DE10315094A1 - Process for the preparation of an aqueous polymer dispersion using a water-insoluble polymerization catalyst - Google Patents

Abstract

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, firstly preparing a solution of a dispersant in water, 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 compound in the aqueous solution of the dispersant, then dispersed the water-insoluble polymerization catalyst by mechanical energy input and then using the aqueous dispersion obtained in this way polymerizes at least one ethylenically unsaturated compound ,

Description

The The present invention relates to a method for producing a 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 watery Medium, which is characterized in that one first solution a dispersant in water, 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 Connection in the watery solution of the dispersant, then the water-insoluble Polymerization catalyst dispersed by mechanical energy input and then with the aid of the aqueous dispersion obtained in this way Polymerization of at least one ethylenically unsaturated Connection.

Farther The present invention relates to the process of the invention accessible aqueous Polymer dispersions and their use for paper applications, paints, Adhesive raw materials, molded foams, Textile or leather applications, carpet backing or pharmaceutical Applications.

Aqueous dispersions of polymers are used in numerous very different applications used commercially. So far it has been difficult to use aqueous dispersions of polyolefins and polyketones because these polymers mostly only poorly water-soluble are. To start from inexpensive monomers such as olefins or carbon monoxide to polymer dispersions based on polyolefins or polyketones, suitable, water-soluble polymerization catalysts are used, that have to be produced synthetically. It is also possible to use aqueous dispersions of Polyolefins or polyketones by a so-called mini emulsion polymerization produce in which the polymerization catalyst in an organic solvent solved and is emulsified. Such mini-emulsion polymerization requires but an additional one 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). The metallocenes used are but 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 reports that certain nickel complexes have nitrogenous annular Polymerize ligands in the presence of small amounts of water can. However, no emulsion polymerization can be carried out under the conditions described carried out become.

Transition metal-catalyzed processes for the production of polyketones are also known (Bianchini C; Meli. A., Coord. Chem. Rev. 2002, 225, 35). For example, in the EP-A 0 121 965 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 in suspension, as in the EP-A 0 305 011 described, or in the gas phase, for example according to EP-A 0 702 045 , be performed. Frequently used suspending agents are, on the one hand, low molecular weight alcohols, especially methanol (see also EP-A 0 428 228 ), on the other hand non-polar or polar aprotic liquids such as dichloromethane, toluene or tetrahydrofuran (cf. EP-A 0 460 743 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 high expenditure 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. In the EP-A 0 485 035 the use of water in proportions of 2.5 to 15% by weight to the alcoholic suspending agent is proposed in order to eliminate the residual amounts of low molecular weight alcohol in the carbon monoxide copolymer. However, this procedure does not lead to methanol-free Co polymers. 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, the increase succeeds the catalyst activity the copolymerization of carbon monoxide and ethene by the Use the chelate ligands mentioned in a much 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 under the comparable polyketone, but made in methanol as solvent lies.

The The above-mentioned syntheses have in common that the carbon monoxide copolymers formed (hereinafter referred to as "copolymers") in the precipitate organic suspending agents by filtration from the separated organic suspending agents and further processed in bulk become. In many areas of application, however, it is advantageous if the copolymers are not in bulk, but in the form of water Copolymer dispersions are present. This is especially then the case when the copolymers, for example as binders in adhesives, sealants, plastic plasters or paints should be used.

The Manufacturing watery In principle, copolymer dispersions can be prepared by appropriate suspension polymerization in organic solvents, Filtration, drying, grinding and dispersing the ground Copolymer particles in aqueous Medium (so-called secondary dispersions). Disadvantageous This step concept is that it is overall very complex and the copolymers, especially due to the high solvent content, are difficult to grind (sticking of the mills) which are obtained by grinding Copolymer particles - if at all - only under Use of large amounts of emulsifier dispersed in aqueous medium can be and this watery secondary dispersions are unstable due to their very broad particle size distribution and tend to coagulate or sediment.

to Production of so-called primary aqueous Copolymer dispersions, i.e. aqueous copolymer dispersions, which directly by copolymerization of carbon monoxide and olefinic unsaturated Compounds in aqueous Medium accessible are based on the following state of the art.

In the 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.

In the DE-A 10125238 stable aqueous copolymer dispersions are disclosed, the preparation of which takes place by copolymerization of carbon monoxide and olefinically unsaturated compounds in an 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.

object WO 97/18266 are secondary dispersions of polyketones that are obtained by first low molecular weight polyketone in an organic solvent is produced and then is dispersed in water with emulsifiers. A disadvantage of the described Manufacturing process is the additional one Emulsification. About that secondary dispersions also stand out through a basically broad particle size distribution on which for some Areas of application unfavorable is.

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

The present invention was therefore based on the object to remedy the disadvantages described fen and provide a new method 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) found using at least one water Polymerization catalyst and at least one dispersant in watery Medium, which is characterized in that one first solution a dispersant in water, 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 Connection in the watery solution of the dispersant, then the water-insoluble Polymerization catalyst dispersed by mechanical energy input and then with the aid of the aqueous dispersion obtained in this way Polymerization of at least one ethylenically unsaturated Connection.

The aqueous Polymer dispersions are obtained by at least polymerization an 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 _{2 0} -1-alkenes are suitable among the pure hydrocarbons. Among these, the low molecular weight olefins, for example ethene or α-olefins with 3 to 20 C 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 α-methylstyrene or vinyl esters such as vinyl acetate can also be used. However, the C ₂ - to C ₂₀ -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 structural element of the general formula (IV) -CH = CH-Q-Pol _π (IV), exhibit.

Q is a non-polar organic group selected from the group consisting of linear or branched C ₁ to C ₂₀ alkyl, often C ₂ to C ₁₈ alkyl and frequently C ₃ to C _{1 4} 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 _{1 4} -cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, C ₆ - to C _{1 4} -aryl, for example phenyl, naphthyl or phenanthryl, and alkylaryl with 1 to 20 C atoms in the alkyl part and 6 to 14 carbon atoms in the aryl part, for example benzyl.

On the non-polar group Q are π polar Groups tied to pole. Where π is one Integer not equal to 0. π is preferably 1, 2, 3 or 4. Of course, π can also be one higher Be a numerical value.

Pol is a polar radical which is selected from the group comprising carboxyl (-CO ₂ H), sulfonyl (-SO 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.

Also included by Pol are the alkanolammonium, pyridinium, imidazolinium, oxazolinium, morpholinium, thiazolinium, quinolinium, isoquinolinium, tropylium, sulfonium, guanidinium and phosphonium compounds, and especially ammonium compounds of the general, accessible by protonation or alkylation Formula (V) -N ^⨁ R ⁶ R ⁷ R ⁸ (V).

Here R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen and linear or branched C ₁ to C ₂₀ alkyl, frequently C ₁ to C ₁₀ alkyl and often C ₁ 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, - Is dodecyl, tridecyl or 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, such as, for example, 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 polar radical Pol can also be a group of the general formula (VI), (VII) or (VIII) - (EO) _k - (PO) _l -R * (VI), - (PO) _l - (EO) _k -R * (VII), - (EO k / PO l ) -R * (VIII) be 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 l for numerical values from 0 to 50, often from 0 to 30 and often from 0 to 15, but k and l are not 0 at the same time.

