DE10303312A1 - Preparation of aqueous dispersion of olefin polymer, useful as binder in e.g. paper and paint, in presence of specific metal complexes and dispersants - Google Patents

Abstract

Method for preparing aqueous polymer dispersions (A) by polymerizing at least one olefin, optionally also carbon monoxide, in aqueous medium, in presence of a metal complex (I) and one or more dispersants. Method for preparing aqueous polymer dispersions (A) by polymerizing at least one olefin, optionally also carbon monoxide, in aqueous medium, in presence of a metal complex of formula (I) and one or more dispersants. M = transition metal of groups VIIIB, IB or IIB; E1 and E2 = group VA atoms; Y = 1-6C alkylene (optionally substituted by hydroxy, 1-6C alkoxy, carboxy, sulfo, amino, ammonium, phosphono, phosphonato, sulfamoyl, amidino, carbamoyl, hydroxysulfonyloxy, sulfino or 1-4C alkyl, or interrupted by oxygen, imino, silylene, or mono- or di-alkylsilylene), a fused cycloaliphatic ring or benzene ring, or 1,8-naphthylene; R1 = 1-20C alkyl (optionally substituted by hydroxy, 1-6C alkoxy, carboxy, sulfo or aryl), 6-14C aryl (optionally substituted by 1-4C alkyl, hydroxy, 1-6C alkoxy, carboxy, cyano or R2) or 3-12C cycloalkyl; R2 = fluoro, sulfo, nitro or 1-10C perfluoroalkyl; R3-R6 = hydrogen or R2; L1 and L2 = (R7)xPH3-x, (R7)xNH3-x, R7OR7, R7OH, water, pyridine substituted by x R7, CO, 1-14C alkyl nitrile, 6-12C aryl nitrile, olefin, (R7)hNH2-h, or anions of 1-6 C alkyl, 3-14C cycloalkyl, (meth)allyl, benzyl, aryl, carboxylic or sulfonic acids, or (di)ketones, optionally linked by one or more covalent bonds; x = 0-3; h = 0-2; R1 = hydrogen, 1-20C alkyl (optionally substituted by 1-6C alkoxy, mono- or di-(1-6C alkyl) amino or 6-14C aryl), 3-12C cycloalkyl or 6-14C aryl; An- = an equivalent of an anion of a non-coordinating acid with pKa less than 4.75; and n = 0-4 Independent claims are also included for the following: (1) aqueous dispersions produced by the new method, having head-to-tail content below 90% and mean particle size 1 mum; and (2) method for preparing polyketones (II) by isolation from (A).

Description

Process for the production of aqueous Polymer dispersions by polymerizing one or more Olefins optionally with carbon monoxide in an aqueous medium, in the presence a) one or more metal complexes and b) one or more Dispersant, the aqueous Copolymer dispersions themselves and their use. Further it relates to the polyketones obtained from the polymer dispersions.

Copolymers of carbon monoxide and olefinically unsaturated Compounds, also called polyketones for short, are high molecular weight Semi-crystalline compounds with advantageous mechanical and rheological properties, high melting point, good heat resistance, good chemical resistance and good barrier properties against water and air. This Properties are characterized by the strictly alternating sequence of Monomers in the main chain also influenced. Of technical interest are polyketones made from carbon monoxide and α-olefins.

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

The production of aqueous copolymer dispersions can in principle by appropriate suspension polymerization 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 often when processing the polymer such as grinding or dispersing Problems occur.

It is therefore a goal, 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 to manufacture.

So describes the DE-A-100 61 877 stable aqueous copolymer dispersions of carbon monoxide and olefinically unsaturated compounds which are prepared in an aqueous medium using special water-soluble metal catalysts and using special comonomers. The production of copolymer dispersions with the same metal catalysts but in the presence of so-called host compounds is described in the DE-A-101 25 238 described. 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.

The German application 101 33 042.1 teaches the making of primary aqueous Copolymer dispersion using the oil-soluble materials customary in suspension polymerization Metal complexes in the presence of solvents.

Precisely because the primary aqueous process Copolymerization makes further processing of the polymer unnecessary are supposed to and customized The aim of dispersions is to make the process products advantageous have application properties. To such properties belong in particular good tensile elongation and improved flexibility, those generally with higher Molecular weight and greater irregularity of the polymer chain.

It was therefore the task of the present Invention to provide a method in the polymer dispersion arise which is a greater irregularity in the polymer chain and higher Have molecular weight average.

