WO2004067603A1 - Method for producing aqueous polymer dispersions based on olefins by means of metal complex catalytic polymerization - Google Patents

Abstract

The invention relates to a method for producing aqueous polymer dispersions by polymerizing one or more olefins, optionally, with carbon monoxide in an aqueous medium in the presence of: a) one or more metal complexes, and; ) one or more dispersants. The invention also relates to the aqueous copolymer dispersions themselves and to the use thereof. The invention also relates to the polyketones of formula (I) obtained from the polymer dispersions. M represents a transition metal of group VIIIB; IB or IIB of the periodic table of elements. E1 and E2, independent of one another, represent an element of group VA of the periodic table of elements; R2 represents fluorine, sulfo, nitro or perfluorinated C1-C10 alkyl.

Description

Process for the preparation of aqueous polymer dispersions based on olefins by metal complex catalytic polymerization

description

Process for the preparation of aqueous polymer dispersions by polymerizing one or more olefins, optionally with carbon monoxide in an aqueous medium, in the presence of a) one or more metal complexes and b) one or more dispersants, the aqueous copolymer dispersions themselves and their use. It also relates to the polyketones obtained from the polymer dispersions.

Copolymers of carbon monoxide and olefinically unsaturated compounds, also referred to briefly as polyketones, are high-molecular, partially crystalline compounds with advantageous mechanical and rheological properties, high melting point, good heat resistance, good chemical resistance and good barrier properties against water and air. These properties are influenced by the strictly alternating sequence of the monomers in the main chain. Polyketones made from carbon monoxide and olefins are of technical interest.

Polyketones are generally made by transition metal catalyzed processes. For example, EP-A 0 121 965 describes a cis-palladium complex chelated with bidentate phosphine ligands, [Pd (Ph ₂ P (CH ₂ ) ₃ PPh ₂ )] (OAc) ₂ (Ph = phenyl, Ac = acetyl), used. The carbon monoxide copolymerization is often carried out as a suspension polymerization, as described in EP-A 0 305 011. Complex compounds with bisphosphine chelate ligands, the residues of which on the phosphorus represent Ar 1 or substituted aryl groups, have proven to be particularly suitable for suspension polymerization. Accordingly, 1,3-bis (diphenylphosphino) propane or 1,3-bis [di- (o-methoxyphenyl) phosphino)] propane are particularly frequently used as chelating ligands (see also Drent et al., Chem. Rev., 1996, 96, pp. 663 to 681). The disadvantage of carbon monoxide copolymerization in suspension is that the solvents chosen as suspending agents can be separated from the product only with great effort. In addition, the carbon monoxide copolymers formed (hereinafter referred to as "copolymers") precipitate in the organic suspending agents and have to be separated off by filtration and further processed in bulk. In many fields of application, however, it is advantageous if the copolymers are not in bulk but in the form of aqueous copolymer dispersions. This is particularly the case when the copolymers are to be used, for example, as binders in adhesives, sealants, plastic plasters or paints. In principle, aqueous copolymer dispersions can be prepared by appropriate suspension polymerization in organic solvents, filtration, drying, grinding and dispersing the ground copolymer particles in an aqueous medium (so-called secondary dispersions). A disadvantage of this step concept is that overall it is very complex and problems often occur when processing the polymer, such as grinding or dispersing.

It is therefore an aim to have so-called primary aqueous copolymer dispersions, i.e. to produce aqueous copolymer dispersions which are directly accessible by copolymerization of carbon monoxide and olefinically unsaturated compounds in an aqueous medium.

For example, DE-A-100 61 877 describes stable aqueous copolymer dispersions composed of carbon monoxide and olefinically unsaturated compounds which are prepared in an aqueous medium using special water-soluble metal catalysts and using special comonomers. The preparation of copolymer dispersions with the same metal catalysts but in the presence of so-called host compounds is described in DE-A-101 25238. In addition, the document discloses that stable copolymer dispersions are accessible even without the use of special comonomers. This is particularly the case when the copolymerization of carbon monoxide and the olefinically unsaturated compounds is carried out in the presence of ethoxylated emulsifiers.

German application 101 33042.1 teaches the preparation of primary aqueous copolymer dispersion using the oil-soluble metal complexes customary in suspension polymerization in the presence of solvents.

Precisely because the processes for primary aqueous copolymerization are intended to make further processing of the polymer superfluous and are aimed at tailor-made dispersions, the process products are said to have advantageous application properties. Such properties include, in particular, good tensile elongation and improved flexibility, which are generally related to the higher molecular weight and greater irregularity of the polymer chain.

It was therefore an object of the present invention to provide a process which gives rise to polymer dispersions which have a greater irregularity in the polymer chain and higher average molecular weights. Accordingly, a process has been found for the preparation of aqueous polymer dispersions, by polymerizing one or more olefins, if appropriate with carbon monoxide in an aqueous medium, in the presence

a) one or more metal complexes of the general formula I.

in der

in the

a transition metal from group VIIIB, IB or IIB of the Periodic Table of the Elements,

E and E ² independently of one another are an element from group VA of the Periodic Table of the Elements,

Y CrC ₅ alkylene, which is substituted by hydroxyl, d-Ce alkoxy, carboxyl, sulfo, amino, ammonium, phosphono, phosphonato, sufamoyl, amidino, carbamoyl, hydroxysufonyloxy, sulfino and CC ₄ alkyl and by oxygen, imino , Alkylimino, silylene or mono- or dialkylsilylene may be interrupted or may have a fused-on cycloaliphatic ring or fused-on benzene or 1,8-naphthylene,

R ¹ CrC ₂ o-alkyl which is optionally substituted by hydroxyl, CC ₆ alkoxy, carboxyl, sulfo or aryl, C ₆ -C ₁ aryl which is optionally substituted by CrC alkyl, hydroxyl, CrC ₆ alkoxyl, carboxyl, Cyano or a radical R ^{2 is} substituted or C ₃ -C ₁₂ cycloalkyl

R ² fluorine, sulfo, nitro, or perfluorinated C ₁ -G ₁₀ -

R, R, R and R independently of one another are hydrogen or a radical R,

L ¹ and L ² independently of one another phosphines (R ⁷ ) _X PH ₃ . _X , amines (R ⁷ ) _X NH _3-X or ether (R ⁷ ) ₂ O, each with the same or different radicals R ⁷ , alcohols R ⁷ OH, H ₂ O, pyridine compounds C ₅ H _5-X (R ⁷ ) _X N, carbon monoxide, Ce-C ^ alkyl nitriles, CrC aryl nitriles or olefins, where x is an integer from 0 to 3, amide ions (R ⁷ ) _h NH _2-h , where h is an integer from 0 to 2, d-Ce alkyl anions, C ₃ -C ₁ cycloalkyl anions, allyl anions, methallyl anions, benzyl anions, aryl anions, carboxylic acid anions, sulfonic acid anions, ketones or diketones, where L ¹ and L ² can be linked to one another by one or more covalent bonds

R ^{7 is} hydrogen, -CC ₂ o-alkyl, which is optionally substituted with CrC ₆ alkoxy, mono- or DKCrCe-alky ^ amino or C ₆ -C ₁₄ aryl, C ₃ -C ₁₂ cycloalkyl, or

C ₆ -C ₁₄ aryl,

An ^" the equivalent of an anion of a noncoordinating acid with pKs <4.75 and

n is an integer 0, 1, 2, 3 or 4, and b) one or more dispersants.

The invention also relates to the aqueous copolymer dispersions obtained by the processes and to the polyketones obtained from the polymer dispersions.

Examples of suitable olefins for the preparation of homopolymers for the process according to the invention are: ethylene, propylene, 1-butene, 2-butene, butadiene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 1-eicosen, but also branched olefins such as isobutene, 4-methyl-1-pentene, norbornene, vinylcyclohexene and vinylcyclohexane, and styrene, para-methylstyrene and para-vinylpyridine, ethylene and propylene being preferred. Ethylene is particularly preferred.

The copolymerization of two or more olefins is also possible with the process according to the invention, it being possible for the coolefins used to be selected from the following groups:

- Nonpolar 1-olefins, such as, for example, ethylene, propylene, 1-butene, 2-butene, butadiene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 1-eicosen, but also branched olefins, such as isobutene, 4-methyl-1-pentene, vinylcyclohexene and vinylcyclohexane and styrene, para-methylstyrene and para-vinylpyridine, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- octene, 1-decene are preferred. - olefins which contain polar groups, such as, for example, acrylic acid, acrylic acid-CrCs-alkyl ester, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid, methacrylic acid-CrC ₈ -alkyl ester, C 1 -C ₆ -alkyl- Vinyl ether and vinyl acetate, but also 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and styrene-4-sulfonic acid. Acrylic acid, acrylic acid methyl ester, acrylic acid ethyl ester, acrylic acid n-butyl ester, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl vinyl ether, vinyl acetate, 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid are preferred.

The proportion of coolefins in the olefin mixture to be polymerized is freely selectable and is usually <50% by weight, frequently <40% by weight and often <30% by weight or <20% by weight. If olefins containing polar groups in particular are used for the copolymerization, their proportion in the olefin mixture to be polymerized is generally> 0.1% by weight,> 0.2% by weight or> 0.5% by weight, and <2 % By weight, <5% by weight or <10% by weight.

For the preparation of aqueous polymer dispersions, preference is given to using only ethylene as the monomer. If at least two olefins are used for the polymerization, these are often selected from the group comprising ethylene, propylene, 1-butene, 1-hexene and styrene. Ethylene is often used in combination with propylene, 1-butene, 1-hexene or styrene.

If aqueous polymer dispersions of polyketones are produced, propene and / or 1-butene are preferably used as monomers in addition to carbon monoxide. Propene and / or 1-butene are often used in combination with ethylene or other 1-olefins.

In the context of this application, an aqueous medium is understood to mean water which contains up to 10% by weight of water-miscible solvents. Water-miscible solvents are to be understood as solvents which are miscible with water in the desired amount at 25 ° C. and 1 bar. In addition to the alcohols mentioned below such as methanol, ethanol, propanol, isopropanol, glycol, glycerin and methoxyethanol, these include water-soluble ethers such as tetrahydrofuran and dioxane.

In the context of this document, the designations for the groups of the Periodic Table of the Elements are based on the nomenclature used by the Chemical Abstracts Service until 1986 (for example, the VA group contains the elements N, P, As, Sb, Bi; the IB group contains Cu, Ag , Au). Suitable metals M of the metal complexes according to the invention are the metals of the groups, VIIIB, IB and IIB of the Periodic Table of the Elements, i.e. in addition to copper, silver or zinc, also iron, cobalt and nickel, and the platinum metals such as ruthenium, rhodium, osmium, iridium and Platinum, the platinum metals, in particular nickel and platinum and very particularly palladium being preferred.

The elements E ¹ and E ^{2 of} the chelating ligands are the non-metallic elements of the 5th main group of the periodic table of the elements, for example nitrogen, phosphorus or arsenic. Nitrogen and / or phosphorus, in particular phosphorus, are particularly suitable. The chelating ligands can contain different elements E ¹ and E ² , for example nitrogen and phosphorus. Both E ¹ and E ² are particularly preferably phosphorus.

If residues of acids are mentioned in the abovementioned formula, these residues can of course also be present in the form of their salts under the process conditions, which of course are also encompassed by the invention.

All alkyl or alkylene groups appearing in the above formula can be both straight-chain and branched.

If substituted alkyl, alkylene or aryl groups occur in the above-mentioned formula, they can be substituted once or three times by the radicals mentioned. Furthermore, they can be substituted with different radicals at the same time.

