-gloss paint, semi-gloss approx. 35

Semi-gloss color, silky gloss approx. 25 exterior façade color, white approx. 45-55

Clearcoat 0

Another object of the invention is a coating composition in the form of an aqueous composition containing

a binder composition as defined above containing a highly branched polymer as an additive,

optionally at least one inorganic filler and / or at least one inorganic pigment,

optionally further aids, and

Water.

In a first preferred embodiment, the coating compositions according to the invention are suitable for the production of clearcoats which contain no pigments and fillers, with high freeze-thaw stability.

In a second particularly preferred embodiment, the coating compositions according to the invention are suitable for the production of emulsion paints having a high freeze-thaw stability.

Preference is given to a coating composition comprising:

From 10 to 60% by weight, based on the solids content of at least one dispersion PD), as defined above, 10 to 70 wt .-% of inorganic fillers and / or inorganic pigments, 0.1 to 20 wt .-% of conventional auxiliaries, and water to 100 wt .-%.

The proportion of PD) in the above coating agent refers to solid, i. H. Emulsion polymer and highly branched polymer (s), without water.

The novel coating compositions in the form of an aqueous composition are preferably used as paints. One embodiment is paint in the form of a clearcoat. Another embodiment is paints in the form of an emulsion paint. The pigmented coating compositions according to the invention are present, for example, in the form of an aqueous silk-gloss or a high-gloss color.

In the following, the composition of a conventional emulsion paint will be explained. Emulsion paints generally contain from 30 to 75% by weight, and preferably from 40 to 65% by weight, of non-volatile constituents. This is to be understood as meaning all constituents of the preparation which are not water, but at least the total amount of binder, filler, pigment, low-volatile solvents (boiling point above 220 ^° C.), eg. As plasticizers, and polymeric adjuvants. This accounts for about

a) 3 to 90 wt .-%, in particular 10 to 60 wt .-%, on the finely divided polymer dispersion PD, b) 0 to 85 wt .-%, preferably 5 to 60 wt .-%, in particular 10 to 50 wt. -%, to at least one inorganic pigment, c) 0 to 85 wt .-%, in particular 5 to 60 wt .-%, of inorganic fillers and d) 0.1 to 40 wt .-%, in particular 0.5 to 20 Wt .-%, on conventional aids.

In the context of this invention, all pigments and fillers, eg. As color pigments, white pigments and inorganic fillers. These include inorganic white pigments, such as titanium dioxide, preferably in rutile form, barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopones (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, Contain antimony black, manganese violet, Paris blue or Schweinfurter green. In addition to the inorganic pigments, the emulsion paints of the invention may also organic color pigments, for. B. sepia, gummi, brown Kassel, Toluidinrot, Para red, Hansa yellow, indigo, azo dyes, anthraquinoid and indigoid dyes and dioxazine, quinacridone, phthalocyanine, isoindolinone and metal complex pigments contained. Also suitable are synthetic white pigments with air inclusions to increase the light scattering, such as the Rhopaque © dispersions. Suitable fillers are for. For example, aluminosilicates, such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates, such as calcium sulfate, silica, etc. In paints naturally finely divided Fillers preferred. The fillers can be used as individual components. In practice, however, filler mixtures have proven particularly useful, for. Calcium carbonate / kaolin, calcium carbonate / talc. Glossy paints generally have only small amounts of very finely divided fillers.

Finely divided fillers can also be used to increase the hiding power and / or to save on white pigments. To adjust the hiding power of the hue and the depth of shade, blends of color pigments and fillers are preferably used.

The proportion of pigments can be determined by the pigment volume concentration (PVK), i. i. the quotient of volume of the pigments to the total volume of the dried paint, will be described. High gloss paints have z. B. a PVK in the range of 12 to 35%, preferably 15 to 30%.

In addition to the polymer dispersion PD), at least one highly branched polymer as additive, optionally additional film-forming polymers and pigment, the coating composition (aqueous coating material) according to the invention may contain further auxiliaries.

The usual auxiliaries include, in addition to the emulsifiers used in the polymerization, wetting agents or dispersants, such as sodium, potassium or ammonium polyphosphates, alkali metal and ammonium salts of acrylic or maleic anhydride copolymers, polyphosphonates, such as 1-hydroxyethane-1, 1 diphosphonic acid sodium and Naphthalinsulfonsäuresalze, especially their sodium salts.

