Method for the production of an aqueous polymer dispersion

The present invention relates to a process for preparing an aqueous polymer dispersion by polymerization of at least one ethylenically unsaturated monomer B in an aqueous medium in the presence of particles of at least one polymer A (polymer particles A) and at least one dispersant, which is characterized the polymerization of the at least one ethylenically unsaturated monomer B takes place in the presence of polymer particles A having a weight-average particle diameter ≥ 1 nm, wherein the polymer A is either<ol id="ol0001" compact="compact" ol-style=""><li>a) by a polymerization initiated with at least one free radical initiator or</li><li>b) by a polymerization initiated with at least one transition metal complex</li></ol>of at least one ethylenically unsaturated monomer A (monomer A) was obtained and the polymerization of the at least one ethylenically unsaturated monomer B (monomer B)<ol id="ol0002" compact="compact" ol-style=""><li>i) in the case a) by at least one transition metal complex and</li><li>ii) in case b) by at least one radical initiator</li></ol>is initiated.

The aqueous polymer dispersions obtainable by the process according to the invention can be used as binders in adhesives, sealants, plastic plasters, paper coating slips, paints, for producing nonwovens and for modifying mineral binders or other plastics. Similar fields of application are also available for the polymer powders obtainable from the aqueous polymer dispersions.

Aqueous polymer dispersions (latices) are well known. These are fluid systems which contain disperse polymer beads (so-called polymer particles) in the form of a dispersed phase in aqueous dispersion medium consisting of a plurality of intimately interlaced polymer chains. The weight-average diameter of the polymer particles is often in the range of 10 to 5000 nm.

As well as polymer solutions in the evaporation of the solvent, aqueous polymer dispersions have the potential for the formation of polymer films on evaporation of the aqueous dispersing medium, which is why they are used in particular as a binder. Due to their environmentally friendly properties, they are becoming increasingly important.

The preparation of aqueous polymer dispersions is frequently carried out by free-radically initiated aqueous emulsion polymerization [cf. eg Encyclopedia of Polymer Science and Engineering, Vol. 8, page 659 ff. (1987); DC Blackley, in High Polymer Latices, Vol. 1, page 35 ff. (1966); H. Warson, The Applications of Synthetic Resin Emulsions, page 246 ff., Chapter 5 (1972); D. Diederich, Chemistry in Our Time 24, pages 135 to 142 (1990); Emulsion Polymerization, Interscience Publishers, New York (1965); DE-A 40 03 422 and dispersions of synthetic high polymers, F. Hölscher, Springer-Verlag, Berlin 1969]. Characteristic of this process is that so-called free-radical formers are used as polymerization catalysts and, as main monomers, generally so-called polar monomers.

The preparation of multiphase aqueous polymer dispersions by free-radically initiated aqueous emulsion polymerization of ethylenically unsaturated compounds (monomers) is also well known to the person skilled in the art. Examples thereof can be found in EP-A 955323, US-A 4,683,269 and in Billig-Peters, "Core-shell dispersions using polymeric azo initiators", Dissertation University of Bayreuth, 1991.

On the other hand, a large number of polymerization catalysts are known whose polymerization effect is based not on radical formation but on a so-called monomer insertion. In particular so-called non-polar monomers are suitable for these polymerization processes. If anything, polar monomers are used only to a minor extent to modify the polymer properties. The polymerization catalysts used for these polymerization processes are in particular catalytically active transition metal complexes or Transition metal complexes in combination with compounds that activate the transition metal complexes, so-called activators. Due to the usually high sensitivity to hydrolysis of the transition metal complexes or Transition metal complex / activator combinations, these polymerization reactions are usually carried out in the form of a bulk polymerization, wherein the monomer is simultaneously reactant and solvent or in the form of a solution polymerization, wherein a nonaqueous, often aprotic organic solvent both the transition metal complex or the transition metal complex / activator combination containing monomer and polymer formed dissolved. Examples include the writings DE-A 10017660, DE-A 10118633, Leclerc et al., Angew. Chem., Int. Ed. Engl. 1998, 37, pages 922ff., Ziegler, Angew. Chem., 1955, 67, pages 541ff., Natta, J. At the. Chem. Soc. 1962, 84, pages 1488ff. as well as Sinn and Kaminsky, Adv. Organomet. Chem. 1980, 18, pages 99ff ..

Recently, the polymerization of monomers by monomer insertion in aqueous medium with hydrolysis-stable transition metal complexes or reinforced Transition metal complex / activator combinations reported. Exemplified here are the writings of Mecking, Angew. Chem. Int. Ed. 2001, 40, pages 534 to 540, Bauer and Mecking, Angew. Chem. Int. Ed. 2001, 40, pages 3020 to 3022, Mecking et al. Chem. Commun. 2000, pages 301 and 302, Tomov et al., Macromol. Symp. 2000, 150, pages 53 to 58 and the published patent applications WO 01/44325, WO 00/20464, DE-A 2923206 and DE-A 3345785.

The polymerization of monomers with carbon monoxide in an aqueous medium via a Monomereninsertion with hydrolysis-stable transition metal complexes or Transition metal complex / activator combinations are known. Examples of this can be found in Held et al., Macromolecules 2002, 35, pages 3342 to 3347, Lindner et al., J. Organomet. Chem. 2000, 602, pages 173ff., Sheldon et al., Angew. Chem. 2000, 112, pages 825ff. and in the published patent applications WO 00/63277, DE-A 19829520, DE-A 19829520, DE-A 19917920 and DE-A 10061877.

In addition, conjugated dienes, such as butadiene, can be polymerized in an aqueous medium with hydrolysis-stable transition metal complexes or transition metal complex / activator combinations by insertion [see, for example, Ono and Kato, J. Polym. Sci. A. 2000, 38, pages 1083 to 1089, Rinehart, J. Polym. Sci. C. 1969, 27, pages 7 to 25 and DE-A 2332921 and EP-A 152175].

Furthermore, German patent application DE-A 10322466.1, unpublished, discloses the polymerization of ethylenically unsaturated monomers in an aqueous medium, carried out by means of a solid polymerization catalyst, the German patent application DE-A 10229977.3 likewise not prepublished, the corresponding polymerization by means of polymerization catalysts contained in wax particles and the German patent application DE-A 10133042.1, also not prepublished, the preparation of aqueous polymer dispersions by transition-metal complex-catalyzed polymerization of ethylenically unsaturated compounds in the presence of Carbon monoxide by means of a Miniemulsionspolymerisationsverfahrens.

The preparation of multiphase aqueous polymer dispersions by polymerization of ethylenically unsaturated monomers by means of hydrolysis-stable transition metal complexes or transition metal complex / activator combinations is also well known to the person skilled in the art. Examples of these are found, for example, in Ono and Kato, J. Polym. Sci. A. 2000, 38, pages 1083-1089.

The preparation of aqueous polymer dispersions by means of free-radical emulsion polymerization has the advantage that the polymer properties, for example the glass transition temperature, can be varied widely by suitable selection of the monomers used for the polymerization and the auxiliaries, such as free-radical initiators, regulators, etc. represent low-cost connections. However, it is disadvantageous that the ethylenically unsaturated compounds customarily used for the polymerization as main monomers, such as esters of acrylic or methacrylic acid, styrene, vinyl chloride, vinylidene chloride and the vinyl esters of organic monocarboxylic acids are relatively expensive due to the reaction steps required for their preparation, or readily available monomers, such as ethene, radically often polymerize only slowly. On the other hand, for the preparation of aqueous polymer dispersions by means of transition metal complex-catalyzed polymerization, it is possible to use readily available and rapidly reacting nonpolar monomers, such as ethene, propene, butene, butadiene, etc. can be used, while polar monomers such as esters of acrylic or methacrylic acid, styrene, vinyl chloride, vinylidene chloride and vinyl esters of organic monocarboxylic acids, although also can be used, but often react much slower. A further disadvantage is that the metal complexes suitable for transition-metal complex-catalyzed polymerization are generally more expensive than the free-radical initiators used for free-radically initiated aqueous emulsion polymerization.

Against this background of the prior art, the object of the present invention was to provide a process for the preparation of aqueous polymer dispersions, which combines the advantages of the free-radically initiated polymerization and the transition metal complex-catalyzed polymerization in itself.

Accordingly, the method defined above was found.

Process is essential, that then, when the polymer A was obtained by a polymerization of at least one ethylenically unsaturated monomer A initiated by at least one free-radical initiator, the polymerization of the at least one ethylenically unsaturated monomer B is initiated by at least one transition metal complex (process 1) and then when the polymer A is replaced by a, with at least one transition metal complex initiated polymerization of at least one ethylenically unsaturated monomer A was obtained, the polymerization of the at least one ethylenically unsaturated monomer B is initiated by at least one free-radical initiator (process 2).