Furthermore, in
Formula (VI) and (VII): (EO) _{k is} a block of k -CH ₂ -CH ₂ -O groups, and
(PO) _{l is} a block of l -CH ₂ -CH (CH ₃ ) -O- or -CH (CH ₃ ) -CH ₂ -O groups, and
Formula (VIII): (EO _k / PO _l ) a mixture of k -CH ₂ -CH ₂ -O groups and
1 -CH ₂ -CH (CH ₃ ) -O- or -CH (CH ₃ ) -CH ₂ -O groups in statistical distribution
mean.

R * stands for hydrogen, linear or branched C ₁ - to C ₂₀ -alkyl, often C ₁ - to C ₁₀ -alkyl and frequently C ₁ - 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 Amount of the structural element of the general formula (IV) containing ethylenically unsaturated Compounds) in the monomer mixture to be polymerized from at least one the structural element of the general formula (IV) containing ethylenically unsaturated compound and at least one of the above-mentioned 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.

As ethylenically unsaturated According to the invention, compounds are in particular ethene, propene, 1-butene, i-butene, 1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene and / or norbornene or in a mixture with 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and / or Styrene-4-sulfonic acid used.

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 Connections exist on the one hand and carbon monoxide on the other hand. 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.

Become only ethylenically unsaturated Polymerized compounds, ultimately aqueous polymer dispersions are formed based on polyolefins.

For the method according to the invention can all those water-insoluble Polymerization catalysts are used, which are able to the aforementioned monomers, ie the ethylenically unsaturated Connections either with each other or in connection with Polymerize carbon monoxide.

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.

in der die Substituenten und Indizes die folgende Bedeutung haben:
G -(CR^b ₂)_r oder -(CR^b ₂)_s-Si(R^a)₂-(CR^b ₂)_t-, -A-O-B- oder -A-Z(R⁵)-B- mit
R⁵ Wasserstoff, lineares oder verzweigtes C₁- bis C_{2 0}-Alkyl, C₃- bis C₁₀-Cycloalkyl, C₆- bis C_{1 4}-Aryl, mit funktionellen Gruppen auf der Basis der nichtmetallischen Elemente der Gruppen IVA, VA, VIA oder VIIA des Periodensystems substituiertes C₆- bis C_{1 4}-Aryl, Aralkyl mit 1 bis 20 C-Atomen im Alkylrest und 6 bis 14 C-Atomen im Arylrest, Heteroaryl, langkettige Reste mit 5 bis 30 C-Atomen in der Kette, die über polare oder geladene Endgruppen verfügen, -N(R^b)₂, -Si(R^c)₃ oder einen Rest der allgemeinen Formel (II)

in der
q eine ganze Zahl von 0 bis 20 bedeutet und die weiteren Substituenten in Formel (II) die gleiche Bedeutung wie in Formel (I) haben,
A, B -(CR^b ₂)_r- oder -(CR^b ₂)_s Si(R^a)₂-(CR^b ₂)_t- oder -N(R^b)-, ein r'-, s- oder t-atomiger Bestandteil eines Ringsystems oder zusammen mit Z ein (r'+1)-, (s+1)- oder (t+1)-atomiger Bestandteil eines Heterocyclus,
R^a unabhängig voneinander lineares oder verzweigtes C₁- bis C₂₀-Alkyl, C₃- bis C₁₀-Cycloalkyl, C₆- bis C_{1 4}-Aryl, mit funktionellen Gruppen auf der Basis der nichtmetallischen Elemente der Gruppen IVA, VA, VIA oder VIIA des Perioden systems substituiertes C₆- bis C_{1 4}-Aryl, Aralkyl mit 1 bis 20 C-Atomen im Alkylteil und 6 bis 14 C-Atomen im Arylteil,
R^b wie R^a und zusätzlich Wasserstoff und -Si(R^c)₃,
R^c lineares oder verzweigtes C₁- bis C₂₀-Alkyl, C₃- bis C₁₀-Cycloalkyl, C₆- bis C_{1 4}-Aryl oder Aralkyl mit 1 bis 20 C-Atomen im Alkylteil und 6 bis 14 C-Atomen im Arylteil,
r 1, 2, 3 oder 4 und
r' 1 oder 2,
s, t 0, 1 oder 2, wobei 1 ≤s+t ≤3
Z ein Element aus der Gruppe VA des Periodensystems der Elemente
M ein Metall ausgewählt aus den Gruppen VIIIB, IB oder IIB des Periodensystems der Elemente,
E¹, E² ein nichtmetallisches Element aus der Gruppe VA des Periodensystems der Elemente,
R¹ bis R⁴ unabhängig voneinander lineares oder verzweigtes C₁- bis C₂₀-Alkyl, C₃- bis C₁₀-Cycloalkyl, C₆- bis C_{1 4}-Aryl, mit funktionellen Gruppen auf der Basis der nichtmetallischen Elemente der Gruppen IVA, VA, VIA oder VIIA des Periodensystems substituiertes C₆- bis C_{1 4}-Aryl, Aralkyl mit 1 bis 20 C-Atomen im Alkylrest und 6 bis 14 C-Atomen im Arylrest oder Heteroaryl,
L¹, L² formal geladene oder neutrale Liganden,
X formal ein- oder mehrwertige Anionen,
p 0, 1, 2, 3 oder 4,
m, n 0, 1, 2, 3 oder 4,
wobei p = m × n,
oder eine Verbindung der allgemeinen Formel (III)

worin
R^d, R^e, R^f, R^g unabhängig voneinander für Wasserstoff, linear oder verzweigtes C₁- bis C₆-Alkyl oder
R^e und R^f zusammen für einen fünf- oder sechsgliedrigen Carbo- oder Heterocyclus stehen und
die übrigen Substituenten und Indizes die unter Formel (I) angegebene Bedeutung annehmen.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 of carbon monoxide in an 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 ^b ₂ ) _t -, -AOB- or -AZ (R ⁵ ) -B- with
R ^{5 is} hydrogen, linear or branched C ₁ - to C _{2 0} -alkyl, C ₃ - to C ₁₀ -cycloalkyl, C ₆ - to C _{1 4} -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 4} aryl, aralkyl having 1 to 20 carbon atoms in the alkyl radical and 6 to 14 C atoms in the aryl, heteroaryl, long-chain radicals having 5 to 30 carbon 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 ^b ₂ ) _r - or - (CR ^b ₂ ) _s Si (R ^a ) ₂ - (CR ^b ₂ ) _t - 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 is} independently linear or branched C ₁ - to C ₂₀ -alkyl, C ₃ - to C ₁₀ -cycloalkyl, C ₆ - to C _{1 4} aryl, with functional groups on the basis of the nonmetallic elements of groups IVA, VA, VIA or VIIA of the periodic system substituted C ₆ - to C _{1 4} aryl, aralkyl having 1 to 20 carbon atoms in the alkyl moiety and 6 to 14 carbon atoms in the aryl part,
R ^b as R ^a and additionally hydrogen and -Si (R ^c ) ₃ ,
R ^c linear or branched C ₁ to C ₂₀ alkyl, C ₃ to C ₁₀ cycloalkyl, C ₆ to C _{1 4} 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 are,} independently of one another, linear or branched C ₁ to C ₂₀ alkyl, C ₃ to C ₁₀ cycloalkyl, C ₆ to C _{1 4} aryl, with functional groups based on the nonmetallic elements of groups IVA , VA, VIA or VIIA of the Periodic Table substituted C ₆ - to C _{1 4} aryl, aralkyl having 1 to 20 carbon atoms in the alkyl radical and 6 to 14 C atoms in the aryl 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 × n,
or a compound of the general formula (III)

wherein
R ^d , R ^e , R ^f , R ^g independently of one another for hydrogen, linear or branched C ₁ - 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 formulas I, II and III is known per se (Lindner et al. J. Organomet. Chem. 2000, 602, 173).

