Polyisobutylene derivatives, method for the production thereof and their use

0001Polyisobutylene derivatives, process for their preparation and their use

0002description

0003The present invention relates to polyisobutylene derivatives containing on average at least one structural unit of the formula I per molecule

0004<img file="WO2005123789A1_D0001.tif" />

0005where the variables are defined as follows: R¹ selected from phenyl and d-Cio-alkyl,

0006R² the same or different and independently selected from hydrogen, phenyl and dC ^ alkyl, with up to three non-adjacent CHR²Groups by oxygen or NR³- Groups can be replaced, a an integer in the range from 1 to 20, b selected from 0 or 1, X selected from

0007<img file="WO2005123789A1_D0002.tif" />

0008<img file="WO2005123789A1_D0003.tif" />

0009<img file="WO2005123789A1_D0004.tif" />

0010Y, Y the same or different and selected from -O- and -NR -

0011R³ the same or different and selected from hydrogen and CC₁₀-Alkyl

0012PIB is a polyisobutylene residue. The present invention further relates to a process for the preparation of polyisobutylene derivatives, aqueous emulsions for the production of isobutylene derivatives and the use of polyisobutylene derivatives according to the invention, for example for the production of leather. The present invention further relates to leather, produced using polyisobutylene derivatives according to the invention.

0013Hydrophobing is an important step in the production of leather. The haptic properties and behavior towards moisture and moisture are decisively influenced by the hydrophobization. Demanding requirements are therefore placed on modern water repellents. They should be applied as well as possible from an aqueous liquor, be distributed evenly over the leather to be made hydrophobic, and have good liquor consumption, ie can be applied with a good yield and lead to the production of leathers that meet the highest demands, for example shoe leather, furniture leather and automotive leather. Furthermore, they should ensure a low water absorption of the hydrophobized leather surface and give the leather dirt-repellent properties. They are said to be difficult to wash out of leather. After all, the leather should not lose its breathability through the hydrophobization.

0014DE-A 197 15513 discloses organosilicon compounds containing oligo- or polyisobutylene groups, in which polyisobutylene groups and silixane group are connected to one another via a polyether group, and their use as a polish for glass.

0015From EP 0969 032 special graft copolymers of polyisobutylene with silicones are known, in which polyisobutylene is grafted directly onto the silicone structure.

0016WO 03/20822 discloses polyisobutene-containing polymer compositions which contain at least one polyisobutylene and their use, for example, as an adhesive and adhesion promoter.

0017However, the compounds disclosed in the above-mentioned applications still have disadvantages when used as water repellents.

0018The object was therefore to provide new hydrophobizing agents which avoid the disadvantages associated with those from the prior art. A further object was to provide formulations which are suitable for waterproofing leather and to provide a process for producing leather. Furthermore, the task was to provide leather that has particularly good properties.

0019Accordingly, the polyisobutylene derivatives defined at the outset were found. Polyisobutylene derivatives containing on average at least one structural unit of the formula I per molecule

0020<img file="WO2005123789A1_D0005.tif" />

0021where the variables are defined as follows: R¹ selected from phenyl and d-Cio-alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n- Decyl; particularly preferably dC-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl,

0022R² identical or different and independently selected from phenyl Ci-Cio-alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl , n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n -Nonyl, n-decyl; particularly preferably dC-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl, and very particularly preferably hydrogen,

0023a is an integer in the range from 1 to 20, preferably 3 to 10 and particularly preferably 3,

0024b selected from 0 or 1, preferably 0,

0025X selected <img file="WO2005123789A1_D0006.tif" />

0026<img file="WO2005123789A1_D0007.tif" />

0027<img file="WO2005123789A1_D0008.tif" />

0028where Y, Y are the same or different and selected from -O- and -NR -, the same or different and selected independently from d-Cι₀Alkyl, branched or unbranched, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC₄Alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl,

0029and especially hydrogen

0030PIB is a polyisobutylene radical, preferably with an average molecular weight M_w in the range from 112 to 50,000 g / mol, preferably from 200 to 5,000 g / mol and particularly preferably from 500 to 2,300 g / mol.

0031Up to three non-adjacent CHR²Groups by oxygen or NR³- groups to be replaced. For example, the polyisobutylene derivative according to the invention can have on average at least one structural unit of the formula I a per molecule:

0032<img file="WO2005123789A1_D0009.tif" />In one embodiment of the present invention, polyisobutylene derivatives according to the invention have on average at least one structural unit of the general formula II

0033<img file="WO2005123789A1_D0010.tif" /> on, the residues R⁴ may be the same or different and are independently selected from phenyl and

0034d-Cio-alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, sec.-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably dC-alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl.