• a) eines oder mehrerer Metallkomplexe der allgemeinen Formel I
  
  in der M ein Übergangsmetall der Gruppe VIIIB, IB oder IIB des Periodensystems der Elemente, E¹ und E² unabhängig voneinander ein Element der Gruppe VA des Periodensystems der Elemente, Y C₁-C₅-Alkylen, das mit Hydroxyl, C₁-C₆-Alkoxy, Carboxyl, Sulfo, Amino, Ammonium, Phosphono, Phosphonato, Sufamoyl, Amidino, Carbamoyl, Hydroxysufonyloxy, Sulfino und C₁-C₄-Alkyl substituiert und durch Sauerstoff, Imino, Alkylimino, Silylen oder Mono- oder Dialkylsilylen unterbrochen sein kann oder einen anellierten cycloaliphatischen Ring oder anelliertes Benzol aufweisen kann oder 1,8-Naphthylen, R¹ C₁-C₂₀-Alkyl, das gegebenenfalls mit Hydroxyl, C₁-C₆-Alkoxy, Carboxyl, Sulfo oder Aryl substituiert ist, C₆-C₁₄-Aryl, das gegebenenfalls mit C₁-C₄-Alkyl, Hydroxyl, C₁-C₆-Alkoxyl, Carboxyl, Cyano oder einem Rest R² substituiert ist oder C₃-C₁₂-Cycloalkyl R² Fluor, Sulfo, Nitro, oder perfluoriertes C₁-C₁₀-Alkyl, R³, R⁴, R⁵ und R⁶ unabhängig voneinander Wasserstoff oder ein Rest R², L¹ und L² unabhängig voneinander Phosphane (R⁷)_xPH₃__x, Amine (R⁷)_xNH_3–x oder Ether (R⁷)₂O mit jeweils gleichen oder verschiedenen Resten R⁷, Alkohole R⁷OH, H₂O, Pyridinverbindungen C₅H_5–x(R⁷)_xN, Kohlenmonoxid, C₆-C₁₂-Alkylnitrile, C₁-C₁₄-Arylnitrile oder Olefine, wobei x eine ganze Zahl von 0 bis 3 bedeutet, Amidionen (R⁷)_hNH_2–h, wobei h eine ganze Zahl von 0 bis 2 bedeutet, C₁-C₆-Alkylanionen, C₃-C₁₄-Cycloalkylanionen, Allylanionen, Methallylanionen, Benzylanionen, Arylanionen, Carbonsäureanionen, Sulfonsäureanionen, Ketone oder Diketone, wobei L¹ und L² miteinander durch eine oder mehrere kovalente Bindungen verknüpft sein können R⁷ Wasserstoff, C₁-C₂₀-Alkyl, das gegebenenfalls mit C₁-C₆-Alkoxy,Mono- oder Di-(C₁-C₆-alkyl)amino oder C₆-C₁₄-Aryl substituiert ist, C₃-C₁₂-Cycloalkyl, oder C₆-C₁₄-Aryl, An^– das Äquivalent eines Anions einer nicht koordinierenden Säure mit pKs < 4,75 und n eine ganze Zahl 0, 1, 2, 3 oder 4 bedeutet, und
• b) eines oder mehrerer Dispergiermittel.

Accordingly, a process has been found for the preparation of aqueous polymer dispersions, by polymerizing one or more olefins, if appropriate with carbon monoxide in an aqueous medium, in the presence

• a) one or more metal complexes of the general formula I.
  
  in which M is a transition metal from Group VIIIB, IB or IIB of the Periodic Table of the Elements, E ¹ and E ² independently of one another an element from Group VA of the Periodic Table of the Elements, Y is C ₁ -C ₅ alkylene which is substituted with hydroxyl, C ₁ -C ₆ -Alkoxy, carboxyl, sulfo, amino, ammonium, phosphono, phosphonato, sufamoyl, amidino, carbamoyl, hydroxysufonyloxy, sulfino and C ₁ -C ₄ alkyl and substituted by oxygen, imino, alkylimino, silylene or mono- or dialkylsilylene can or can have a fused-on cycloaliphatic ring or fused benzene or 1,8-naphthylene, R ¹ C ₁ -C ₂₀ -alkyl which is optionally substituted by hydroxyl, C ₁ -C ₆ -alkoxy, carboxyl, sulfo or aryl, C ₆ -C ₁₄ aryl which is optionally substituted by C ₁ -C ₄ alkyl, hydroxyl, C ₁ -C ₆ alkoxyl, carboxyl, cyano or a radical R ² or C ₃ -C ₁₂ cycloalkyl R ² fluorine, Sulfo, nitro, or perfluorinated C ₁ -C ₁₀ alkyl, R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another W Hydrogen or a radical R ² , L ¹ and L ² independently of one another phosphines (R ⁷ ) _x PH ₃ _ _x , amines (R ⁷ ) _x NH _3-x or ethers (R ⁷ ) ₂ O with the same or different radicals R ⁷ , alcohols R ⁷ OH, H ₂ O, pyridine compounds C ₅ H _5-x (R ⁷ ) _x N, carbon monoxide, C ₆ -C ₁₂ alkyl nitriles, C ₁ -C ₁₄ aryl nitriles or olefins, where x is an integer from 0 to 3 means amide ions (R ⁷ ) _h NH _2-h , where h is an integer from 0 to 2, C ₁ -C ₆ -alkyl anions, C ₃ -C ₁₄ -cycloalkyl anions, allyl anions, methallyl anions, benzyl anions, Aryl anions, carboxylic acid anions, sulfonic acid anions, ketones or diketones, where L ¹ and L ² can be linked to one another by one or more covalent bonds. R ^{7 is} hydrogen, C ₁ -C ₂₀ alkyl, optionally with C ₁ -C ₆ alkoxy, mono - or di- (C ₁ -C ₆ alkyl) amino or C ₆ -C ₁₄ aryl is substituted, C ₃ -C ₁₂ cycloalkyl, or C ₆ -C ₁₄ aryl, An ^- the equivalent of an anion is not coordinating S acid with pKs <4.75 and n denotes an integer 0, 1, 2, 3 or 4, and
• b) one or more dispersants.