In Reference to the preparation of the polymer dispersions based of polyketones is the designation for the groups of the periodic table of the elements used by the Chemical Abstracts Service until 1986 Nomenclature (so contains for example the group VA the elements N, P, As, Sb, Bi; the Group IB contains Cu, Ag, Au).

As Metals M of those to be used according to the invention Metal complexes are suitable for Group VIIIB, IB and IIB of the Periodic Table of the Elements, e.g. next to Copper, silver or zinc, also iron, cobalt and nickel as well as the Platinum metals such as ruthenium, rhodium, osmium, iridium and platinum, where Nickel and palladium is very particularly 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 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.

The structural unit G in the metal complex (I) is a mono- 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 C ₁ - to C ₁₀ -alkyl, for example methyl, ethyl, i-propyl or t-butyl, C ₃ - to C ₆ -cycloalkyl, such as cyclopropyl or cyclohexyl, C ₆ - to C ₁₀ -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 C ₁₀ 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 ^{b are} in particular hydrogen and also represent the meanings given above for R ^a , preferred. R ^a represents in particular a methyl group, R ^{b represents} in particular hydrogen.

Under the multi-atom bridge Systems, the two and three atom bridged structural units are to be emphasized, the latter being generally preferred.

worin
R^d, R^e, R^f, R^g unabhängig voneinander für Wasserstoff, geradkettig oder verzweigtes C₁- bis C₆-Alkyl, wie Methyl, Ethyl oder i-Propyl, oder
R^e und R^f zusammen für einen fünf- oder sechsgliedrigen Carbo- oder Heterocyclus stehen und
die übrigen Substituenten und Indizes die unter Formel (I) angegebene allgemeine und bevorzugte Bedeutung annehmen können.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 ^g independently of one another are hydrogen, straight-chain or branched C ₁ -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).

On bridged Structural units go for example chelating ligands such as 1,10-phenanthroline, 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine or their substituted derivatives.

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 C ₁ to C ₆ alkyl, such as methyl, ethyl or t-butyl, C ₆ to C ₁₀ aryl, such as phenyl, or by functional groups such as triorganosilyl, dialkylamino or Halogen substituted. Suitable substituted propylene bridges are, for example, those with a methyl, phenyl or methoxy group in the 2-position.

in der die Substituenten und Indizes die folgende Bedeutung haben:
q eine ganze Zahl von 1 bis 20,
A, B -(CR^b ₂)_r- oder -(CR^b ₂)_s-Si(R^a)₂-(CR^b ₂)_t- oder -N(R^b)-, ein r'-, s- oder t-atomiger Bestandteil eines Ringsystems oder zusammen mit Z ein (r'+1)-, (s+1)- oder (t+1)-atomiger Bestandteil eines Heterocyclus,
R^a unabhängig voneinander Wasserstoff, lineares oder verzweigtes C₁- bis C₁₀-Alkyl, wie Methyl, Ethyl, i-Propyl oder t-Butyl, C₃- bis C₆-Cycloalkyl, zum Beispiel Cyclohexyl, C₆- bis C₁₀-Aryl, zum Beispiel Phenyl, mit funktionellen Gruppen auf der Basis der nichtmetallischen Elemente der Gruppen IVA, VA, VIA oder VIIA des Periodensystems substituiertes C₆- bis C₁₀-Aryl, wie Tolyl, Trifluormethylphenyl, Aminophenyl, Hydroxyphenyl, Anisyl oder Mono- oder Dichlorphenyl, Aralkyl mit 1 bis 6 C-Atomen im Alkylteil und 6 bis 10 C-Atomen im Arylteil, beispielsweise Benzyl,
R^b wie R^b und zusätzlich Wasserstoff und -Si(R^c)₃,
R^c lineares oder verzweigtes C₁- bis C₁₀-Alkyl, wie Methyl oder Ethyl, C₃- bis C₆-Cycloalkyl, zum Beispiel Cyclohexyl, C₆- bis C₁₀-Aryl, zum Beispiel Phenyl oder Aralkyl mit 1 bis 6 C-Atomen im Alkylteil und 6 bis 10 C-Atomen im Arylteil, beispielsweise Benzyl, womit z.B. Trimethyl-, Triethyl-, Triphenyl- oder t-Butyldiphenylsilyl unter die Formel -Si(R^c)₃ fallen
und die übrigen Substituenten und Indizes die unter Formel (I) angegebene Bedeutung haben.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 ₁ 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 C ₁₀ -aryl, such as tolyl, mesityl, aralkyl with 1 up 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 in general 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 en rest 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 ^b ₂ ) _r - or - (CR ^b ₂ ) _s -Si (R ^a ) ₂ - (CR ^b ₂ ) _t - 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 is hydrogen, linear or branched C ₁ to C ₁₀ alkyl, such as methyl, ethyl, i-propyl or t-butyl, C ₃ to C ₆ cycloalkyl, for example 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 C ₁₀ aryl, such as tolyl, trifluoromethylphenyl, aminophenyl, hydroxyphenyl, anisyl or mono- or dichlorophenyl, aralkyl with 1 to 6 C atoms in the alkyl part and 6 to 10 C atoms in the aryl part, for example benzyl,
R ^b as R ^b and additionally hydrogen and -Si (R ^c ) ₃ ,
R ^c linear or branched C ₁ to C ₁₀ alkyl, such as methyl or ethyl, C ₃ to C ₆ cycloalkyl, for example cyclohexyl, C ₆ to C ₁₀ aryl, for example phenyl or aralkyl with 1 to 6 C atoms in the alkyl part and 6 to 10 C atoms in the aryl part, for example benzyl, with which 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 present as divalent positively charged palladium, the elements E ¹ and E ² phosphorus and the bridging structural unit G 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, -octyl, -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 C ₁ to C ₂₀ alkyl, frequently C ₁ to C ₁₀ alkyl and often C ₁ 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 is substituted and unsubstituted C ₃ - to C ₆ -cycloalkyl, such as cyclopropyl, cyclohexyl or 1-methylcylohexyl, in particular cyclohexyl, C ₆ - to C ₁₀ -aryl, such as phenyl or naphthyl, in particular phenyl, with functional groups based on 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 C ₁ to C ₆ alkyl, for example methyl, ethyl, i-propyl, t-butyl, partially or perhalogenated C ₁ -C ₆ -alkyl, for example trifluoromethyl or 2,2,2-trifluoroethyl, triorganosilyl such as trimethylsilyl, triethylsilyl or t-butyldiphen ylsilyl, 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 C 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 tetraarylborates such as tetrakis (pentafluorophenyl) borate or tetrakis (3,5-bis (trifluoromate) borate)
p 0, 1, 2, 3 or 4,
m, n 0, 1, 2, 3 or 4,
where p = m × 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 C ₁ to C ₂₀ alkyl, frequently C ₁ to C ₁₀ alkyl and often C ₁ 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 is substituted and unsubstituted C ₃ - to C ₆ -cycloalkyl, such as cyclopropyl, cyclohexyl or 1-methylcylohexyl, in particular cyclohexyl, C ₆ - to C ₁₀ -aryl, such as phenyl or naphthyl, in particular phenyl, with functional groups based on 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 C ₁ to C ₆ alkyl, for example methyl, ethyl, i-propyl, t-butyl, partially or perhalogenated C ₁ -C ₆ -alkyl, for example trifluoromethyl or 2,2,2-trifluoroethyl, triorganosilyl such as trimethylsilyl, triethylsilyl or t-butyldiphen ylsilyl, 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 C 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, benzonitrile, acetone, acetylacetone, diethyl ether, tetrahydrofuran, acetate, trifluoroacetate or benzoate, and also methyl, ethyl, propyl, butyl, phenyl or benzyl,
X p-toluenesulfonate, methylsulfonate, trifluoromethanesulfonate, perchlorate, acetate, trifluoroacetate, tetrafluoroborate, tetraphenylborate, hexafluorophosphate, tetrakis (pentafluorophenyl) borate, tetrakis (3,5-bis (trifluoromethyl) phenyl
A, B - (CR ^b ₂ ) _r - with r 'equal to 1 or 2, in particular 1, and R ^b 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 = m × 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 (iso-hexyl) 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 (acetonitrile) [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-trifluoromethyl) 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 can be used as non-coordinating counterions.