0035In one embodiment, polyisobutylene derivatives according to the invention have at least one structural unit of the general formula lil a

0036-Si (R⁴)₃ MI a

0037or III b

0038-O-Si (R⁴)₃ III b

0039on where R⁴ as defined above.

0040In preferred polyisobutylene derivatives according to the invention, R¹ and R⁴ each the same and methyl, R² stands for hydrogen, and a is an integer in the range from 3 to 10.

0041In one embodiment of the present invention, polyisobutylene derivatives according to the invention have on average at least one structural unit of the general formula I, preferably at least two, per molecule.

0042In one embodiment of the present invention, polyisobutylene derivatives according to the invention have on average up to 20 structural units of the general formula I per molecule, preferably up to 15. In one embodiment of the present invention, polyisobutylene derivatives according to the invention have on average at least two structural elements of the general formula II per molecule, preferably at least three.

0043In one embodiment of the present invention, polyisobutylene derivatives according to the invention have on average up to 100 structural elements of the general formula II, preferably up to 50, per molecule.

0044Polyisobutylene derivatives according to the invention which have at least three structural elements of the general formula I and at least three structural elements of the general formula II can contain the structural elements of the general formulas I and II alternately, in blocks or preferably in a statistical arrangement.

0045In one embodiment of the present invention, polyisobutylene derivatives according to the invention have an average molecular weight M_w from 350 to 5,100 g / mol, preferably from 600 to 2,400 g / mol.

0046Polyisobutylene residues in the sense of the present invention are derived from so-called reactive polyisobutylenes.

0047The preparation of polyisobutylene derivatives according to the invention can be carried out, for example, by reacting at least one reactive polyisobutylene, if appropriate after functionalization, with at least one silicone compound which carries at least one functional group which is capable of reacting with reactive polyisobutylene.

0048Reactive polyisobutylenes can be obtained, for example, by oligomerizing isobutylene (isobutylene) or isobutene-containing starting materials in the presence of a suitable catalyst, preferably a Lewis acid such as, for example, boron trifluoride or titanium tetrachloride, see for example DE-A 27 02604, and carry a functional group, for example a C = C double bond, which can be functionalized by methods known per se, for example by hydroboration and subsequent oxidative workup, epoxidation and subsequent ring opening, hydroformylation, hydroxylation or amination and subsequent reaction with, for example, triphosgene, halogenation or ene reaction with suitable enophiles such as, for example, maleic anhydride.

0049Both isobutene itself and isobutene-containing C are suitable as isobutene-containing feedstocks₄Hydrocarbon streams, for example C raffinates, C cuts from isobutane dehydrogenation, C₄Cuts from steam crackers or so-called FCC crackers (FCC: Fluid Catalysed Cracking), provided that the C cuts in question are largely freed of 1,3-butadiene contained therein. The concentration of isobutene is typically in C.₄-Carbon streams in the range from 40 to 60% by weight, but also 90 to 99.9% by weight hydrocarbon streams containing isobutene are suitable. Suitable C₄-Carbon streams should generally contain less than 500 ppm, preferably less than 200 ppm 1,3-butadiene. Suitable methods for functionalizing reactive polyisobutylene are disclosed, for example, in WO 03/20822.

0050Reactive polyisobutylenes in the sense of the present invention and thus polyisobutylene residues can have a broad or preferably a narrow molecular weight distribution, for example in the range from 1 to 10, preferably in the range from 1.2 to 3 and particularly preferably in the range from 1.4 to 2.5.

0051For example, silicone compound which carries at least one functional group which is capable of reacting with reactive polyisobutylene can also be referred to simply as a silicone compound below, and reactive polyisobutylene can carry the following pairs of functional groups:

0052<img file="WO2005123789A1_D0011.tif" /> The silicone compound or silicone compounds used have on average at least one functional group per molecule, preferably at least two and particularly preferably at least three.

0053One or more catalysts can be used to react silicone compound with reactive polyisobutylene, for example acids, bases or a suitable transition metal catalyst for the purpose of hydrosilylation.