DC-alkyl is understood to mean the radicals methyl, ethyl, propyl, isopropyl, butyl isobutyl, sec-butyl, tert-butyl. Among C-ι-C ₂ -alkyl, the radicals already listed under CC ₄ and further pentyl, isopentyl, neopentyl be, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl , Decyl, (the terms isooctyl, isononyl and isodecyl above are trivial names and come from the alcohols obtained from oxo synthesis - cf. Ulimann's Encyclopedia of Industrial Chemistry, 4th edition, volume 7, pages 215 to 217, and volume 11 , Pages 435 and 436).

C ₃ -C ₁₂ cycloalkyl is preferably understood to mean the radicals cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl. C ₆ -C ₁ -Aryl is preferably phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Understood phenanthryl.

Among d-Ce-alkoxy are preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy.

Y radicals are, for example, methylene, ethylene, 1,2- or 1,3-propylene, 12-, 2,3- or 1,4-butylene, (CH ₂ ) ₂ O (CH ₂ ) ₂₎ (CH ₂ ) ₃ O (CH ₂ ) ₂ , (CH ₂ ) 3θ (CH ₂ ) ₃ , (CH2) 2θ (CH2) O (CH ₂ ) _2l (CH ₂ ) 2NH (CH ₂ ) ₂ , (CH ₂ ) ₃ NH (CH ₂ ) _2j (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ , (CH ₂ ) ₂ N (CH ₃ ) (CH ₂ ) ₂ , (CH ₂ ) ₃ N (CH ₃ ) (CH ₂ ) ₂ or (CH ₂ ) ₂ N (CH ₃ ) (CH ₂ ) ₂ H (CH ₃ XCH ₂ ) _2> norboman-2,3-diylene, cyclopropane-1,2-diylene, 1,2-phenylene, 1 , 8-naphthylene, dimethylsilylene or diphenylsilylene.

In addition to the above-mentioned alkyl radicals, R ¹ are, for example, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, acetyl, propionyl, butyryl, isobutyryl, sulfomethyl, 2-sulfoethyl, 2- or 3-sulfopropyl , 2- or 4-sulfobutyl.

R ¹ and R ⁷ are, for example, benzyl, 1- or 2-phenylethyl, 1-phenylprop-1 -yl, 2-phenylprop-1 -yl, 3-phenylprop-1 -yl, 1-phenylbut-1 -yl, 2 -Phenylbut-1-yl, 3-phenylbut-1-yl, 4-phenylbut-1-yl, -1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenylbut-2-yl, 4- Phenylbut-2-yl, 1- (phenylmethyl) -1-eth-1-yl, 1- (phenylmethyl) -1- (methyl) -eth-1-yl, 1- (phenylmethyl) -I-prop-1 - yl,

R ⁷ radicals are furthermore, for example, dimethylamino, diethylamino and diisopropylamino.

L ¹ and L ² are selected independently of one another from:

- Phosphanes of the formula (R ⁷ ) _X PH _3-X , with x for an integer between 0 and 3

Amines of the formula (R ⁷ ) _X NH _{3 -X>} with x for an integer between 0 and 3 - ethers (R ⁷ ) ₂ O such as dimethyl ether, diethyl ether or preferably tetrahydrofuran,

Alcohols (R ⁷ ) OH such as methanol or ethanol,

Pyridine compounds of the formula C ₅ H _5-X (R ⁷ ) _X N with x for an integer between 0 and 3, such as pyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2, 4-lutidine, 2,5-lulidine, 2,6-lutidine or 3,5-lutidine, - G-ι-Cι ₂ alkyl nitriles or C ₆ -C ₁₄ aryl nitriles, such as acelonitrile, propionitrile, butyronitrile or benzonitrile

Olefins such as ethenyl, propenyl, cis-2-butenyl, trans-2-butenyl, cyclohexenyl or norbornenyl,

- Amide ions (R ⁷ ) _h NH ₂ _ _h , where h is an integer between 0 and 2 - CC ₆ alkyl anions and C ³ -C ¹⁴ cycloalkyl anions such as Me ^" , (C ₂ H ₅ ) ^" , (C ₃ H ₇ ) ^" , (nC ₄ H ₉ ) ^" , (tert.-C ₄ H ₉ ) - or (C ₆ H ₁₃ ) ^"

Allyl ions or methallyl ions,

- Benzyl anions or aryl anions, such as (C ₆ H ₅ ), - Carboxylic acid anions, in particular C to C ₇ carboxylic acid anions such as, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, preferably acetate

- Ketones and diketones such as acetone, acetylacetone

- Sulfonic acid anions such as methyl sulfonate, trifluoromethyl sulfonate and preferably p-toluenesulfonate.

Suitable ligands are also L and L ² H ₂ O, carbon monoxide, nitrates and hydride.

In a particular embodiment, L ¹ and L ² are linked to one another by one or more covalent bonds. Examples of such ligands are 1,5-cyclooctadienyl ligands ("COD"), cyclooct-1-en-4-yl, 1,6-cyclodecenyl ligands or 1,5,9-all-trans-cyclododecatrienyl ligands.

In a further special embodiment, L ^{1 is} tetramethylethylenediamine, only one nitrogen coordinating with the metal.

Preferably used as L ¹ and L ^{2 are} acetonitrile, acetylacetone, trifluoroacetate, benzonitrile, tetrahydrofuran, diethyl ether, acetate, tosylate or water, and also methyl, ethyl, propyl, butyl, phenyl, benzyl, methanesulfonate, trifluoromethanesulfonate, sulfate, carbonate and nitrate , In particular, preferred ligands L ¹ and L ^{2 are} acetate, acetonitrile and tetrahydrofuran.

Basically, the ligands L ¹ and L ^{2 can be} in any ligand combination. The metal complexes L ¹ and L ² are frequently present as identical ligands.

In general, the metals M can be present in the complexes in a formally uncharged, formally single positive or preferably formally double positive. Depending on the formal

Charge of the complex fragment containing the metal M and the charge of the ligands L ¹ and L ² , the metal complexes are present as a neutral compound or as a cation. Accordingly, they have anions X for charge neutralization. However, if the M-containing complex fragment is formally uncharged, the metal complex according to formula (I) contains no anion X. Advantageously, anions X are used which are as little nucleophilic as possible, ie have as little tendency as possible, with the central metal M a strong one Interaction, whether ionic, coordinative or covalent. Suitable anions X are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as, for example, acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, for example methylsulfonate, trifluoromethylsulfonate and p-toluenesulfonate Tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate. Perchlorate, trifluoroacetate, sulfonates such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate, tetrafluoroborate or hexafluorophosphate and in particular trifluoromethyl sulfonate, trifluoroacetate, perchlorate or p-toluenesulfonate are preferably used.

The complex compounds I to be used according to the invention are characterized in that the radical R ² and optionally the radicals R ³ , R ⁴ , R ⁵ and / or R ⁶ carry fluorine, sulfo, nitro or perfluorinated CrC ₁₀ alkyl. It is believed that due to their electron-withdrawing nature, such residues bring about the beneficial properties of the complexes. Compounds of the formula I in which the radicals R ² , R ³ and / or R ^{4 represent} trifluoromethyl are particularly preferred.

It has been found that the dispersions prepared according to the above process have particularly good properties when the R ¹ radicals differ from the rest of the formula II

verschieden sind. Das heißt, dass der Rest R¹ für G_t-C₂₀-Alkyl, das gegebenenfalls mit Hydroxyl, d-Ce-Alkoxy, Carboxyl, Sulfo oder Aryl substituiert ist oder C₃-C₁₂-Cycloalkyl steht und wenn R¹ C₆-C₁₄-Aryl, das gegebenenfalls mit CrC₄-Alkyl, Hydroxyl, Gι-C₆- Alkoxyl, Carboxyl, Cyano oder einem Rest R² substituiert ist, bedeutet, sich der Rest in Art und/oder Zahl der Substituenten vom Rest der Formel II unterscheidet. Insbesondere weist Aryl als Bedeutung von R¹ keinen der unter R² genannten Reste auf.

are different. This means that the radical R ^{1 is} G _t -C ₂₀ alkyl, which is optionally substituted by hydroxyl, d-Ce-alkoxy, carboxyl, sulfo or aryl or is C ₃ -C ₁₂ cycloalkyl and when R ^{1 is} C ₆ -C ₁₄ aryl, which is optionally substituted with CrC ₄ alkyl, hydroxyl, Gι-C ₆ - alkoxyl, carboxyl, cyano or a radical R ² , means the radical in nature and / or number of substituents from the rest of the Formula II differs. In particular, aryl as the meaning of R ^{1 has} none of the radicals mentioned under R ² .

Examples of radicals of the formula II are 3,5-bis (trifluoromethyl) phenyl, 2,6-bis (trifluoromethyl) phenyl and 2,4,6-tris (trifluoromethyl) phenyl.

Metal complexes 1 are preferably used in which

M stands for nickel, palladium or platinum, in particular palladium and E for nitrogen or in particular phosphorus and Y, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , L ¹ , L ² , R ⁷ , An ^" and n have the meaning given above. In particular, metal complexes I are used in which

M for nickel, palladium or platinum, in particular palladium E for nitrogen or in particular phosphorus and R ¹ Ce-Cu aryl, which is optionally substituted by CrC ₄ alkyl, hydroxyl, CrC ₆ alkoxyl, carboxyl, cyano or a radical R ² , and Y, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , L ¹ , L ² , R ⁷ , An ^" and n have the meaning given above.

Metal complexes I in which

M for palladium E for phosphorus and

R ^{1 is} C ₆ -C ₁ aryl, which is optionally substituted with dC ₄ alkyl, hydroxyl, CrC ₆ alkoxyl, carboxyl or cyano and Y, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , L ¹ , L ² , R ⁷ , An ^" and n have the meaning given above.

The synthesis of the metal complexes of the general formula I is known per se. The synthesis of the complexes of the formula I can be carried out analogously to the teachings of the Lindner et al, J. Organomet Chem. 2000, 602, 173.

The total amount of metal complex I used is generally 10 ^"7 to 10 ^{" 2} mol / l, often 10 ^'6 to 10 ^"3 mol / l and often 10 ^{" 5} to 10 ^"4 mol / l, each based on the total amount of water, olefinically unsaturated compounds and optionally organic solvents.

The metal complexes of the formula I to be used according to the invention can be used either by first isolating them after the reaction of the ligands with the metal compound and then introducing them into the polymerization system comprising monomers, aqueous medium and dispersant, and also as a so-called in-situ system , the isolation of the complex compound being dispensed with. The polymerization is preferably carried out in the presence of one or more metals from subgroup VIIIB, which is in salt or complex form, and a chelate ligand of the general formula III Rl • R ¹

:1

in der E¹, E², Y, R¹, R², R³, R⁴ und R⁵ obengenannte Bedeutung haben, eines Dispergiermittels und gegebenenfalls einer Säure a2) durch.

in which E ¹ , E ² , Y, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have the} abovementioned meaning, of a dispersant and optionally an acid a2).

In a preferred process, the aforementioned metal complexes I are used in the presence of acids a2), which are also referred to as activators.

Both mineral protonic acids and Lewis acids are suitable as activator compounds a2). Suitable protonic acids are, for example, sulfuric acid, nitric acid, boric acid, tetrafluoroboric acid, perchloric acid, p-toluenesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid or methanesulfonic acid. P-Toluenesulfonic acid and tetrafluoroboric acid are preferably used. Examples of Lewis acids are boron compounds such as triphenylborane, tris (pentafluorophenyl) borane, tris (p-chlorophenyl) borane or tris (3,5-bis (trif Iuormethyl) phenyl) borane or aluminum, zinc, Antimony or titanium compounds with a Lewis acidic character in question. Mixtures of protonic acids or Lewis acids and protonic and Lewis acids in a mixture can also be used.

The molar ratio of optionally used acid a2) to metal complex a1) of the formula I, based on the amount of metal M, is generally in the range from 60: 1 to 1: 1, frequently from 25: 1 to 2: 1 and often from 12: 1 to 3: 1.

