DE102009009209A1 - Preparing comb polymers comprises providing polymers having 1,3-dicarbonyl group and polymerization of ethylenically unsaturated monomer in presence of polymers in aqueous polymerization medium, initiated by peroxidase and peroxide source - Google Patents

Abstract

Preparing comb polymers comprises: (a) providing a polymer P1 having 1,3-dicarbonyl groups D, which carry 1 or 2 hydrogen atoms at C-atom between the carbonyl groups; and (b) polymerizing ethylenically unsaturated monomer M2 in the presence of the polymer P1 in an aqueous polymerization medium. The polymerization of the monomer M2 is initiated by an initiator system comprising a peroxidase and a peroxide source. An independent claim is included for the comb polymer prepared by the above method.

Description

The The present invention relates to a process for the preparation of Comb polymers and those obtainable by this process Comb polymers.

• 1. Anpolymerisieren der die Seitenketten bildenden Monomere an das die Hauptkette bildende Polymer. Hierzu werden in dem die Hauptkette bildenden Polymer reaktive Zentren (z. B. radikale, kationische Zentren oder anionische Zentren) erzeugt, welche eine Polymerisation der die Seitenkette bildenden Monomere initiieren. Die Erzeugung der reaktiven Zentren kann im Falle radikalischer Zentren beispielsweise durch Kettenübertragung, Bestrahlung oder chemische Aktivierung von Radikale bildenden Gruppen, im Falle der kationischen Zentren durch Behandlung geeigneter funktionalisierter Polymere mit einer Lewissäure oder im Falle anionischer Zentren zum Beispiel durch Behandlung des Polymeren mit einer starken Base erfolgen.
• 2. Anknüpfen von polymeren Seitenketten an die polymere Hauptkette, z. B. durch Umsetzung terminal funktionalisierter Polymere, welche die Seitenkette bilden, mit einem funktionalisierten, die Hauptkette bildenden Polymer im Sinne einer polymeranalogen Umsetzung, wobei das die Hauptkette bildende Polymer eine Vielzahl funktioneller Gruppen aufweist, die eine komplementäre Reaktivität zu der funktionellen Gruppe des die Seitenkette bildenden Polymers aufweisen. Zu nennen sind beispielsweise die Veresterung von Hydroxyl- oder Amino-Gruppen funktionalisierten Polymeren mit Polymeren, die eine Vielzahl von Carboxyl- oder Carbonsäureanhydrid-Gruppen aufweisen.
• 3. Homo- oder insbesondere Copolymerisation sogenannter Makromonomere. Unter Makromonomeren versteht man Polymere, die eine, vorzugsweise terminal angeordnete polymerisierbare Gruppe, in der Regel eine ethylenisch ungesättigte Gruppe, aufweisen.

Comb polymers, often referred to as graft polymers, are known to be branched polymers having a polymeric backbone and a plurality of polymeric side chains attached to the polymeric backbone by a covalent bond. The preparation of comb polymers can in principle be carried out according to the synthesis concepts described below:

• 1. Initial polymerizing the side chain-forming monomers to the main chain-forming polymer. For this purpose, reactive centers (eg, radical, cationic centers or anionic centers) are generated in the main chain-forming polymer which initiate polymerization of the side-chain-forming monomers. The generation of the reactive centers in the case of radical centers, for example, by chain transfer, irradiation or chemical activation of radical-forming groups, in the case of cationic centers by treating suitable functionalized polymers with a Lewis acid or in the case of anionic centers, for example by treatment of the polymer with a strong Base done.
• 2. Tying of polymeric side chains to the polymeric backbone, z. Example, by reacting terminally functionalized polymers which form the side chain, with a functionalized, the main chain-forming polymer in the sense of a polymer-analogous reaction, wherein the main chain-forming polymer having a plurality of functional groups having a complementary reactivity to the functional group of the side chain having forming polymer. Examples include the esterification of hydroxyl or amino functionalized polymers with polymers having a plurality of carboxyl or carboxylic anhydride groups.
• 3. Homo- or in particular copolymerization of so-called macromonomers. Macromonomers are polymers which have a preferably terminally arranged polymerizable group, generally an ethylenically unsaturated group.

The hitherto known methods for the preparation of graft polymers associated with a number of disadvantages. That's the way it is with the methods the first synthesis concept is usually difficult, deliberately reactive Creating centers on the polymer chain. Often comes it leads to unwanted side reactions such as crosslinking reactions, Cyclenbildung by so-called. "Backbiting", degradation of the as a main chain serving polymers, and polymerization of the Side chain forming monomers without attachment to the polymeric backbone. This leads to a very strong contamination of the comb polymers by linear polymers resulting from the polymerization the side chain forming monomers result. Leave these As a rule, no longer separate from the comb polymer.

With turn the methods of the second and third synthesis concept turn only comb polymers with comparatively short polymeric side chains because the yields of polymer-analogous reactions and the Yields in the polymerization of macromonomers with increasing Molecular weight of the functionalized side chains forming Polymer, or the macromonomer, decrease. Therefore lead the methods described under the second and third methods, in particular at higher molecular weights of the functionalized polymers or the macromonomer, to comb polymers, which are still considerable amounts contained in polymeric starting materials, which are poor or not at all to be separated from the comb polymers obtained.

Of the The present invention is therefore based on the object, an efficient To provide a process for the preparation of comb polymers, which overcomes the disadvantages of the prior art. Especially The procedure should be easy to perform and too Products that do not result from polymeric by-products are contaminated. The process should also include the manufacture of comb polymers with high-molecular-weight side chains of, for example,> 10000, in particular> 50,000 daltons (weight average) allow.

From the WO 00/78988 For example, there is known a method of polymerizing ethylenically unsaturated monomers in an organic solvent in the presence of a peroxide source, a peroxidase and a transfer agent, for example a 1,3-dicarbonyl compound having free α-hydrogen atom. The preparation of comb polymers is not described.

It has surprisingly been found that comb polymers can be prepared in a particularly efficient manner by the process described below. In this process, the ethylenically unsaturated monomers which form the side chains (hereinafter monomers M2) are present of a polymer P1 having 1,3-dicarbonyl groups D bearing one or two hydrogen atoms (α-hydrogen atom) on the carbon atom between the carbonyl groups (α-C-atom), polymerized in an aqueous polymerization medium using an initiator system which a peroxidase (EC 1.11.1) and a peroxide source.

• i. Bereitstellung eines Polymers P1, das 1,3-Dicarbonylgruppen D aufweist, welche am C-Atom zwischen den Carbonylgruppen 1 oder 2 Wasserstoffatome (α-Wasserstoffatome) tragen; und
• ii. Polymerisation ethylenisch ungesättigter Monomere M2 in Gegenwart des Polymers P1 in einem wässrigen Polymerisationsmedium, wobei die Polymersation der Monomere M2 durch ein Initiatorsystem initiiert wird, das eine Peroxidase (EC 1.11.1) und eine Peroxid-Quelle umfasst.

Accordingly, the present invention relates to a process for the preparation of comb polymers, comprising:

• i. Providing a polymer P1 having 1,3-dicarbonyl groups D bearing hydrogen atoms (α-hydrogen atoms) between carbonyl groups 1 or 2 at the C atom; and
• ii. Polymerization of ethylenically unsaturated monomers M2 in the presence of the polymer P1 in an aqueous polymerization medium wherein the polymerization of the monomers M2 is initiated by an initiator system comprising a peroxidase (EC 1.11.1) and a peroxide source.

The inventive method is one row connected by advantages. On the one hand finds in the inventive Process a polymerization of the monomers M2 exclusively under linkage with the polymer P1 instead. polymers which result from the isolated polymerization of the monomers M2 not or not significantly observed. moreover this procedure allows the use of mild polymerization conditions, so that crosslinking reactions or cycle formation by so-called "backbiting" not or not observed to any appreciable extent. moreover The conversion of monomers M2 is usually very high and it will be high molecular weights of the side chain of usually above 10,000 daltons, often even above 20,000 daltons or 50,000 Dalton (number average) achieved.

The The inventors believe that the peroxidase by abstraction of an α-hydrogen atom the 1,3-dicarbonyl group generates a radical in this position, which initiates the polymerization of the monomers M2. The peroxide source acts as acceptor for the abstracted α-hydrogen atom and regenerate the peroxidase.

worin R¹ für Wasserstoff oder einen beliebigen, über ein Kohlenstoff gebundenen organischen Rest mit in der Regel 1 bis 10 C-Atomen steht, wobei R¹ auch in ein Ringsystem eingebunden sein kann, für die Polymerkette des Polymers P1 steht oder ein bivalenter Rest (Spacer) ist, der eine Verknüpfung mit der Polymerkette des Polymers P1 vermittelt.Here and below is meant by 1,3-dicarbonyl D functional groups of the arrangement shown below:

in which R ^{1 is} hydrogen or any carbon-bonded organic radical having generally 1 to 10 C atoms, where R ^{1 may} also be incorporated in a ring system, represents the polymer chain of the polymer P1 or a bivalent radical ( Spacer), which mediates a linkage with the polymer chain of the polymer P1.

A spacer is understood here and below to mean a bivalent organic radical having generally 1 to 20 C atoms and optionally 1 to 5 heteroatoms selected from oxygen and nitrogen. Examples of spacers are, in particular, C ₁ -C ₁₀ -alkanediyl bound directly or via an oxygen atom, a carboxyl or carbamoyl group and the polymer chain of P1, in which 1, 2 or 3 CH ₂ groups which are not adjacent to one another are replaced by oxygen and / or a CH ₂ group may also be replaced by phenylene, wherein alkanediyl may have 1, 2 or 3 substituents R ^b , which are independently selected from OH and C ₁ -C ₄ alkyl. R ¹ in formula D is in particular hydrogen or C ₁ -C ₁₀ -alkyl.

