DE10005648A1 - Sulfonic acid group containing compounds, useful in production of wetting agents, dispersing agents, and plating bath adjuvants give products of increased main and side chain flexibility - Google Patents

Abstract

Sulfonic acid group containing compounds for introduction of sulfonic acid groups into a polymer, which compounds can be easily modified so as to increase the flexibility of the main chain and the sulfonic acid group bearing side chains and in which the degree of hydrophilic character can be varied are new. Sulfonic acid group containing compounds of formula (I), useful for introduction of sulfonic acid groups into a polymer, which compounds can be easily modified so as to increase the flexibility of the main chain and the sulfonic acid group bearing side chains and in which the degree of hydrophilic character can be varied. [Image] R1H or linear or branched optionally saturated aliphatic 1-20C hydrocarbon, optionally saturated and substituted 4-20C cycloaliphatic hydrocarbon, or 6-40C optionally substituted araliphatic hydrocarbon; R21-20C optionally branched or saturated hydrocarbon, 4-20C cycloaliphatic hydrocarbon, or optionally 6-18C optionally substituted aromatic hydrocarbon; Z1, Z2R3-QH, R3-Q-(X-O-)mX-QH or R3-O-Y-Q-; Q : O, NH, NR3 or S; R3optionally branched or optionally unsaturated, optionally aromatic substituted 2-44C alkyl; X : optionally aromatic substituted 2-14C alkyl; Y : polymer obtained by polymerisation, polyaddition, or polycondensation, of molecular weight 150-5000; and n : 1-300; provided that one of Z1 or Z2 is CH2-CH2-OH or salt. Independent claims are included for: (1) preparation of a sulfonic acid compound of formula Z1-NH-Z2 (II) or (III) by a Michael addition reaction; (2) a polyurethane, built up as a block copolyurethane having at least one hard and at least one soft segment; and (3) an aqueous dispersion containing at least one of the above sulfonic acid compounds, and a polyaddition or polycondensation product. [Image]

Description

The invention relates to a sulfonic acid compound of the general formula I,

wherein R ^{1 is} H or a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to 20 C atoms, a saturated or unsaturated, optionally substituted cycloaliphatic hydrocarbon radical having 4 to 20 C atoms or an optionally substituted araliphatic hydrocarbon radical having 6 to 40 C atoms, R ^{2 represents} a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to 20 C atoms or a cycloaliphatic hydrocarbon radical having 4 to 20 C atoms or an optionally substituted aromatic hydrocarbon having 6 to 18 C atoms , Z ¹ and Z ² each independently represent R ³ -QH, R ³ -Q- (XO-) _m X-QH or R ³ -OYQ-, where Q is O, NH, NR ³ or S, R ³ for a linear or branched, saturated or unsaturated, optionally aromatically substituted alkyl radical having 2 to 44 C atoms, X for an alkyl rest with 2 to 10 carbon atoms, Y stands for a polymer obtainable by polymerization, polyaddition or polycondensation with a molecular weight M _w of 150 to 5000 and n for a value of 1 to 300 and not both residues Z ¹ and Z ² at the same time represent CH ₂ -CH ₂ -OH, or a salt thereof.

Polymers containing sulfonic acid groups have a broad spectrum Applications on. They are in organic chemistry as well polymer chemistry used especially when the used Polymers should have special dispersion properties because the Sulfonic acid group is known for its excellent dispersing effect. Frequently However, it is problematic to use a simple procedure Inclusion of sulfonic acid group in polymers to provide the in particular ensures that the incorporated in the polymer Sulfonic acid group the desired properties as optimally and tailor-made fulfilled.

For example, US Pat. No. 5,695,884 describes a thermoplastic Polyurethane that has at least one sulfonate group. The sulfonate group is in the polyurethane via a corresponding sulfonate group Introduced polyester polyol, which is the sulfonate group in the form of a Sulfophthalic acid derivative is incorporated into the polyester polyol. Problematic affects such polyurethanes that the sulfonate group due to rigid phthalic acid body to which it is bound, only via a restricted Mobility has, which often negatively affects the dispersion properties of the corresponding polyurethane affects. There are also such Sulfonate groups after incorporation into the polyurethane directly in the main chain, thereby possibly flexibility and mobility of the main chain be restricted.  

DE-C 34 07 563 describes an alternative way of introducing Sulfonic acid groups in polyaddition or polycondensation products. Here becomes a terminally unsaturated diol carrying two terminal OH groups converted into a terminal sulfonate by the bisulfite addition reaction. The Sulfonate is then, for example, via the two OH groups Polyurethane incorporated. In this way, the disadvantage can be avoided that the sulfonate group attached to a rigid framework directly on the main chain is, the method described and the compounds obtainable thereafter however also has a number of disadvantages. For example disadvantageous from that the bisulfite addition reaction usually in aqueous Environment must take place. In addition, the bisulfite addition reaction usually the last processing step before incorporation into a polymer represents, which may make adequate drainage difficult.

If a relatively hydrophobic diol for the bisulfite Addition reaction used, so the isolation of the Reaction product i. d. R. difficult. Therefore, in such reactions Usually used hydrophilic compounds, for example those in the described polyether. Such sulfonated polyethers can subsequently be incorporated into polymeric compounds, but they do on the one hand, nothing to make the main chain more flexible, on the other hand, due to the reaction conditions in the implementation of the hydrophilicity of the Vary the sulfonate-bearing side chain only within narrow limits.

There was therefore a need for sulfonic acid groups Compounds that are both polyaddition and Have polycondensation reactions built into polymers, the Flexibilization of the main chain as well as the flexibility of the sulfonate group load-bearing side chain can be varied within wide limits.  

DE-B 19 54 090 describes a process for the preparation of 2- (β-amino propionamido) alkanesulfonic acid salts and their use as anionic Building component in the production of polyurethane dispersions. Disadvantageous has an effect on the substances described there that an integration into Polyurethane is only possible via an amino group. The resulting However, polyureas have a number of properties, which can be seen in their Applications as polymeric surfactants or for the dispersion of solids in one Adversely affect the plastic matrix. In addition, they are described Compounds can only be processed in the aqueous phase, as a result of which the person skilled in the art its freedom of formulation is restricted. Processing the Polyureas in organic solvents with lower polarity are usually not possible.

