WO2004087772A1 - Method for producing an aqueous polymer dispersion using a water-insoluble polymerisation catalyst - Google Patents

Abstract

The invention relates to a method for producing an aqueous polymer dispersion by the polymerisation of at least one ethylenically unsaturated compound (monomer) using at least one water-insoluble polymerisation catalyst and at least one dispersant in an aqueous medium. According to the invention, a solution of a dispersant in water is first produced and then the water-insoluble polymerisation catalyst is introduced into the aqueous solution, in solid form, or mixed with a solvent miscible in water, or mixed with a self-dispersing ethylenically unsaturated compound. The water-insoluble polymerisation catalyst is subsequently dispersed by the application of mechanical energy and finally a polymerisation of at least one ethylenically unsaturated compound is carried out with the aid of the aqueous dispersion that has been obtained in this manner.

Description

Process for the preparation of an aqueous polymer dispersion using a water-insoluble polymerization catalyst

description

The present invention relates to a process for the preparation of an aqueous polymer dispersion by polymerizing at least one ethylenically unsaturated compound (monomer) using at least one water-insoluble polymerization catalyst and at least one dispersant in an aqueous medium, which is characterized in that a solution of a dispersant in water is first prepared , then introduces the water-insoluble polymerization catalyst either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated compound in the aqueous solution of the dispersant, then disperses the water-insoluble polymerization catalyst by mechanical energy input and with the aid of this Aqueous dispersion thus obtained is then subjected to polymerization of at least one ethylenically unsaturated compound leads.

The present invention further relates to the aqueous polymer dispersions obtainable by the process according to the invention and to their use for paper applications, paint coatings, adhesive raw materials, molded foams, textile or leather applications, carpet backing coatings or pharmaceutical applications.

Aqueous dispersions of polymers are used commercially in numerous very different applications. Until now it has been difficult to produce aqueous dispersions of polyolefins and polyketones, since these polymers are usually only poorly water-soluble. In order nevertheless to arrive at polymer dispersions based on polyolefins or polyketones starting from inexpensive monomers such as olefins or carbon monoxide, suitable, water-soluble polymerization catalysts are used, which have to be prepared in a synthetically complex manner. It is also possible to produce aqueous dispersions of polyolefins or polyketones by a so-called miniemulsion polymerization, in which the polymerization catalyst is dissolved and emulsified in an organic solvent. Such a miniemulsion polymerization, however, requires an additional manufacturing step and is relatively expensive in terms of equipment.

The production of polyolefins with the help of so-called metallocenes has been used for a long time (H.-H. Brintzinger et al, in Angew. Chem. 1995, 107, 1255 or in Int. Ed. Engl. 1995, 34, 1143). However, the metallocenes used are sensitive to moisture and are therefore not very suitable for the synthesis of polyolefins in emulsion polymerization. In addition, WO 98/42665 and WO 98/42664 report that certain nickel complexes with nitrogen-containing ring-shaped ligands can polymerize ethylene in the presence of small amounts of water. However, no emulsion polymerization can be carried out under the conditions described.

Transition metal-catalyzed processes for the production of polyketones are also known (Bianchini C; Meli. A., Coord. Chem. Rev. 2002, 225, 35). For example, EP-A 0 121 965 uses a cis-palladium complex chelated with bidentate phosphine ligands, [Pd (Ph2P (CH2) 3PPh2)] (OAc) 2 (Ph = phenyl, Ac = acetyl). The carbon monoxide copolymerization can be carried out in suspension, as described in EP-A 0305 011, or in the gas phase, for example in accordance with EP-A 0702 045. Frequently used suspending agents are, on the one hand, low molecular weight alcohols, in particular methanol (see also EP-A 0428228), and on the other hand non-polar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460743 and EP-A 0 590 942). Complex compounds with bisphosphine chelate ligands whose residues on the phosphorus represent aryl or substituted aryl groups have proven to be particularly suitable for the copolymerization processes mentioned. 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). In the cases mentioned, the carbon monoxide copolymerization is usually carried out in the presence of acids.

The carbon monoxide copolymerization in low molecular weight alcohols such as methanol has the disadvantage that the carbon monoxide copolymer which forms has a high absorption capacity for these liquids and up to 80% by volume of, for example, methanol is bound or absorbed by the carbon monoxide copolymer. As a result, a large amount of energy is required to dry and isolate the carbon monoxide copolymers. A further disadvantage is that even after an intensive drying process, residual amounts of alcohol still remain in the carbon monoxide copolymer. EP-A 0485035 proposes the use of additions of water in proportions of 2.5 to 15% by weight to the alcoholic suspending agent in order to eliminate the residual amounts of low molecular weight alcohol in the carbon monoxide copolymer. However, this procedure also does not lead to methanol-free copolymers. The use of halogenated hydrocarbons or aromatics such as dichloromethane or chlorobenzene or toluene, on the other hand, brings with it problems in particular in handling and disposal. Verspui et al., Chem. Commun., 1998, pp. 401 to 402, succeed in increasing the catalyst activity in the copolymerization of carbon monoxide and ethene by using the chelate ligands mentioned in a substantially purer form. Furthermore, the presence of a Bronsted acid is necessary in order to achieve better catalyst activities. The polyketones described in the publication, made from carbon monoxide and ethylene, have the disadvantage that their molecular weight is lower than that of comparable polyketones, which are produced in methanol as solvents.

Common to the above-mentioned syntheses is that the carbon monoxide copolymers formed (hereinafter referred to as "copolymers") precipitate in the organic suspension media, are separated from the organic suspension media by filtration and are further processed in bulk. In many areas 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). The disadvantage of this step concept is that it is very complex overall and the copolymers, particularly owing to the high solvent content, are difficult to grind (adhesive bonding of the mills), and the copolymer particles obtained by grinding, if at all, are dispersed in an aqueous medium, if at all, using large amounts of emulsifier can and these aqueous secondary dispersions are unstable due to their very wide particle size distribution and tend to form coagulate or sedimentation.

For the production of so-called primary aqueous copolymer dispersions, i.e. Aqueous copolymer dispersions which are directly accessible by copolymerization of carbon monoxide and olefinically unsaturated compounds in an aqueous medium can be assumed from the following prior art.

In DE-A 10061877 stable aqueous copolymer dispersions are obtained when the copolymerization of carbon monoxide and olefinically unsaturated compounds takes place in an aqueous medium using special water-soluble metal catalysts and using special comonomers.

DE-A 10125238 discloses stable aqueous copolymer dispersions whose preparation is carried out by copolymerizing carbon monoxide and olefinically unsaturated compounds in aqueous medium using the water-soluble metal catalysts mentioned in the abovementioned application and using special comonomers in the presence of so-called host compounds. 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.

WO 97/18266 relates to secondary dispersions of polyketones which are obtained by first producing a low molecular weight polyketone in an organic solvent and then dispersing it in water with emulsifiers. A disadvantage of the manufacturing process described is the additional emulsification step. In addition, secondary dispersions are characterized by a broad particle size distribution, which is unfavorable for some areas of application.

In addition, P.W. Mul et al., Inorg. Chim. Acta 2002, 327, 147-159 describes the catalyzed terpolymerization of ethylene, propylene and carbon monoxide in mixtures of water, alcohol and other solvents. The dissolved terpolymer can be separated from the aqueous phase in which the catalyst is also by phase separation. The catalyst is a sulfonated diphos-palladium (II) acetate complex that is activated with strong acids. However, there is no polymer dispersion.

The present invention was therefore based on the object, the described

To remedy disadvantages and to provide a new process for producing an aqueous polymer dispersion, in which synthetically simple, water-insoluble polymerization catalysts can be used without the polymerization catalysts having to be dissolved directly in a solvent.

Accordingly, a process for the preparation of an aqueous polymer dispersion by polymerizing at least one ethylenically unsaturated compound (monomer) has been found using at least one water-insoluble polymerization catalyst and at least one dispersant in an aqueous medium, which is characterized in that firstly a solution of a dispersant in Water, then introduces the water-insoluble polymerization catalyst either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated compound in the aqueous solution of the dispersant, then the water-insoluble polymerization catalyst by mechanical energy input dispersed and then with the aid of the aqueous dispersion obtained in this way a polymerization of at least one ethylenically unsaturated compound.

