WO2015150508A1

WO2015150508A1 - Aqueous polymer compositions

Info

Publication number: WO2015150508A1
Application number: PCT/EP2015/057282
Authority: WO
Inventors: Peter Nesvadba; Matthias ZORN; Olof Wallquist; Bernd Reck
Original assignee: Basf Se
Priority date: 2014-04-04
Filing date: 2015-04-02
Publication date: 2015-10-08

Abstract

The present invention relates to an aqueous polymer composition containing at least one first polymer P1 which is composed of ethylenically unsaturated monomers and which on average has more than two functional groups of the formula -O-NR¹R², and to the use of said polymers for crosslinking polymers P2 which have functional groups F that can react with the groups of the formula -O-NR¹R² with formation of a covalent bond. The polymer compositions comprise: a) at least one first polymer P1 which is composed of ethylenically unsaturated monomers and which on average has more than two functional groups of the formula -O-NR¹R² in which R¹ and R² are hydrogen or together represent a =CR^aR^b group in which R^a and R^b are mutually independently hydrogen or C₁-C₆-alkyl, or together with the carbon atom to which they are bonded form a C₅-C₈-cycloalkylidene group; b) and at least one second polymer P2 which is preferably composed of ethylenically unsaturated monomers and which has functional groups F that can react with the groups of the formula -O-NR¹R² with formation of a covalent bond.

Description

Aqueous polymer compositions

The present invention relates to aqueous polymer composition containing at least a first, built up from ethylenically unsaturated monomers

Polymer P1, which has on average more than 2 functional groups of the formula -O-NR ¹ R ² , and the use of these polymers for crosslinking polymers P2 which have functional groups F which are bonded to the groups of the formula -O-NR ¹ R ² can react to form a covalent bond. Aqueous polymer compositions, in particular aqueous polymer dispersions, are widely used for the production of coatings or as adhesive raw materials. The polymer films forming upon removal of the water are typically uncrosslinked and therefore have only limited mechanical strength or cohesion and only limited chemical resistance, in particular limited resistance to organic solvents.

In principle, these disadvantages can be overcome by crosslinking the polymer film during or after its formation. An overview of the post-crosslinking of polymer films can be found in M. Ooka, H. Ozawa, Progress in Organic Coatings, 23 (1994) 325-338. As a rule, aqueous polymer compositions whose film-forming polymers have reactive functional groups F, for example carboxyl groups, hydroxyl groups, aldehyde or keto groups or oxirane groups, will be used for this purpose. The aqueous polymer compositions are then admixed with a low molecular weight, water-soluble crosslinking agent having a reactivity complementary to the functional groups of the film-forming polymer and thus drying the polymer film with the functional groups of the film-forming polymer to form a covalent bond or bond

Complex formation reacts. It is generally known that low molecular weight compounds which have aminoxy groups can be used for crosslinking polymers which have keto or aldehyde groups as reactive groups.

EP 519074 describes aqueous polymer compositions based on aqueous dispersions of polymers which comprise copolymerized ethylenically unsaturated monomers with keto or aldehyde groups, the aqueous polymer compositions containing a low molecular weight compound which has 2 aminoxy groups or one aminox group and one hydrazide group. Similar compositions are known from DE 42 19 384 and DE 43 14 623. MR Hill et al. Polym. Chem., 3 (2012), 1758 describe homopolymers of O- (4-vinylbenzyl) hydroxylamine ethers and its copolymers with styrene. Basically, however, low molecular weight compounds have the disadvantage that they can easily be washed out of the polymer film if they are not completely crosslinked. In addition, they generally have a comparatively high volatility, which is disadvantageous from the point of view of occupational hygiene. In addition, the low molecular weight compounds are often toxic. In addition, the cross-linking effect is not always satisfactory.

It has surprisingly been found that in aqueous polymer compositions of polymers having functional groups F which are resistant to aminoxy groups, i. H. h N-O groups have a complementary reactivity, effective crosslinking is also possible by means of polymeric additives having an average of more than 2 functional aminoxy groups in the polymer molecule.

Surprisingly, the crosslinking also succeeds when the h NO groups are in the form of their ketimines, ie are present as groups of the formula -O-N =CR ^a R ^b , where R ^a and R ^b independently of one another are hydrogen or C 1 -C 4 Alkyl or together with the carbon atom to which they are attached, form a Cs-Cs Cycloalkylidengruppe. Presumably, in the aqueous medium, hydrolysis of the ketimine groups occurs, releasing the aminoxy groups, which then cause crosslinking.

Accordingly, a first aspect of the invention relates to aqueous

Polymer compositions comprising: a) at least one first polymer P1 made up of ethylenically unsaturated monomers which has on average more than 2 functional groups of the formula

-O-NR ¹ R ² , wherein

R ¹ , R ^{2 are} hydrogen or together form a group = CR ^a R ^b

in which R ^a and R ^b independently of one another are hydrogen or C 1 -C 6 -alkyl or together with the carbon atom to which they are attached form a C 5 -C 8 -cycloalkylidene group; b) and at least a second, preferably from ethylenically unsaturated

Monomeric polymer P2 having functional groups F which can react with the groups of formula -O-NR ¹ R ² to form a covalent bond. Some of the polymers P1 are new, namely copolymers which on average have more than 2 functional groups of the formula -O-NR ¹ R ² and which are composed of the following repeat units MA and MB:

MA repeating units MA which are derived from a monoethylenically unsaturated monomer A which carries a functional group of the formula -O-NR ¹ R ² , in which R ¹ and R ^{2 have} the meanings given in Claim 1 or 2;

MB repeating units MB, that of monoethylenically unsaturated

Monomers B are derived, which are not a functional group of the formula

-O-NR ¹ R ² , wherein the repeating units MB such

Repeat units include MBI, monoethylenically

unsaturated monomers B1 having a water solubility of at least 50 g / l, at 20 ° C and 1 bar, are derived.

Copolymers of this kind, which are also referred to below as copolymers P1 ', are particularly suitable as crosslinking agents for the abovementioned polymers P2 and are therefore themselves also the subject of the present invention. The invention also relates to the use of polymers P1 and of

Copolymers P1 ', as described in more detail here and in the following and in the claims, as crosslinkers for polymers P2, the functional groups F, which with the groups of formula -0-NR ¹ R ^{2 of} the polymer P1 to form a covalent Binding can react.

The aqueous polymer compositions of the invention have a number of advantages. By using the polymers P1 or the copolymers P1 ', it is possible to achieve improved crosslinking in comparison to low molecular weight crosslinkers. This gives polymer films increased mechanical strength and less susceptible to exposure to chemicals such as organic

Solvents, greases or oils. In addition, the property profile of the polymer films obtained can be better controlled via the modification of the polymers P1 and adapted to the desired application by modifying the polymer structure, rather than by low molecular weight crosslinkers. Furthermore, in contrast to the partially toxic low molecular weight crosslinkers, such polymers have a significantly less pronounced potential to be sensitizing and toxic. Without wishing to be bound by theory, it is believed that the functional groups F of the polymer P2 with the aminoxy (h NO groups) of the

Polymer P1 or the copolymer PV react during drying of the polymer composition to form covalent bonds and thus effect an intermolecular crosslinking of the polymers P2 and the polymers P1 or copolymers PV. Surprisingly, the crosslinking is more pronounced than when using low molecular weight crosslinking agents such as dicarboxylic acid dihydrazides, alkylenediamines or Bisaminoxyalkane. If the functional groups of the formula -O-NR ¹ R ² are present in the form of their ketimines, ie as groups of the formula -O-N = CR ^a R ^b , hydrolysis of the ketimine groups presumably takes place in the aqueous medium

Release of the aminoxy groups, which then cause crosslinking. It is also conceivable that the functional groups of the formula -0-N = CR ^a R ^b with the functional groups F = formation of a covalent bond and elimination of a ketone or aldehyde of the formula 0 CR ^a R ^b is reacting.

Here and below, the term "alkyl" includes straight-chain and branched alkyl groups, preferably having 1 to 6 and in particular 1 to 4 carbon atoms (C 1 -C 6 -alkyl or C 1 -C 4 -alkyl), such as, for example, methyl, ethyl, propyl, isopropyl, n-butyl, 2-butyl, sec-butyl, tert-butyl, n-pentyl, 2-pentyl, 2-methylbutyl, 3-methylbutyl, 1, 2-dimethylpropyl, 1, 1-dimethylpropyl, 2,2- Dimethylpropyl, 1-ethylpropyl, n-hexyl, 2-hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 2-dimethylbutyl,

1, 3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl,

3,3-dimethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2-trimethylpropyl, 1-ethylbutyl,

2-ethylbutyl or 1-ethyl-2-methylpropyl.

Suitable long-chain alkyl groups are, for example, straight-chain and branched alkyl groups having up to 30 carbon atoms and in particular up to 20 carbon atoms, for. B. C7-C30 alkyl groups, preferably C7-C20 alkyl groups. These are preferably predominantly linear alkyl radicals, as they are also available in natural or synthetic

Fatty acids and fatty alcohols and Oxoalkoholen occur. These include, for example, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and n-nonadecyl. Also suitable are branched alkyl radicals having 7 to 30 C atoms, in particular 7 to 20 C atoms, such as 2-heptyl, 3-heptyl, 2-ethylpentyl, 1-propylbutyl, 2-ethylhexyl, isononyl, 2-propylheptyl, isotridecyl and the same.

The above comments on alkyl also apply analogously to the alkyl groups in alkanol, alkylamine and alkanecarboxylic acids. The term "cycloalkylidene" in the context of the present invention represents a cyclic hydrocarbon radical bonded via a double bond and preferably having 5 to 8 C atoms, such as cyclopentylidene, cyclohexylidene, cycloheptylidene and cyclooctylidene.

The term "alkylene" in the context of the present invention represents straight-chain or branched alkanediyl groups having 1 to 12 carbon atoms, such as, for example, methylene, 1-ethane-1,2-diyl, 1,2-propanediyl, 2-methyl-1,2 propanediyl or 1,2,3,3 or 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1,9-nonanediyl, 1 , 10-decanediyl, 1,1,1-undecanediyl or 1,12-dodecanediyl etc.

In the context of the present invention, preference is given to those polymers P1 and copolymers P1 in which the variables R ¹ and R ^{2 of} the functional groups of the formula -O-NR ¹ R ^{2 are} hydrogen.

If the functional groups have the formula -O-N =CR ^a R ^b , R ^a and R ^{b are} preferably methyl or ethyl or together with the carbon atom to which they are attached form a cyclopentylidene or cyclohexylidene ring. The polymers P1 and the copolymers P1 'are of ethylenically unsaturated

Monomers built. Accordingly, they have a built-up of carbon atoms polymer backbone, hereinafter also referred to as carbon backbone. The functional groups of the formula -O-NR ¹ R ² may be bonded to the carbon backbone directly or via a linker A. Where A stands

preferably a bivalent radical of the formula X- [O-alk] _n , in which

X represents a chemical bond or is a bivalent radical which is bonded to a carbon atom of the polymer backbone and which is selected from phenylene, phenylene-CH ₂ -, C (O), CH ₂ , 0-C ₂ -C ₂ -alkanediyl and

C (O) -NR ^c - (C ₂ -Cio-alkanediyl), wherein R ^{c is} hydrogen, Ci-C ₄ alkyl or

- (C ₂ -C ₂ -alkanediyl) -O-NR ¹ R ² , where R ^{c is} in particular hydrogen; n is a number from 0 to 20, where n is other than 0, when X is C (O) and n is in particular 0;

Alk is C ₂ -C ₄ alkanediyl and in particular CH ₂ CH ₂ (= ethane-1, 2-diyl). Preferably, n is other than 0 when X is a chemical bond.