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

As for the method according to the invention Suitable olefins for the production of homopolymers are mentioned: Ethylene, propylene, 1-butene, 2-butene, butadiene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 1-eicosen, but also branched olefins such as isobutene, 4-methyl-1-pentene, Norbornene, vinylcyclohexene and vinylcyclohexane as well as styrene, para-methylstyrene and para-vinyl pyridine, with ethylene and propylene being preferred. Ethylene is particularly preferred.

• – Unpolare 1-Olefine, wie beispielsweise Ethylen, Propylen, 1-Buten, 2-Buten, Butadien, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen, 1-Decen und 1-Eicosen, aber auch verzweigte Olefine, wie beispielsweise Isobuten, 4-Methyl-1-penten, Vinylcyclohexen und Vinylcyclohexan sowie Styrol, para-Methylstyrol und para-Vinylpyridin, wobei Ethylen, Propylen, 1-Buten, 1-Penten, 1-Hexen, 1-Hepten, 1-Octen, 1-Decen bevorzugt sind.
• – Olefine, welche polare Gruppen enthalten, wie beispielsweise Acrylsäure, Acrylsäure-C₁-C₈-alkylester, 2-Hydroxyethylacrylat, 3-Hydroxypropylacrylat, 4-Hydroxybutylacrylat, Methacrylsäure, Methacrylsäure-C₁-C₈-alkylester, C₁-C₆-Alkyl-Vinylether und Vinylacetat, aber auch 10-Undecensäure, 3-Butensäure, 4-Pentensäure, 5-Hexensäure sowie Styrol-4-sulfonsäure. Bevorzugt sind Acrylsäure, Acrylsäuremethylester, Acrylsäureethylester, Acrylsäure-n-butylester, 2-Ethylhexylacrylat, 2-Hydroxyethylacrylat, Methylmethacrylat, Ethylmethacrylat, n-Butylmethacrylat, Ethylvinylether, Vinylacetat, 10-Undecensäure, 3-Butensäure, 4-Pentensäure und 5-Hexensäure.

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

• - Non-polar 1-olefins, such as ethylene, propylene, 1-butene, 2-butene, butadiene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and 1-eicosen, but also branched olefins , such as isobutene, 4-methyl-1-pentene, vinylcyclohexene and vinylcyclohexane and styrene, para-methylstyrene and para-vinylpyridine, where ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Octene, 1-decene are preferred.
• - Olefins which contain polar groups, such as, for example, acrylic acid, acrylic acid-C ₁ -C ₈ -alkyl esters, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, methacrylic acid, methacrylic acid-C ₁ -C ₈ -alkyl esters, C ₁ -C _6- alkyl vinyl ether and vinyl acetate, but also 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid and styrene-4-sulfonic acid. Acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, ethyl vinyl ether, vinyl acetate, 10-undecenoic acid, 3-butenoic acid, 4-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid and 5-pentenoic acid are preferred.

The proportion of coolefins in the olefin mixture to be polymerized is freely selectable and is more usual wise ≤ 50 wt .-%, often ≤ 40 wt .-% and often ≤ 30 wt .-% or ≤ 20 wt .-%. If olefins containing polar groups in particular are used for the copolymerization, their proportion in the olefin mixture to be polymerized is generally 0,1 0.1% by weight, 0,2 0.2% by weight or 0,5 0.5% by weight, and ≤ 2 % By weight, ≤ 5% by weight or ≤ 10% by weight.

Aqueous is preferred for the production Polymer dispersions used only ethylene as a monomer. If at least two olefins are used for the polymerization, this often from the group comprising ethylene, propylene, 1-butene, 1-hexene and Styrene selected. Frequently ethylene is used in combination with propylene, 1-butene, 1-hexene or styrene.

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

Under aqueous medium is in the frame this application water to understand that up to 10 wt .-% with water miscible solvents contains. Under water-miscible solvents are solvents understand that in the desired Use at 25 ° C and 1 bar can be mixed with water. In addition to the alcohols mentioned below, these include such as methanol, ethanol, propanol, isopropanol, glycol, glycerin and Methoxyethanol water soluble Ethers such as tetrahydrofuran and dioxane.

In the context of this document lies the Terms for the groups of the Periodic Table of the Elements from Chemical Abstracts Service used nomenclature up to 1986 (for example, the Group VA the elements N, P, As, Sb, Bi; group IB contains Cu, Ag, Au).

As metals M of the metal complexes according to the invention are the metals of groups, VIIIB, IB and IIB of the periodic table the elements, for example in addition to copper, silver or zinc, also iron, cobalt and nickel as well as the platinum metals like ruthenium, Rhodium, osmium, iridium and platinum, the platinum metals, in particular Nickel and platinum and very particularly palladium are preferred.

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

If residues in the above formula of acids are named, so can these residues naturally also in the form of their salts under the process conditions are present, which are of course also encompassed by the invention.

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

If in the above formula substituted alkyl, alkylene or aryl groups occur, so they can one or two or three times substituted with the radicals mentioned. Can also they can be substituted with different radicals at the same time.