The aqueous polymer dispersions are obtained by polymerizing at least one ethylenically unsaturated compound (monomer) using a water-insoluble polymerization catalyst.

Suitable ethylenically unsaturated compounds are both pure hydrocarbon compounds and heteroatom-containing α-olefins, such as (meth) acrylic acid esters or amides, and homoallyl or allyl alcohols, ethers or halides. C ₂ - to C _ao -1 -alkenes are suitable among the pure hydrocarbons. Among these, the low molecular weight olefins, for example ethene or α-olefins having 3 to 20 carbon atoms, such as propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, are to be emphasized. Of course, cyclic olefins, for example cyclopentene, cyclohexene, norbornene, aromatic olefin compounds, such as styrene or a-methylstyrene, or vinyl esters, such as vinyl acetate, can also be used. However, the C ₂ - to C ₂ o-1 alkenes are particularly suitable. Among these, ethene, propene, 1-butene, 1-pentene, 1-hexene or 1-octene and 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene and olefin fractions of a cracker containing them are to be emphasized. It is of course possible according to the invention to use the aforementioned olefinically unsaturated compounds individually or in a mixture.

In addition, it is also possible to use the aforementioned olefinically unsaturated compounds in a mixture with those compounds which have the structure of the general formula (IV)

-CH = CH-Q-Pol _π (IV),

exhibit.

Q is a non-polar organic group selected from the group comprising linear or branched C to C ₂ o -alkyl, often C ₂ to C ₁₈ alkyl and often C ₃ to C ₁₄ alkyl, for example methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl, -octyl, -nonyl, -decyl, -undecyl, -dodecyl, -tridecyl or - Tetradecyl, C ₃ - to C -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, C ₆ - to Cu-aryl, for example phenyl, naphthyl or phenanthryl and alkylaryl with 1 to 20 C atoms in the alkyl part and 6 to 14 C- Atoms in the aryl part, for example benzyl. Π polar groups Pol are bound to the nonpolar group Q. Π is an integer other than 0. π is preferably 1, 2, 3 or 4. Of course, π can also be a higher numerical value.

Pol is a polar radical which is selected from the group comprising carboxyl (- C0 ₂ H), sulfonyl (-S0 ₃ H), sulfate (-OSO ₃ H), phosphonyl (-PO ₃ H), phosphate (-OPO ₃ H ₂ ) and their alkali metal salts, in particular sodium or potassium salts, alkaline earth metal salts, for example magnesium or calcium salts and / or ammonium salts.

Pol also includes the alkanolammonium, pyridinium, imidazolinium, oxazolinium, morpholinium, thiazoline, quinolinium, isoquinolinium, tropylium, sulfonium, guanidinium and phosphonium compounds, and especially ammonium compounds, which are accessible by protonation or alkylation of the general formula (V)

-N ^® R ^b RΕ ⁸ (V).

Here R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen and linear or branched d- to C ₂₀ -alkyl, frequently C to Cio-alkyl and often d- to C ₅ -alkyl, alkyl being for example methyl, ethyl, n - or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl, -octyl, -nonyl, -decyl, -undecyl, -dodecyl, -tridecyl or - is tetradecyl. The corresponding anions of the abovementioned compounds are non-nucleophilic anions, such as, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, for example Methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexatluafluoroarsenate.

The polar radical Pol can also be a group of the general formula (VI), (VII) or (VIII)

- (EO) _k - (PO), - R ^* (VI),

- (PO), - (EO) _k -R * (VII),

- (EO _k / PO,) - R * (VIII), where

EO for a -CH ₂ -CH ₂ -O group, PO stands for a -CH ₂ -CH (CH ₃ ) -O- or a -CH (CH ₃ ) -CH ₂ -O group and k and I for numerical values from 0 to 50, often from 0 to 30 and often from 0 to 15, but k and I are not 0 at the same time.

Furthermore, in

Formula (VI) and (VII): (EO) _{k is} a block of k -CH ₂ -CH ₂ -0 groups, and (PO) is a block of I -CH ₂ -CH (CH ₃ ) -O- or -CH (CH ₃ ) -CH ₂ -O groups, and

Formula (VIII): (EO _k / PO,) a mixture of k -CH ₂ -CH ₂ -0 groups and

I -CH ₂ -CH (CH ₃ ) -0- or -CH (CH ₃ ) -CH ₂ -O groups in statistical distribution

mean.

R ^* stands for hydrogen, linear or branched C to C ₂ o-alkyl, often C _r to Cι ₀ - alkyl and often d- to C ₆ -alkyl or -SO ₃ H and its corresponding alkali metal, alkaline earth metal and / or ammonium salt. Here, alkyl is, for example, methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -

Heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl, alkali metal for example for sodium or potassium and alkaline earth metal for example for calcium or magnesium.

According to the invention, the compounds containing the structural element of the general formula (IV) are, in particular, α-olefins of the general formula (IX)

H ₂ C = CH-Q-Polπ (IX),

used, wherein Q, Pol and π have the meanings given above.

Preferred olefins (IX) are 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and styrene-4-sulfonic acid.

The proportion of the amount of the ethylenically unsaturated compound (s) containing the structural element of the general formula (IV) in the monomer mixture to be polymerized, consisting of at least one ethylenically unsaturated compound containing the structural element of the general formula (IV) and at least one of the aforementioned ethylenically unsaturated compound is 0 to 100% by weight, often 0.5 to 80% by weight and often 1.0 to 60% by weight or 2.0 to 40% by weight. The ethylenically unsaturated compounds according to the invention are, in particular, ethene, propene, 1-butene, i-butene, 1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene and / or norbornene or these in a mixture with 10-undecenoic acid, 3-butenoic acid , 4-pentenoic acid, 5-hexenoic acid and / or styrene-4-sulfonic acid.

In addition to the ethylenically unsaturated compounds, carbon monoxide can also be used according to the invention, which ultimately results in polymer dispersions based on polyketones, which generally consist of alternating structural elements based on suitable ethylenically unsaturated compounds on the one hand and carbon monoxide on the other. It is advisable to set the quantitative ratio between the ethylenically unsaturated compound or compounds on the one hand and the carbon monoxide on the other hand to 80 mol% to 20 mol%, in particular to 60 mol% to 40 mol%. Particularly suitable ethylenically unsaturated compounds for the production of polyketones are nonpolar ethylenically unsaturated compounds, for example ethylene or α-olefins having 3 to 20 carbon atoms.

If only ethylenically unsaturated compounds are polymerized in, the result is aqueous polymer dispersions based on polyolefins.

All those water-insoluble polymerization catalysts which are capable of polymerizing the abovementioned monomers, that is to say the ethylenically unsaturated compounds, either with one another or in conjunction with carbon monoxide can be used for the process according to the invention.

The term water-insoluble polymerization catalysts means in particular those polymerization catalysts which have a water solubility of less than 10 ^"4 g catalyst per 100 g water, preferably less than 10 ^{" 5} g catalyst per 100 g water.