In The aforementioned metal complexes are a preferred method in the presence of acids, which one also referred to as so-called activators.

As Mineral protonic acids come as activator compounds also Lewis acids in question. Suitable as protonic acids are for example sulfuric acid, Nitric acid, boric acid, tetrafluoroboric acid, perchloric acid, p-toluenesulfonic acid, trifluoroacetic, trifluoromethanesulfonic or methanesulfonic acid. P-Toluenesulfonic acid and tetrafluoroboric acid are preferably used. When Lewis acids come for example 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 Lewis acid Character in question. It can also mixtures of protonic acids or Lewis acids as well Proton and Lewis acids can be used in a mixture.

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

In The aforementioned metal complexes are also a preferred method together with the acids used 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 from optionally used hydroxy compound to metal complex the amount of metal M is generally in the range of 0 to 100,000, often from 500 to 50,000 and often from 1,000 to 10,000.

As a general rule can the metals M in the complexes formally uncharged, formally simple are positively or preferably formally double positively charged.

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 C ₁ to C _{2 0} carboxylates and in particular C ₁ 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 ₁ - to C _{2 0} -aliphatic radicals, C ₃ - to C _{1 4} -cycloaliphatic radicals, C ₁ - to C ₂₀ -arylalkyl radicals with C ₆ - to C _{1 4} Aryl radicals and C ₁ to C ₆ alkyl radicals and C ₆ to C _{1 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, for example nitriles, R-CN, ketones, ethers, alcohols or water, are particularly suitable. Preferably used C ₁ - to C ₁₀ nitriles such as acetonitrile, propionitrile, benzonitrile, or C ₂ - to C ₁₀ ketones such as acetone, acetylacetone, or C ₂ - to C ₁₀ ethers 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.

ever after formal loading of the complex fragment containing the metal M. the metal complexes contain anions X. Is the M-containing complex fragment however formally unloaded, so contains the complex according to the invention according to formula (I) or (III) no anion X. Advantageously, anions X used that as possible are less nucleophilic, i.e. have as little tendency as possible a strong interaction with the central metal M, whether ionic, coordinative or covalent.

suitable Anions X are, for example, perchlorate, sulfate, phosphate, nitrate and carboxylates, such as acetate, trifluoroacetate, trichloroacetate, Propionate, oxalate, citrate, benzoate, and conjugated anions of organo such as methyl sulfonate, trifluoromethyl sulfonate and p-toluenesulfonate Tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, Tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, Hexafluorophosphate, Hexafluoroarsenate or Hexafluoroantimonate. Perchlorate, trifluoroacetate and sulfonates are preferably used such as methyl sulfonate, trifluoromethyl sulfonate, p-toluenesulfonate, tetrafluoroborate or hexafluorophosphate and in particular trifluoromethyl sulfonate, Trifluoroacetate, perchlorate or p-toluenesulfonate.