The 1,3-dicarbonyl groups may be part of the polymer chain of polymer P1 or may be functionalities attached to the polymer backbone of P1. Preferably, the polymer P1 is a polymer having a CC backbone to which the 1,3-dicarbonyl groups D are bonded directly or preferably via a spacer. In the 1,3-dicarbonyl groups, the carbon atom between the two carbonyl groups preferably carries 2 hydrogen atoms, ie R ¹ in formula D is preferably hydrogen.

worin
* die Bindung an das Kohlenstoffrückgrat der Polymerkette von P1 bedeutet;
X für eine chemische Bindung oder eine Gruppe der Formeln

steht, worin die Carbonylgruppe an das Kohlenstoffrückgrat der Polymerkette gebunden ist und R^a Wasserstoff oder C₁-C₄-Alkyl bedeutet;
A für lineares C₁-C₁₀-Alkandiyl steht, worin 1, 2 oder 3 CH₂-Gruppen, die nicht zueinander benachbart oder an X gebunden sind, durch Sauerstoff ersetzt sein können, und/oder eine CH₂-Gruppe auch durch Phenylen ersetzt sein kann, wobei Alkandiyl 1, 2 oder 3 Substituenten R^b aufweisen kann, die unabhängig voneinander ausgewählt sind unter OH und C₁-C₄-Alkyl;
R¹ Wasserstoff oder C₁-C₄-Alkyl bedeutet;
R² C₁-C₆-Alkyl, C₁-C₆-Alkoxy oder gegebenenfalls substituiertes Phenyl steht;
R¹ mit R² auch gemeinsam für C₃-C₆-Alkandiyl stehen kann oder
R¹ mit R^b auch gemeinsam für C₁-C₆-Alkandiyl stehen kann.Preferably, the 1,3-dicarbonyl groups have the following formula D1:

wherein
* means the bond to the carbon backbone of the polymer chain of P1;
X for a chemical bond or a group of the formulas

wherein the carbonyl group is bonded to the carbon backbone of the polymer chain and R ^{a is} hydrogen or C ₁ -C ₄ alkyl;
A is linear C ₁ -C ₁₀ alkanediyl in which 1, 2 or 3 CH ₂ groups which are not adjacent to one another or bonded to X may be replaced by oxygen, and / or a CH ₂ group also by phenylene may be substituted, wherein alkanediyl may have 1, 2 or 3 substituents R ^b , which are independently selected from OH and C ₁ -C ₄ alkyl;
R ^{1 is} hydrogen or C ₁ -C ₄ alkyl;
R ^{2 is} C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or optionally substituted phenyl;
R ¹ with R ² together may also be C ₃ -C ₆ alkanediyl or
R ¹ with R ^b together can also be C ₁ -C ₆ alkanediyl.

Here and in the following, the terms alkyl, alkoxy and alkanediyl represent collective terms for individual meanings. The term "C _n -C _m " in each case indicates the possible number of carbon atoms of a radical.

C ₁ -C ₆ -alkyl is, for example, an aliphatic, saturated hydrocarbon radical having 1 to 6 and in particular 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl, 2-methylpropyl (isobutyl) 1,1-dimethylethyl (tert-butyl), n-pentyl or n-hexyl.

alkoxy is an oxygen-bonded alkyl radical as previously defined, e.g. For methoxy, ethoxy, n-propoxy Etc.

Alkanediyl represents a linear or branched, divalent hydrocarbon radical. Linear alkanediyl is a radical of the formula (CH ₂ ) _m , where m is an integer in the range of 1 to 10. Examples of linear alkanediyl are methylene, 1,2-ethanediyl, 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,8-octanediyl, 1 , 9-nonanediyl and 1,10-decanediyl. Examples of branched alkanediyl are 1-methyl-1,2-ethanediyl, propane-1,1-diyl, propane-2,2-diyl, 2-methylpropane-1,2-diyl, 1,1-dimethylpropane-1,3 -diyl, 2,2-dimethylpropane-1,3-diyl etc.

The term "optionally substituted phenyl" means a phenyl radical having 1, 2, 3 or 4 substituents, typically C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, OH or halogen, such as chlorine, bromine or Iodine, are selected.

C ₁ -C ₁₀ -alkanediyl in which 1, 2 or 3 CH ₂ groups may be replaced by oxygen is, for example, a following radical: (CH ₂ ) _k O; (CH ₂ ) _m O (CH ₂ ) _n O; (CH ₂ ) _o O (CH ₂ ) _p O (CH ₂ ) _q O; wherein k is a number from 1 to 9 and in particular 2 to 6,
m and n independently of one another are an integer in the range from 1 to 6, in particular 2 to 4, where n + m is in the range from 2 to 8 and in particular in the range from 4 to 6;
o, p and q independently of one another are an integer in the range from 1 to 6, in particular 2 to 4, where o + p + q is in the range from 3 to 7 and in particular in the range from 4 to 6.

worin R^a die zuvor genannten Bedeutungen aufweist und insbesondere für Wasserstoff steht und worin die Carbonylgruppe an das Kohlenstoffrückgrat der Polymerkette gebunden ist;
A lineares, C₂-C₈-Alkandiyl oder eine Gruppe (CH₂)_k-O, worin k für eine ganze Zahl von 2 bis 8 und insbesondere 2 bis 6 steht und das Sauerstoffatom an die Carbonylgruppe der 1,3-Dicarbonyleinheit gebunden ist;
R^a Wasserstoff;
R¹ Wasserstoff; und
R² C₁-C₆-Alkyl oder C₁-C₆-Alkoxy, insbesondere C₁-C₄-Alkyl.In formula D1, the variables X, A, R ¹ and R ² independently of one another, but in particular together, have the following preferred meanings:
X is a group of formulas

wherein R ^{a has} the abovementioned meanings and is in particular hydrogen and in which the carbonyl group is bonded to the carbon backbone of the polymer chain;
A is linear, C ₂ -C ₈ alkanediyl or a group (CH ₂ ) _k -O in which k is an integer from 2 to 8 and in particular 2 to 6 and the oxygen atom is bonded to the carbonyl group of the 1,3-dicarbonyl unit is;
R ^a hydrogen;
R ^{1 is} hydrogen; and
R ^{2 is} C ₁ -C ₆ -alkyl or C ₁ -C ₆ -alkoxy, in particular C ₁ -C ₄ -alkyl.

worin * die zuvor genannten Bedeutungen aufweist, Y für O oder NH steht, R² die zuvor genannten Bedeutungen aufweist und insbesondere für C₁-C₄-Alkyl steht und A' für lineares C₂-C₆-Alkandiyl steht.In particular, the 1,3-dicarbonyl groups D present in polymer P1 have the following general formula D1 '

in which * has the abovementioned meanings, Y is O or NH, R ^{2 has} the abovementioned meanings and is in particular C ₁ -C ₄ -alkyl and A 'is linear C ₂ -C ₆ -alkanediyl.

In Typically, the polymer P1 becomes 0.01 to 2.5 moles, frequently 0.02 to 2 mol, especially 0.03 to 1.5 mol and especially 0.05 to 1 mol of 1,3-dicarbonyl groups D, especially those of the formula D1 or D1 ', per kg of polymer P1.

According to the invention, the reaction, ie the polymerization of the monomers M2, takes place in an aqueous polymerization medium. An aqueous polymerization medium is understood as meaning water as well as mixtures of water with one or more organic, water-miscible solvents. The proportion of organic, water-miscible solvents will typically not exceed 50% by volume, in particular 20% by volume and especially 10% by volume, based on the total amount of water and organic solvent. Examples of water-miscible organic solvents are C ₁ -C ₄ -alkanols, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, cyclic ethers, such as dioxane and tetrahydrofuran, and also alkylene carbonates, such as ethylene carbonate (2-oxo-1,3- dioxolane) and propylene carbonate (2-oxo-1,3-dioxane). Preferred aqueous polymerization medium is water.

According to the invention initiated the polymerization of the monomers M2 by an initiator system, which comprises a peroxidase and a peroxide source.

A peroxidase is understood as meaning an enzyme which catalyzes the oxidation of CH or CH ₂ groups by peroxides, such as hydrogen peroxide. During the oxidation, carbon radicals are intermediately formed by abstraction of hydrogen, the peroxide source serving as an acceptor for the abstracted hydrogen. Such enzymes are summarized under the enzyme class EC 1.11.1 (systematic name: hydrogen peroxide oxidoreductases). These include NADH peroxidases (EC 1.11.1.1), NADPH peroxidases (EC 1.11.1.2), fatty acid peroxidases (EC 1.11.1.3), peroxidases of the enzyme class EC 1.11.1.4, cytochrome C peroxidases (EC 1.11.1.5), Catalases (EC 1.11.1.6), peroxidases (EC 1.11.1.7), iodide peroxidases (EC 1.11.1.8), glutathione peroxidases (EC 1.11.1.9), chloride peroxidases (EC 1.11.1.10), L-ascorbate Peroxidases (EC 1.11.1.11), phospholipid-hydrogen peroxide-glutathione peroxidases (EC 1.11.1.12), manganese peroxidases (EC 1.11.1.13), lignin peroxidases (EC 1.11.1.14), peroxiredoxins (EC 1.11.1.15), tryptophan 2,3-dioxigenases (EC 1.11.1.14) and multipurpose peroxidase (versatile peroxidase, EC 1.11.16). In the process according to the invention peroxidases of the enzyme classes EC 1.11.1.5, 1.11.1.7, 1.11.1.10, 1.11.1.13 and 1.11.1.14 are preferred. These include in particular enzymes of the enzyme class EC 1.11.1.7 (Recommended name: peroxidase) is preferred. These include, for example, peroxidase from soybeans and horseradish peroxidase, as well as comparable enzymes of synthetic or natural origin. The peroxidases may be of natural origin or synthetic peroxidases, for example modified peroxidases. Examples of modified peroxidases are those having an increased temperature stability of, for example, up to 40 ° C, preferably up to 60 ° C or especially to 80 ° C (so-called termophilic peroxidases), peroxidases with increased activity at low temperatures (cryophilic peroxidases), eg. B. at temperatures below 20 ° C or even below 0 ° C. The peroxidases used can also be recombinant enzymes, ie enzymes which have been produced with the aid of genetically modified organisms. Such peroxidases also include homologs of authentic peroxidase, for example, versions with increased stability to chemical or thermal denaturation, increased activity at low temperatures, etc. The peroxidases useful in this invention also include those enzymes which have undergone post-translational modification. Such peroxidases are known to the person skilled in the art and are commercially available, for example as horseradish peroxidase from Sigma (number P-8250) or from Biosynth (number P-2000).

preferred Peroxidases have an activity at 25 ° C Purpurogallin of at least 1 U / mg and especially at least 5 U / mg, z. 1 to 1000 U / mg or 5 to 500 U / mg, especially 10 to 400 U / mg or aminoantipyrine of at least 1 U / mg, in particular at least 5 U / mg, z. B. 1 to 1000 U / mg or 5 to 500 U / mg, especially 10 to 400 U / mg.

The necessary to initiate the polymerization of the monomers M2 amount naturally depends on the peroxidase Activity of the peroxidase used and is typically in the range of 0.01 to 5 wt .-%, often in the range of From 0.02 to 2% by weight and in particular from 0.05 to 1.5% by weight, based on the total amount of polymer P1 and monomer M2.

When Peroxide sources are basically all compounds with a peroxide group into consideration. These include, for example organic peroxides and hydroperoxides, e.g. B. diazyl peroxides such as Dibenzoyl peroxide, mono- and dialkyl peroxides such as tert-butyl hydroperoxide, organic peracids such as peracetic acid, perbenzoic acid, Metachloroperbenzoic acid, alkali metal and alkaline earth metal peroxides, Peroxomonosulfuric acid and its salts, such as sodium and Potassium peroxomonosulfate, peroxodisulfuric acid and their Salts such as sodium, ammonium and potassium peroxodisulfate, as well as hydrogen peroxide. Preferred peroxide sources are hydrogen peroxide and substances, which release hydrogen peroxide under the reaction conditions Perborates, percarbonates, alkali metal and alkaline earth metal peroxides, Alkali metal carbonate perhydrates, hydrogen peroxide-urea adducts, Peroxomonosulphuric acid and its salts, and peroxodisulphuric acid and their salts. Particularly preferred peroxide source is hydrogen peroxide.