In a first embodiment, X is a chemical bond or CH ₂ and n is an integer from 1 to 20, especially 1 to 10, where n can also be 0 when X is CH ₂ . In a second embodiment, X is phenylene and n is 0 or an integer from 1 to 20, in particular 1 to 10 and in particular 0. In a third embodiment, X is phenylene-Ch - and n is 0 or a whole Number from 1 to 20, in particular 1 to 10 and in particular for 0.

In a fourth embodiment, X is C (O) and n is an integer from 1 to 20, in particular 1 to 10 and especially for 1.

In a fifth embodiment, X is C (O) -NR ^C - ( ^C 2 -C 10 -alkanediyl), where R ^{c has} the abovementioned meanings and in particular denotes hydrogen, and n is 0 or an integer from 1 to 20, in particular 1 to 10 and in particular for O.

In a sixth embodiment, X is C 2 -C 12 -alkanediyl or O-C 2 -C 12 -alkanediyl and n is 0 or 1.

In a specific embodiment, X is phenylene-Ch - and n is 0.

The content of functional groups of the formula -O-NR ¹ R ² can be varied over wide ranges and in principle allows adaptation of the polymer P1 or of the copolymer P1 'to the desired degree of crosslinking. In general, the polymers P1 and the copolymers P1 'have on average (number average) more than 2, preferably at least 2.5 and in particular at least 3 groups of the formula -O-NR ¹ R ² . The upper limit of the number of functional groups of the formula -O-NR ¹ R ² is limited only by the molecular weight of the polymers P1 or the copolymers P1 'and may be, for example, up to 1000 or more. Preferably, the polymers P1 and the copolymers P1 '0.05 to 6 mol / kg, in particular 0.1 to 3 mol / kg of functional groups of the formula -O-NR ¹ R ² .

The number-average molecular weight M _{n of} the polymers P1 and the copolymers P1 'will generally be at least 500 g / mol, in particular at least 750 g / mol and especially at least 1000 g / mol. Frequently, the number average molecular weight will not exceed 10 ⁶ g / mol, in particular 5 × 10 ⁵ g / mol and especially 2 × 10 ⁵ g / mol. The weight-average molecular weight M _{w of} the polymers P1 and the copolymer P1 'is typically in the range from 550 to 5 × 10 ⁶ g / mol, frequently in the range from 900 to 2 × 10 ⁶ g / mol and in particular in the range from 1200 to 10 ⁶ g / mol. The ratio of weight average molecular weight to number average molecular weight M _w / M _n is typically in the range of 1 to 1 to 10, and more preferably in the range of 1 to 2 to 5.

The molecular weight values reported here are as determined by size exclusion chromatography using defined polystyrene standards. For details reference is made to the details of the examples.

The glass transition temperature T _{g of} the polymer P1 is of minor importance and is usually in the range of -60 ° C to 150 ° C, especially in the range of -50 ° C to 150 ° C and especially in the range of -40 ° C to 120 ° C. Under the

Glass transition temperature is understood as the so-called midpoint temperature according to ASTM 3418/82, as can be determined by differential scanning calorimetry (DSC). The glass transition temperature of a polymer can also be determined by dynamic mechanical analysis (DMTA) as described in connection with the examples

Method to be determined. The glass transition temperature can be adjusted by suitable choice of the monomers B1 and B2.

The polymers P1 as well as the copolymers P1 'are composed of ethylenically unsaturated monomers. Accordingly, they have on average more than 2

Repeat units MA, which are derived from a monoethylenically unsaturated monomer A, which carries a functional group of the formula -O-NR ¹ R ² . The polymers P1 may be homopolymers or copolymers. Preferably, the monoethylenically unsaturated monomer A has the formula I:

wherein

R ¹ , R ^{2 have} the meanings given above and in particular for

Stand for hydrogen;

R ^{3 is} hydrogen or methyl, and

A is a group of the formula X- [O-Alk] _n , where X, Alk and n are the above

meanings mentioned and in particular those as preferred or in

Having context with the embodiments 1 to 6 mentioned meanings. Examples of monomers of the formula (I) are those indicated below

Monomer types 1) to 6):

1) monomers of the formula I in which X is a chemical bond or Ch and n is an integer from 1 to 20, in particular 1 to 10, where n can also be 0 when X is Ch. Alk is in particular ethane-1, 2-diyl.

In particular, A is O-CH ₂ CH ₂ or CH ₂ -OCH ₂ CH ₂ .

2) monomers of the formula I in which X is phenylene and n is 0 or an integer from 1 to 20, in particular 1 to 10 and especially 0. Alk, if present, especially for ethane-1, 2-diyl.

3) monomers of the formula I in which X is phenylene-Ch - and n is 0 or an integer from 1 to 20, in particular 1 to 10, and n is in particular 0. Alk, if present, especially for ethane-1, 2-diyl.

4) monomers of the formula I in which X is C (O) and n is an integer from 1 to 20, in particular 1 to 10 and n is in particular 1. Alk, if present, in particular for ethane-1, 2-diyl, 1, 2-propanediyl, 2-methyl-1, 2-propanediyl or 1, 2, 2,3 or 1, 4-butanediyl.

5) monomers of the formula I in which X is C (O) -NR ^C - ( ^C 2 -C 10 -alkanediyl), where R ^{c has} the abovementioned meanings and in particular denotes hydrogen, and n is 0 or an integer from 1 to 20, in particular 1 to 10 and in particular stands for 0. Alk, if present, is especially for

Ethane-1,2-diyl.

6) monomers of the formula I, wherein X is Ci-Ci2-alkanediyl, in particular CH2, or 0-C ₂ -Ci2-alkanediyl, in particular 0-C ₂ -C ₄ -alkanediyl, such as 0- (1, 2-ethanediyl ), O- (1, 2-propanediyl), O- (2-methyl-1,2-propanediyl) or O- (1,2,3,3 or 1,4 butanediyl), and n is 0 or 1 stands. Alk, if present, is especially for ethane-1, 2-diyl

Among the monomer types 1 to 6, preference is given to those monomers of the formula (I) in which the groups of the formula -O-NR ¹ R ^{2 are} -O-NH ² , ie R ¹ and R ^{2 are} hydrogen.

In preferred embodiments of the invention, polymers P1 and copolymers P1 'and those polymers are selected in which the repeating units MA derived from the monomers A are derived from the monomer type 3). In specific embodiments, the monomers A are selected from the monomers of the formula I in which R ¹ , R ² and R ^{3 are} hydrogen and A is phenylene-Ch.

In further preferred embodiments of the invention, polymers P1 and copolymers P1 'and those polymers are selected in which those of the monomers A derived repeat units MA of the monomer type 1) are derived. In specific embodiments, the monomers A are selected from the monomers of the formula I in which R ¹ , R ² and R ^{3 are} hydrogen and A is O-CH 2 CH 2 or CH 2 -OCH 2 CH 2.

Among the polymers P, preference is given to copolymers which, in addition to the repeat units MA, have one or more further repeat units MB which are derived from monoethylenically unsaturated monomers B which have no functional group of the formula -O-NR ¹ R ² . Also preferred are polymers which in addition to the repeat units MA repeating units MB ', which are derived from vinyl alcohol, and optionally repeating units MB. In principle, all monomers B are suitable as comonomers which have an ethylenically unsaturated group. The monomers B may be neutral, basic, acidic, nonionic, anionic or cationic.

In the preferred polymers P1, in particular the copolymers P1 ', the molar ratio of repeat units MA to repeat units MB is generally in the range from 1: 100 to 10: 1, in particular in the range from 1:80 to 2: 1 and especially in the range from 1: 75 to 1: 1.

In the polymers P1 and copolymers P1 ', the proportion of repeating units MA, based on the total weight of the repeating units constituting the polymer P1 or the copolymer P1', is generally at least 5% by weight, preferably at least 10% by weight and in particular at least 15% by weight. Accordingly, the proportion of repeating units MA in the polymers P1 is generally in the range of 10 to 100 wt .-% or 5 to 90 wt .-%, in particular in the range of 10 to 100 wt .-% or in the range of 10 bis 80 wt .-%, especially in the range of 15 to 100 wt .-% or in the range of 15 to 50 wt .-%, each based on the total amount of the polymer P1 constituent

Repeating units. The proportion of repeating units MB or ΜΒΜΒ, if present, is generally in the range from 10 to 95% by weight, in particular in the range from 20 to 90% by weight or in the range from 50 to 85% by weight. , in each case based on the total amount of repeating units constituting the polymer P1. In the polymers P1 and copolymers P1 ', the proportion of the monomers A, based on the total amount of the monomers constituting the polymer P1 or the copolymer P1', is generally at least 5% by weight, preferably at least 10% by weight and in particular at least 15% by weight. Accordingly, the proportion of the monomers A in the polymers P1 is generally in the range from 10 to 100% by weight. or 5 to 90 wt .-%, in particular in the range of 10 to 100 wt .-% or in the range of 10 to 80 wt .-%, especially in the range of 15 to 100 wt .-% or in the range of 15 to 50 % By weight, based in each case on the total amount of monomers A and B constituting the polymer P1. The proportion of monomers B, if present, is generally in the range from 10 to 95% by weight, in particular in the range from 20 to 90% by weight or in the range from 50 to 85% by weight, in each case based on the total amount of the monomers P1 and B constituting the polymer P1.

In the copolymers P1 'the proportion of the monomers A is generally in the range of 5 to 90 wt .-%, in particular in the range of 10 to 80 wt .-% and especially in

Range from 15 to 50% by weight and the proportion of monomers B in the range from 10 to 95% by weight, in particular in the range from 20 to 90% by weight or in the range from 50 to 85% by weight, in each case based on the total amount of monomers A and B constituting the copolymer P1.

In preferred embodiments, the repeating units MB or MB 'of the polymers P1 comprise one or more repeat units which comprise monomers B1 having a water solubility of at least 50 g / l, in particular at least 100 g / l at 20 ° C. and 1 bar, or derived from vinyl alcohol.

Accordingly, in preferred embodiments, comonomers B of the polymers P1 comprise one or more monomers B1 which have a water solubility of at least 50 g / l, in particular at least 100 g / l at 20 ° C. and 1 bar.

Examples of monomers B1 are the following monomer classes B1 -a to B1 -j:

B1-a: monoethylenically unsaturated Cs-Cs monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid or vinylacetic acid, and salts thereof, in particular their alkali metal salts and ammonium salts;

B1 -b: monoethylenically unsaturated C4-C8 dicarboxylic acids, such as fumaric acid,

Itaconic acid, citraconic acid or maleic acid, and their salts, in particular their alkali metal salts and ammonium salts;

B1 -c: monoethylenically unsaturated sulfonic acids, such as vinylsulfonic acid,

Allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acids and 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid and derivatives thereof, such as styrene-4-sulfonic acid and styrene 3-sulfonic acid, and the salts, especially the alkaline earth or alkali metal salts of the aforementioned acids, such as sodium styrene-3-sulfonate and sodium styrene-4-sulfonate; B1 -d monoethylenically unsaturated phosphonic acids and phosphoric acids, such as vinylphosphonic acid, allylphosphonic acid, phosphonoethyl acrylate,

Phosphonoethyl methacrylate, phosphonopropyl acrylate,

Phosphonopropyl methacrylate, and 2-acrylamido-2-methyl-propanephosphonic acid, and the salts, in particular the alkaline earth or alkali metal salts of the abovementioned acids;

B1 -e amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids, such as

Acrylamide or methacrylamide;

B1 -f: hydroxy-C2-C4-alkyl esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids, in particular the hydroxy-C2-C4-alkyl esters of

Acrylic acid and methacrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate,

3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate or

4-hydroxybutyl methacrylate;

Poly-C2-C4-alkylene oxide esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids, in particular the esters of acrylic acid or the

Methacrylic acid, for example monomers of the following formula A '

wherein

k is an integer from 4 to 40, R ^{a is} hydrogen or C 1 -C 4 -alkyl and R ^{b is} hydrogen or methyl.