Further suitable auxiliaries are leveling agents, defoamers, biocides and thickeners. Suitable thickeners are z. B. Associative thickener, such as polyurethane thickener. The amount of thickener is preferably less than 1 wt .-%, more preferably less than 0.6 wt .-% thickener, based on the solids content of the An-line agent.

The preparation of the paint according to the invention is carried out in a known manner by mixing the components in mixing devices customary for this purpose. It has proven useful to prepare an aqueous paste or dispersion from the pigments, water and optionally the adjuvants, and then to first mix the polymeric binder, ie, as a rule, the aqueous dispersion of the polymer with the pigment paste or pigment dispersion. The paints according to the invention generally contain from 30 to 75% by weight and preferably from 40 to 65% by weight of nonvolatile constituents. These are to be understood as meaning all constituents of the preparation which are not water, but at least the total amount of binder, pigment and auxiliary agent based on the solids content of the paint. The volatile constituents are predominantly water.

Suitable paints are high gloss paints. The gloss of the paint can be determined according to DIN 67530. The paint with 240 μm gap width is applied to a glass plate and dried for 72 hours at room temperature. The specimen is placed in a calibrated reflectometer and, at a defined angle of incidence, the extent to which the reflected light has been reflected or scattered is determined. The determined reflectometer value is a measure of the gloss (the higher the value, the higher the gloss).

The gloss of the high-gloss coatings is preferably greater than 60 at 20 ° and greater than 80 at 60 °. The reflectometer value is determined at 23 ⁰ C and dimensionless given as a function of the angle of incidence, z. B. 40 at 20 °.

The paint of the invention can be applied in a conventional manner to substrates, for. B. by brushing, spraying, dipping, rolling, knife coating, etc.

It is preferably used as a decorative paint, i. H. used for coating buildings or parts of buildings. It may be mineral substrates such as plasters, gypsum or plasterboard, masonry or concrete, wood, wood materials, metal or paper, z. B. wallpaper or plastic, z. B. PVC act.

Preferably, the paint for building interior parts, z. As interior walls, interior doors, wainscoting, banisters, furniture, etc. use.

The paints of the invention are characterized by easy handling, good processing properties and high hiding power. The paints are low in emissions. They have good performance properties, eg. B. a good water resistance, good wet adhesion, especially on alkyd paints, good blocking resistance, good paintability and they show a good course when applied. The tool used can be easily cleaned with water.

The invention will be more apparent from the following non-limiting examples. Examples:

I. Synthesis of highly branched polymers

HBP 1: hyperbranched polycarbonate

In a 6 L flask equipped with stirrer, internal thermometer and reflux condenser, 1183.0 g of diethyl carbonate (10.00 mol) and 2700.0 g of a triol (10.00 mol), previously prepared by ethoxylation of trimethylolpropane with three Ethylene oxide units was obtained, in the presence of potassium carbonate (0.5 g) at atmospheric pressure and with slight nitrogen gassing at about 130 ⁰ C reacted. The ethanol formed in the course of the reaction lowered the boiling point of the reaction mixture to 100 ^° C. over 4 h. After the boiling temperature remained constant, the reflux condenser was passed through a distillation apparatus consisting of a 20 cm packed column, a descending condenser and a receiver. exchanged and distilled off the ethanol formed in the reaction continuously. After a total of about 810 g of ethanol had been removed, which corresponds to a total ethanol conversion of about 88%, the reaction mixture was cooled to 100 ⁰ C and to neutralize the potassium carbonate 85% phosphoric acid (0.5 g) was added until a pH Value of less than 7. The mixture was stirred for a further 1 h at 100 ^° C. Then, 10 minutes nomer at 140 ⁰ C and 40 mbar Restmo- and residues of ethanol away. Subsequently, the product was cooled and analyzed.

The OH number was determined to be 265 mg KOH / g, the molecular weights determined by GPC (eluent = DMAC, calibration = PMMA) were M _n = 2100 g / mol and M _w = 7400 g / mol.

HBP 2: hyperbranched polycarbonate

In a 6 L flask equipped with stirrer, internal thermometer and reflux condenser, were added 590.7 g of diethyl carbonate (5.00 mol) and 3350.0 g of a triol (5.00 mol) previously prepared by ethoxylation of trimethylolpropane with 12 Ethylene oxide units was obtained in the presence of potassium carbonate (0.5 g) at atmospheric pressure with slight nitrogen gassing at about 140 ⁰ C reacted. The ethanol formed in the course of the reaction lowered the boiling point of the reaction mixture to 120 ^° C. over 4 h. After the boiling temperature remained constant, the reflux condenser was replaced by a distillation apparatus consisting of a 20 cm packed column, a descending condenser and a receiver and continuously distilling off the ethanol formed in the reaction. After a total of about 405 g of ethanol had been removed, which corresponds to a total ethanol conversion of about 88%, the reaction mixture was cooled to 100 ⁰ C and for neutralization of potassium carbonate added 85% phosphoric acid (0.5 g) until a pH of less than 7 had been established. The mixture was stirred at 100 ^° C. for a further 1 h. Subsequently, residual monomers and residues of ethanol were removed at 140 ^° C. and 40 mbar for 10 minutes. Subsequently, the product was cooled and analyzed.