The amount of peroxide source is of minor importance to the process of the invention. It is usually 0.01 to 10 wt .-%, in particular 0.02 to 5 wt .-%, based on the total amount of the monomers M2, and calculated as the content of peroxide (O ₂ ).

• a) wenigstens ein monoethylenisch ungesättigtes Monomer a, das eine 1,3-Dicarbonylgruppe D aufweist, und
• b) wenigstens ein monoethylenisch ungesättigtes Monomer b, das keine 1,3-Dicarbonylgruppe D aufweist, und das mit dem Monomer a) radikalisch polymerisierbar ist, umfassen.

According to the invention, the polymerization takes place in the presence of a polymer P1 which has 1,3-dicarbonyl groups D. The polymer P1 is preferably a polymer having a backbone composed of carbon atoms, that is to say a polymer which is made up of ethylenically unsaturated monomer units, where the 1,3-dicarbonyl groups are attached to the carbon atoms directly or via a spacer as described above the backbone of the polymer chain are bonded. Accordingly, such polymers P1 are composed of ethylenically unsaturated monomers M1, which

• a) at least one monoethylenically unsaturated monomer a, which has a 1,3-dicarbonyl group D, and
• b) at least one monoethylenically unsaturated monomer b which has no 1,3-dicarbonyl group D and which is free-radically polymerizable with the monomer a).

Of the Proportion of monomers a, based on the total amount of monomers M1, typically in the range of 0.1 to 50 wt%, is common in the range of 0.2 to 30 wt .-%, in particular in the range of 0.5 to 15% by weight. Accordingly, the proportion of the monomers b typically 50 to 99.9% by weight, in particular 70 to 99.8% by weight and especially 85 to 99.5 wt .-%, based on the total amount of Monomers M1.

worin X, A, R¹ und R² die für Formel D1, und insbesondere die dort als bevorzugt angegebenen Bedeutungen aufweisen, und R³ für Wasserstoff oder C₁-C₄-Alkyl, insbesondere für Wasserstoff oder Methyl steht.Preferred monomers a can be described by the general formula A:

wherein X, A, R ¹ and R ^{2 have} the meanings given for formula D1, and in particular those given there as preferred, and R ^{3 is} hydrogen or C ₁ -C ₄ -alkyl, in particular hydrogen or methyl.

worin Y für O oder NH steht, R² eine der zuvor genannten Bedeutungen aufweist und insbesondere für C₁-C₄-Alkyl steht, R³ eine der zuvor angegebenen Bedeutungen aufweist und speziell für Wasserstoff oder Methyl steht und A' für lineares C₂-C₆-Alkandiyl steht.Particularly preferred monomers a can be described by the general formula A *

wherein Y is O or NH, R ^{2 has} one of the abovementioned meanings and is in particular C ₁ -C ₄ -alkyl, R ^{3 has} one of the meanings given above and is especially hydrogen or methyl and A 'is linear C ₂ -C ₆ alkanediyl.

Examples of monomers a the compounds A1 to A12 indicated in the following table: Y A ' R ² R ³ A1 O (CH ₂ ) ₂ CH ₃ H 3-Oxobutanoic acid 2-acryloxyethyl ester or 2- (acetylacetoxy) ethyl acrylate (AAEA) A2 O (CH ₂ ) ₃ CH ₃ H 3-Oxobutanoic acid 3-acryloxypropyl ester or 3- (acetylacetoxy) propyl acrylate (AAPrA) A3 O (CH ₂ ) ₄ CH ₃ H 3-Oxobutanoic acid 4-acryloxybutyl ester or 4- (acetylacetoxy) butyl acrylate (AABuA) A4 O (CH ₂ ) ₂ CH ₃ CH ₃ 3-Oxobutanoic acid 2-methacryloxyethyl ester or 2- (acetylacetoxy) ethyl methacrylate (AAEMA) A4 O (CH ₂ ) ₃ CH ₃ CH ₃ 3-Oxobutanoic acid 3-methacryloxypropyl ester or 3- (acetylacetoxy) propyl methacrylate (AAPrA) A6 O (CH ₂ ) ₄ CH ₃ CH ₃ 3-Oxobutanoic acid 4-methacryloxybutyl ester or 4- (acetylacetoxy) butyl methacrylate (AABuA) A7 NH (CH ₂ ) ₂ CH ₃ H 2- (acetylacetoxy) ethylacrylamide A8 NH (CH ₂ ) ₃ CH ₃ H 3- (acetylacetoxy) propylacrylamide A9 NH (CH ₂ ) ₄ CH ₃ H 4- (acetylacetoxy) butylacrylamide A10 NH (CH ₂ ) ₂ CH ₃ CH ₃ 2- (acetylacetoxy) ethylmethacrylamide A11 NH (CH ₂ ) ₃ CH ₃ CH ₃ 3- (acetylacetoxy) propylmethacrylamide A12 NH (CH ₂ ) ₄ CH ₃ CH ₃ 4- (acetylacetoxy) butylmethacrylamide

• b1: Vinylaromatische Monomeren wie Styrol, α-Methylstyrol, Vinylpyridine etc.
• b2: Vinylester und Allylester aliphatischer Monocarbonsäuren, insbesondere von C₁-C₁₈-Monocarbonsäuren wie Vinylacetat, Vinylproprionat, Vinylbutyrat, Vinylexanoat, Vinyllaurat, Vinylstearat sowie die entsprechenden Allylester;
• b3: N-Vinylamide aliphatischer Monocarbonsäuren wie N-Vinylformamid, N-Vinylacetamid, N-Vinylpropionamid, N-Vinylbutyramid, N-Vinlylauroylamid und N-Vinylstearylamid;
• b4: N-Vinyllactame wie N-Vinylpyrrolidon und N-Vinylcaprolactam;
• b5: Vinyl-substituierte Heteroaromaten wie N-Vinylpyrrol, N-Vinylpyrazol und N-Vinylimidazol sowie deren Quaternisierungsprodukte;
• b6: monethylenisch ungesättigte C₃-C₈-Monocarbonsäuren wie Acrylsäure, Methacrylsäure, Vinylessigsäure und Crotonsäure;
• b7: monoethylenisch ungesättigte C₄-C₈-Dicarbonsäuren wie Maleinsäure, Fumarsäure, Itaconsäure und Citraconsäure;
• b8: Ester monoethylenisch ungesättigter C₃-C₈-Monocarbonsäuren, insbesondere Ester der Acrylsäure und der Methacrylsäure, beispielsweise b8.1: Ester der vorgenannten monoethylenisch ungesättigten Monocarbonsäuren mit C₁-C₂₀-Alkanolen, insbesondere Ester der Acrylsäure und der Methacrylsäure wie Methylacrylat, Ethylacrylat, Propylacrylat, n-Butylacrylat, tert.- Butylacrylat, Isobutylacrylat, Hexylacrylat, 2-Ethylhexylacrylat, Heptylacrylat, 2-Propylheptylacrylat, Octylacrylat, Isononylacrylat, Decylacrylat, Dodecylacrylat, Tridecylacrylat, Isotridecylacrylat, Stearylacrylat und die entsprechenden Methacrylate wie Methylmethacrylat, Ethylmethacrylat, Propylmethacrylat, n-Butylmethacrylat, tert.-Butylmethacrylat, Isobutylmethacrylat, Hexylmethacrylat, 2-Ethylhexylmethacrylat, Heptylmethacrylat, 2-Propylheptylmethacrylat, Octylmethacrylat, Isononylmethacrylat, Decylmethacrylat, Dodecylmethacrylat, Tridecylmethacrylat, Isotridecylmethacrylat und Stearylmethacrylat; b8.2 Ester der vorgenannten Monocarbonsäuren mit C₅-C₈-Cycloalkanolen, Phenylalkanolen oder Phenoxyalkanolen, insbesondere Ester der Acrylsäure und der Methacrylsäure wie Cyclohexylacrylat, Cyclohexylmethacrylat, 2-Phenoxyethylacrylat, 2-Phenoxyethylmethacrylat, Benzylacrylat und Benzylmethacrylat; b8.3 funktionalisierten Ester der vorgenannten Monocarbonsäuren, insbesondere der Acrylsäure und der Methacrylsäure, z. B. Hydroxy-substituierte Alkylester wie 2-Hydroxyethylacrylat, 2-Hydroxyethylmethacrylat, 4-Hydroxybutylacrylat und 4-Hydroxybutylmethacrylat sowie Imidazolin-2-on-1-ylalkylester wie 2-(Imidazolin-2-on-1-yl)ethylacrylat und -methacrylat; b8.4 Ester der vorgenannten Monocarbonsäuren mit Poly-C₂-C₄-alkylenglykolen oder Poly-C₂-C₄-alkylenglykol-monoalkylethern, insbesondere Ester der Acrylsäure und der Methacrylsäure wie Polyethylenglykolacrylate, Polyethylenglykolmethacrylate, Polyethylenglykolmonomethyletheracrylat und Polyethylenglykolmonomethylethermethacrylat;
• b9: Mono- und Diester monoethylenisch ungesättigter C₄-C₈-Dicarbonsäuren mit C₁-C₂₀-Alkanolen, insbesondere die Mono- und Diester der Maleinsäure und der Fumarsäure, z. B. Dimethylmaleat, Di-n-butylmaleat und Di-n-butylfumarat;
• b10: Amide monoethylenisch ungesättigter C₃-C₈-Monocarbonsäuren, insbesondere der Acrylsäure und der Methacrylsäure, wobei die Amide primär sein können (Monomere b10.1) wie Acrylamid und Methacrylamid oder am Stickstoff durch hydrophobe Reste wie C₁-C₂₀-Alkyl, C₅-C₈.Cycloalkyl etc. (Monomere b10.2 und b10.3) oder durch hydrophile Reste wie C₁-C₄-Hydroxyalkyl, Imidazolin-2-an-1-yl-C₂-C₄-alkyl und dergleichen (Monomere b10.4 und B10.5) substituiert sein können;
• b11: Imide und Anhydride monoethylenisch ungesättigter C₄-C₈-Dicarbonsäuren wie Maleinsäureanhydrid, Maleinimid und Itaconsäureanhydrid;
• b12: Vinyl- und Allylether von Poly-C₂-C₄-alkylenglykolen oder von Poly-C₂-C₄-alkylenglykol-monoalkylethern;
• b13: Vinyl- und Allylether von C₁-C₂₀-Alkanolen; Vinylhalogeniden wie Vinylchlorid;
• b14: konjugierte C₄-C₈-Diene wie Butadien und Isopren (hierbei handelt es sich um ”monoethylenisch” ungesättigte Monomere, da bei der Polymerisation nur eine der beiden Doppelbindungen, gegebenenfalls unter Allylverschiebung, polymerisiert;
• b15: C₂-C₈-Monoolefine wie Ethen, Propen, 1-Buten, 2-Buten, Isobuten, 1-Penten, 1-Hexen und 1-Octen;
• b16: monoethylenisch ungesättigte C₃-C₈-Nitrile wie Acrylnitril und Methacrylnitril; sowie
• b17: monoethylenisch ungesättigten Sulfonsäuren und deren Salze, z. B. Vinylsulfonsäure, Allylsulfonsäure, Methallylsulfonsäure, Styrolsulfonsäure, 2-Acrylamido-2-methylpropansulfonsäure, 2-Methacrylamido-2-methylpropansulfonsäure, 2-Acrylamidoethansulfonsäure, 2-Methacrylamidoethansulfonsäure, 2-Acryloxyethansulfonsäure, 2-Methacryloxyethansulfonsäure, 3-Acryloxypropansulfonsäure und 2-Methacryloxypropansulfonsäure.