B1 -h-di-C 1 -C 4 -alkylamino-C 2 -C 4 -alkyl esters of monoethylenically unsaturated C 3 -C 8 -monocarboxylic acids, in particular the dimethylamino-C 2 -C 4 -alkyl esters and the diethylamino-C 2 -C 4 -alkyl esters, especially of acrylic acid or of

Methacrylic acid such as 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) propyl acrylate, 2- (diethylamino) propyl methacrylate, 3- (dimethylamino) propyl acrylate, 3- (diethylamino) propyl methacrylate and their acid addition salts;

in particular their hydrochlorides, hydrobromides and hydrosulfates;

B1 -i: N-vinyllactams, such as N-vinylpyrrolidone or N-vinylcaprolactam

B1 -j: Olefinically unsaturated nitriles such as acrylonitrile or methacrylonitrile. Among the monomers B1 -a to B1-h are the monomers B1 -a, B1-c, B1 -d, B1 -e, B1 -f and B1 -g and especially the monomers B1 -a, B1 -e and B1 - f is preferred. In addition to or instead of the abovementioned repeating units, used by the

Monomers B1 or vinyl alcohol are derived, the repeating units MB can also include such repeating units derived from monomers B2, which have only a low solubility in water, which typically does not exceed 40 g / L and in particular 30 g / L at 20 ° C. ,

Which includes:

B2-a: esters and diesters of monoethylenically unsaturated Cs-Cs-mono- and C4-C8-dicarboxylic acids with C 1 -C 30 -alkanols, in particular with C 1 -C 10 -alkanols,

B2-b: esters of vinyl or allyl alcohol with C 1 -C 8 -monocarboxylic acids,

B2-c: vinyl aromatics,

B2-d: amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids with C 1 -C 30 -alkylamines or C 1 -C 30 -alkylamines, in particular with C 1 -C 10 -alkylamines or C 1 -C -alkylamines, and mixtures thereof;

B2-e: vinyl halides and chloroprene;

B2-f: olefins and conjugated diolefins. Suitable esters and diesters of monoethylenically unsaturated Cs-Cs-mono- and C4-C8-dicarboxylic acids with C 1 -C 30 -alkanols, in particular with C 1 -C 10 -alkanols, are, above all, the esters of monoethylenically unsaturated C 3 -C 5 -monocarboxylic acids,

in particular the esters of acrylic acid and the esters of methacrylic acid with C 1 -C 8 -alkanols, in particular with C 1 -C 10 -alkanols, such as methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl ethacrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 1,1,3,3-tetramethylbutyl (meth) acrylate, ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-undecyl ( meth) acrylate,

Tridecyl (meth) acrylate, myristyl (meth) acrylate, pentadecyl (meth) acrylate,

Palmityl (meth) acrylate, heptadecyl (meth) acrylate, nonadecyl (meth) acrylate,

Arachinyl (meth) acrylate, behenyl (meth) acrylate, lignoceryl (meth) acrylate,

Cerotinyl (meth) acrylate, melissinyl (meth) acrylate, palmitoleinyl (meth) acrylate,

Oleyl (meth) acrylate, linolyl (meth) acrylate, linolenyl (meth) acrylate, stearyl (meth) acrylate and lauryl (meth) acrylate, but also the diesters of monoethylenically unsaturated C4-C8 dicarboxylic acids, especially the diesters of maleic acid with ci C 5 -alkanols such as dimethyl maleate, diethyl maleate, di- (n-propyl) maleate, diisopropyl maleate, di (n-butyl) maleate, di (n-hexyl) maleate, di (1, 1, 3, 3) tetramethylbutyl) maleate, di (n-nonyl) maleate, ditridecyl maleate, dimyristyl maleate, dipentadecyl maleate, dipalmityl maleate, Diarachinyl maleate and mixtures thereof. The term "(meth) acrylate" encompasses both the corresponding ester of acrylic acid and the corresponding esters of methacrylic acid. Suitable esters of vinyl alcohol and allyl alcohol with Ci-C3o monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl versatate, allyl formate, allyl acetate, allyl propionate, allyl butyrate, allyl laurate and mixtures thereof. Suitable vinyl aromatics are styrene, 2-methylstyrene, 4-methylstyrene, 2- (n-butyl) styrene, 4- (n-butyl) styrene, 4- (n-decyl) styrene, in particular styrene.

Suitable amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids with C 1 -C 30 -alkylamines or C 1 -C 30 -alkylamines, in particular with C 1 -C 10 -alkylamines or C 1 -C -alkylamines, are, above all, the amides of acrylic acid and of methacrylic acid with Ci-C3o-alkylamines or di-Ci-C3o-alkylamines, in particular with C1-C10-alkylamines or di-Ci-Cio-alkylamines, such as. N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl) (meth) acrylamide, N-ethylhexyl (meth) acrylamide,

N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide,

N- (n-undecyl) (meth) acrylamide, N-tridecyl (meth) acrylamide, N-myristyl (meth) acrylamide, N-pentadecyl (meth) acrylamide, N-palmityl (meth) acrylamide,

N-heptadecyl (meth) acrylamide, N-nonadecyl (meth) acrylamide,

N-arachinyl (meth) acrylamide, N-behenyl (meth) acrylamide, N-lignoceryl (meth) acrylamide, N-cerotinyl (meth) acrylamide, N-melissinyl (meth) acrylamide,

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

"(meth) acrylamide" includes both the corresponding amide of acrylic acid and the corresponding amide of methacrylic acid.

Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.

Suitable olefins and conjugated diolefins are ethene, propene, 1-butene, isobutene, 1-hexene, butadiene and isoprene. Preferably, B2 is selected from the monomers B2-a, B2-b and B2-c, especially among the esters of monoethylenically unsaturated C3-C8 monocarboxylic acids, in particular the esters of acrylic acid (acrylates) and the esters of methacrylic acid (methacrylates), with Ci -Cio-alkanols and vinylaromatics, more preferably from C 1 -C 10 -alkyl acrylates and C 1 -C 10 -alkyl methacrylates and vinylaromatics, and especially from methyl acrylate, ethyl acrylate, n-propyl acrylate,

Isopropyl acrylate, n-butyl acrylate, tert-butyl acrylate, 2-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate and styrene.

Preferably, the monomers B comprise at least one monomer B1 or a combination of at least one monomer B1 with at least one monomer B2. Preferably, the molar fraction of the monomers B1, based on the total number of monomers B, is at least 10 mol% and in particular at least 20 mol%, and is in particular in the range from 10 to 100 mol% and especially in the range from 20 to 100 mol%, based on the total amount of monomers B.

Accordingly, in this embodiment, the proportion of the monomers B2

80 mol% and in particular 90 mol%, based on the total amount of the monomers B does not exceed.

Preferred among the polymers P1 and the copolymers P1 'are those which are soluble or at least dispersible in water. In particular, among the polymers P1 and the copolymers P1 'are those polymers which are soluble in water at least at pH> 10 and 20 ° C and especially those which are already at pH 8 and 20 ° C or pH <8 and 20 ° C are soluble. Such polymers P1 and

Copolymers P1 'usually contain at least 10 wt .-%, in particular at least 20 wt .-% and especially at least 30 wt .-%, based on the

Total amount of the polymer P1 or the copolymer P1 'constituent

Monomers A and B, at least one monomer B1 polymerized in particular among the monomers B1 -a, B1 -c, B1 -d, B1e, B1 -f and Bi g is selected.

In particular, polymers P1 and copolymers P1 'are preferred which

5 to 90 wt .-%, in particular 10 to 80 wt .-% and especially 15 to

50% by weight of at least one monomer A, in particular a monomer of the formula I and especially of a type 3 monomer; and

- 10 to 95 wt .-%, in particular 20 to 90 wt .-% and especially 30 to 85

Wt .-% of at least one monomer B1, in particular among the

Monomers B1 -a, B1 -c, B1 -d, B1e, B1 -f and Bi g is selected; 0 to 85% by weight, or 5 to 85% by weight, in particular 0 to 70% by weight or 5 to 70% by weight and especially 0 to 55% by weight or 5 to 55% by weight one or more monomers B2, which is selected in particular from the monomers B2-a and B2-c;

contained in copolymerized form, all stated in wt .-% on the total amount of the polymer P1 or the copolymer PV constituent monomers A and B are based.

Also preferred are polymers P1 and copolymers PV

- 5 to 90 wt .-%, in particular 10 to 80 wt .-% and especially 15 to

50 wt .-% of at least one monomer A, in particular a monomer of

Formula I and especially a type 1 monomer;

- 10 to 95 wt .-%, in particular 20 to 90 wt .-% and especially 30 to 85

% By weight of repeating units derived from vinyl alcohol;

0 to 85% by weight, or 5 to 85% by weight, in particular 0 to 70% by weight or 5 to 70% by weight and especially 0 to 55% by weight or 5 to 55% by weight % of one or more monomers B1, in particular among the monomers B1 -a, B1-c,

B1 -d, B1 -e, B1-f and Bi g is selected;

0 to 85% by weight, or 5 to 85% by weight, in particular 0 to 70% by weight or 5 to 70% by weight and especially 0 to 55% by weight or 5 to 55% by weight one or more monomers B2, which is selected in particular from the monomers B2-a and B2-b;

polymerized, all stated in wt .-% on the total amount of the polymer P1 or the copolymer P1 'constituent monomers A and B are related.

The polymers P1 and the copolymer P1 'are usually uncrosslinked, d. H. they contain substantially no copolymerized monomers which have two or more non-conjugated double bonds. In particular, the proportion is

Monomers having two or more non-conjugated double bonds at less than 0.1 wt .-%, in particular less than 0.05 wt .-% or less than 0.01 wt .-%, based on the total amount of the Polymer P1 or the copolymer P1 'constituting monomers A and B. The preparation of the polymers P1 and the copolymers P1' can be carried out in analogy to known methods of polymer synthesis.

In general, the polymers P1 and the copolymers P1 'are prepared by free-radically initiated polymerization of monomers A or by copolymerization of the monomers A with the monomers B produce. Both classical methods of free radical initiated polymerization and methods of controlled radical polymerization, such as RAFT, SFRP or ATRP can be used. The polymerization of the monomers A or the copolymerization of the monomers A with the monomers B can both as a solution or precipitation, as

Emulsion polymerization or be carried out as a polymerization in bulk.