As at least one ethylenically unsaturated monomer for the free-radically initiated polymerization (monomers A in process 1 and monomers B in process 2), radically polymerizable ethylenically unsaturated monomers are particularly suitable in a simple manner, such as ethylene, vinylaromatic monomers, like styrene, α-methyl styrene, o-chlorostyrene or vinyltoluenes, halides, such as vinyl chloride or vinylidene chloride, Esters of vinyl alcohol and 1 to 18 carbon atoms monocarboxylic acids, like vinyl acetate, propionate, Vinyl n-butyrate, Vinyl laurate and vinyl stearate, Esters of preferably from 3 to 6 carbon atoms having α, β-monoethylenically unsaturated mono- and dicarboxylic acids, especially acrylic acid, methacrylic acid, maleic acid, Fumaric acid and itaconic acid, with generally 1 to 12, preferably 1 to 8 and in particular 1 to 4 C atoms alkanols, such as especially acrylic and methacrylic acid methyl, ethyl, -n-butyl-, -Isobutyl-, pentyl, hexyl, -heptyl, octyl, nonyl, decyl and 2-ethylhexyl esters, Fumaric and maleic acid dimethyl ester or di-n-butyl ester, Nitriles of α, β-monoethylenically unsaturated carboxylic acids, like acrylonitrile, methacrylonitrile, fumarodinitrile, Maleic dinitrile and C_4-8-conjugated dienes, such as 1,3-butadiene and isoprene. The monomers mentioned usually form the main monomers which, based on the total amount of monomers, account for more than 50% by weight, preferably more than 80% by weight. As a rule, these monomers in water at normal conditions [20 ° C, 1 bar (absolute)] only a moderate to low solubility.

Monomers which have an increased water solubility under the abovementioned conditions are those which either have at least one acid group and / or their corresponding anion or at least one amino, amido, ureido or N-heterocyclic group and / or their nitrogen protonated or alkylated ammonium derivatives. Examples include α, β-monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as Acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic, Acrylamide and methacrylamide, also vinylsulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, Styrenesulfonic acid and its water-soluble salts and N-vinylpyrrolidone, 2-vinylpyridine, 4-vinylpyridine, 2-vinylimidazole, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl methacrylate, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-diethylamino) ethyl methacrylate, 2- (N-tert-butylamino) ethyl methacrylate, N- (3-N ', N'-dimethylaminopropyl) methacrylamide and 2- (1-imidazolin-2-onyl) ethyl methacrylate. In the normal case, the abovementioned monomers are used only as modifying monomers in amounts, based on the total monomer amount, of less than 10% by weight, preferably less than 5% by weight.

Monomers, which usually increase the internal strength of the films of the polymer matrix, usually have at least one epoxy, hydroxy, N-methylol or carbonyl group, or at least two non-conjugated ethylenically unsaturated double bonds. Examples include two vinyl radicals containing monomers, two vinylidene radicals having monomers and two alkenyl radicals having monomers. Particularly advantageous are the diesters of dihydric alcohols with α, β-monoethylenically unsaturated monocarboxylic acids, among which acrylic and methacrylic acid are preferred. Examples of such two non-conjugated ethylenically unsaturated double bonds monomers are alkylene glycol diacrylates and - dimethacrylates, such as ethylene glycol diacrylate, 1,2-propylene glycol diacrylate, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol diacrylates and ethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol dimethacrylate and divinylbenzene, vinyl methacrylate, vinyl acrylate, allyl methacrylate, allyl, diallyl maleate, diallyl fumarate, methylenebisacrylamide, Cyclopentadienylacrylat, Triallyl cyanurate or triallyl isocyanurate. Of particular importance in this context are the methacrylic acid and acrylic acid-C₁-C_8thHydroxyalkyl esters such as n-hydroxyethyl, n-hydroxypropyl or n-hydroxybutyl acrylate and methacrylate and compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate. Frequently, the abovementioned monomers are used in amounts of up to 10% by weight, but preferably less than 5% by weight, in each case based on the total amount of monomers.

Monomer mixtures which are particularly suitable for use according to the invention for the free-radical polymerization stage are those which<ul id="ul0001" list-style="dash"><li>50 to 99.9 wt .-% esters of acrylic and / or methacrylic acid having 1 to 12 carbon atoms alkanols and / or styrene, or</li><li>50 to 99.9 wt .-% of styrene and / or butadiene, or</li><li>50 to 99.9 wt .-% of vinyl chloride and / or vinylidene chloride, or</li><li>40 to 99.9% by weight of vinyl acetate, vinyl propionate, vinyl esters of versatic acid and / or vinyl esters of long-chain fatty acids</li></ul>contain.

In particular, according to the invention, such monomer mixtures can be used for the free-radical polymerization stage, which<ul id="ul0002" list-style="dash"><li>0.1 to 5 wt .-% of at least one 3 to 6 C-atoms having α, β-monoethylenically unsaturated mono- and dicarboxylic acid and / or their amide and</li><li>50 up to 99.9% by weight of at least one ester of acrylic and / or methacrylic acid having alkanols and / or styrene having 1 to 12 C atoms, or</li><li>0.1 to 5 wt .-% of at least one 3 to 6 C-atoms having α, β-monoethylenically unsaturated mono- and dicarboxylic acid and / or their amide and</li><li>50 to 99.9 wt .-% of styrene and / or butadiene, or</li><li>0.1 to 5 wt .-% of at least one 3 to 6 C-atoms having α, β-monoethylenically unsaturated mono- and dicarboxylic acid and / or their amide and</li><li>50 to 99.9 wt .-% of vinyl chloride and / or vinylidene chloride, or</li><li>0.1 to 5 wt .-% of at least one 3 to 6 C-atoms having α, β-monoethylenically unsaturated mono- and dicarboxylic acid and / or their amide and</li><li>40 to 99.9% by weight of vinyl acetate, vinyl propionate, vinyl esters of versatic acid and / or vinyl esters of long-chain fatty acids</li></ul>contain.

Correspondingly, the free-radical polymerization gives polymers which are synthesized from the abovementioned monomers in copolymerized form.

It is important that the monomers or monomer mixtures can also be polymerized in the stepwise or gradient procedure known to those skilled in the art. It should also be noted at this point that in the context of this document, the term monomer should also include monomer mixtures and the term polymer also copolymers.

It is essential that the polymer particles A are frequently used as stable aqueous dispersions in both processes. These can be present both in the form of a primary and in the form of a secondary dispersion.

The preparation of an aqueous secondary polymer dispersion in process 1, for example via a free-radical solution polymerization, introduction of this solution polymer with removal of the solvent in the aqueous medium to form an aqueous dispersion of the polymer A, is familiar to the expert (see, for example, EP-A 467 906, EP-A). A 691384 or Schlarb et al., Prog. Org. Coat. 1995 (29), pages 201 to 208). However, the polymer particles A are preferably used in process 1 in the form of an aqueous primary dispersion.

As is the case with the radical polymerization of monomer B in process 2, the formation of a primary dispersion of polymer A particles in process 1 is also carried out by the method of the free-radically initiated aqueous emulsion polymerization familiar to the person skilled in the art. This is usually carried out by dispersing the at least one monomer A or B with the addition of at least one dispersant in an aqueous medium and polymerizing it by means of at least one free-radical polymerization initiator.

Suitable free-radical polymerization initiators are all those which are capable of initiating a free-radical aqueous emulsion polymerization. In principle, these can be both peroxides and azo compounds. Of course, redox initiator systems come into consideration. As peroxides may in principle inorganic peroxides, such as hydrogen peroxide or peroxodisulfates, such as the mono- or di-alkali metal or ammonium salts of peroxodisulfuric, such as their mono- and di-sodium, potassium or ammonium salts or organic peroxides, such as alkyl hydroperoxides, for example tert-butyl, p-menthyl or cumyl hydroperoxide, as well as dialkyl or diarylperoxides, such as di-tert-butyl or di-cumyl peroxide are used. As the azo compound, there are used substantially 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (amidinopropyl) dihydrochloride (corresponding to V-50 of Wako Chemicals). Suitable oxidizing agents for redox initiator systems are essentially the abovementioned peroxides. Suitable reducing agents may be sulfur compounds having a low oxidation state, like alkali metal sulphites, for example, potassium and / or sodium sulfite, alkali metal hydrogen, for example, potassium and / or sodium bisulfite, alkali metal metabisulfites, for example, potassium and / or sodium metabisulfite, formaldehydesulfoxylates, for example, potassium and / or sodium formaldehyde sulfoxylate, Alkali metal salts, especially potassium and / or sodium salts, aliphatic sulfinic acids and alkali metal hydrogensulfides, such as potassium and / or sodium hydrosulfide, Salts of polyvalent metals, such as ferrous sulfate, Iron (II) ammonium sulfate, phosphate, iron (II), endiols, like dihydroxymaleic acid, Benzoin and / or ascorbic acid and reducing saccharides, like sorbose, Glucose, Fructose and / or dihydroxyacetone are used. In general, the amount of the radical polymerization initiator is 0.05 to 5.0 parts by weight, often 0.1 to 3.0 parts by weight, and often 0.2 to 2.0 parts by weight, based in each case on 100 parts by weight of monomers used in the radical polymerization stage.