0054For the reaction of silicone compound with reactive polyisobutylene, silicone compound and reactive polyisobutylene can preferably be metered in such a way that the respective functional groups are each present in a molar ratio of 1: 1 in the respective reaction mixture. However, one of the two reactants silicone compound and reactive polyisobutylene can also be metered in a molar excess, for example in 0.1 to 0.5 equivalent excess, based on the respective functional groups.

0055In one embodiment of the present invention, the preparation of the polyisobutylene derivative according to the invention is carried out at temperatures in the range from 0^C.C to 200 ° C through, preferably at 20 ° C to 100 ° C.

0056In one embodiment of the present invention, the preparation of the polyisobutylene derivative according to the invention is carried out at atmospheric pressure. However, a pressure in the range of 0.1 to 0.99 atmospheres can also be selected. A pressure in the range of 1.01 to 20 atmospheres can also be selected.

0057It is of course also possible within the scope of the present invention to react at least two reactive polyisobutylenes with a silicone compound in a one-pot reaction or in succession with one another. Of course, it is also possible within the scope of the present invention to react two silicone compounds with one reactive polyisobutylene.

0058Polyisobutylene derivatives according to the invention can be purified. In another embodiment of the present invention, the purification of polyisobtylene derivatives according to the invention is dispensed with and, if appropriate, used in a mixture with starting materials.

0059The present invention further provides aqueous emulsions containing at least one polyisobutylene derivative according to the invention.

0060In addition to the polyisobutylene derivative according to the invention, aqueous emulsions according to the invention can have further constituents, for example one or more emulsifiers, which can be anionic, cationic, nonionic or zwitterionic.

0061Examples of preferred nonionic emulsifiers are

0062- alkoxylated C₈- to C₂₂Alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. C.₈- to C₂₂Alcohols can be alkoxylated with ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two equivalents, preferably at least three equivalents, of at least one of the abovementioned alkylene oxides added can be used as emulsifiers. Here, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the abovementioned alkylene oxides in a statistical distribution. Preferred nonionic emulsifiers generally contain 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide and particularly preferably ethylene oxide as alkylene oxide per mole of alcohol. Fatty alcohols or oxo alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the production, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;

0063Alkylphenol alkoxylates such as alkylphenol ethoxylates with C₆- to C₁ Alkyl chains and 5 to 30 alkylene oxide units;

0064Alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain and generally 1 to 20, preferably 1.1 to 5, glucoside units of sorbitan alkanoates, also alkoxylated;

0065N-alkyl glucamides, fatty acid alkoxylates, fatty acid amine alkoxylates, fatty acid amide alkoxylates, fatty acid alkanolamide alkoxylates, block copolymers of ethylene oxide, propylene oxide and / or butylene oxide, polyisobutene ethoxylates, polyisobutene-maleic anhydride derivatives, monoglycerides, and also alkoxylated and bisalkoxylated.

0066Particularly suitable nonionic emulsifiers are alkyl alkoxylates or mixtures of alkyl alkoxylates, as described, for example, in DE-A 10243363, DE-A 10243 361, DE-A 10243360, DE-A 10243 365, DE-A 10243366, DE-A 10243 362 or in DE -A 4325237 are described. These are alkoxylation products obtained by reacting alkanols with alkylene oxides in the presence of alkoxylation catalysts or mixtures of alkoxylation products. Particularly suitable starter alcohols are the so-called Guerbet alcohols, in particular 2-ethylhexanol, 3-n-propylheptanol and 2-n-butyloctanol. 3-n-Propylheptanol is particularly preferred. Preferred alkylene oxides are propylene oxide and ethylene oxide, alkyl alkoxylates with direct attachment of a preferably short polypropylene oxide block to the starter alcohol, as described, for example, in DE-A 10243365, are preferred in particular because of their good biodegradability.

0067The preparation of the emulsifiers mentioned above is known per se. Appropriate alcohols, such as, for example, fatty alcohols, oxoalcohols or other alkanols, are usually alkoxylated.

0068Bases can be used as alkoxylation catalysts, for example alkali metal hydroxides or alkali metal alcoholates, but also Lewis acids, for example BF₃, SbCI₅, SnCI₄ x 2H₂0, BF₃ x H₃BO₄, or BF₃-Dietherat. Particularly suitable alkoxylation catalysts are double hydroxide clays such as hydrotalcite, which can in particular be modified with additives, as described in DE-A 43 25 237.