The preparation of the polymers P1 and the copolymers PV can also be carried out by polymer-analogous reaction. For example, it is possible to use polymers which have a plurality of nucleophilically displaceable groups, for example halogen atoms bound to aliphatic carbon atoms or sulfate or sulfonate groups bonded to aliphatic carbon atoms, eg. As tosylate or mesylate groups, for example a

Chlormethylgruppe, with hydroxylamine or an oxime of the hydroxylamine of the formula HO-N = CR ^a R ^b , wherein R ^a and R ^{b have} the meanings mentioned above, implement. The reaction is preferably carried out in the presence of a base, for. An alkali metal hydroxide or carbonate such as lithium hydroxide, sodium hydroxide,

Potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate or

Cesium carbonate. In addition, polymers containing hydroxyl groups bonded to aliphatic C atoms can be prepared by reaction with chloramine in the presence of a strong base, for example in the presence of an alkali metal hydride, such as

Sodium, potassium or lithium hydride, into the corresponding H2N-0-functionalized polymer. Monomers of the formula I are known or can be prepared in analogy to methods known from the prior art, for. B. by conversion of haloalkyl groups in aminoxy groups or by conversion of hydroxyl groups into aminoxy be prepared - see, for. Wen-Jing Zhou et al., Macromolecules, 30 (1997) 30, 7063; W. Traube et al., Chem. Ber. 1920, 1477-1492; DE 3631071 or DE 3501616.

According to a preferred embodiment of the invention, the preparation of the polymers P1 or the copolymers P1 'is carried out by free-radically initiated homo- or copolymerization of the at least one monomer A with optionally the monomer (s) B, preferably in an aqueous reaction medium. The free-radically initiated homopolymerization or copolymerization of the at least one monomer A with the monomer (s) B can be carried out analogously to known processes and is preferably carried out by the solution polymerization method or method

Emulsion polymerization. The free-radical initiated polymerization is typically carried out in the presence of a polymerization initiator or a polymerization initiator system. Suitable radical polymerization initiators are, in particular, initiators and initiator systems which form free radicals on their decomposition. These include in particular:

Peroxo compounds, for example alkali metal or ammonium peroxidisulfates, diacetyl peroxide, dibenzoyl peroxide, succinyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl perpivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl permalate, cumene hydroperoxide, diisopropyl peroxydicarbamate, tert Butyl perisobutyrate, tert-butyl peracetate, di-tert-amyl peroxide, tert-butyl hydroperoxide,

Azo compounds such as 2,2'-azo-bis-isobutyronitrile, azo-bis (2-amidinopropane) dihydrochloride, azobis (2,4-dimethylvaleronitrile) or 2,2'-azobis (2-methylbutyronitrile) ;

Initiator mixtures or redox initiator systems, such. B.

Ascorbic acid / ferrous sulfate sodium peroxodisulfate,

tert-butyl hydroperoxide / sodium disulfite,

tert-butyl hydroperoxide / sodium hydroxymethanesulfinate,

The amount of polymerization initiator used to prepare the polymer P1 or the copolymer PV is typically in the range of 0.2 to 5 wt .-%, in particular in the range of 0.3 to 3 wt .-%, based on the total amount of monomers to be polymerized. If necessary, it is advantageous to

Polymerization during the polymerization over a longer period, for example, in parallel with the addition of the monomers A and B, admit. The addition can then take place at a continuous feed rate or increasing or decreasing feed rate.

In one embodiment of the invention, the preparation of the polymer P1 or of the copolymer PV takes place in the presence of at least one regulator. As a result, molecular weight of the polymer P1 or of the copolymer PV is controlled. As regulators, especially compounds with a thiol group are suitable, such as tert-butylmercaptan,

Mercaptoethanol, mercaptopropanol, mercaptobutanol, thioglycolic acid, thioglycollic acid alkyl esters such as thioglycolic acid ethyl ester, butyl thioglycolate or 2-ethylhexyl thioglycolate, mercaptopropionic acid,

Mercaptopropionsäurealkylester and tert-Dodecylmercaptan. As regulators alkali metal phosphonates and hypophosphites are also suitable. As regulators also act organic solvents, at least one of an aliphatic carbon atom

having bound OH group, such as Ci-C4-alkanols, z. Ethanol, Isopropanol, 2-butanol or part. Butanol. The amount of mercapto group regulator used to prepare the polymer P1 or the copolymer PV is preferably in the range from 0.5 to 20% by weight, in particular in the range from 1 to 15% by weight, based on the total amount of monomers to be polymerized.

Organic solvents with OH groups can also be used in larger amounts, since they have only a weakly regulating action.

The homopolymerization of the monomers A or the copolymerization of the monomers A and B can be carried out as a batch process and is preferably carried out as a monomer feed, d. H. the major amount, preferably at least 80% and especially at least 90% of the monomers A and B to be polymerized in the course of polymerization under polymerization in the

Added polymerization. The addition can be continuous or stepwise. In the course of the polymerization, the monomer composition can be changed once, repeatedly or continuously (gradient procedure).

Preferably, the copolymerization of the monomers A and B takes place in an alcoholic or aqueous reaction medium. An aqueous reaction medium is understood as meaning water or a mixture of water and one or more water-miscible organic solvents, water forming the main constituent of the reaction medium. Water-miscible organic solvents are, for example, C 1 -C 4 -alkanols, eg. As methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-butanol or tert. Butanol, glycols such as ethylene glycol, diethylene glycol. Preferably, aqueous reaction media contain at least 60% by weight of water, based on the total amount of water and organic solvents. By an alcoholic reaction medium is meant

Reaction medium consisting mainly of one or more alcoholic

Solvents, in particular one or more of the aforementioned Ci-C4 alkanols and may still contain water, wherein the alcoholic solvent forms the main component of the reaction medium.

Optionally, the homopolymerization of the monomers A or the

Copolymerization of the monomers A and B in the presence of one or more surfactants perform, especially when the

Polymerization is carried out as aqueous emulsion polymerization. These include, in particular, ionic and nonionic emulsifiers and ionic and nonionic protective colloids or stabilizers. In contrast to protective colloids, emulsifiers are understood as meaning surface-active substances whose molecular weight (number average) is usually below 2000 g / mol and especially below 1500 g / mol. at In turn, protective colloids are usually water-soluble polymers having a number average molecular weight above 2000 g / mol, eg. B. in the range of 2000 to 100000 g / mol and in particular in the range of 5000 to 50,000 g / mol. Of course, protective colloids and emulsifiers can be used in the mixture.

Especially suitable are anionic emulsifiers. These include usually aliphatic, araliphatic and aromatic sulfonic acids having generally at least 6 carbon atoms and their salts, in particular their ammonium and

Alkali metal salts, sulfuric acid semi-esters ethoxylated alkanols and alkylphenols and salts thereof, in particular their ammonium and alkali metal salts and alkyl, aralkyl and aryl phosphates including phosphoric monoesters of

Alkanols and alkylphenols, and their salts, in particular their ammonium and alkali metal salts. Examples of suitable anionic emulsifiers are: alkali metal and ammonium salts of dialkyl esters of sulfosuccinic acid, alkali metal and ammonium salts of alkyl sulfates (alkyl group: Cs to Cie), alkali metal and

Ammonium salts of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: Cs to Cie), alkali metal and ammonium salts of

Sulfuric acid semi-esters of ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ - to Ci6), alkali metal and ammonium salts of alkylsulfonic (alkyl: Cs to Cie) and of alkylarylsulfonic (alkyl: C ₄ - to Cis). Examples of suitable anionic emulsifiers are also the compounds of the general formula given below

wherein R ¹ and R ² is hydrogen or C ₄ - to C ₄ represent alkyl and are not simultaneously hydrogen, and X and Y can be alkali metal ions and / or ammonium ions. Preferably, R ¹ and R ^{2 are} hydrogen or linear or branched alkyl radicals having 6 to 18 C atoms and in particular having 6, 12 and 16 C atoms, wherein R ¹ and R ^{2 are} not both simultaneously hydrogen. X and Y are preferably sodium, potassium or ammonium ions, with sodium being particularly preferred. Particularly advantageous are compounds in which X and Y are sodium, R ^{1 is} a branched alkyl radical having 12 C atoms and R ^{2 is} hydrogen or one of those indicated for R ¹ , of Hydrogen has different meanings. Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ^® 2A1 (trademark of Dow Chemical Company). Also suitable are nonionic emulsifiers. These include typically ethoxylated alkanols having 8 to 36 carbon atoms in the alkyl radical, ethoxylated mono-, di- and trialkylphenols having typically 4 to 12 carbon atoms in the alkyl radicals, wherein the ethoxylated alkanols and alkylphenols typically have a degree of ethoxylation in the range of 3 to 50 exhibit.

Further suitable emulsifiers can be found, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pages 192 to 208. Polymerization temperature and polymerization pressure are of secondary importance

Importance. The emulsion polymerization is typically carried out at temperatures in the range of 30 to 130, preferably in the range of 50 to 100 ° C. Of the

Polymerization pressure is usually in the range of atmospheric pressure, d. H. at ambient pressure, but may also be slightly above or below, z. B. in the range of 800 to 1500 mbar.

For further details on the polymerization conditions, reference is made to the examples. The polymers P1 and the copolymers P1 'are typically obtained in the polymerization in the form of a solution or dispersion, which, optionally after replacement of organic solvents by water, directly in the aqueous according to the invention

Compositions can be used. Of course, it is also possible, the polymers P1 and the copolymers P1 'separate from the reaction medium and optionally purified. However, preference is given to obtaining the polymers P1 or the copolymers P1 'in the form of aqueous compositions which can then be incorporated directly into the aqueous composition according to the invention. The compositions of the invention also contain a polymer P2 having functional groups F which can react with the groups of the formula -O-NR ¹ R ² to form a covalent bond. The functional groups F include, in particular, aldehyde groups, keto groups, eg. B. groups of the formula C (0) -Ci-C ₄ alkyl or C (0) CH ₂ C (0) -Ci-C ₄ alkyl, oxirane groups and cyclic carbonate groups, in particular 1, 3-dioxolane-3 -one groups.

The number of functional groups can be varied over wide ranges and is preferably in the range of 0.01 to 2 mol / kg, in particular in the range of 0.05 to 1 mol / kg and especially in the range of 0, 1 to 0.5 mol / kg of polymer P2.

The polymers P2 can in principle be selected from any polymer groups and in principle include all polymers which are in the form of aqueous

Compositions are used, for. As polyurethanes, polyether urethanes, polyethers, polyesters, polyester urethanes, polyether esters and in particular polymers which are composed of ethylenically unsaturated monomers M.

The functional groups F can be bound directly, that is via a chemical bond, the polymer backbone or via a bivalent linker L, z. B. a radical of the formula Y- [Alk'0] _p -Z. Here, Y, Z, Alk 'and p have the following

Meanings: is a bivalent radical, which is bound to a carbon atom of the polymer backbone and is selected from Q, QO, Q-NR ^d, C (0) 0, C (0) NR ^d, wherein R ^d is hydrogen or Ci-C ₄ alkyl and in particular hydrogen and Q is a chemical bond, Ci-C ₄ alkanediyl or phenylene and wherein Y is in particular C (0) 0 or C (0) -NR ^d ;

represents a chemical bond or Ci-Ci2-alkanediyl, which may optionally be substituted by 1 or 2 OH groups,

represents a number from 0 to 20, in particular 0 or 1;

represents _{C2-C4-alkanediyl} and especially CH2CH2. Particular preference is given to polymers P2 which are composed of ethylenically unsaturated

Monomers M are constructed, in particular those in which the monomers P1 constituting the polymer P1 comprise the following monomers M1 and M2:

50 to 99.9 wt .-%, in particular 70 to 99.5 wt .-% and especially 80 to 99 wt .-%, based on the total mass of the polymer P1 forming

Monomers, at least one monoethylenically unsaturated monomer M1, which has no functional groups F and which has a water solubility of less than 50 g / l, at 20 ° C and 1 bar;

0, 1 to 50 wt .-%, in particular 0.5 to 30 wt .-% and especially 1 to

20 wt .-%, based on the total mass of the polymer P2 forming Monomers, at least one monoethylenically unsaturated monomer M2 having at least one functional group F.