In a likewise preferred process, the aforementioned metal complexes a1) are used together with the acids a2) in the presence of organic hydroxy compound a3).

Suitable organic hydroxy compounds a3) are all low molecular weight organic substances (M _w <500) which have one or more hydroxyl groups. Lower alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, n- or i-propanol, n-butanol, s-butanol or t-butanol, are preferred. Aromatic hydroxy compounds, such as phenol, can also be used. Sugars such as fructose, glucose or lactose are also suitable. Also suitable are polyalcohols, such as Ethylene glycol, glycerin or polyvinyl alcohol. Mixtures of several hydroxy compounds a3) can of course also be used.

The molar ratio of optionally used hydroxy compound a3) to metal complex a1), based on the amount of metal M, is generally in the range from 0 to 100,000, often from 500 to 50,000 and often from 1,000 to 10,000.

The dispersants likewise used in the process according to the invention can be emulsifiers or protective colloids.

Suitable protective colloids are, for example, polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic acids, gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, 2-acrylamido-2-methylpropane sulfonic acid and / or 4-styrenesulfonic acid and vinyl alcohols, as well as alkali metal sulfonates, and their alkali metal sulfonates, too. N-vinylcaprolactam, N-vinylcarbazole, 1-

Vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, methacrylates, acrylamides and / or homo- and copolymers containing methacrylamides. A detailed description of other suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 411 to 420.

Mixtures of protective colloids and / or emulsifiers can of course also be used. Often only emulsifiers are used as dispersants b), the relative molecular weights of which, in contrast to the protective colloids, are usually below 1000. They can be of anionic, cationic or nonionic nature. Of course, if mixtures of surface-active substances are used, the individual components must be compatible with one another, which can be checked in the case of doubt using a few preliminary tests. In general, anionic emulsifiers are compatible with one another and with nonionic emulsifiers. The same applies to cationic emulsifiers, while anionic and cationic emulsifiers are usually not compatible with one another. An overview of suitable emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Substances, Georg-Thieme-Verlag, Stuttgart, 1961, pp. 192 to 208.

According to the invention, anionic, cationic and / or nonionic emulsifiers are used in particular as dispersants b). Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C ₄ to C ₁₂ ) and ethoxylated fatty alcohols (EO grade: 3 to 80; alkyl radical: C ₈ to C) ₃₆ ). Examples of these are the Lutensol ^® A brands (C ₁₂ C ₁₄ fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol ^® AO brands (C ₁₃ C ₅ - oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol ^® AT brands (Cι ₆ C ₁₈ -

Fatty alcohol ethoxylates, EO grade: 11 to 80), Lutensol ^® ON grades (C ₁₀ oxo alcohol ethoxylates, EO grade: 3 to 11) and the Lutensol ^® TO grades (C ₁₃ oxo 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 ₈ to C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ₁₂ to C ₁₈ ) and ethoxylated alkyl phenols (EO Grade: 3 to 50, alkyl radical: C to C ₁₂ ), of alkyl sulfonic acids (alkyl radical: C ₁₂ to C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to C ₁₈ ).

Compounds of the general formula (IV) have also proven to be further anionic emulsifiers.

wherein R ⁸ and R ^{9 are} hydrogen or C ₄ - to C ₂₄ -alkyl and not simultaneously

Are hydrogen, and D ¹ and D ^{2 can be} alkali metal ions and / or ammonium ions. In the general formula IV, R ⁸ and R ^{9 are} preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or hydrogen, where R ⁸ and R ^{9 are} not both hydrogen at the same time. D ¹ and D ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Compounds IV in which D and D ^{2 are} sodium, R ^{8 is} a branched alkyl radical having 12 C atoms and R ^{9 is} hydrogen or R ⁸ are particularly advantageous. Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ^® 2A1 (trademark of Dow Chemical Company). The compounds IV are generally known, for example from US Pat. No. 4,269,749, and are commercially available.

Suitable cationic emulsifiers are usually a C ₆ - to C ₁₈ -alkyl, C ₆ - having Ciβ-alkylaryl or heterocyclic group, primary, secondary, tertiary or quaternary ammonium salts, Aikanolammoniumsalze, pyridinium salts, Imidazolini- 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 sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl paraffinates, N-cetylpyridinium sulfate, N-laurylpyridinium sulfate and N-cetyl-N, N, N-trimethylammonium sulfate , N-Dodecyl-N, N, N-trimethylammonium sulfate, N-Octyl-N, N, N, N-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate and the gemini surfactant N, N'- (lauryl) ethylendiamindisuIfat, ethosulfate xyliertes tallow alkyl-N-methyl ammonium sulfate and ethoxyliert.es oleylamine (beispiels- as Uniperol.RTM ^® AC from. BASF AG, about 12 ethylene oxide). Numerous other examples can be found in H. Stächen, Tensid-Taschenbuch, Carl-Hanser-Verlag, Munich, Vienna, 1981 and in McCutcheon's, Emulsifiers & Detergents, MC Publishing Company, Glen Rock, 1989. It is essential that the anionic countergroups are as possible are low nucleophilic, such as perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate , furthermore tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

The emulsifiers preferably used as dispersants b) are advantageously used in a total amount of 0.005 to 10 parts by weight, preferably 0.01 to 7 parts by weight, in particular 0.1 to 5 parts by weight, based in each case on 100 parts by weight. Parts of the olefinically unsaturated compounds used. The amount of emulsifier is frequently chosen so that the critical micelle formation concentration of the emulsifiers used is essentially not exceeded within the aqueous phase.

The total amount of protective colloids additionally or instead used as dispersant b) is often 0.1 to 10 parts by weight and often 0.2 to 7 parts by weight, based in each case on 100 parts by weight of the olefinically unsaturated compounds.

According to a preferred process variant, organic solvents c) which are only slightly soluble in water can optionally be used. Suitable solvents c) are liquid aliphatic and aromatic hydrocarbons with 5 to 30 carbon atoms, such as, for example, 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, eicosane, benzene, toluene, ethylbenzene, cumene, o- , m- or p-xylene, mesitylene, and generally hydrocarbon mixtures in the boiling range from 30 to 250 ° C. Hydroxy compounds, such as saturated and unsaturated fatty alcohols with 10 to 32 C atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, ceryl alcohol or myricylic alcohol (mixture of C ₃₀ - and C ₃₁ -Alcohols) esters, such as fatty acid esters with 10 to 32 carbon atoms in the acid part and 1 to 10 carbon atoms in the alcohol part or esters of carboxylic acids and fatty alcohols with 1 to 10 carbon atoms in the carboxylic acid part and 10 to 32 carbon atoms in the alcohol part , Of course, it is also possible to use mixtures of the aforementioned solvents.

Depending on the hydrophilic residues of the metal complex, no or only small amounts of solvent c) are required. The total amount of solvent is up to 15 parts by weight, preferably 0.001 to 10 parts by weight and particularly preferably 0.01 to 5 parts by weight, in each case based on 100 parts by weight of water.

It is advantageous if the solubility of solvent c) or of the solvent mixture under reaction conditions in the aqueous reaction medium is preferably <50% by weight, <40% by weight, <30% by weight, <20% by weight or <10 % By weight, based in each case on the total amount of solvent.

Solvents c) are used in particular when the olefinically unsaturated compounds are gaseous under reaction conditions (pressure / temperature), as is the case, for example, with ethene, propene, 1-butene and / or i-butene.

According to a preferred process, one or more olefins are optionally polymerized with carbon monoxide in an aqueous medium in the presence of

a) one or more metal complexes of the general formula I b) dispersants and optionally c) slightly water-soluble organic solvents,

wherein the metal complexes a) are dissolved in a part or the total amount of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c) and the part or the total amount of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents Solvent c), which contains dissolved metal complexes I, is present in the aqueous medium as a disperse phase with an average droplet diameter <1000 nm.

The copolymerization is preferably carried out in the presence of a1) metal complexes of the general formula I a2) an acid and a3) optionally an organic hydroxy compound

carried out.

According to a preferred embodiment, the total amount of the metal complexes a1), including any acids a) and organic hydroxy compounds a3), is dissolved in a part or the total amount of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c). Then the partial or total amount of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c), which contains the metal complexes a1) in solution, in the presence of dispersants b) in the aqueous medium as a disperse phase with a medium Droplet diameter <1000 nm dispersed and at the reaction temperature carbon monoxide and any remaining amounts of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c) added continuously or discontinuously.

A preferred process variant is carried out in such a way that in a first step the total amount of the metal complexes a1) and the optionally used acids a2) and the organic hydroxy compounds a3) in a part or the total amount of the olefinically unsaturated compounds and / or the small amount in water soluble organic solvents c) dissolves. This solution is then dispersed together with the dispersants b) in an aqueous medium with the formation of oil-in-water dispersions with an average droplet diameter> 1000 nm, the so-called macroemulsions. These macroemulsions are then converted into oil-in-water emulsions with an average droplet diameter <1000 nm, the so-called mini emulsions, using known measures, and carbon monoxide and any remaining or total amount of the olefinically unsaturated compounds and / or the small amount are added to them at the reaction temperature Water-soluble organic solvents c).

The average size of the droplets of the disperse phase of the aqueous oil-in-water emulsions to be used according to the invention can be determined according to the principle of quasi-elastic dynamic light scattering (the so-called z-average droplet diameter d _{z of} the unimodal analysis of the autocorrelation function). In the examples in this document, a Coulier N4 Plus Particle Analyzer from Coulter Scientific Instruments was used (1 bar, 25 ° C.). The measurements were carried out on dilute aqueous mini-emulsions whose content of non-aqueous constituents was 0.01% by weight. The dilution was carried out using water which had previously been mixed with the olefinically unsaturated saturated compounds and / or slightly water-soluble organic solvents c) had been saturated. The latter measure is intended to prevent a change in the droplet diameter associated with the dilution.

According to the invention, the values for d _z determined in this way for the so-called mini-emulsions are normally <700 nm, frequently <500 nm. According to the invention, the d ₂ range from 100 nm to 400 nm or from 100 nm to 300 nm is favorable. In the normal case, d _{2 of} the aqueous miniemulsion to be used according to the invention> 40 nm.

The general production of aqueous mini-emulsions from aqueous macroemulsions is known to the person skilled in the art (cf. PL Tang, ED Sudol, CA. Silebi and MS El-Aasser in Journal of Applied Polymer Science, Vol. 43, pp. 1059 to 1066 [1991]) ,

High-pressure homogenizers, for example, can be used for this purpose. The fine distribution of the components in these machines is achieved through a high local energy input. Two variants have proven particularly useful in this regard.

In the first variant, the aqueous macroemulsion is compressed to over 1000 bar using a piston pump and then expanded through a narrow gap. The effect here is based on an interaction of high shear and pressure gradients and cavitation in the gap. An example of a high-pressure homogenizer that works on this principle is the Niro-Soavi high-pressure homogenizer type NS1001 L Panda.

In the second variant, the compressed aqueous macroemulsion is expanded into a mixing chamber via two opposing nozzles. The fine distribution effect is primarily dependent on the hydrodynamic conditions in the mixing chamber. An example of this type of homogenizer is the M 120 E microfluidizer from Microfluidics Corp. In this high-pressure homogenizer, the aqueous macroemulsion is compressed to a pressure of up to 1200 atm by means of a pneumatically operated piston pump and expanded via a so-called "interaclion chamber". In the "interaction chamber", the emulsion jet is divided into two jets in a microchannel system, which are brought together at an angle of 180 °. Another example of a homogenizer working according to this type of homogenization is the Nanojet type Expo from Nanojet Engineering GmbH. However, instead of a fixed duct system, two homogenizing valves are installed in the Nanojet, which can be adjusted mechanically. In addition to the principles explained above, homogenization can also be carried out, for example, by using ultrasound (eg Branson Sonifier II 450). The fine distribution here is based on cavitation mechanisms. In principle, the devices described in GB-A 22 50 930 and US-A 5,108,654 are also suitable for homogenization by means of ultrasound. The quality of the aqueous miniemulsion generated in the sound field depends not only on the sound power introduced, but also on other factors such as e.g. B. the intensity distribution of ultrasound in the mixing chamber, the residence time, the temperature and the physical properties of the substances to be emulsified, for example on the toughness, the interfacial tension and the vapor pressure. The resulting droplet size depends, inter alia, on the concentration of the emulsifier and on the energy introduced during the homogenization and can therefore be set in a targeted manner, for example by changing the homogenization pressure or the corresponding ultrasound energy.