The manner in which the polymerization initiator is added to the polymerization mixture is of minor importance in terms of the success of the process according to the invention. The polymerization initiator can be introduced either completely into the polymerization vessel or continuously or in stages according to its consumption in the course of the free-radically aqueous emulsion polymerization. In detail, this depends in a manner known per se to those skilled in the art both on the chemical nature of the initiator system and on the polymerization temperature and the monomers to be polymerized.

To adjust the molecular weight, it is also possible if appropriate for molecular weight regulators known to the person skilled in the art, for example alcohols, such as butenediol or isopropanol, mercapto compounds, such as 2-mercaptoethanol or tert-dodecyl mercaptan or haloform compounds, such as bromoform or chloroform, to be used in amounts of from 0.1 to 5 Wt .-%, based on the total amount of the monomers used in the radical polymerization step can be added.

The reaction temperature for the free-radical aqueous emulsion polymerization is the entire range from 0 to 170 ° C into consideration. In this case, temperatures of 50 to 120 ° C, often 60 to 110 ° C and often ≥ 70 to 100 ° C are usually applied. The free-radical aqueous emulsion polymerization can be carried out at a pressure of less than, equal to or greater than 1 bar (absolute). Preferably, volatile monomers such as ethylene, butadiene or vinyl chloride are polymerized under elevated pressure. The pressure can be 1.2, 1.5, 2, 5, 10, 15 bar or even higher values. If emulsion polymerizations are carried out under reduced pressure, pressures of ≦ 950 mbar, frequently ≦ 900 mbar and often ≦ 850 mbar (absolute) are set. The free-radical aqueous emulsion polymerization is advantageously carried out under an inert gas atmosphere, for example under nitrogen or argon.

Usually, the monomers are polymerized to a conversion of at least 80%, but in general a monomer conversion ≥ 90%, ≥ 95% or ≥ 98% is preferred.

According to the invention, as at least one ethylenically unsaturated monomer for the polymerization initiated by means of at least one transition metal complex (monomers B in process 1 and monomers A in process 2) come both pure ethylenically unsaturated nonpolar hydrocarbon compounds and polar heteroatom-containing α-olefins, such as (meth) acrylic esters and homoallyl - Or allyl alcohols, ethers or halides into consideration. Among the pure ethylenically unsaturated non-polar hydrocarbons are C₂- to C₂₀1-alkenes suitable. Among them, the low molecular weight alkenes, such as ethene or α-alkenes having 3 to 20 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene or 1-decene are highlighted. Of course, cyclic olefins such as cyclopentene, cyclohexene, dicyclopentadiene or norbornene, conjugated dienes such as 1,3-butadiene (butadiene), 2-chlorobutadiene, 2-methylbutadiene or 2,3-dimethylbutadiene, aromatic olefin compounds such as styrene, α-methylstyrene or ortho-, meta- or para-vinyltoluene and vinyl esters, such as vinyl acetate or vinyl propionate. Particularly suitable, however, are the C₂- to C₂₀-1-alkenes. Among these are ethene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene, and 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene, as well as containing these olefin fractions of a cracker. Of course, it is possible according to the invention to use the aforementioned monomers individually or in a mixture. The monomers mentioned generally form the main monomers, which, based on the total amount of monomers, account for ≥50% by weight, in particular ≥80% by weight or ≥90% by weight. Frequently, the monomer mixture to be polymerized by means of at least one transition metal complex consists of at least 100% by weight of at least one of the abovementioned monomers.

In addition, however, it is also possible to use the aforementioned monomers in admixture with such polar ethylenically unsaturated monomers which contain as structural element at least one amide group, an acid group and / or their corresponding anion. Examples include α, β-monoethylenically unsaturated mono- and dicarboxylic acids and their amides, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, acrylamide, methacrylamide, furthermore vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, styrenesulfonic acid, 10-undecenoic acid, 3 Butene acid, 4-pentenoic acid, 5-hexenoic acid and their corresponding alkali metal and ammonium salts. In the normal case, the monomers containing amide or acid groups are present merely as modifying monomers in amounts of ≦ 50% by weight, ≦ 10% by weight, preferably ≦ 5% by weight, in each case based on the total monomer amount.

It is important that the polymer A particles obtainable by polymerization of at least one mononer A with at least one transition metal complex can also be in the form of a primary dispersion as well as a secondary dispersion.

The preparation of an aqueous secondary polymer dispersion in process 2, for example via a transition metal complex-catalyzed solution polymerization, introduction of this solution polymer with removal of the solvent in the aqueous medium to form an aqueous dispersion of the polymer A, is known in the art in principle (see, for example, DE-A 19821746 or Echersley et al., Am. Chem. Soc., Div. Polym. Chemistry, 1977 (38) pages 630ff.). However, the polymer particles A are preferably used in process 2 in the form of an aqueous primary dispersion.

Like the transition metal complex-catalyzed polymerization of monomer B in process 1, the formation of a primary dispersion of polymer A particles in process 2 is also carried out by the method of transition metal complex-catalyzed polymerization in an aqueous medium familiar to the person skilled in the art. This is usually carried out by polymerizing the at least one monomer A or B with the addition of at least one dispersant by means of at least one suitable transition metal complex in an aqueous medium. It is important that this polymerization can also be carried out in the presence of carbon monoxide.

For transition metal complex catalyzed polymerization, all those transition metal complexes capable of initiating polymerization of ethylenically unsaturated monomers in an aqueous medium are suitable. For example, the complexes mentioned in the prior art are suitable for the polymerization according to the invention.

Examples of suitable transition metal complexes which can be used in aqueous medium for the polymerization of monomer A or monomer B are the complexes disclosed in DE-A 10133042<ul id="ul0003" list-style="none" compact="compact"><li>[1,3-bis (diphenylphosphino) propane] -,</li><li>[1,3-bis (di (2-methoxyphenyl) phosphino) propane] -,</li><li>[1,3-bis (dimethylphosphino) propane] -,</li><li>[1,3-bis (dietyhlphosphino) propane] -,</li><li>[1,3-bis (di (n-propyl) phosphino) propane] -,</li><li>[1,3-bis (di (iso-propyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-butyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-pentyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-hexyl) phosphino) propane] -,</li><li>[1,3-bis (di (iso-hexyl) phosphino) propane] -,</li><li>[1,3-bis (di (neo-hexyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-heptyl) phosphino) propane] -,</li><li>[1,3-bis (di (3- (cyclopentyl) propyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-octyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-nonyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-decyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-dodecyl) phosphino) propane] -,</li><li>[1,3-bis (di (n-tetradecyl) phosphino) propane] -,</li><li>[1,3-bis (di (3- (cyclohexyl) propyl) phosphino) propane] - or</li><li>[1,3-bis (di (n-hexadecyl) phosphino) propane] palladium acetate (11)</li><li>the complexes disclosed in DE-A 10061877</li><li>[1,3-bis (di-hydroxyphenyl) phosphinopropane] -,</li><li>[1,3-bis (di-4-hydroxybutyl) phosphinopropane] -,</li><li>[1,3-bis (di-4-methylol-5-hydroxypentyl) phosphinopropane] -,</li><li>[1,3-bis (di-5-hydroxypentyl) phosphinopropane] -,</li><li>[1,3-bis (di-6-hydroxyhexyl) phosphinopropane] -,</li><li>[1,3-bis (di (3-hydroxycyclopentyl) propyl) phosphinopropane] -,</li><li>[1,3-bis (di-8-hydroxyoctyl) phosphinopropane] -,</li><li>[1,3-bis (di-3-hydroxycyclohexyl) propyl) phosphinopropane] -,</li><li>[1,3-bis (di-sulfonatophenyl) phosphinopropane] -,</li><li>[1,3-bis (di-4-sulfonatobutyl) phosphinopropane] -,</li><li>[1,3-bis (di-4-methylol-5-sulfonatopentyl) phosphinopropane] -,</li><li>[1,3-bis (di-5-sulfonatopentyl) phosphinopropane] -,</li><li>[1,3-bis (di-6-sulfonatohexyl) phosphinopropane] -,</li><li>[1,3-bis (di (3-sulfonatocyclopentyl) propyl) phosphinopropane] -,</li><li>[1,3-bis (di-8-sulfonatooctyl) phosphinopropane] -,</li><li>[1,3-bis (di-3-sulfonatocyclohexyl) propyl) phosphinopropane] -,</li><li>[1,3-bis (di-carboxyphenyl) phospinopropan] -,</li><li>[1,3-bis (di-4-carboxybutyl) phosphinopropane] -,</li><li>[1,3-bis (di-4-methylol-5-carboxypentyl) phosphinopropane] -,</li><li>[1,3-bis (di-5-carboxypentyl) phosphinopropane] -,</li><li>[1,3-bis (di-6-carboxyhexyl) phosphinopropane] -,</li><li>[1,3-bis (di (3-carboxycyclopentyl) propyl) phosphinopropane] -,</li><li>[1,3-bis (di-8-carboxyctyl) phosphinopropane] - or</li><li>[1,3-bis (di-3-carboxycyclohexyl) propyl) phosphinopropane] palladium (II) acetate, the complexes disclosed in DE-A 10107452</li><li>N, N, N-trimethyl-1-hexadecanaminium- (T-4) - [1- (diphenylphosphino-κP) -2- (hydroxy-κO) -2- (4-methylphenyl) ethylensulfonato] phenyl-nickel (II) (triphenylphosphine) or sodium (T-4) - [1- (diphenylphosphino-κP) -2- (hydroxy-κO) -2- (4-methylphenyl) -ethylenesulfonato] -phenyl-nickel (II) (triphenylphosphine),</li><li>the complexes disclosed in German Patent Application No. DE-A 10240577.8, which is not prepublished</li><li>[2 - [[[2,6-bis (1-methylethyl) phenyl] imino-KN] methyl] -4,6-diiodophenolato-κO] methyl-nickel (II) (pyridine),</li><li>[2 - [[[2,6-bis (1-methylethyl) phenyl] imino-KN] methyl] -4,6-diiodophenolato-κO] phenyl-nickel (II) (triphenylphosphine),</li><li>[2 - [[[2,6-bis (1-methylethyl) phenyl] imino-KN] methyl] -4,6-diphenylphenolato-κO] phenyl-nickel (II) (triphenylphosphine),</li><li>[2 - [[[2,6-bis (phenyl) phenyl] imino-κN] methyl] -4,6-diphenylphenolato-κO] phenyl-nickel (II) (triphenylphosphine) or</li><li>[2 - [[[2,6-bis (phenyl) phenyl] imino-KN] methyl] -4,6-diiodophenolato-κO] phenyl-nickel (II) (triphenylphosphine),</li></ul>as well as in the also not previously published German patent application with the file number DE-A 10234005.6 disclosed complex systems.

