WO2005123789A1

WO2005123789A1 - Polyisobutylene derivatives, method for the production thereof and their use

Info

Publication number: WO2005123789A1
Application number: PCT/EP2005/006241
Authority: WO
Inventors: Rainer Erhardt; Ralph Lunkwitz; Mirjam Herrlich-Loos; Peter Danisch
Original assignee: Basf Aktiengesellschaft
Priority date: 2004-06-18
Filing date: 2005-06-10
Publication date: 2005-12-29
Also published as: DE102004029467A1

Abstract

The invention relates to polyisobutylene derivatives containing, per molecule on average, at least on structural unit of formula (I) in which the variables are defined as follows: R1 is selected from phenyl and C1-C10 alkyl; R2 is identical or different and, independent of one another, selected from hydrogen, phenyl and C1-C10 alkyl; a is an integer ranging from 1 to 20; b is either 0 or 1; X is selected from the formulas (X.1), (X.2), (X.3), (X.4), (X.5), (X.6); Y1 and Y2, are identical or different and are selected from -O- and -NR3-; R3 is selected from hydrogen and C1-C10 alkyl, and; PIB represents a polyisobutylene radical.

Description

Polyisobutylene derivatives, process for their preparation and their use

description

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

where the variables are defined as follows: R ¹ selected from phenyl and d-Cio-alkyl,

R ^{2, the} same or different and independently selected from hydrogen, phenyl and dC ^ alkyl, where up to three non-adjacent CHR ² groups can be replaced by oxygen or NR ³ groups, a an integer in the range from 1 to 20, b selected from 0 or 1, X selected from

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

R ^{3 are the} same or different and selected from hydrogen and CC ₁₀ alkyl

PIB 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.

Hydrophobing is an important step in the production of leather. The haptic properties and the 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, i.e. can be applied with 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.

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

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

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

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

The 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.

Accordingly, 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

where the variables are defined as follows: R ¹ 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,

R ² 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,

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

b selected from 0 or 1, preferably 0,

X selected

wherein Y, Y are identical or different and are selected from -O- and -NR - are the same or different and are independently selected from d-Cι ₀ 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 ₄ -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and very particularly preferably methyl,

and especially hydrogen

PIB 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.

Up to three non-adjacent CHR ² groups can be replaced by oxygen or NR ³ groups. 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:

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

on, where the radicals R ^{4 may be the} same or different and are independently selected from phenyl and

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

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

-Si (R ⁴ ) ₃ MI a

or III b

-O-Si (R ⁴ ) ₃ III b

in which R ⁴ is defined as above.

In preferred polyisobutylene derivatives according to the invention, R ¹ and R ^{4 are} each the same and methyl, R ² is hydrogen and a is an integer in the range from 3 to 10.

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 I, preferably at least two, per molecule.

In 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, preferably at least three, per molecule.

In 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 per molecule, preferably up to 50.

Polyisobutylene 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.

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

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

The 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.

Reactive polyisobutylenes can be obtained, for example, by oligomerizing isobutylene (isobutylene) or isobutene-containing feedstocks in the presence of a suitable catalyst, preferably a Lewis acid such as, for example, boron trifluoride or titanium tetrachloride, see e.g. 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.

Suitable isobutene-containing feedstocks are both isobutene itself and isobutene-containing C ₄ hydrocarbon streams, for example C raffinates, C cuts from isobutane dehydrogenation, C ₄ cuts from steam crackers or so-called FCC crackers (FCC: Fluid Catalysed cracking), provided that the C-sections in question are largely freed from 1,3-butadiene contained therein. The concentration of iso- Butenes in C ₄ hydrocarbon 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 C ₄ hydrocarbon 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.

Reactive 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.

For 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:

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.

One 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.

To react 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, you can also use one of the two reactants Dose silicone compound and reactive polyisobutylene in a molar excess, for example in 0.1 to 0.5 equivalent excess, based on the respective functional groups.

In one embodiment of the present invention, the production of inventive polyisobutylene derivative is carried out at temperatures ranging from 0 ^C C to 200 ° C, preferably at 20 ° C to 100 ° C.

In 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.

Of course, it is also possible in the context 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. It is of course also possible within the scope of the present invention to react two silicone compounds with one reactive polyisobutylene.

Polyisobutylene 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.

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

In 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.

Examples of preferred nonionic emulsifiers are

- Alkoxylated C ₈ - to C ₂₂ alcohols such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. C ₈ to C ₂₂ alcohols 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 above-mentioned alkylene oxides in a statistical distribution. Preferred nonionic emulsifiers generally contain 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide per mole of alcohol and particularly preferably ethylene oxide as alkylene oxide. Fatty alcohols or oxo alcohols preferably have 10 to 18 carbon atoms. Depending on the type of alkoxylation catalyst used in the preparation, the alkoxylates have a broad or narrow alkylene oxide homolog distribution;

Alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ - to C ₁ -alkyl chains and 5 to 30 alkylene oxide units;

Alkyl 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;

N-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.