WO 91/06597 relates to curable aminoplast compounds and catalysts to harden them. Various implementation products are described, such as them from the reaction of primary or secondary amines and a vinyl or allyl compound bearing a sulfonate group. Exemplary the reaction with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) with various amines listed. However, the publication does not mention any Compounds that can be built into polyurethanes and are used both for Control of hydrophilicity as well as making the main chain more flexible can.

DE-A 26 56 687 relates to aminodi- and aminopolyalkylamidoalkane sulfonic acids, process for their preparation and their use. The However, the compounds described are not suitable for incorporation into polymers.

The present invention was therefore based on the object To provide compounds containing sulfonic acid groups, which are  suitable for example for introducing sulfonic acid groups into polymers, the connections can be modified in a simple manner in such a way that for example the flexibility of the main chain, the flexibility of the Side chain bearing sulfonic acid group and the degree of hydrophilicity of the Connection varies. Furthermore, such connections are said to be good Have dispersing properties and, if they are anionic for incorporation Groups are used in polymers, the resulting polymer impart such properties. In addition, the appropriate Compounds containing sulfonic acid groups great variability in terms of Have adjustability of the solubility parameters.

The object of the invention is achieved by sulfonic acid compounds Art described below.

The present invention therefore relates to a sulfonic acid compound of the general formula I.

wherein R ^{1 is} H or a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to 20 C atoms, a saturated or unsaturated, optionally substituted cycloaliphatic hydrocarbon radical with 4 to 20 C atoms or an optionally substituted araliphatic or aromatic hydrocarbon radical with 6 is up to 40 carbon atoms, R ^{2 is} a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to 20 carbon atoms or a cycloaliphatic hydrocarbon radical with 4 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon with 6 to 18 carbon atoms Atoms, Z ¹ and Z ² each independently represent R ³ -QH, R ³ -Q- (XO-) _m X-QH or R ³ -OYQ-, where Q is O (oxygen), NH, NR ³ or S, R ³ for a linear or branched, saturated or unsaturated, optionally aromatically substituted alkyl radical with 2 to 44 carbon atoms, X for an optionally aromatically substituted alkyl radical having 2 to 14 carbon atoms, Y for a polymer obtainable by polymerization, polyaddition or polycondensation with a molecular weight M _w of 150 to 5000 and n for a value of 1 to 300 and wherein both Z ¹ and Z ^{2 are not} simultaneously CH ₂ -CH ₂ -OH, or a salt thereof.

A "sulfonic acid compound" is used in the context of the present text understood a compound according to general formula I, which at least one Carries sulfonic acid group, but the term "sulfonic acid compound" also includes the salts of such sulfonic acids. Salt, for example understood the reaction products of the claimed sulfonic acids with bases, the bases can be both inorganic and organic in nature. Examples of corresponding salts are the salts of the alkali metals such as lithium, Sodium, potassium, rubidium or cesium or the salts of alkaline earth metals such as Magnesium, calcium or strontium. In addition to the salts mentioned with however, inorganic compounds are suitable in the context of the present Compound also salts of the above sulfonic acids with organic salts. In the context of a preferred embodiment of the present invention are salts with salts of the above sulfonic acids Understanding amino compounds. Particularly suitable amino compounds are Pyridines, alkanolamines or trialkylamines, the corresponding alkyl radicals independently of one another have from 1 to about 22 carbon atoms. In another preferred embodiment, the invention relates to salts of the above Sulfonic acids with pyridines, alkanolamines or trialkylamines, the  Alkyl radicals independently of one another have 1 to about 5 carbon atoms.

The molecular weights given in this text are in units of g / mol unless otherwise stated. Molecular weights of compounds that have a statistical molecular weight distribution were determined by GPC. The following materials were used:

• - Column material: PL-Gel 5 µm 2 × 500 Å 1X 1000 1 × 10,000
• - eluent: THF 1 ml / min
• - Pump: Waters type 510
• - Autosampler: Waters type 717
• - UV detector: Waters Lambda - Max 481
• - RI detector: Waters type 410

The radical R ¹ in the context of the present invention represents H or a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to about 30 C atoms, a saturated or unsaturated, optionally substituted cycloaliphatic hydrocarbon radical having 4 to about 30 C atoms or an optionally substituted araliphatic or aromatic hydrocarbon radical having 6 to about 40 C atoms. Within the stated ranges, the radical R ^{1 can} be selected such that the sulfonic acid compound claimed, for example, fulfills a certain solubility profile, for example in connection with its production or its later use, or with regard to another property which is dependent on the presence of certain alkyl chains in the molecule can be tailored to a corresponding application. In a preferred embodiment of the present invention, the radical R ^{1 is} hydrogen or a linear or branched, saturated hydrocarbon radical having 1 to about 16, in particular 1 to 6, carbon atoms or an aromatic hydrocarbon having 6 to about 12 carbon atoms. In a further preferred embodiment of the invention, the radical R ^{1 is} hydrogen, CH ₃ or phenyl.

In the context of the present invention, the radical R ² stands for a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to about 30 C atoms or a cycloaliphatic hydrocarbon radical with 4 to about 30 C atoms. In addition to influencing the solubility parameters already described in the context of the remainder of the radical R ¹ , a change in the radical R ^{2 can} also be used in the context of the present invention to increase the flexibility and the distance of the sulfonic acid group from the rest of the molecule, especially when incorporating the invention Sulphonic acid compounds in a polymer to vary. In the context of a preferred embodiment of the invention, the radical R ^{2 represents} a linear or branched aliphatic hydrocarbon radical having 3 to 8 carbon atoms.

In a preferred embodiment of the invention, the two radicals Z ¹ and Z ² independently of one another are R ³ -QH, R ³ -Q- (XO-) _m X-QH or R ³ -OYQ-, where Q is O (oxygen ), NH, NR ³ or S, R ³ for a linear or branched, saturated or unsaturated, optionally aromatically substituted alkyl radical with 2 to 44 C atoms, X for an optionally aromatically substituted alkyl radical with 2 to 14 C atoms, Y for a polymer obtainable by polymerization, polyaddition or polycondensation with a molecular weight M _w of 150 to 5000 and n stands for a value of 1 to 300 and where not both Z ¹ and Z ^{2 are} simultaneously CH ₂ -CH ₂ -OH.

