EP1776391A1

EP1776391A1 - Copolymers, production and use thereof

Info

Publication number: EP1776391A1
Application number: EP05778453A
Authority: EP
Inventors: Gerhard Wolf; Matthias KLÜGLEIN; Stephan Hüffer; Susanne Petrovic
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-08-05
Filing date: 2005-07-30
Publication date: 2007-04-25
Also published as: US20080201864A1; WO2006015745A1; DE102004038217A1; AR050094A1; CN1993382A; BRPI0514114A

Abstract

The invention relates to copolymers which are produced by copolymerisation in at least two steps. The invention is characterised by the following steps: (A) at least one (co)polymer is produced from a monomer or a mixture of comonomers, comprising (a1) 80 - 100 wt. % of at least one ethylenically unsaturated carboxylic acid, (a2) 0 - 20 wt.- % of at least one C1-C22-alkylester of at least one ethylenically unsaturated carboxylic acid, (a3) 0 - 10 wt. % of at least one additional ethylenically unsaturated compound, whereby the percentages in wt. % are related to the total amount of comonomers of the related step, and the thus obtained (co)polymer undergoes the following step (B) wherein the (co)polymer is converted with an additional comonomer or another mixture of comonomers, comprising (b1) 0 - 30 wt. % of at least one ethylenically unsaturated carboxylic acid, (b2) 70 - 100 wt. % of at least one C1-C22-alkylester of at least one ethylenically unsaturated carboxylic acid, (b3) 0 - 10 wt. % of at least one additional ethylenically unsaturated compound, whereby the percentages in wt. % are related to the total amount of comonomers of the related additional step.

Description

Copolymers, their preparation and use

description

The present invention relates to copolymers prepared by copolymerization in at least two stages, characterized in that in one step

(A) from a monomer or a mixture of comonomers comprising

(a1) 80 to 100% by weight of at least one ethylenically unsaturated carboxylic acid,

(a2) 0 to 20 wt .-% of at least one at least one ethylenically unsaturated carboxylic acid,

(a3) 0 to 10% by weight of at least one further ethylenically unsaturated compound,

where data in% by weight are based on the total amount of comonomers of the respective stage,

produces at least one (co) polymer

and the (co) polymer thus obtained in a subsequent step

(B) is reacted with a further comonomer or a further mixture of comonomers comprising (b1) 0 to 30% by weight of at least one ethylenically unsaturated carboxylic acid,

(b2) 70 to 100% by weight of at least one C 1 -C ₂₂ -alkyl ester of at least one ethylenically unsaturated carboxylic acid,

(b3) 0 to 10% by weight of at least one further ethylenically unsaturated compound,

where in wt .-% are based on the total amount of comonomers of the relevant further stage.

Furthermore, the present invention relates to a process for the preparation of copolymers according to the invention and to uses of the copolymers according to the invention.

There is a demand for soft but mechanically strong leathers, for example in the clothing sector, in the automotive sector and in the field of furniture leather. The leathers available in many cases either fall into comparatively hard form or harden in the course of use. EP 0 418 661 describes the use of copolymers containing 50 to 90% by weight of C ₈ -C ₄₀ -alkyl (meth) acrylates and / or vinyl esters of C ₈ -C ₄₀ -carboxylic acids and

10 to 50 wt .-% of monoethylenically unsaturated C ₃ -C ₂ carboxylic acids, monoethylenically unsaturated C ₄ -C ₁₂ -dicarboxylic acids and / or monoethylenically unsaturated C ₄ -C ₂ -dicarboxylic anhydrides and / or Halbester or monoamides of nisch monoethyle¬ unsaturated C ₄ -C- ₁₂ dicarboxylic acids or amides of monoethylenically ungesät¬ saturated C ₃ -C ₁₂ carboxylic acids as copolymerized units and which have molecular weights from 500 to 30,000 g / mo) have. Furthermore, it is disclosed that the copolymers described are suitable in at least partially neutralized form in aqueous solution or aqueous dispersion for the hydrophobization of leather. However, the resulting leathers are unsatisfactory in terms of their grain firmness.

WO 95/20056 describes aqueous polymer dispersions in which the polymer is in each case composed of 50 to 90% by weight of alkyl acrylate and 10 to 50% by weight.

(Meth) acrylic acid is obtained, and its use for fats and filling of leather countries described. The polymer dispersions prepared according to WO 95/20056 also show defects in the grain-tightness of the leather. In addition, the ability to combine with other products used in tanning or retanning is limited and can lead to negative results in terms of softness, fullness, coloration and, in particular, grain firmness.

The object was to provide leather treatment compositions which provide improved leather in terms of softness, fullness, dyeability and grain firmness and which can be used well in combination with leather treatment agents known from the prior art. It was a further object to provide a process for the production of leather treatment agents. A further object was to provide uses for treated leathers.

Accordingly, the copolymers defined above were found. The copolymers according to the invention are prepared by copolymerization in at least two stages, ie by a multistage process, for example a two-stage process or a three-stage process or a four-stage process.

Copolymers of the invention are obtained by reacting in one stage

(A) from a monomer or a mixture of comonomers comprising

(a1) 80 to 100% by weight, preferably 90 to 100% by weight, of at least one ethylenically unsaturated carboxylic acid, (a2) 0 to 20% by weight, preferably up to 10% by weight of at least one C ₁ C ₂₂ -alkoxylates of at least one ethylenically unsaturated carboxylic acid, (a3) 0 to 10% by weight, preferably 0.1 to 5% by weight, of at least one further ethylenically unsaturated compound,

data in% by weight being based on the total amount of comonomers of the stage in question,

produces at least one (co) polymer,

and the (co) polymer thus obtained in a subsequent step

(B) with a further comonomer or another mixture of Comonome¬ reindeers comprising (b1) 0 to 30 wt .-%, preferably up to 20 wt .-% of at least one ethylenically unsaturated carboxylic acid, (b2) 70 to 100 wt. -%, preferably 80 to 100 wt .-% of at least one

C 1 -C 4 -alkyl esters of at least one ethylenically unsaturated carboxylic acid, (b3) 0 to 10% by weight, preferably 0.1 to 5% by weight of at least one further ethylenically unsaturated compound,

Polymers according to the invention and a process for the preparation of polymers according to the invention, which is likewise the subject matter of the present invention, will be described in more detail below.

As ethylenically unsaturated carboxylic acids (a1) are particularly suitable ren Carbonsäu¬ of the general formula I.

In formula I, the radicals are defined as follows:

R ^{1 is} selected from hydrogen,

CH ₂ -COOH, CH ₂ -COOCH ₃ , CH ₂ -COOC ₂ H ₅ and d-Cio-alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyf, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl and very particularly preferably methyl;

R ² selected from

C ₁ -C ₀ -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-Hexyi, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, be¬ particularly preferably d -CrAlkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl,

COOH, COOCH ₃ , COOC ₂ H ₅ ,

and most preferably hydrogen.

Most preferably, R ^{2 is} hydrogen and R ^{1 is} hydrogen or methyl.

Very particular preference is given to using ethylenically unsaturated carboxylic acid (a1) as acrylic acid, methacrylic acid or mixtures of acrylic acid and methacrylic acid.

As C 2 -C ₂₂ -alkyl esters of at least one ethylenically unsaturated carboxylic acid (a2), preference is given to choosing those of the formula II

where the variables are defined as follows:

R ^{3 is} selected from C 1 -C ₂₂ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec. -Pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl, more preferably n-butyl and 2-ethylhexyl.