Particularly 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.

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

Bases can be used as alkoxylation catalysts, for example alkali metal hydroxides or alkali metal alcoholates, but also Lewis acids, for example BF ₃ , SbCl ₅ , SnCl ₄ × 2H ₂ O, BF ₃ × H ₃ BO ₄ , or BF ₃ dietherate. Particularly suitable alkoxylie tion catalysts are double hydroxide clays such as hydrotalcite, which can in particular be modified with additives, as described in DE-A 43 25 237.

Depending 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.

The 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.

Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkyl phenols (degree of ethoxylation: 3 to 50, alkyl radical: C ₄ -C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ -Cι ₈ ), of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ), of fatty acids such as, for example, stearic acid and of sulfosuccinates such as, for example, sulfosuccinic acid mono- and diester ,

Suitable cationic emulsifiers are usually a C ₆ -C ₁₈ alkyl, aralkyl or heterocyclyl-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxa zoliniumsalze, morpholinium, thiazolinium, and salts of amine oxides , Quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (Λ /, Λ, / V-trimethylammonium) ethyl paraffinic acid esters, -C / -cetylpyridinium chloride, Λ / -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. Stächen, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989. Particularly suitable emulsifiers are N-acylated amino acid derivatives, for example of the formula IV

R ⁵ "OOH

in which the variables are defined as follows:

R ^{5 is} hydrogen, -CC ₄ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl, especially 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;

R ⁶ CC alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl; especially methyl;

The group CO-R ⁷ is preferably derived from saturated or unsaturated fatty acids. Saturated fatty acids are to be understood as carboxylic acids with C ₉ -C ₂₀ alkyl groups, which can be linear or branched, substituted or unsubstituted. R ⁶ can be, for example: n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-octadecyl, n-eicosyl.

CO-R ⁷ can be derived from an unsaturated fatty acid with 9 to 20 C atoms and one to 5 CC double bonds, where the CC double bonds can, for example, be isolated or allylic, for example the acyl residue of linoleic acid, linolenic acid, and very particularly preferably oleic acid.

In 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, ethylene diamine, and very particularly alkanolamines such as ethanolamine are also suitable for neutralization , 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.

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

in which the variables are defined as follows:

R ⁸ , R ^{9 are the} same or preferably different and are selected from hydrogen, dC ₃ o-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-te-tradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, preferably in the β position branched radicals of the formula V a

- (CH ₂ CH ₂ O) _x -OR ¹³ or - [CH (CH ₃ ) CH ₂ O) _x -OR ¹³ , where x is an integer in the range from 1 to 20,

C ₆ -C ₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9th -Phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, particularly preferably phenyl;

R ¹⁰ is selected from dC ₄ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and in particular hydrogen; R ¹¹ , R ^{12 are the} same or preferably different and are selected from C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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;

the sum of the C atoms of R ¹¹ and R ^{12 is} a maximum of 30. R ¹¹ preferably has two more C atoms than R ¹² ; preferred are, for example, the combinations R ¹¹ = n-undecyl and R ¹² = n-nonyl, R ¹¹ = n-dodecyl and R ¹² = n-decyl, R ¹¹ = n-tridecyl and R ¹² = n-undecyl, R ¹¹ = n-tetradecyl and R ¹² = n-dodecyl, R ¹¹ = n-pentadecyl and R ¹² = n-tridecyl.

R ¹³ is selected from dC ₄ 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 especially hydrogen.

In a preferred embodiment of the present invention, exactly one of the radicals R ⁸ and R ^{9 is} hydrogen and the other radical is selected from C 1 -C ₃₀ -alkyl.

In a particularly preferred embodiment of the present invention, a mixture of several emulsifiers, for example of the formula V, which can differ, for example, in that in the first compound of the formula VR ⁸ is hydrogen and R ^{9 is selected} from CC ₃ o-alkyl and in the second R ⁹ is hydrogen and R ^{8 is} chosen from dC ₃ o-alkyl.

In 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 are also suitable for neutralization for example ethanolamine, diethanolamin, triethanolamine, N-methylethanolamine, N-methyldiethanolamine or N- (n-butyl) diethanolamine. The preparation of compounds of formula V is known per se and in

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

Esterification of dicarboxylic acid anhydrides of the general formula VI

with corresponding alcohols, which need not be pure, followed by reaction with disulfite, for example Na ₂ S ₂ O ₅ .

Emulsions 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.

In 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

included, wherein in formula VII the variables R ¹¹ and R ¹² are defined as above.

In 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.

In 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.

Aqueous 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.

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

Examples of synthetic waxes are polyethylene waxes or ethylene copolymer waxes, such as are obtainable, for example, by radical polymerisation of ethylene or radical copolymerisation 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.

Examples of natural oils are triglycerides which are liquid at room temperature, for example fish oil, beef claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil.