The nature of the monomers P1 constituting the polymer P1 depends primarily on the desired application and is of minor importance for the success of the process according to the invention. Suitable monomers b are, for example:

• b1: vinylaromatic monomers such as styrene, α-methylstyrene, vinylpyridines etc.
• b2: vinyl esters and allyl esters of aliphatic monocarboxylic acids, in particular C ₁ -C ₁₈ monocarboxylic acids such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyllexanoate, vinyl laurate, vinyl stearate and the corresponding allyl esters;
• b3: N-vinylamides of aliphatic monocarboxylic acids such as N-vinylformamide, N-vinylacetamide, N-vinylpropionamide, N-vinylbutyramide, N-vinyl-lauroylamide and N-vinylstearylamide;
• b4: N-vinyllactams such as N-vinylpyrrolidone and N-vinylcaprolactam;
• b5: vinyl-substituted heteroaromatics such as N-vinylpyrrole, N-vinylpyrazole and N-vinylimidazole and their quaternization products;
• b6: monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, such as acrylic acid, methacrylic acid, vinylacetic acid and crotonic acid;
• b7: monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, such as maleic acid, fumaric acid, itaconic acid and citraconic acid;
• b8: esters of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, in particular esters of acrylic acid and methacrylic acid, for example b8.1: esters of the abovementioned monoethylenically unsaturated monocarboxylic acids with C ₁ -C ₂₀ -alkanols, in particular esters of acrylic acid and of methacrylic acid, such as methyl acrylate , Ethylacrylate, propylacrylate, n-butylacrylate, tert-butylacrylate, isobutylacrylate, hexylacrylate, 2-ethylhexylacrylate, heptylacrylate, 2-propylheptylacrylate, octylacrylate, isononylacrylate, decylacrylate, dodecylacrylate, tridecylacrylate, isotridecylacrylate, stearylacrylate and the corresponding methacrylates Propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, 2-propylheptyl methacrylate, octyl methacrylate, isononyl methacrylate, decyl methacrylate, dodecyl methacrylate, tridecyl methacrylate, isotridecyl methacrylate and stearyl methacrylate; b8.2 esters of the abovementioned monocarboxylic acids with C ₅ -C ₈ -cycloalkanols, phenylalkanols or phenoxyalkanols, in particular esters of acrylic acid and of methacrylic acid, such as cyclohexyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, benzyl acrylate and benzyl methacrylate; b8.3 functionalized esters of the abovementioned monocarboxylic acids, in particular of acrylic acid and of methacrylic acid, eg. Hydroxy-substituted alkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate and 4-hydroxybutyl methacrylate and imidazolin-2-one-1-ylalkyl esters such as 2- (imidazolin-2-one-1-yl) ethyl acrylate and methacrylate ; b8.4 esters of the abovementioned monocarboxylic acids with poly-C ₂ -C ₄ -alkylene glycols or poly-C ₂ -C ₄ -alkylene glycol monoalkyl ethers, in particular esters of acrylic acid and of methacrylic acid, such as polyethylene glycol acrylates, polyethylene glycol methacrylates, polyethylene glycol monomethyl ether acrylate and polyethylene glycol monomethyl ether methacrylate;
• b9: Mono- and diesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids with C ₁ -C ₂₀ -alkanols, in particular the mono- and diesters of maleic acid and fumaric acid, eg. Dimethyl maleate, di-n-butyl maleate and di-n-butyl fumarate;
• b10: amides of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, in particular of acrylic acid and of methacrylic acid, where the amides may be primary (monomers b10.1) such as acrylamide and methacrylamide or on the nitrogen by hydrophobic radicals such as C ₁ -C ₂₀ -alkyl , C ₅ -C ₈ .Cycloalkyl etc. (monomers b10.2 and b10.3) or by hydrophilic radicals such as C ₁ -C ₄ -hydroxyalkyl, imidazolin-2-an-1-yl-C ₂ -C ₄ -alkyl and the like (monomers b10.4 and B10.5) may be substituted;
• b11: imides and anhydrides of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, such as maleic anhydride, maleimide and itaconic anhydride;
• b12: vinyl and allyl ethers of poly-C ₂ -C ₄ -alkylene glycols or of poly-C ₂ -C ₄ -alkylene glycol monoalkyl ethers;
• b13: vinyl and allyl ethers of C ₁ -C ₂₀ -alkanols; Vinyl halides such as vinyl chloride;
• b14: conjugated C ₄ -C ₈ dienes, such as butadiene and isoprene (these are "monoethylenically" unsaturated monomers, since only one of the two double bonds is polymerized in the polymerization, if appropriate under allyl shift;
• b15: C ₂ -C ₈ monoolefins such as ethene, propene, 1-butene, 2-butene, isobutene, 1-pentene, 1-hexene and 1-octene;
• b16: monoethylenically unsaturated C ₃ -C ₈ -nitriles such as acrylonitrile and methacrylonitrile; such as
• b17: monoethylenically unsaturated sulfonic acids and their salts, eg. For example, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, 2-acrylamidoethanesulfonic acid, 2-methacrylamidoethanesulfonic acid, 2-acryloxyethanesulfonic acid, 2-methacryloxyethanesulfonic acid, 3-acryloxypropanesulfonic acid and 2-methacryloxypropanesulfonic acid.

preferred Monomers b are monomers of groups b1, b6, b8 and b10, in particular Groups b1, b6, b8.1, b8.3 and b10.1.

Next The above-mentioned monomers b may constitute the polymer P1 Monomers M1 also multi-ethylenically unsaturated monomers include. Their share is usually not more than 2 wt .-%, in particular not more than 1 wt .-% and especially not more than 0.1 wt .-%, based on the total amount of monomers M1. Examples of these are diesters and triesters ethylenically unsaturated carboxylic acids, in particular the bis- and trisacrylates of diols or polyols having 3 or more OH groups, z. B. the bisacrylates and the bismethacrylates of ethylene glycol, Diethylene glycol, triethylene glycol, neopentyl glycol or polyethylene glycols, furthermore divinylbenzene, cycloalkenol acrylates and methacrylates, Divinyl and diallyl ethers of aliphatic or cycloaliphatic Diols, vinyl and allyl esters of acrylic acid and of methacrylic acid, Anhydrides of monoethylenically unsaturated monocarboxylic acid such as acrylic anhydride and methacrylic anhydride and the same.

ever according to the type of the polymer P1 constituent monomers M1 are the Polymers P1 become soluble in the aqueous polymerization medium or insoluble. Accordingly, the polymers P1 dissolved in the aqueous polymerization medium or suspended or dispersed form.

Therefore relates to a first preferred embodiment of the invention a process in which the polymer P1 is in the form of an aqueous Polymer solution is used.

In In another preferred embodiment, the polymer P1 used in the form of an aqueous polymer dispersion. In this aqueous polymer dispersion is the polymer P1 in the form of fine polymer particles. The particle diameter The polymer particles of the polymer P1 are preferably 2 μm do not exceed and are especially in the area from 10 nm to 1000 nm, especially in the range of 20 nm to 800 nm and in particular in the range of 25 nm to 500 nm.

The particle sizes of the polymer P1 given here are weight-average particle sizes, as can be determined by dynamic light scattering. Processes for this are familiar to the person skilled in the art, for example from H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p. 40ff and literature cited there as well H. Auweter, D. Horn, J. Colloid Interf. Sci. 105 (1985) 399 . D. Lilge, D. Horn, Colloid Polym. Sci. 269 (1991) 704 or H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429 ,

in the Traps of Water Soluble Polymers P1 include the polymer constituent monomers M1 as monomers b predominantly hydrophilic monomers, d. H. those with a water solubility above 50 g / l, in particular above 80 g / l (at 25 ° C and 1 bar). Examples of hydrophilic monomers are the Monomers a) and monomers from groups b4, b5, b6, b7, b8.3, b8.4, b10.1, b10.4, b10.5, b11, b12, b16 and b17, and N-vinylformamide and the monoesters from group b9. Preferred hydrophilic monomers in particular the monomers a and the monomers of the groups b6, b8.3 and b10.1.

Of the Proportion of hydrophilic monomers becomes water soluble in the case Polymers P1 usually at least 80 wt .-%, in particular at least 90 wt .-%, based on the total amount of the monomers b, and at least 50 wt .-%, in particular at least 80 wt .-%, based on the total amount the monomers M1, make up.

Next The hydrophilic monomers may be the water-soluble polymer P1 also copolymerized hydrophobic monomers in a limited amount contain. Hydrophobic monomers are understood as meaning monomers a water solubility below 50 g / l, in particular below 30 g / l (at 25 ° C and 1 bar).

typical Hydrophobic monomers are, for example, monomers of the aforementioned Groups b1, b2, b3 (except N-vinylformamide and N-vinylacetamide), b8.1, b8.2, the diesters from group b9, the monomers of the groups b10.2 and b10.3, the monomers of groups b13, b14 and b15. preferred hydrophobic monomers are in particular the monomers of groups b1, b8.1 and b8.2.

Of the Proportion of hydrophobic monomers becomes water soluble in the case Polymers P1 usually 50 wt .-%, in particular 30 wt .-%, based on the total amount of monomers M1, do not exceed.

in the Trap of water-insoluble polymers P1, in particular in the case of such polymers P1, in the form of an aqueous Polymer dispersion are used, the proportion the hydrophobic monomers on the monomers constituting the polymer M1 usually at least 50 wt .-%, in particular at least 70 Wt .-% and especially at least 80 wt .-%, based on the total amount the monomer P1 constituting the polymer P1. Accordingly is the proportion of hydrophilic monomers in the monomers M1 usually not more than 50 wt .-%, especially not more as 30 wt .-%, based on the total amount of monomers M1.

Provided the polymers P1 are used in the form of an aqueous dispersion contains the aqueous dispersion in the Usually at least one for stabilizing aqueous polymer dispersions usually used surface-active substance. Which includes anionic, nonionic and cationic emulsifiers and protective colloids.

preferred Emulsifiers are anionic and nonionic emulsifiers which are used in the Difference to the protective colloids usually a molecular weight below 2000 g / mol. Surface-active substances are typically in amounts of 0.2 to 10 wt .-%, preferably 0.5 to 5 wt .-%, based on the polymer P1 used.