In the context of the present invention, the radicals Z ¹ and Z ² each have at least two C atoms. The number of carbon atoms does not necessarily refer to carbon atoms covalently bonded to one another in a chain, but the present invention also includes those sulfonic acid compounds whose Z ¹ and Z ² radicals each comprise at least two carbon atoms that are not directly covalent but are connected to each other, for example, via a further atom Q, which is preferably O or N. In the context of the present invention, the radicals Z ¹ and Z ² have at least one QH group. In a preferred embodiment of the present invention, the number of QH groups can be, for example, 1 to about 8, in particular 1 to about 4. In a further preferred embodiment of the invention, the number of QH groups in the radicals Z ¹ and Z ^{2 is} 2 or 3. The QH groups can either be located only on one of the two radicals Z ¹ or Z ² , but it is it is equally possible that the QH groups are located on both residues. In the context of a preferred embodiment of the invention, each of the Z ¹ and Z ² radicals has at least one QH group. In a further preferred embodiment of the invention, each of the two radicals Z ¹ and Z ² each has a QH group.

Since the compounds according to the invention are intended to provide sulfonic acid compounds which can also be processed in non-aqueous solution, in particular in a solvent which is at least largely free of protic constituents, the above definition is subject to a significant restriction. If one of the two radicals Z ¹ and Z ^{2 has} 2 carbon atoms and a QH group, the remaining radical must have at least 3 carbon atoms.

In a further preferred embodiment of the invention, R ^{3 represents} a linear or branched, saturated, optionally aromatically substituted alkyl radical having 2 to about 10, in particular 3 to about 8, carbon atoms.

If Z ¹ or Z ^{2 stands} for R ³ -Q- (XO-) _n X-QH, then in a preferred embodiment of the invention X stands for a saturated, linear or branched alkyl radical having 2 to 4, in particular 2 or 3 C- Atoms or an aromatic, substituted, linear or branched alkyl radical with a total of 8 to about 18 carbon atoms and Q for NH, NR ² or O. Z ¹ or Z ² , or both, then stand for a polyether chain, the molecular weight M _{w of} one depends on X, but mainly on the value of n. In a preferred embodiment of the invention, n stands for a value from 1 to about 200, in particular from about 3 to about 50. If the value for n is greater than 1, then X can represent different alkyl radicals, the number of carbon atoms in the already lies above range. With larger values for n, for example in a range from about 5 to about 100, the various alkyl radicals X can be arranged in a statistical sequence or in blocks as desired. The value n does not necessarily have to be an integer value, n can just as well take any values that lie between two integers in the range mentioned above. If n assumes a non-integer value, then n represents an average value as occurs in the context of conventional polyether syntheses due to the statistical distribution of molecular weights during polyaddition. In a further preferred embodiment of the invention X is CH ₂ - (CH ₃₎ -CH ₂ or CH ₂ -CH (CH) or a random or block sequence of these radicals CH ₂ or CH.

Polyethers of the type mentioned above can, for example, by polymerization of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with themselves, for. B. in the presence of basic catalysts such as sodium methylate, potassium methylate, sodium ethylate, potassium ethylate, sodium hydroxide, potassium hydroxide or BF ₃ , or by addition of the compounds mentioned, optionally in a mixture or in succession, components at the start with reactive hydrogen atoms such as alcohols or amines, for. B. water, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-bis (4-hydroxydiphenyl) propane or aniline can be obtained.

In a further preferred embodiment of the present invention, the radical Z ¹ or the radical Z ² , or both, represent R ³ -QY-QH. Y stands for a polyester, a polyamide, a polycarbonate, a polyurethane or a polylactone with a molecular weight M _w of about 200 to about 2000. In a further preferred embodiment of the invention, the polymers mentioned are linear polymers.

Suitable polyesters can be obtained, for example, by polycondensation of linear or branched, aliphatic or cycloaliphatic, saturated or unsaturated diols with linear or branched, saturated or unsaturated, aliphatic or cycloaliphatic dicarboxylic acids or with aromatic dicarboxylic acids. Suitable diols are, for example, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butenediol, 1,4-butynediol, 1,5-pentanediol, neopentyl glycol, Bis- (hydroxy methyl) cyclohexanes such as 1,4-bis (hydroxymethyl) cyclohexane, 2-methylpropane-1,3-diol, methylpentanediols, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, dibutylene glycol and other higher oligomers of the glycols mentioned , Mixed oligomers are also suitable. Within the scope of the present inventions, polyesters are preferred, the production of which using alcohols of the general formula HO- (CH ₂ ) _x -OH, where x is a number from 2 to about 44, for example an even number from about 2 to about 20 , stands, was carried out. Examples of such alcohols are ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and decanediol -1.10, undecanediol-1.11, or dodecanediol-1.12, or mixtures of two or more thereof.

Suitable dicarboxylic acids are, for example, dicarboxylic acids of the general formula HOOC- (CH ₂ ) _y -COOH, where y is a number from 1 to about 20, for example an even number from 2 to about 20. Examples of such dicarboxylic acids are succinic acid, adipic acid, dodecanedicarboxylic acid and sebacic acid. are also suitable as acids for the construction of the above polyester suberic acid, azelaic acid, phthalic acid, isophthalic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, endomethylenetetrahydrophthalic anhydride, glutaric anhydride, maleic acid, maleic anhydride, fumaric acid, or dimer fatty acids, or mixtures of two or more thereof.

In a preferred embodiment of the present invention, the polyester used has a molecular weight of about 150 to about 1500.

In the context of the present invention, suitable polyamides can be used as radical Y. itself, for example, by reacting the above-mentioned dicarboxylic acids produce the corresponding diamines. Suitable diamines are, for example those which have a molecular weight of about 32 to about 200 g / mol and at least two primary, 2 secondary or one primary and one secondary Have amino groups. Examples include diaminoethane, diaminopropanes, Diaminobutanes, diaminohexanes, piperazine, 2,5-dimethylpiperazine, amino-3 aminomethyl-3,5,5-trimethylcyclohexane (isophoronediamine, IPDA), 4,4'-diamino dicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, Hydrazine hydrate or, optionally in small amounts, diamines such as Diethylenetriamine or 1,8-diamino-4-aminomethyloctane. As part of the Polyamides which can be used in the present invention have in a preferred Embodiment has a molecular weight from about 100 to about 1500.  

Are also suitable as diols for the construction of appropriate polyesters Polycarbonate diols such as those obtained by reacting phosgene with a Excess of the above diols are available.