If polymer dispersions based on polyketones are to be produced using the process according to the invention, it is advisable to carry out the reaction of the ethylenically unsaturated compounds and carbon monoxide in the aqueous medium using the following polymerization catalyst:

Metal complexes of the general formula (I)

in which the substituents and indices have the following meaning:

G - (CR ^b ₂ ) _r - or - (CR ^b ₂ ) _s -Si (R ^a ) ₂ - (CR ₂ ) _t -, -AOB- or -AZ (R ⁵ ) -B- with

R is hydrogen, linear or branched d to C ₂₀ alkyl, C ₃ to Cio-cycloalkyl, C ₆ to C ₁ aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des Periodic table-substituted C ₆ to C ₁₄ aryl, aralkyl with 1 to 20 C atoms in the alkyl radical and 6 to 14

C atoms in the aryl radical, heteroaryl, long-chain radicals with 5 to 30 C atoms in the chain, which have polar or charged end groups, -N (R ^b ) ₂ , - Si (R ^c ) ₃ or a radical of the general formula (II)

in the

q denotes an integer from 0 to 20 and the further substituents in formula (II) have the same meaning as in formula (I),

A, B - (CR ₂ ) or - (CR ^b ₂ ) s-Si (R ^a ) ₂ - (CR ^b ₂ ) r or -N (R ^b ) -, an r'-, s- or t-atomic Part of a ring system or together with Z a (r '+ 1) -, (s + 1) - or (t + 1) -atomic part of a heterocycle,

R ^a independently linear or branched C to C ₂₀ alkyl, C ₃ - to Cio-cycloalkyl, C ₆ - to C ₁₄ -aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des accrual Systems substituted C ₆ to C ₁₄ aryl, aralkyl with 1 to 20 C atoms in the alkyl part and 6 to 14 C atoms in the aryl part,

R ^b as R ^a and additionally hydrogen and -Si (R ^c ) ₃ ,

R ^c linear or branched d to C ₂₀ alkyl, C ₃ to Cio-cycloalkyl, C ₆ to C ₁₄ aryl or aralkyl having 1 to 20 C atoms in the alkyl part and 6 to 14 C atoms in the aryl part,

r 1, 2, 3 or 4 and

r '1 or 2,

s, t 0, 1 or 2, where 1 ≤ s + t <3

Z is an element from the VA group of the Periodic Table of the Elements

M is a metal selected from Groups VIIIB, IB or IIB of the Periodic Table of the Elements,

E ¹ , E ^{2 is} a non-metallic element from group VA of the periodic table of the elements,

R ¹ to R ⁴ independently of one another are linear or branched d- to C ₂₀ -alkyl, C ₃ - to Cio-cycloalkyl, C ₆ - to C ₁₄ -aryl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted C ₆ to C 1 aryl, aralkyl with 1 to 20 C atoms in the alkyl radical and 6 to 14 C atoms in the aryl radical or heteroaryl,

L ¹ , L ² formally charged or neutral ligands,

X formally mono- or polyvalent anions,

p 0, 1, 2, 3 or 4,

m, n 0, 1, 2, 3 or 4,

where p = m x n,

or a compound of the general formula (III)

wherein

R ^d , R ^e ,

R ^f , R ⁹ independently of one another for hydrogen, linear or branched d- to C ₆ -alkyl or

R ^e and R ^f together represent a five- or six-membered carbo- or heterocycle and

the other substituents and indices assume the meaning given under formula (I).

The synthesis of such metal complexes of the formulas I, II and III is known per se (Lindner et al. J. Organomet. Chem. 2000, 602, 173).

With regard to the preparation of the polymer dispersions based on polyketones, the designations for the groups in 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; group IB contains Cu, Ag, Au).

Suitable metals M of the metal complexes to be used according to the invention are the metals from 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, with nickel and palladium being very particularly preferred.

The elements E 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 or phosphorus are particularly suitable, especially phosphorus. The chelating ligands can contain different elements E ¹ and E ² , for example nitrogen and phosphorus.

The structural unit G in the metal complex (I) is a single or multi-atom bridging structural unit. A bridging structural unit is basically understood to mean a grouping which connects the elements E ¹ and E ² in structure (I) to one another.

Among the monatomic bridged structural units are those with a bridging atom from group IVA of the Periodic Table of the Elements, such as -C (R ^b ) ₂ - or - Si (R ^a ) ₂ -, in which R ^a independently of one another in particular for linear or branched d- to Cio-alkyl, for example methyl, ethyl, i-propyl or t-butyl, C ₃ - to C ₆ - cycloalkyl, such as cyclopropyl or cyclohexyl, C _B - to Cio-aryl, such as phenyl or naphthyl, with functional Groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table substituted C ₆ - to Cio-aryl, for example tolyl, (trifluoromethyl) phenyl, dimethylaminophenyl, p-methoxyphenyl or partially or perhalogenated phenyl, aralkyl with 1 to 6 carbon atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, and R in particular represents hydrogen and also represents the meanings given above for R ^a . R ^a represents in particular a methyl group, R ^{b represents} in particular hydrogen.

Among the multi-atom bridged systems, the two- and three-atom bridged structural units should be emphasized, the latter generally being preferred.

In general, compounds of the general formula (III) are also suitable as complexes with diatomically bridged structural units

wherein R ^d , R ^e ,

R ^f , R ⁹ independently of one another are hydrogen, straight-chain or branched C to C ₆ alkyl, such as methyl, ethyl or i-propyl, or

R ^e and R ^f together represent a five- or six-membered carbo- or heterocycle and

the other substituents and indices can assume the general and preferred meaning given under formula (I).

For example, chelate ligands such as 1, 10-phenanthroline, 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine or their substituted derivatives can be traced back to diatomically bridged structural units.

Suitable three-atom bridged structural units are generally based on a chain of carbon atoms, for example propylene (-CH ₂ CH ₂ CH ₂ -), or on a bridging unit with a heteroatom from group IVA, VA or VIA of the periodic table of the elements, such as Silicon, nitrogen, phosphorus or oxygen in the chain structure.

In the case of bridges made entirely of carbon atoms, the free valences can be substituted by d- to C ₆ -alkyl, such as methyl, ethyl or tert-butyl, C ₆ - to cio-aryl, such as phenyl, or by functional groups such as triorganosilyl, dialkylamino or halogen , Suitable substituted propylene bridges are, for example, those with a methyl, phenyl or methoxy group in the 2-position.

Among the tri-atomic structural units with a heteroatom in the chain skeleton, compounds are advantageously used in which Z is nitrogen (see formula (I) above). The radical R ⁵ on Z can in particular mean: hydrogen, linear or branched C to C ₁₀ alkyl, such as methyl, ethyl, i-propyl or t-butyl, C ₃ to C ₆ cycloalkyl, such as cyclopropyl or cyclohexyl , C ₆ - to C ₁₀ -aryl, for example phenyl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, substituted C ₆ - to cio-aryl, such as tolyl, mesityl, aralkyl with 1 to 6 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical, pyridyl, long-chain radicals with 12 to 22 carbon atoms in the chain, which have polar or charged end groups, such as -SO ₃ -, -CO ₂ -, -CO ₂ R, - CONR ₂ , halogen, in particular -F, -Cl, -Br or -I, hydroxy, -OR, tosyl, -NR ₂ or - NR ₃ ⁺ , -NH ₂ (R stands whole generally for an aryl or alkyl radical or for hydrogen), dialkylamino, for example dimethyl-, dibenzyl- or diphenylamino, triorganosilyl, such as trimethyl-, triphenyl-, triethyl- or t-butyldiphenylsilyl or a radical of the general formula (II)

in which the substituents and indices have the following meaning:

q an integer from 1 to 20,

A, B - (CR ₂ ) r ~ or - (CR ^b ₂ ) _s -Si (R ^a ) ₂ - (CR ₂ ) r or -N (R ^b ) -, an r'-, s- or t- atomic component of a ring system or together with Z a (r '+ 1) -, (s + 1) - or (t + 1) -atomic component of a heterocycle,

R ^a independently of one another hydrogen, linear or branched Cr to Cι ₀ - alkyl, such as methyl, ethyl, i-propyl or t-butyl, C ₃ - to C ₆ -cycloalkyl, for example

Cyclohexyl, C ₆ - to Cι ₀ aryl, for example phenyl, with functional groups on the basis of the nonmetallic elements of groups IVA, VA, VIA or VIIA of the Periodic Table substituted C ₆ - to Cio-aryl, such as tolyl, trifluoro- methylphenyl , Aminophenyl, hydroxyphenyl, anisyl or mono- or dichlorophenyl, aralkyl with 1 to 6 carbon atoms in the alkyl part and 6 to 10 carbon atoms in

Aryl part, for example benzyl,

R as R and additionally hydrogen and -Si (R ^c ) ₃ ,

R ^c is linear or branched Cr to C ₁₀ -alkyl such as methyl or ethyl, C ₃ - to C ₆ - cycloalkyl, for example cyclohexyl, C ₆ - to Cι ₀ aryl, for example phenyl, or aralkyl with 1 to 6 C- Atoms in the alkyl part and 6 to 10 carbon atoms in the aryl part, for example benzyl, which, for example, trimethyl-, triethyl-, triphenyl- or t-butyldiphenylsilyl fall under the formula -Si (R ^c ) ₃

and the other substituents and indices have the meaning given under formula (I).