Suitable monomers M1 are in principle all monomers which are suitable as

Monomers B2 in connection with the polymers P1 and the copolymers P1 'were called.

Preferably, M1 is selected from the monomers B2-a, B2-b and B2-c, especially among the esters of monoethylenically unsaturated C3-C8 monocarboxylic acids, in particular the esters of acrylic acid (acrylates) and the esters of methacrylic acid (methacrylates), with Ci -Cio-alkanols and vinylaromatics, more preferably from C 1 -C 10 -alkyl acrylates and C 1 -C 10 -alkyl methacrylates and vinylaromatics, and especially from methyl acrylate, ethyl acrylate, n-propyl acrylate,

Suitable monomers M2 are compounds of the formula (II):

R ^{4 is} hydrogen or methyl;

L is a radical of the formula Y- [Alk'0] _p -Z, in which Y, Z, Alk 'and p have the abovementioned meanings and in which L is in particular C (O) O-Z, C (O) O -Alk'0-Z, C (0) -NR ^d -Alk'0-Z or C (0) -NR ^d -Z, wherein Z is a chemical bond or Ci-Ci2-alkanediyl, which is optionally substituted by 1 or 2 OH groups may be substituted;

F is a functional group which can react with the groups of the formula -O-NR ¹ R ² to form a covalent bond and which preferably represents an aldehyde group, a keto group, for. B. a group of the formula

C (O) -Ci-C ₄ -alkyl or a group of the formula C (0) -CH ₂ -C (O) -Ci-C ₄ -alkyl, an oxirane group or a cyclic carbonate group, in particular a 1, 3 - dioxolan-3-one group stands.

Examples of monomers of the formula (II) are

11-1 Aldehydgruppen carrying monomers such as acrolein, methacrolein, formylstyrene (vinylbenzaldehyde), esters of acrylic acid with hydroxyaldehydes and the corresponding esters of methacrylic acid, for example

Acryloxyalkylpropanals and Methacryloxyalkylpropanale as z. As described in DE 2722097;

Keto-containing monomers such as vinyl alkyl ketones and allyl alkyl ketones wherein the alkyl radicals each have 1 to 20 carbon atoms, acetylstyrene

(Vinylacetophenone), esters of acrylic acid with hydroxy ketones and the corresponding esters of methacrylic acid, eg. B. 1, 1-dimethyl-3-oxobutyl acrylate and 1, 1-dimethyl-3-oxobutyl methacrylate, amides of acrylic acid with

Aminoketonen and the corresponding amides of methacrylic acid, as z. B. in DE 2207209, z. N- (1,1-dimethyl-3-oxobutyl) acrylamide (= diacetone acrylamide) or N- (1,1-dimethyl-3-oxobutyl) methacrylamide, esters of hydroxy-C 2 -C 4 -alkyl acrylates or hydroxy-C 2 -C 4 -alkyl acrylates. C4-alkyl methacrylates with ß-keto acids of the formula

HOC (0) -CH ₂ -C (O) -Ci-C ₄ -alkyl, e.g. Acetoacetoxyethyl acrylate and

acetoacetoxyethyl;

Monomers having an oxirane group, e.g. B. glycidyl allyl ether,

Glycidyl methallyl ether, glycidyl acrylate and glycidyl methacrylate;

Monomers having a cyclic carbonate group, in particular a 1, 3-dioxolan-3-one group, for. B. glycerol carbonate acrylate (= (2-oxo-1, 3-dioxolan-4-yl) methyl-prop-2-enoate) or glycerol carbonate methacrylate (= (2-oxo-1, 3-dioxolan-4-yl) methyl-2 -methylprop-2-enoate).

Preference is given to the monomers of groups II-2, 11-3 and II-4, in particular of group II-2.

In addition to the monomers M1 and M2, the monomers M constituting the polymer P1 may comprise one or more further, different ethylenically unsaturated monomers M3, which have no functional group F and which are different from the monomers M1 and M2. The total amount of the monomers of other monomers will usually not exceed 30% by weight, in particular 20% by weight and especially 15% by weight and, if present, is in the range from 0.01 to 40% by weight, in particular in the range of 0.05 to 20 wt .-% and especially in the range of 0.1 to 15 wt .-%, based on the total amount of the monomers M. It is understood that the total amount of monomers M1, M2 and M3 added to 100 wt .-%.

Suitable monomers M3 are monoethylenically unsaturated monomers having an increased water solubility of at least 50 g / l, in particular at least 100 g / l at 20 ° C and 1 bar. These monomers are referred to below as monomers M3a

designated. Suitable monomers M3a are the abovementioned monomers B1. Among the monomers M3a, the monomers B1-a, B1-c, B1 -d, B1-e, B1 -f and Bi g are preferred. The proportion of these monomers M3a is usually 30 wt .-%,

especially 20 wt .-% and especially 10 wt .-%, based on the total amount of the monomers M, not exceed.

Suitable monomers M3 are also polyethylenically unsaturated monomers containing at least 2, z. B. 2, 3, 4 or 5 non-conjugated C = C double bonds. These monomers are referred to below as monomers M3b. The proportion of these monomers M3b will generally not exceed 10 wt .-%, in particular 5 wt .-% and especially 1 wt .-%, based on the total amount of the monomers M. In a preferred embodiment of the invention, the monomers constituting the polymer P2 comprise no or less than 0.1% by weight, based on the total amount of the monomers M, of monomers M3b. The polymers P2 generally have a weight-average molecular weight M _w in the range of about 10,000 to 20,000,000 and in particular in the range of about 50,000 to 10,000,000. The molar mass determination can by

Gel permeation chromatography with a standard, such as polymethyl methacrylate or polystyrene.

The glass transition temperature T _{g of} the polymer P2 depends on the desired use and is usually in the range of -60 ° C to 60 ° C, preferably in the range of -50 ° C to 50 ° C and more preferably in the range of -40 ° C to 40 ° C. The glass transition temperature is understood to be the so-called midpoint temperature according to ASTM 3418/82, as can be determined by differential scanning calorimetry (DSC). The glass transition temperature of a polymer can also be determined by dynamic mechanical analysis (DMTA) according to the method given in connection with the examples. The glass transition temperature can be adjusted by suitable choice of the monomers M1.

The polymers P2 are known, for. B. from the documents cited above

EP 516074, DE 4219384 or DE 4314623 or can be prepared in analogy to known polymerization, for. B. in analogy to those for the

Preparation of the polymers P1 mentioned processes and in particular by a radical aqueous emulsion polymerization.

The aqueous polymer dispersion of the polymer P2 may be the direct product of a free-radical, aqueous emulsion polymerization of the monomers M or a secondary dispersion, ie the polymer P2 suspended or dispersed in water following its preparation. In this case, the free-radical, aqueous emulsion polymerization may also be referred to as so-called

Miniemulsionspolymerisation be carried out, d. H. the monomers to be polymerized are used in the form of an aqueous miniemulsion, wherein the monomer droplets have very small diameters (volume-average

Droplet diameter of the monomer emulsion <1 μm, in particular <0.6 μm). A secondary dispersion is understood as meaning an aqueous polymer dispersion whose polymer is first prepared in a solution polymerization or in another manner and subsequently dispersed or emulsified in an aqueous medium, optionally with removal of organic solvent from the solution polymerization. In terms of applications, preferred are polymer dispersions prepared by free radical aqueous emulsion polymerization. Polymer dispersions are preferred in which the dispersed polymer particles have an average particle diameter, determined by hydrodynamic fractionation, in the range from 0.01 to 1.5 μm and in particular in the range from 0.02 to 1 μm.

The polymers P2 are preferably those which are obtained by a free-radical, aqueous emulsion polymerization of the ethylenically unsaturated

Monomers M are available. If the aqueous dispersions of the polymer P2 are prepared by free-radical aqueous emulsion polymerization, this can be carried out in a manner known per se, and preferably according to a monomer feed process. The free-radical, aqueous emulsion polymerization is typically carried out in

Presence of surface active substances as described above. Preferably, only emulsifiers are used in the process according to the invention. In particular, it has proven to be a combination of at least one

anionic and at least one nonionic emulsifier to use as a surfactant.

Typically, the surface-active substances are used in amounts of from 0.1 to 10% by weight, in particular in amounts of from 0.2 to 5% by weight, based on the weight of the monomers M to be polymerized.

The initiators used for free-radical emulsion polymerization are usually water-soluble, radical-forming substances. Water-soluble initiators for the emulsion polymerization are organic or inorganic peroxide compounds, ie compounds having at least one peroxide or hydroperoxide group, for. B. ammonium and alkali metal salts of

Peroxodisulfuric acid, e.g. For example, sodium peroxodisulfate, hydrogen peroxide or organic peroxides, z. B. tert-butyl hydroperoxide.

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

Hydroxymethanesulfinic acid and sodium disulfite.

The initiators mentioned are usually used in the form of aqueous solutions, the lower concentration being determined by the amount of water acceptable in the dispersion and the upper concentration by the solubility of the compound in question in water. In general, the concentration is 0.1 to 30 wt .-%, preferably 0.5 to 20 wt .-%, particularly preferably 1, 0 to 10 wt .-%, based on the solution. The amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.2 to 5 wt .-%, based on the monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization. In the emulsion polymerization of the monomers M regulators can be used, for. B. in amounts of 0 to 1 wt .-%, based on the monomers to be polymerized M. This reduces the molecular weight of the polymer. Are suitable

for example, compounds having a thiol group such as tert-butylmercaptan,

Mercaptoethanol, mercaptopropanol, thioglycolic acid, thioglycolic acid alkyl ester, Thiopropionic acid, thiopropionic acid ester, mercaptopropyltrimethoxysilane and tert-dodecylmercaptan. If appropriate, it is advantageous to add the regulator in the course of the polymerization over a relatively long period of time, for example in parallel with the addition of the monomers M. The addition can then take place at a continuous feed rate or increasing or decreasing feed rate.

The process of the invention is preferably carried out as feed process, d. H. At least 90% of the monomers M to be polymerized are added to the polymerization reactor in the course of the polymerization under polymerization conditions. The addition can be continuous or stepwise. In the course of the polymerization, the monomer composition can be changed once, repeatedly or continuously (gradient procedure).