Also, the specific reaction conditions, such as temperatures, pressures, amounts of catalyst, etc. are disclosed in the corresponding prior art. The transition metal complex-catalyzed polymerization is often carried out under exclusion of oxygen, for example under an inert gas atmosphere, such as nitrogen or argon and under carbon monoxide or Monomerenatmosphäre. The polymerization temperature and the polymerization pressure is highly dependent on the activity of the transition metal complex used and the reactivity of the monomers to be reacted. In this case, the Polymeristionstemperatur 0 to 200 ° C, or 20 to 150 ° C and 40 to 120 ° C and the polymerization pressure measured in the gas phase 1 to 300 bar, or 5 to 200 bar and 10 to 100 bar (in each case absolute values).

It is also important that the transition metal complex-catalyzed polymerization of ethylenically unsaturated monomers A (process 2) or B (process 1) in an aqueous medium can also be carried out in the presence and under the copolymerization of carbon monoxide. The transition metal complexes suitable for this purpose and the conditions under which polymerization takes place in an aqueous medium are disclosed, for example, in DE-A 10061877 or DE-A 10125238.

In addition, the transition metal complex-catalyzed polymerization of ethylenically unsaturated monomers A (process 2) or B (process 1) in an aqueous medium can also take place in the form of so-called ring-opening metathesis polymerizations disclosed, for example, in DE-A 19859191.

In the process according to the invention, at least one dispersant is used which keeps the polymer particles A used for the polymerization and the polymer particles formed during the polymerization of monomer B dispersed in the aqueous phase and thus ensures the stability of the aqueous polymer dispersion produced. Suitable dispersants are both protective colloids and emulsifiers.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene Alkali metal salts of polyacrylic acids and polymethacrylic acids, cellulose, Starch and gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid-containing copolymers and their alkali metal salts but also N-vinylpyrrolidone, N-vinyl caprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, methacrylates, Acrylamides and / or methacrylamides containing homo- and copolymers. 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, pages 411-420.

Of course, mixtures of emulsifiers and / or protective colloids can be used. Frequently, dispersants used are exclusively emulsifiers whose relative molecular weights, in contrast to the protective colloids, are usually below 1500. They may be anionic, cationic or nonionic in nature. Of course, in the case of the use of mixtures of surfactants, the individual components must be compatible with each other, which can be checked in case of doubt by hand on fewer preliminary tests. In general, anionic emulsifiers are compatible with each other and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually incompatible with each other. An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg-Thieme-Verlag, Stuttgart, 1961, pages 192 to 208.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO degree: 3 to 50, alkyl radical: C₄ to C₁₂) as well as ethoxylated fatty alcohols (EO grade: 3 to 80; alkyl group: C_8th to C₃₆). Examples are the Lutensol^® A-marks (C₁₂C₁₄Fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol^® AO brands (C₁₃C₁₅Oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol^® AT marks (C₁₆C₁₈Fatty alcohol ethoxylates, EO grade: 11 to 80), Lutensol^® ON marks (C₁₀Oxo alcohol ethoxylates, EO grade: 3 to 11) and the Lutensol^® TO marks (C₁₃Oxo alcohol ethoxylates, EO grade: 3 to 20) from BASF AG.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C_8th to C₁₂), of sulfuric monoesters of ethoxylated alkanols (EO degree: 4 to 50, alkyl: C₁₂ to C₁₈) and ethoxylated alkylphenols (EO grade: 3 to 50, alkyl: C₄ to C₁₂), of alkylsulfonic acids (alkyl group: C₁₂ to C₁₈) and of alkylarylsulfonic acids (alkyl group: C₉ to C₁₈).

Further anionic emulsifiers further compounds of general formula I have<chemistry id="chem0001" num="0001"><img file="EP1636282B1_D0001.tif" /></chemistry>wherein R¹ and R² H atoms or C₄- to C₂₄Alkyl and are not H atoms simultaneously, and A and B may be alkali metal ions and / or ammonium ions proved. In the general formula I mean R¹ and R² preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or -H, where R¹ and R² not both are simultaneously H atoms. A and B are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Particularly advantageous compounds I, in which A and B sodium, R¹ a branched alkyl radical with 12 C atoms and R² a H ​​atom or R¹ is. Frequently, technical mixtures are used which have a proportion of 50 to 90 wt .-% of the monoalkylated product, such as Dowfax^® 2A1 (trademark of the Dow Chemical Company). The compounds I are generally known, for example. from US-A 4,269,749, and commercially available.

Suitable cationic emulsifiers are usually a C₆- to C₁₈Alkyl, aralkyl or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinsäureester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N-octyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini-surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide. Numerous other examples can be found in H. Stache, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981, and Mc-Cutcheon's, Emulsifiers &amp; Detergents, MC Publishing Company, Glen Rock, 1989.

However, particularly suitable are nonionic and / or anionic emulsifiers.

As a rule, a total of 0.05 to 20 parts by weight, often 0.1 to 10 parts by weight and often 1 to 7 parts by weight of dispersant, in each case based on 100 parts by weight of aqueous medium formed from the amounts of deionized water and the at least one dispersant.

The amount of deionized water is calculated so that the polymer solids content of the aqueous polymer dispersion obtained according to the invention 5 to 75 wt .-%, often 10 to 65 wt .-% and often 20 to 55 wt .-%, each based on the aqueous polymer , is.

In the process according to the invention, at least a portion of the deionized water and the at least one dispersing agent are introduced together with at least one subset of the polymer particles A in the polymerization vessel and the residual amounts of polymer particles A, deionized water and the at least one dispersant remaining in the polymerization of the monomer B continuously or discontinuously added. As a rule, the monomer B is also fed to the polymerization vessel in a continuous or discontinuous manner during the polymerization, in accordance with its reaction. Often, the total amount of the polymer particles A in the polymerization before the start of the polymerization of the monomer B is submitted. According to process 1, the total amount of the at least one dispersant and / or deionized water in the polymerization is often submitted before the start of the polymerization of monomer B, while according to method 2 is often a subset of the at least one dispersant and / or deionized water together with the monomers B is supplied in the form of an aqueous monomer emulsion under polymerization conditions of the aqueous dispersion of the polymer A particles.