wobei die Reste wie folgt definiert sind:
M_d ein Übergangsmetall der Gruppen 7 bis 10 des Periodensystems der Elemente (gemäß der ab 1987 verwendeten Nomenklatur), vorzugsweise Mangan, Eisen, Kobalt, Nickel oder Palladium,
L¹ _d Phosphane (R¹⁶ _d)_xPH_3-x oder Amine (R¹⁶ _d)_xNH_3-x mit gleichen oder verschiedenen Resten R¹⁶ _d, Ether (R¹⁶ _d)₂O, H₂O, Alkoholen (R¹⁶ _d)OH, Pyridin, Pyridinderi vate der Formel C₅H_5-x(R¹⁶ _d)_xN, CO, C₁-C₁₂-Alkylnitrile, C₆-C₁₄-Arylnitrile oder ethylenisch ungesättigten Doppelbindungssystemen, wobei x eine ganze Zahl von 0 bis 3 bedeutet,
L² _d Halogenidionen, Amidionen RdhNH_2-h, wobei h eine ganze Zahl von 0 bis 2 bedeutet, und weiterhin C₁-C₆-Alkylanionen, Allylanionen, Benzylanionen oder Arylanionen, wobei L¹ _d und L² _d miteinander durch eine oder mehrere kovalente Bindungen verknüpft sein können,
E_d Stickstoff, Phosphor, Arsen oder Antimon,
X_d -SO₃-, -O-PO₃ ²-, NH(R^{1 5} _d)₂ ⁺, N(R^{1 5} _d)₃ ⁺ oder -(OCH₂CH₂)_nOH,
n eine ganze Zahl von 0 bis 15,
Y_d Sauerstoff, Schwefel, N-R¹⁰ _d oder P-R¹⁰ _d,
R¹ _d Wasserstoff, C₁-C₁₂-Alkylgruppen, C₇-C_{1 3}-Aralkylresten und C₆-C₁₄-Arylgruppen, unsubstituiert oder substituiert mit einer hydrophilen Gruppe X_d,
R² _d und R³ _d Wasserstoff,
hydrophile Gruppen X_d,
C₁-C₁₂-Alkyl, wobei die Alkylgruppen verzweigt oder unverzweigt sein können,
C₁-C₁₂-Alkyl, ein- oder mehrfach gleich oder verschieden substituiert durch C₁-C₁₂-Alkylgruppen, Halogene, hydrophile Gruppen X_d, C₁-C₁₂-Alkoxygruppen oder C₁-C₁₂-Thioethergruppen,
C₇-C_{1 3}-Aralkyl,
C₃-C₁₂-Cycloalkyl,
C₃-C₁₂-Cycloalkyl, ein- oder mehrfach gleich oder verschieden substituiert durch C₁-C₁₂-Alkylgruppen, Halogene, hydrophile Gruppen X_d, C₁-C₁₂-Alkoxygruppen oder C₁-C₁₂-Thioethergruppen,
C₆-C₁₄-Aryl,
C₆-C₁₄-Aryl, gleich oder verschieden substituiert durch eine oder mehrere C₁-C₁₂-Alkylgruppen, Halogene, hydrophile Gruppen X_d, ein- oder mehrfach halogenierte C₁-C₁₂-Alkylgruppen, C₁-C₁₂-Alkoxygruppen, Silyloxygruppen O-SiR¹⁰ _dR¹¹ _dR¹² _d, Aminogruppen NR^{1 3} _dR¹⁴ _d oder C₁-C₁₂-Thioethergruppen,
C₁-C₁₂-Alkoxygruppen,
Silyloxygruppen OSiR¹⁰ _dR¹¹ _dR¹² _d,
Halogene
oder Aminogruppen NR^{1 3} _dR¹⁴ _d,
wobei die Reste R² _d und R³ _d miteinander einen gesättigten oder ungesättigten 5- bis 8-gliedrigen Ring bilden können,
und wobei
mindestens ein Rest R¹ _d, R² _d oder R³ _d eine hydrophile Gruppe X_d trägt;
R⁴ _d bis R⁷ _d Wasserstoff,
hydrophile Gruppen X_d,
C₁-C₁₂-Alkyl, wobei die Alkylgruppen verzweigt oder unverzweigt sein können,
C₁-C_{1 2}-Alkyl, ein- oder mehrfach gleich oder verschieden substituiert durch C₁-C₁₂-Alkylgruppen, Halogene, hydrophile Gruppen X_d, C₁-C₁₂-Alkoxygruppen oder C₁-C₁₂-Thioethergruppen,
C₇-C_{1 3}-Aralkyl,
C₃-C₁₂-Cycloalkyl,
C₃-C₁₂-Cycloalkyl, ein- oder mehrfach gleich oder verschieden substituiert durch
C₁-C₁₂-Alkylgruppen, Halogene, hydrophile Gruppen X_d, C₁-C₁₂-Alkoxygruppen oder C₁-C₁₂-Thioethergruppen,
C₆-C_{1 4}-Aryl,
C₆-C_{1 4}-Aryl, gleich oder verschieden substituiert durch eine oder mehrere C₁-C₁₂-Alkylgruppen, Halogene, hydrophile Gruppen X_d, ein- oder mehrfach halogenierte C₁-C₁₂-Alkylgruppen, C₁-C₁₂-Alkoxygruppen, Silyloxygruppen O-SiR¹⁰ _dR¹¹ _dR^{1 2} _d, Aminogruppen NR^{1 3} _dR^{1 4} _d oder C₁-C₁₂-Thioethergruppen,
C₁-C₁₂-Alkoxygruppen,
Silyloxygruppen OSiR¹⁰ _dR¹¹ _dR^{1 2} _d,
Halogene,
NO₂-Gruppen
oder Aminogruppen NR^{1 3} _dR^{1 4} _d,
wobei jeweils zwei benachbarte Reste R⁴ _d bis R⁷ _d miteinander einen gesättigten oder ungesättigten 5-8-gliedrigen Ring bilden können,
R⁸ _d und R⁹ _d Wasserstoff, C₁-C₆-Alkylgruppen, C₇-C_{1 3}-Aralkylgruppen und C₆-C_{1 4}-Arylgruppen, unsubstituiert oder substituiert mit einer hydrophilen Gruppe X_d,
R¹⁰ _d bis R¹⁵ _d Wasserstoff, C₁-C₂₀-Alkylgruppen, die ihrerseits mit O(C₁-C₆-Alkyl) oder N(C₁-C₆-Alkyl)₂-Gruppen substituiert sein können, C₃-C₁₂-Cycloalkylgruppen, C₇-C_{1 3}-Aralkylresten und C₆-C_{1 4}-Arylgruppen;
R¹⁶ _d Wasserstoff, C₁-C₂₀-Alkylgruppen, die ihrerseits mit O(C₁-C₆-Alkyl) oder N(C₁-C₆-Alkyl)₂-Gruppen substituiert sein können,
C₃-C₁₂-Cycloalkylgruppen, C₇-C_{1 3}-Aralkylresten und C₆-C_{1 4}-Arylgruppen, unsubstituiert oder substituiert mit einer hydrophilen Gruppe X_d.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