The anionic emulsifiers include alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ -C ₂₀ ), of sulfuric monoesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: C ₈ -C ₂₀ ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ -C ₂₀ ), of alkylsulfonic acids (alkyl radical: C ₈ to C ₂₀ ), of sulfonated mono- and di-C ₆ -C ₁₈ -alkyldiphenyl ethers, as described in US Pat US Patent No. 4,269,749 and of alkylarylsulfonic acids (alkyl radical: C ₄ -C ₂₀ ). Other suitable anionic emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208 ,

Suitable nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO degree: 3 to 50, alkyl radical: C ₄ -C ₉ ), ethoxylates of long-chain alcohols (EO degree: 3 to 50, alkyl radical : C ₈ -C ₃₆ ), as well as polyethylene oxide / polypropylene oxide block copolymers. Preferred are ethoxylates of long-chain alkanols (alkyl radical: C ₁₀ -C ₂₂ , average degree of ethoxylation: 3 to 50) and particularly preferably those based on oxo alcohols and native alcohols with a linear or branched C ₁₂ -C ₁₈ -alkyl radical and a degree of ethoxylation of 8 until 50.

Suitable protective colloids are polyvinyl alcohol, including partially saponified polyvinyl acetates, starch and cellulose derivatives, carboxyl group-containing polymers such as homo- and copolymers of acrylic acid and / or methacrylic acid with comonomers such as styrene, olefins or hydroxyalkyl esters, or vinylpyrrolidone-containing homopolymers and copolymers, caseins, hydroxymethylcellulose, polyethers such as polyethylene oxides, ethylene oxide-propylene oxide block copolymers but also inorganic Pickering systems, which find particular application in a suspension polymerization. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart 1961, pp. 411-420 , Mixtures of emulsifiers and / or protective colloids can also be used.

The molecular weight of the polymer P1 is of secondary importance to the process according to the invention. The weight average molecular weight of polymer P1 is typically in the range of 5,000 daltons to 2 × 10 ⁶ daltons, often in the range of 10,000 daltons to 1 × 10 ⁶ daltons, and more particularly in the range of 20,000 to 500,000 daltons. The weight-average molecular weight can be determined in a manner known per se by gel permeation chromatography and by methods of light scattering.

in the Processes according to the invention are the polymers P1 typically in amounts of 0.01 to 20 parts by weight, often in amounts of 0.02 to 10 parts by weight, especially in amounts from 0.05 to 5 parts by weight and especially in amounts of 0.1 to 2 parts by weight, based on 1 part by weight of the monomers M2 used.

In the method of the invention can in step b basically any ethylenically unsaturated Monomers (hereinafter monomers M2) are polymerized. In the As a rule, these are monoethylenically unsaturated monomers M2, wherein the monomers M2 also small amounts, preferably not more as 2% by weight, especially not more than 1% by weight and especially not more than 0.1 wt .-% polyethylenically unsaturated Monomers, as indicated above for the monomers M1. In a preferred embodiment, the monomers include M2 no polyethylenically unsaturated monomers. Farther It is preferred that the monomers M2 are not monomers with a 1,3-dicarbonyl group (monomers a, as in connection with the monomers M1 defines).

Examples suitable monomers M2 are in particular those as monomers b mentioned monomers. Preferred monomers M2 are in particular from the groups of preferred monomers b, in particular from the groups b1, b6, b8 and b10, especially from groups b1, b6, b8.1, b8.3 and b10.1 selected.

According to one In the first embodiment, the monomers M2 comprise predominantly, d. H. at least 50% by weight, in particular at least 70% by weight and especially at least 80% by weight, based on the total weight of the monomers M2, hydrophobic monomers, ie those having a water solubility below 50 g / l and especially below 30 g / l at 25 ° C and 1 bar. Suitable hydrophobic monomers M2 of this embodiment are those in the aforementioned groups b1, b2, b3 (except N-vinylformamide and N-vinylacetamide), b8.1 and b8.2 monomers, the diesters from group b9 and the monomers from groups b10.2, b10.3, b13, b14 and b15. Preferred hydrophobic monomers are hereunder in particular the monomers of groups b1, b8.1 and b8.2.

In this embodiment, the proportion of hydrophilic monomers, ie monomers having a water solubility above 50 g / l and in particular above 80 g / l at 25 ° C and 1 bar, is usually not more than 50 wt .-%, in particular not more than 30 wt .-% and especially not more than 10 wt .-%, based on the total amount of the monomers M2. Suitable hydrophilic monomers are, in particular, monomers of groups b4, b5, b6, b7, b8.3, b8.4, b10.1, b10.4, b10.5, b11, b12, b16 and b17, and also N-vinylformamide and Monoester from group b9. Preferred hydrophilic monomers are, in particular, the monomers of groups b6, b8.3 and b10.1.

The according to this embodiment of the invention Method available polymers have accordingly hydrophobic side chains, resulting in reduced water solubility of the polymer. Depending on the used Polymer is obtained in this embodiment amphiphilic polymers, if the polymer used is P1 is a water-soluble polymer, or hydrophobic Polymers, when the polymer P1 is a water-insoluble Polymer acts.

typically, fall in this embodiment, the polymers in the form aqueous polymer dispersions. In these aqueous Polymer dispersions is the average particle diameter (weight average, determined by light scattering) of the polymer particles usually in the range of 10 nm to 2000 nm, often in the range of 50 nm to 1000 nm and especially in the range of 100 nm to 800 nm.

In A second embodiment of the invention comprises Monomers M2, based on the total weight of the monomers M2, predominantly, d. H. at least 50% by weight, in particular at least 70% by weight and especially to at least 90% by weight of hydrophilic monomers, d. H. monoethylenically unsaturated monomers with a water solubility of at least 50 g / l, in particular at least 80 g / l. suitable Hydrophilic monomers are, in particular, monomers of groups b4, b5, b6, b7, b8.3, b8.4, b10.1, b10.4, b10.5, b11, b12, b16 and b17, and N-vinylformamide and the monoesters from the group b9. preferred Hydrophilic monomers are in particular the monomers of the groups b6, b8.3 and b10.1.

Of the Proportion of hydrophobic monomers, d. H. those with a water solubility of not more than 50 g / l, especially not more than 30 g / l Accordingly, not more than 50 wt .-%, especially not more as 30 wt .-% and especially not more than 10 wt .-%, based on the total amount of monomers M2. Suitable hydrophobic monomers M2 this embodiment are in the aforementioned Groups b1, b2, b3 (except N-vinylformamide and N-vinylacetamide), b8.1, b8.2 monomers and the diesters from the group b9 and the monomers of groups b10.2, b10.3, b13, b14 and b15. preferred Hydrophobic monomers are hereunder in particular the monomers of Groups b1, b8.1 and b8.2.

Also in this embodiment may be used as polymers P1 both water-soluble polymers P1, as defined above, as well as water-insoluble polymers P1 are used, the former preferably in the form of an aqueous solution, the latter preferably in the form of an aqueous polymer dispersion be used.

Provided as polymer P1, a water-soluble polymer is used, one obtains in this embodiment of the invention Method usually water-soluble comb polymers.

Provided In this embodiment of the invention, a water-insoluble Polymer P1, in particular an aqueous dispersion of a water-insoluble polymers P1, receives in this embodiment, as a rule, an amphiphilic one Comb polymer having a hydrophobic backbone and a variety of hydrophilic ones Has side chains. These polymers are usually as well not water soluble and are in the form of an aqueous Polymer dispersion obtained. In these polymer dispersions the average particle diameter (volume average) usually in the range of 10 nm to 2000 nm, often in the range of 50 nm to 1000 nm and especially in the range of 100 nm to 800 nm.

in the The process according to the invention is usually carried out Proceed as follows to obtain the polymer P1 in the aqueous polymerization medium and, in addition, the enzyme, the peroxide source and the monomers M2 admits.

The Order of addition is generally of minor importance Importance. In general, however, you will get the peroxidase and at least a portion of the peroxide source to that in the aqueous polymerization medium give polymer P1 before adding the monomers M2.

The Addition of monomers M2 can be in one portion, in several portions or continuously with constant, increasing or decreasing Feed rate done.

The peroxide source can be added in one portion. In general, however, you will at least a subset, usually at least 10 wt .-%, in particular at least 20 wt .-%, based on the total amount of the peroxide source, prior to the addition of the monomers M2 in the polymerization together with the enzyme and the polymer P1 in the aqueous polymerization medium submit , and any remaining amount, ie not more than 90 wt .-%, in particular not more than 60 wt .-%, z. B. 10 to 90 wt .-%, in particular 20 to 60 wt .-% under polymerization. The addition can then be carried out in portions or continuously.

The Monomers M2 can be used as such, i. H. undiluted, or in the form of an aqueous solution or emulsion be added. If the monomers M2 in the form of an aqueous Emulsifying is used to stabilize the aqueous emulsion preferably at least one of the aforementioned surfactants Substances.

The Concentration of polymer P1 in the aqueous polymerization medium is usually in the range of 0.1 to 50 wt .-%, often in the range of 0.5 to 40 wt .-% and in particular in the range of 1 to 30 wt .-%, based on the total amount of polymer P1, monomer M2 and aqueous polymerization medium.

The Concentration of monomer M2 in the aqueous polymerization medium is at the beginning of the polymerization of the monomers M2 in the rule in the range of 0.1 to 40 wt .-%, often in the range of From 0.2 to 30% by weight and in particular from 0.5 to 25% by weight, based on the total amount of polymer P1, monomer M2 and aqueous Polymerization medium.

The Polymerization temperature depends of course the type of enzyme used and is typically in the range from 10 to 60 ° C, especially in the range of 20 to 40 ° C.

Of the pH of the aqueous polymerization medium in the polymerization the monomer M2 usually depends on the for the enzyme has optimal pH and is typically in the range from pH 2 to 7, in particular in the range of pH 2 to 5.

Of the Polymerization pressure is for the invention Procedures of minor importance and is typically at ambient pressure or in the range of 900 to 1100 mbar. higher Pressures can be applied when the monomers are fleeting.

The Polymerization of the monomers M2 in the presence of the polymer P1 can in the usual equipment for polymerization respectively. These include, stirred tanks, the batchwise or can be operated continuously, and possibly the usual Incorporation may have to increase the mixing. These include tube reactors and micro tube reactors, the also internals to increase the mixing may have the components.

at a continuous implementation of the polymerization You will usually do that, that you have a current, which the polymer P1 in the aqueous polymerization medium in contains dissolved or dispersed form, in a Reaction zone and there with the monomers M2, the peroxide source and the peroxidase brings into contact. The reaction zone can thereby as a reaction vessel, preferably with mixing agents the components is equipped, such as stirrer and internals, or designed as a tubular reactor. The obtained Polymer is in the form of its desired residence time aqueous solution or dispersion from the reaction zone discharged.

The Provision of the polymer P1 takes place in a manner known per se. In general, this one is the monomers M1 for a conventional Polymerize process. In the case of ethylenically unsaturated Monomers M1 are usually a radical Polymerization process, d. H. the polymerization of the monomers M1 is triggered by an initiator system.

When Initiator system are basically all for the radical polymerization of ethylenically unsaturated Monomers known initiators into consideration. This is it usually initiators based on organic or inorganic Peroxides, azo initiators or so-called redox initiator systems, excluding systems comprising a peroxide source and a peroxidase. The amount of initiator is usually 0.1 to 5 wt .-%, in particular 0.2 to 2 wt .-%, based on the total amount the monomers M1 to be polymerized.