R ^{4 is} selected from hydrogen,

CH ₂ -COOH, CH ₂ -COOCH ₃ , CH ₂ -COOC ₂ H ₅ and C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo-pentyl, 1, 2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, particularly preferably C ₁ - C ₄ -AlkVl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and most preferably methyl;

R ⁵ selected,

C _t -C -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, n-octyl, n-nonyl, n-decyl; particularly preferably C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl,

COOCH ₃ , COOC ₂ H ₅

and most preferably hydrogen.

Most preferably, R ^{5 is} hydrogen and R ^{4 is} hydrogen or methyl.

Most preferably, R ^{5 is} hydrogen and R ^{4 is} hydrogen or methyl and R ^{3 is} selected from methyl, ethyl, n-butyl and 2-ethylhexyl.

Suitable further ethylenically unsaturated compound (a3) are, for example:

Vinyl esters of formic acid or of C 1 -C 6 -alkylcarboxylic acids, in particular vinyl acetate,

(Meth) acrylonitrile, (meth) acrylamide,

Vinylphosphonic acid, N-vinylformamide, itaconic acid, by at least one SO ₃ H group-substituted compounds having at least one CC double bond, preferably vinylsulfonic acid or 2-acrylamido-2-methyl-propanesulfonic acid

or their corresponding alkali metal or ammonium salts, 2- (N, N-dimethylamino) ethyl (meth) acrylate metochloride. After completion of the (co) polymerization, the formed (co) polymer can be isolated and purified. It is also possible to mechanically work the formed (co) polymer, for example to comminute it.

In one embodiment of the present invention, the Aufreini¬ conditions of the formed (co) polymer dispensed with and sets it in a further stage with

(B) a further comonomer or a further mixture of comonomers comprising (b1) 0 to 30% by weight, preferably up to 20% by weight of at least one ethylenically unsaturated carboxylic acid,

(b2) 70 to 100 wt .-%, preferably 80 to 100 wt .-% at least. a C 1 -C ₂₂ -alkyl ester of at least one ethylenically unsaturated carboxylic acid, (b3) 0 to 10% by weight, preferably 0.5 to 5% by weight of at least one further ethylenically unsaturated compound,

Ethylenically unsaturated carboxylic acid (b1) are preferably selected from those of the general formula I. Here, it is possible that ethylenically unsaturated carboxylic acid (a1) and ethylenically unsaturated carboxylic acid (b1) are the same or different. For example, it is possible to choose methacrylic acid as ethylenically unsaturated carboxylic acid (a1) and acrylic acid as ethylenically unsaturated carboxylic acid (b1). It is also possible that is selected as ethylenically unsaturated carboxylic acid (a1) acrylic acid and ^' as ethylenically unsaturated carboxylic acid (b1) methacrylic acid.

In another variant of the present invention, ethylenically unsaturated carboxylic acid (a1) and ethylenically unsaturated carboxylic acid (b1) are each the same and selected from (meth) acrylic acid.

C 1 -C ₂₂ -alkyl esters of ethylenically unsaturated carboxylic acid (b2) are preferably selected from those of the general formula II. It is possible that C 1 -C ₂₂ -alkyl esters of ethylenically unsaturated carboxylic acid (a2) and C 1 -C ₂₂ -alkyl esters of ethylenically unsaturated Carboxylic acid (b2) are the same or different. Thus, for example, C _r C ₂₂ alkyl esters of ethylenically unsaturated carboxylic acid (a2) (meth) acrylate and choose as CrC ₂₂ -A! Alkyl ester of ethylenically unsaturated carboxylic acid (b2) (meth) acrylic acid 2-ethylhexylester or (meth ) n-butyl acrylate. It is also possible to use (meth) acrylic acid 2-ethylhexyl ester or (meth) acrylic acid as the C 1 -C ₂₂ -alkyl ester of ethylenically unsaturated carboxylic acid (a2). acid-n-butyl ester and as C _r C ₂₂ alkyl esters of ethylenically unsaturated carboxylic acid (b2) methyl (meth) acrylate.

In another variant of the present invention Ci-C ₂₂ alkyl esters of ethylenically unsaturated carboxylic acid (a2) and C _r C ₂₂ alkyl esters of ethylenically ungesät¬-saturated carboxylic acid (b2) each identical and selected for example from (meth) methyl acrylate, (Meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid n-butyl ester.

Of course, in step (B), mixtures of two or more different C ₁ -C ₂₂ alkyl esters of ethylenically unsaturated carboxylic acid (b2) may be used, for example a mixture of 50% by weight of ethyl acrylate and 50% by weight of n-butyl acrylate.

Suitable further ethylenically unsaturated compound (b3) are, for example:

(Meth) acrylonitrile, (meth) acrylamide,

Vinylphosphonic acid, N-vinylformamide, itaconic acid, by at least one SO ₃ HG group substituted compounds having at least one

C-C double bond, preferably vinylsulfonic acid or 2-acrylamido-2-methylpropanesulfonic acid

or their corresponding alkali metal or ammonium salts, 2- (N, N-dimethylamino) ethyl (meth) acrylate metochloride.

One can choose (b3) different or preferably the same (a3). In one embodiment of the present invention, in at least one further step (C) it is possible to react with at least one further monomer selected from

(D) at least one C _r C ₂₂ alkyl ester of at least one ethylenically unsaturated carboxylic acid.

C 1 -C ₂₂ -alkyl esters of ethylenically unsaturated carboxylic acid (d) are preferably selected from those of the general formula II. It is possible for C 1 -C ₂₂ -alkyl esters of ethylenically unsaturated carboxylic acid (d) and C 1 -C ₂₂ -alkyl esters of ethylenically unsaturated carboxylic acid (a2) or (b2) are identical or different. So For example, it is possible to choose C 1 -C 4 -alkyl esters of ethylenically unsaturated carboxylic acid (d) (meth) acrylate and, as C 1 -C 4 -alkyl esters of ethylenically unsaturated carboxylic acid (a2) or (b2), (meth) acrylic acid 2-ethylhexyl ester or (meth) acrylic acid n-butyl. It is also possible to select (2-ethylhexyl (meth) acrylate or (meth) acrylic acid n-butyl ester as the C 1 -C ₂₂ -alkyl ester of ethylenically unsaturated carboxylic acid (d) and, as C 1 -C ₂₂ -alkyl ester of ethylenically unsaturated Carboxylic acid (a2) or (b2) (meth) acrylic acid methyl ester.

In another variant of the present invention -C ₂₂ alkyl esters of ethylenically unsaturated carboxylic acid (d), and -C ₂₂ alkyl esters of ethylenically ungesät¬-saturated carboxylic acid (a2) and (b2) each identical and selected for example from (meth) methyl acrylate, (Meth) acrylic acid 2-ethylhexyl ester and (meth) acrylic acid n-butyl ester.

In one embodiment of the present invention, the mass of monomer or comonomers from stage (A) to the mass of monomer or comonomers from stage (B) behaves as 1 to 100 to 1 to 1, preferably 1 to 20 to 1 to 2.

If it is desired to carry out one or more stages (C) in the preparation of copolymer according to the invention, then the masses of the sum of monomers or comonomers of (A) and (B) can behave to the mass of (C) as 50 to 1 to 1 to 1, preferably 20 to 1 to 2 to 1.