Among the metal complexes (I) chelated with monatomic ligands, those are preferred, for example, in which M is palladium positively charged as divalent is present, the elements E ¹ and E ^{2 are} phosphorus and the bridging structural unit G is methylene, ethylidene, 2-propylidene, dimethylsilylene or diphenylsilylene, in particular methylene. The monatomically bridged metal complexes advantageously have radicals R1 to R4, at least one of which is a non-aromatic radical. Among the aromatic radicals, phenyl and tolyl and o-, m- or p-anisyl are particularly noteworthy, among the aliphatic radicals are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, n -, i- or neo-pentyl, -hexyl, -heptyl, -ctyl, -nonyl, -decyl, -undecyl, -dodecyl, -tridecyl or -tetradecyl.

Metal complexes (I) which have a three-atom bridge are particularly preferred. This includes, for example, compounds in which the elements E1 and E2 are connected by a propylene unit (-CH ₂ CH ₂ CH ₂ -) and the further substituents in formula (I) have the following meaning:

M palladium or nickel, especially palladium,

E ¹ , E ² phosphorus or nitrogen, in particular phosphorus,

R ¹ to R ⁴ independently of one another are linear or branched d- to C ₂₀ -alkyl, frequently Cr to Cio-alkyl and often d- to C ₅ -alkyl, where alkyl is, for example, methyl,

Ethyl, n- or i-propyl, n-, i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl, -octyl, -nonyl, -decyl, -undecyl, -dodecyl, -Tridecyl or -Tetradecyl, substituted and unsubstituted C ₃ - to C ₆ -cycloalkyl, such as cyclopropyl, cyclohexyl or 1-methylcylohexyl, in particular cyclohexyl, C ₆ - to Cio-aryl, such as phenyl or naphthyl, in particular phenyl, with functional groups on the

Based on the non-metallic elements of groups IVA, VA, VIA or VIIA of the periodic table, substituted C ₆ to C 10 aryl, such as linear or branched d to C ₆ alkyl, for example methyl, ethyl, i-propyl, t-butyl, partially or perhaogenized d to C ₆ alkyl, for example trifluoromethyl or 2,2,2-trifiuorethyl, triorganosilyl such as trimethylsilyl, triethylsilyl or t

Butyldiphenylsilyl, amino, for example dimethylamino, diethylamino or di-i-propylamino, alkoxy, for example methoxy, ethoxy or t-butoxy, or halogen, such as fluorine, chlorine, bromine or iodine, aralkyl with 1 to 3 carbon atoms in the alkyl radical and 6 up to 10 carbon atoms in the aryl radical, for example benzyl, or heteroaryl, such as pyridyl,

L ¹ , L ² acetonitrile, acetylacetone, trifluoroacetate, benzonitrile, tetrahydrofuran, diethyl ether, acetate, tosylate or water, and also methyl, ethyl, propyl, butyl, phenyl or benzyl, X tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, pentafluorobenzoate, trifluoromethanesulfonate, trifluoroacetate, perchlorate, p-toluenesulfonate or tetraaryl borates such as tetrakis (pentafluorophenyl) borate or tetrakis (3,5-bis) trifluoromethyl

p 0, 1, 2, 3 or 4,

m, n 0, 1, 2, 3 or 4,

where p = m x n.

Examples of preferred propylene-bridged metal complexes are

[1,3-bis (diphenylphosphino) propane] -, [1,3-bis (di (2-methoxyphenyl) phosphino) propane] -,

[1,3-bis (dimethylphosphino) propane] -,

[1,3-bis (diethylphosphino) propane] -,

[1,3-bis (di (n-propyl) phosphino) propane] -,

[1,3-bis (di (iso-propyl) phosphino) propane] -, [1,3-bis (di (n-butyl) phosphino) propane] -,

[1,3-bis (di (2-methoxyphenyl) phosphino) -2,2-diethyl-propane] -,

[1,3-bis (di (n-pentyl) phosphino) propane] -,

[1,3-bis (di (n-hexyl) phosphino) propane] -,

[1,3-bis (di (iso-hexyl) phosphino) propane] -, [1,3-bis (di (neo-hexyl) phosphino) propane] -,

[1,3-bis (di (n-heptyl) phosphino) propane] -,

[1,3-bis (di (3- (cyclopentyl) propyl) phosphino) propane] -,

[1,3-bis (di (n-octyl) phosphino) propane] -,

[1,3-bis (di (n-nonyl) phosphino) propane] -, [1,3-bis (di (n-decyl) phosphino) propane] -,

[1,3-bis (di (n-dodecyl) phosphino) propane] -,

[1,3-bis (di (n-tetradecyl) phosphino) propane] -,

[1,3-bis (di (3- (cyclohexyl) propyl) phosphino) propane] - or [1,3-bis (di (n-hexadecyl) phosphino) propane] palladium (II) acetate.

Further preferred metal complexes have bidentate ligands which contain bipyridine structures.

Among the three-atom bridged metal complexes (I), those with a bridging structural unit -AN (R ⁵ ) -B- are also preferred. The substituents and indices in these metal complexes (I) advantageously assume the following meaning:

M palladium or nickel, especially palladium,

E ¹ , E ² phosphorus or nitrogen, in particular phosphorus,

R ¹ to R ⁴ independently of one another are linear or branched Cr to C ₂₀ alkyl, frequently d- to do-alkyl and often C to C ₅ alkyl, alkyl being for example methyl, ethyl, n- or i-propyl, n- , i- or t-butyl, n-, i- or neo-pentyl, -hexyl, -heptyl,

-Octyl, -Nonyl, -Decyl, -Undecyl, -Dodecyl, -Tridecyl or -Tetradecyl, substituted and unsubstituted C ₃ - to C ₆ -cycloalkyl, such as cyclopropyl, cyclohexyl or 1-methylcylohexyl, especially cyclohexyl, C ₆ - bis Cio-aryl, such as phenyl or naphthyl, especially phenyl, with functional groups based on the non-metallic elements of groups IVA, VA, VIA or VIIA des

Periodic table substituted C ₆ - to Cio-aryl, such as linear or branched d to C ₆ alkyl, for example methyl, ethyl, i-propyl, t-butyl, partially or perhalogenated d to C ₆ alkyl, for example trifluoromethyl or 2 , 2,2-trifluoroethyl, triorganosilyl, such as trimethylsilyl, triethylsilyl or t-butyldiphenylsilyl, amino, for example dimethylamino, diethylamino or di-i-propylamino, alkoxy, for example methoxy, ethoxy or t-butoxy, or halogen, such as fluorine, chlorine, Bromine or iodine, aralkyl with 1 to 3 carbon atoms in the alkyl radical and 6 to 10 carbon atoms in the aryl radical, for example benzyl, or heteroaryl, such as pyridyl,

L ¹ , L ² acetonitrile, benzonitrile, acetone, acetylacetone, diethyl ether, tetrahydrofuran, acetate, trifluoroacetate or benzoate, and also methyl, ethyl, propyl, butyl, phenyl or benzyl,

X p-toluenesulfonate, methyl sulfonate, trifluoromethanesulfonate, perchlorate, acetate, trifluoroacetate, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bis (trifluoromethyl) phenyl

A, B - (CR ₂ ) _r - with r 'equal to 1 or 2, in particular 1, and R as described under formula II, in particular hydrogen, methyl or ethyl,

p 0, 1, 2, 3 or 4,

m, n 0, 1, 2, 3 or 4, where p = mx n.

The preferred radicals R ⁵ correspond to those already mentioned above.

examples for this are

[N, N-bis (di (2-methoxyphenyl) phosphinomethyl) phenylamine] palladium (II) acetate, [N, N-bis (diphenylphosphinomethyl) t-butylamine] palladium (II) acetate, [N, N Bis (di (2-methoxy) phenylphosphinomethyl) t-butylamine] palladium (II) acetate.