The polycarbonates suitable as radical Y in the context of the present invention correspond to the polycarbonates already mentioned above, for example by reacting phosgene with one or a mixture of two or more of the above diols are available. In a preferred one Embodiment of the invention, the polycarbonates have a molecular weight from about 100 to about 10,000, for example about 200 to about 5000.

As polyurethanes are, for example, such polyurethanes as in Be presented within the scope of the present invention. Suitable as Y. Polyurethanes have a molecular weight of about 100 to about 3000, for example about 300 to about 2000.

Polylactones as are obtainable by homopolymerization or mixed polymerization of lactones, optionally in the presence of a suitable difunctional starter molecule, are also suitable for use as radical Y according to the invention. Preferred lactones are those which are derived from compounds of the general formula HO- (CH ₂ ) _z -COOH, where z is a number from 1 to about 20. Examples are ε-caprolactone, β-propiolactone, γ-butyrolactone or methyl-ε-caprolactone or mixtures of two or more thereof. Polylactones preferably used in the context of the present invention have a molecular weight of about 100 to about 1500, in particular about 200 to about 800.

It is not necessary in the context of the present invention that the two radicals Z ¹ and Z ^{2 are} identical. Each of the two radicals mentioned can independently represent a radical as defined above.

The sulfonic acid compounds of the invention can be according to the rules of organic chemistry in different ways. As special However, the compounds according to the invention have proven to be advantageous by implementing corresponding components A and B in the sense of a Michael To produce addition.

The invention therefore also relates to a process for the preparation of a sulfonic acid compound of the general formula I, in which a compound of the general formula II

Z ¹ -NH-Z ² (II),

wherein Z ¹ and Z ^{2 are} as defined above, as component A, with a compound of general formula III

wherein R ¹ and R ^{2 are} as defined above, as component B, are implemented.

If the compound of the general formula III (component B) If acid is used, component A should be at least molar Excess are used.

Compounds of the general formula II (component A) can be prepared according to generally known principles of organic chemistry. The starting point for the preparation of such molecules is generally the compound NH (R ³ OH) ₂ , which are reacted with corresponding alkylene oxides, for example for the preparation of the above-mentioned polyethers, as already described above. Analogously, a molecule of the general formula II can be obtained by condensation reaction of this compound with appropriately functionalized polyesters, polyamides, polycarbonates or polylactones.

In a first embodiment of the manufacturing method according to the invention is therefore an amine of the general formula II with an ethylenic unsaturated amidosulfonic acid compound under suitable conditions implemented.

The reaction can be carried out with or without a solvent. Suitable Solvents are, for example, alcohols such as methanol, ethanol, isopropyl alcohol, ethers such as ethylene glycol, dimethyl ether or tetrahydrofuran, ketones such as acetone or methyl ethyl ketone (MEK), N-methylpyrrolidone (NMP), N, N- Dimethylformamide (DMF), acetonitrile, trichloromethane or toluene, or Mixtures of two or more of them. If necessary, in addition to the above mentioned solvents, especially together with the above polar Solvents, water are present in the solvent mixture during the reactions. If the compounds of the invention for the preparation of substantially anhydrous polymers are to be used, then it is within the present invention preferred the reaction in the absence of water  perform. In this case, particularly preferred solvents are Tetrahydrofuran, acetone or methyl ethyl ketone or a mixture of two or more of that. The reaction temperature is between about 0 ° C and about 200 ° C. Good results can be achieved, for example, in a temperature range of approx Achieve 20 ° C to about 90 ° C. The reaction can optionally be carried out by adding of a basic catalyst can be accelerated. Suitable basic Examples of catalysts are triethylamine, pyridine, benzyltrimethyl ammonium hydroxide, sodium hydroxide or potassium hydroxide.

If necessary, a polymerization inhibitor can also be added during the reaction Reaction mixture are present. Suitable polymerization inhibitors are for example hydroquinone monomethyl ether, stable radicals such as 2,2,6,6- Tetramethyl-piperidine-1-oxyl radical (TEMPO) or 2,2,6,6-tetramethyl-4- hydroxypiperidine-1-oxyl radical (TEMPOL), polymerization inhibitors from the Group of sterically hindered amines (HALS) or from the group of Nitroxides.

The sulfonic acid compounds according to the invention generally have Formula I at least two OH groups and a sulfonic acid group or a salt a sulfonic acid group. Because of the above-mentioned extensive Possibilities of variation with regard to the hydrophilicity of the invention Sulfonic acid compounds and their flexibility and molecular weight, the sulfonic acid compounds according to the invention are suitable for incorporation into Polyaddition or polycondensation products.

The present invention therefore also relates to a polyaddition or polycondensation product which has at least one structural unit according to the general formula IV

in which R ^{1 is} H or a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to 20 C atoms, a saturated or unsaturated, optionally substituted cycloaliphatic hydrocarbon radical having 4 to 20 C atoms or an optionally substituted araliphatic or aromatic hydrocarbon radical with 6 to 40 carbon atoms, R ^{2 is} a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to 20 carbon atoms or a cycloaliphatic hydrocarbon radical with 4 to 20 carbon atoms or an optionally substituted aromatic hydrocarbon with 6 to 18 C atoms, X ¹ and X ² each independently represent R ³ -Q-, R ³ -Q- (XO-) _m XQ- or R ³ -OYQ-, where Q is O (oxygen), NH, NR ³ or S, R ³ for a linear or branched, saturated or unsaturated, optionally aromatically substituted alkyl radical m it has 2 to 44 C atoms, X for an optionally aromatically substituted alkyl radical with 2 to 14 C atoms, Y for a polymer obtainable by polymerization, polyaddition or polycondensation with a molecular weight M _w of 150 to 5000 and n for a value of 1 to 300 and where not both X ¹ and X ² simultaneously represent CH ₂ -CH ₂ -OH, or a salt thereof.

The radicals X ¹ and X ² thus essentially correspond to the above definition for Z ¹ and Z ² , taking into account the fact that a linkage to a polymer chain has taken place. In addition, the structural unit according to general formula IV also includes those polyaddition or polycondensation products in which the radicals X ¹ and X ² each have only 2 carbon atoms.