The device described in the older German patent application DE 197 56 874 has proven particularly useful for producing the aqueous mini-emulsion from conventional macroemulsions according to the invention by means of ultrasound. This is a device which has a reaction space or a flow-through reaction channel and at least one means for transmitting ultrasound waves to the reaction space or the flow-through reaction channel, the means for transmitting ultrasound waves being designed in such a way that the entire reaction space , or the flow-through reaction channel in one section, can be irradiated uniformly with ultrasonic waves. For this purpose, the radiation surface of the means for transmitting ultrasound waves is designed such that it essentially corresponds to the surface of the reaction space or, if the reaction space is a partial section of a flow-through reaction channel, extends essentially over the entire width of the channel , and that the depth of the reaction space, which is essentially perpendicular to the radiation surface, is less than the maximum effective depth of the ultrasound transmission means.

The term “depth of the reaction space” here essentially means the distance between the radiation surface of the ultrasound transmission means and the bottom of the reaction space.

Reaction space runs up to 100 mm are preferred. The depth of the reaction space should advantageously not be more than 70 mm and particularly advantageously not more than 50 mm. The reaction spaces can in principle also have a very small depth, but in view of the lowest possible risk of clogging and easy cleaning and a high product throughput, reaction space depths are preferred. trains that are much larger than, for example, the usual gap heights in high-pressure homogenizers and are usually over 10 mm. The depth of the reaction space can advantageously be changed, for example by means of ultrasound transmission means immersed in the housing at different depths.

According to a first embodiment of this device, the radiation area of the means for transmitting ultrasound corresponds essentially to the surface of the reaction space. This embodiment serves for the batchwise production of the mini-emulsions used according to the invention. With this device, ultrasound can act on the entire reaction space. In the reaction chamber, a turbulent flow is generated by the axial sound radiation pressure, which causes intensive cross-mixing.

According to a second embodiment, such a device has a flow cell. The housing is designed as a flow-through reaction channel, which has an inflow and an outflow, the reaction space being a partial section of the flow-through reaction channel. The width of the channel is the channel extension which is essentially perpendicular to the direction of flow. The radiation area covers the entire width of the flow channel transverse to the direction of flow. The length of the radiation surface perpendicular to this width, that is to say the length of the radiation surface in the direction of flow, defines the effective range of the ultrasound. According to an advantageous variant of this first embodiment, the flow-through reaction channel has an essentially rectangular cross section. If a likewise rectangular ultrasound transmission medium with corresponding dimensions is installed in one side of the rectangle, a particularly effective and uniform sound system is guaranteed. Due to the turbulent flow conditions prevailing in the ultrasonic field, however, a round transmission means can also be used without disadvantages, for example. In addition, instead of a single ultrasound transmission means, a plurality of separate transmission means can be arranged, which are connected in series as seen in the flow direction. Both the radiation surfaces and the depth of the reaction space, that is to say the distance between the radiation surface and the bottom of the flow channel, can vary.

The means for transmitting ultrasound waves is particularly advantageously designed as a sonotrode, whose end facing away from the free radiation surface is coupled to an ultrasound transducer. The ultrasonic waves can be generated, for example, by utilizing the reverse piezoelectric effect. With the help of generators, high-frequency electrical vibrations (usually in the range from 10 to 100 kHz, preferably between 20 and 40 kHz) are generated via one piezoelectric transducer converted into mechanical vibrations of the same frequency and coupled with the sonotrode as a transmission element in the medium to be sonicated.

The sonotrode is particularly preferably designed as a rod-shaped, axially radiating λ / 2 (or multiple of λ / 2) longitudinal oscillators. Such a sonotrode can be fastened in an opening of the housing, for example, by means of a flange provided on one of its vibration nodes. The lead-through of the sonotrode into the housing can thus be made pressure-tight, so that the sonication can also be carried out under increased pressure in the reaction space. The oscillation amplitude of the sonotrode can preferably be regulated, that is to say the respectively set oscillation amplitude is checked online and, if necessary, automatically readjusted. The current vibration amplitude can be checked, for example, by a piezoelectric transducer mounted on the sonotrode or a strain gauge with downstream evaluation electronics.

According to a further advantageous embodiment of such devices, baffles are provided in the reaction space to improve the flow and mixing behavior. These internals can be, for example, simple deflection plates or a wide variety of porous bodies.

If necessary, the mixing can also be further intensified by an additional agitator. The reaction space can advantageously be temperature-controlled.

From the above statements it is clear that, according to a preferred process variant, only those organic solvents c) or solvent mixtures can be used whose solubility in the aqueous medium is small enough under reaction conditions to form <1000 nm solvent droplets as a separate phase. In addition, the solubility of the solvent droplets formed must be large enough to take up the metal complexes a1), the acids a2) and the organic hydroxy compounds a3). The same applies to the olefinically unsaturated compounds if they are used without organic solvents c) and for mixtures of olefinically unsaturated compounds and organic solvents c).

One embodiment of the process according to the invention is, for example, such that the total amounts of the metal complex a1) and the optionally added acids a2) and organic hydroxy compounds a3) are dissolved in a part or the total amount of the slightly water-soluble organic solvents c). Then this organic metal complex solution together with a Part or all of the dispersant b) dispersed in water to form a macroemulsion. The macroemulsion is converted into a mini emulsion by means of one of the aforementioned homogenizing devices. Carbon monoxide, the total amount of olefinically unsaturated compounds and, if appropriate, the remaining amounts of organic solvents c) or dispersants b) are metered into these at reaction temperature and with constant stirring. This process variant is chosen in particular when the olefinically unsaturated compounds used are gaseous under reaction conditions, as is the case, for example, with ethene, propene, 1-butene and / or i-butene.

In a further embodiment, the total amount of the metal complex a1) and the optionally added acids a2) and organic hydroxy compounds a3) is dissolved in a part or the total amount of the olefinically unsaturated compounds. This organic metal complex solution is then dispersed together with some or all of the dispersants b) in water to form a macroemulsion. The macroemulsion is converted into a mini emulsion by means of one of the aforementioned homogenizing devices. Carbon monoxide, the remaining amounts of olefinically unsaturated compounds or dispersants b) and, if appropriate, the total amount of the slightly water-soluble organic solvents c) are metered into these miniemulsions at the reaction temperature and with constant stirring. This process variant is chosen in particular when the olefinically unsaturated compounds used are liquid under reaction conditions, as is the case, for example, with 1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene, 1- Tetradecene and / or 1-Hexadecen is the case.

As a rule, the metal complexes a1), especially oil-soluble metal complexes, are dissolved in at least a portion of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c), so that this solution in aqueous medium under reaction conditions as a separate phase with a mean droplet size <1000 nm is present. Any remaining amounts of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c) can be added to the aqueous reaction medium in bulk, in solution or together with any remaining amounts of dispersant b) in the form of an aqueous macroemulsion. If solvents c) are used, the total amount of solvents is usually used to dissolve the metal complexes a1) and then dispersed in an aqueous medium. It is important that the liquid droplets <1000 nm present as a separate phase in the aqueous medium may contain further components in addition to the aforementioned compounds a1), a2), a3) and c) and the olefinically unsaturated compounds. These are, for example, 1,4-quinone compounds which have a positive effect on the activity of the metal complexes a1) and on their service life. In addition to optionally alkyl-substituted 1,4-benzoquinones, further 1,4-quinone compounds, such as optionally alkyl-substituted 1,4-naphthoquinones, can be used. The molar ratio of optionally used 1,4-quinone compounds to metal complex a1), based on the amount of metal M, is generally in the range from up to 1000, often from 5 to 500 and often from 7 to 250. Other components are For example, formulation auxiliaries, antioxidants, light stabilizers, but also dyes, pigments and / or waxes for hydrophobicization. If the solubility of the other components in the organic phase forming the droplets is greater than in the aqueous medium, they remain in the droplets during the polymerization. Since the droplets of olefinically unsaturated compounds and / or slightly water-soluble solvents c) containing the metal complexes a1) ultimately represent the sites for the polymerization of carbon monoxide and the olefinically unsaturated compounds, the polymer particles formed generally contain these additional components in copolymerized form.

The molar ratio of carbon monoxide to the olefinically unsaturated compounds is generally in the range from 10: 1 to 1:10, usually values in the range from 5: 1 to 1: 5 or from 2: 1 to 1: 2 are set.

The polymerization temperature is generally set in a range from 0 to 200.degree. C., preferably at temperatures in the range from 20 to 130.degree. C. and in particular in the range from 40 to 100.degree. The carbon monoxide partial pressure is generally in the range from 1 to 300 bar and in particular in the range from 10 to 220 bar. It is advantageous if the total partial pressure of the olefinically unsaturated compounds under the reaction conditions is less than the carbon monoxide partial pressure. In particular, the total partial pressure of the olefinically unsaturated compounds under reaction conditions is <50%, <40%, <30% or even <20%, in each case based on the total pressure. The polymerization reactor is usually rendered inert before being pressed on with carbon monoxide by flushing with carbon monoxide, olefinically unsaturated compounds or inert gas, for example nitrogen or argon. However, polymerization is often also possible without prior inertization. Average catalyst activities are obtained in the polymerization process according to the invention, which are generally> 0.17 kg, frequently> 0.25 kg and often> 0.5 kg of polymer per gram of complex metal and hour.

According to the invention, aqueous polymer dispersions are obtained whose number-average polymer particle diameters, as determined by quasi-elastic light scattering (ISO standard 13321), are in the range from up to 1000 nm, frequently from 100 to 800 nm and often from 200 to 400 nm. It is important that the polymer particles generally have a narrow, monomodal particle size distribution.

The weight-average molecular weights of the polymers obtainable according to the invention, determined by means of gel permeation chromatography with polymethyl methacrylate as standard, are generally in the range from 1000 to 1,000,000, frequently in the range from 1,500 to 800,000 and often in the range from 2,000 to 600,000.

As can be seen from the ¹³ C or ¹ H NMR spectroscopic investigations, the polymers obtainable by the processes according to the invention are generally linear, aging carbon monoxide copolymer compounds. This is to be understood as meaning polymer compounds in which, in the polymer chain, on each carbon monoxide unit, a -CH ₂ -CH ₂ -, -CH ₂ -CH- or -CH-CH- unit and resulting from the olefinic double bond of the at least one olefinically unsaturated compound each -CH ₂ -CH ₂ -, -CH ₂ -CH- or -CH-CH unit is followed by a carbon monoxide unit. In particular, the ratio of carbon monoxide units to -CH ₂ - CH ₂ -, -CH ₂ -CH or -CH-CH units is generally from 0.9 to 1 to 1 to 0.9, frequently from 0.95 to 1 to 1 to 0.95 and often from 0.98 to 1 to 1 to 0.98.

The process according to the invention gives aqueous dispersions with a head / tail linkage content of <90% and a particle size 1 // m. The head / tail linkage component is according to Lindner et al. J. Organomet. Chem. 2000, 602, 173 determined by means of inverse gated decoupling ³ C { ¹ H} NMR. Head / tail linkage means alternating α-olefin / CO copolymers the polymer microstructure -CH (R) -C (O) -CH ₂ -. The structural element is responsible for the brittle character of highly regioregular polyketones.