0069Depending on the choice of the alkoxylation catalyst, specific properties of the alkoxylates result, in particular with regard to the distribution of the degree of alkoxylation. Thus, when using the latter double hydroxide clays, alkoxylation products with a narrow molecular weight distribution or homolog distribution are obtained which are suitable for use in the mixtures according to the invention with cosurfactants are particularly suitable.

0070The advantageous properties described above, in particular with regard to the degree of alkoxylation, are also achieved by using double metal cyanide (DMC) compounds, as are described, for example, in DE-A 102 43 361 as alkoxylation catalysts.

0071Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C₈ to C₁₂), of sulfuric acid half-esters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C₁₂-C₁₈) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C₄-C₁₂), of alkyl sulfonic acids (alkyl radical: C₁₂-Cι₈), of alkylarylsulfonic acids (alkyl radical: C₉-C₁₈), of fatty acids such as stearic acid and sulfosuccinates such as monosuccinic acid and diesters.

0072Suitable cationic emulsifiers are usually a C.₆-C₁₈-Alkyl-, -Aralkyl- or heterocyclic radical having primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts and phosphonium salts, sulfonium salt, isoquinolinium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (Λ /, Λ, / V-trimethylammonium) ethyl paraffinates, Λ / -cetylpyridinium chloride,, / -laurylpyridinium sulfate and Λ-cetyl- Λ /, NΛ / -trimethylammonium bromide, Λ -dodecyl-Λ /, Λ /, Λ / -trimethylammoniumbromid, Λ /, Λ / -distearyl-Λ /, Λ / -dimethylammonium chloride and the Gemini surfactant W, / V- (Laui dimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stäch, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers &amp; Detergents, MC Publishing Company, Glen Rock, 1989. Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula IV

0073R⁵"OOH

0074in which the variables are defined as follows:

0075R⁵ Hydrogen, -C-C₄Alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, in particular methyl; C.₆-C-aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl , 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

0076R⁶ CC alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; especially methyl;

0077The group CO-R⁷ is preferably derived from saturated or unsaturated fatty acids. Among saturated fatty acids are carboxylic acids with C₉-C₂₀-Understand alkyl groups that can be linear or branched, substituted or unsubstituted. R⁶ can be, for example: n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-octadecyl, n-eicosyl.

0078CO-R⁷ can be derived from an unsaturated fatty acid with 9 to 20 C atoms and one to 5 CC double bonds, the CC double bonds being, for example, isolated or allylic, for example the acyl radical of linoleic acid, linolenic acid, and very particularly preferably that oleic acid.

0079In one embodiment of the present invention, all or at least a certain proportion, for example a third or half, of the carboxyl groups in N-acylated amino acid derivatives of the formula IV used as emulsifiers are neutralized. For example, basic salts such as hydroxides or carbonates of the alkali metals such as Na or K are suitable for neutralization. Ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and very particularly alkanolamines such as ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-methyldiethanolamine or N- (n Butyl) diethanolamine. Exemplary representatives for compounds of the formula IV are N-oleylsarcosine, N-stearylsarcosine, N-lauroylsarcosine and N-isononanoylarcosine and the respective ethanolammonium salts, diethanolammonium salts and N-methyldiethanolammonium salts.

0080Other particularly suitable examples of emulsifiers are those of the general formula V.

0081<img file="WO2005123789A1_D0012.tif" />

0082in which the variables are defined as follows:

0083R⁸, R⁹ the same or preferably different and selected from hydrogen, dC₃o-alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec.-butyl, tert.-butyl, n-pentyl, iso-pentyl, sec.- Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl, n -Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, preferably branched radicals of the formula V a in the β position

0084<img file="WO2005123789A1_D0013.tif" />

0085- (CH₂CH₂O)_x-OR¹³ or - [CH (CH₃) CH₂O)_x-OR¹³where x is an integer ranging from 1 to 20,

0086C.₆-Cι₄Aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

0087R¹⁰ is chosen from dC₄Alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and in particular hydrogen; R¹¹, R¹² the same or preferably different and selected from dC ^ alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl , sec.-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec.-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n -Decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl;

0088where the sum of the C atoms of R¹¹ and R¹² is a maximum of 30. Preferably R¹¹ two more C atoms than R¹²; the combinations R are preferred, for example¹¹ = n-undecyl and R¹² = n-nonyl, R¹¹ = n-dodecyl and R¹² = n-decyl, R¹¹ = n-tridecyl and R¹² = n-undecyl, R¹¹ = n-tetradecyl and R¹² = n-dodecyl, R¹¹ = n-pentadecyl and R¹² = n-tridecyl.