Further examples of particularly preferred metal complexes (I) are

Bis (acetonitrile) [N, N-bis (diphenylphosphinomethyl) phenylamine] -, bis (acetonitrile) [N, N-bis (di (2-methoxyphenyl) phosphinomethyl) phenylamine] -,

Bis (acetonitrile) [N, N-bis (diphenylphosphinomethyl) t-butylamine] -,

Bis (acetonitrile) [N, N-bis (di (2-methoxy) phenylphosphinomethyl) t-butylamine] -,

Bis (acetonitrile) [1,3-bis (diphenylphosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (2-methoxyphenyl) phosphino) propane] -, bis (acetonitrile) [1,3-bis (dimethylphosphino) propane] -,

Bis (acetonitrile) [1,3-bis (diethylphosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-propyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (iso-propyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-butyl) phosphino) propane] -, bis (acetonitrile) [1,3-bis (di (n-pentyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-hexyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (isohexyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (neo-hexyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-heptyl) phosphino) propane] -, bis (acetonitrile) [1,3-bis (di (3- (cyclopentyl) propyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-octyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-nonyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-decyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (n-dodecyl) phosphino) propane] -, bis (acetonitrile) [1,3-bis (di (n-tetradecyl) phosphino) propane] -,

Bis (acetonitrile) [1,3-bis (di (3- (cyclohexyl) propyl) phosphino) propane] - or

Bis (acetonitrii) [1,3-bis (di (n-hexadecyl) phosphino) propane] palladium (II) bis (tetrafluoroborate) and the corresponding bis (perchlorate), bis (tetraphenylborate) or bis ( tetrakis (tris (2,4,6-trif luormethyl) phenyl) borate) and the corresponding Complexes in which the bis (acetonitrile) unit is replaced by a bis (tetrahydrofuran) or a bis (aqua) unit.

If the metal complexes used are positively charged, in particular BF ₄ ^" , SO ₄ ^2" , trifluoroacetate, nitrate, perchlorate, tosylate, trifluoromethanesulfonate or methanesulfonate are suitable as non-coordinating counterions.

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

Both mineral protonic acids and Lewis acids are suitable as activator compounds. Examples of suitable protic acids are 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 (trifluoromethyl) phenyl) borane or aluminum, zinc, antimony or titanium compounds with a Lewis acid 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 to metal complex, 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 are used together with the acids in the presence of organic hydroxy compound.

Suitable organic hydroxy compounds 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 can of course also be used. The molar ratio of optionally used hydroxy compound to metal complex, 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.

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

Suitable formally charged anionic ligands L ¹ , L ² are hydride, sulfates, phosphates or nitrates. Carboxylates or salts of organic sulfonic acids such as methyl sulfonate, trifluoromethyl sulfonate or p-toluenesulfonate are also suitable. Among the salts of organic sulfonic acids, p-toluenesulfonate is preferred. Preferred formally charged ligands L ¹ , L ² are carboxylates, preferably d to C ₂₀ carboxylates and in particular Cr to C ₇ carboxylates, that is to say, for example, acetate, trifluoroacetate, propionate, oxalate, citrate or benzoate. Acetate is particularly preferred.

Suitable formally charged organic ligands L ¹ , L ² are also C to C ₂₀ aliphatic radicals, C ₃ to C ₄ cycloaliphatic radicals, C ₇ to C ₂₀ arylalkyl radicals with C ₆ to C aryl radicals and d to C ₆ alkyl radicals and C ₆ - to -C ₄ aromatic radicals, for example methyl, ethyl, propyl, i-propyl, t-butyl, n-, i-pentyl, cyclohexyl, benzyl, phenyl and aliphatic or aromatic substituted phenyl radicals.

Lewis bases, ie compounds with at least one lone pair of electrons, are generally suitable as formally uncharged ligands L ¹ , L ² . Lewis bases whose free electron pair or whose free electron pairs are located on a nitrogen or oxygen atom, ie, for example, nitriles, R-CN, ketones, ethers, alcohols or water, are particularly suitable. Preference is given to using d- to C ₁₀ -nitriles such as acetonitrile, propionitrile, benzonitrile or C ₂ - to -C- ₀ ketones such as acetone, acetylacetone or C ₂ - to cioethers such as dimethyl ether, diethyl ether, tetrahydrofuran. In particular, acetonitrile, tetrahydrofuran or water are used.

Basically, the ligands L ¹ and L ² can be present in any ligand combination, ie the metal complexes (I) or (III) or the rest according to formula (II) can be, for example, a nitrate and an acetate residue, a p-toluenesulfonate and contain an acetate residue or a nitrate and a formally charged organic ligand such as methyl. L ¹ and L ² are preferably present as identical ligands in the metal complexes.

Depending on the formal charge of the complex fragment containing the metal M, the metal complexes contain anions X. However, if the M-containing complex fragment is formally uncharged, the complex according to the invention according to formula (I) or (III) contains none Anion X. Anions X are advantageously used which are as little nucleophilic as possible, ie which have as little tendency as possible to interact strongly with the central metal M, 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 such as, for example, methylsulfonate, trifluoromethylsulfonate and p-toluene tetronate, Tetraphenylborate, 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.

If polymer dispersions based on polyolefins are to be produced using the process according to the invention, it is advisable to carry out the polymerization of the ethylenically unsaturated compounds in an aqueous medium using the following polymerization catalyst:

Complex compounds of the general formula A or B or a mixture of these complex compounds A and B

B

where the residues are defined as follows:

M _{d is} a transition metal from groups 7 to 10 of the Periodic Table of the Elements (according to the nomenclature used from 1987), preferably manganese, iron, cobalt, nickel or palladium,

L ¹ _C phosphines (R ¹⁶ _d ) χPH ₃ . _x or amines (R ⁶ _d ) _x NH ₃ . _x with identical or different radicals R ¹⁶ _d , ether (R ¹⁶ _d ) ₂ O, H ₂ O, alcohols (R ¹⁶ _d ) OH, pyridine, pyridine vate of the formula C ₅ H _5-x (R ¹⁶ _d ) _x N, CO, CrCι ₂ alkyl nitriles, C ₆ -C ₁₄ aryl nitriles or ethylenically unsaturated double bond systems, where x is an integer from 0 to 3, L ² _d Halide ions, amide ions RdhNH ₂ . _h , where h is an integer from 0 to 2, and furthermore CrC ₆ alkyl anions, allyl anions, benzyl anions or

Aryl anions, where L ¹ _d and L ² _d are covalent to one another

Bonds can be linked, E _d nitrogen, phosphorus, arsenic or antimony, X _d -SO ₃ -, -O-PO ₃ ² -, NH (R ¹⁵ _d ) ₂ ⁺ , N (R ¹⁵ _d ) ₃ ⁺ or - ( OCH ₂ CH ₂ ) _n OH, n is an integer from 0 to 15,

Y _d oxygen, sulfur, NR ¹⁰ _d or PR ¹⁰ _d ,

R ¹ _d hydrogen, CrCι ₂ alkyl groups, C ₇ -Cι ₃ aralkyl radicals and C ₆ -Cι -

Aryl groups, unsubstituted or substituted with a hydrophilic group X _d , R ² _d and R ³ _d hydrogen, hydrophilic groups X _d ,

CrCι ₂ alkyl, where the alkyl groups can be branched or unbranched, d-Cι ₂ alkyl, one or more times the same or differently substituted by d-

C ₂ alkyl groups, halogens, hydrophilic groups X _d , d-C ₂ alkoxy groups or the d-C ₂ thioether groups, C ₇ -C ₃ aralkyl,

C ₃ -C ₂ cycloalkyl,

C ₃ -C ₂ cycloalkyl, substituted one or more times identically or differently by

CrC ₁₂ alkyl groups, halogens, hydrophilic groups X _d , d-C ₂ alkoxy groups or d-C ₂ thioether groups, C ₆ -C ₄ aryl,

Cβ-Cu-aryl, identical or differently substituted by one or more d-

C ₁₂ alkyl groups, halogens, hydrophilic groups X _d , mono- or polyhalogenated d-C ₂ alkyl groups, CrC ₂ alkoxy groups, silyloxy groups O-