By specifically varying the olefinically unsaturated compounds, it is possible according to the invention to prepare polymers whose glass transition temperature or melting point is in the range from -60 to 270 ° C.

With the glass transition temperature T _g , the limit value of the glass transition temperature is meant, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift für Polymer, Vol. 190, p. 1, equation 1) with increasing molecular weight. The glass transition temperature is determined by the DSC method (differential scanning calorimetry, 20 K / min, midpoint measurement, DIN 53765).

After Fox (TG Fox, Bull. Am. Phys. Soc. 1956 [Ser. II] 1, p. 123 and according to Ullmann's Encyclopedia of Technical Chemistry, Vol. 19, p. 18, 4th edition, Verlag Chemie, Weinheim, 1980) applies to the glass transition temperature of at most weakly cross-linked copolymers in good approximation:

1 / T _g = x ¹ / T _g ¹ + x ² / T _g ² + .... x7T _g ⁿ ,

where x ¹ , x ² , .... x ^{n are} the mass fractions of the monomers 1, 2 n and T _g ¹ , T _g ² , .... T _g ⁿ the

Glass transition temperatures of the polymers built up in each case from only one of the monomers 1, 2, .... n in degrees Kelvin. The T _g values for the homopolymerizations of most monomers are known and are listed, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, Vol. 5, Vol. A21, p. 169, VCH Weinheim, 1992; Further sources for glass transition temperatures of homopolymers are, for example, J. Brandrup, EH Immergut, Polymer Handbook, 1 ^st Ed., J. Wiiey, New York 1966, 2 ^πd Ed. J. Wiley, New York 1975, and 3 ^rd Ed. J. Wiley, New York 1989).

The polymer dispersions according to the invention often have minimum film-forming temperatures. temperatures MFT <80 ° C, often <50 ° C or <30 ° C. Since the MFT is no longer measurable below 0 ° C, the lower limit of the MFT can only be specified by the T _g values. The MFT is determined in accordance with DIN 53787.

The process according to the invention makes it possible to obtain aqueous polymer dispersions whose solids content is 0.1 to 70% by weight, frequently 1 to 65% by weight and often 5 to 60% by weight and all values in between.

Of course, the residual monomers remaining in the aqueous polymer system after the main polymerization reaction has ended can be vaporized and / or

Inert gas stripping can be removed without adversely affecting the polymer properties of the polymers present in the aqueous medium.

The aqueous polymer dispersions obtainable according to the invention are frequently stable for several weeks or months and generally show virtually no phase separation, deposition or coagulum formation during this time. They are particularly suitable as binders in the manufacture of adhesives, such as pressure sensitive adhesives, construction adhesives or industrial adhesives, sealing compounds, plastic plasters and paints, such as for paper coating, disc Persistent colors or for printing inks and varnishes for printing on plastic films as well as for the production of nonwovens or for the production of protective layers and water vapor barriers, such as in priming. These aqueous polymer dispersions can also be used to modify mineral binders or other plastics. They are preferably used for paper applications, paints, textile and leather applications, adhesives, molded foams, sealants, curative plasters, carpet back coatings or pharmaceutical applications.

It should also be noted that the aqueous polymer dispersions obtainable according to the invention can be easily dried into redispersible polymer powders (e.g. freeze drying or spray drying). This applies in particular if the glass transition temperature of the polymers is> 50 ° C, preferably> 60 ° C, particularly preferably 70 ° C, very particularly preferably> 80 ° C and particularly preferably> 90 ° C or> 100 ° C , The polymer powders are also suitable as binders in adhesives, sealants, plastic plasters and paints, as well as for the production of nonwovens or for modifying mineral binders, such as mortar or cement, for example in factory dry mortars, repair mortars, gypsum mortars, gypsum building materials, flooring compounds, plasters and leveling compounds and heating compounds , Another use is as modifying additives in other plastics.

Because of their preparation, the aqueous polymer dispersions accessible according to the invention have polymer particles which contain no or only very small amounts [optionally, for example, organic hydroxy compound a3)] of organic solvents. However, if the process according to the invention is carried out in the presence of solvents c) which are sparingly soluble in water, an odor pollution when polymer films are formed can be avoided by selecting high-boiling solvents c). On the other hand, the optionally used solvents c) often act as coalescing agents and thus promote film formation. Due to the process, the polymer dispersions accessible according to the invention have polymer particles with a narrow, monomodal particle size distribution. The aqueous polymer dispersions obtained are moreover stable for weeks and months even with small amounts of dispersant and generally show virtually no phase separation, deposition or coagulum formation during this time. However, aqueous polymer dispersions are also accessible by the process according to the invention, the polymer particles of which contain, in addition to the polymer, further additives, such as, for example, formulation auxiliaries, antioxidants, light stabilizers, but also dyes, pigments and / or waxes. Another advantage of the process according to the invention is that the additives used, for example, the stabilizers used are already in the particle, which makes the mixing very good. This further enables the formulation steps to be reduced.

The present invention is illustrated by the following examples.

A. Production of the metal complexes

All tests were carried out under an argon atmosphere using conventional Schlenk tube technology. The solvents were dried by distillation over drying agents (CaH ₂ for dichloromethane, P ₂ O ₅ for CCI ₄ , LiAIH ₄ for diethyl ether and n-pentanes) and freed from oxygen. Dry acetonitrile was freed from oxygen in vacuo and stored over a molecular sieve 3A. DMSO and H ₂ O were freed from oxygen in vacuo.

1 a) 1, 3-Bis {bis [3,5-bis (trif luoromethyl) phenyl] phosphino} propane

Bis (3,5-bis (trifluoromethyl) phenyl) phosphine (7.06 g, 15.41 mmol) was suspended in 60 ml DMSO. After adding an aqueous KOH solution (1, 12 g, 20.03 mmol, 1, 5 ml H ₂ O), a dark red solution was obtained. After stirring for 30 minutes, 1,3

- Dibromopropane (1.55 g, 7.71 mmol) added and stirring continued for 48 h at room temperature. The reaction mixture was poured into water. This precipitate was separated and dissolved in ether, washed three times with water, dried over Na ₂ SO ₄ and the solvent removed in vacuo. The residue was washed with n-pentane and dried in vacuo.

Yield: 5 g (68%). ¹ H NMR (CDCI ₃ ): δ 7.88 (s, 4H, para Ar), 7.77 (d, 8H, ortho Ar), 2.35 (t, 4H, -CH ₂ P), 1.61 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCI ₃ ): o 139.93 (d, ipso Ar), 132.7-132.1 (m, ortho Ar, meta Ar), 123.65 (sept, para Ar), 122.89 ( q, CF ₃ ), 28.86 (vt, - CH ₂ P), 21, 92 (t, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ -14.88 (s). ¹⁹ F { ¹ H} NMR (CDCI ₃ ): δ - 63.62 (s). MS (El, m / z (%)): 743 (100) [M -Ar] ⁺ , 956 (15) [M] ⁺ , 937 (8) [M -F] ⁺ .

1 b) 1 -Diphenylphosphino-3- {bis [3,5-bis (trifluoromethyl) phenyl] phosphino} propane

Bis (3,5-bis (trifluoromethyl) phenyl) phosphine (6.34 g, 13.84 mmol) was suspended in DMSO (50 ml) and by adding an aqueous KOH solution (1.01 g, 17.99 mmol .

2 ml water) deprotonated. The dark red solution was stirred for 30 minutes. A solution of 3-chloropropyldiphenylphosphine (3.40 g, 12.94 mmol) in DMSO (15 ml) was added to the mixture and stirred for 24 hours at room temperature and for a further 2 hours at 50 ° C. After cooling, the mixture was poured into 300 ml of water. After adding NaCl, the oil phase was separated, dissolved in ether and three times with Washed water, dried over Na ₂ SO ₄ and the solvent removed. Excess bis (3,5-bis (trifluoromethyl) phenyl) phosphine was removed by vacuum distillation.

Yield: 6.6 g (70%). ¹ H NMR (CDCI ₃ ): δ 7.86 (s, 2H, para Ar), 7.75 (d, 4H, ortho Ar), 7.39-7.32 (m, 4H, Ph), 7.31 - 7.27 (m, 6H, Ph), 2.27 (t, 2H, -CH ₂ -PAr _2), 2.22 (t, 2H, - CH ₂ PPh _2), 1, 59 (m, 2H, CH ₂ ). ¹³ C NMR (CDCI ₃ ): δ 140.65 (d, ipso Ar), 138.00 (d, ipso Ph), 132.8-132.3 (m, ortho Ph, meta Ar, ortho Ar), 123 , 34 (sept, para Ar), 122.99 (q, CF ₃ ), 29.37 (vt, -CH ₂ P '), 28.97 (vt, -CH ₂ P ^' ), 22.15 (vt, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ - 13.84 (s, PAr ₂ ), -17.16 (s, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CDCI ₃ ): δ -63.45 (s). MS (Cl, m / z (%)): 665 (100) [M -F] ⁺ , 685 (89) [MH] ⁺ , 607 (6) [M -Ph] ⁺ , 471 (5) [M - Ar] ⁺ .

A) Diphenyl (3-phosphinopropyl) phosphine

A solution of diisopropyl 3- (diphenylphosphino) propyl phosphonate (23.12 g, 58.8 mmol) in ether (100 ml) slowly became a suspension of LiAIH ₄ (4.5 g, 118 mmol) in ether (150 ml) dosed at 0 ° C. The reaction mixture was stirred for a further 30 min at 0 ° C. and overnight at room temperature. The mixture was then hydrolyzed at 0 ° C. The organic phase was separated and the residue extracted with ether. The combined organic phases were washed with water, dried and freed from the solvent in vacuo. A colorless air sensitive oil was obtained.

Yield: 13.4 g (88%). ¹ H NMR (CDCI ₃ ): δ 7.43-7.38 (m, 4H, Ph), 7.34-7.27 (m, 6H, Ph), 2.64 (dt, 2H, -PH ₂ ), 2.11 (t, 2H, -CH ₂ P _(Ph) ), 1.70-1, 57 (m, 4H, -CH ₂ -CH ₂ -P _(prim) ). ¹³ C NMR (CDCI3): δ 138.57 (d, ipso Ph), 132.65 (d, ortho Ph), 128.52 (s, para Ph), 128.38 (d, meta Ph), 29, 27 (dd, -CH ₂ -P), 29.02 (dd, -CH ₂ -P ^' ), 15.39 (dd, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ -16.29 (s, PPh ₂ ), -137.97 (s, P ₍ p _rim) ). MS (Cl, m / z (%)): 261 (100) [MH] ⁺ .

B) [3- (Dibromo) phosphino) propyl] (diphenyl) phosphonium bromide

Diphenyl (3-phosphinopropyl) phosphine (4.18 g, 16.05 mmol) was dissolved in carbon tetrachloride (180 ml). At 10 ° C, bromine (5.13 g, 32.10 mmol) in CCI ₄ (20 ml) was quickly added. After stirring for 10 minutes, the solvent and HBr were removed at 10 ° C under vacuum. ³¹ P { ¹ H} NMR (CDCI3): δ 182.91 (s, -PBr ₂ ), 59.10 (s, -Pphosp _h o _n ium) -

General procedure for the preparation of asymmetrical ligands

[3- (Dibromo) phosphino) propyl] (diphenyl) phosphonium bromide prepared according to B) was cooled to -78 ° C. The solid was suspended in precooled solvent (THF in the case of 1 e and diethyl ether at 1c, 1d, 1f). A previously filtered arylmagnesium bromide solution in THF was slowly added to this suspension at -78 ° C. After 15 minutes, the mixture was allowed to warm to room temperature and stirred for a further 12 hours. The mixture was then hydrolyzed and neutralized. After extractive work-up, the ligands were obtained with only minor impurities, which were easy to remove after conversion to the palladium complexes. If desired, the pure ligand with sodium cyanide can also be released from these palladium complexes.