In one embodiment of the present invention, the difference of the glass transition temperatures T ₉ of polymer or random copolymer from stage (A) and polymer or random copolymer from stage (B) is at least 80 ^° C., preferably at least 100 ^° C. For example, the glass transition temperatures T _{9 are} calculated according to the Fox equation or determined by DSC (Differential Thermal Analysis, Differential Scanning Calorimetry) in accordance with DIN 53765, for example.

Polymer or random copolymer from stage (A) is understood to mean polymer which can be isolated after carrying out stage (A). Polymer or random copolymer from stage (B) are understood to mean those polymers or copolymers which are obtained by polymerization or copolymerization of the (co) monomers (b2), optionally (b1) and, if appropriate, (b3) in the absence of polymer Stage (A) are available.

In one embodiment of the present invention, polymer from step (A) has a molecular weight M _w in the range from 30,000 g / mol to 750,000 g / mol, preferably in the range from 50,000 g / mol to 550,000 g / mol. In one embodiment of the present invention, polymer or random copolymer from step (B) has a molecular weight M _w in the range from 1000 g / mol to 200,000 g / mol, preferably in the range from 2000 g / mol to 100,000 g / mol.

The polydispersity MjM _n copolymers of the invention may be in the range of 1, 1 and 40, preferably from 2 to 20

Another object of the present invention is a process for the preparation of novel copolymers according to the invention also mentioned below manufacturing method.

Another object of the present invention is a process for the preparation of copolymers, characterized in that in one step

(A) from a monomer or a mixture of comonomers comprising

(b1) 80 to 100% by weight of at least one ethylenically unsaturated carboxylic acid, (a2) 0 to 20% by weight of at least one C 1 -C ₂₂ -alkyl ester of at least one ethylenically unsaturated carboxylic acid, (a3) 0 to 10 % By weight of at least one further ethylenically unsaturated compound,

where weight percentages are based on the total amount of comonomers in the stage concerned,

produces at least one (co) polymer

and the (co) polymer thus obtained in a subsequent step

(B) with a further comonomer or a further mixture of Comonome¬ reindeer, comprising

(b1) 0 to 30% by weight of at least one ethylenically unsaturated carboxylic acid, (b2) 70 to 100% by weight of at least one C 1 -C ₂₂ -alkyl ester of at least one ethylenically unsaturated carboxylic acid, (b3) 0 to 10% by weight at least one further ethylenically unsaturated

Connection,

(Co) polymer from stage (A) can be prepared by any methods known per se from polymer chemistry, for example by solution polymerization, precipitation polymerization, bulk polymerization, suspension polymerization and, in particular, emulsion polymerization.

Typically, (co) polymer is prepared from step (A) using at least one initiator. At least one initiator may be a peroxide. Examples of suitable peroxides are alkali metal peroxodisulfates, e.g. Sodium peroxodisulfate, ammonium peroxodisulfate, hydrogen peroxide, organic peroxides such as diacetyl peroxide, di-tert-butyl peroxide, diamyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dibenzoyl peroxide, bis (o-toloyl) peroxide, succinyl peroxide, tert-butyl peracetate, tert. Butyl permalate, tert-butyl perisobutyrate, tert-butyl perpivalate, tert-butyl peroctoate, tert-butyl perodecanoate, tert-butyl perbenzoate, tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butyl peroxy-2-ethylhexanoate and diisopropyl peroxydicarbamate. Also suitable are azo compounds such as azobisisobutyronitrile, azobis (2-amidopropane) dihydrochloride and 2,2'-azobis (2-methylbutyronitrile).

Redox initiators are also suitable, for example from peroxides and oxidizable sulfur compound. Very particular preference is given to systems composed of acetone bisulfite and organic peroxide such as tert-C ₄ H ₉ -OOH, Na ₂ S ₂ O ₅ (sodium disulfate) and organic peroxide such as tert-C ₄ H ₉ -OOH or combinations of alkali metal salts of HO-CH ₂ SO ₂ H and organic peroxide such as tert-C ₄ H ₉ -OOH. Also, systems such as ascorbic acid / H ₂ O _{2 are} particularly preferred.

In general, initiator is used in amounts of from 0.1 to 20% by weight, preferably from 0.2 to 15% by weight, calculated on the mass of all comonomers.

For example, temperatures in the range from 20 to 100 ^° C., preferably from 50 to 90 ^° C., can be selected as the (co) polymerization temperature. The selected temperature is dependent on the decay characteristic of the initiator used.

The pressure conditions are generally not critical, suitable, for example, pressures in the range of atmospheric pressure to 10 bar.

It is possible to use at least one emulsifier which may be anionic, cationic or nonionic.

Suitable nonionic emulsifiers are ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C ₄ -C ₂₎ and also ethoxylated fatty alcohols (degree of ethoxylation: 3 to 80; alkyl radical: C ₈ to C ₃ S) - Examples are the Lutensol ^® brands from BASF Aktiengesellschaft and the Triton ^® grades from Union Carbide. Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C ₁₂ -C ₁₈ ) of ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical : C ₄ -C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ), of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ), of sulfosuccinates such as, for example, monobasic acid mono- and diesters, and of carboxylates, for example N-oleylsarcosine ,

Suitable cationic emulsifiers are generally C ₆ -C ₁₈ -alkyl-, aralkyl- or heterocyclic radical-containing 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 , 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) ethylparaffinsäureester, Λ / -Cetylpyridiniumchlorid, / V-Laurylpyri- diniumsulfat and Λ / - Cetyl-Λ /, Λ /, / V-trimethylammonium bromide, Λ / -dodecyl-Λ /, Λ /, Λ / -trimethylammonium bromide, Λ /, Λ / -distearyl-Λ /, Λ / -dimethylammonium chloride and the gemini Surfactant Λ /, / V- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stäche, Tensid-Taschenbuch, Carl-Hanser-Verlag,

Munich, Vienna, 1981, and McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989.

In one embodiment of the present invention, the amount of emulsifier is chosen such that the mass ratio between monomer or comonomer on the one hand and emulsifier on the other hand is greater than 1, preferably greater than 10 and particularly preferably greater than 20.

According to the invention, the reaction is preferably carried out in the absence of oxygen, for example in a nitrogen or argon atmosphere, preferably in a nitrogen stream.

For the production process according to the invention conventional equipment can be used, for. As autoclave and boiler.

It is possible to use one or more regulators for the preparation of (co) polymer in stage (A), for example C ₁ to C ₄ aldehydes, formic acid and compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, mercaptoacetic acid, tert Butyl mercaptan, n-dodecylmercaptan. Polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the total weight of the (co) monomers used. Preference is given to working without the use of controllers. The duration of the (co) polymerization in step (A) is generally from 30 minutes to 10 hours, preferably from 1 to 5 hours, more preferably from 3 to 5 hours.

After addition of (a1), if appropriate (a2) and optionally (a3), it is possible to react further until (a1), optionally (a2) and optionally (a3) have been copolymerized completely or at least to a total of at least 50% by weight ie until completion of the copolymerization in step (A). However, it is also possible to proceed immediately after the addition of monomer or comonomers from stage (A) and starting (co) polymerization with stage (B).