A "polymer" is used in the context of the present invention Understand polyaddition or polycondensation product. A polymer in For the purposes of the present invention, a lower molecular weight have as the structural unit according to the general formula IV. It can but also have an essentially identical molecular weight or a molecular weight above that of the structural unit according to the general formula IV is. In a preferred embodiment of the In the present invention, the polymer is above molecular weight the structural unit according to the general formula IV Molecular weight.

The polyadducts include, for example, the reaction products the sulfonic acid compounds according to the invention with compounds which have a Can enter into a polyaddition reaction with an OH group. Which includes for example the epoxy group and the isocyanate group. Polycondensation Products in the sense of the invention are implementation products of Sulfonic acid compounds according to the invention with functional groups with OH groups can undergo a condensation reaction. Examples of such functional groups are carboxylic acids or carboxylic acid chlorides.

In the context of a preferred embodiment of the invention, the polyaddition and polycondensation products around polyurethanes, polyesters, Polyethers, polycarbonates, polyether esters, polyamides, polyester amides, polyethers amides, polylactones or polylactams.

The reaction of the sulfonic acid compounds according to the invention with the corresponding functional groups in the context of a polyaddition or Polycondensation follows the general rules of organic chemistry  or polymer chemistry.

In a particularly preferred embodiment of the present invention the polyaddition product is a polyurethane. Polyurethanes can pass through Implementation of the sulfonic acid bearing OH groups according to the invention compounds with polyisocyanates, for example diisocyanates or Get triisocyanates. Suitable isocyanates are both monomeric, low molecular weight polyisocyanates as well as isocyanate groups Prepolymers.

Particularly suitable as monomeric polyisocyanates are the diisocyanates of the general formula X (NCO) ₂ , where X is an aliphatic hydrocarbon radical with 4 to about 12 C atoms, a cycloaliphatic or aromatic hydrocarbon radical with 6 to about 15 C atoms or an aliphatic hydrocarbon radical with 7 to about 15 carbon atoms. Examples of such diisocyanates are tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanatocyclohexane, 1-diisocyanato-3,5,5-trimethyl-5-isocyanatomethylcyclohexane (IPDI), 2,2-bis (4-isocyanatocyclohexyl) propane, trimethylhexane diisocyanate , 1,4-diisocyanatobenzene, 2,4-diiso cyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanatodiphenylmethane, 2,4'-diisocyanatodiphenylmethane, p-xylylene diisocyanate, tetramethylxylylene diisocyanate (TMXDI), the isomers of bis- ( 4-isocyanatocyclohexyl) methane, or mixtures of two or more of the compounds mentioned.

Mixtures of these isocyanates are, in particular, the mixtures of the respective Structural isomers of diisocyanatotoluene and diisocyanatodiphenylmethane from Significance, in particular the mixture of 80 mol% 2,4-diisocyanatotoluene and 20 mol% 2,6-diisocyanatotoluene suitable. Mixtures of aromatic polyisocyanates such as 2,4-diisocyanatotoluene and 2,6-  Diisocyanatotoluene with aliphatic or cycloaliphatic polyisocyanates such as Hexamethylene diisocyanate or IPDI is particularly advantageous, the preferred one Mixing ratio of the aliphatic to aromatic polyisocyanates 4: 1 to Is 1: 4.

In a further preferred embodiment, the Polyurethanes that have at least one structural element according to the general formula I have, by reacting the sulfonic acid compounds of the invention with polymers bearing isocyanate groups.

Such polymers carrying isocyanate groups can be, for example, by Reaction of diisocyanates with diols and optionally others Compounds that are reactive groups to polyisocyanates have obtained. Examples of diols are higher molecular weight diols suitable having a molecular weight of about 500 to about 5000, for example from about 1000 to about 3000 g / mol. Are suitable as diols in particular the polyesters, polycarbonates or Polylactones, or mixtures of two or more thereof, provided they are at least have two OH groups.

Also suitable as diols are polyether diols such as those obtained by polyaddition of Ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or Epichlorohydrin with itself, e.g. B. in the presence of basic catalysts or by addition of these compounds, optionally in a mixture or successively, on starting components with reactive hydrogen atoms are available. The implementation takes place as already described above. The Diols mentioned can also be a mixture of two or more of the above Connections are used.  

In the production of such polymers carrying isocyanate groups, in minor amounts of low molecular weight diols can also be used. Suitable low molecular weight diols have already been mentioned above in the context of this text described.

In a preferred embodiment of the invention, diisocyanate groups supporting polymers used using polyester diols or Polyether diols or a mixture thereof, optionally together with low molecular weight diols by reaction with polyisocyanates Polyurethane prepolymers carrying isocyanate groups were implemented. The The proportion of polyether diols in such polyurethane prepolymers is for example about 10 to about 100 mol%, the proportion of low molecular weight Diols, based on the total amount in the polyurethane prepolymer contained diols, about 0 to about 90 mol%. In a preferred one Embodiment of the present invention is the ratio of Polyether diols to the low molecular weight diols about 0.2: 1 to 5: 1, for example about 0.5: 1 to about 2: 1.

The polyurethanes of the invention can in addition to those from the Structural elements derived from sulfonic acid compounds according to the invention according to the general formula I, further anionic or cationic Have groups.

Under "anionic" or "cationic" groups within the scope of present invention understood such groups, which are simple Neutralization, hydrolysis or quaternization reactions in ionic hydro Have phile groups transferred. Examples of such groups are carboxylic acid groups, anhydride groups or tertiary amino groups.  

Suitable for introducing anionic or cationic groups Compounds are, for example, tris (hydroxyalkyl) amines, N, N'-bis (hy droxyalkyl) alkylamines, N-hydroxyalkyldialkylamines, tris (aminoalkyl) amines, N, N'-bis (aminoalkyl) alkylamines, N-aminoalkyldialkylamines, where the Alkyl residues and alkanediyl units of these tertiary amines are independent have about 2 to about 6 carbon atoms from one another. The tertiary amines mentioned can for example with acids, preferably with strong mineral acids such as Phosphoric acids, sulfuric acid, hydrohalic acid or strong organic acids or by reaction with suitable ones Quaternizing agents such as C1 to C6 alkyl halides, e.g. B. bromides, Chlorides or iodides, converted into the corresponding ammonium salts become. The introduction of anionic groups into the polyurethane usually aliphatic, cycloaliphatic, aliphatic or aromatic Carboxylic acids into consideration that have at least one OH group or at least one have primary or secondary amino group. Are preferred Dihydroxyalkyl carboxylic acids, especially those which contain about 3 to about 10 C Have atoms. Such compounds are described, for example, in US Pat. No. 3,412,054 described.