1 c) 1 -Diphenylphosphino-3- [bis (3,5-dimethylphenyl) phosphino] propane

Diphenyl (3-phosphinopropyl) phosphine (2.19 g, 8.41 mmol, 80 ml CCl ₄ ) was brominated (2.69 g bromine, 16.83 mmol, 10 ml CCI) and suspended in diethyl ether (100 ml). The product was quenched with 3,5-dimethylphenyl magnesium bromide (made from 5-bromo-m-xylene (4.68 g, 25.24 mmol, 20 ml THF) and Mg (0.77 g, 31.56 mmol, 20 ml THF )) implemented. After the hydrolysis, the mixture was worked up extractively with dichloromethane. After purification by column chromatography on silica gel with dichloromethane, an oily product was obtained.

Yield: 0.9 g (38%). ¹ H NMR (CDCI ₃ ): δ 7.38-7.33 (m, 4H, Ph), 7.30-7.26 (m, 6H, Ph), 6.98 (br d, 4H, ortho Ar ), 6.91 (br s, 2H, para Ar), 2.25 (s, 12H, CH ₃ ), 2.21-2.12 (m, 4H, -CH ₂ P), 1.60 (m , 2H, -CH ₂ -). ¹³ C NMR (CDCI ₃ ): δ 138.69 (d, ipso), 138.31 (d, ip- so ^' ), 137.66 (d, meta Ar), 132.65 (d, ortho Ph), 130.35 (d, ortho Ar), 129.04 (s, para Ar), 128.42 (s, para Ph), 128.32 (d, meta Ph), 29.87-29.40 (m, -CH ₂ -P, -CH ₂ -P '), 22.55 (vt, -CH ₂ -), 21, 27 (s -CH ₃ ). ³¹ P {H} NMR (CDCI ₃ ): δ -16.74 (s), -16.96 (s). MS (Cl, m / z (%)): 469 (100) [MH] ⁺ , 391 (15) [M -Ph] ⁺ , 363 (8) [M -Arj ⁺ . Anal, calculated for C ₃₁ H ₃₄ P ₂ : C, 79.46; H, 7.31. found: C, 79.21; H, 7.17.

1 d) 1 -Diphenylphosphino-3- [bis (3,5-difluorophenyl) phosphino] propane

Diphenyl (3-phosphinopropyl) phosphine (4.40 g, 16.91 mmol, 180 ml CCI ₄ ) was brominated (5.40 g bromine, 33.81 mmol, 20 ml CCI ₄ ) and suspended in 200 ml ether. The product was quenched with 3,5-difluorophenyl magnesium bromide (made from 1-bromo-3,5-difluorobenzene (9.80 g, 50.72 mmol, 20 ml THF)) and Mg (1.55 g, 63.39 mmol, 20 ml THF)) implemented. The organic phase was worked up in water extractively with ether. The product thus obtained was extracted several times with pentane. After removal of the solvent and purification on silica gel (dichloromethane), the product was obtained.

Yield: 2.1 g (42%). ¹ H NMR (CDCI ₃ ): δ 7.40-7.34 (m, 4H, Ph), 7.32-7.28 (m, 6H, Ph), 6.83 (m, 4H, ortho Ar) , 6.75 (tt, 2H, para Ar), 2.19 (t, 2H, -CH ₂ P), 2.13 (t, 2H, - CH ₂ P ^' ), 1.56 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCI ₃ ): δ 162.89 (ddd, meta Ar), 142.05 (dt, ipso Ar), 138.21 (d, ipso Ph), 132.63 (d, ortho Ph), 128 , 67 (s, para Ph), 128.44 (d, meta Ph), 115.03 (vsex, ortho Ar), 104.63 (t, para Ar), 29.44 (vt, -CH ₂ -P ), 29.07 (vt, -CH ₂ -P ^' ), 22.01 (vt, -CHjr). ³¹ P {H} NMR (CDCI ₃ ): δ -12.42 (s, PAr ₂ ), -17.17 (s, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CDCI ₃ ): δ -109.01 (s). MS (Cl, m / z (%)): 485 (100) [MH] ⁺ , 371 (49) [M -Ar] ⁺ , 407 (9) [M -Ph] ⁺ .

1 e) 1 -Diphenylphosphino-3- {bis [(2- (trifluoromethyl) phenyl] phosphino} propane

Diphenyl (3-phosphinopropyl phosphine (2.83 g, 18.87 mmol, 140 ml CCI ₄ ) was brominated (3.47 g bromine, 21, 75 mmol, 15 ml CCI ₄ ) and suspended in 120 ml THF. One equivalent of the bromination product was treated with five equivalents of 2- (trifluoromethyl) phenylmagnesium bromide (made from 1-bromo-2-

(trifluoromethyl) benzene (12.23 g, 54.35 mmol, 40 ml THF) and Mg (1.65 g, 67.94 mmol, 30 ml THF)). After hydrolysis, the THF was removed in vacuo. The solid was filtered, washed with water and taken up in acetone. The acetone extract was evaporated to dryness and taken up in dichloromethane. After drying and concentration, the residue was washed with pentane and diethyl ether and purified by column chromatography (silica gel / dichloromethane). Yield: 2.2 g (38%). ¹ H NMR (CDCI ₃ ): δ 7.71-7.65 (m, 2H, aroma), 7.45-7.32 (m, 10H, aroma), 7.30-7.25 (m , 6H, aroma), 2.24-2.12 (m, 4H, -CH ₂ P), 1.62 (m, 2H, -CH ₂ -). ³ C NMR (CDCI ₃ ): δ 138.26 (d, ipso Ph), 136.84 (d, ipso Ar), 134.12 (qd, CCF ₃ ), 133.19 (s, Ar), 132, 64 (d, ortho Ph), 131, 46 (s, Ar), 128.74 (s, Ar), 128.57 (s, para Ph), 128.40 (d, meta Ph), 126.67 ( br, m, Ar), 124.15 (q, CF ₃ ), 30.19 (vt, -CH ₂ P), 29.57 (vt, -CH ₂ P ^' ), 22.40 (dd, -CH ₂ -). ³¹ P {H} NMR (CDCI ₃ ): δ -17.28 (s, PPh ₂ ), -26.70 (sept, PAr ₂ ). ¹⁹ F { ¹ H} NMR (CDCI ₃ ): δ -57.66 (d). MS (Cl, m / z (%)): 594 (100) [MH] ⁺ , 529 (57) [M -Ff, 403 (37) [M -Ar] ⁺ .

1 f) 1 -Diphenylphosphino-3- [bis (2,4,6-trif luorphenyl) phosphino] propane

Diphenyl (3-phosphinopropyl) phosphine (4.18 g, 16.05 mmol, 180 ml CCI ₄ ) was brominated (5.13 g bromine, 32.1 mmol, 20 ml CCI) and suspended in 200 ml diethyl ether. The product was made with 2,4,6-trifluorophenyl magnesium bromide (made from 1 -Bromo-

2,4,6-trifluorobenzene (10.16 g, 48.15 mmol, in 30 ml THF) and Mg (1, 47 g, 60.18 mmol, in 20 ml THF)). After the pH had been adjusted to 8, the organic phase was worked up in an aqueous extractive manner with ether. The product was purified by column chromatography (silica gel / dichloromethane). Yield: 3.8 g (51%). ¹ H NMR (CDCI ₃ ): δ 7.39-7.33 (m, 4H, Ph), 7.31 -7.27 (m, 6H, Ph), 6.58 (m, 4H, meta Ar) , 2.57 (m, 2H, -CH ₂ -PAr _2), 2.19 (t, 2H, -CH ₂ PPh _2), 1, 54 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCI ₃ ): δ 164.73 (dm, ortho Ar), 163.91 (dm, para Ar), 138.30 (d, ipso Ar), 132.62 (d, ortho Ph), 128 , 53 (s, para Ph), 128.36 (d, meta Ph), 108.7-107.3 (m, ipso Ar), 101.0-100.2 (m, meta Ar), 29.26 (dd, -CH ₂ -PPh ₂ ), 25.31 (m, -CH ₂ -PAr ₂ ), 22.82 (dd, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ - 16.54 (s, PPh ₂ ), -53.12 (quint, PAr ₂ ). ¹⁹ F { ¹ H} NMR (CDCI3): δ -98.39 (dd, ortho F), -106.30 (t, para F). MS (Cl, m / z (%)): 521 (100) [MH] ⁺ , 389 (26) [M -Ar] ⁺ , 501 (14) [M -Ff, 443 (8) [M -Ph] ⁺ .

2a) dichloro {1,3-bis [bis [3,5-bis (trifluoromethyl) phenyl] phosphino] propane} palladium (II)

A solution of (COD) PdCI ₂ (0.76 g, 2.65 mmol) in CH CI ₂ (40 ml) was treated with a solution of the product of 1 a) (2.53 g, 2.65 mmol) in CH ₂ CI ₂ (25 ml) implemented. After stirring for an hour, the bulk of dichloromethane was removed in a stream of argon. After adding pentane, the product precipitated out. After drying in vacuo, a slightly yellow product was obtained.

Yield: 2.9 g (95%). ¹ H NMR (acetone-d ₆ ): δ 8.53 (br d, 8H, ortho Ar), 8.28 (br s, 4H, para Ar), 3.29 (m, 4H, -CH ₂ P) , 2.38 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (acetone-d ₆ ): δ 16.11 (s). ¹⁹ F { ¹ H} NMR (acetone-d ₆ ): δ -62.45 (s). MS (FAB, m / z (%)): 1097 (100) [M - Cl] ⁺ , 1062 (23) [M -2 Cl] ⁺ , 849 (23) [M - 2CI, Ar] ⁺ . Anal, calculated for C ₃₅ H ₁₈ CI ₂ F ₂₄ P ₂ Pd: C, 37.08; H, 1.60. found: C, 36.89; H, 1.66.

2b) dichloro {1 -diphenylphosphino-3- [bis [3,5- bis (trifluoromethyl) phenyl] phosphino] propane} palladium (II)

A solution of the product from 1 b) (2.16 g, 3.16 mmol in CH ₂ CI ₂ (20 ml) became a solution of (COD) PdCI ₂ (0.9 g, 3.16 mmol) in CH ₂ CI ₂ ( After stirring for one hour, the reaction mixture was concentrated in vacuo and the product was eliminated by adding pentane. After drying in vacuo, a pale yellow product was obtained. Yield: 2.6 g (96%). ¹ H NMR (CDCI ₃ ): δ 8.13 (br d, 4H, ortho Ar), 7.96 (br s, 2H, para Ar), 7.71 (m, 4H, Ph), 7.47 (m, 2H, Ph ) 7.37 (m, 4H, Ph), 2.64-2.48 (m, 4H, - CH ₂ P), 2.09 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ 13.33 (d), 13.02 (d). ¹⁹ F { ¹ H} NMR (CDCI ₃ ): δ -63.38 (s). MS (FAB, m / z ( %)): 827 (100) [M -Cl] ⁺ , 790 (18) [M -2 Cl] ⁺ , 749 (12) [M -CI, Ph] ⁺ , 577 (9) [M -2 CI, Ar] ⁺ . Anal, calculated for C ₃ ιH ₂₂ CI ₂ F ₁₂ P ₂ Pd: C, 43.21; H, 2.57. Found: C, 43.01; H, 2.57.