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

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

Examples of synthetic polymers are maleic anhydride-α-olefin copolymers, for example copolymers of maleic anhydride and CH ₂ = CH-n -CC ₈ H ₃₇ , CH ₂ = CH-nC ₂₀ H ₄ , or CH ₂ = CH- nC ₂₂ H ₄₅ , still styrene

Maleic anhydride copolymers that can be partially esterified with d-C alkanol ethoxylates.

In 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.

In 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.

Aqueous emulsions according to the invention can also contain additives, for example biocides and / or oxidation stabilizers.

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

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

0 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.

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

For 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.

Another 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 fur skins using polyisobutylene derivatives according to the invention and in particular aqueous emulsions according to the invention, hereinafter also as invented designated manufacturing process. The present invention furthermore relates to leather or fur skins, produced using polyisobutylene derivatives according to the invention and in particular aqueous emulsions according to the invention.

To 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 or skins to be treated can have been produced by any desired methods, 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 the aforementioned tannins.

In 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 fold weight of the tanned animal skin or the wet weight of the fur.

The manufacturing method 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.

Temperatures 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.

The 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 reduced pressure, for example 0.5 to 0.99 atm, or at elevated pressure, for example 1.01 to 2 atm.

At the start 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 manufacturing 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.

The 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.

Conventional 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.

If one wishes to carry out the production process according to the invention with retanning, one can do this 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.

Organic solvents such as alcohols can be added while the production process according to the invention is being carried out. However, it is preferred to work without the addition of organic solvents.

After 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.

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

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

Another 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 is 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.

The 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.

General remarks:

I. Preparation of polyisobutylene derivatives according to the invention

1.1. 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:

1.1 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 an amine titer of 0.257 mmol / g.

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

After 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).

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

122.7 g of an α, ω-bis (3-aminopropyl) polydimethylsiloxane, which had an average molecular weight M _n of 981.7 g / mol, were placed in a 500 ml 4-necked flask equipped with a stirrer, reflux condenser and internal thermometer had an amine titer of 2.038 mmol / g.

173.2 g of a reaction product were added

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

After 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.

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

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

50 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

The 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.

III. Production of leather according to the invention

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.

Example 3.1

The 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.

2.5 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% by weight of NaHCO _{3 was} added and deacidified at 35 ° C. over a period of 120 minutes, so that a pH of 5 was established.

The 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:

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

In 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 tannin was made EP-B 0459 168 added. Treatment was continued for one hour. Then 2% by weight of a brown dye mixture was added for 60 minutes, which was composed as follows:

70 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.

In 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.

100% by weight of water at a temperature of about 70 ° C. were then added, so that a temperature of 50 ° C. was established, and then a pH of 3.5 was set with formic acid.

The 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.

Finally, 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.

Example 3.2

Example 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.

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

Table 2 Properties of the leathers according to the invention

The 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.

Claims

claims

1. Polyisobutylene derivatives containing on average at least one structural unit of the formula I per molecule

where the variables are defined as follows: R ¹ selected from phenyl and d-Cio-alkyl, R ² identical or different and independently selected from hydrogen, phenyl and dC ₁₀ alkyl, with up to three non-adjacent CHR ² groups can be replaced by oxygen or NR ³ groups, a an integer in the range from 1 to 20, b selected from 0 or 1, X selected from

YA, v2 identical or different and selected from -O- and -NR - R ³ identical or different and selected from hydrogen and d-do-alkyl PIB a polyisobutylene radical.

Polyisobutylene derivatives according to Claim 1, characterized in that they have on average at least one structural unit of the general formula II per molecule have, where R ^{4 may be the} same or different and are independently selected from phenyl and dC ₁₀ alkyl.

3. polyisobutylene derivatives according to claim 1 or 2, characterized in that they have at least one structural unit of the general formula III a -Si (R ⁴ ) ₃ III a or III b

-O-Si (R) ₃ MI b, wherein R ^{4 is} as defined above.

4. Polyisobutylene derivatives according to one of claims 1 to 3, characterized in that PIB for a polyisobutylene radical with an average molecular weight M _w in the range from 112 to 50,000 g / mol.

5. polyisobutylene derivatives according to any one of claims 1 to 4, characterized in that R ¹ and R ^{4 are} each methyl and R ^{2 is} each hydrogen and a is an integer in the range from 3 to 10.

6. A process for the preparation of polyisobutylene derivatives according to one of claims 1 to 5, characterized in that at least one reactive polyisobutylene is reacted with at least one silicone compound which carries at least one functional group which is capable of reacting with the reactive polyisobutylene.

7. Aqueous emulsions containing at least one polyisobutene derivative according to one of claims 1 to 5.

8. Use of aqueous emulsions according to claim 7 in the manufacture of leather or fur.

9. A method for producing leather or fur using at least one aqueous emulsion according to claim 7.

10. Leather made by a method according to claim 9.

11. Use of leather according to claim 10 for the production of clothing, furniture, furniture parts or auto parts.

12. Fur skins produced by a method according to claim 9.