Optionally, in the emulsion polymerization of the monomers M, use will be made of a particulate seed polymer which is obtained in particular in the

Polymerization reactor presents. In this context, "submit" means that the seed polymer is either added before the beginning of the polymerization or is formed by in-situ emulsion polymerization before the actual emulsion polymerization in the polymerization reactor. The term "seed polymer" is understood by the person skilled in the art to mean a finely divided polymer in the form of an aqueous polymer dispersion. The weight-average particle size of the seed polymers used in the process according to the invention (weight average, d.sub.50 value) is typically below 200 nm, frequently in the range from 10 to 150 nm and in particular in the range from 20 to 120 nm. The monomer composition of the seed polymers is of secondary importance. Suitable are both seed polymers, which are predominantly vinyl aromatic

Monomers and in particular of styrene are constructed (so-called styrene seed), as well as seed polymers, mainly from Ci-Cio-alkyl acrylates and / or C1-C10 alkyl methacrylates, eg. B. are composed of a mixture of butyl acrylate and methyl methacrylate. In addition to these main monomers, which typically make up at least 80% by weight and especially at least 90% by weight of the seed polymer, the seed polymers may also contain various monomers, especially those having an increased water solubility, e.g. B. monomers having at least one

Acid function and / or neutral monomers with increased water solubility, and / or monomers with two or more ethylenically unsaturated double bonds in copolymerized form (monomers M3b). The proportion of such monomers will typically not exceed 20% by weight, and more preferably 10% by weight, and, if present, is typically in the range of 0.1 to 10% by weight, based on the total amount of the seed polymer constituting monomers. In the process according to the invention, preference is given to using water and a subset of the surface-active substance and, if appropriate, one

Subset of the monomers M and / or an externally produced seed polymer in the form of an aqueous dispersion presents. Alternatively, the seed polymer may pass through in situ

Emulsion polymerization, preferably using a small subset of the monomers M, be prepared in advance. Then it will open

Heating polymerization and then a subset of

Polymerization initiator, e.g. B. 1 to 20 wt .-% and in particular 5 to 15 wt .-%, based on the total amount of the initiator added. It is also possible to proceed by first adding the partial amount of the polymerization initiator and

then heated to polymerization temperature. Preferably, at this time, the polymerization reactor less than 5 wt .-% of the monomers to be polymerized M. Subsequently, the addition of the monomers to be polymerized in the polymerization reactor is carried out under polymerization conditions. The addition is usually over a longer period of usually at least 30 minutes, z. B. 30 minutes to 10 hours, especially over a period of 1 h to 6 h. As already explained, the addition can be carried out with a constant, increasing or decreasing rate of addition. According to a first preferred embodiment, the addition takes place at the beginning of the polymerization with increasing feed rate. According to another, likewise preferred embodiment of the process according to the invention, the addition takes place at a constant rate of addition. The monomers can be added as such. Preferably, the addition of the monomers takes place in the form of an aqueous monomer emulsion which typically comprises at least a portion, preferably at least 70% by weight of those employed in the emulsion polymerization

contains surface-active substances. Typically, this monomer emulsion has a monomer content in the range of 60 to 85 weight percent, and more preferably in the range of 65 to 80 weight percent. It is possible in principle, the monomers or the

Monomer emulsion over multiple feeds in the polymerization reactor, wherein the monomer composition of the individual feeds may be different from each other. In general, however, it is sufficient to give the monomers as a mixture via an inlet in the polymerization reactor. If the monomers are added to the polymerization reactor in the form of an aqueous emulsion, it may be advantageous to freshly emulsify the monomers immediately prior to their addition and according to their addition in the polymerization reactor, for example by a continuous process. It is also possible first to prepare the monomer emulsion and then add it to the desired addition rate in the

Introduce polymerization reactor. Usually, the addition of at least one partial amount or the total amount of the polymerization initiator takes place in parallel with the monomer addition. Typically, at least 80% of that required for emulsion polymerization will be needed

Polymerization initiator, in particular 85 to 95% of the polymerization initiator in the course of the polymerization reaction in the polymerization reactor. The addition of the polymerization initiator may be carried out at a constant rate or with a varying, e.g. B. a decreasing or increasing rate of addition.

The polymerization medium may consist of water only, as well as of mixtures of water and thus miscible liquids such as methanol.

Preferably, only water is used.

Polymerization temperature and polymerization pressure are of secondary importance. The emulsion polymerization is typically carried out at temperatures in the range of 30 to 130, preferably in the range of 50 to 100 ° C. Of the

Polymerization pressure is usually in the range of atmospheric pressure, d. H. at ambient pressure, but may also be slightly above or below, z. B. in the range of 800 to 1500 mbar. For further details on the polymerization conditions, reference is made to the examples.

In general, it is best to stop after the actual

Polymerization reaction, d. H. after completion of the addition of the monomers to be polymerized or after a conversion of the monomers present in the polymerization reactor of at least 95%, a chemical and / or physical

Deodorization to remove unpolymerized monomers. As a rule, at least one chemical deodorization will be carried out. Chemical deodorization is understood as meaning a postpolymerization phase which is triggered by the addition of at least one further polymerization initiator, in particular one of the abovementioned redox initiator systems. Methods for this purpose are known, for example from DE-A-4435422, DE-A-4435423 and DE-A-4419518. The

Reduction of the residual monomers can also be carried out by combined measures of chemical and physical deodorization, wherein preferably the physical deodorization is carried out after the chemical deodorization. The polymer dispersions obtained in this way preferably contain less than 1500 ppm, in particular less than 1000 ppm and more preferably less than 500 ppm of volatile organic components TVOC. Under TVOC (Total Volatile Organic Compounds) are all organic compounds with a boiling point of a maximum of 250 ° C at 1 bar understood. The determination of the residual volatile content is typically carried out according to DIN 55649.

The aqueous polymer compositions according to the invention contain

According to the invention at least one polymer P1 and at least one polymer P2.

According to its solubility in water or aqueous alkaline solutions, the polymer P1 can be dissolved in the aqueous composition in dissolved form or in dispersed form, i. H. in the form of an aqueous polymer dispersion.

Preference is given to aqueous compositions in which the polymer P1 is present in dissolved form in the aqueous composition. If the polymer P1 or the copolymer PV is in the form of an aqueous polymer dispersion, the polymer particles of the dispersion preferably have an average particle diameter, determined by hydrodynamic fractionation of not more than 500 nm, and in particular not more than 300 nm, z. B. in the range of 5 to 500 nm or in the range of 10 to 300 nm. By the mean particle diameter is meant the hydrodynamic mean diameter, d. H. the hydrodynamic particle diameter determined by hydrodynamic fractionation according to the method of large exclusion of dilute polymer dispersions (absorption of 0.03 AU / μΙ, 22 ° C).

In the aqueous polymer compositions according to the invention, the polymer P2 may in principle be in dissolved or disperse form. In particular, the polymer P2 in the aqueous polymer compositions according to the invention is the polymer P2 in disperse form, d. H. as a heterogeneous phase in the form of finely divided

Polymer particles which are dispersed in a homogeneous aqueous phase or

are suspended. Polymer dispersions in which the dispersed polymer particles of the polymer P2 have an average particle diameter, determined by hydrodynamic fractionation, in the range from 0.01 to 1.5 μm and in particular in the range from 0.02 to 1 μm, are preferred. The polymer particles can have both a monomodal particle size distribution, ie a

Particle size distribution with only one maximum, or a polymodal distribution having at least two distinct maxima, which differ in the rule by at least 0.05 μηη have.

In general, the polymer P1 and the polymer P2 will be used in an amount ratio such that the molar ratio of the groups of the formula -O-NR ¹ R ² to the functional groups F is in the range from 10: 1 to 1:10 and in particular in the range from 1: 5 to 5: 1. The weight ratio of polymer P1 to polymer P2 is preferably in the range from 1: 500 to 2: 1, in particular in the range from 1: 100 to 1: 1 and especially in the range from 1:50 to 1: 2.

The concentration of polymer P1 in the aqueous polymer composition is typically in the range of 0.1 to 50% by weight, in particular in the range of 0.5 to 30% by weight and especially in the range of 1 to 20% by weight, based on the

Total weight of the polymer composition.

The concentration of polymer P2 in the aqueous polymer composition is typically in the range of 4.9 to 69.9% by weight, in particular in the range of 10 to 64.5% by weight and especially in the range of 10 to 54% by weight. %, based on the total weight of the polymer composition.

The total content of polymers P1 and P2 in the aqueous polymer composition is usually from 5 to 70 wt .-%, preferably 10 to 65 wt .-% and especially from 30 to 55 wt .-%, wherein the polymer composition prior to its application with water to a suitable for the application

Concentration can be diluted.

The aqueous polymer compositions according to the invention also have a coherent aqueous phase in which the polymer P1 and the polymer P2 are present in dissolved or dispersed form. In addition to water and the auxiliaries typically used in the preparation, the aqueous phase may include

Surface-active substances and organic solvents also other

Contain ingredients.

The amount of surface-active substances will generally not exceed 20% by weight, in particular 10% by weight, based on the total weight of the polymers P1 and P2, and is typically in the range from 0.1 to 20% by weight, in particular in the range of 0.2 to 10 wt .-%, based on the total weight of the polymers P1 and P2. The proportion of water-miscible organic

Solvents is usually less than 1 wt .-%, in particular less than 0.2 wt .-%, based on the total weight of the aqueous

Polymer composition. The pH of the aqueous polymer composition according to the invention is preferably in the range of pH 3 to pH 9, in particular in the range of pH 5 to pH 8.5 and especially in the range of pH 6 to pH 8. The other ingredients are especially biocides (preservatives ), which the aqueous polymer composition against infestation with

Stabilize microorganisms. These include, for example, alkyl esters of para-hydroxybenzoic acid, sodium benzoate, 2-bromo-2-nitropropane-1,3-diol, ortho-phenylphenol, dichlorophene, benzyl alcohol hemiformal, pentachlorophenol,

2,4-dichlorobenzyl alcohol and in particular substituted isothiazolones such. B.

Ci-Cio-Alkylisothiazolinone, 5-chloro-2-methyl-4-isothiazolinone and

Benzoisothiazolinones, e.g. B. the products sold under the names Proxel ^® the Fa. Avecia (or Fa. Arch) or Acticide ^® the company Thor Chemie products.

Preservatives are usually used in amounts of from 0.01 to 10 grams per liter of the polymer dispersion.

Further ingredients are mainly dependent on the nature of the desired application and include, for example, means for adjusting the pH,

Film-forming aids, thickeners, defoamers, dispersing agents, leveling agents, colorants, in particular pigments, fillers, tackifiers and tackifier resins.

The binder compositions according to the invention are suitable for a multiplicity of applications in which aqueous polymer dispersions are usually used as binders, eg. As coating agents such as in paints for interior and exterior applications, in paper coating slips, in coating systems for leather and textiles, in printing inks, in coating systems for mineral moldings, in primers for coating metals, as a binder in the production of polymer-bonded fiber webs, as sticking raw materials , as additives for inorganic, hydraulic binders such as CaSCv O, 5 H2O, anhydride or cement, and the hydraulic binding compositions prepared therefrom such as gypsum or concrete, as additives for clay or earth building materials, for the production of membranes and the like.

The following examples serve to illustrate the invention.

analytics:

The molecular weight of the polymers was determined by size exclusion chromatography. The eluent used was tetrahydrofuran. The sample was present of the injection on Macherey-Nagel PTFE.20 / 25 (0.2 pm) and filtered over a separation column combination (Pl-gel precolumn (PI Gel 5pm, ID: 7.5 mm, L: 5 cm), PLgel MIXED B (PL gel 10 pm, ID: 7.5 mm, L: 30 cm)). The calibration was carried out using narrowly distributed polystyrene standards from Polymer Laboratories with molecular weights of M = 580 to M = 6,870,000, and hexylbenzene (M = 162). The values outside this elution range were extrapolated.