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 _d phosphines (R ¹⁶ _d ) _x PH _3-x or amines (R ¹⁶ _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 derivatives of the formula C ₅ H _5-x (R ¹⁶ _d ) _x N, CO, C ₁ -C ₁₂ 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 C ₁ -C ₆ alkyl anions, allyl anions, benzyl anions or aryl anions, where L ¹ _d and L ² _d are linked together by one or several covalent bonds can be linked,
E _d nitrogen, phosphorus, arsenic or antimony,
X _d -SO ₃ -, -O-PO ₃ ² -, NH (R ^{1 5} _d ) ₂ ⁺ , N (R ^{1 5} _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 is} hydrogen, C ₁ -C ₁₂ alkyl groups, C ₇ -C _{1 3} aralkyl radicals and C ₆ -C ₁₄ aryl groups, unsubstituted or substituted by a hydrophilic group X _d ,
R ² _d and R ³ _{d are} hydrogen,
hydrophilic groups X _d ,
C ₁ -C ₁₂ alkyl, where the alkyl groups can be branched or unbranched,
C ₁ -C ₁₂ alkyl, substituted one or more times identically or differently by C ₁ -C ₁₂ alkyl groups, halogens, hydrophilic groups X _d , C ₁ -C ₁₂ alkoxy groups or C ₁ -C ₁₂ thioether groups,
C ₇ -C _{1 3} aralkyl,
C ₃ -C ₁₂ cycloalkyl,
C ₃ -C ₁₂ cycloalkyl, substituted one or more times, identically or differently, by C ₁ -C ₁₂ alkyl groups, halogens, hydrophilic groups X _d , C ₁ -C ₁₂ alkoxy groups or C ₁ -C ₁₂ thioether groups,
C ₆ -C ₁₄ aryl,
C ₆ -C ₁₄ aryl, identical or differently substituted by one or more C ₁ -C ₁₂ alkyl groups, halogens, hydrophilic groups X _d , mono- or polyhalogenated C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ - Alkoxy groups, silyloxy groups O-SiR ¹⁰ _d R ¹¹ _d R ¹² _d , amino groups NR ^{1 3} _d R ¹⁴ _d or C ₁ -C ₁₂ thioether groups,
C ₁ -C ₁₂ alkoxy groups,
Silyloxy groups OSiR ¹⁰ _d R ¹¹ _d R ¹² _d ,
halogens
or amino groups NR ^{1 3} _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 where
at least one radical R ¹ _d, R ² _d R ³ _d or a hydrophilic group X _d wears;
R ⁴ _d to R ⁷ _{d are} hydrogen,
hydrophilic groups X _d ,
C ₁ -C ₁₂ alkyl, where the alkyl groups can be branched or unbranched,
, Mono- C ₁ -C _{1 2} alkyl or polysubstituted by identical or different substituents from C ₁ -C ₁₂ alkyl groups, halogens, hydrophilic groups X _d, C ₁ -C ₁₂ -alkoxy groups or C ₁ -C ₁₂ -thioether groups,
C ₇ -C _{1 3} aralkyl,
C ₃ -C ₁₂ cycloalkyl,
C ₃ -C ₁₂ cycloalkyl, mono- or polysubstituted identically or differently by
C ₁ -C ₁₂ alkyl groups, halogens, hydrophilic groups X _d , C ₁ -C ₁₂ alkoxy groups or C ₁ -C ₁₂ thioether groups,
C ₆ -C _{1 4} aryl,
C ₆ -C _{1 4} aryl, identical or different substituted by one or more C ₁ -C ₁₂ alkyl groups, halogens, hydrophilic groups X _d, mono- or poly-halogenated C ₁ -C ₁₂ alkyl groups, C ₁ -C ₁₂ Alkoxy groups, silyloxy groups O-SiR ¹⁰ _d R ¹¹ _d R ^{1 2} _d , amino groups NR ^{1 3} _d R ^{1 4} _d or C ₁ -C ₁₂ thioether groups,
C ₁ -C ₁₂ alkoxy groups,
Silyloxy groups OSiR ¹⁰ _d R ¹¹ _d R ^{1 2} _d ,
halogens,
NO ₂ groups
or amino groups NR ^{1 3} _d R ^{1 4} _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, C ₁ -C ₆ alkyl groups, C ₇ -C _{1 3} aralkyl groups and C ₆ -C _{1 4} aryl groups, unsubstituted or substituted with a hydrophilic group X _d ,
R ¹⁰ _d to R ¹⁵ _{d are} hydrogen, C ₁ -C ₂₀ alkyl groups, which in turn can be substituted by O (C ₁ -C ₆ alkyl) or N (C ₁ -C ₆ alkyl) ₂ groups, C ₃ -C ₁₂ cycloalkyl groups, C ₇ -C _{1 3} aralkyl radicals and C ₆ -C _{1 4} aryl groups;
R ¹⁶ _{d is} hydrogen, C ₁ -C ₂₀ alkyl groups which in turn can be substituted by O (C ₁ -C ₆ alkyl) or N (C ₁ -C ₆ alkyl) ₂ groups,
C ₃ -C ₁₂ cycloalkyl groups, C ₇ -C _{1 3} aralkyl radicals and C ₆ -C _{1 4} 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-alltrans cyclododecatrienyl ligands.

such Complex compounds of the general formula A or B, their preparation, their special designs and particularly suitable representatives these complex compounds are described in detail in WO 01/44325, to the full extent of their disclosure content becomes.

The Connections A and B can in a relationship from 0: 100 to 100: 0 mol% can be used. 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 are particularly suitable, for example rhodium acetylacetonate-ethylene Rh (acac) (CH ₂ = CH ₂ ) ₂ , rhodium-benzoylacetonate-ethylene Rh (C ₆ H ₅ -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 by the method according to the invention dispersants used 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-methylpropanesulfonic acid and / or 4-styrenesulfonic but also containing copolymers and their alkali metal salts N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylcarbazole, 1-vinylimidazole, 2-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, acrylamide, methacrylamide, amine group-bearing acrylates, Homo- containing methacrylates, acrylamides and / or methacrylamides and copolymers. A detailed one A 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.

It it is advisable to design the method according to the invention in such a way that as possible above the so-called critical micelle concentration is worked. This means the emulsifier concentration, from which in the watery solution Form micelles. In this way it is possible to use the polymerization catalyst into an emulsifier micelle, where the emulsifier is then offered Converts monomers into polymers.

Of course you can too Mixtures of protective colloids and / or emulsifiers can be used. Frequently only emulsifiers are used as dispersants, their relative molecular weights in contrast to the protective colloids usually less than 1000. You can be both anionic, cationic or nonionic in nature. Of course have to in the case of the use of mixtures of surfactants Individual components should be compatible with one another, which in case of doubt be checked on the basis of a few preliminary tests can. In general, anionic emulsifiers are among themselves and compatible with nonionic emulsifiers. The same applies for cationic Emulsifiers while Anionic and cationic emulsifiers usually do not coexist compatible are. An overview 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 as dispersants, in particular anionic, cationic and / or nonionic emulsifiers used.

Common nonionic emulsifiers are, for example, ethoxylated mono-, di- and tri-alkylphenols (EO grade: 3 to 50, alkyl radical: C ₄ to C _{1 2} ) and ethoxylated fatty alcohols (EO degree: 3 to 80; alkyl radical: C ₈ to C ₃₈ ). Examples of these are the Lutensol ^® A grades (C ₁₂ C ₁₄ fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol ^® AO grades (C _{1 3} C _{1 5} oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol ^® AT-marks (C _{1 6 1} C ₈ fatty alcohol EO 11 to 80), Lutensol ^® ON brands (C ₁₀ -Oxoalkoholethoxylate, EO units: 3 to 11) and the Lutensol ^® tO brands (C _{1 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 _{1 2} ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ₁₂ to C ₁₈ ) and ethoxylated alkylphenols (EO degree : 3 to 50, alkyl radical: C ₄ to C _{1 2} ), of alkylsulfonic acids (alkyl radical: C ₁₂ to C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to C _{1 8} ).

worin R^y und R^z H-Atome oder C₄- bis C₂₄-Alkyl bedeuten und nicht gleichzeitig H-Atome sind, und D¹ und D² Alkalimetallionen und/oder Ammoniumionen sein können, erwiesen. In der allgemeinen Formel (X) bedeuten R^y und R^z bevorzugt lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen, insbesondere mit 6, 12 und 16 C-Atomen oder Wasserstoff, wobei R^y und R^z nicht beide gleichzeitig H-Atome sind. D¹ und D² sind bevorzugt Natrium, Kalium oder Ammonium, wobei Natrium besonders bevorzugt ist. Besonders vorteilhaft sind Verbindungen (X), in denen D¹ und D² Natrium, R^y ein verzweigter Alkylrest mit 12 C-Atomen und R^z ein H-Atom oder R^y ist. Häufig werden technische Gemische verwendet, die einen Anteil von 50 bis 90 Gew.-% des monoalkylierten Produktes aufweisen, wie beispielsweise Dowfax^® 2A1 (Marke der Dow Chemical Company). Die Verbindungen (X) sind allgemein bekannt, z.B. aus US-A 4 269 749 , und im Handel erhältlich.Compounds of the general formula (X) have also proven to be further anionic emulsifiers:

in which R ^y and R ^{z are} 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 ^{z 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 ^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. 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 (X) are generally known, for example from US-A 4,269,749 , and commercially available.