Upon completion of the (co) polymerization, step (B) can be immediately followed. After completion of the (co) polymerization, it is possible first to isolate and, if necessary, to purify the (co) polymer produced and then to add step (B). It is also possible to partially or quantitatively neutralize the carboxyl groups of (co) polymer prepared according to step (A) by addition of, for example, a basic alkali metal compound or at least one amine.

In step (B), the (co) polymer obtained and optionally isolated and / or purified and / or partially or completely neutralized after step (A) is reacted with a further monomer or a further mixture of comonomers. A further mixture of comonomers is also referred to below if in step (A) only one ethylenically unsaturated carboxylic acid (a1) has been polymerized. In the context of the following invention, a further monomer or a further mixture of comonomers is also used if the same comonomers are used in stages (A) and (B), but in different proportions.

The reaction in step (B) is preferably carried out as a free-radical (co) polymerization, for example in the form of a bulk or solution polymerization and particularly preferably in the form of an emulsion polymerization. It is very particularly preferred to do without the isolation of (co) polymer from stage (A) and to continue working in the same dispersion or solution or emulsion.

It is possible to add one or more initiators before, after and / or during the addition of (b2), optionally (b1) and optionally (b3), the initiator (s) being identical or different from the initiator or initiators from stage (A) can or can be.

It is possible to add one or more emulsifiers before, after and / or during the addition of (b2), optionally (b1) and optionally (b3), the one or more T / EP2005 / 008278

13

Emulsifiers may be the same or different from the emulsifier or emulsifiers of step (A) or may.

It is possible to add one or more regulators before, after and / or during the addition of (b2), optionally (b1) and optionally (b3), the regulator (s) being identical or different from the regulator (s) of step (A ) can or can be. Preferably, one works in step (B) with regulator.

For example, temperatures in the range from 20 to 100 ^° C., preferably from 50 to 90 ^° C., can be selected as the (co) polymerization temperature in step (B). The selected temperature depends on the decay characteristic of the initiator used.

The pressure conditions in step (B) are generally not critical, for example pressures in the range from atmospheric pressure to 10 bar are suitable.

The duration of the (co) polymerization in stage (B) is generally from 30 minutes to 10 hours, preferably from 1 to 8 hours, more preferably from 90 minutes to 6 hours.

If it is desired to add a step (C) after step (B), after completion of step (B) it is possible first to isolate and purify a copolymer of the invention and then to carry out step (C) by reaction with (d). However, in another variant, it is possible to continue working without isolation of copolymer of the invention and to carry out stage (C) by reacting with (d).

It is possible to add one or more emulsifiers before, after and / or during the addition of (d), where the emulsifier (s) may be identical or different from the emulsifier or emulsifiers from stage (A) or (B) or can.

It is possible to add one or more controllers before, after and / or during the addition of (d), wherein the regulator (s) may be the same as or different from the regulator (s) of stage (A) and (B), respectively can. Preferably, one works in step (C) with regulator.

When (co) polymerization in step (C) can be, for example, Temperatu¬ ren is in the range of 20 to 100 ⁰ C, preferably 50 to select 90 ⁰ C. The selected temperature is dependent on the decay characteristic of the initiator used.

The pressure conditions in step (C) are generally not critical, for example, pressures in the range of atmospheric pressure to 10 bar are suitable. The duration of the (co) polymerization in step (C) is generally from 30 minutes to 10 hours, preferably from 1 to 5 hours.

It is possible for the polymer or copolymer from step (B) to be grafted onto the polymer or copolymer from stage (A). It is also possible for the polymer or copolymer from stage (B) to encase or physically penetrate the polymer (s) or the copolymer (s) from step (A), but that no covalent linkage takes place.

If the addition of monomer or comonomer from step (B) has begun before monomer or comonomers from step (A) have completely reacted, a mixture of copolymers having a different comonomer incorporation ratio is obtained. The mixture obtainable in this way can then contain, for example, copolymers which are composed of comonomers of stage (A), which are composed of copolymers of stages (A) and (B) and which are composed of comonomers of stage (B).

If the inventive preparation of copolymer according to the invention has been carried out as a solution polymerization, it is possible to isolate copolymer according to the invention by evaporation of the solvent, for example.

If the inventive production of copolymer according to the invention has been carried out as an emulsion polymerization, it is obtained in the form of aqueous dispersions or emulsions, which are also the subject of the present invention, and from which it can be isolated, for example, by filtration or by evaporation of the water in which the evaporation can be carried out, for example, by spray drying in one or more spray towers. However, in many cases it is possible to dispense with the isolation of copolymer of the invention and to use it in the form of aqueous dispersions or emulsions according to the invention.

In one embodiment of the present invention, a copolymer according to the invention is neutralized partially or completely, for example with a basic alkali metal compound or with amine. Examples of basic alkali metal compounds are alkali metal hydroxide such as NaOH and KOH, alkali metal carbonate such as Na ₂ CO ₃ and K ₂ CO ₃ , alkali metal bicarbonate such as

NaHCO ₃ and KHCO ₃ . Examples of amines in the context of the present invention are ammonia and organic amines such as trimethylamine, triethylamine, diethylamine, ethanolamine, N, N-diethanolamine, N, N, N-triethanolamine, N-methylethanolamine. If it is desired to neutralize with basic alkali metal compound or with ammonia, it is advantageous to use basic alkali metal compound or ammonia as the aqueous solution. Aqueous dispersions or emulsions according to the invention may have a solids content in the range from 1% by weight to 70% by weight, preferably from 20% by weight to 60% by weight.

Another object of the present invention is the use of inventive copolymers, for example in the form of aqueous dispersions of the invention, for the production of leather. A further subject of the present invention is a process for the production of leather using copolymers according to the invention, for example in the form of aqueous dispersions according to the invention.

Leather is to be understood below by means of optionally chrome tanning agents, mineral tannins, polymer tanning agents, aldehyde tanning agents such as glutardialdehyde, synthetic tanning agents, vegetable tanning agents, resin tanning agents or combinations of at least two of the aforementioned tanning agents pretanned and preferably tanned animal hides.

In one embodiment of the present invention, leather is animal skin tanned with the aid of chrome tanning agents (wet-blue) or semi-finished products.

In a preferred embodiment of the present invention, leather is leather made of chromium-free tanned animal skin (wet-white) or semi-finished products.

Copolymers according to the invention, for example in the form of dispersions according to the invention, can be used in tanning and preferably in retanning, in the following referred to as tanning process or inventive retanning process. It is possible to use dispersions according to the invention in a separate treatment step

The tanning process according to the invention is generally carried out by adding er¬ inventive dispersion or inventive copolymer in one portion or in several portions immediately before or during tanning. The tanning process according to the invention is preferably carried out at a pH of from 2.5 to 8, preferably from 3 to 5.5.

In one embodiment of the present invention, the pH can be increased by adding blunting agents by about 0.3 to three units.

In another embodiment of the present invention, the tanning process according to the invention can be started at a pH in the range from 4 to 8, and copolymer according to the invention can be prepared by addition of an acidic component such as formic acid at a pH in the range from 3 to 5 , 5 fix. The novel tanning process is generally carried out at temperatures of 10 to 45 ° C, preferably ⁰ to 30 C at 20th Has proven useful a duration of 10 minutes to 12 hours, preferably one to three hours. The tanning process according to the invention can be carried out in any conventional tanning vessel, for example by walking in barrels or in rotated drums.