The particle sizes were determined herein and in the appended

Claims by means of hydrodynamic fractionation with a PSDA (Particle Size Distribution Analyzer) from the company Polymer Labs. The column type Cartridge PL0850-1020 used was operated at a flow rate of 2 ml / min. The samples were diluted with the eluent solution to an absorbance of 0.03 AU / μΙ. The sample is eluted by the size exclusion principle depending on the hydrodynamic diameter. The eluent contains 0.2% by weight of dodecylpoly (ethylene glycol ether) 23,

0.05% sodium dodecylsulfonate, 0.02% sodium dihydrogen phosphate and 0.02% sodium azide in deionized water. The pH is 5.8. The

Elution time is calibrated with polystyrene calibration latices. The measurement is carried out in the range from 20 nm to 1200 nm. Detection is carried out with a UV detector at a wavelength of 254 nm.

The glass transition temperature was determined by differential scanning calorimetry according to ASTM 3418/82. For conditioning, the polymers were poured out, dried overnight, then dried for 1 h in a vacuum oven at 120 ° C. In the measurement, the sample is heated to 150 ° C, cooled rapidly and then measured at 20 K / min heating. Indicated is the so-called mid-point temperature.

Starting Materials:

4-aminoxymethylstyrene: A monomer of the formula I in which R1, R2 and R are H and A is 4-phenylene-CH2, prepared according to the instructions of Wen-Jing Zhou, Mark E. Wilson, Mark J. Kurth, You-Lo Hsieh, John M. Krochta, Charles F. Shoemaker Macromolecules 1997, 30, 7063-7068.

Emulsifier Composition 1: 32% solution of a C12 / C14 alkyl

Polyethylene glycol sulfate sodium salt in water

Emulsifier Composition 2: 45% solution of a dodecyldiphenyl ether disulfonic acid sodium salt in water

Emulsifier Composition 3: 15% solution of sodium lauryl sulfate in water Emulsifier Composition 4: 20% solution of a C16 / C18 alkyl

polyethylene glycol having an ethoxylation degree of 18 in water. Polystyrene seed latex: 33% polystyrene latex in water, mean particle size of 30 nm.

Preparation of Polymers P1: Example 1: Copolymer of methacrylic acid and 4-aminoxymethylstyrene

128 g of water and 32 g of 2-propanol were heated to 85 ° C. in a 2 l glass reactor with an anchor stirrer. After reaching the reaction temperature, a mixture of 90 g (1, 045 mol) of methacrylic acid and 1 g (0.0094 mol) of 3-mercaptopropionic acid was dissolved in a mixture of 143.2 g of water and 35.8 g of 2-propanol and a solution from 10 g (0.067 mol) of 4-aminoxymethylstyrene in 50 g of 2-propanol within 1, 5 h metered. At the same time, a feed of 5.33 g (0.0306 mol) of f-butyl perpivalate in 24.67 g of 2-propanol was metered in over 2 hours. After the end of the Initiatorzulaufs was the

Reaction temperature maintained at 85 ^° C for a further 30 min. Subsequently, 30 ml of the 2-propanol-water mixture were distilled off. The resulting polymer solution was neutralized with 73.1 g of 25% (1, 073 mol) aqueous ammonia solution. A clear solution having a solids content of 24.9% and a pH of 5.2 was obtained. The resulting polymer had a weight average molecular weight M _w of 130 kg / mol

[Example 2: Copolymer of methacrylamide and 4-aminoxymethylstyrene

128 g of water and 32 g of 2-propanol were heated to 85 ° C. in a 2 l glass reactor with an anchor stirrer. After reaching the reaction temperature, a mixture of 90 g (1.058 mol) of methacrylamide and 2 g (0.0217 mol) of 1-mercapto-2-propanol was dissolved in a mixture of 261, 35 g of water and 53.98 g of 2- Propanol and a solution of 10 g (0.067 mol) of 4-aminoxymethylstyrene within 1, 5 h metered. At the same time, an addition of 4 g (0.023 mol) of f-butyl perpivalate in 26 g of 2-propanol was metered in over 2 h. After the end of the Initiatorzulaufs the reaction temperature was maintained at 85 ^° C for a further 30 min. Subsequently, 100 ml of the 2-propanol-water mixture were distilled off at 100 ° C. The resulting clear solution had a solids content of 28.8% and a pH of 8.6. The resulting polymer had a weight average molecular weight M _w of 2500 g / mol. [Example 3: Terpolymer of methacrylic acid sodium salt, n-butyl methacrylate and 4-aminoxymethylstyrene

75 g of water and 75 g of 2-propanol were heated to 80 ° C. in a 2 l glass reactor with anchor stirrer and introduction of nitrogen. After reaching the reaction temperature, a solution of 200 g (1.851 mol) of sodium methacrylate, 10 g (0.067 mol) of 4-aminoxymethylstyrene in 5 g of water and 45 g of 2-propanol and a solution of 40 g (0.281 mol) of n-butyl methacrylate in 30 g of 2-propanol within 1, 5 h dosed. At the same time, an addition of 2.67 g (0.0153 mol) of f-butyl perpivalate in 227.33 g of 2-propanol was metered in over 2 hours. After the end of the Initiatorzulaufs was the

Reaction temperature maintained at 80 ^° C for a further 30 min. Subsequently, 80 g of water were added within 15 min while iso-propanol was completely distilled off. The resulting dispersion had a solids content of 16.6%, an average particle size of 918 nm and a pH of 8.6. The resulting polymer had a weight average molecular weight Mw of 20400 g / mol.

[Example 4: 4-Aminoxymethylstyrene-containing emulsion polymer

From 121, 38 g of water, 4.13 g of emulsifier composition 1, 1, 47 g

Emulsifier composition 2, 19.8 g (0.097 mol) of 2-ethylhexyl thioglycollate, 33.00 g (0.221 mol) of 4-aminoxymethylstyrene and 99 g (0.989 mol) of methyl methacrylate were prepared as a monomer emulsion.

94.98 g of water were initially charged together with 4.8 g of a polystyrene seed latex and 1.89 g of a 7% strength aqueous sodium peroxodisulfate solution in a 2 l reactor with anchor stirrer, thermocouple and reflux condenser and stirred at 90 ° C. for 5 min.

Subsequently, 278.77 g of the monomer emulsion in 3 h and 7.54 g of 7% sodium peroxodisulfate in 3.25 h were added. At the end of the feeds, 1.61 g of a 13% strength acetone bisulfite solution and 1.32 g of a 10% strength f-butyl hydroperoxide solution were added dropwise within one hour. The dispersion was then cooled to room temperature and adjusted to pH 9.3 with 25% ammonia solution.

The dispersion had a solids content of 37.4%. The particle size was 137 nm. The glass transition temperature was 25.9 ° C. Example 5: Alkali-soluble dispersion

From 345.15 g of water, 24.64 g Emulgatorzsuammensetzung 1, 2.58 g of sodium hydroxide solution (25% solution in water), 9.2 g (0.045 mol) of 2-ethylhexyl thioglycolate, 92.00 g (1, 069 mol) of methacrylic acid, 18.40 g (0.123 mol) of 4-aminoxymethylstyrene and 349.6 g (2.459 mol) of n-butyl methacrylate, a monomer emulsion was prepared.

257.6 g of water were introduced together with 43.76 g of the monomer emulsion and 9.2 g of a 7% aqueous sodium peroxodisulfate in a 2 I reactor equipped with anchor stirrer, thermocouple and reflux condenser and stirred at 85 ° C for 5 min.

Subsequently, a further 797.8 g of the monomer emulsion in 2.5 h and 58.8 g of a 2.5% aqueous sodium peroxodisulfate solution in 3 hours were added. After the end of the feeds, 4.6 g of a 10% hydrogen peroxide solution and 7.58 g of a 9% ascorbic acid solution were metered in within one hour. Subsequently, the dispersion was cooled to room temperature.

The dispersion had a solids content of 40.6% The particle size was 380 nm, the glass transition temperature was 60 ° C. Example 6: Copolymer of 4-vinylbenzenesulfonic acid sodium salt and 4-aminoxymethylstyrene

1.49 g (0.01 mol) of 4-aminoxymethylstyrene was added together with 6.19 g (0.03 mol) of 4-vinylbenzenesulfonic acid sodium salt and 0.23 g (0.0014 mol) of azoisobutyronitrile in a mixture of 50 ml of water and 50 ml of ethanol submitted. The solution was then stirred for 13 h under argon at 80 ^° C and then evaporated at 90 ^° C and 6 mbar. 8.46 g of the still slightly water-containing copolymer were obtained as a colorless, glassy solid. The resulting polymer had a weight average molecular weight M _w = 47040 g / mol and a number average molecular weight MN = 9921 g / mol.

Preparation of Polymers P2:

Preparative Example D1: Polymer dispersion with diacetone acrylamide (DAAM) From 182.5 g of water, 55.2 g of emulsifier composition 3, 276 g (2.757 mol) of methyl methacrylate, 300 g (2.341 mol) of n-butyl acrylate and 120 g of a 20% solution of diacetone acrylamide in water (0.142 mol), a monomer emulsion was prepared.

210.5 g of water was charged together with 4.8 g of emulsifier composition 3, 28.0 g of the monomer emulsion and 15.0 g of a 4% aqueous sodium peroxodisulfate solution in a 2 l reactor with anchor stirrer, thermocouple and reflux condenser and at 90 ° C for Stirred for 10 min. Subsequently, a further 905.69 g of

Monomer emulsion and 60.0 g of Natriumperoxodisulfatlösung metered in 3 h. After the end of the feeds, the solution was stirred for a further 60 minutes at 90 °. Subsequently the dispersion was cooled to room temperature and neutralized to pH 8.1 with 25% ammonia solution.

The dispersion had a solids content of 49.4%, the particle size was 1 14 nm. The glass transition temperature was 12.1 ° C.

Preparation Example D2: Polymer Dispersion with Acetoacetoxyethyl Methacrylate (AAEMA)

From 278.5 g of water, 57.96 g of emulsifier composition 3, 276.0 g (2.757 mol) of methyl methacrylate, 300.0 g (2.341 mol) of n-butyl acrylate and 24.00 g (0.1 12 mol)

Acetoacetoxyethyl methacrylate, a monomer emulsion was prepared.

Monomer emulsion and 60.0 g of Natriumperoxodisulfatlösung metered in 3 h. After the end of the feeds, the solution was stirred for a further 60 minutes at 90 °. The dispersion was then cooled to room temperature and washed with 25%

Ammonia solution neutralized to pH 8.1.

The dispersion had a solids content of 49.1%, the particle size was 120 nm. The glass transition temperature was 12.3 ° C.

Preparation D3: Polymer dispersion with glycidyl methacrylate (GMA) From 293.96 g of water, 28.13 g of emulsifier composition 1, 15.0 g

Emulsifier composition 4, 276 g (2.757 mol) of methymethacrylate, 300 g (2.341 mol) of n-butyl acrylate and 24 g (0.169 mol) of glycidyl methacrylate became a

Monomer emulsion prepared.

210.5 g of water were added together with 21, 82 g of polystyrene seed latex, 15.0 g of a 4% aqueous sodium peroxodisulfate solution in a 2 l reactor with anchor stirrer,

Introduced thermocouple and reflux condenser and stirred at 90 ° C for 10 min.

Subsequently, a further 937.09 g of the monomer emulsion and 60.0 g of the

Sodium peroxodisulfate added in 3 h. After the end of the feeds, the solution was stirred for a further 60 minutes at 90 °. Subsequently, the dispersion was cooled to room temperature and neutralized with 25% ammonia solution to pH 8.1. The dispersion had a solids content of 49%, the particle size was 137 nm. The glass transition temperature was 12.1 ° C.