Suitable cationic emulsifiers are usually a C ₆ - to C _{1 8} alkyl, alkylaryl or heterocyclyl-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and also 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 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-trimethylammonium sulfate, N, N-distearyl-N, N-dimethylammonium sulfate as well as the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine disulfate, ethoxylated tallow fatty alkyl -N-methyl ammonium sulfate and ethoxylated oleylamine (for example Uniperol.RTM ^® AC from. BASF AG, about 12 ethylene oxide). Numerous other examples can be found in H. Stache, 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 counter groups if possible are low nucleophilic, such as 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 methylsulfonate, trifluoromethylsulfonate and para-toluene furthermore tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

The Emulsifiers which are preferably used as dispersants are advantageous 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 the olefinically unsaturated Connections. The amount of emulsifier is often like this selected that within the watery Phase the critical micelle formation concentration of the used Emulsifiers are essentially not exceeded.

The Total amount of the dispersants used additionally or instead Protective colloid 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 olefinic unsaturated Links.

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 of 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 _{3 O} - and C _{3 1} -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.

The Total amount of solvent is up to 15 parts by weight, preferably 0.001 to 10 parts by weight and in particular preferably 0.01 to 5 parts by weight, based in each case on 100 parts by weight Water.

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

The inventive method is characterized in that you first find a solution of one or more of the manufactures dispersants described above in water and then the water-insoluble Polymerization catalyst in the aqueous solution of the dispersant brings.

The water Polymerization catalyst can either be in solid form or blended with a water-miscible solvent or blended with a self-dispersing ethylenically unsaturated Connection in the watery solution of the dispersant are introduced.

If the water-insoluble Polymerization catalyst as a solid or oily metal complex in the aqueous solution of the Dispersant is introduced, it is recommended to do so Temperatures from 0 to 100 ° C, especially from 20 to 80 ° C and particularly preferably at 40 to 60 ° C.

It is possible, too, the water-insoluble Polymerization catalyst before or during the mechanical energy input by reacting the corresponding metal salts with the corresponding ones Production of ligands (in-situ production).

Farther can the water insoluble Polymerization catalyst mixed with a water-miscible solvent into the watery solution of the dispersant are introduced. Suitable solvents for this exhibit solubility in watery Reaction medium of at least 50 wt .-%, in particular at least 60% by weight, particularly preferably at least 70% by weight, in particular of at least 80% by weight, based in each case on the total amount of solvent, on. Therefor Suitable water-miscible solvents include alcohols such as methanol, ethanol, n- or iso-propanol, butenol or else polyethylene glycols, Acetone or tetrahydrofuran.

Furthermore can the water insoluble Polymerization catalyst also blended with a self-dispersing, ethylenically unsaturated Connection in the watery solution of the dispersant are introduced. Suitable self-dispersing, ethylenically unsaturated Connections 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.

in the Following it takes place according to the inventive method the dispersion of the water-insoluble Polymerization catalyst by mechanical energy input, preferably at temperatures from 0 to 100 ° C, especially from 20 to 80 ° C. The mechanical energy input is preferably made with the help of more suitable ones Shearers, homogenizers, ultrasonic units (sonotrodes) or stirring devices. It is also possible with the help of suitable homogenizers, ultrasonic units or others shearing apparatus from the first present aqueous Macro emulsion an aqueous To produce mini emulsion.

The general production of aqueous mini emulsions from aqueous macro emulsions is this Known to those 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]).

To can use this purpose for example, high pressure homogenizers can be used. The fine distribution The components in these machines are characterized by a high local Energy input achieved. Two variants are special in this regard proven.

at the first variant is the watery one Macroemulsion over a piston pump on over Compressed 1000 bar and then through a narrow gap relaxed. The effect here is based on an interaction of high Shear and pressure gradients and cavitation in the gap. An example for one High pressure homogenizer that works on this principle is the Niro-Soavi high-pressure homogenizer type NS1001L Panda.

at the second variant is the compressed aqueous macroemulsion over two opposed nozzles relaxed in a mixing chamber. The distribution effect is here especially the hydrodynamic conditions in the mixing chamber dependent. An example for this type of homogenizer is the Microfluidizer Type M 120 E from Microfluidics Corp. The aqueous macroemulsion is in this high pressure homogenizer by means of a pneumatically operated piston pump at pressures of compressed up to 1200 atm and over a so-called "interaction chamber "relaxed. In the "interaction chamber "will be the Emulsion beam divided into two beams 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. Indeed are two homogenizing valves in the Nanojet instead of a fixed channel system built-in, 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. For homogenization using ultrasound, those in the GB-A 22 50 930 and the US-A 5,108,654 described devices suitable. 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.

For the production of an aqueous miniemulsion from conventional macroemulsions by means of ultrasound, in particular that in the DE-A 197 56 874 described device proven. 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 Flow reaction channel in one section, can be irradiated evenly 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 depth of action of the ultrasound transmission means.

Under the term "depth of the reaction space "understands essentially the distance between the radiation area of the Ultrasound transmission means and the floor of the reaction space.

Prefers reaction chamber depths of up to 100 mm. That should be advantageous Depth of the reaction space not more than 70 mm and particularly advantageous be no more than 50 mm. In principle, the reaction spaces can also be one have very shallow depth, but are possible with regard to one low risk of constipation and easy cleanability as well prefers a high product throughput depth to the reaction chamber much larger than for example the usual gap heights in high-pressure homogenizers and are usually over 10 mm. The depth the reaction space can advantageously be changed, for example by different depths in the housing immersed ultrasound transmission means.

According to a first embodiment of this device, the radiation area of the means corresponds to Transmitting ultrasound essentially 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 chamber by the axial sound radiation pressure, which causes intensive cross-mixing.

According to one second embodiment Such a device has a flow cell. there is the housing designed as a flow-through reaction channel, which has an inflow and has a drain, the reaction chamber being a partial section of the flow reaction channel. The width of the channel is that channel extension running essentially perpendicular to the direction of flow. Covered here the radiation area the entire width of the flow channel transverse to the direction of flow. The length of the radiation surface perpendicular to this width, the is called the length the radiation area in the direction of flow, defines the area of effect of ultrasound. According to one The flow-through reaction channel has advantageous variants of this first embodiment a substantially rectangular cross section. Will be in one page a rectangular ultrasound transmission means of the rectangle installed with appropriate dimensions, is one special effective and even sound guaranteed. Due to the turbulent flow conditions in the ultrasonic field, can also be a round transmission medium without disadvantages, for example be used. Moreover can several instead of a single ultrasound transmission means separate transmission means are arranged in the direction of flow seen are connected in series. Both the radiation surfaces and also the depth of the reaction space, i.e. the distance between the radiating and the bottom of the flow channel vary.