The weight-average particle size of the polymer particles A is ≥ 1 nm and often ≦ 1000 nm. Frequently, the weight-average particle diameter is ≥ 5 nm, ≥ 10 nm, ≥ 20 nm, ≥ 30 nm, ≥ 40 nm, ≥ 50 nm, ≥ 60 nm, ≥ 70 nm, ≥ 80 nm, ≥ 90 nm or ≥ 100 nm and all Values ​​between and also ≤ 700 nm, ≤ 500 nm, ≤ 400 nm, ≤ 350 nm, ≤ 300 nm, ≤ 250 nm, ≤ 200 nm, ≤ 150 nm, ≤ 100 nm, ≤ 90 nm, ≤ 80 nm, ≤ 70 nm , ≤60 nm, ≤50 nm or ≤40 nm and all values ​​in between. The determination of the weight-average particle diameter is known to the person skilled in the art and is carried out, for example, by the method of the analytical ultracentrifuge. Weight-average particle diameter in this document is determined by the method of the analytical ultracentrifuge weight average D_w50(See, for example, SE Harding et al., Analytical Ultracentrifugation in Biochemistry and Polymer Science, Royal Society of Chemistry, Cambridge, Great Britain 1992, Chapter 10, Analysis of Polymer Dispersions with an Eight-Cell AUC Multiplexer: High Resolution Particle Size Distribution and Density Gradient Techniques, W. Mächtle, pages 147 to 175).

It may be advantageous if the polymer particles A are monomodal and have a narrow particle size distribution. Within the scope of this document, narrow particle size distribution is to be understood as meaning the ratio of the weight-average particle diameter D determined by the method of the analytical ultracentrifuge_w50 and number average particle diameter D_N50 [D_w50/ D_N50] ≤ 2.0, preferably ≤ 1.5, and particularly preferably ≤ 1.2 or ≤ 1.1.

Substantially dependent on the emulsifier concentration during the polymerization, the process according to the invention can be controlled such that virtually no new polymer particles are formed during the polymerization of the at least one monomer B in addition to the already present polymer particles A and thus two-phase, of polymer A and polymer B , obtained by the polymerization of the monomers B, formed, form polymerizate. This is particularly the case when the emulsifier concentration is controlled during the polymerization so that no new emulsifier micelles are formed. The corresponding measures are known to the person skilled in the art. The resulting polymerizate particles formed from polymer A and polymer B can have different particle morphologies, such as, for example, core / shell, raspberry or crescent structure, etc. respectively. Frequently, the weight-average particle diameter of the formed two-phase polymer particles is 50 to 1000 nm, often 70 to 700 nm or 80 up to 500 nm or 90 to 400 nm or 100 up to 300 nm.

If, on the other hand, the emulsifier concentration is controlled in such a way that new emulsifier micelles are formed, not only the polymer particles A but also particles of the polymer B (polymer particles B) can be formed. The formation of aqueous polymer dispersions which contain polymer particles A, polymer particles B and two-phase polymer particles (composed of polymers A and B) is also possible. The measures to be carried out for this purpose are familiar to the expert or can be determined by him in a few preliminary tests.

In general, the quantitative ratio of polymer A to at least one ethylenically unsaturated monomer B is 1: 1000 to 1000: 1, but it may also be 1: 500 to 500: 1, 1: 200 to 200: 1, 1: 100 to 100: 1, 1: 50 to 50: 1, 1: 20 to 20: 1 or 1:10 to 10: 1. Preference is given to a quantitative ratio of 1: 100 to 100: 1, 1: 50 to 50: 1, 1:20 to 20: 1 and 1:10 to 10: 1.

It is important that the process according to the invention can also be carried out in the presence of an organic solvent. This is especially true when transition metal complexes are used for the polymerization, which are slightly soluble in aqueous medium. Frequently, in such a case, the complex is taken up in an organic solvent and supplied to the aqueous medium in the form of an organic solution. If polymer particles A which have already been produced by free radicals are present (process 1), then the solvent and the transition metal complex frequently diffuse into the present polymer particles A, whereby they can swell. In this case, polar protic or polar aprotic organic compounds having a molecular weight ≦ 200 g / mol can be used as organic solvents. Examples of these are polar aprotic organic solvents, such as the halogenated hydrocarbons, for example dichloromethane, dichloroethane or chloroform, aromatic hydrocarbons, for example benzene, toluene, ethylbenzene, xylene or chlorobenzene or aliphatic ethers, such as tetrahydrofuran or any mixtures of these compounds. Furthermore, acetonitrile or acetone can be used as liquid polar aprotic solvents or as one component among several. Polar protic organic solvents are, for example, C₁- to C₁₀Alkanols, especially C₁- to C₆Alkanols, such as methanol, ethanol, n-propanol, iso-propanol, 1-butanol, 2-butanol, 2-methyl-2-propanol, and the corresponding isomeric pentanols, hexanols or heptanols.

It is also possible to take up a transition medium complex which is sparingly soluble in an aqueous medium in a organic solvent which is also slightly soluble in an aqueous medium. This takes place in particular if no radical polymerized particles A are present (method 2). In this case, the transition metal complex is taken up in a slightly aqueous medium-soluble organic solvent and stirred into the aqueous medium in the presence of at least one dispersant to form solvent droplets ≦ 1000 nm, ≦ 500 nm or ≦ 300 nm. The measures and facilities required for this, for example ultrasound or high-pressure homogenizers, such as pressure gaps or other homogenizers, such as sprocket dispersers, etc. are known in the art (see. for example GB-A 2250930, US-A 5,108,654 and PL Tang, ED Sudol, CA Silebi and MS EI-Aasser in Journal of Applied Polymer Science 1991 (43), pages 1059 to 1066). Subsequently, the preparation of the Polymeriatteilchen A by polymerization of corresponding monomers A. As in aqueous medium sparingly soluble organic solvents find liquid aliphatic and aromatic hydrocarbons having 5 to 30 carbon atoms, such as n-pentane and isomers, Cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n-nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, Eicosan, docosane Benzene, Toluene, ethylbenzene, cumene, O-, m- or p-xylene, mesitylene, and generally hydrocarbon mixtures in the boiling range of 30 to 250 ° C use. Also usable are hydroxy compounds, such as saturated and unsaturated fatty alcohols having 10 to 28 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, esters, such as fatty acid esters having 10 to 28 carbon atoms in the acid moiety and 1 to 10 carbon atoms in the alcohol part or esters of carboxylic acids and fatty alcohols having 1 to 10 carbon atoms in the carboxylic acid part and 10 to 28 carbon atoms in the alcohol part. Of course it is also possible to use mixtures of the abovementioned solvents.

The amount of the organic solvent, based on the aqueous medium, consisting of water and dispersing agent is often ≦ 20% by weight, ≦ 10% by weight, ≦ 5% by weight, or ≦ 3% by weight or ≦ 1% by weight. Often the polymerization reaction takes place without addition of organic solvent.

In addition, it may be advantageous for at least one water-soluble macromolecular host compound having a hydrophobic cavity and a hydrophilic shell to be present during the polymerization of monomer A and / or monomer B in an aqueous medium. Frequently, only the polymerization of monomer B occurs in the presence of a corresponding water-soluble macromolecular host compound. In this document, a water-soluble macromolecular host compound is to be understood as meaning those host compounds which have a solubility of ≥ 10 g per liter of water at 25 ° C. and 1 bar (absolute). It is favorable if the solubility of the macromolecular host compounds under the abovementioned conditions is ≥ 25 g / l, ≥ 50 g / l, ≥ 100 g / l, ≥ 200 g / l or ≥ 300 g / l.

As water-soluble macromolecular host compounds, for example, calixarenes, cyclic oligosaccharides, noncyclic oligosaccharides and / or derivatives thereof can be used to advantage.

Calixarenes which can be used according to the invention are described in US Pat. No. 4,699,966, international patent application WO 89/08092 and Japanese patents 1988/197544 and 1989/007837.

As cyclic oligosaccharides, for example, those described by Takai et al. in the Journal of Organic Chemistry, 1994, 59 (11), pages 2967 to 2975 described cycloinulohexose and heptose but also cyclodextrins and / or their derivatives are used.

Particularly suitable cyclodextrins are α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin and their methyl, triacetyl, hydroxypropyl or hydroxyethyl derivatives. Particularly preferred are the commercially available underivatized compounds, Cavamax^® W6, Cavamax^® W7 or Cavamax^® W8, the partially methylated compounds Cavasol^® W6M, Cavasol^® W7M or Cavasol^® W8M and the partially hydroxypropylated compounds Cavasol^® W6HP, Cavasol^® W7HP or Cavasol^® W8HP (trademarks of Wacker-Chemie GmbH).

For example, starches and / or their degradation products are used as noncyclic oligosaccharides.