0089R¹³ is chosen from dC₄-Alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, ortho-tolyl, meta-tolyl, para-tolyl and in particular hydrogen.

0090In a preferred embodiment of the present invention, exactly one of the radicals R⁸ and R⁹ Hydrogen and the other radical selected from Cι-C₃₀-Alkyl.

0091In a particularly preferred embodiment of the present invention, a mixture of several emulsifiers, for example of the formula V, is chosen, which can differ, for example, in that in the first compound of the formula VR⁸ equal to hydrogen and R⁹ from CC₃o-alkyl is selected and in the second R⁹ equal to hydrogen and R⁸ from dC₃o-alkyl is selected.

0092In one embodiment of the present invention, all or at least a certain proportion, for example a third or half, of the sulfonyl groups in emulsifiers of the formula V are neutralized. For example, basic salts such as hydroxides or carbonates of the alkali metals such as Na or K are suitable for neutralization. Ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylene diamine, and very particularly alkanolamines such as ethanolamine, diethanolamin, triethanolamine, N-methylethanolamine, N-methyldiethanolamine or are also suitable for neutralization N- (n-butyl) diethanolamine. The preparation of compounds of formula V is known per se and in

0093WO 01/68584. It can be achieved, for example, through single or double

0094Esterification of dicarboxylic acid anhydrides of the general formula VI

0095<img file="WO2005123789A1_D0014.tif" />

0096with corresponding alcohols, which need not be pure, followed by a reaction with disulfite, for example Na₂S₂O₅.

0097Emulsions according to the invention can contain, instead of purified emulsifiers, for example of the formula V, mixtures of different emulsifiers. For example, it is possible to add the mixture known as oxo oil 135 or oxodick oil 135 (WO 01/68584) for the esterification and to use the mixture of esters obtainable as an emulsifier.

0098In one embodiment of the present invention, emulsifiers contained in emulsions according to the invention can contain up to 40% by weight, preferably up to 20% by weight, based on the emulsifier, of at least one alcohol of the formula VII

0099<img file="WO2005123789A1_D0015.tif" />

0100included, wherein in formula VII the variables R¹¹ and R¹² as defined above.

0101In one embodiment of the present invention, emulsifiers contained in emulsions according to the invention can contain up to 50% by weight, preferably up to 30% by weight, based on the formulation, of at least one compound of the formula VII.

0102In a preferred embodiment of the present invention, emulsifiers contained in emulsions according to the invention can contain up to 40% by weight, particularly preferably up to 20% by weight, of mixtures which comprise at least one alcohol of the general formula VII; examples of such mixtures include oxo oil 135 and oxo oil 13.

0103Aqueous emulsions according to the invention furthermore contain water, which can be deionized or also saline. In one embodiment of the present invention, aqueous emulsions according to the invention contain at least one further hydrophobic compound. At least one further hydrophobic compound is a hydrocarbon-based compound, for example natural or synthetic wax, native or synthetic oil, native or synthetic fat, or synthetic polymer, or a silicone-based compound.

0104Examples of natural waxes are beeswax, cork wax, montan waxes or carnaύba wax.

0105Examples of synthetic waxes are polyethylene waxes or ethylene copolymer waxes, as are obtainable, for example, by radical polymerization of ethylene or radical copolymerization of ethylene with, for example, (meth) acrylic acid or by Ziegler-Natta catalysis. Polyisobutylene waxes may also be mentioned. Paraffin mixtures may also be mentioned; this includes mixtures of hydrocarbons which have 12 or more carbon atoms and usually have a melting point in the range from 25 to 45 ° C. Such paraffin mixtures can be obtained, for example, in refineries or crackers and are known to those skilled in the art as paraffin gums and sasol waxes. Another example of synthetic waxes are montan ester waxes.

0106Examples of natural oils that can be mentioned are liquid triglycerides at room temperature, for example fish oil, cattle claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil.

0107Examples of synthetic oils are white oil, paraffin oil, functionalized paraffins such as chlorinated or sulfochlorinated paraffins or polyalkylene glycols such as polyethylene glycol.

0108Examples of natural fats include native triglycerides which are solid at room temperature, such as lanolin, shellac wax and mixtures thereof.