Especially the means of transmission is advantageous formed by ultrasonic waves as a sonotrode, the free of which radiating opposite end is coupled to an ultrasonic transducer. The Ultrasound waves can for example, by utilizing the reverse piezoelectric Effect. With the help of generators, high frequencies are generated electrical vibrations (usually in the range from 10 to 100 kHz, preferably between 20 and 40 kHz) generated over a piezoelectric transducer in mechanical vibrations the same Frequency converted and using the sonotrode as a transmission element in the sonic medium coupled.

Especially the sonotrode is preferred as a rod-shaped, axially radiating λ / 2 (or multiples of λ / 2) longitudinal transducers educated.

According to one are a further advantageous embodiment of such devices internals in the reaction chamber to improve the flow and Mixing behavior provided. With these internals it can for example simple baffles or a wide variety of porous body act.

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

In that after the dispersion of the water-insoluble polymerization catalyst obtained aqueous Dispersion becomes a polymerization according to the inventive method performed by one or more ethylenically unsaturated compounds. If the polymerization should lead to polyketone dispersions, it is necessary the ethylenically unsaturated Polymerize compound together with carbon monoxide. It should the partial pressure of carbon monoxide generally in the range of 1 to 300 bar, in particular in the range from 1 to 80 bar. The polymerization reactor is usually used before pressing with carbon monoxide by rinsing with carbon monoxide, ethylenically unsaturated compounds or inert gas, inerted for example nitrogen or argon.

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

The inventive method can in the usual, polymerization apparatus used in technology are carried out, preferably in stirred reactors, Autoclaves, especially high pressure autoclaves, as well as in continuous Tube reactors or in so-called bubble columns, which also act as a cascade can be switched.

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 especially in 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.

By It is targeted variation of the olefinically unsaturated compounds et al possible, To produce polymers whose glass transition temperature or melting point in the range of -60 up to 270 ° C lies.

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 / T _g ¹ + x ² / T _g ² + .... x ⁿ / T _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 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 often have minimum film-forming temperatures MFT 80 80 ° C, often ≤ 50 ° C or 30 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.

By the inventive method are watery Polymer dispersions accessible, their solids content 0.1 to 70 wt .-%, often 1 to 65 wt .-% and often 5 to 60 wt .-% and all values in between.

Of course they can after completion of the Main polymerization reaction remaining in the aqueous polymer system Residual monomers are removed by steam and / or inert gas stripping, without the polymer properties of those present in the aqueous medium Adversely change copolymers.

The using the method according to the invention accessible, also aqueous according to the invention Polymer dispersions can in addition to the polymer as further components, for example formulation auxiliaries, Antioxidants, light stabilizers, dyes, pigments, as well Waxes or rheology modifiers or other polymer dispersions contain.

The also aqueous according to the invention Polymer dispersions are often over several Stable for weeks or months and usually show during this time practically no phase separation, deposition or coagulation. They are excellent especially as a binder for Paper applications such as paper coating or surface sizing, for paints, Adhesive raw materials, molded foams such as for example mattresses, textile and leather applications, carpet backing or pharmaceutical applications, as well 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 even synthetically simple, water-soluble polymerizations are possible Talysators can also be used for the production of aqueous polymer dispersions.

Examples

A. General methods of determination

NMR spectra were recorded on a Bruker ARX 300 ( ^{1 3} C: 75 MHz) or on a Bruker Avance 200 ( ^{3 1} P: 81 MHz). ^{1 3} C { ¹ H} NMR chemical shifts were calibrated against deuterolbenzene and referenced to TMS. ^{1 3} C-NMR spectra of the copolymers and terpolymers have been propanol, 1,1,1,3,3,3-hexafluoro-2-measured as the 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 were carried out using the process according to the invention on the one hand watery Dispersions based on copolymers of ethylene and carbon monoxide (Examples 1 to 4) and secondly aqueous dispersions based terpolymers of ethylene, carbon monoxide and undecenoic acid (example 5 to 13). First of all, a solution was found Emulsifier prepared in water, then the one used was used Catalyst 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) into the watery solution of the emulsifier introduced. This was followed by homogenization with ultrasound and following it 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. The mixture was then heated with stirring (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 became produced by a mixture of catalyst precursor complex, one tenth of the total amount of emulsifier used and 10 ml of water was homogenized by ultrasound (2 min, 120 W). This solution became the agitated aqueous solution already in the reactor Emulsifier solution, the para-toluenesulfonic acid (p-TsOH) contained about injected a 0.45μm micron filter. Otherwise, the procedure was the same as in Section I.

III. Solubilization with solvent

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 magnetically touched. The solution was mixed with para-toluenesulfonic acid (10 equivalents based on Pd) and filtered through a 0.45 μm filter.

C. Results of polymerizations carried out

Table 1 Ethylene-carbon monoxide 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.
• / = not determined.

Claims (13)

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 compound in the aqueous solution of the dispersant, then introduces the water-insoluble polymerization catalyst dispersed by mechanical energy input and then with the aid of the aqueous dispersion obtained in this way a polymerization of at least one ethylenically unsaturated compound. A method according to claim 1, characterized in that in addition to the ethylenically unsaturated compound or carbon monoxide copolymerized. Method according to claims 1 or 2, characterized in that that at least one α-olefin polymerized with 3 to 20 carbon atoms as an ethylenically unsaturated compound becomes. Method according to claims 1 to 3, characterized in that the water-insoluble polymerization catalyst or catalysts used before or during the mechanical energy input by implementing the corresponding Metal salts with the corresponding ligands can be obtained. Process according to claims 1 to 4, characterized in that the water-insoluble polymerization catalysts used have a water solubility of less than 10 ^-4 g catalyst per 100 g water. Method according to claims 1 to 5, characterized in that that the mechanical energy input with the help of suitable shear equipment, Homogenizers, ultrasonic units or stirring devices. Method according to claims 1 to 6, characterized in that the mechanical energy input is carried out at temperatures from 0 to 100 ° C. Method according to claims 1 to 7, characterized in that the polymerization of the ethylenically unsaturated Connections are carried out in an autoclave. Method according to claims 1 to 8, characterized in that that the water-insoluble Polymerization catalyst in solid form in the aqueous solution of the Introduces dispersant. Method according to claims 1 to 8, characterized in that that the water-insoluble polymerization catalyst mixed in a water-miscible solvent in the aqueous solution of the Introduces dispersant, the water-miscible solvent a solubility in the aqueous reaction medium of more than 50% by weight, based in each case on the total amount of solvent, having. Method according to claims 1 to 8, characterized in that that the water-insoluble polymerization catalyst blended in a self-dispersing ethylenically unsaturated Connection in the watery solution of the dispersant. aqueous Polymer dispersions, produced by a process according to a of claims 1 to 11. Use of the aqueous Polymer dispersions according to claim 12 for Paper applications such as paper coating or surface sizing, for paints, Adhesive raw materials, molded foams such as mattresses, textile and leather applications, carpet backing or pharmaceutical applications, as well as additives in polymer blends or in building materials.