2c) dichloro {1-diphenylphosphino-3- [bis (3,5-dimethylphenyl) phosphino] propane} palladium (II)

C, 57.65; H, 5,31. gefunden: C, 57,48; H, 5,24.A solution of the product of 1 c) (0.75 g, 1.60 mmol) in was added to a solution of (COD) PdCI ₂ (0.46 g, 1.60 mmol) in CH ₂ CI ₂ (40 ml) CH ₂ CI ₂ (20 ml) added and stirred for one hour. The reaction mixture was concentrated in vacuo and the product was eliminated by adding pentane. After washing with ether and pentane and drying in vacuo, the product was obtained as a pale yellow solid. Yield: 1.0 g (94%). ¹ H NMR (CDCI ₃ ): δ 7.81-7.74 (m, 4H, Ph), 7.47-7.33 (m, 10H, aroma), 7.04 (br s, 2H, para Ar ), 2.39-2.28 (m, 4H, -CH ₂ P), 2.26 (s, 12H, -CH ₃ ), 1.99 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ 12.7 (d), 11, 4 (d). MS (FAB, m / z (%)): 609 (100) [M -Cl] ⁺ , 574 (20) [M -2CI] ⁺ , 533 (6) [M -CI, Ph] ⁺ . Anal, calculated for

C, 57.65; H, 5.31. found: C, 57.48; H, 5.24.

2d) dichloro {1-diphenylphosphino-3- [bis (3,5-difluorophenyl) phosphino] propane} - palladium (II)

A solution of the product of 1 d) (1.96 g, 4.06 mmol) in CH ₂ CI ₂ (20 ml) became a solution of (COD) PdCI ₂ (1, 16 g, 4.06 mmol) in CH ₂ CI ₂ (80 ml) was given. After stirring for one hour, the reaction mixture was concentrated in vacuo and the product was precipitated out by adding pentane. After washing with ether and pentane and drying in vacuo, a microcrystalline solid was obtained.

Yield: 2.6 g (95%). ¹ H NMR (DMSO-d ₆ ): δ 7.76 (m, 4H, aroma), 7.57-7.44 (m, 12H, aroma), 2.83 (m, 2H, -CH ₂ P) , 2.72 (m, 2H, -CH ₂ P ^' ), 1.78 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (DMSO-de): δ 16.5 (br), 13.3 (br). ¹⁹ F { ¹ H} NMR (DMSO-d ₆ ): δ -107.5 (s). MS (FAB, m / z (%)): 625 (100) [M -Cl] ⁺ , 589 (37) [M -2CI] ⁺ , 547 (26) [M -CI, Ph] ⁺ . Anal, calculated for C ₂₇ H ₂₂ CI ₂ F ₄ P ₂ Pd: C, 49.01; H, 3.35. found: C, 48.79; H, 3.48.

2e) dichloro {1-diphenylphosphino-3- [bis [2- (trifluoromethyl) phenyl] phosphino] propane} - palladium (II)

A solution of (COD) PdCI ₂ (1.96 g, 6.87 mmol) in CH ₂ CI ₂ (120 ml) was mixed with a solution of the bisphosphine from Example 1 e) (3.77 g, 6.87 mmol) added in CH ₂ CI ₂ (40 ml). After stirring for one hour, the reaction mixture was concentrated in vacuo and the product was eliminated by adding pentane. After washing with ether and pentane and drying in vacuo, the product was obtained as a solid. Yield: 4.8 g (96%). ¹ H NMR (C ₂ D ₂ CI ₄ ): δ 9.41 (m, 1 H, Ar) 7.82-7.32 (m, 16H, aromatic), 7.02 (m, 1 H, Ar), 2.80-2.62 (m, 2H), 2.30-2.04 (m, 3H), 1.71-1.50 (m, 1H). ³¹ P { ¹ H} NMR (C ₂ D ₂ CI ₄ ): δ 37.14 (m, PAr ₂ ), 12.47 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (C ₂ D ₂ CI ₄ ): δ -54.27 (s), -54.37 (d). MS (FAB, m / z (%)): 689 (100) [M -Cl] ⁺ , 653 (48) [M -2CI] ⁺ , 611 (7) [M - Cl.Phf.

2f) Dichloro {1 -diphenylphosphino-3- [bis (2,4,6-trifluorophenyl) phosphino] propane} palladium (II) ligand 1f (3.58 g, 6.88 mmol) was dissolved in CH ₂ CI ₂ (30 ml) and added to a solution of (COD) PdCI ₂ (1.96 g, 6.88 mmol) in CH ₂ CI ₂ (120 ml). After one hour the product was concentrated in vacuo and fell as precipitation. The precipitation was completed by adding pentane. The product was washed with ether and pentane and dried in vacuo. Yield: 4.6 g (97%). ¹ H NMR (DMSO-d ₆ ): δ 7.84 (m, 4H, Ph), 7.63-7.51 (m, 6H, Ph), 7.40 (m, 4H, Ar), 2, 62 (m, 2H, -CH ₂ P), 2.54 (m, 2H, -CH ₂ P ^' ), 1.88 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (DMSO-d ₆ ): δ 16.37 (d), -16.23 (m). ¹⁹ F { ¹ H} NMR (DMSO-d ₆ ): δ - 93.18 (vt, ortho F), -100.99 (t, para F). MS (FAB, m / z (%)): 661 (100) [M -Ci] ⁺ , 625 (37) [M - 2CI] ⁺ . Anal, calculated for C ₂₇ H ₂₀ CI ₂ F ₆ P ₂ Pd: C, 46.48; H, 2.89. found: C, 46.17; H, 2.99.

3e) diiod {1 -diphenylphosphino-3- [bis [2- (trifluoromethyl) phenyl] phosphino] propane} - palladium (II)

A solution of the dichloro complex from Example 2e) (3.68 g, 5.07 mmol) in DMSO (80 ml) was mixed with sodium iodide (3.04 g, 20.3 mmol) and stirred for 48 hours at room temperature. Subsequently, aqueous extractive (dichloromethane) was worked up. The product thus obtained was purified by chromatography on silica gel (dichloromethane) and excreted with pentane as a red-orange solid. Yield: 3.27 g (71%). ¹ H NMR (CDCI ₃ ): δ 9.58 (m, 1 H, Ar), 7.91-7.34 (m, 16H, aroma), 7.09 (m, 1 H, Ar), 2.90-2.71 (m, 2H), 2.34-2.17 (m, 2H), 2.17-2.04 (m, 1H), 1.91-1.70 (m, 1 H). ³¹ P { ¹ H} NMR (CDCI ₃ ): δ 23.06 (m, PAr ₂ ), -0.40 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CDCI ₃ ): δ - 54.7 (s), -55.55 (d). MS ^' (FAB, m / z (%)): 781 (100) ^" [M-1] ⁺ , 653 (44) [M-1, HI] ⁺ . Anal, calculated for C ₂₉ H ₂ F ₆ l ₂ P ₂ Pd: C, 38.33; H, 2.66. Found: C, 38.21; H, 2.54.

3d) diiod {1 -diphenylphosphino-3- [bis (3,5-difluorophenyl) phosphino] propane} palladium (II)

Analogously to Example 3e), the dichloro complex from Example 2d) (0.45 g, 0.68 mmol), DMSO (10 ml) and sodium iodide (0.41 g, 2.72 mmol) was reacted. A red-orange solid was obtained. Yield: 0.31 g (54%). ¹ H NMR (acetone-d ₆ ): δ 7.83-7.76 (m, 4H, aroma), 7.54-7.43 (m, 10H, aroma), 7.20 (tt, 2H, para Ar), 2.92 (m, 2H, -CH ₂ P), 2.82 (m, 2H, -CH ₂ P ^' ), 2.12 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (acetone-d ₆ ): δ 3.37 (dquint, PAr ₂ ), 1.42 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (acetone-d ₆ ): δ -108.12 (d). MS (FAB, m / z (%)): 844 (6) [M] ⁺ , 717 (100) [M -l] ⁺ , 589 (29) [M -l, Hel.

4a) Diacetonitrile {1,3-bis [bis [3,5- bis (trifluoromethyl) phenyl] phosphino] propane} palladium (II) ditetrafluoroborate

AgBF ₄ (0.61 g, 3.12 mmol) was added to a solution of the product of Example 2a) (1.77 g, 1.56 mmol) in acetonitrile (80 ml). After stirring for two hours, the mixture was filtered and concentrated in vacuo. After filtration and further concentration, the product fell after the addition of ether. The solid was washed with ether and pentane and dried in vacuo.

Yield: 1.4 g (68%). ¹ H NMR (acetone-d ₆ ): δ 8.55 (d, 8H, ortho Ar), 8.44 (s, 4H, para Ar), 3.58 (m, 4H, -CH ₂ P), 2 , 71 (m, 2H, -CH ₂ -), 2.09 (s, 6H, CH ₃ CN). ³¹ P { ¹ H} NMR (acetone-de): δ 18.57 (s). ¹ F { ¹ H} NMR (acetone-d ₆ ): δ -62.32 (s, CF ₃ ), -148.16 (s, BF ₄ ). MS (FAB, m / z (%)): 1061 (25) [M -2CH ₃ CN, 2BF ₄ , 605 (100) [M - 2CH ₃ CN, 2BF ₄ , PAr ₂ ] ⁺ .

4b) Diacetonitrile {1 -diphenylphosphino-3- [bis [3,5- bis (trifluoromethyl) phenyl] phosphino] propane} palladium (II) ditetrafluoroborate

The product of Example 2b (1.12 g, 1.30 mmol) was dissolved in acetonitrile (70 ml) and AgBF ₄ (0.51 g, 2.50 mmol) was added. After stirring for two hours, the mixture was filtered and concentrated to dryness in vacuo. The residue was extracted with dichloromethane, the extract was concentrated and filtered. After adding pentane, the product was obtained as a solid.

Yield: 1.1 g (81%). ¹ H NMR (CD ₃ CN): δ 8.28 (s, 2H, para Ar), 8.11 (d, 4H, ortho Ar), 7.68-7.59 (m, 6H, Ph), 7 , 56-7.49 (m, 4H, Ph), 2.98-2.85 (m, 4H, -CH ₂ P), 2.30 (m, 2H, -CH ₂ -), 1.95 ( s, CH ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 14.3 (d), 14.1 (d). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -62.1 (s, CF ₃ ), -150.1 (s, BF ₄ ). MS (FAB, m / z (%)): 790 (100) [M - 2CH ₃ CN, 2BF ₄ f.

4c) Diacetonitrile {1 -diphenylphosphino-3- [bis (3,5-dimethylphenyl) phosphino] propane} palladium (II) ditetrafluoroborate

AgBF ₄ (0.24 g, 1.26 mmol) was added to the solution of the product from Example 2c) (0.41 g, 0.63 mmol) in acetonitrile (80 ml). After stirring for two hours, working up was carried out analogously to Example 4b). Yield: 0.41 g (78%). ¹ H NMR (CD ₃ CN): δ 7.66-7.58 (m, 6H, Ph), 7.55-7.49 (m, 4H, Ph), 7.23 (br s, 4H, ortho Ar) , 7.20 (br s, 2H, para Ar), 2.77 (m, 4H, -CH ₂ P), 2.29 (s, 12H, -CH ₃ ), 2.22 (m, 2H, - CH ₂ -), 1.95 (s, CH ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 13.0 (br), 12.0 (br). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -150.2 (s, BF ₄ ). MS (FAB, m / z (%)): 593 (56) [M - 2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 574 (100) [M -2CH ₃ CN, 2BF ₄ ] ⁺ .

4d) Diacetonitrile {1 -diphenylphosphino-3- [bis (3,5-difluorophenyl) phosphino] propane} palladium (II) ditetrafluoroborate AgBF ₄ (0.92 g, 4.72 mmol) was used to dissolve the product from Example 2d) (1.56 g, 2.36 mmol) in acetonitrile (80 ml). After stirring for twelve hours, working up was carried out analogously to Example 4b). Yield: 1.6 g (80%). ¹ H NMR (CD ₃ CN, 343 ° K): δ 7.72-7.63 (m, 6H, Ph), 7.58-7.53 (m, 4H, Ph), 7.32-7, 25 (m, 4H, ortho Ar), 7.20 (tt, 2H, para Ar), 2.86-2.77 (m, 4H, - CH ₂ P), 2.29 (m, 2H, -CH ₂ - ), 1.95 (s, CH ₃ CN). ³ P { ¹ H} NMR (CD ₃ CN): δ 14.4 (m) 12.7 (m). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -105.5 (s, meta F), -150.0 (s, BF ₄ ). MS (FAB, m / z (%)): 609 (39) [M -2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 590 (100) [M -2CH ₃ CN, 2BF ₄ ] ⁺ .