SiR ¹⁰ _d R ¹¹ _d R ¹² _d , amino groups NR ¹³ _d R ¹⁴ _d or CC ₁₂ thioether groups, CrCι ₂ alkoxy groups,

Silyloxy groups OSiR ¹⁰ _d R ¹¹ _d R ² _d ,

Halogens or amino groups NR ¹³ _d R ¹⁴ d, where the radicals R ² _d and R ³ _d can form a saturated or unsaturated 5- to 8-membered ring with one another, and at least one radical R ¹ _d , R ² _d or R ³ _d bears a hydrophilic group X _d ; R ⁴ _d to R ⁷ _{d are} hydrogen, hydrophilic groups X _d , d -CC ₂ alkyl, where the alkyl groups can be branched or unbranched, CC ₁₂ alkyl, substituted one or more times identically or differently by C C ₂ alkyl groups, halogens, hydrophilic groups X _d , CrC ₁₂ alkoxy groups or the d C 1 -C ₂ thioether groups, C ₇ -C ₃ aralkyl, C ₃ -C ₂ cycloalkyl,

C ₃ -C ₂ -cycloalkyl, substituted one or more times, identically or differently, by dd≥-alkyl groups, halogens, hydrophilic groups X _d , d-C ₂ alkoxy groups or CrC ₂ thioether groups,

C ₆ -C ₄ aryl, identical or different substituted by one or more C

C ₂ alkyl groups, halogens, hydrophilic groups X _d , mono- or polyhalogenated d-C ₂ alkyl groups, CrC ₁₂ alkoxy groups, silyloxy groups O-SiR ¹⁰ _d R ¹¹ dR ¹² d, amino groups NR ¹³ _d R ¹⁴ _d or CrCι ₂ thioether groups, CrC ₁₂ alkoxy groups, silyloxy groups OSiR ¹⁰ _d R ¹ _d R ¹² d,

Halogens, NO ₂ groups or amino groups NR ¹³ _d R ¹⁴ _d , where two adjacent radicals R ⁴ _d to R ⁷ _d can form a saturated or unsaturated 5-8-membered ring with one another,

R ⁸ _d and R ⁹ _{d are} hydrogen, dC ₆ alkyl groups, C ₇ -Ci ₃ aralkyl groups and C ₆ -d ₄ -

Aryl groups, unsubstituted or substituted with a hydrophilic group X _d , R ¹⁰ _d to R ¹⁵ _d hydrogen, dC ₂₀ alkyl groups, which in turn can be substituted with O (dC ₆ alkyl) or N (CrC ₆ alkylI) ₂ groups , C ₃ -C ₂ cycloalkyl groups, C ₇ -C ₃ aralkyl radicals and C ₆ -C aryl groups;

R ^{6 is} hydrogen, dC ₂₀ -alkyl groups, which in turn can be substituted by O (CrC ₆ -alkyl) or N (d-C ₆ -alkyl) ₂ groups,

C ₃ -C ₂ cycloalkyl groups, C ₇ -C ₃ aralkyl radicals and C ₆ -C aryl groups, unsubstituted or substituted with a hydrophilic group X _d .

In a preferred embodiment, L ¹ d and L ² d are linked to one another by one or more covalent bonds. Examples of such ligands are 1,5-cyclooctadienyl ligands (“COD”), 1,6-cyclodecenyl ligands or 1,5,9-all-trans-cyclododecatrienyl ligands.

Such complex compounds of the general formula A or B, their preparation, their special configurations and particularly suitable representatives of these complex compounds are described in detail in WO 01/44325, the disclosure content of which is hereby incorporated in its entirety. The compounds A and B can be used in a ratio of 0: 100 to 100: 0 mol%. Preferred embodiments are 0: 100 mol%, 10: 90 mol%, 50: 50 mol%, 90: 10 mol% and 100: 0 mol%.

Numerous complexes of the general formula A or B are polymerization-inactive by themselves. You need an activator that, according to popular belief, abstracts the ligand L ¹ d. The activator can be olefin complexes of rhodium or nickel.

Preferred nickel (olefin) _y complexes commercially available from Aldrich are

Ni (C ₂ H ₄ ) ₃ , Ni (1, 5-cyclooctadiene) ₂ "Ni (COD) ₂ ", Ni (1, 6-cyclodecadiene) ₂ , or Ni (1, 5,9-all-trans-cyclododecatriene ) ₂ . Ni (COD) ₂ is particularly preferred.

Mixed ethylene / 1,3-dicarbonyl complexes of rhodium, for example rhodium-acetylacetonate-ethylene Rh (acac) (CH ₂ = CH ₂ ) ₂ , rhodium-

Benzoylacetonate ethylene Rh (C ₆ H5-CO-CH-CO-CH ₃ ) (CH ₂ = CH ₂ ) ₂ or Rh (C ₆ H ₅ -CO-CH-CO-C ₆ H ₅ ) (CH ₂ = CH ₂ ) ₂ . Rh (acac) (CH ₂ = CH ₂ ) ₂ is most suitable. This connection can be made according to the recipe by R. Cramer from Inorg. Synth. 1974, 15, 14 synthesize.

Some complexes of the general formula A or B can be activated by ethylene. The ease of the activation reaction depends crucially on the nature of the ligand L ¹ d. It could be shown that in the case that L ¹ d is a tetramethylethylenediamine ligand, no activator is required.

The dispersants 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, copolymers containing vinyl-2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid and their alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, also alkali metal nitrate, as well as their alkali metal nitrate, as well N- vinyl carbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, methacrylates, acrylamides and / or methacrylamides containing homo- and copolymers. A detailed description of further 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. It is advisable to design the method according to the invention in such a way that work is carried out above the so-called critical micelle concentration, if possible. This is the emulsifier concentration from which micelles form in the aqueous solution. In this way, it is possible to load the polymerization catalyst into an emulsifier micelle, where it then converts the monomers on offer into polymers.

Mixtures of protective colloids and / or emulsifiers can of course also be used. Often only emulsifiers are used as dispersants, whose relative molecular weights, 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 XI V / 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.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri- alkylphenols (EO grade: 3 to 50, alkyl radical: C ₄ to Cι ₂ ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C ₈ to C ₃₆ ). Examples of this are the Lutensol® A brands (C ₁₂ C fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol® AO brands (Cι ₃ Ci ₅ oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol® AT Brands (C ₁₆ d ₈ - fatty alcohol ethoxylates, EO grade: 11 to 80), Lutensol® ON brands (C ₁₀ -

Oxo alcohol ethoxylates, EO grade: 3 to 11) and the Lutensol® TO brands (Cι ₃ - 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 ₂ ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ₂ to C ₈ ) and ethoxylated alkyl phenols (EO- Degree: 3 to 50, alkyl radical: C to C ₂ ), of alkyl sulfonic acids (alkyl radical: C ₂ to Cι ₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to Cι ₈ ). Compounds of the general formula (X) have also proven to be further anionic emulsifiers:

wherein R ^y and R ^{z represent} H atoms or C ₄ - to C ₂₄ -alkyl and are not simultaneously H atoms, and D ¹ and D ^{2 can be} alkali metal ions and / or ammonium ions. In the general formula (X), R ^y and R ^{E are} preferably linear or branched alkyl radicals having 6 to 18 C atoms, in particular having 6, 12 and 16 C atoms or hydrogen, where R ^y and R ^{z are} not both H Atoms are. D ¹ and D ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Compounds (X) in which D ¹ and D ^{2 are} sodium, R ^{y is} a branched alkyl radical having 12 C atoms and R ^{z is} an H atom or R ^y are particularly advantageous. Technical mixtures are frequently used which have a proportion of 50 to 90% by weight of the monoalkylated product, such as Dowfax® 2A1 (brand of the Dow Chemical Company). The compounds (X) 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 ₈ alkyl, - alkylaryl or heterocyclic radical having primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts and thiazolinium salts 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 paraffinic acid esters, 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-trimethlyammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate as well as the gemini surfactant N, N'- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl -N-methylammonium sulfate and ethoxylated oleylamine (for example Uniperol® AC from BASF AG, approx. 12 ethylene oxide units). 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 white acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as, for example, methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate, furthermore tetrafluoroborate, tetraphenylborate (tetrakis), tetrakis (tetrakis), tetrakis (tetrakis, tetrakis (tetrakis, 5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

The emulsifiers which are preferably used as dispersants 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 of the olefinically unsaturated compounds. 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 dispersants 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.