0109Examples of synthetic polymers are maleic anhydride-α-olefin copolymers, for example copolymers of maleic anhydride and CH₂= CH-n-Cι₈H₃₇, CH₂= CH-nC₂₀H₄, or CH₂= CH-nC₂₂H₄₅, still styrene

0110Maleic anhydride copolymers that can be partially esterified with dC alkanol ethoxylates.

0111In a preferred embodiment of the present invention, the further hydrophobic compound is at least one native triglyceride. In a further preferred embodiment, a combination of at least one native triglyceride which is solid or liquid at room temperature and a paraffin mixture having a melting point in the range from 25 to 40 ° C. are used. The quantitative ratio is not critical per se; weight ratios of native triglyceride: paraffin mixture in the range from 10: 1 to 1:10 are suitable.

0112In a further preferred embodiment of the present invention, a multiply fluorinated and preferably perfluorinated alkane with preferably 10 to 40 C atoms is used as the further hydrophobic substance.

0113Aqueous emulsions according to the invention may further contain additives, for example biocides and / or oxidation stabilizers.

0114In one embodiment of the present invention, aqueous emulsions according to the invention contain

01150.1 to 40% by weight, preferably 40 to 60% by weight, of at least one polyisobutylene derivative according to the invention,

01160 up to 20% by weight, preferably 1 to 15% by weight of at least one emulsifier, 0 to 30% by weight, preferably 1 to 15% by weight of at least one further hydrophobic compound, in total 0 to 9% by weight, preferably up to 5% by weight of further additives, the rest is water.

0117Aqueous emulsions according to the invention are distinguished, for example, by good storage stability.

0118For the preparation of aqueous emulsions according to the invention, one can proceed, for example, by mixing at least one polyisobutylene derivative according to the invention with water and optionally with at least one emulsifier, at least one further hydrophobic compound and optionally with at least one additive. Conventional mixing apparatuses are suitable for mixing, for example stirring vessels, shaking vessels and ultrathurrax stirrers. If desired, it can be homogenized after the mixing, for example with the aid of a gap homogenizer or a high-pressure homogenizer.

0119Another object of the present invention is the use of polyisobutylene derivatives according to the invention and in particular of aqueous emulsions according to the invention for the production of leather or fur skins. Another object of the present invention is a process for the production of leather or furskins using polyisobutylene derivatives according to the invention and in particular aqueous emulsions according to the invention, hereinafter also referred to as the production process according to the invention. The present invention further relates to leather or Fur skins produced using polyisobutylene derivatives according to the invention and in particular aqueous emulsions according to the invention.

0120To carry out the manufacturing process according to the invention, tanned animal skins or skins are treated in a liquor before, during or after retanning with the formulations used according to the invention. The treatment according to the invention can be carried out once or repeatedly. The animal skins to be treated or Furs can have been produced by any method, for example by mineral tanning, in particular chrome tanning, or by polymer tanning, tanning with syntans, resin tanning, aldehyde tanning with, for example, glutaraldehyde, tanning with vegetable tanning agents or tanning with combinations of the aforementioned tanning agents.

0121In one embodiment of the production process according to the invention, at least one polyisobutylene derivative according to the invention and preferably at least one aqueous emulsion according to the invention are added in one or more portions to the tanned animal skin or fur to be treated. This addition can be done in an aqueous liquor. The liquor length can preferably be 50 to 2000% by weight, preferably up to 200% by weight, based on the folded weight of the tanned animal skin or the wet weight of the fur.

0122The manufacturing process according to the invention is generally carried out by rolling the tanned animal skin or the fur to be treated in suitable vessels, for example in barrels, in particular in rotatable barrels with internals. Other methods of mixing known to the person skilled in the art are also possible.

0123Temperatures in the range from 20 to 65 ° C., preferably 30 to 60 °, can be selected as the temperature for the production process according to the invention.

0124The printing conditions of the manufacturing process according to the invention are generally not critical. It is preferred to work at normal pressure (1 atm), but it is also possible to work at a reduced pressure, for example 0.5 to 0.99 atm, or at an increased pressure, for example 1.01 to 2 atm.

0125At the beginning of the production process according to the invention, the pH can be set in the range from 4 to 8, preferably 4.5 to 8. At the end of the production process according to the invention, the pH can be lowered to a pH of 3 to 5 by adding an acid, for example formic acid. The preparation process according to the invention is generally ended after a time of 20 minutes to 24 hours, preferably 30 minutes to 12 hours. If the treatment is carried out repeatedly, one speaks in the context of the present invention of treatment steps according to the invention.