C ₁ -C ₄ -alkyl is understood to mean the radicals methyl, ethyl, propyl, isopropyl, butyl isobutyl, sec-butyl, tert-butyl. C ₁ -C ₂₀ -alkyl are the radicals already listed under C ₁ -C ₄ and also pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, Isononyl, decyl, (the above designations isooctyl, isononyl and isodecyl are trivial designations and come from the alcohols obtained from oxosynthesis - see also Ullmanns Encyklopadie der Technische Chemie, 4th edition, volume 7, pages 215 to 217, and volume 11, Pages 435 and 436).

C ₃ -C ₁₂ -cycloalkyl is preferably understood to mean the radicals cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl.

C ₆ -C ₁₄ -Aryl is preferably phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9- Understood phenanthryl.

C ₁ -C ₆ -alkoxy preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, iso-pentoxy, n- Hexoxy and iso-hexoxy.

Residues Y are, for example, methylene, ethylene, 1,2- or 1,3-propylene, 12-, 2,3- or 1,4-butylene, (CH ₂ ) ₂ O (CH ₂ ) ₂ , (CH ₂ ) ₃ O (CH ₂ ) ₂ , (CH ₂ ) ₃ O (CH ₂ ) ₃ , (CH ₂ ) ₂ O (CH ₂ ) O (CH ₂ ) ₂ , (CH ₂ ) ₂ NH (CH ₂ ) ₂ , (CH ₂ ) ₃ NH (CH ₂ ) ₂ , (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ , (CH ₂ ) ₂ N (CH ₃ ) (CH ₂ ) ₂ , (CH ₂ ) ₃ N (CH ₃ ) (CH ₂ ) ₂ or (CH ₂ ) ₂ N (CH ₃ ) (CH ₂ ) ₂ H (CH ₃ ) (CH ₂ ) ₂ , norbornane-2,3-diylene, cyclopropane-1,2- diylene, 1,2-phenylene, 1,8-naphthylene, dimethylsilylene or diphenylsilylene.

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

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

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

• – Phosphanen der Formel (R⁷)_xPH_3–x, mit x für eine ganze Zahl zwischen 0 und 3
• – Aminen der Formel (R⁷)_xNH_3–x, mit x für eine ganze Zahl zwischen 0 und 3
• – Ethern (R⁷)₂O wie Dimethylether, Diethylether oder bevorzugt Tetrahydrofuran,
• – Alkoholen (R⁷)OH wie Methanol oder Ethanol,
• – Pyridinverbindungen der Formel C₅H_5–x(R⁷)_xN mit x für eine ganze Zahl zwischen 0 und 3, wie Pyridin, 2-Picolin, 3-Picolin, 4-Picolin, 2,3-Lutidin, 2,4-Lutidin, 2,5-Lutidin, 2,6-Lutidin oder 3,5-Lutidin,
• – C₁-C₁₂-Alkylnitrilen oder C₆-C₁₄-Arylnitrilen, wie Acetonitril, Propionitril, Butyronitril oder Benzonitril
• – Olefinen wie Ethenyl, Propenyl, cis-2-Butenyl, trans-2-Butenyl, Cyclohexenyl oder Norbornenyl,
• – Amidionen (R⁷)_hNH_2–h, wobei h eine ganze Zahl zwischen 0 und 2 bedeutet
• – C₁-C₆-Alkylanionen und C³-C¹⁴-Cycloalkylanionen wie Me^–, (C₂H₅)^–, (C₃H₇)^–, (n-C₄H₉)^– (tert.-C₄H₉)^– oder (C₆H₁₃)
• – Allylanionen oder Methallylanionen,
• – Benzylanionen oder Arylanionen, wie (C₆H₅),
• – Carbonsäureanionen insbesondere C₁- bis C₇-Carbonsäureanionen wie, Trifluoracetat, Trichloracetat, Propionat, Oxalat, Citrat, Benzoat, bevorzugt Acetat
• – Ketonen und Diketonen wie Aceton, Acetylaceton
• – Sulfonsäureanionen wie Methylsulfonat, Trifluormethylsulfonat und bevorzugt p-Toluolsulfonat.

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

• - Phosphanes of the formula (R ⁷ ) _x PH _3-x , with x for an integer between 0 and 3
• - Amines of the formula (R ⁷ ) _x NH _3-x , with x for an integer between 0 and 3
• Ethers (R ⁷ ) ₂ O such as dimethyl ether, diethyl ether or preferably tetrahydrofuran,
• Alcohols (R ⁷ ) OH such as methanol or ethanol,
• Pyridine compounds of the formula C ₅ H _5-x (R ⁷ ) _x N with x for an integer between 0 and 3, such as pyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2, 4-lutidine, 2,5-lutidine, 2,6-lutidine or 3,5-lutidine,
• - C ₁ -C ₁₂ alkyl nitriles or C ₆ -C ₁₄ aryl nitriles, such as acetonitrile, propionitrile, butyronitrile or benzonitrile
• Olefins such as ethenyl, propenyl, cis-2-butenyl, trans-2-butenyl, cyclohexenyl or norbornenyl,
• - Amide ions (R ⁷ ) _h NH _{2 – h} , where h is an integer between 0 and 2
• - C ₁ -C ₆ alkyl anions and C ³ -C ¹⁴ cycloalkyl anions such as Me ^- , (C ₂ H ₅ ) ^- , (C ₃ H ₇ ) ^- , (nC ₄ H ₉ ) ^- (tert.-C ₄ H ₉ ) ^- or (C ₆ H ₁₃ )
• Allyl ions or methallyl ions,
• Benzyl anions or aryl anions, such as (C ₆ H ₅ ),
• - Carboxylic acid anions, in particular C ₁ - to C ₇ -carboxylic acid anions such as trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, preferably acetate
• - Ketones and diketones such as acetone, acetylacetone
• - Sulfonic acid anions such as methyl sulfonate, trifluoromethyl sulfonate and preferably p-toluenesulfonate.