• – Peroxidverbindungen: Hierzu zählen beispielsweise organische Peroxide und Hydroperoxide wie Acetylperoxid, Benzoylperoxid, Lauroylperoxid, tert.-Butylperoxy-isobutyrat, Caproylperoxid, Cumolhydroperoxid, tert.-Butylhydroperoxid, tert.-Amylhydroperoxid; anorganische Peroxide wie Wasserstoffperoxid, Peroxodischwefelsäure und deren Salze wie Ammonium-, Natrium und Kaliumperoxodisulfat;
• – Azoverbindungen wie 2,2'-Azobis-isobutyronitril, 2,2'-Azobis(2-methylbutyronitril), 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamid], 1,1'-Azobis(1-cyclohexancarbonitril), 2,2'-Azobis(2,4-dimethylvaleronitril), 2,2'-Azobis(N,N'-dimethylenisobutyroamidin) 2,2'-Azobis(N,N'-dimethylenisobutyroamidin), 2,2'-Azobis(2-methylpropioamidin), N-(3-Hydroxy-1,1-bis-hydroxymethylpropyl)-2-[1-(3-hydroxy-1,1-bis-hydroxymethyl-propylcarbamoyl)-1-methyl-ethylazo]-2-methyl-propionamid sowie N-(1-Ethyl-3-hydroxypropyl)-2-[1-(1-ethyl-3-hydroxypropylcarbamoyl)-1-methyl-ethylazo]-2-methyl-propionamid;
• – Redoxinitiatoren: hierunter versteht man Initiatorsysteme, die ein Oxidationsmittel, beispielsweise ein Salz der Peroxodischwefelsäure, Wasserstoffperoxid oder ein organisches Peroxid wie tert.-Butylhydroperoxid und ein Reduktionsmittel enthalten. Als Reduktionsmittel enthalten sie vorzugsweise eine Schwefelverbindung, die insbesondere ausgewählt ist unter Natriumhydrogensulfit, Natriumhydroxymethansulfinat und dem Hydrogensulfit-Addukt an Aceton. Weitere geeignete Reduktionsmittel sind phosphorhaltige Verbindungen wie phosphorige Säure, Hypophosphite und Phosphinate, sowie Hydrazin bzw. Hydrazinhydrat und Ascorbinsäure. Weiterhin können Redoxinitiatorsysteme einen Zusatz geringer Mengen von Redoxmetallsalzen wie Eisensalze, Vanadiumsalze, Kupfersalze, Chromsalze oder Mangansalze enthalten wie beispielsweise das Redoxinitiatorsystem Ascorbinsäure/Eisen(II)sulfat/Natriumperoxodisulfat.

Examples of suitable polymerization initiators are given below:

• - Peroxide compounds: These include, for example, organic peroxides and hydroperoxides such as acetyl peroxide, benzoyl peroxide, lauroyl peroxide, tert-butyl peroxy-isobutyrate, caproyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide; inorganic peroxides such as hydrogen peroxide, peroxodisulfuric acid and their salts such as ammonium, sodium and potassium peroxodisulfate;
• Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 1,1'- Azobis (1-cyclohexanecarbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (N, N'-dimethyleneisobutyroamidine) 2,2'-azobis (N, N'-dimethyleneisobutyroamidine), 2,2'-azobis (2-methylpropioamidine), N- (3-hydroxy-1,1-bis-hydroxymethylpropyl) -2- [1- (3-hydroxy-1,1-bis-hydroxymethyl-propylcarbamoyl) -1 methyl-ethylazo] -2-methylpropionamide and N- (1-ethyl-3-hydroxypropyl) -2- [1- (1-ethyl-3-hydroxypropylcarbamoyl) -1-methyl-ethylazo] -2-methyl- propionamide;
• - Redox initiators: this means initiator systems containing an oxidizing agent, for example a salt of peroxodisulfuric acid, hydrogen peroxide or an organic peroxide such as tert-butyl hydroperoxide and a reducing agent. As the reducing agent, they preferably contain a sulfur compound, which is particularly selected from sodium hydrogensulfite, sodium hydroxymethanesulfinate and the bisulfite adduct of acetone. Further suitable reducing agents are phosphorus-containing compounds such as phosphorous acid, hypophosphites and phosphinates, as well as hydrazine or hydrazine hydrate and ascorbic acid. Furthermore, redox initiator systems may contain an addition of small amounts of redox metal salts, such as iron salts, vanadium salts, copper salts, chromium salts or manganese salts, for example the redox initiator system ascorbic acid / iron (II) sulfate / sodium peroxodisulfate.

The Polymerization of the monomers M1 can be used to control the molecular weight the polymers P1 also in the presence of chain transfer agents (Controllers). Examples of suitable regulators are in particular compounds with an SH group, for. B. alkylmercaptans such as octylmercaptan, decylmercaptan, dodecylmercaptan, water-soluble Mercaptans such as mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoglycolic acid, 1,4-Dimercaptobutane-2,3-diol and the like. Suitable are also allylic compounds such as allyl alcohol and alkanols, e.g. For example, propanol, Isopropanol or tert-butanol. If desired, set typically the regulator in an amount of 0.01 to 3 wt .-%, in particular in an amount of 0.1 to 1 wt .-%, based on the to be polymerized monomers M1.

• a) wenigstens ein monoethylenisch ungesättigtes Monomer a, wie zuvor definiert, und
• b) wenigstens ein monoethylenisch ungesättigtes Monomer b, wie zuvor definiert, erfolgen.

The preparation of the polymers P1 can be carried out by customary processes for the polymerization of the monomers M1, in particular by a free-radical solution or emulsion polymerization of the monomers M1

• a) at least one monoethylenically unsaturated monomer a, as defined above, and
• b) at least one monoethylenically unsaturated monomer b, as defined above, take place.

Preferably the polymerization of the monomers M1 takes place in an aqueous state Solvent, so that, depending on the solubility of the polymer P1, an aqueous solution or a aqueous dispersion of the polymer P1 in the aqueous Solvent receives.

It however, it is also possible to polymerize the monomers To carry out M1 in an organic solvent, so that a solution of the polymer P1 in the organic Solvent receives. The solution thus obtained of the polymer P1 in the organic solvent, depending on the solubility of the polymer P1 in the aqueous polymerization medium, in a solution of the polymer P1 in an aqueous solvent or in an aqueous dispersion of the polymer P1 in the aqueous solvent become. In the case of water-soluble polymers P1 this usually succeeds by replacing the organic solvent with a aqueous solvent as defined above for example, by partially adding the organic solvent or completely distilled off and during the Abdestillierens replaced by water. In the case of water insoluble Polymers can be customary techniques for the production of Apply secondary dispersions, for example by the solution of the polymer P1 in an aqueous solvent enters and removes the organic solvent, or by isolating polymer P1 from the polymer solution, for example, by precipitation or removal of the solvent and then in the aqueous solvent emulsified or dispersed.

Preferably the provision of the polymer P1 is initiated by free-radical initiation Solution or emulsion polymerization of the monomers M1, comprising the monomers a and b in an aqueous solvent. This gives an aqueous solution directly or dispersion of the polymer P1 in the aqueous solvent, so that the dispersion or solution directly in the subsequent step ii can be used without requiring isolation or workup of the polymer P1 is required.

• i. das Polymer P1 durch eine radikalische Lösungs- oder Emulsionspolymerisation der Monomere M1, umfassend a) wenigstens ein monoethylenisch ungesättigtes Monomer a, das eine 1,3-Dicarbonylgruppe D aufweist; und b) wenigstens ein monoethylenisch ungesättigtes Monomer b, das keine 1,3-Dicarbonylgruppe D aufweist und das mit dem Monomer a) radikalisch copolymerisierbar ist, in einem wässrigen Lösungsmittel bereitstellt, wobei man eine wässrige Lösung oder Dispersion des Polymers P1 in dem wässrigen Lösungsmittel erhält, und
• ii. die Polymerisation der ethylenisch ungesättigter Monomere M2 in der in Schritt i. erhaltenen wässrigen Lösung oder Dispersion des Polymers P1 durchführt.

Accordingly, a preferred embodiment of the method according to the invention relates to a Procedure in which one

• i. the polymer P1 by a free-radical solution or emulsion polymerization of the monomers M1, comprising a) at least one monoethylenically unsaturated monomer a which has a 1,3-dicarbonyl group D; and b) providing at least one monoethylenically unsaturated monomer b having no 1,3-dicarbonyl group D and which is radically copolymerizable with the monomer a) in an aqueous solvent, wherein an aqueous solution or dispersion of the polymer P1 in the aqueous solvent receives, and
• ii. the polymerization of the ethylenically unsaturated monomers M2 in the step i. obtained aqueous solution or dispersion of the polymer P1.

to Polymerization of the monomers M1 may be the usual Polymerization techniques are used. Here are in particular Batch process in which the bulk, i. H. at least 60% by weight, in particular at least 80% by weight and often the total amount of polymerizing monomers M1 presented in the polymerization vessel as well as the monomer feed process, in which the bulk the monomers M1 to be polymerized, often at least 60 wt .-%, in particular at least 80 wt .-% and especially at least 90% by weight are added to the polymerization vessel in the course of the polymerization reaction, to call. For reasons of practicality is at larger approaches the polymerization often performed as a monomer feed.

Provided the polymerization of the monomers M1 as a radical aqueous Emulsion polymerization is carried out (i.e., when the Polymer P1 is insoluble in water) has become a Zulauffahrweise proved advantageous. This is especially true proved to be advantageous when the composition of the supplied Monomers in the course of the polymerization changes such that the proportion of monomers a to the monomers M1 in the course of the addition is increased. In particular, you will proceed so that you first the majority or the total amount of monomers b, which with the Monomers are a copolymerizable, polymerized and against End of the polymerization, the monomers a, optionally together with the residual amount of monomers b not yet fed, under polymerization in the polymerization vessel. In this way one achieves that the monomers a and thus also the 1,3-dicarbonyl groups D are in the outer region accumulate the polymer particles and so an efficient connection facilitate the polymer chains formed from the monomers M2.

By receives the inventive method one comb polymers with a polymeric main chain, the polymer P1 is formed, and polymeric side chains derived from the polymerized ones Monomers M2 are formed. This way is a very efficient one Control of the polymer architecture possible. This has happened shown that the connection exclusively via the 1,3-dicarbonyl groups take place. A polymerization of the monomers M2 without attachment to the polymer M1 does not occur or not appreciably Scope on, so that one by the inventive Method comb polymers that are not or not appreciably by polymers consisting exclusively of the monomers M2 are built up, are contaminated. The proportion of such exclusively from the monomers M2 built up polymers, based on the total weight of the invention available Comb polymer usually less than 15 wt .-%, in particular less as 5% by weight and especially less than 2% by weight. The size the polymeric side chains naturally depends on Behavior of the polymerized monomers M2 to the number of 1,3-dicarbonyl groups in polymer P1. Usually you will however, polymer chains with molecular weights> 10000 daltons, in particular> 50,000 daltons (weight average) receive. Such polymers are described with the above Methods of the prior art not yet accessible been.