0126The amount of the aqueous emulsion used according to the invention can be 0.1 to 40% by weight, in particular 0.5 to 20% by weight, based on the folded weight of the tanned animal skin to be treated or the wet weight of the fur to be treated.

0127Conventional leather dyes can be added to the liquor during the production process according to the invention. Examples include acidic, nouns or basic aniline dyes that can be used in tannery-usual amounts.

0128If one wishes to carry out the production process according to the invention with the retanning, it can be done with any tanning agents customary in tanning, for example mineral tanning agents, in particular chrome tanning agents, or polymer tanning agents, syntans, aldehyde tanning agents such as glutardialdehyde, resin tanning agents, vegetable tanning agents or combinations of the aforementioned tanning agents do in one or more treatment baths.

0129Organic solvents such as alcohols can be added while the production process according to the invention is being carried out. However, preference is given to working without the addition of organic solvents.

0130After the production process according to the invention has been carried out, it can be acidified to a pH of about 3-4 using acids such as formic acid.

0131After the production process according to the invention has been carried out, it can be fixed with commercially available mineral tanning agents.

0132Following the implementation of the manufacturing method according to the invention, leather or fur skins obtained according to the invention can be worked up as usual in terms of preparation technology.

0133Another object of the present invention are leather, produced by the manufacturing process according to the invention. Leather produced by the process according to the invention are distinguished by very good usage properties, for example by very good hydrophobicity, very good feel and excellent level coloring. Another object of the present invention is the use of the leather according to the invention for the production of clothing, for example jackets, coats, shoes and in particular boots. Another object of the present invention is the use of the leather according to the invention for the production of> furniture and furniture parts, for example leather sofas, leather armchairs, armrests for chairs, armchairs or sofas or benches. Another object of the present invention is the use of the leather according to the invention for the production of auto parts, for example car seats, parts of dashboards and interior trim parts, for example in car doors.

0134The present invention further relates to fur skins treated by the production process according to the invention. Fur skins according to the invention are particularly suitable for the production of clothing. The invention is illustrated by working examples.

0135General remarks:

0136I. Preparation of polyisobutylene derivatives according to the invention

01371.1. Preparation of Polyisobutylene Derivative PIB-1 According to the Invention In a 500 ml 4-necked flask equipped with a stirrer, reflux condenser and internal thermometer, 233.5 g of a silicone compound which was liquid at room temperature and was composed of the following structural units were placed in:

0138<img file="WO2005123789A1_D0016.tif" />

01391.1 11.1 .a.1 .b.1 where structural units 1.1 and 11.1 were arranged in statistical order and the silicone compound had an equivalent weight of 3891 g / mol, determined as M_n/ Amino group and had an amine titer of 0.257 mmol / g.

014041.6 g of a reaction product of polyisobutylene with a molecular weight M were added_n of 550 g / mol and a vinyl group / molecule and succinic anhydride (ene reaction) dropwise. An exothermic reaction was observed, the temperature rose to about 60 ° C. and the viscosity increased.

0141After the addition of polyisobutylene had ended, the mixture was stirred at 60 ° C. for 4 hours and the progress of the reaction was monitored by taking an aliquot from time to time and determining the anhydride titer. The mixture was allowed to cool to room temperature after 5 hours. 275 g of polyisobutylene derivative PIB-1 according to the invention with an anhydride titer of 0.012 mmol / g were obtained, which corresponded to a conversion of 94.5%, based on the reaction product of polyisobutene with succinic anhydride (PIBSA).

0142I.2 Preparation of the polyisoutylene derivative PIB-2 according to the invention

0143122.7 g of an .alpha.,. Omega.-bis (3-aminopropyl) polydimethylsiloxane which had an average molecular weight M. Were placed in a 500 ml_n of 981.7 g / mol and had an amine titer of 2.038 mmol / g.

0144173.2 g of a reaction product were added

0145Polyisobutylene with a molecular weight M_n of 550 g / mol and a vinyl group / molecule and succinic anhydride (ene reaction) dropwise. An exothermic reaction was observed, the temperature rose to about 60 ° C. and the viscosity increased.

0146After the addition of polyisobutylene had ended, the mixture was stirred at 60 ° C. for 4 hours and the progress of the reaction was monitored by taking an aliquot from time to time and determining the anhydride titer. The mixture was allowed to cool to room temperature after 5 hours. This gave 294 g of polyisobutylene derivative PIB-2 according to the invention with an anhydride titer of 0.027 mmol / g, which corresponded to a conversion of 96.8%, based on PIBSA.