The water-soluble starches or starch degradation products are often native starches made water soluble by cooking with water, or starch degradation products derived from the native starches by hydrolysis, especially acid catalyzed hydrolysis, enzymatically catalyzed hydrolysis, or oxidation become. Such degradation products are also referred to as dextrins, roasted dextrins or saccharified starches. Their preparation from native starches is known to the person skilled in the art and is described, for example, in G. Tegge, starch and starch derivatives, EAS Verlag, Hamburg 1984, pages 173ff. and pages 220ff. as well as in EP-A 0441 197. Virtually all starches of plant origin, for example corn starches, wheat, potatoes, tapioca, rice, sago and sorghum sorghum, can be used as native starches.

Chemically modified starches or starch degradation products are also used according to the invention. Chemically modified starches or starch degradation products are to be understood as those starches or starch degradation products in which the OH groups are at least partially derivatized, eg in etherified or esterified form. The chemical modification can be carried out on both the native starches and the degradation products. Likewise, it is possible to subsequently convert the chemically modified starches into their chemically modified degradation products.

The esterification of starch or Starch degradation products can be made with both inorganic and organic acids, their anhydrides or their chlorides. Common esterified starches are phosphated and / or acetylated starches or Starch degradation products. An etherification of the OH groups can be carried out, for example, with organic halogen compounds, epoxides or sulfates in aqueous alkaline solution. Examples of suitable ethers are alkyl ethers, hydroxyalkyl ethers, carboxyalkyl ethers, allyl ethers and cationically modified ethers, for example (Trisalkylammonium) alkyl ethers and (trisalkylammonium) hydroxyalkyl ethers. Depending on the type of chemical modification, the strengths or the starch degradation products are neutral, cationic, anionic or amphiphilic. The production of modified starches and starch degradation products is known to the person skilled in the art (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5^th ed., Vol. 25, pages 12 to 21 and references cited therein).

In one embodiment of the present invention, water-soluble starch degradation products and their chemically modified derivatives obtainable by hydrolysis, oxidation or enzymatic degradation of native starches or chemically modified starch derivatives are used. Such starch degradation products are also referred to as saccharified starches (cf. G. Tegge, starch and starch derivatives, EAS Verlag, Hamburg 1984, pages 220ff.). Saccharified starches and their derivatives are commercially available as such (eg C * Pur^®-Produkte 01906, 01908, 01910, 01912, 01915, 01921, 01924, 01932 or 01934 Cerestar Germany GmbH, Krefeld) or can be prepared by degradation of commercial starches by known methods, for example by oxidative hydrolysis with peroxides or enzymatic hydrolysis of the starches or chemically modified starches are produced. Favorable are hydrolytically accessible starch degradation products that are not chemically modified further.

Within the aforementioned embodiment, starch degradation products or chemically modified starch degradation products having a weight-average molecular weight M are used_w in the range of 1000 to 30,000 daltons, and more preferably in the range of 3,000 to 10,000 daltons. Such starches are completely soluble in water at 25 ° C. and 1 bar, the solubility limit generally being above 50% by weight, which proves to be particularly favorable for the preparation of the copolymers according to the invention in an aqueous medium. In particular, C * Pur^® 01906 (m_w about 20000) and C * Pur^® 01934 (m_w approx. 3000).

Information on the molecular weight of the abovementioned starch degradation products or chemically modified starch degradation products is based on determinations by gel permeation chromatography under the following conditions:<tables id="tabl0001" num="0001"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="27mm" /><colspec colnum="2" colname="col2" colwidth="139mm" /><tbody><row><entry>Columns:</entry><entry>3 Piece 7.5 x 600 mm steel filled with TSK gel G 2000 PW and G 4000 PW. Pore ​​size 5 μm.</entry></row><row><entry>eluent:</entry><entry>deionized water</entry></row><row><entry>Temperature:</entry><entry>20 up to 25 ° C (room temperature)</entry></row><row><entry>detection:</entry><entry>Differential refractometer (eg ERC 7511)</entry></row><row><entry>River:</entry><entry>0.8 ml / min. Pump: (eg ERC 64.00)</entry></row><row><entry>Injection valve:</entry><entry>20 μl valve: (eg VICI 6-way valve)</entry></row><row><entry>Evaluation:</entry><entry>Bruker Chromstar GPC software</entry></row><row><entry>Calibration:</entry><entry>The calibration was carried out in the low molecular weight range with glucose, raffinose, maltose and maltopentose. For the higher molecular weight range, pullulan standards with a polydispersity &lt;1.2 were used.</entry></row></tbody></tgroup></table></tables>

The amount of water-soluble macromolecular host compound used in the present process is generally from 0.1 to 50 parts by weight, often from 0.2 to 20 parts by weight and often from 0.5 to 10 parts by weight, based in each case on 100 Parts by weight of monomer A and / or monomer B.

By targeted variation of the monomers A and / or B, it is possible according to the invention to prepare aqueous polymer dispersions whose polymers have a glass transition temperature or a melting point in the range from -60 to 270 ° C.

With the glass transition temperature T_G, it is meant the limit of the glass transition temperature, which according to G. Kanig (Kolloid-Zeitschrift &amp; Zeitschrift fur Polymere, Vol. 190, p. 1, Equation 1) tends to increase with increasing molecular weight. The glass transition temperature or the melting point is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).

According to Fox (TG Fox, Bull. Am. Phys Soc. 1956 [Ser II] 1, page 123 and Ullmann's Encyclopedia of Industrial Chemistry, Vol. 19, page 18, 4th edition, Verlag Chemie, Weinheim, 1980) applies to the glass transition temperature of at most weakly crosslinked copolymers in a good approximation: <maths id="math0001" num=""><math display="block"><mn mathvariant="normal">1</mn><mo mathvariant="normal">/</mo><msub><mi mathvariant="normal">T</mi><mi mathvariant="normal">G</mi></msub><mo mathvariant="normal">=</mo><msup><mi mathvariant="normal">x</mi><mn mathvariant="normal">1</mn></msup><mo mathvariant="normal">/</mo><msup><msub><mi mathvariant="normal">T</mi><mi mathvariant="normal">G</mi></msub><mn mathvariant="normal">1</mn></msup><mo mathvariant="normal">+</mo><msup><mi mathvariant="normal">x</mi><mn mathvariant="normal">2</mn></msup><mo mathvariant="normal">/</mo><msup><msub><mi mathvariant="normal">T</mi><mi mathvariant="normal">G</mi></msub><mn mathvariant="normal">2</mn></msup><mo mathvariant="normal">+</mo><mo mathvariant="normal">...</mo><msup><mi mathvariant="normal">x</mi><mi mathvariant="normal">n</mi></msup><mo mathvariant="normal">/</mo><msup><msub><mi mathvariant="normal">T</mi><mi mathvariant="normal">G</mi></msub><mi mathvariant="normal">n</mi></msup><mo mathvariant="normal">.</mo></math><img file="EP1636282B1_D0002.tif" /></maths>where x¹, x², .... xⁿ the mass fractions of the monomers 1, 2, .... n and T_G¹, T_G², .... T_Gⁿ the glass transition temperatures of each of only one of the monomers 1, 2, .... n constructed polymers in degrees Kelvin. The T_GValues ​​for the homopolymers of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, page 169, VCH Weinheim, 1992; Further sources of glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1^st Ed., J. Wiley, New York 1966, 2^nd Ed. J. Wiley, New York 1975, and 3^rd Ed. J. Wiley, New York 1989).

The aqueous polymer dispersions obtainable by the process according to the invention often have polymers whose minimum film-forming temperature MFT ≦ 80 ° C. is frequently ≦ 50 ° C. or ≦ 30 ° C. Since the MFT is no longer measurable below 0 ° C, the lower limit of the MFT can only be determined by the T_GValues ​​can be specified. The determination of the MFT is carried out according to DIN 53787.

Frequently, in the aqueous polymer dispersions obtained, the residual contents of unreacted monomers are also chemical and / or physical methods known to the person skilled in the art [see, for example, EP-A 771328, DE-A 19624299, DE-A 19621027, DE-A 19741184, DE-A 19741187, DE-A 19805122, DE-A 19828183, DE-A 19839199, DE-A 19840586 and 19847115].

The aqueous polymer dispersions obtained according to the invention are frequently stable for several weeks or months and generally show virtually no phase separation, precipitation or coagulation during this time. They are especially suitable as binders in the production of adhesives, such as pressure-sensitive adhesives, Building adhesives or industrial adhesives, Sealants, Plastic plasters and paints, such as for paper-making, Emulsion paints or for printing inks and printing varnishes for printing on plastic films and for producing nonwovens or for producing protective layers and water vapor barriers, such as the primer. Likewise, these aqueous polymer dispersions can be used for modifying mineral binders or other plastics.