The The following examples serve to illustrate the invention.

I. Abbreviations

• S

  styrene

  MA

  methyl acrylate

  EA

  ethyl acrylate

  EHA

  2-ethylhexyl acrylate

  n-BA

  n-butyl acrylate

  t-BA

  tert-butyl acrylate

  MMA

  methyl methacrylate

  MBA

  n-butyl methacrylate

  AT

  acrylonitrile

  AA

  acrylic acid

  MAA

  methacrylic acid

  AT THE

  acrylamide

  AAEA

  2- (acetylacetoxy) ethyl acrylate

  AAEMA

  2- (acetylacetoxy) ethyl methacrylate

  AAEBuA

  4- (acetylacetoxy) butyl acrylate

  SDS

  sodium

  NAPS,

  sodium

  t-DMP

  tert-dodecyl

  AIBN

  2,2'-azobisisobutyronitrile

  V-50

  2,2'-azobis (2-aminodinopropan) hydrochloride

  VA-086

  2,2'-azobis (2-methyl-N- (2-hydroxyethyl) propionamide)

  E1

  Emulan ^® NP3070 (Ethoxylated alkylphenol, BASF SE)

  E2

  Lutensol AT25 ^® (ethoxylated fatty alcohol, BASF SE)

  E3

  Lutensol TO11 ^® (ethoxylated fatty alcohol, BASF SE)

  PD

  particle size, determined by light scattering

  MW

  Molecular weight, weight average

  HRP

  Horseradish peroxidase

  MP

  manganese peroxidase

  LTV

  Laccase (trametes versicolor)

II. Analytics

The Determination of the molecular weights of the polymers P1 was carried out by Size exclusion chromatography (SEC) using a PL mixed B column and a refractive index detector (Differential refractometer of the company HP-1100 of the company Hewlett Packard) and a UV detector (type 2487 UV from Waters) at one temperature of 35 ° C in tetrahydrofuran at a flow rate of 1.2 ml / min. The reference material was polystyrene standards with a defined molecular weight.

The Determination of the particle size was carried out by means of Light scattering at 0.1 wt .-% samples of the polymers in water at 22 ° C with a Malvern High Performance Particle Sizer.

Of the Polymerization conversion of the monomers was determined by adding a defined amount of a sample of the aqueous polymer solution or dispersion 30 min. at 120 ° C (Libra Moisture Balance Fa. Satorius) completely dried and the so determined Solids content compared to the theoretical solids content.

III. Starting Materials:

When Peroxidase 1 became a salt-free, lyophilized horseradish peroxidase (HRP type I) with an activity of 100 U / mg (purpurogallin) the company Biosynth used.

When Peroxidase 2 became a salt-free, lyophilized manganese peroxidase MP with an activity of> 7000 U / g (Nematoloma frowardii) of the Fa. ASA Spezialchemi GmbH used.

To For comparison purposes, a commercial laccase (Trametes versicolor, LTV) from Fluka (No. 53739).

hydrogen peroxide was as a 30 wt .-% aqueous solution (medical Quality).

IV. General Polymerization Rules for the preparation of the polymers P1

Regulation 1: Emulsion Polymerization as a batch process

500 g of deionized water, the monomers M1 to be polymerized and the emulsifier were placed in a polymerization vessel. The mixture was stirred under nitrogen for 20 minutes and then warmed to 70 ° C. While stirring, the initiator and optional regulator were added and the temperature was maintained for a further 5 hours with stirring. The mixture was cooled to room temperature, thus obtaining an aqueous dispersion of the polymer P1. The feeds of polymer P1 are given in Table 1a. The properties of the Polymers P1 are given in Table 1b.

Regulation 2: Emulsion Polymerization with delayed addition of the monomer a

The Production took place analogously to regulation 1 with the difference that initially only the monomer b was submitted. 40 minutes after the beginning of the addition of the initiator, the monomer a was then added within 30 minutes to the polymerization mixture. In this way An aqueous polymer dispersion was obtained in which the polymerized monomers a in the outer region the polymer particles are enriched. The feeds of the Polymers P1 are given in Table 1a. The properties of the Polymers P1 are given in Table 1b.

Regulation 3: Solution Polymerization

In a polymerization vessel with stirrer 410 g of deionized water and the one to be polymerized were placed Monomers before. The mixture was under nitrogen atmosphere heated to 60 ° C with stirring. Then gave Add the initiator in one portion and keep the temperature 6 hours with stirring. Then cooled to room temperature and certain monomer conversion. One received in this way a clear aqueous solution of the Polymers P1. The feedstocks of polymer P1 are in Table 1a indicated. The properties of polymer P1 are shown in Table 1b indicated.

Protocol 4: Solution Polymerization with delayed addition of the monomer a

• * Polymerlösung

The preparation was carried out analogously to Regulation 3 with the difference that initially only the monomer b was submitted. Forty minutes after the start of the addition of the initiator, the monomer a was then added to the polymerization mixture over 30 minutes. In this way, an aqueous polymer solution having the properties shown in Table 2 was obtained. The feeds of polymer P1 are given in Table 1a. The properties of polymer P1 are given in Table 1b. Table 1a: Polymer P1 Manufacturing regulation Monomer a type, amount Monomer b type, amount Initiator, regulator emulsifier 1 1 AABuA, 2 g S, 40g NaPS, 1.3 g SDS, 1 g 2 1 AABuA, 2 g S, 40g NaPS, 1.3 g t-DMK 0.2 g SDS, 1 g 3 1 AAEA, 2 g S, 40g NaPS, 1.3 g t-DMK 0.2 g SDS, 1 g 4 1 AABuA, 2 g S, 20 g n-BA, 20 g NaPS, 1.3 g SDS, 1 g 5 1 AABuA, 2 g S, 15 g AA, 5 g NaPS, 1.3 g SDS, 1 g 6 2 AABua, 10 g S, 35 g NaPS, 0.5 g SDS, 0.03 g 7 2 AABua, 15 g S, 20 g NaPS, 0.5 g SDS, 0.03 g 8th 3 AABua, 1 g AM, 20 g NaPS, 0.5 g - 9 3 AABuA, 2 g AM, 20 g NaPS, 0.5 g - 10 3 AABua, 8 g AM, 20 g NaPS, 0.5 g - 11 3 AAEA, 8 g AM, 20 g NaPS, 0.5 g - 12 3 AABua, 1 g AA, 20g NaPS, 0.5 g - 13 4 AABuA, 2 g AA, 40g NaPS, 0.5 g - Table 1b: Polymer P1 MW [g / mol] PD [nm] Sales [%] 1 259 × 10 ³ 48 93 2 69 × 10 ³ 50 86 3 78 × 10 ³ 48 86 4 nd 45 91 5 nd 52 85 6 189 × 10 ³ 53 92 7 245 × 10 ³ 55 78 8th 63 × 10 ³ * 89 9 74 × 10 ³ * 92 10 48 × 10 ³ * 78 11 49 × 10 ³ * 90 12 56 × 10 ³ * 91 13 276 × 10 ³ * 79

• * Polymer solution

V. Enzymatically Catalyzed Graft Polymerization the monomers M2

When Peroxidase was horseradish peroxidase (HRP) or manganese peroxidase (MP) used. As the oxidizing agent was a 30 wt .-%, aqueous Hydrogen peroxide solution, medical grade Fa. Merck, used. Put in a polymerization vessel 10 g of the aqueous polymer dispersion prepared according to instructions 1 or 2, or 10 or 25 g of the polymer solution according to the preparation example 2 or 10 g of the polymer solution prepared according to instructions 3 or 4, and 40 g of deionized water before. For this one gave the Peroxidase and hydrogen peroxide in the specified in Table 2a Amount and stirred the mixture for 30 min. at 25 ° C under nitrogen. Subsequently, the polymer to be polymerized was added Monomer M2 in the amount indicated in Table 2a and stirred the mixture 24 hours. The resulting polymers were with respect the monomer conversion, the molecular weight and in the case of dispersions examined in terms of particle size.

• 1) Die angegebene Menge bezieht sich auf das Polymer in der Lösung oder Dispersion
• 2) Vergleichsbeispiel

Tabelle 2b: Beispiel MW [g/mol] PD [nm] Umsatz [%] 1 970 × 10³ 237 57 2 842 × 10³ 279 64 3 1232 × 10³ 167 74 4 754 × 10³ 178 79 5 882 × 10³ 240 67 6 491 × 10³ 157 n. d. 7 603 × 10³ 155 n. d. 8 1034 × 10³ 196 n. d. 9 668 × 10³ 214 49 10 855 × 10³ 168 63 11 437 × 10³ 162 n. d. V12²⁾ n. d. n. d. 27 13 n. d. n. d. 48 V14²⁾ 259 × 10³ 49 0 V15²⁾ 259 × 10³ 48 0 16 n. d. ¹⁾ 89 17 n. d. ¹⁾ 92 18 n. d. ¹⁾ 93 19 n. d. ¹⁾ 88 20 n. d. ¹⁾ 86 21 n. d. ¹⁾ 90 22 n. d. ¹⁾ 93 23 287 × 10³ 326 87 24 425 × 10³ 309 88 25 n. d. ¹⁾ 91 26 n. d. ¹⁾ 91 27 173 × 10^{3 1)} n. d. 28 539 × 10³ 102 57 29 762 × 10³ 126 64 30 936 × 10³ 137 82 31 869 × 10³ 129 85 32 927 × 10³ 116 89 33 704 × 10³ 324 68 34 974 × 10^{3 1)} 92

• 1) Polymerlösung
• 2) Vergleichsbeispiel

The starting materials are given in Table 2a. The properties of the polymers obtained are given in Table 2b. Table 2a: example Polymer P1 No., Quantity ¹⁾ Monomer M2 type, amount H ₂ O ₂ [g] Enzyme type, amount 1 1.10 g S, 2 g 0.05 HRP, 0.03 g 2 1.10 g S, 4 g 0.05 HRP, 0.03 g 3 1.10 g AM, 2 g 0.05 HRP, 0.3 g 4 1.10 g AM 4 g 0.05 HRP, 0.3 g 5 1.10 g MMA, 2 g 0.05 HRP, 0.3 g 6 2.10 g S, 2 g 0.05 HRP, 0.1 g 7 3.10 g S, 4 g 0.05 HRP, 0.03 g 8th 2.10 g S, 2 g 0.05 HRP, 0.05g 9 4.10 g S, 2 g 0.05 HRP, 0.03 g 10 4.10 g EA, 2 g 0.05 HRP, 0.03 g 11 5.10 g S, 2 g 0.05 HRP, 0.03 g V12 ²⁾ 1.10 g S, 2 g 0.05 LTV, 0.04 g 13 1.10 g S, 2 g 0.05 MP, 0.03 g V14 ²⁾ 1.10 g S, 2 g - HRP, 0.05g V15 ²⁾ 1.10 g S, 2 g 0.05 - 16 8.25 g AM, 1 g 0.03 HRP, 0.02 g 17 8.25 g AM, 1 g 0.03 HRP, 0.05g 18 8.25 g AM, 1 g 0.03 HRP, 0.1 g 19 8.25 g AM, 1 g 0.03 HRP, 0.4 g 20 8.25 g AM, 3 g 0.03 HRP, 0.02 g 21 8.25 g AM, 9 g 0.03 HRP, 0.02 g 22 9.25 g AA, 2 g 0.03 HRP, 0.02 g 23 9.25 g S, 2 g 0.03 HRP, 0.02 g 24 10.25 g S, 2 g 0.03 HRP, 0.02 g 25 10.25 g AM, 1 g 0.03 HRP, 0.02 g 26 11.25 g AM, 2 g 0.03 HRP, 0.02 g 27 12.25 g AM, 1 g 0.03 HRP, 0.02 g 28 6.10 g S, 2 g 0.05 HRP, 0.03 g 29 7.10 g S, 2 g 0.05 HRP, 0.03 g 30 7.10 g S, 2 g 0.05 HRP, 0.03 g 31 7.10 g S, 2 g 0.05 HRP, 0.03 g 32 7.10 g n BA, 2 g 0.05 HRP, 0.03 g 33 13.10 g S, 2 g 0.05 HRP, 0.03 g 34 13.10 g AM, 2 g 0.05 HRP, 0.03 g