Organic solvents which are only slightly soluble in water can optionally be used in the process according to the invention. Suitable solvents are liquid aliphatic and aromatic hydrocarbons with 5 to 30 carbon atoms, such as n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n- Nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, 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 having 10 to 32 carbon atoms, for example n-dodecanol, n-tetradecanol, n-hexadecanol and their isomers or cetyl alcohol, ceryl alcohol or myricyl alcohol (mixture of C ₃₀ and C ₃ alcohols) can also be used. Esters, such as fatty acid esters with 10 to 32 C atoms in the acid part and 1 to 10 C atoms in the alcohol part or esters from carboxylic acids and fatty alcohols with 1 to 10 C atoms in the carboxylic acid part and 10 to 32 C atoms in the alcohol part. Of course, it is also possible to use mixtures of the aforementioned solvents.

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. Solvents 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.

The process according to the invention is characterized in that a solution of one or more of the dispersing agents described above is first prepared in water and then the water-insoluble polymerization catalyst is introduced into the aqueous solution of the dispersing agent.

The water-insoluble polymerization catalyst can be introduced into the aqueous solution of the dispersant either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated compound.

If the water-insoluble polymerization catalyst is introduced as a solid or oily metal complex into the aqueous solution of the dispersant, it is advisable to do this at temperatures from 0 to 100 ° C., in particular from 20 to 80 ° C. and particularly preferably at 40 to 60 ° C.

It is also possible to prepare the water-insoluble polymerization catalyst before or during the mechanical energy input by reacting the corresponding metal salts with the corresponding ligands (in-situ preparation).

Furthermore, the water-insoluble polymerization catalyst can be mixed with a water-miscible solvent and introduced into the aqueous solution of the dispersant. Solvents suitable for this have a solubility in the aqueous reaction medium of at least 50% by weight, in particular at least 60% by weight, particularly preferably at least 70% by weight, in particular at least 80% by weight, in each case based on the total amount of solvent , on. Suitable water-miscible solvents include: Alcohols such as methanol, ethanol, n- or iso-propanol, butanol or polyethylene glycols, acetone or tetrahydrofuran.

In addition, the water-insoluble polymerization catalyst can also be mixed with a self-dispersing, ethylenically unsaturated compound in the aqueous solution of the dispersant. Suitable self-dispersing, ethylenically unsaturated compounds include 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid or styrene-4-sulfonic acid, or 1-butenol, 1-pentenol, 1-hexenol or with 1-20 Eo units ethoxylated 1-butenol, 1-pentenol, 1-hexenol. Subsequently, the water-insoluble polymerization catalyst is dispersed by mechanical energy input, preferably at temperatures from 0 to 100 ° C., in particular from 20 to 80 ° C., using the process according to the invention. The mechanical energy input is preferably carried out with the aid of suitable shearers, homogenizers, ultrasonic units (sonotrodes) or stirring devices. It is also possible here to use suitable homogenizers, ultrasound units or other shearing devices to produce an aqueous mini-emulsion from the aqueous macroemulsion initially present.

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 depends above all 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 "interaction 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. The devices described in GB-A 2250 930 and US-A 5,108,654 are in principle 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 DE-A 19756874 has proven particularly useful for producing an aqueous miniemulsion from conventional macroemulsions 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 can be irradiated uniformly with ultrasonic waves in one section. For this purpose, the radiation surface of the means for transmitting ultrasound waves is designed such that it substantially corresponds to the surface of the reaction space or, if the reaction space is a 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 depth of action 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 chamber depths of 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 cleanability and a high product throughput, reaction space depths are preferred which are considerably larger than, for example, the usual gap heights at high pressure are 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 is used for batch production of mini emulsions. With this device, ultrasound can act on the entire reaction space. A turbulent flow is generated in the reaction space 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 by means of a piezoelectric transducer into mechanical vibrations of the same frequency converted 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.

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.

In the aqueous dispersion obtained after the dispersion of the water-insoluble polymerization catalyst, polymerization of one or more ethylenically unsaturated compounds is carried out by the process according to the invention. If the polymerization should lead to polyketone dispersions, it is necessary to polymerize the ethylenically unsaturated compound together with carbon monoxide. The partial pressure of carbon monoxide should generally be in the range from 1 to 300 bar, in particular in the range from 1 to 80 bar. The polymerization reactor is usually rendered inert before being pressed on with carbon monoxide by flushing with carbon monoxide, ethylenically unsaturated compounds or inert gas, for example nitrogen or argon.

The polymerization temperature is generally set in a range from 0 to 120 ° C., in particular in a range from 20 to 100 ° C. and particularly preferably in a range from 40 to 80 ° C.

The process according to the invention can be carried out in the customary polymerization apparatus used in industry, preferably in stirred reactors, autoclaves, in particular high-pressure autoclaves, and in continuous tubular reactors or in so-called bubble columns, which can also be connected as a cascade.

The polymers obtained by the process according to the invention have molar masses (weight average), determined by means of gel permeation chromatography and 1, 1, 1, 3,3,3-hexafluoro-2-propanol as solvent, which are in the range from 1000 to 1,000,000, frequently in the range from 1500 to 800000 and in particular in the range from 2000 to 600000. The polyketones which are likewise accessible by the processes according to the invention are, as ¹³ C or ¹ H NMR spectroscopic studies show, generally linear, alternating carbon monoxide copolymer compounds. These are to be understood as copolymer compounds in which in the polymer chain on each carbon monoxide unit a -CH ₂ -CH ₂ -, -CH ₂ -CH- or -CH-CH unit originating from the olefinic double bond of the at least one olefinically unsaturated compound and on 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.

Through targeted variation of the olefinically unsaturated compounds it is among other things possible to produce polymers whose glass transition temperature or melting point is in the range from -60 to 270 ° C.

The glass transition temperature T _{g means} the limit value of the glass transition temperature which, according to G. Kanig (Kolloid-Zeitschrift & Zeitschrift fur Polymer, Vol. 190, p. 1, equation 1), strives with increasing molecular weight. The glass transition temperature is determined using 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 / Tg + X ^ g ² + .... x7T _g ⁿ ,

where x ¹ , x ² , .... x ^{π are} the mass fractions of the monomers 1, 2, .... n and T _g ¹ , T _g ² , .... T _g ^{n are} the glass transition temperatures of only one of the Monomers 1, 2, .... n built up polymers in degrees Kelvin. The T _g values for the homopolymers 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. Wiley, New York 1966, 2 ^nd Ed. J. Wiley, New York 1975, and 3 ^rd Ed. J. Wiley, New York 1989).

The polymer dispersions likewise according to the invention frequently have minimum film-forming temperatures MFT <80 ° C., often <50 ° C. or <30 ° C. Since the MFT is below 0 ° C is no longer measurable, the lower limit of the MFT can only be given 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, often 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 completion of the main polymerization reaction can be removed by steam and / or inert gas stripping without adversely affecting the polymer properties of the copolymers present in the aqueous medium.

The aqueous polymer dispersions which are also accessible with the aid of the process according to the invention can contain, in addition to the polymer, as further components, for example formulation auxiliaries, antioxidants, light stabilizers, dyes, pigments, and waxes or else rheology modifiers or other polymer dispersions.

The aqueous polymer dispersions which are likewise according to the invention are frequently stable over several weeks or months and generally show virtually no phase separation, deposition or coagulum formation during this time. They are particularly suitable as binders for paper applications such as paper coating or surface sizing, for paint varnishes, adhesive raw materials, molded foams such as mattresses, textile and leather applications, carpet backing or pharmaceutical applications, and as additives in polymer blends or in building materials.

With the aid of the method according to the invention, aqueous polymer dispersions can be prepared easily and with high productivity without great technical outlay. In addition, the process according to the invention has the advantage that synthetically simple, water-soluble polymerization catalysts can also be used for the preparation of aqueous polymer dispersions.