Suitable ligands are also L ¹ and L ² H ₂ O, carbon monoxide, nitrates and hydride.

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

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

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

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

In general, the metals M can be present in the complexes in a formally uncharged, formally single positive or preferably formally double positive. Depending on the formal charge of the complex fragment containing the metal M and the charge of the ligands L ¹ and L ² , the metal complexes are present as a neutral compound or as a cation. Accordingly, they have anions X for charge neutralization. However, if the M-containing complex fragment is formally uncharged, the metal complex according to formula (I) does not contain any anion X. Anions X are advantageously used which are as little nucleophilic as possible, ie have as little tendency as possible to have 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, as well as conjugated anions of organosulfonic acids such as for example methyl sulfonate, trifluoromethyl sulfonate and p-toluenesulfonate Tetrafluoroborate, tetraphenyl borate, tetrakis (pentafluorophenyl) borate, Tetrakis [bis (3,5-trifluoromethyl) phenyl] borrows 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.

The complex compounds I to be used according to the invention are characterized in that the radical R ² and optionally the radicals R ³ , R ⁴ , R ⁵ and / or R ⁶ carry fluorine, sulfo, nitro or perfluorinated C ₁ -C ₁₀ -alkyl. It is believed that due to their electron-withdrawing nature, such residues bring about the beneficial properties of the complexes. Compounds of the formula I in which the radicals R ² , R ³ and / or R ^{4 represent} trifluoromethyl are particularly preferred.

verschieden sind. Das heißt, dass der Rest R¹ für C₁-C₂₀-Alkyl, das gegebenenfalls mit Hydroxyl, C₁-C₆-Alkoxy, Carboxyl, Sulfo oder Aryl substituiert ist oder C₃-C₁₂-Cycloalkyl steht und wenn R¹ C₆-C₁₄-Aryl, das gegebenenfalls mit C₁-C₄-Alkyl, Hydroxyl, C₁-C₆-Alkoxyl, Carboxyl, Cyano oder einem Rest R² substituiert ist, bedeutet, sich der Rest in Art und/oder Zahl der Substituenten vom Rest der Formel II unterscheidet. Insbesondere weist Aryl als Bedeutung von R¹ keinen der unter R² genannten Reste auf.It has been found that the dispersions prepared according to the above process have particularly good properties when the R ¹ radicals differ from the rest of the formula II

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

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

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

In particular, metal complexes I are used in which
M for nickel, palladium or platinum, especially palladium
E for nitrogen or especially phosphorus and
R ^{1 is} C ₆ -C ₁₄ aryl, which is optionally substituted by C ₁ -C ₄ alkyl, hydroxyl, C ₁ -C ₆ alkoxyl, carboxyl, cyano or a radical R ²
and Y, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , L ¹ , L ² , R ⁷ , An ^- and n have the meaning given above.

Metal complexes I in which
M for palladium
E for phosphorus and
R ^{1 is} C ₆ -C ₁₄ aryl, which is optionally substituted by C ₁ -C ₄ alkyl, hydroxyl, C ₁ -C ₆ alkoxyl, carboxyl or cyano
and Y, R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , L ¹ , L ² , R ⁷ , An ^- and n have the meaning given above.

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

The total amount of metal complex I used is generally 10 ⁻⁷ to 10 ⁻² mol / I, often 10 ⁻⁶ to 10 ⁻³ mol / I and often 10 ⁻⁵ to 10 ⁻⁴ mol / I, in each case based on the total amount of water, olefinically unsaturated compounds and optionally organic solvents.

in der E¹, E², Y, R¹, R², R³, R⁴ und R⁵ obengenannte Bedeutung haben, eines Dispergiermittels und gegebenenfalls einer Säure a2) durch.The metal complexes of the formula I to be used according to the invention can be used either by first isolating them after the reaction of the ligands with the metal compound and then introducing them into the polymerization system from monomers, aqueous medium and dispersant, and also as a so-called in-situ system , the isolation of the complex compound being dispensed with. The polymerization is preferably carried out in the presence of one or more metals from subgroup VIIIB, which is in salt or complex form, and a chelate ligand of the general formula III

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

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

Both mineral protonic acids and Lewis acids are suitable as activator compounds a2). 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. As Lewis acids For example, Boner 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 acidic character in question. Mixtures of protonic acids or Lewis acids and protonic and Lewis acids in a mixture can also be used.

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

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

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

The molar ratio of optionally used Hydroxy compound a3) to metal complex a1), based on the amount on metal M, generally ranges from 0 to 100,000, often from 500 to 50,000 and often from 1000 to 10000.