• 1) The stated amount refers to the polymer in the solution or dispersion
• 2) Comparative Example

Table 2b: example MW [g / mol] PD [nm] Sales [%] 1 970 × 10 ³ 237 57 2 842 × 10 ³ 279 64 3 1232 × 10 ³ 167 74 4 754 × 10 ³ 178 79 5 882 × 10 ³ 240 67 6 491 × 10 ³ 157 nd 7 603 × 10 ³ 155 nd 8th 1034 × 10 ³ 196 nd 9 668 × 10 ³ 214 49 10 855 × 10 ³ 168 63 11 437 × 10 ³ 162 nd V12 ²⁾ nd nd 27 13 nd nd 48 V14 ²⁾ 259 × 10 ³ 49 0 V15 ²⁾ 259 × 10 ³ 48 0 16 nd ¹⁾ 89 17 nd ¹⁾ 92 18 nd ¹⁾ 93 19 nd ¹⁾ 88 20 nd ¹⁾ 86 21 nd ¹⁾ 90 22 nd ¹⁾ 93 23 287 × 10 ³ 326 87 24 425 × 10 ³ 309 88 25 nd ¹⁾ 91 26 nd ¹⁾ 91 27 173 × 10 ^{3 1)} nd 28 539 × 10 ³ 102 57 29 762 × 10 ³ 126 64 30 936 × 10 ³ 137 82 31 869 × 10 ³ 129 85 32 927 × 10 ³ 116 89 33 704 × 10 ³ 324 68 34 974 × 10 ^{3 1)} 92

• 1) polymer solution
• 2) Comparative Example

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• WO 00/78988 [0006]
• - US 4269749A [0051]

Cited non-patent literature

• H. Wiese in D. Distler, Aqueous Polymer Dispersions, Wiley-VCH 1999, Chapter 4.2.1, p. 40ff [0042]
• H. Auweter, D. Horn, J. Colloid Interf. Sci. 105 (1985) 399 [0042]
• D. Lilge, D. Horn, Colloid Polym. Sci. 269 (1991) 704 [0042]
• H. Wiese, D. Horn, J. Chem. Phys. 94 (1991) 6429 [0042]
• - Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192-208 [0051]
• - Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart 1961, pp. 411-420 [0053]

Claims (24)

Process for the preparation of comb polymers, full: i. Providing a polymer P1, the 1,3-dicarbonyl groups D, which at the carbon atom between the carbonyl groups 1 or Carry 2 hydrogen atoms; and ii. Polymerization ethylenic unsaturated monomers M2 in the presence of the polymer P1 in an aqueous polymerization medium, wherein the polymerization the monomer M2 is initiated by an initiator system which has a Peroxidase (EC 1.11.1) and a peroxide source. Process according to claim 1, wherein the polymer P1 is 0.01 to 2.5 moles of 1,3-dicarbonyl groups D, per kg of polymer P1. Method according to one of the preceding claims, wherein the 1,3-dicarbonyl groups are present in the form of functional groups of the formula D1:

wherein * denotes the bond to the carbon backbone of the polymer chain of P1; X for a chemical bond or a group of the formulas

wherein the carbonyl group is bonded to the carbon backbone of the polymer chain and R ^{a is} hydrogen or C ₁ -C ₄ alkyl; A is linear C ₁ -C ₁₀ alkanediyl in which 1, 2 or 3 CH ₂ groups which are not adjacent to one another or bonded to X may be replaced by oxygen, and / or a CH ₂ group also by phenylene may be substituted, wherein alkanediyl may have 1, 2 or 3 substituents R ^b , which are independently selected from OH and C ₁ -C ₄ alkyl; R ^{1 is} hydrogen or C ₁ -C ₄ alkyl; R ^{2 is} C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or optionally substituted phenyl; R ¹ with R ² together may also be C ₃ -C ₆ -alkanediyl or R ¹ with R ^b together may also be C ₁ -C ₆ -alkanediyl. Process according to claim 3, wherein the 1,3-dicarbonyl groups are in the form of functional groups of formula D1 ':

in which * has the abovementioned meanings, Y is O or NH, R ^{2 is} C ₁ -C ₄ -alkyl and A 'is linear C ₂ -C ₆ -alkanediyl. Method according to one of the preceding claims, wherein the peroxidase under peroxidases of the enzyme class EC 1.11.1.7 is selected. Method according to one of the preceding claims, wherein the peroxidase in an amount of 0.01 to 2 wt .-%, based based on the total amount of polymer P1 and monomers M2. Method according to one of the preceding claims, wherein the peroxide source is hydrogen peroxide and hydrogen peroxide releasing substances is selected. Method according to one of the preceding claims, wherein the polymer P1 is in the form of an aqueous polymer dispersion is used. Method according to one of claims 1 to 7, wherein the polymer P1 in the form of an aqueous polymer solution is used. Method according to one of the preceding claims, wherein the polymer P1 is ethylenically unsaturated Monomers M1 is constructed, wherein monomers M1 include: a) at least one monoethylenically unsaturated monomer a, which has a 1,3-dicarbonyl group D; and b) at least a monoethylenically unsaturated monomer b, which is no Has 1,3-dicarbonyl D and that with the monomer a) radical is copolymerizable. Method according to one of the preceding claims, where you are i. the polymer P1 by a radical solution or emulsion polymerization of the monomers M1 a) at least one monoethylenically unsaturated monomer a, which has a 1,3-dicarbonyl group D; and b) at least a monoethylenically unsaturated monomer b, which is no Has 1,3-dicarbonyl D and that with the monomer a) radical is copolymerizable, in an aqueous solvent provides, wherein an aqueous solution or Dispersion of polymer P1 in the aqueous solvent receives, and ii. the polymerization of ethylenic unsaturated monomers M2 in the in step i. received aqueous solution or dispersion of the polymer P1 performs. The method of claim 10 or 11, wherein the Polymer P1 constituent monomers M1 include: a) 0.1 to 50 wt .-%, based on the total amount of monomers M1, at least a monoethylenically unsaturated monomer a; and b) From 50 to 99.9% by weight, based on the total amount of monomers M1, at least one monoethylenically unsaturated monomer b. A process according to any one of claims 10 to 12 wherein the monomers a of general formula A are:

wherein X is a chemical bond or a group of the formulas

wherein the polymer chain is bonded and R ^{a is} hydrogen or C ₁ -C ₄ alkyl; A is linear C ₁ -C ₁₀ alkanediyl in which 1, 2 or 3 CH ₂ groups which are not adjacent to one another or bonded to X may be replaced by oxygen, and / or a CH ₂ group also by phenylene may be substituted, wherein alkanediyl may have 1, 2 or 3 substituents R ^b , which are independently selected from OH and C ₁ -C ₄ alkyl; R ^{1 is} hydrogen or C ₁ -C ₄ alkyl; R ^{2 is} C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy or optionally substituted phenyl; R ¹ with R ² together may also be C ₃ -C ₆ -alkanediyl or R ¹ with R ^b together may also be C ₁ -C ₆ -alkanediyl; and R ^{3 is} hydrogen or C ₁ -C ₄ alkyl. A process according to any one of claims 10 to 13, wherein the monomers a of the general formula A * obey:

wherein Y is O or NH, R ^{2 is} C ₁ -C ₄ alkyl, R ^{3 is} hydrogen or methyl and A 'is linear C ₂ -C ₆ alkanediyl. A process as claimed in any of claims 10 to 14, wherein the monomers b are selected from vinylaromatic monomers, vinyl esters and allyl esters of aliphatic monocarboxylic acids, N-vinylamides of aliphatic monocarboxylic acids, N-vinyllactams, vinyl-substituted heteroaromatics, monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, the esters of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, the mono- and diesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, the amides of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, the Amides, imides and anhydrides of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, the vinyl and allyl ethers of poly-C ₂ -C ₄ -alkylene glycols, vinyl halides, conjugated C ₄ -C ₈ -dienes, C ₂ -C ₈ - Monoolefins and monoethylenically unsaturated C ₃ -C ₈ nitrites. Process according to one of the preceding claims, wherein the monomers M2 are selected from vinylaromatic monomers, vinyl esters and allyl esters of aliphatic monocarboxylic acids, N-vinylamides of aliphatic monocarboxylic acids, N-vinyllactams, vinyl-substituted heteroaromatics, monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, monoethylenically unsaturated C C ₄ -C ₈ -dicarboxylic acids, the esters of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, the mono- and diesters of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, the amides of monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, the amides, imides and anhydrides of monoethylenically unsaturated C ₄ -C ₈ -dicarboxylic acids, the vinyl and allyl ethers of poly-C ₂ -C ₄ -alkylene glycols, vinyl halides, conjugated C ₄ -C ₈ -dienes, C ₂ -C ₈ -monoolefins and monoethylenically unsaturated C ₃ -C ₈ nitrites. Method according to one of the preceding claims, wherein the monomers M2 in an amount of 0.01 to 20 parts by weight, are used based on 1 part by weight of the polymer P1. Method according to one of the preceding claims, wherein the monomers M2 to at least 50 wt .-%, based on the total weight of the monomers M2, monomers with a water solubility below 50 g / L at 25 ° C. The method of claim 18, wherein the polymer is P1 is used in the form of an aqueous polymer dispersion. The method of claim 18, wherein the polymer is P1 used in the form of an aqueous polymer solution becomes. Method according to one of claims 1 to 17, wherein the monomers M2 to at least 50 wt .-%, based on the Total weight of monomers M2, monomers with a water solubility above 50 g / L at 25 ° C. The method of claim 21, wherein the polymer is P1 is used in the form of an aqueous polymer dispersion. The method of claim 21, wherein the polymer is P1 used in the form of an aqueous polymer solution becomes. Comb polymer obtainable by a process according to one of the preceding claims.