In a variant of the tanning process according to the invention, the dispersion or copolymer of the invention is used together with one or more conventional tanning agents, for example with chrome tanning agents, mineral tannins, preferably with syntans, polymer tanning agents or vegetable tanning agents, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume A15, pages 259 to 282 and especially page 268 ff., 5th Edition, (1990), Verlag Chemie Weinheim.

In a variant of the tanning process according to the invention, the novel dispersion or copolymer according to the invention is used together with fatliquoring agents such as native triglycerides, white oil, paraffin, wax, silicone oil, and also emulsifiers.

From 0.5 to 40% by weight, preferably from 2 to 20% by weight, of the dispersion or copolymer of the invention, based on the pelt weight, can be used in the tanning process according to the invention.

The process according to the invention for treating leather can preferably be carried out as a process for retanning leather using a dispersion according to the invention or copolymer of the invention. The retanning process according to the invention is based on conventional, i. For example, with chrome tanning agents, mineral tannins based on Al, Ti, Zr, Fe and Si, preferably semi-finished products tanned with polymer tanning agents, aldehydes, vegetable tannins, syntans or resin tanning or semi-finished products according to the invention. To carry out the retanning according to the invention, copolymer according to the invention is allowed to act on semi-finished products.

The retanning process according to the invention can be carried out under otherwise customary conditions. It is expedient to choose one or more, ie 2 to 6, single action steps and to rinse with water between the reaction steps. The structure is Tempera¬ during the individual treatment respectively in the range of 5 to 60 ⁰ C, bevor¬ Trains t 20 to 45 ° C. From 0.5 to 40% by weight, preferably from 2 to 20% by weight, of the dispersion or copolymer of the invention, based on the shaved weight, can be used in the retanning process according to the invention.

Of course, dispersion or copolymer according to the invention can be used in the tanning or retanning process according to the invention during the retanning, for example fatliquors, polymer tanning agents, acrylate- and / or methacrylate-based or silicone-based retanning agents based on Resin and Vegetabilgerbstoffen, fillers, leather dyes or emulsifiers or combinations of at least 2 of the aforementioned substances.

The treatment according to the invention leather is hydrophobicized or greased, that is, there is an improved fiber insulation. On the one hand, this improves the softness of the leather and, on the other hand, reduces the specific weight of the leather, resulting in advantages in terms of comfort when using leather produced according to the invention in furniture, car upholstery, clothing upper leather such as, for example, shoe upper leathers. The inventive treatment of the leather, on the basis of wet-white or on the basis of wet-blue produced leathers, further improves the fullness and the tangible properties of leather produced according to the invention. Here the term grip includes a soft, not fat-heavy, velvety surface grip, which combined with an inner softness of the leather leads to an optimal overall impression of the leather. The inventive treatment of the leather, the grain tightness According to the invention of leather produced is improved, that is a so-called undesirable to those skilled Doppelhäutigkeit the leather is avoided, the ^scars' is snug and does not tend to Splissigkeit.

Another aspect of the present invention is leather, for example leather based on wet-white or wet-blue and particularly preferably leather on the basis of wet-white, produced by the tanning process according to the invention or the retanning process according to the invention or by a combination of the novel process The tanning process and the retanning process according to the invention. The leathers according to the invention are characterized by an overall advantageous quality, for example they have a particularly pleasant feel and are very soft and full. The leathers according to the invention contain a copolymer described above which has penetrated particularly well into micro-regions of the elementary fibers.

Another aspect of the present invention is the use of leather according to the invention, for example leather of the invention based on wet-white or wet-blue, for the production of items of clothing such as, for example, shoes or furniture or car upholstery. Another aspect of the present invention is a Process for the production of articles of clothing such as, for example, shoes, furniture or automotive parts such as car upholstery using leather according to the invention, for example leathers based on wet white or wet blue according to the invention. For the purposes of the present invention, garment items are, for example, jackets, trousers, belts or suspenders, and in particular shoes, in particular shoe soles, shoe upper leather, shoe lining material and shoe insole. In the context of the present invention, furniture is to be understood as meaning all such furniture which contains components of leather, for example as a seat or on armrests. Examples include seating, such as armchairs, chairs, sofas. Car parts are exemplified by car upholstery such as car seats and furthermore steering wheels and dashboards and door interior parts.

Another aspect of the present invention are garments comprising or made of leather according to the invention. Another aspect of the present invention are furniture comprising or made of leathers according to the invention. Another aspect of the present invention are car parts containing or manufactured from leathers according to the invention.

A further aspect of the present invention are formulations comprising at least one copolymer according to the invention and at least one hydrophobic or amphiphilic substance selected from oils, waxes and synthetic polymers. A further aspect of the present invention are formulations containing at least one copolymer according to the invention, at least one hydrophobic or amphiphilic substance selected from oils, waxes and synthetic polymers, and at least one emulsifier.

At least one hydrophobic substance, selected from oils and waxes, may be a carbon-based compound, for example natural or synthetic wax, virgin or synthetic oil or native or synthetic fat.

Examples of natural waxes include beeswax, cork wax, montan waxes or carnaύbawachs.

Examples of synthetic waxes are polyethylene waxes or ethylene copolymer waxes, as obtainable, for example, by free-radical polymerization of ethylene or free-radical copolymerization of ethylene with, for example, (meth) acrylic acid or by Ziegler-Natta catalysis. Furthermore, polyisobutylene waxes may be mentioned. Furthermore, be mentioned paraffin mixtures; including Gemi¬ are specific understanding of hydrocarbons 12 or more carbon atoms have auf¬ and usually have a melting point in the range of 25 to 45 ⁰ C. Such paraffin mixtures can be obtained, for example, in refineries or crackers and are known to the person skilled in the art as slack wax and Sasol waxes. Another example of synthetic waxes are montan ester waxes.

As examples of natural oils, liquid triglycerides are mentioned at room temperature, for example fish oil, cattle claw oil, olive oil, cottonseed oil, castor oil, sunflower oil and peanut oil.

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

As examples of natural fats, solid native triglycerides, such as, for example, lanolin, shellac wax and mixtures thereof, are mentioned at room temperature.

Examples of synthetic polymers include maleic anhydride-α-olefin copolymers as disclosed in EP-A 0 412 389, furthermore copolymers obtainable by copolymerization of at least one ethylenically unsaturated dicarboxylic acid anhydride derived from at least one dicarboxylic acid having 4 to 8 C atoms, at least one oligomer of branched or unbranched C ₃ -C 10 _-alkene , where at least one oligomer has an average molecular weight M _n in the range from 300 to 5,000 g / mol or by oligomerization of at least 3 equivalents of C ₃ - Cio-alkene is available, and hydrolysis of the anhydride groups, wherein one can react before hydrolysis optionally with at least one simple to 100-fold ethoxylated vorzugs¬ linear C ₁ -C ₃₀ alkanol.

In a preferred embodiment of the present invention, a hydrophobic substance is at least one native triglyceride.

In a preferred embodiment of the present invention, an amphiphilic substance is at least one synthetic polymer. In a further preferred embodiment, a combination of at least one native or liquid native triglyceride 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; suitable ratios are, for example, weight ratios of native triglyceride: paraffin mixture in the range from 10: 1 to 1:10.

For example, it is possible to use from 10 to 70, preferably from 20 to 40,% by weight of one or more further hydrophobic compounds, based on the formulation according to the invention. In one embodiment of the present invention, formulations according to the invention comprise one or more emulsifiers which may be anionic, cationic, nonionic or zwitterionic.