Corresponding dihydroxysulfonic acids and Dihydroxyphosphonic acids such as 2,3-dihyroxypropanephosphonic acid. About that In addition, dihydroxy compounds are suitable which have a molecular weight of about Have 500 to about 10,000 g / mol and at least two carboxyl groups exhibit. Such connections are for example from DE-A 39 11 827 known.

If in the manufacture of the polyurethanes according to the invention or in the Production of the above-described polyurethane prepolymer monomers with ionic groups can be used, their conversion into the ionic Form before, during or after the polyaddition.  

In the production of the polyurethanes according to the invention, in addition to the already mentioned compounds there are additional compounds, which are used for networking or chain extension. With these Compounds are generally aliphatic or cycloaliphatic alcohols, amines with two or more primary or secondary Amino groups and compounds in addition to one or more OH groups carry one or more primary or secondary amino groups. Likewise Compounds which are a mixture of two or more of the above are suitable have functional groups mentioned.

Polyamines with two or more primary or secondary amino groups or one Mixtures of these groups are mainly used when one Chain extension or crosslinking should take place in the presence of water, since amines are generally faster than alcohols or water with polyisocyanates react. This is often necessary when aqueous dispersions of cross-linked polyurethanes or of high molecular weight polyurethanes be desired.

Suitable amines are generally polyfunctional amines with a Molecular weight from about 32 to about 500 g / mol, preferably from about 60 to about 300 g / mol, which is at least 2 primary, 2 secondary or one primary and have a secondary amino group. Suitable amines are included of the present text mentioned above. If necessary, at Production of the polyurethanes according to the invention still further compounds in Reaction mixture are present which crosslink or branch the resulting polyurethane molecules result. These include, for example Alcohols with more than two OH groups such as trimethylolpropane, Triethylolpropane, glycerin, pentaerythritol or the group of sugars,  for example glucose, sorbitol or mannitol or oligomeric sugars such as Sucrose, maltose or dextrose. For the same purpose, at Reaction also use polyisocyanates that have more than two Have isocyanate groups. Suitable compounds are, for example Isocyanurates or biuret compounds, such as those characterized by corresponding reaction of hexamethylene diisocyanate can be obtained.

In addition, in the implementation of the polyurethanes according to the invention in the reaction mixture there are still compounds which are compared to those in Functional groups present reaction mixture are monofunctional. These include, for example, monoisocyanates, mono alcohols and mono-primary ones or secondary amines. In general, the proportion of such compounds is of the total reaction mixture a maximum of 10 mol%, based on the total Amount of starting materials. Such monofunctional compounds usually wear further functional groups such as olefinically unsaturated groups or carboxyl groups and serve to introduce them to polyurethane. The above Functional groups then allow a further, polymer-analogous implementation of the Polyurethane too. Suitable monomers are, for example, isopropyl-α, α-di methylbenzyl diisocyanate (TMI) or esters of acrylic or methacrylic acid such as Hydroxyethyl acrylate or hydroxyethyl methacrylate.

The individual components are used in such amounts that a is obtained according to the desired molecular weight. The selection of the Quantities of the individual components to each other and from it resulting molecular weight are according to the general rules of Polyurethane chemistry made. In a preferred embodiment of the The present invention will therefore be used to manufacture the invention Educts used in such an amount that the Ratio of isocyanate groups to polyisocyanates reactive Groups about 0.5: 1 to about two: 1, for example about 0.8: 1 to 1.5: 1 or  is about 0.9: 1 to about 1.2: 1 or about 1: 1.

The molecular weight of the polymers of the invention, which is a structural unit according to the general formula IV, is usually about 3000 to about 500,000 g / mol, depending on the desired field of application.

The polymers according to the invention can only have one structural unit according to the have general formula IV, but it is equally possible that a polymer of the invention two or more structural units of the general Formula IV has. In a preferred embodiment of the invention the polyurethane of the invention about 1 to about 500, for example about 2 to about 100 structural units of the general formula IV.

In a further embodiment of the present invention, the Polyurethanes according to the invention, thermoplastic polyurethanes, for example thermoplastic block copolyurethanes.

The polyurethanes according to the invention are generally produced in a solvent or in the melt. Suitable solvents are, for example Acetone, methyl ethyl ketone or cyclic ethers such as tetrahydrofuran or dioxane as well as cyclic ketones such as cyclohexanone. Are also suitable, each depending on the area of application of the polyurethanes, also other strongly polar solvents such as dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide or ethylene glycol acetate. The solvents mentioned can optionally be mixed with aromatic Compounds such as toluene or xylene or with esters such as ethyl or butyl acetate be mixed. Catalysts may also be used in the manufacture to be present. Suitable catalysts are tertiary amines such as triethylamine, Triethylenediamine, N-methylpyridine or N-methylmorpholine, metal salts such as  Tin octoate, lead octoate or zinc stearate or organic metal compounds such as Dibutyltin dilaurate. The appropriate amount of catalyst depends on the Effectiveness of the catalyst in question. In general it has proven to be useful, from about 0.005 to about 0.3 part by weight for every 100 Parts by weight of polyurethane.

The compounds of the general formula I and the invention poly produced using the compounds of the invention addition or polycondensation products are suitable for example Production of aqueous dispersions.

When compounds of general formula I or prepared therefrom Polyaddition or polycondensation products as dispersing agents can be used, for example, aqueous dispersions obtained that have excellent long-term stability. Depending on The proportion of compounds can be used for the dispersions obtainable in this way of the general formula I or the polyaddition and Polycondensation products on the entire aqueous dispersion in wide Ranges vary. Will the compounds of the invention for example as dispersants for stabilizing a dispersion, the one contains not self-dispersible solid, the amount used of the compounds of the invention in a range from about 0.01 to about 40% by weight, for example about 0.1 to about 20 or about 0.5 to about 10 or about 1 to about 5% by weight. The proportion of solids in such Dispersion can vary over a wide range. Depending on the application, can be so using the compounds of the invention Receive dispersions which have a solids content of up to about 99% by weight exhibit. Especially when such dispersions are used to coat You should preferably assign one to surfaces Solids content of about 30 to about 95% by weight, for example about 40 to  about 90 or about 50 to about 80 weight percent.