It should also be noted that the aqueous polymer dispersions obtainable according to the invention can be dried in a simple manner to give redispersible polymer powders (eg Freeze drying or spray drying). This applies in particular if the glass transition temperature of the polymer A or B quantitatively predominant in the aqueous polymer dispersion is generally ≥ 50 ° C., often ≥ 60 ° C. or ≥ 70 ° C., frequently ≥ 80 ° C. or ≥ 90 ° C. ≥ 100 ° C. The polymer powders are also suitable as binders in adhesives, sealants, plastic plasters and paints, and for the production of nonwovens or for the modification of mineral binders, such as mortar or cement, or as modifying additives in other plastics.

It is also possible to subject the aqueous polymer dispersions obtainable according to the invention to a coagulation step familiar to the person skilled in the art, whereby the polymer can coagulate and be separated off from the aqueous medium by simple filtration. Subsequent drying gives a polymer which can be used in particular for the modification of other plastics as well as for the production of molded parts, in particular by injection molding or extrusion processes as well as for the coating of surfaces.

The process according to the invention provides an economical, ecological, preparatively simple and largely harmless safety-related access to novel aqueous polymer systems which combines the advantages of the free-radically initiated polymerization and the transition metal complex-catalyzed polymerization.

The present invention will be explained in more detail with reference to the following examples.

Examples

example 1

Preparation of [1,3-bis (di (n-hydroxypentyl) phosphino) propane] palladium (II) diacetate (according to Lindner et al., J. Organomet. Chem. 2000, 602, pages 173ff.)

642 mg (1.25 mmol) of 1,3-bis (di (n-hydroxypentyl) phosphino) propane were weighed into a Schlenk tube at 20 to 25 ° C. (room temperature) under an argon atmosphere and dissolved in 20 ml of anhydrous, degassed dichloromethane (Aldrich GmbH). solved. In a second Schlenk tube 286 mg (1.27 mmol) of palladium (II) acetate (99 wt .-%, Aldrich GmbH) were dissolved in 20 ml of anhydrous degassed dichloromethane at room temperature with stirring. The 1,3-bis (di (n-hydroxypentyl) phosphino) propane solution was added to the palladium acetate solution at room temperature and under an argon atmosphere within 10 minutes, then stirred for 30 minutes and then the solvent was evaporated in vacuo (ca. 1 mbar absolute). 925 mg (yield: 99%) of [1,3-bis (di (n-hydroxypentyl) phosphino) propane] palladium (II) diacetate in the form of a yellow-brown oil were obtained.

Example 2

a) Transition metal complex-catalyzed polymerization of 1-butene / carbon monoxide in an aqueous medium

In 2000 ml of deionized water was successively at room temperature 200 mg of [1,3-bis (di (n-hydroxypentyl) phosphino) propane] palladium (II) diacetate from Example 1, 25.6 g of a 1 wt .-% aqueous Dissolved solution of tetrafluoroboric acid (Aldrich GmbH) and 10 g of sodium dodecyl sulfate (99 wt .-%, Aldrich GmbH) with stirring and nitrogen atmosphere. The mixture was transferred to a 9 l steel autoclave with mechanical stirrer and electrically heated jacket. Subsequently, 1600 g of 1-butene were passed into the steel autoclave at room temperature. Carbon monoxide was then pressed into the autoclave with stirring at room temperature until a pressure of 50 bar had been reached. While stirring, the contents of the autoclave were heated to 60 ° C. and the carbon monoxide pressure was adjusted to 60 bar and stirred for 10 hours while maintaining this constant carbon monoxide pressure. After cooling the autoclave contents to a temperature of approx. 40 ° C and depressurized to 4 bar (absolute), the contents of the autoclave were transferred to a 5 l glass container with mechanical stirrer, gas inlet tube and exhaust pipe, thereby releasing to atmospheric pressure. Subsequently, unreacted 1-butene or Carbon monoxide by passage of nitrogen at about 1 hour 40 ° C. This gave a 2580 g of an aqueous polymer dispersion. The solids content of the polymer dispersion was determined after filtration through a 60 micron filter to 23 wt .-%, based on the obtained after filtration aqueous polymer dispersion. The content of the coagulum remaining on the sieve was determined to be 0.7% by weight, based on the aqueous polymer dispersion used. The weight average particle size D_w50 The obtained polymerizate particle was 112 nm. The aqueous polymer dispersion obtained was stable and showed no phase separation or sedimentation within 10 weeks.

The coagulum content was generally determined by filtering the resulting aqueous polymer dispersion through a 60 μm filter cloth. The filter cloth was then rinsed with 100 ml of deionized water and dried in a drying oven at 100 ° C and atmospheric pressure to constant weight. From the difference in weight of the filter fabric before filtration and the filter fabric after filtration and drying, the coagulum content of the aqueous polymer dispersion, in each case based on the aqueous polymer dispersion before filtration, was determined.

The solids content was generally determined by 1 g of the aqueous polymer dispersion obtained after filtration in an open aluminum crucible with an internal diameter of approx. 3 Was dried cm in a drying oven at 100 ° C and atmospheric pressure to constant weight. To determine the solids content, two separate measurements were carried out in each case and the corresponding mean value was formed. The solids content is in each case based on the aqueous polymer dispersion after filtration.

The particle sizes were determined either by the method of analytical ultracentrifuge (W. Mächtle, Macromolecular Chemistry 1984 (185), pages 1025 to 1039) or determined by dynamic light scattering (Autosizer IIC Fa. Malvern Instruments, England,) wherein the average diameter of Cumulant evaluation [cumulant z-average] of the measured autocorrelation function according to ISO standard 13321 is given.

10 ml of the obtained aqueous polymer dispersion were poured into a polyethylene dish with an inner diameter of approx. 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. A brittle, cracked polymer film was obtained. The glass transition temperature of the polymer was determined to be 9 ° C. In addition, the polymer still had a wide melting point range of 80 to 120 ° C. The determination of the glass transition temperature or the melting point (melting range) was generally carried out according to DIN 53765 by means of a DSC 820 device, series TA 8000 of the Fa. Mettler-Toledo.

The molecular weight of the dried polymer film was determined by gel permeation chromatography (GPC) (hexafluoroisopropanol with 0.05% by weight trifluoroacetic acid potassium salt, the calibration was carried out with narrowly distributed polymethacrylate standards from the company. PSS with molecular weights of M = 505 to M = 2740000; Elution areas outside this interval were estimated by extrapolation; the detection was carried out with a differential refractometer HP 1100 Fa. Hewlett Packard). The number average molecular weight was M_n 9000 g / mol and the weight average molecular weight M_w 21000 g / mol.

b) Radical emulsion polymerization in the presence of the polyketone dispersion a)

In a glass reactor, which is thermostated in a heating bath and equipped with a mechanical stirrer, reflux condenser and two stirred feed vessels, 265.5 g of the aqueous Polyketondispersion a) were placed under a nitrogen atmosphere. The feed vessel 1 was filled with an emulsion consisting of 119 g of deionized water, 4.8 g of a 15 wt .-% aqueous solution of n-dodecylbenzenesulfonate sodium salt, 119 g of n-butyl acrylate and 1.2 g of acrylic acid. The feed vessel 2 was filled with a solution consisting of 0.84 g of sodium peroxodisulfate and 40 g of deionized water.

The contents of the original were heated to 80 ° C. while stirring under a nitrogen atmosphere, admixed with 4 g of feed 2 and stirred for 10 minutes. Thereafter, feed 1 was added continuously within one hour and the remainder of feed 2 continuously within one and a half hours at the aforementioned temperature and then cooled to room temperature.

The aqueous polymer dispersion obtained had a coagulum content of 0.5% by weight and the solids content was determined to be 33% by weight. The weight average particle size D_w50 the polymer particles obtained was 188 nm.

10 ml of the obtained aqueous polymer dispersion were placed in a polyethylene dish with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. A closed, flexible and transparent polymer film was obtained. The glass transition temperature of the polymer was determined to be 40 ° C. In addition, the polymer still had a wide melting point range of about 80 to 120 ° C.

Example 3

A polystyrene dispersion having a weight-average particle diameter D prepared by radical emulsion polymerization_w50 of 30 nm and a polydispersity index of &lt;1.5 was diluted with deionized water to a solids content of 10% by weight.

100 ml of this aqueous Polystyroldispersion were in a Schlenk tube with 10 ml of a 10 wt .-% solution of [1,3-bis (di (n-hexyl) phosphino) propane] palladium (II) diacetate (preparation analogous to Example 1) in Styrene and stirred for 24 hours at room temperature under nitrogen atmosphere. Thereafter, the polystyrene particles were swollen with styrenic catalyst solution and no separate styrene droplets more visible (light microscope, magnification: 40-fold).