Suitable nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (degree of ethoxylation: from 3 to 50, alkyl radical: C ₄ -C ₁₂ ) and ethoxylated fatty alcohols (degree of ethoxylation: from 3 to 80, alkyl radical: C ₈ -C ₃₆ ). Examples are the Lutensol ^® brands of BASF Aktiengesellschaft.

Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: C ₁₂ -C ₁₈ ) and ethoxylated alkylphenols (degree of ethoxylation: from 3 to 50, Alkyl radical: C ₄ -C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ -C ₁₈ ), of alkylarylsulfonic acids (alkyl radical: C ₉ -C ₁₈ ), and of sulfosuccinates, such as, for example, succinic acid mono- and diesters.

Suitable cationic emulsifiers are generally a C ₆ -C ₁₈ -alkyl, aralkyl or heterocyclic radical-containing 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, 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- (N, N, N-trimethylammonium) ethylparaffinsäureester, Λ / -Cetylpyridiniumchlorid, Λ / -Laurylpyridiniumsulfat and Λ / -Cetyl-Λ /, / , Λ / -trimethylammonium bromide, Λ / -dodecyl- / V, Λ /, / V-trimethylammonium bromide, Λ /, Λ / -istearyl-Λ /, Λ / -dimethylammonium chloride and the gemini surfactant Λ /, / V- (lauryldimethyl ) ethylendiamindibromid. Numerous other examples can be found in H. Stäche, 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 beispiels¬ the formula III

where the variables are defined as follows: R ^{6 is} C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl; especially methyl;

R ^{7 is} hydrogen, C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, in particular methyl;

C ₆ -C ₁₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-Phe - Nanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl.

The group CO-R ⁸ is preferably derived from saturated or unsaturated fatty acids. Saturated fatty carboxylic acids having C ₉ -C ₂ are to be understood O-alkyl groups, which may be linear or branched, substituted or unsubstituted. R ⁸ may be, for example: n-nonyl, n-decyl, n-dodecyl, n-tetradecyl, n-pentadecyl, n-octadecyl, n-eicosyl.

CO-R ⁸ can be derived from an unsaturated fatty acid having 9 to 20 C atoms and one to 5 CC double bonds, wherein the CC double bonds can be, for example, isolated or allylic, for example the acyl radical of linoleic acid, the linolenic acid, and most preferably the oleic acid.

In one embodiment of the present invention, all or at least one certain proportion, for example one third or one-half, of the carboxyl groups in N-acylated amino acid derivatives of the formula IV used as emulsifiers is neutralized. For neutralization, for example, basic salts such as hydroxides or carbonates of alkali metals such as Na or K. For neutralization are also suitable ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, and very particularly alkanolamines such as for example, ethanolamine, diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.

Exemplary representatives of compounds of the formula III are N-oleylsarcosine, N-stearylsarcosine, N-lauroylsarcosine and N-isononanoylsarcosine, and also the respective ethanolammonium salts, diethanolammonium salts and N-methyldiethanolammonium salts.

Other particularly suitable examples of emulsifiers are those of the general formula IV

where the variables are defined as follows:

R ⁹ , R ^{10 are the} same or preferably different and selected from hydrogen,

C ₁ -C ₃₀ -alkyl, branched or unbranched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isobutyl 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, be¬ preferably in the ß-position branched radicals of the formula IV a

- (CH ₂ CH ₂ O) _x -OR ¹⁴ or - [CH (CH ₃ ) CH ₂ O) _x -OR ¹⁴ , where x is an integer in the range of 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 9-phenanthryl, preferably phenyl, 1-naphthyl and 2-naphthyl, more preferably phenyl;

R ¹¹ is selected from C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and especially hydrogen;

R ¹² , R ^{13 is the} same or preferably different and selected from G-ι-C ₂₇ -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 Dimethyl-ethyl, 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; wherein the sum of the C atoms of R ¹² and R ^{13 is} a maximum of 30. Preferably, R ^{11 has} two C atoms more than R ¹² ; For example, the combinations R ¹² = n-undecyl and R ¹³ = n-nonyl, R ¹² = n-dodecyl and R ¹³ = n-decyl are preferred.

R ¹² = n-tridecyl and R ¹³ = n-undecyl, R ¹² = n-tetradecyl and R ¹³ = n-dodecyl, R ¹² = n-pentadecyl and R ¹³ = n-tridecyl.

R ¹⁴ is selected from C 1 -C ₄ -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 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 R ⁹ and R ^{10 is} hydrogen and the other is selected from C 1 -C ₃₀ -alkyl.

In a particularly preferred embodiment of the present invention, a mixture of a plurality of emulsifiers, for example of the formula IV, which may differ, for example, in that in the first compound the

Formula IV R ⁹ is hydrogen and R ^{10 is selected} from CrC ₃₀ alkyl and in the zwei¬ th R ¹⁰ is hydrogen and R ^{9 is selected} from CrC ₃ o-alkyl.

In one embodiment of the present invention, all or at least one certain portion, for example one third or one-half, of the sulfonyl groups is neutralized in emulsifiers of the formula VI. Suitable for neutralization are, for example, basic salts such as hydroxides or carbonates of the alkali metals such as Na or K. Further suitable for neutralization are ammonia, alkylamines such as methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine and most particularly Alkanolamines such as ethanolamine, diethanolamine, triethanolamine, N-methyl-ethanolamine, N-methyldiethanolamine or N- (n-butyl) -diethanolamine.

The preparation of compounds of the formula IV is known per se and described in WO 01/68584. It succeeds, for example, by simple or double Ve¬ resterung of dicarboxylic anhydrides of the general formula V.

V

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

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

In one embodiment of the present invention, emulsifiers present in formulations according to the invention may contain up to 40% by weight, preferably up to 20% by weight, based on emulsifier, of at least one alcohol of the formula VI

in formula VI, the variables R ¹² and R ^{13 are} as defined above.

In a preferred embodiment of the present invention, emulsifiers present in dispersions of the invention may 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 X; oxo oil 135 and oxo oil 13 may be mentioned as examples of such mixtures.

In one embodiment, formulations according to the invention comprise a combination of two emulsifiers, of which one emulsifier is selected from emulsifiers of the general formula III and IV and the other of ethoxylated fatty alcohols having a degree of ethoxylation: 3 to 80; Alkyl radical: nC ₈ -C ₃₆ .

In one embodiment of the present invention, formulations according to the invention contain α) 50 to 100% by weight, preferably 60 to 90% by weight of copolymer of the invention, β) 0 to 50% by weight, preferably 10 to 40% by weight hydrophobic substance selected from

Oils, waxes and synthetic polymers, γ) 0 to 20 wt .-%, preferably 1 to 15 wt .-% emulsifier,

where in wt .-% in each case based on the solids content of the entire inventive formulation. The remainder of the formulation according to the invention is preferably water.

Formulations according to the invention allow a particularly simple metering of copolymers according to the invention. Inventive formulations are further characterized by good performance properties such as storage stability.

Formulations according to the invention can be prepared by methods known per se, for example by mixing the individual components water, α), optionally β) and optionally γ). The order of addition of the individual components water, α), optionally β) and optionally γ) is not critical. The mixing can take place, for example, by simply stirring the components together, for example in a stirred tank, for example using a mixer or an Ultra Thurax stirrer. Preferably, further homogenization is carried out, e.g. with a

Slit homogenizer or in a stirred tank. Particularly storage-stable formulations according to the invention are obtained if at least one further homogenization is carried out.