The according to the inventive method Dispersants also used can be emulsifiers or protective colloids his.

Suitable protective colloids are, for example Polyvinyl alcohols, polyalkylene glycols, alkali metal salts of polyacrylic acids and polymethacrylic Gelatin derivatives or acrylic acid, methacrylic acid, maleic anhydride, Containing 2-acrylamido-2-methylpropanesulfonic acid and / or 4-styrenesulfonic acid Copolymers and their alkali metal salts but also 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.

Mixtures of protective colloids can of course also be used and / or emulsifiers are used. Often used as dispersants b) exclusively Emulsifiers used, their relative molecular weights differ 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 a dispersant b) 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 ₁₂ ) and ethoxylated fatty alcohols (EO grade: 3 to 80; alkyl radical: C ₈ to C) ₃₆ ). Examples of these are the Lutensol ^® A brands (C ₁₂ C ₁₄ fatty alcohol ethoxylates, EO grade: 3 to 8), Lutensol ^® AO brands (C ₁₃ C ₁₅ oxo alcohol ethoxylates, EO grade: 3 to 30), Lutensol ^® AT grades (C ₁₆ C ₁₈ fatty alcohol ethoxylates, EO grade: 11 to 80), Lutensol ^® ON grades (C ₁₀ oxo alcohol ethoxylates, EO grade: 3 to 11) and the Lutensol ^® TO grades (C ₁₃ - Oxo alcohol ethoxylates, EO grade: 3 to 20) from BASF AG.

Typical anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C ₈ to C ₁₂ ), of sulfuric acid semiesters of ethoxylated alkanols (EO degree: 4 to 30, alkyl radical: C ₁₂ to C ₁₈ ) and ethoxylated alkyl phenols (EO degree: 3 to 50, alkyl radical: C ₄ to C ₁₂ ), of alkylsulfonic acids (alkyl radical: C ₁₂ to C ₁₈ ) and of alkylarylsulfonic acids (alkyl radical: C ₉ to C ₁₈ ).

worin R⁸ und R⁹ Wasserstoff oder C₄- bis C₂₄-Alkyl bedeuten und nicht gleichzeitig Wasserstoff sind, und D¹ und D² Alkalimetallionen und/oder Ammoniumionen sein können, erwiesen. In der allgemeinen Formel IV bedeuten R⁸ und R⁹ bevorzugt lineare oder verzweigte Alkylreste mit 6 bis 18 C-Atomen, insbesondere mit 6, 12 und 16 C-Atomen oder Wasserstoff, wobei R⁸ und R⁹ nicht beide gleichzeitig Wasserstoff sind.Compounds of the general formula IV have also been found as further anionic emulsifiers

wherein R ⁸ and R ^{9 are} hydrogen or C ₄ - to C ₂₄ -alkyl and are not simultaneously hydrogen, and D ¹ and D ^{2 can be} alkali metal ions and / or ammonium ions. In the general formula IV, R ⁸ and R ^{9 are} preferably linear or branched alkyl radicals having 6 to 18 carbon atoms, in particular having 6, 12 and 16 carbon atoms or hydrogen, where R ⁸ and R ^{9 are} not both hydrogen at the same time.

D ¹ and D ² are preferably sodium, potassium or ammonium, with sodium being particularly preferred. Compounds IV in which D ¹ and D ^{2 are} sodium, R ^{8 is} a branched alkyl radical having 12 C atoms and R ^{9 is} hydrogen or R ⁸ are particularly advantageous. Industrial mixtures are used which have a share of 50 to 90 wt .-% of the monoalkylated product, for example Dowfax ^® 2A1 (trademark of Dow Chemical Company). The compounds IV are generally known, for example from US-A 4,269,749 , and commercially available.

Suitable cationic emulsifiers are usually a C ₆ - to C ₁₈ -alkyl, C ₆ -C ₁₈ alkylaryl or heterocyclyl-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, Imidazolini umsalze, oxazolinium, morpholinium, Thiazolinium salts and salts of amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts. Examples include dodecylammonium acetate or the corresponding sulfate, the sulfates or acetates of the various 2- (N, N, N-trimethylammonium) ethyl 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 acetate, trifluoroacetate, trichloroacetate, propionate, oxalate, citrate, benzoate, and conjugated anions of organosulfonic acids, such as methyl sulfonate, trifluoromethyl sulfonate and para-toluenesulfonate Tetrafluoroborate, tetraphenylborate, tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-trifluoromethyl) phenyl] borate, hexafluorophosphate, hexafluoroarsenate or hexafluoroantimonate.

Preferred as dispersant b) Emulsifiers used are advantageous in a total amount from 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 olefinic 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 dispersant b) additionally or protective colloids used instead is often 0.1 up 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.