The present invention therefore also relates to aqueous dispersions, at least containing a sulfonic acid compound according to the invention.

In a further preferred embodiment, the However, compounds according to the invention also as the sole constituent of a such dispersion, especially as a discontinuous phase of an aqueous Dispersion. Such dispersions can be used, for example, as Use coating agents to produce surface coatings. In the context of such an application, it is advantageous if as the invention Connection a connection is used which is removed after the continuous phase results in a surface coating that meets the requirements of the user. It is therefore within the scope of such an operation preferred according to the invention if a as the compound according to the invention Compound with a molecular weight of at least about 1000 used becomes.

In the context of the present invention, in particular those are aqueous Preferred dispersions are at least one of the above polyaddition or polycondensation products according to the invention, in particular have at least one of the polyurethanes according to the invention.

In addition to water and a of the above-mentioned compounds according to the invention, or a mixture of two or more of them, or one or more further compounds.  

If the aqueous dispersion according to the invention as surfaces coating agent is to be used, the dispersion can for example contain at least one polymer by polymerizations of monomers is available with ethylenically unsaturated double bonds. Suitable Monomers are, for example, acrylic acid, methacrylic acid, acrylonitrile, Acrylic acid esters or methacrylic acid esters as obtained by esterification from Acrylic acid or methacrylic acid with methanol, ethanol, n-butanol, isobutanol or 2-ethylhexyl alcohol are available, vinyl esters of carboxylic acids with 1 to 16 carbon atoms or 1-alkenes such as ethylene, propylene, butylene or styrene. Such polymers can already be dispersed or at least polymerized form of the dispersion according to the invention become. However, it is also possible to use the polymers mentioned in the to produce aqueous dispersion according to the invention. Here, the respective compounds and reaction conditions are chosen so that for example at least some of the polymers produced in the dispersion in the In the sense of a graft reaction to those present in the dispersion compounds of the invention are attached. The production Appropriate polymers are carried out according to methods known to the person skilled in the art as described, for example, in D.C. Blackley, Emulsion Polymerization - Theory and Practice, London, Applied Science Publishers, 1975 or in H. Warson, Application of Synthetic Resin Emulsions, London, Benn Publishers, 1972 or in I. Piirma, Emulsion Polymerization, New York, Academic Press Inc. 1982, are described.

The compounds according to the invention can also contain additives such as organic solvents, pigments, dyes, emulsifiers, surfactants, thickeners, Stabilizers, leveling agents, fillers, sedimentation inhibitors, Contain flame retardants, UV stabilizers or antioxidants.

Suitable solvents are, for example, acetone, methyl ethyl ketone,  Tetrahydrofuran, dimethylformamide, dimethylacetamide, dioxane, ethyl acetate and the like, or a mixture of two or more thereof. The Dispersions according to the invention can the organic solvents in a Amount up to about 20% by weight, preferably up to about 10% by weight contain.

Suitable thickeners are, for example, polymers of hydrophilic, radically polymerizable monomers such as acrylic acid, acrylic acid, Polyvinyl pyrrolidone or thickener based on cellulose or starch derivatives such as carboxymethyl cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, Hydroxypropyl cellulose, hydroxyethyl starch, hydroxypropyl starch and the like. The thickeners mentioned can each be used individually or as a mixture two or more of them are present in the dispersions according to the invention.

Suitable fillers or pigments are, for example, titanium dioxide, Antimony oxide, zinc oxide, basic lead carbonate, basic lead sulfate, Barium carbonate, porcelain flour, clay, aluminum silicate, silicon dioxide, Magnesium carbonate, magnesium silicate or calcium carbonate. As colored Pigments can, for example, cadmium yellow, cadmium red, soot, Phthalocyanine blue, chrome yellow, toluidyl red and hydrated iron oxide are used become.

The dispersions according to the invention are generally prepared usual methods known to those skilled in the art. Suitable methods are for example in Plastic Handbook, No. 7, Polyurethane, Karl Hanser Verlag, 1993.

The aqueous dispersions of the invention can in particular as  Surface coating agents are used. You can use a Variety of substrates can be associated. Examples of suitable ones Substrates are wood, metal, glass, textiles, songs, paper, plastics and the like. The aqueous dispersions according to the invention can be applied by any conventional methods such as dipping, spraying, knife coating, Brush application or the like.

The present invention further relates to the use of a compound according to the general formula I or a polyaddition or polycondensation sationsverbindung, which is a structural unit according to the general formula IV has, as a wetting agent, dispersing aid, surfactant, coupling agent, auxiliary agent in galvanic baths, acid catalysts in chemical syntheses or as Hardener component in coating materials.

The invention is explained in more detail below by examples.

Examples example 1

100 g were added to a stirred flask with a thermometer and feed vessel Methyl ethyl ketone, 1100 g polycaprolactone (CAPA 200, 1.0 mol), 208 g 2-acrylic amido-2-methylpropanesulfonic acid (AMPS, 1.0 mol) and 0.5 g hydroquinone monomethyl ether heated to 60 ° C. with stirring. It became cloudy Suspension in the 190 g tributylamine (1 mol + 5 g) with vigorous stirring were added dropwise within 20 minutes. The reaction was exothermic the temperature rose to about 80 ° C. The reaction mixture turned 20 Minutes at this temperature. A slightly cloudy solution was formed  150 g of diethanolamine (1 mol) were added dropwise at about 80 ° C. The approach was further stirred under reflux for about an hour. Then 1 g Dibutyltin dilaurate added and then under reflux for about 20 Minutes 336 g of hexamethylene diisocyanate (2 mol) were slowly added dropwise. To The exothermic reaction was held at 80 ° C. for one hour. The result was a slightly cloudy, viscous solution of an oligomeric urethane compound in a statistical distribution sulfonic acid / tributylamine salt groups and had terminal OH groups. The solution was arbitrary with water dilutable.

Example 2

103.5 g (0.5 mol) of 2-acrylamido-2- methylpropanesulfonic acid and 0.5 g 4-methoxyphenol dissolved in 100 g water. Then 20 g (0.5 mol) of sodium hydroxide, dissolved in 60 g of water, at added dropwise at a maximum of 30 ° C. Then 59.85 g (0.45 mol) of diiso propanolamine and 60 g of water are added and the mixture is heated to 20 ° C. After a reaction time of 8 hours, the mixture was cooled to room temperature and with Neutralized 49.3 g (0.5 mol) of concentrated hydrochloric acid. Then that was Solvent removed and the residue dissolved in 53 g of warm ethanol. That included precipitated sodium hydroxide was separated off. The filtrate crystallized on Cool off.