The invention will be explained by working examples.

General remarks:

All reactions were carried out under an atmosphere of nitrogen unless otherwise specified.

The characterization of copolymers according to the invention was carried out with the aid of the preparative ultracentrifuge and subsequent size exclusion chromatography (SEC), the serum and the dispersed phase being separated. The serum was diluted in distilled water with 0.08 mol / l tris (hydroxymethyl) aminomethane buffer at pH 7 with the addition of 0.15 mol / l Cl ions (as NaCl) and 0.001 mol / l NaN ₃ , The calibration was carried out with a widely distributed Na-PAA mixture 23250/158/2 (sodium salt of polyacrylic acid) whose integral molecular weight distribution curve had been determined by SEC laser light scattering, according to the calibration method of MJR Cantow et al. (J. Polym., Vol. A-1, 5 (1967) 1391-1394), but without the concentration correction proposed therein. The glass transition temperature T _g was calculated according to the Fox equation.

1. Synthesis Procedure for Copolymers of the Invention 1.1 Preparation of Inventive Copolymer 1.1

The following mixtures were used as feed 1 to feed 4:

Feed 1: 31 g of acrylic acid

60 g of water

Feed 2: 294 g 2-ethylhexyl acrylate 30 g acrylic acid 190 g water

15 g 15% by weight aqueous solution of sodium lauryl sulfate 33 g 31% by weight aqueous solution of isononylphenol polyethoxysulfate

(average degree of ethoxylation: 25) 10 g of n-dodecylmercaptan

Feed 3: 147 g of 2-ethylhexyl acrylate 70 g of water

8.1 g 15% by weight aqueous solution of sodium lauryl sulfate 16 g 31% by weight aqueous solution of isononylphenol polyethoxysulfate (average degree of ethoxylation: 25) 5.2 gn dodecylmercaptan

Feed 4: 10 g of sodium peroxodisulfate 160 g of water

In a 2-liter polymerization vessel was a mixture of 11 1 g water and 10 g of a 15 wt .-% aqueous solution of sodium lauryl sulfate and submitted to so under Rüh¬ within 10 min heated to 80 ⁰ C. At 80 ⁰ C Zu¬ were run 1 was added continuously over one hour, and feed 4 within 4.5 hours, beginning simultaneously. After completion of the addition of feed 1, feed 2 was added continuously to the polymerization vessel at 80 ^° C. within 2 hours. After termination of the addition of Feed 2 Feed 3 was metered in continuously supply at 80 ⁰ C to the polymerization vessel in one hour. Thereafter, the resulting reaction mixture was stirred at 80 ⁰ C for 90 minutes. It was then cooled to room temperature and the resulting reaction mixture was treated with a solution of 16.5 g of NaOH in 80 g of water. The resulting reaction mixture was stirred at room temperature for 30 minutes. Copolyme invention CP1.1 was obtained as an aqueous dispersion. The aqueous dispersion of CP1.1 thus prepared had a solids content of 42.9% and a pH of 5.0. Step A: T ₉ = 130 ⁰ C, step B: T ₉ = -48 ⁰ C, step c: T ₉ = -58 ⁰ C.

Serum: M _w = 87,000 g / mol

1.2 Preparation of Inventive Copolymer 1.2

The following mixtures were used as feed 1 or feed 2:

Feed 1: 441 g of ethylhexyl acrylate

9.3 g of acrylic acid 220 g of water

23 g 15% by weight aqueous solution of sodium lauryl sulfate

49 g 31% by weight aqueous solution of isononylphenol polyethoxysulfate (average degree of ethoxylation: 25)

12 g of n-dodecylmercaptan

Feed 2: 7.8 g of sodium peroxodisulfate 124 g of water

In a 2-liter polymerization vessel, a mixture of 200 g of water, 10 g of a 15 wt .-% aqueous solution of sodium lauryl sulfate and 52 g of a high molecular weight polyacrylic acid (M _w = 310,000 g / mol) was added and stirred for 10 min heated to 80 ⁰ C. At 80 ^° C., feed 1 was added continuously at the same time within 3 hours and feed 2 within 3.5 hours. Thereafter, the resulting reaction mixture wur¬ de 90 minutes at 80 ⁰ C stirred. The mixture was then cooled to room temperature and the resulting reaction mixture was admixed with a solution of 16.5 g of NaOH in 80 g of water. The resulting reaction mixture was stirred at room temperature for 30 minutes. Copolymers of the invention CP1.2 were obtained as an aqueous dispersion. The aqueous dispersion of CP1.2 thus prepared had a solids content of 43.8% and a pH of 5.3.

Step A: T ₉ = 130 ⁰ C, step B: T ₉ = -56 ⁰ C.

Serum: M _w = 310,000 g / mol

1.3. Preparation of Inventive Copolymer 1.3

The following mixtures were used as feed 1 to feed 4:

Feed 1: 36 g of methacrylic acid 140 g of water

Feed 2: 287 g of 2-ethylhexyl acrylate 35 g of methacrylic acid

130 g of water

(average degree of ethoxylation: 25)

10 g of n-dodecylmercaptan

Feed 3: 143 g of 2-ethylhexylacryate at 65 g of water

8.1 g 15% by weight aqueous solution of sodium lauryl sulfate 16 g 31% by weight aqueous solution of isononylphenol polyethoxysulfate (average degree of ethoxylation: 25) 5.2 g of n-dodecylmercaptan

Feed 4: 10 g of sodium peroxodisulfate 160 g of water

In a 2-liter polymerization vessel a mixture of 130 g water and 10 g of a 15 wt .-% aqueous solution of sodium lauryl sulfate was introduced and so under Rüh¬ within 10 min heated to 80 ⁰ C. At 8O ⁰ C were added simultaneously starting Zu¬ run 1 within one hour and feed 4 within 4.5 hours continuously. After completion of the addition of feed 1, feed 2 was added continuously to the polymerization vessel at 80 ^° C. within 2 hours. After Beendi¬ the addition of Feed 2 Feed 3 was metered in continuously supply at 80 ⁰ C to the polymerization vessel in one hour. Thereafter, the resulting reaction mixture was stirred at 80 ⁰ C for 90 minutes. The mixture was then cooled to room temperature and the resulting reaction mixture was admixed with a solution of 16.4 g of NaOH in 62 g of water. The resulting reaction mixture was stirred at room temperature for 30 minutes. Copolyester CP1.3 according to the invention was obtained as an aqueous dispersion. The aqueous dispersion of CP1.3 thus prepared had a solids content of 41.6% and a pH of 6.1.

Step A: T ₉ = 162 ⁰ C, step B: T _g = 45 ° C, Step C: T ₉ = -58 ⁰ C.