10 g of the aforementioned "swollen" polystyrene dispersion were stirred under nitrogen atmosphere in 2000 g of deionized water and successively at room temperature with 12 g of a 1 wt .-% solution of tetrafluoroboric in deionized water, 10 g of sodium dodecyl sulfate (Aldrich GmbH) and 20 g of cyclodextrin Cavasol.RTM^® W7 M (Fa. Wacker-Chemie GmbH). The aqueous mixture was transferred to a 9 l steel autoclave with mechanical stirrer and electrically heated jacket. 100 g of 1-hexene were then added to the autoclave at room temperature, and carbon monoxide was introduced up to a pressure of 50 bar and the autoclave contents were heated to 60.degree. The carbon monoxide pressure was regulated to a constant 60 bar. With stirring and constant carbon monoxide pressure, 900 g of 1-hexene were metered in over 10 hours via an HPLC pump. The reaction mixture was then left for a further 2 hours at this temperature, the autoclave was depressurized to 4 bar and the autoclave contents were transferred to a 5 l glass container equipped with a mechanical stirrer and a gas inlet and exhaust pipe. By passing gaseous nitrogen through the aqueous dispersion heated to 70 ° C. for one hour, unreacted 1-hexene was removed. This gave 2830 g of an aqueous polymer dispersion. The aqueous polymer dispersion obtained had a coagulum content of 0.1% by weight. The solids content was determined to be 28% by weight. The determined by dynamic light scattering average particle size of the polymerizate particles obtained was 260 nm.

10 ml of the obtained aqueous polymer dispersion were placed in a polyethylene dish with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. It was a brittle, closed film received. The glass transition temperature of the polymer was determined to be -10.degree.

From the resulting polymer film, the molecular weight was determined by gel permeation chromatography. The number average molecular weight was M_n 8600 g / mol and the weight average molecular weight M_w 20000 g / mol.

Example 4

a) Transition metal complex-catalyzed preparation of a polyethylene dispersion

19 mg tetrachlorobenzoquinone (Fa. Aldrich GmbH) were dissolved under argon atmosphere in a Schlenk tube in an anhydrous and degassed mixture of 4 g of toluene, 0.2 g of hexadecane and 1 ml of methanol, the solution was then stirred at room temperature with 18 mg of triphenylphosphane and 20 mg of bis (cydooctadiene) nickel ( 0) (Fa. Strem Chemicals Inc.) was added and the resulting solution stirred for 30 minutes. This solution was then added with stirring 95 ml of a 1 wt .-% solution of sodium dodecyl sulfate in deionized water, with an oil-in-water macroemulsion formed. With the aid of a microfluidizer (type 120 of the Fa. Microfluidics Corp.) was made therefrom by high-pressure homogenization at 750 bar, a so-called miniemulsion. The average droplet size of the emulsion droplets was determined by means of quasi-elastic dynamic light scattering with a Coulter N4 Plus Particle Analyzer from the company. Coulter Scientific Instruments to 150 nm. The resulting aqueous miniemulsion was transferred under an argon atmosphere to a 300 ml autoclave equipped with a mechanical stirrer, electric heating and two separate feeds. Ethene was then introduced with stirring to a pressure of 50 bar and the reaction mixture was heated to 50 ° C. under constant ethylene pressure and left at this temperature for two hours with stirring. Subsequently, a 5 ml sample was taken via a riser. The solids content of the resulting polymer dispersion was determined to be 19% by weight.

The aqueous polymer dispersion obtained was placed in a polyethylene dish with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. A colorless, cracked polymer film without detectable glass transition temperature was obtained. However, the polymer had a melting point of about 126 ° C.

The molecular weight was determined from the resulting polymer film by GPC (o-xylene; the calibration was carried out with narrowly dispersed polystyrene of the company PSS with molecular weights of M = 400 to M = 2.5 million g / mol, and elution ranges lying outside this interval were determined by extrapolation the detection was carried out with a HP 1100 differential refractometer from Hewlett Packard). The number average molecular weight was M_n 6000 g / mol and the weight average molecular weight M_w 16000 g / mol.

b) Radical emulsion polymerization in the presence of the polyethylene dispersion a)

The temperature of the autoclave contents obtained under a) was increased from 50 to 85 ° C. while maintaining the ethene pressure. Thereafter, with stirring, 5 g of an inlet 1, consisting of an emulsion of 60 g of vinyl acetate, 40 g of deionized water, 0.2 g of Mowiol 4088 (polyvinyl alcohol from the company. Clariant) and 0.5 g of sodium dodecyl sulfate (Fa. Aldrich GmbH) in the autoclave. After 5 minutes, the remainder of feed 1 and the total amount of feed 2, consisting of a solution of 1 g of sodium peroxodisulfate in 5 g of deionized water, were metered in at the same time over two separate feeds for 1.5 hours. After a postreaction time of half an hour, the autoclave contents were cooled to room temperature and vented to atmospheric pressure.

The aqueous polymer dispersion was filtered through a 60 micron filter cloth, with only traces of coagulum found. The solids content of the aqueous polymer dispersion obtained was 38% by weight and the average particle size of the polymer particles determined by means of dynamic light scattering was 210 nm.

10 ml of the obtained aqueous polymer dispersion were placed in a polyethylene dish with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. A clear flexible film was obtained. The glass transition temperature of the polymer was determined to be 5 ° C. In addition, the polymer still had a melting point of about 120 ° C.

Example 5

a) Transition-metal complex-catalyzed preparation of a polybutadiene dispersion

In a Schlenk tube with magnetic stirrer under argon atmosphere 82 mg of cobalt (II) octanoate (Fa. Strem Chemicals Inc.) and then the Schlenk tube with a cryostat to -10 ° C cooled. After that, the Schlenk tube was approx. 300 1,3-butadiene (butadiene for short) condensed, then 470 mg of a 30 wt .-% solution of triisobutylaluminum in toluene (Fa. Aldrich GmbH) was added and the resulting mixture stirred at -10 ° C for 10 minutes. The mixture was transferred to a nitrogen-neutralized, 50 ° C tempered steel autoclave of 300 ml volume in the previously 100 ml of deionized and degassed water, 1 g of sodium dodecyl sulfate, 18 mg carbon disulfide and 30 g of butadiene were filled. This reaction mixture was allowed to react for 2 hours at 50 ° C with stirring. Subsequently, a 5 ml sample was taken from a riser.

The solids content of the aqueous polymer dispersion obtained was 18% by weight and the average particle size of the polymer particles determined by means of dynamic light scattering was 230 nm.

1 ml of the obtained aqueous polymer dispersion were placed in a polyethylene dish with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. A white powder was obtained. The glass transition temperature of the polymer was determined to be -17.degree. In addition, the polymer still had a melting point of about 175 ° C.

b) Radical emulsion polymerization in the presence of the polybutadiene dispersion a)

The autoclave contents obtained from a) were heated with stirring to 90 ° C, then added to this 1 g of an inlet 3 and the mixture stirred for 10 minutes at the above reaction temperature. Thereafter, at the same time starting from the total amounts of feed 1 and feed 2 were added within 2 hours and the remainder of feed 3 within 2.5 hours continuously. After complete addition of feed 3 was stirred at the reaction temperature for 15 minutes, then to ca. 30 cooled to 35 ° C and the reactor contents are vented to atmospheric pressure. For depletion of unreacted butadiene was then led then for about One hour of gaseous nitrogen through the resulting aqueous polymer dispersion.<tables id="tabl0002" num="0002"><table frame="none"><tgroup cols="2" colsep="0" rowsep="0"><colspec colnum="1" colname="col1" colwidth="18mm" /><colspec colnum="2" colname="col2" colwidth="148mm" /><tbody><row><entry>Feed 1:</entry><entry>50 g of butadiene</entry></row><row><entry>Feed 2:</entry><entry>aqueous emulsion formed from 50 g of styrene, 1 g of acrylic acid, 0.2 g of tert-dodecyl mercaptan, 3.0 g of a 28 wt% aqueous solution of Texapon^® NSO (Cognis) and 40 g of deionized water</entry></row><row><entry>Feed 3:</entry><entry>0.5 g of sodium peroxodisulfate dissolved in 10 g of deionized water</entry></row></tbody></tgroup></table></tables>

The aqueous polymer dispersion obtained had a coagulum content of 0.4% by weight and the solids content was determined to be 46% by weight. The determined by dynamic light scattering average particle size of the resulting Polymeriatteilchen was 303 nm.

10 ml of the obtained aqueous polymer dispersion were placed in a polyethylene dish with an inner diameter of about 5 cm and dried for 24 hours at 23 ° C and 50% relative humidity. A clear flexible film was obtained. The glass transition temperature of the polymer was determined to be -5 ° C. In addition, the polymer still had a melting point of about 170 ° C.