The OH number was determined to be 146 mg KOH / g, the molecular weights determined by GPC (eluent = DMAC, calibration = PMMA) were M _n = 2700 g / mol and M _w = 5500 g / mol. The glass transition temperature was determined by DSC to Tg = -56 ⁰ C.

II. Preparation of Polymer Dispersions

Dispersion D1:

Dispersion of acrylic acid, acrylamide, n-butyl acrylate and methyl methacrylate

Original: 32.80 g of feed 1 10.92 g of feed 2 201, 24 g of demineralized water 0.13 g of copper 11 sulfate (0.1%)

3.25 g of Maranil A 20® (20%) (sodium n- (C 1 -C ₃ -alkyl) benzenesulfonate, Cognis)

Addition 1: 7.22 g of demineralized water

Feed 1: 248.09 g of demineralized water

8.67 g Dowfax 2A1® (45%) (alkyldiphenyloxide disulfonate, Dow Co.)

26.00 g of Lutensol TO 89® (20%) (ethoxylated cis-oxo-alcohol,

Fa. BASF Aktiengesellschaft) 8.45 g of acrylic acid

19.50 g of acrylamide (50% in water) 364.00 g of n-butyl acrylate 267.80 g of methyl methacrylate

Feed 2: 31, 20 g of sodium peroxodisulfate (2.5%)

Feed 3: 3.90 g demineralized water 2.6 g ammonia (25%)

Feed 4: 5.92 g of deionized water 3.90 g of tert-butyl hydroperoxide (10%) Feed 5: 9.3 g of demineralized water

4.96 g of acetone bisulfite (13.10%)

Feed 6: 37.90 g of demineralized water

Feed 7: 4.35 g Acticid MBS (5%) (biocide, Thor chemistry)

Feed 8: 1 1.05 g of sodium hydroxide solution (10%)

11, 57 g of demineralized water

In a flask equipped with metering means and temperature control polymerization vessel belonging to the original amounts of deionized water, copper-II-sulphate and Maranil® A20 initially were initially charged and heated with stirring to 95 ⁰ C. Subsequently, the original amount of feed 1 was added and stirred for 10 minutes. Thereafter, the original amount of feed 2 was added and the original polymerized for 5 minutes. After the initial polymerization, the residual amounts of feeds 1 and 2 were metered in over the course of 150 minutes and, after the end of feed 1, these were flushed with feed 1. Polymerization was continued for fifteen minutes, during which the temperature was set in the reaction vessel at 90 ⁰ C. For neutralization, feed 3 was then metered in within 15 minutes and then the feeds 4 and 5 were added in parallel within 1 hour, after which stirring was continued for 15 minutes. The reaction mixture was then allowed to cool to 30 ^° C. in the course of 90 minutes and, after reaching this temperature, feed 6 was added. Finally, the feeds 7 and 8 were also added successively at 30 ⁰ C and then the reaction mixture was cooled to room temperature.

Table 1: Analytics

III. Application examples

1. Preparation of aqueous paints

The individual components were metered in the amount (parts by weight) and order, as indicated in Table 2, with stirring with a toothed disc stirrer. In this case, a paste was first prepared by dispersing at 1000 rpm for 15 minutes before the dispersion D1 was added, and then the remaining components were likewise added at 1000 rpm. It was dispersed until the pigment paste was smooth, ie free from lumps. Dispersion D1 and the hyperbranched polymers had already been mixed in advance. Comparative formulation F1 contained no hyperbranched polymer.

Table 2: Color formulations

Table 3: Results

Brookfield viscosity determined with spindle n ° 6 at 23 ⁰ C, the color films have been coated with a 60 .mu.m doctor blade, Stipp rating: 0 (= very good) to 6 (= very poor)

Claims

claims

1. Process for the preparation of an aqueous polymer dispersion PD) with improved freeze-thaw stability by free-radical emulsion polymerization of at least one ethylenically unsaturated monomer M) with the addition of at least one highly branched polymer.