Examples

A. General methods of determination

NMR spectra were recorded on a Bruker ARX 300 ( ¹³ C: 75 MHz) or on a Bruker Avance 200 ( ³¹ P: 81 MHz). ¹³ C { ¹ H} NMR chemical shifts were calibrated against deuterolbenzene and referenced to TMS. ¹³ C NMR Spectra of the copolymers and terpolymers were measured in 1, 1, 1, 3,3,3-hexafluoro-2-propanol as a solvent. Gel permeation chromatography (GPC) was carried out in 1, 1,1, 3,3,3-hexafluoro-2-propanol at 40 ° C with PL HFIP columns against polymethyl methacrylate standard. Dynamic light scattering on dilute dispersions was carried out using a Malvern Particle Sizer. Transmission electron microscopy (TEM) was performed on a LEO 912 Omega microscope at 12 kV acceleration voltage. Differential scanning calorimetry (DSC) data were determined in the second heating cycle at 10 K min ^"1 .

B. Preparation of the polymer dispersions

In Examples 1 to 13 below, using the process according to the invention, aqueous dispersions based on copolymers of ethylene and carbon monoxide (Examples 1 to 4) and aqueous dispersions based on terpolymers of ethylene, carbon monoxide and undecenoic acid (Example 5 to 13). A solution of an emulsifier in water was first prepared, then the catalyst used was either in solid form (Examples 2-4) or solubilized in a water-miscible solvent (Examples 5) or mixed with a self-dispersing olefin (Examples 12-14) introduced into the aqueous solution of the emulsifier. This was followed by homogenization with ultrasound and then the actual polymerization.

Types of polymerization

I. Mini emulsion

The polymerization was carried out in a mechanically stirred 250 ml pressure reactor with a double jacket. The reaction temperature was controlled by a thermal sensor immersed in the reaction mixture. The volume of the reaction mixture was 100 ml. For the in situ catalyst miniemulsion, palladium acetate and 1,3-bis (diphenylphosphino) propane (DPPP) were dissolved separately in a little toluene or in toluene / undecenoic acid and combined to form a yellow solution. In the case of terpolymerization, the catalyst precursor complex 1,3-bis (diphenylphosphino) propane palladium (II) diacetate [(DPPP) Pd (Oac) ₂ ] was dissolved in undecenoic acid. After the addition of hexadecane, the catalyst solution was added to the aqueous emulsifier solution containing p-toluenesulfonic acid. The homogenization was carried out by ultrasound treatment (Bandelin HD2200 with KE76 tip; 2 min at 120 W). The mini emulsions obtained were transferred to the reactor and a pressure of 40 bar (ethylene / carbon monoxide 1: 1) was applied. Subsequently, heated (1000 rpm) either with a thermostat or with a polyethylene glycol bath. After the specified reaction time, the mixture was cooled and then ethene and carbon monoxide were discharged. In the experiments with precipitated polymers, these were filtered off and washed with water and methanol. If a latex was obtained, it was filtered through glass wool. A measured amount was precipitated in methanol to analyze and determine the yield.

II. "Solubilized" catalyst

The “solubilized” catalyst was prepared by homogenizing a mixture of catalyst precursor complex, one tenth of the total amount of emulsifier used and 10 ml of water by means of ultrasound (2 min, 120 W). This solution already became that The stirred and stirred aqueous emulsifier solution containing para-toluenesulfonic acid (p-TsOH) was injected through an O.45 μm micron filter, otherwise the procedure was as described in Section I.

III. Solubilization with solvents

Proceed as in II. But shearers can be dispensed with. However, the catalyst precursor complex is dissolved in 1 ml of methanol and added dropwise in 10 ml of an emulsifier solution at 40 ° C. and stirred magnetically. Para-toluenesulfonic acid was added to the solution (10 equivalents based on Pd) and the mixture was filtered through a 0.45 μm filter.

Results of the polymerizations carried out

Table 1

Ethylene-CO copolymerization

Reaction conditions: [Pd (DPPP) (OAc) ₂ ] (12.8 mg, 20 µmol); Total pressure 40 bar, ethylene / CO (1: 1); organic phase in catalyst miniemulsion: toluene (2 ml) and hexadecane (50 μl, 0.17 mmol); p-TsOH (47.6 mg, 0.26 mmol); Sodium dodecyl sulfate (SDS) (0.75 g, 2.6 mmol); 100 ml water; Reaction temperature 70 ° C.

a) TO = mol of converted substrate (E + COVmol palladium. b) in the presence of hexadecane and in the absence of p-TsOH. c) GPC vs. PMMA standard in hexafluoroisopropanol.

/ = not determined.

Table 2

Ethylene-carbon monoxide-undecenoic terpolymerization

Reaction conditions: [Pd (DPPP) (Oac) ₂ ] (12.8 mg, 20 µmol); Total pressure 40 bar, ethylene / CO (1: 1); p-TsOH (47.6 mg, 0.26 mmol); SDS (0.75 g, 2.6 mmol); 100 ml water; Hexadecane (50 μl, 0.17 mmol) in catalyst miniemulsion. a) Heated internally by means of a thermostat. b) Heated with polyethylene glycol bath, therefore no exact temperature value. c) In the presence of hexadecane (50 μl, 0.17 mmol). d) TO = mol of converted substrate (olefin + CO) / mol of palladium. e) polymer has completely failed. / = not determined.

Claims

claims

1. A process for the preparation of an aqueous polymer dispersion by polymerizing at least one ethylenically unsaturated compound (monomer) using at least one water-insoluble polymerization catalyst and at least one dispersant in an aqueous medium, characterized in that a solution of a dispersant in water is first prepared, then the water-insoluble polymerization catalyst either in solid form or mixed with a water-miscible solvent or mixed with a self-dispersing ethylenically unsaturated

Introduces the compound into the aqueous solution of the dispersant, then disperses the water-insoluble polymerization catalyst by mechanical energy input and then carries out a polymerization of at least one ethylenically unsaturated compound with the aid of the aqueous dispersion obtained in this way.

2. The method according to claim 1, characterized in that carbon monoxide is also polymerized in addition to the ethylenically unsaturated compound or compounds.

3. The method according to claims 1 or 2, characterized in that at least one α-olefin having 3 to 20 carbon atoms is polymerized as an ethylenically unsaturated compound.

4. Process according to claims 1 to 3, characterized in that the water-insoluble polymerization catalyst or catalysts used are obtained before or during the mechanical energy input by reacting the corresponding metal salts with the corresponding ligands.

5. The method according to claims 1 to 4, characterized in that the or the water-insoluble polymerization catalysts used have a water solubility of less than 10 ^"4 g of catalyst per 100 g of water.

6. The method according to claims 1 to 5, characterized in that the mechanical energy input takes place with the aid of suitable shearers, homogenizers, ultrasonic units or stirring devices.

7. The method according to claims 1 to 6, characterized in that the mechanical energy input is carried out at temperatures from 0 to 100 ° C.

8. The method according to claims 1 to 7, characterized in that the polymerization of the or the ethylenically unsaturated compounds is carried out in an autoclave.

9. The method according to claims 1 to 8, characterized in that the water-insoluble polymerization catalyst is introduced in solid form in the aqueous solution of the dispersant.

10. The method according to claims 1 to 8, characterized in that the water-insoluble polymerization catalyst is mixed in a water-miscible solvent in the aqueous solution of the dispersant, the water-miscible solvent having a solubility in the aqueous reaction medium of more than 50 wt. -%, each based on the total amount of solvent.

11. The method according to claims 1 to 8, characterized in that the water-insoluble polymerization catalyst is mixed in a self-dispersing ethylenically unsaturated compound in the aqueous solution of the dispersant.

12. Aqueous polymer dispersions, prepared by a process according to one of claims 1 to 11.

13. Use of the aqueous polymer dispersions according to claim 12 for paper applications such as paper coating or surface sizing, for paint coatings, adhesive raw materials, molded foams such as mattresses, textile and leather applications, carpet backing or pharmaceutical applications, and as additives in polymer blends or in building materials.