Serum: M _w = 73,000 g / mol

2. Preparation of the formulations according to the invention

2.1 Preparation of Formulation According to the Invention 2.1 Template: 650 g aqueous dispersion of Copoiymerisat CP1.1 (42.9 wt .-%) Feed 1: 370 g of aqueous dispersion of MSA / C ₂ o-2 _4-olefin copolymer

(25% by weight) Feed 2: 40 g of N-oleoylsarcosine

Feed 3: 20 g of C ₁₃ -oxo alcohol ethoxylate (7 ethylene oxide / mol)

A 2 l polymerization vessel was charged with 650 g of an aqueous dispersion of copolymer CP1.1 and admixed with the inlets 1 to 3 at room temperature within 1 hour. The reaction mixture was then stirred for 1 hour at room temperature. The aqueous formulation 2.1 thus prepared had a solids content of 40.0% by weight and a pH of 5.2.

2.2 Preparation of Formulation According to the Invention 2.2

Original: 650 g of aqueous dispersion of copolymer CP1.1 (42.9% by weight)

Feed 1: 80 g of N-oleoylsarcosine

Feed 2: 40 g ₃ Ci -Oxoalkoholethoxylat (7 ethylene oxide / mol)

A 2 l polymerization vessel was charged with 650 g of an aqueous dispersion of copolymer CP1.1 and admixed with the inlets 1 to 2 at room temperature within 1 hour. The reaction mixture was then stirred for 1 hour at room temperature. The aqueous formulation 2.2 thus prepared had a solids content of 52.0% and a pH of 4.7.

3. Technical testing

The data in% by weight are based on the shaved weight, unless stated otherwise.

3.1 Application in the retanning of leather - production of shoe upper leather

Two commercial bovine wet blue were folded to a thickness of 1, 2 to 1, 4 mm ge and cut in half. Subsequently, the halves were in a barrel (50 l) and a fleet length of 100 wt .-% at 40 ⁰ C with 2 wt .-% sodium formate and 1, 0 wt .-% of a naphthalenesulfonic acid-formaldehyde condensate sationsprodukts forth No. 5,186,846, for example "dispersant 1." After 60 minutes, the liquor was drained off. Together with 100 wt .-% water at 25 to 35 ° C with 1 wt .-% of a 50 wt .-% (solids content) aqueous solution of dyes were dosed whose Feststof¬ fe were put together as follows: 70 parts by weight of dye from EP-B 0 970 148, Example 2.18, 30 parts by weight Acid Brown 75 (iron complex), Color Index 1.7.16;

and drummed for 10 minutes in the barrel.

Subsequently, in each case 6% by weight of formulation 2.1 or 2.2 according to the invention was added and the mixture was tumbled for 30 minutes. Subsequently, in each case 8% by weight of sulfone tanning agent from EP-B 0 459 168, Example K1, were added and the mixture was tumbled for a further 30 minutes at 15 revolutions / min in the barrel. Thereafter, the strips were treated for 45 minutes with 3% by weight vegetable tanning material Mimosa® and 1.5% each of the abovementioned solution of colorants.

It was then acidified to a pH of 3.6 to 3.8 with formic acid. After 20 minutes, the fleets were drained. Thereafter, it was washed with 200 wt .-% Was¬ water. Recently% water at 50 ⁰ C for 2 wt .-% were dosed by means of a tung Fet¬ in 100 wt .-, prepared as described under 4. After a waiting time of 45 minutes, acidification was carried out with 1% by weight of formic acid.

The washed leathers were dried and dressed and milled for 15 hours.

The leather 3.1 according to the invention was obtained. and 3.2.

The leathers 3.1 and 3.2 according to the invention had excellent fullness and softness and feel with excellent through-dyeing of the fibers. In addition, the leathers show a pronounced hydrophobization without having been treated with water-repellents based on silicone compounds, wherein the hydrophobization according to the invention can even exceed the effect of silicone oils.

Comparative Example C1

For Comparative Example C1, the procedure was as above, but according to the invention

Formulation omitted. The further steps were carried out as above. The comparative leather obtained was significantly harder, less full and substantially less pitted compared to the examples with the erfindungsge¬ MAESSEN formulations. In addition, the handle was much rougher and less soft or velvety. 4. Preparation of a fatliquoring agent In a 2 l kettle were mixed: 230 g of a polyisobutene with M _n = 1000 g / mol and M _w = 1800 g / mol, 30 g of C ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) ₂₅ -OH 5 g of 11-C ₁₈ H ₃₇ O- (CH ₂ CH ₂ O) -OH _8O

40 g of oleic acid

230 g sulfited oxidized triolein

The mixture was heated with stirring to 60 ⁰ C and 470 g of water and 10 g of n-

Ci ₆ H ₃₃ O- (CH ₂ CH ₂ O) ₇ -OH added. The resulting emulsion was then passed through a split homogenizer. A finely divided, stable emulsion was obtained.

Claims

claims

1. Copolymers prepared by copolymerization in at least two stages, characterized in that in one step

(A) from a monomer or a mixture of comonomers comprising (a1) 80 to 100% by weight of at least one ethylenically unsaturated carboxylic acid,

(a2) 0 to 20% by weight of at least one C 1 -C ₂₂ -alkyl ester of at least one ethylenically unsaturated carboxylic acid,

figures in% by weight are based on the total amount of comonomers of the stage in question,

produces at least one (co) polymer

and the (co) polymer thus obtained in a subsequent step

(B) with a further comonomer or a further mixture of comonomers, comprising

(b1) 0 to 30% by weight of at least one ethylenically unsaturated carboxylic acid, (b2) 70 to 100% by weight of at least one C 1 -C ₂₂ -alkyl ester of at least one ethylenically unsaturated carboxylic acid,

wherein amounts in wt .-% based on the total amount of comonomers of the affected ff further stage.

2. Copolymers according to claim 1, characterized in that at least one further stage (C) is reacted with at least one further monomer, selected from

(d) at least one C _t -Cag alkyl ester of at least one ethylenically unsaturated carboxylic acid.

3. Copolymers according to claim 1 or 2, characterized in that the difference of the glass transition temperatures T ₉ of polymer or of statistical

Copolymer of step (A) and polymer or random copolymer of step (B) is at least 80 ° C.

4. Copolymers according to one of claims 1 to 3, characterized in that they have a molecular weight M _w in the range of 30,000 to 750,000 g / mol auf¬.

5. Copolymers according to one of claims 1 to 4, characterized in that they are partially or completely neutralized with basic alkali metal compound or basic amine.

6. A process for the preparation of copolymers, characterized in that in one step

(A) from a monomer or a mixture of comonomers, comprising (b1) 80 to 100% by weight of at least one ethylenically unsaturated carboxylic acid,

(a2) 0 to 20 wt .-% of at least one CrC ₂₂ alkyl ester of at least one ethylenically unsaturated carboxylic acid, (a3) 0 to 10 wt .-% of at least one further ethylenically unsaturated

Connection,

produces at least one (co) polymer

and the (co) polymer thus obtained in a subsequent step

(B) is reacted with a further comonomer or a further mixture of comonomers, comprising (b1) 0 to 30% by weight of at least one ethylenically unsaturated carboxylic acid,

7. Use of copolymers according to one of claims 1 to 5 for the production of leather.

8. A process for producing leather using at least one copolymer according to any one of claims 1 to 5.

9. Formulation comprising at least one copolymer according to any one of claims 1 to 5 and at least one hydrophobic or amphiphilic substance, selected from oils, waxes and synthetic polymers.

10. A formulation according to claim 9, comprising at least one emulsifier.

11. Leather, produced using at least one copolymer according to any one of claims 1 to 5 or of at least one formulation according to ei¬ nem of claims 9 or 10.

12. Car parts manufactured using at least one leather according to claim 11.