2. The method of claim 1, wherein as hyperbranched polymer at least one hyperbranched polymer is used as an additive.

3. The method according to claim 2, wherein the hyperbranched polymer has a degree of branching DB of 10 to 95%, preferably 25 to 90%, in particular 30 to

80%.

4. The method according to any one of the preceding claims, wherein the highly branched polymers are selected from polycarbonates, polyesters, polyethers, polyurethanes, polyureas, polyamines, polyamides, poly (urea urethanes), poly (ether amines), poly (esteramines), poly (ether amides ), Poly (esteramides), poly (amidoamines), poly (ester carbonates), poly (ether carbonates), poly (ether esters), poly (etherester carbonates) and mixtures thereof.

5. A process as claimed in any of claims 1 to 4, in which the hyperbranched polymer used is a hyperbranched polycarbonate, poly (ether carbonate), poly (ester carbonate) or poly (etherester carbonate) or a mixture of hyperbranched polymers containing at least one hyperbranched polycarbonate, poly (ether),

Poly (ester carbonate) or poly (ether ester carbonate) is used.

6. The method according to any one of the preceding claims, wherein the monomer M) is selected from esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C2o-alkanols, vinylaromatics, esters of vinyl alcohol with

C 1 -C 30 -monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, monoethylenically unsaturated carboxylic and sulfonic acids, phosphorus-containing monomers, esters of α, β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 3 -oxanediols, amides α, β-ethylenic unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group, primary amides of α, ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives, N-vinyl lactams, open-chain N -Vinylamidverbindungen, esters of allyl alcohol with Ci-C3o monocarboxylic acids, esters of α, ß-ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols, amides α, ß-ethylenisch unsaturated

Mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group, N, N-diallylamines, N, N-diallyl N-alkylamines, vinyl- and allyl-substituted nitrogen heterocycles, vinyl ethers, C 2 -C 8 monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, polyether (meth) acrylates, urea group-containing monomers and mixtures thereof.

7. The method according to any one of the preceding claims, wherein at least 40 wt .-%, preferably at least 60 wt .-%, more preferably at least 80 wt .-%, of at least one monomer M1) are used for the emulsion polymerization, which is selected from esters α , ß-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 20 -alkanols, vinylaromatics, esters of vinyl alcohol with C 1 -C 3 -monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides and mixtures thereof.

8. The method according to claim 7, wherein in addition to the emulsion polymerization up to 60 wt .-%, preferably up to 40 wt .-%, particularly preferably up to 20 wt .-% of at least one monomer M2) are used, which is selected from ethylenic unsaturated mono- and dicarboxylic acids and the anhydrides and half esters of ethylenically unsaturated dicarboxylic acids, (meth) acrylamides, Ci-Cio-hydroxyalkyl (meth) acrylates, Ci-Cio-hydroxyalkyl (meth) acrylamides and mixtures thereof.

9. The method according to any one of the preceding claims, wherein the addition of the highly branched polymer takes place following the emulsion polymerization.

10. Aqueous polymer dispersion PD) obtainable by a process as defined in any one of claims 1 to 9.

1 1. A binder composition containing an aqueous polymer dispersion PD) obtainable by a process as defined in any one of claims 1 to 9, at least one highly branched polymer and optionally at least one further film-forming polymer.

12. Coating composition in the form of an aqueous composition containing

a binder composition as defined in claim 11,

optionally at least one inorganic filler and / or at least one inorganic pigment,

- If necessary, further aids, and

Water.

13. Coating composition according to claim 12 in the form of a paint.

14. paint according to claim 13 in the form of a clearcoat.

15. paints according to claim 13 in the form of an emulsion paint.

16. A method for improving the freeze / thaw stability of an aqueous polymer dispersion PD) obtainable by free-radical emulsion polymerization of at least one ethylenically unsaturated monomer M) by adding at least one highly branched polymer.

17. Use of at least one highly branched polymer as defined in any one of claims 1 to 5, as an additive for aqueous polymer dispersions to improve the freeze / thaw stability.

18. Use of at least one highly branched polymer as an additive for a product comprising an emulsion polymer based on at least one ethylenically unsaturated monomer M) as defined in any one of claims 6 to 8 for improving the freeze / thaw stability of the product.

19. Use according to claim 18 as an additive for a paint, in particular as an additive for a clearcoat or an emulsion paint.

20. Use of an aqueous polymer dispersion PD), which is a highly branched

A polymer as defined in any one of claims 1 to 5 as an additive, as a component in paints.