0147II. Preparation of aqueous emulsions according to the invention 11.1 Preparation of the aqueous emulsion D1 according to the invention

0148In a stirring apparatus, the mixture was heated to 70 ° C. and mixed using a hand blender:

014950 g PIB-1, 2.6 g N-oleyl sarcosine and 60.3 g fully deionized (deionized) water. After cooling to room temperature, the milky, cloudy liquid aqueous emulsion D1 was obtained, which showed no tendency to segregate even after storage for 30 days at room temperature. II.2. Preparation of the aqueous emulsion D2 according to the invention

0150The procedure was as described under 11.1, but 50 g of PIB-2 were used instead of PIB-1. After cooling to room temperature, the milky, cloudy liquid aqueous emulsion D2 was obtained, which showed no tendency to segregate even after storage for 30 days at room temperature.

0151III. Production of leather according to the invention

0152The data in% by weight relate in each case to the fold weight, unless stated otherwise. In all operations, the barrel was rotated about 10 times a minute unless otherwise stated.

0153Example 3.1

0154The following general recipe was used. The data in% by weight relate in each case to the fold weight, unless stated otherwise. In all operations, the barrel was rotated about 10 times a minute unless otherwise stated.

01552.5 kg of chrome-tanned cowhide leather (wet blue) with a fold thickness of 2.2 mm was mixed with 50% by weight of water and 2% by weight of sodium formate in a rotatable 50-liter barrel with internals. After 15 minutes, 0.5 wt% NaHCO₃ added and deacidified at 35 ° C. over a period of 120 minutes, so that a pH of 5 was established.

0156The liquor was drained and the leather was washed with 200% by weight of water at a temperature of 35 ° C. The leather was then mixed with 75% by weight of water at a temperature of 35 ° C. and 3% by weight of polymer with the following characteristic data:

015730th % By weight aqueous, partially neutralized with NaOH polymer solution; Homopolymer of methacrylic acid, M “approx. 10,000; K value according to Fikentscher: 12, viscosity of the 30% by weight solution: 65 mPa-s (DIN EN ISO 3219, 23 ° C), pH 5.1. It was tumbled for 30 minutes.

0158In the first treatment step, 10% by weight of aqueous emulsion D1 according to the invention was added and drummed for a further 30 minutes. Then 3% by weight of the vegetable tannin mimosa extract, 3% by weight of a commercially available resin tanning agent based on melamine and 1% by weight of a further commercially available resin tanning agent (phenol condensation product with organic nitrogen bases) were added within 10 minutes. In addition, 4% by weight of the sulfone tanning agent from EP-B 0459 168 was added. Treatment was continued for an hour. Then 2% by weight of a brown dye mixture was added for 60 minutes, which was composed as follows:

015970 Parts by weight of brown dye according to WO 98/41581, Example 2.18 and 30 parts by weight of Acid Brown 75 (iron complex), Color Index 1.7.16.

0160In the second treatment step, 8% by weight of aqueous emulsion D1 according to the invention were added and further tumbling at a pH of 4.8 over 90 minutes.

0161100% by weight of water at a temperature of about 70 ° C. were then added, so that a temperature of 50 ° C. was established, and a pH of 3.5 was then set using formic acid.

0162The liquor was drained and the leather was washed twice with 200% by weight of water at a temperature of 40 ° C. The leather was then mixed with 100% by weight of water and treated at a temperature of 30 ° C. with 3% by weight of Cr (III) sulfate at a pH of 3.5. The fleet was then drained.

0163Finally, it was washed twice with water, dried and worked up as usual in the tannery. The leather 3.1 according to the invention was obtained.

0164Example 3.2

0165Example 3.1 was repeated, but formulation D2 was used in the first and in the second treatment step. The leather 3.2 according to the invention was obtained.

0166The properties of the leather according to the invention obtained are shown in Table 2.

0167Table 2 Properties of the leathers according to the invention

0168<img file="WO2005123789A1_D0017.tif" />

0169The measurements and the water absorption were carried out with a Bally penetrometer. The measurements on the Bally penetrometer were carried out in accordance with DIN EN ISO 5403 and in each case as double determinations. The static water absorption was carried out at 15% compression by placing a test specimen in water for 1 hour and then determining the weight increase and indicating it in% by weight, based on the finished leather.