Preparation Example D4: Polymer dispersion with glycerol carbonate acrylate (GCA) From 277.75 g of water, 28.13 g of emulsifier composition 1, 15.0 g

Emulsifier Composition 4, 12 g (0.169 mol) acrylamide, 270 g (2.697 mol) Methyl methacrylate, 300 g (2.341 mol) of n-butyl acrylate and 24 g of glycerol carbonate acrylate (20% solution in water) was prepared as a monomer emulsion.

Introduced thermocouple and reflux condenser and stirred at 90 ° C for 10 min.

Subsequently, a further 926.88 g of the monomer emulsion and 60.0 g of the

Sodium peroxodisulfate added in 3 h. After the end of the feeds, the solution was stirred for a further 60 minutes at 90 °. Subsequently, the dispersion was cooled to room temperature and neutralized with 25% ammonia solution to pH 8.1. The dispersion had a solids content of 50% by weight. The particle size was 134 nm. The glass transition temperature was 13 ° C.

Preparation of Polymer Compositions According to the Invention The polymer dispersions of Preparation Examples D1 to D4 were blended with the aqueous polymer compositions of Examples 1 to 5. The mixing ratio was calculated so that the molar number of reactive functional groups (keto groups, acetoacetoxy groups, epoxide groups,

Carbonate groups) of the molar number of aminoxy groups of the polymeric

Alkoxyaminvernetzers corresponded.

For comparative purposes, known low molecular weight crosslinkers were added to the polymer dispersions of Preparation Examples D1 to D4, so that also the

Molar ratio of the reactive groups to the functional groups of the crosslinker was 1: 1. The following low molecular weight crosslinkers were used:

Adipic dihydrazide (ADDH), hexamethylenediamine (HMDA) and 1,4-bisaminoxybutane (BAOB),

The aqueous polymer compositions thus obtained were then diluted to a solids content of 20% and then in a silicone mold 170h at

Room temperature dried to about 60 μηη thick polymer films. The crosslinking of the films thus obtained was characterized by determining their degree of swelling as described below. Determination of the degree of swelling:

The films were placed on a laboratory shaker at room temperature for 24 h

Shaken tetrahydrofuran (THF). Then they were from the THF

removed, blotted dry and weighed. The ratio of the weight of the swollen film to the unswollen film is given as the degree of swelling. One low degree of swelling means high crosslinking of the film. The results are summarized in Tables 1 and 2. In some cases, the film was completely soluble in THF. TABLE 1 Crosslinking of Dispersions D1, D2, D3 or D4 with Low Molecular Crosslinkers and the Copolymer from Example 2

Low swelling levels mean higher crosslinking densities. Numbers are the measured degrees of swelling. Table 2: Swelling degrees of the polymer films of the dispersions D1, D2 and D3 which were crosslinked with the copolymers of Examples 1, 2, 5 or 6.

swelling degree

D1 D2 D3 without crosslinker soluble soluble 35

[Example 1 5 8 8

Example 2 3 4 4

Example 5 10 13 14

Example 6 7 5 6

Claims

claims:

An aqueous polymer composition comprising:

a) at least a first, from ethylenically unsaturated monomers

built-up polymer P1, which has on average more than 2 functional groups of the formula

-O-NR ¹ R ² , wherein

R ¹ , R ^{2 are} hydrogen or together form a group = CR ^a R ^b

in which R ^a and R ^b independently of one another are hydrogen or C 1 -C 4 -alkyl or together with the carbon atom to which they are attached form a C 5 -C 8 -cycloalkylidene group; b) and at least one second polymer P2 having functional groups F which can react with the groups of formula -O-NR ¹ R ² to form a covalent bond.

The polymer composition of claim 1, wherein R ¹ , R ^{2 are} hydrogen.

A polymer composition according to any one of the preceding claims, wherein the polymer P1 is a homo- or copolymer having on average more than 2

Repeating units MA has a monoethylenic

unsaturated monomer A, which carries a functional group of the formula -O-NR ¹ R ² .

A polymer composition according to claim 3, wherein the monoethylenically unsaturated monomer A t:

(I)

wherein

R ¹ , R ^{2 have} the meanings given above;

R ^{3 is} hydrogen or methyl, and

A is a group of the formula X- [O-Alk] _n , in which

X is a chemical bond or is a bivalent radical which is bonded to the carbon atom which carries R ³ and which is selected from phenylene, phenylene-CH ₂ -, C (O), CH ₂ 0-C ₂ -Ci ₂ Alkanediyl and C (O) -NR ^c - (C ₂ -Cio-alkanediyl), wherein R ^{c is} hydrogen, C ₁ -C ₄ -alkyl or - (C ₂ -C ₂ -alkanediyl) -O-NR ¹ R ² stands; n is a number from 0 to 20, where n is different from 0, if

X is C (O);

Alk is C ₂ -C ₄ alkanediyl.

A polymer composition according to claim 4, wherein in formula I the variables R ¹ , R ² and R ^{3 are} hydrogen and A is phenylene-Ch.

6. A polymer composition according to any one of claims 3 to 5, wherein the

Polymer P1 is a copolymer which, in addition to the repeat units of the formula MA, has one or more further repeat units MB which are derived from monoethylenically unsaturated monomers B which have no functional group of the formula -O-NR ¹ R ² .

A polymer composition according to claim 6, wherein the monomers B comprise monomers B1 having a water solubility of at least 50 g / l, at 20 ° C and 1 bar.

The polymer composition of claim 7, wherein the monoethylenic

unsaturated monomers B1 are selected from monoethylenic

unsaturated Cs-Cs monocarboxylic acids, monoethylenically unsaturated C3-C8

Monocarboxylic acids, monoethylenically unsaturated sulfonic acids, amides of monoethylenically unsaturated Cs-Cs-monocarboxylic acids, hydroxy-C2-C ₄ - alkyl esters of monoethylenically unsaturated Cs-Cs-monocarboxylic acids, poly-C2-C ₄ - alkylene oxide esters of monoethylenically unsaturated Cs-Cs-monocarboxylic acids, di- C 1 -C ₄ -alkylamino-C ₂ -C ₄ -alkyl esters of monoethylenically unsaturated Cs-Cs

Monocarboxylic acids and N-vinyl lactams.

The polymer composition according to any one of claims 6 to 8, wherein the molar ratio of repeating units MA to repeating units MB ranges from 1: 100 to 10: 1.

10. A polymer composition according to any one of claims 6 to 9, wherein the molar proportion of the monomers B1, based on the total number of monomers B, 10 bis

100 mol%.

1 1. A polymer composition according to any one of the preceding claims, wherein the polymer P1 is in dissolved form in the aqueous composition.

The polymer composition according to any one of claims 1 to 10, wherein the polymer P1 is present in the aqueous composition in the form of an aqueous polymer dispersion. A polymer composition according to any one of the preceding claims, wherein the polymer P1 has a number average molecular weight of at least 500 g / mol.

14. Polymer composition according to one of the preceding claims, wherein the functional groups F of the polymer P2 are selected from oxirane

Groups, cyclic carbonate groups, aldehyde groups and keto groups.

A polymer composition according to any one of the preceding claims wherein the polymer P2 is in dispersed or dissolved form in the aqueous composition.

A polymer composition according to any one of the preceding claims wherein the polymer P2 is constructed from ethylenically unsaturated monomers M comprising:

- 50-99.9 wt .-%, based on the total mass of the polymer P1

forming monomers, at least one monoethylenically unsaturated monomer M1, which has no functional groups F and the one

Water solubility of less than 50 g / l, at 20 ° C and 1 bar; 0.1 -50 wt .-%, based on the total mass of the polymer P2-forming monomers, at least one monoethylenically unsaturated monomer M2 having at least one functional group F.

17. A polymer composition according to any one of the preceding claims, wherein the weight ratio of polymer P1 to polymer P2 is in the range of 1: 500 to

2: 1 lies

18. Copolymer P1 ', which is composed of

Repeating units MA derived from a monoethylenically unsaturated monomer A bearing a functional group of formula -O-NR ¹ R ² , wherein R ¹ and R ² are as defined in claim 1 or 2;

Repeat units MB derived from monoethylenically unsaturated monomers B which do not represent a functional group of the formula -O-NR ¹ R ² , wherein the repeating units MB such

Repeat units include MBI derived from monoethylenically unsaturated monomers B1 having a water solubility of at least 50 g / l, at 20 ° C and 1 bar; wherein the copolymer P1 'carries on average more than 2 functional groups of the formula - 0-NR ¹ R ² .

19. Copolymer P1 'according to claim 18, which has a number average molecular weight of at least 500 g / mol.

20. Copolymer P1 'according to claim 18 or 19, wherein the monoethylenic

unsaturated monomer A

wherein

R ¹ , R ^{2 have} the meanings given above and in particular stand for hydrogen;

R ^{3 is} hydrogen or methyl, and

A is a group of the formula X- [O-Alk] _n , in which

X is a chemical bond or is a bivalent radical which is bonded to the carbon atom which carries R ³ and which is selected from phenylene, phenylene-CH ₂ -, C (O), CH ₂ , 0-C ₂ - Ci2-alkanediyl and C (0) -NR ^c - (C ₂ -Cio-alkanediyl), wherein R ^{c is} hydrogen, Ci-C ₄ -alkyl or - (C ₂ -C ₂ -alkanediyl) -O-NR ¹ R ² is t; n is a number from 0 to 20, where n is other than 0, when X is C (O) and n is in particular 0;

Alk is C ₂ -C 4 alkanediyl and in particular CH ₂ CH ₂ .

21. Copolymer P1 'according to any one of claims 18 to 20, wherein the monoethylenically unsaturated monomers B1 are selected from monoethylenic

unsaturated Cs-Cs monocarboxylic acids, monoethylenically unsaturated C3-C8 monocarboxylic acids, monoethylenically unsaturated sulfonic acids, amides of monoethylenically unsaturated Cs-Cs monocarboxylic acids, hydroxy-C ₂ -C ₄ -alkyl esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids, poly-C ₂ - C ₄ -alkylene oxide esters of monoethylenically unsaturated Cs-Cs monocarboxylic acids, di- C 1 -C 4 -alkylamino-C 2 -C 4 -alkyl esters of monoethylenically unsaturated C 3 -C 8 -monocarboxylic acids and N-vinyllactams.

Copolymer PV according to one of claims 18 to 21, wherein the molar ratio of repeat units MA to repeat units MB in the range of 1: 100 to 10: 1.

Copolymer P1 'according to any one of claims 18 to 22, wherein the molar proportion of repeating units MBI, based on the total number of

Repeat units MB, 10 to 100 mol%.

Use of polymers P1 as defined in any one of claims 1 to 13 or of copolymers P1 'as defined in any one of claims 18 to 23 as crosslinkers for polymers P2 which have functional groups F which are substituted with the groups of the formula 0-NR ¹ R ^{2 of} the polymer P1 can react to form a covalent bond.

25. Use according to claim 24, wherein the functional groups F of

Polymers P2 are selected from oxirane groups, cyclic carbonate groups, aldehyde groups and keto groups.

26. Use according to any one of claims 24 or 25, wherein the polymer P2 in the form of an aqueous polymer solution or in the form of an aqueous

Polymer dispersion is present.