According to a preferred process variant, organic solvents c) which are only slightly soluble in water can optionally be used. Suitable solvents c) are liquid aliphatic and aromatic hydrocarbons with 5 to 30 carbon atoms, such as, for example, n-pentane and isomers, cyclopentane, n-hexane and isomers, cyclohexane, n-heptane and isomers, n-octane and isomers, n- Nonane and isomers, n-decane and isomers, n-dodecane and isomers, n-tetradecane and isomers, n-hexadecane and isomers, n-octadecane and isomers, eicosane, benzene, toluene, ethylbenzene, cumene, o-, m- or p-xylene, mesitylene, and generally hydrocarbon mixtures in the boiling range from 30 to 250 ° C. Hydroxy compounds, such as saturated and unsaturated fatty alcohols with 10 to 32 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 ₃₁ alcohols) can also be used ) Esters, such as fatty acid esters with 10 to 32 carbon atoms in the acid part and 1 to 10 carbon atoms in the alcohol part or esters of carboxylic acids and fatty alcohols with 1 to 10 carbon atoms in the carboxylic acid part and 10 to 32 carbon atoms in the alcohol part. Of course, it is also possible to use mixtures of the aforementioned solvents.

Depending on the hydrophilic residues of the metal complex needed no or only small amounts of solvent c). 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.

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

solvent c) are used in particular 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.

• a) einem oder mehreren Metallkomplexen der allgemeinen Formel 1
• b) Dispergiermitteln und gegebenenfalls
• c) gering in Wasser löslichen organischen Lösemitteln,

wobei die Metallkomplexe a) in einer Teil- oder der Gesamtmenge der olefinisch ungesättigten Verbindungen und/oder der gering in Wasser löslichen organischen Lösemitteln c) gelöst sind und die Teil- oder die Gesamtmenge der olefinisch ungesättigten Verbindungen und/oder der gering in Wasser löslichen organischen Lösemittel c), welche die Metallkomplexe I gelöst enthält, im wässrigen Medium als disperse Phase mit einem mittleren Tröpfchendurchmesser ≤ 1000 nm vorliegt.According to a preferred process, one or more olefins are polymerized, if appropriate, with carbon monoxide in an aqueous medium in the presence of

• a) one or more metal complexes of the general formula 1
• b) dispersants and optionally
• c) slightly water-soluble organic solvents,

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

• a1) Metallkomplexen der allgemeinen Formel I
• a2) einer Säure und
• a3) gegebenenfalls einer organischen Hydroxyverbindung

durchgeführt.The copolymerization is preferably carried out in the presence of

• a1) Metal complexes of the general formula I
• a2) an acid and
• a3) optionally an organic hydroxy compound

carried out.

According to a preferred embodiment the total amount of metal complexes a1) including the optionally used acids a) and organic hydroxy compounds a3) in a partial or Total amount of olefinically unsaturated Compounds and / or the slightly water-soluble organic solvents c) solved. Subsequently becomes the partial or total amount of the olefinically unsaturated Compounds and / or the slightly water-soluble organic solvents c), which contains the metal complexes a1) in solution, in the presence of dispersants b) in water Medium dispersed as a disperse phase with an average droplet diameter ≤ 1000 nm and at the reaction temperature carbon monoxide and the optionally remaining amounts of the olefinically unsaturated compounds and / or the slightly soluble in water organic solvents c) added continuously or discontinuously.

A preferred process variant is done so that in a first step the total amount of metal complexes a1) and the optionally used acids a2) and the organic Hydroxy compounds a3) in part or all of the olefinically unsaturated Compounds and / or the slightly water-soluble organic solvents c) triggers. Subsequently will this solution together with the dispersants b) in an aqueous medium with formation of oil-in-water dispersions with an average droplet diameter> 1000 nm, the so-called Macroemulsions, dispersed. Then these macroemulsions are transferred with known measures in oil-in-water emulsions with an average droplet diameter ≤ 1000 nm, the so-called mini emulsions and move them at the reaction temperature with carbon monoxide and any remaining or total amount the olefinically unsaturated Compounds and / or the slightly water-soluble organic solvents c).

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

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

The general manufacture of aqueous Mini emulsions from aqueous Macroemulsions are known to the person skilled in the art (see P.L. Tang, E.D. Sudol, C.A. Silebi and M.S. El-Aasser in Journal of Applied Polymer Science, Vol. 43, pp. 1059-1066 [1991]).

For this purpose, high-pressure homogenizers can be used, for example be applied. The fine distribution of the components is in these Machines achieved through a high local energy input. Two options have in this regard especially proven.

In the first variant, the aqueous 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.

In the second variant, the compressed aqueous macroemulsion is ge against each other over two directed nozzles relaxed into a mixing chamber. The fine distribution effect is primarily dependent on the hydrodynamic conditions in the mixing chamber. An example of this type of homogenizer is the M 120 E microfluidizer from Microfluidics Corp. In this high-pressure homogenizer, the aqueous macroemulsion is compressed to a pressure of up to 1200 atm by means of a pneumatically operated piston pump and expanded via a so-called "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. 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 the aqueous miniemulsion from conventional macroemulsions according to the invention by means of ultrasound, there is in particular that in the older German patent application DE 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.

The term "depth of the reaction space" is understood here essentially the distance between the radiation area of the Ultrasound transmission means and the floor of the reaction space.

Reaction chamber depths are preferred up to 100 mm. The depth of the reaction space should not be advantageous more than 70 mm and particularly advantageously not more than 50 mm. The reaction rooms can in principle also have a very shallow depth, but are considered on one if possible 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 this device corresponds to the radiation surface of the means for transmission of ultrasound essentially the surface of the reaction space. This embodiment is used for the batch-wise production of the used according to the invention Mini emulsions. With this device, ultrasound on the affect the entire reaction space. In the reaction chamber, the axial sound radiation pressure creates a turbulent flow, 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 areas and the depth of the reaction space can be means the distance between the radiation surface and the bottom of the flow channel vary.