4e) Diacetonitrile {1 -diphenylphosphino-3- [bis [2- (trifluoromethyl) phenyl] phosphino] propane} palladium (II) ditetrafluoroborate

AgBF ₄ (0.43 g, 2.22 mmol) was added to the solution of the product from Example 2e) (1.01 g, 1.11 mmol) in acetonitrile (80 ml). After stirring for two hours, working up was carried out analogously to Example 4b).

Yield: 0.9 g (89%). H NMR (CD ₃ CN): δ 8.61-8.47 (br, 1H, aroma), 8.07-7.37 (m, 17H, aroma), 3.12-2.94 (br, 2H ), 2.71 (br, 2H), 2.53-2.29 (br, 1H), 2.10-1, 96 (br, 1H), 1.95 (s, CH ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 31, 4 (m, PAr ₂ ), 13.2 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -54.1 (s, br, CF ₃ ), -54.4 (s, br, CF ₃ ), -150.4 (s, BF ₄ ) , MS (FAB, m / z (%)): 673 (22) [M -2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 654 (100) [M -2CH ₃ CN, 2BF ₄ ] ⁺ .

4f) Diacetonitrile {1 -diphenylphosphino-3- [bis (2,4,6-trifluorophenyl) phosphino] propane} palladium (II) ditetrafluoroborate

AgBF ₄ (1.07 g, 5.52 mmol) was added to the suspension of the product from Example 2f) (1.93 g, 2.76 mmol) in acetonitrile (100 ml). After stirring for twelve hours, working up was carried out analogously to Example 4b). Yield: 1.9 g (76%). ¹ H NMR (CD ₃ CN): δ 7.75-7.65 (m, 6H, Ph), 7.64-7.54 (m, 4H, Ph), 7.03 (m, 4H, Ar) , 2.99 (m, 2H, -CH ₂ P), 2.77 (m, 2H, -CH ₂ P ^' ), 2.32 (m, 2H, -CH ₂ -), 1.95 (s, CH ₃ CN). ³ P { ¹ H} NMR (CD ₃ CN): δ 14.4 (d, PPh ₂ ), -19.6 (m, PAr ₂ ). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -93.4 (vt, ortho F), -96.0 (t, para F), -150.5 (s, BF ₄ ). MS (FAB, m / z (%)): 645 (20) [M -2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 626 (100) [M -2CH ₃ CN, 2BF ₄ f.

B. Polymerization Examples Example P1

At room temperature, 10 mg of complex 4b were dissolved in 5 g of toluene (99% by weight; from Aldrich) in a Schlenk tube under an argon atmosphere and with stirring, then with 0.5 g of n-hexadecane (99% by weight, from . Aldrich), and 1 g of 10-undecenoic acid (98% by weight; Aldrich) and stirred for 5 minutes. The organic complex solution thus obtained was stirred at room temperature and under an argon atmosphere in an aqueous solution consisting of 100 g deionized water and 1, 0 g Texapon ^® NSO (Schwefelsäurehalbester sodium salt of n-Dodecanolethoxylat, average ethoxylation Degree of efficiency: 25; Henkel brand) to form an oil-in-water emulsion. This emulsion was brought into contact with a sonotrode (Sonifier II 450 from Branson) for 10 minutes and then the average droplet size was determined.

The average droplet size of the aqueous emulsions was generally determined by means of quasi-elastic dynamic light scattering using a Coulter N4 Plus Particle Analyzer from Coulter Scientific Instruments. In the present case, the mean droplet size was 200 nm.

The aqueous emulsion obtained was then transferred to a 300 ml steel autoclave equipped with a bar stirrer and the air was displaced by repeated flushing with propylene. Then 10 bar propene and 30 bar carbon monoxide were injected at room temperature. While stirring (500 revolutions per minute), the reaction mixture was heated to 80 ° C. and stirred at this temperature for 2 hours. The reaction mixture was then cooled to room temperature and the contents of the steel autoclave were released to atmospheric pressure. 100 g of an aqueous copolymer dispersion having a solids content of 10% by weight and a coagulum content of <1% by weight were obtained. The average particle size was 350 nm. The melting point was determined to be 150.degree. The glass transition temperature is 20 ° C. The weight average molecular weight was determined by GPC at 30,000 g / mol. In addition, the aqueous copolymer dispersion was stable and showed no phase separation, deposition or coagulum formation for 10 weeks.

The solids content was generally determined by drying about 1 g of the aqueous copolymer dispersion in an open aluminum crucible with an inside diameter of about 3 cm in a drying cabinet at 100 ° C. and 10 mbar (absolute) to constant weight. To determine the solids content, two separate measurements were carried out and the corresponding average was formed.

The coagulum content was generally determined by filtering about 50 g of the aqueous copolymer dispersion obtained through a 45 μm filter fabric. The filter fabric was then rinsed with 50 ml of deionized water and dried to constant weight at 100 ° C./1 bar (absolute). The coagulum content was determined from the difference in weight of the filter fabric before filtration and the filter fabric after filtration and drying.

The average particle diameter of the copolymer particles was generally determined by dynamic light scattering on a 0.005 to 0.01 percent by weight aqueous dispersion at 23 ° C. using an Autosizer IIC from Malvern Instruments, England, determined. The average diameter of the cumulative evaluation (cumulant z-average) of the measured autocorrelation function is given (ISO standard 13321).

The glass transition temperature or melting point was generally determined in accordance with DIN 53765 using a DSC820 instrument, series TA8000 from Mettler-Toledo.

Comparative example

Example P1 was repeated with the exception that complex 1, 3-bis (diphenylphosphino) propane-bis-acetonitrile-palladium (II) bis (tetrafluoroborate) was used instead of complex compound 4b.

After the steel autoclave was let down to atmospheric pressure, a dispersion with a solids content of 3% was obtained. An oligomeric propene / CO copolymer with a weight average molecular weight of 3000 g / mol was formed.

Example P2

Example P1 was repeated with the exception that 5 g of styrene were used instead of hexadecane. A dispersion with a solids content of 10% is obtained.

Example P3

Example P1 was repeated with the exception that 10 g of 1-hexene were used instead of hexadecane. A dispersion with 18% solids content is obtained. The ratio of the olefins in the propene / 1-hexene / CO terpolymer was determined by 13C NMR and is approximately 70 mol% propene and 30 mol% 1-hexene.

Example P4

Example P1 was repeated with the exception that complex 4a was used instead of complex compound 4b. A dispersion with a 4% solids content is obtained.

Claims

claims 1. Process for the preparation of aqueous polymer dispersions by polymerizing one or more olefins, if appropriate with carbon monoxide, in an aqueous medium, in the presence a) one or more metal complexes of the general formula I.

in the M is a transition metal from group VIIIB, IB or IIB of the Periodic Table of the Elements, E ¹ and E ² independently of one another an element from group VA of the periodic table of the elements, YCC ₅ alkylene, which with hydroxyl, -CC ₆ alkoxy, carboxyl, sulfo, amino, Ammonium, phosphono, phosphonato, sufamoyl, amidino, carbamoyl, hydroxysufonyloxy, sulfino and dC ₄ -alkyl and may be interrupted by oxygen, imino, alkylimino, silylene or mono- or dialkylsilylene or may have an attached cycloaliphatic ring or fused benzene or 1 , 8-naphthylene, R ¹ -C ₂ rralkyl, optionally with hydroxyl, dC-β-alkoxy, carboxyl, Sulfo or aryl is substituted, C ₆ -C ₁₄ aryl, which is optionally substituted with d C ₄ alkyl, hydroxyl, d C ₆ alkoxyl, carboxyl, cyano or a radical R ² or C ₃ -d ₂ cycloalkyl R ² fluorine, sulfo, nitro, or perfluorinated dC ₁₀ alkyl, R, R, R and R independently of one another are hydrogen or a radical R, L ¹ and L ² independently of one another phosphines (R ⁷ ) _X PH _3-X , amines (R ⁷ ) _x NHs- _x or ethers (R ⁷ ) ₂ O with the same or different radicals R ⁷ , alcohols R ⁷ OH, H ₂ O, pyridine compounds C ₅ H ₅ -X (R ⁷ ) _X N, carbon monoxide, C ₆ -C ₁₂ alkyl nitriles, CrC ₄ aryl nitriles or olefins, where x denotes an integer from 0 to 3, amide ions (R ⁷ ) _h NH _2-h , where h is a whole Number from 0 to 2 means CC ₆ alkyl anions, C ₃ -C ₁₄ cycloalkyl anions, allyl anions, methallyl anions, benzyl anions, aryl anions, carboxylic acid anions, sulfonic acid anions, ketones or diketones, where L ¹ and L ² are linked together by one or several covalent bonds can be linked R ^{7 is} hydrogen, d-do-alkyl, which is optionally substituted by dC ₆ -alkoxy, mono- or di- (dC ₆ -alkyl) amino or C ₆ -C ₁₄ -aryl, C ₃ -C ₁₂ -cycloalkyl, or C ₆ -Cι ₄ aryl, An ^" the equivalent of a noncoordinating acid anion with pKs <4.75 and n denotes an integer 0, 1, 2, 3 or 4 and b) one or more dispersants. 2. The method according to claim 1, characterized in that in the general formula I the radical R ¹ from the radical of the formula II

is different. 3. The method according to any one of claims 1 or 2, characterized in that in the general formula IR ² , R ³ and / or R ^{4 is} trifluoromethyl. 4. The method according to any one of claims 1 to 3, characterized in that in the general formula I M stands for nickel, palladium or platinum. 5. The method according to any one of claims 1 to 3, characterized in that in the general formula IM stands for palladium. 6. The method according to any one of claims 1 to 5, characterized in that in the general formula IE ¹ and E ^{2 is} nitrogen and / or phosphorus. 7. The method according to any one of claims 1 to 6, characterized in that only ethylene is polymerized. 8. The method according to any one of claims 1 to 6, characterized in that one or more olefins are polymerized with carbon monoxide. 9. The method according to any one of claims 1 to 6, characterized in that propene and / or 1-butene are polymerized with carbon monoxide. 10. The method according to any one of claims 1 to 9, characterized in that the polymerization in the presence of one or more metals of subgroup VIII B, which is in salt form or complex form, and a chelate ligand of the general formula III

in which E ¹ , E ² , Y, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meaning given in Claim 1, a dispersant and optionally an acid a2) is carried out. 11. The method according to any one of claims 1 to 10, characterized in that one or more olefins optionally with carbon monoxide in an aqueous medium in the presence of a) one or more metal complexes I b) dispersants and optionally c) slightly water-soluble organic solvents are polymerized, wherein the metal complexes I are dissolved in a part or the total amount of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c) and the part or the total amount of the olefinically unsaturated compounds and / or the slightly water-soluble organic African solvent c), which contains the metal complexes I dissolved, is present in the aqueous medium as a disperse phase with an average droplet diameter <1000 nm. 12. Aqueous dispersions with a head / tail linkage content of <90% and a particle size of 1 μm, obtainable by a process according to claims 1 to 11. 13. A process for the preparation of polyketones by isolation from polymer dispersions which have been prepared according to claims 1 to 11. 14. A process for the preparation of polyketones according to claim 13, characterized in that the isolation is carried out by spray drying. 15. Uses of the aqueous dispersions according to claim 12 as binders for paper applications, paints, textile and leather applications, adhesives, molded foams, sealants, plastic plasters, carpet back coatings or pharmaceutical applications. 16. Use of the dispersion powder according to claim 13 or 14 as a binder or for modifying mineral binders. ,