Example 3

17.0 g of the Michael adduct from Example 1 were mixed with 66.6 g (0.3 mol) Isophorone diisocyanate and 0.5 g dibutyltin dilaurate in 31 g N-methylpyrrolidone reacted at 100 ° C with stirring. As the solution an NCO content  reached 9.83%, 48.0 g (0.3 mol) of 2-butyl-2-ethyl-1,3-propanediol and 0.1 g of dibutyltin dilaurate were added. The reaction mixture was until End of the reaction kept at 100 ° C. This resulted in a product that Removing the solvent was soluble in tetrahydrofuran, toluene and methanol.

Example 4 Production of a polyurethane dispersion Production of the Michael adduct

227.7 g (1.1 mol) of acrylamido-2-methylpropanesulfonic acid (AMPS) and 1.0 g Hydroquinone monomethyl ether was dissolved in 200 g of water. Subsequently was a solution of 44.2 g (1.1 mol) of sodium hydroxide in ice cooling 150 g of water were added so that the temperature did not exceed 30 ° C. Then 118 g (1.0 mol) of diisopropanolamine, dissolved in 50 g of water added and the mixture stirred at 120 ° C for 8 hours. A clear one emerged Editorial solution with a slightly yellowish tinge.

For the exact determination of the amount of hydrochloric acid required for neutralization a sample of the reaction solution was titrated with 1 M HCl. The whole The calculated equivalent amount of HCl (37%) became slow admitted. The water was then distilled off until a viscous Porridge emerged. This was dissolved warm in 700 ml of ethanol. The one that fails NaCl was filtered off. When the filtrate cooled, the end product crystallized slowly out.  

Preparation of the polyurethane dispersion

27.9 g (0.0894 mol) of the Michael adduct, 70 g of N-methylpyrrolidone and 133 g (0.0665 mol) of a polyester polyol from adipic acid, 1,6-hexanediol and Neopentyl glycol with an OH number of 56 were in a stirred flask submitted. 42 g (0.1889 mol) were added to this mixture at 50 ° C. Isophorone diisocyanate and 0.2 ml of dibutyltin dilaurate added and at 60 minutes 80 ° C stirred. The mixture was then diluted with 200 g of acetone, with 8.6 g (0.085 mol) Neutralized triethylamine and dispersed by adding 530 g of water. After distilling the acetone, a finely divided, stable was obtained Polyurethane dispersion with a solids content of 40% by weight.

Claims (12)

1. Sulfonic acid compound of the general formula I
wherein R ^{1 is} H or a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical having 1 to 20 C atoms, a saturated or unsaturated, optionally substituted cycloaliphatic hydrocarbon radical having 4 to 20 C atoms or an optionally substituted araliphatic hydrocarbon radical having 6 to 40 C atoms, R ^{2 represents} a linear or branched, saturated or unsaturated aliphatic hydrocarbon radical with 1 to 20 C atoms or a cycloaliphatic hydrocarbon radical with 4 to 20 C atoms or an optionally substituted aromatic hydrocarbon with 6 to 18 C atoms , Z ¹ and Z ² each independently represent R ³ -QH, R ³ -Q- (XO-) _m X-QH or R ³ -OYQ-, where Q is O (oxygen), NH, NR ³ or S , R ³ for a linear or branched, saturated or unsaturated, optionally aromatically substituted alkyl radical having 2 to 44 carbon atoms, X for an optionally aromatically substituted alkyl radical having 2 to 14 carbon atoms, Y is a polymer obtainable by polymerization, polyaddition or polycondensation with a molecular weight M _w of 150 to 5000 and n is a value of 1 to 300 and not both radicals Z ¹ and Z ² simultaneously represent CH ₂ -CH ₂ -OH, or a salt thereof. 2. Sulfonic acid compound according to claim 1, characterized by one or more of the following features:

• - R ¹ stands for H or CH ₃ ,
• R ² stands for a linear or branched aliphatic hydrocarbon radical with 3 to 8 carbon atoms,
• R ³ represents a linear or branched alkyl radical having 2 to 44 carbon atoms,
• - X stands for CH ₂ -CH ₂ or CH (CH ₃ ) -CH ₂ or CH ₂ - CH (CH ₃ ),
• - Y stands for an aliphatic polyester with a molecular weight M _w of 150 to 300 and
• - n stands for a value from 1 to 200.

3. polyaddition product or polycondensation product, thereby characterized in that there is at least one structural unit according to claim 1 or claim 2. 4. polyaddition product according to claim 3, characterized in that it is a polyurethane. 5. Polyurethane, according to claim 4, characterized in that it as Block copolyurethane is constructed and at least one hard segment and has at least one soft segment. 6. Polyurethane according to one of claims 4 or 5, characterized in that that it is the structural unit according to claim 1 or claim 1 in Hard segment.   7. A process for the preparation of a sulfonic acid compound according to one of claims 1 or 2, characterized in that a compound of general formula II
Z ¹ -NH-Z ² (II),
wherein Z ¹ and Z ^{2 are} as defined above, and a compound of general formula III
implemented in the sense of a Michael addition. 8. Use of a sulfonic acid compound according to claim 1 or 2 for Manufacture of polyaddition or polycondensation products. 9. Use according to claim 8, characterized in that it is the polyaddition and polycondensation products around polyurethanes, Polyesters, polyethers, polycarbonates, polyether esters, polyamides, Polyester amides, polyether amides, polylactones or polylactams. 10. Use of sulfonic acid compounds according to one of claims 1 or 2 or of polyaddition and polycondensation compounds according to one of claims 3 to 6 as wetting agents, dispersing agents, Surfactant, adhesion promoter, auxiliary agents in electroplating baths, Acid catalyst in chemical syntheses or as a hardener component in Coating agents.   11. Aqueous dispersion containing at least one sulfonic acid compound according to one of claims 1 to 4, a polyaddition or Polycondensation product according to claim 5 or a polyurethane according to one of claims 6 to 8. 12. Aqueous dispersion according to claim 11, characterized in that it at least 20% by weight of a polyurethane according to one of claims 6 contains up to 8.