The agent is particularly advantageous to transfer 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.

The sonotrode is particularly preferred as a rod-shaped, axially radiating λ / 2 (or multiples of λ / 2) longitudinal oscillators educated. Such a sonotrode can, for example, by means of a at one of their vibration nodes provided flange in an opening of the housing be attached. This allows the execution of the sonotrode in the casing be designed to be pressure-tight so that the sound can also be increased Pressure carried out in the reaction space can be. The oscillation amplitude of the sonotrode is preferably controllable, that is the respectively set vibration amplitude is checked online and if necessary automatically adjusted. The review of the current vibration amplitude can, for example, by a the piezoelectric transducer or a Strain gauges with downstream evaluation electronics.

According to another advantageous Such devices are built into the reaction chamber to improve the flow and mixing behavior provided. With these internals can for example, simple baffles or a wide variety of porous body act.

If necessary, the mixing can Moreover with an additional agitator be further intensified. The reaction space is advantageous temperature-controlled.

From the aforementioned statements it becomes clear that according to a preferred process variant only such organic solvents c) or solvent mixtures can be used their solubility in watery Medium under reaction conditions is small enough to comply with the specified Amounts of solvent droplets ≤ 1000 nm as train separate phase. About that In addition, the solvency the solvent droplets formed are large enough be the metal complexes a1), the acids a2) and the organic To take up hydroxy compounds a3). The same applies to the olefinic unsaturated Compounds if they are used without organic solvents c) also for Mixtures of olefinically unsaturated compounds and organic solvents c).

An embodiment of the method according to the invention, is, for example, such that the total amounts of the metal complex a1) and the optionally added acids a2) and organic hydroxy compounds a3) in part or all of the slightly soluble in water organic solvents c) solved become. Subsequently is this organic metal complex solution together with a partial or the total amount of dispersant b) in water with formation dispersed a macro emulsion. Using one of the aforementioned The macroemulsion is converted into a mini emulsion by homogenizers. In these are metered in at reaction temperature and with constant stirring carbon monoxide, the total amount of olefinically unsaturated compounds and optionally the remaining amounts of organic solvents c) or dispersants b). This variant of the method will in particular then chosen if the olefinically unsaturated used Compounds are gaseous under reaction conditions, such as this is the case with ethene, propene, 1-butene and / or i-butene.

In another embodiment is the total amount of the metal complex a1) and, if appropriate added acids a2) and organic hydroxy compounds a3) in a partial or the total amount of olefinically unsaturated compounds dissolved. Then will this organic metal complex solution together with some or all of the dispersants b) dispersed in water to form a macroemulsion. through The macroemulsion becomes one of the aforementioned homogenizers converted into a mini emulsion. In these mini emulsions are metered in at the reaction temperature and below constant stir Carbon monoxide, the remaining amounts of olefinic unsaturated Compounds or dispersants b) and optionally the total amount the slightly soluble in water organic solvents c). This process variant is chosen in particular if the olefinically unsaturated used Compounds are liquid under reaction conditions, such as this for 1-pentene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene and / or 1-hexadecene is the case.

As a rule, the metal complexes a1), especially oil-soluble metal complexes, are dissolved in at least a portion of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c), so that this solution in aqueous medium under reaction conditions as a separate phase with a mean droplet size ≤ 1000 nm. Any remaining amounts of the olefinically unsaturated compounds and / or the slightly water-soluble organic solvents c) can be added to the aqueous reaction medium in bulk, in solution or together with, if appropriate Add remaining amounts of dispersant b) also in the form of an aqueous macroemulsion. If solvents c) are used, the total amount of solvents is usually used to dissolve the metal complexes a1) and then dispersed in an aqueous medium.

It is important that the as separate Phase in aqueous Medium present liquid droplets ≤ 1000 nm in addition the aforementioned compounds a1), a2), a3) and c) and the olefinic unsaturated Connections may contain other components. in this connection it is, for example, 1,4-quinone compounds, which positive about the activity of metal complexes a1) and their service life. Besides optional alkyl-substituted 1,4-benzoquinones can also contain other 1,4-quinone compounds, such as optionally alkyl substituted 1,4-naphthoquinones be used. The molar ratio of optionally used 1,4-quinone compounds to metal complex a1), based on the amount of metal M, is in generally in the range up to 1000, often from 5 to 500 and often from 7 to 250. Additional components include, for example, formulation auxiliaries, Antioxidants, light stabilizers, but also dyes, pigments and / or waxes for hydrophobing in question. Is the solubility of the other components in the organic droplets Phase greater than in watery Medium, so they remain during polymerization in the droplets. Since the droplets containing the metal complexes a1) from olefinically unsaturated Compounds and / or slightly water-soluble solvents c) ultimately the Places of polymerization of carbon monoxide and the olefinically unsaturated Represent compounds contain the polymer particles formed usually these additional ones Components polymerized.

The molar ratio of carbon monoxide to the olefinically unsaturated Connections typically range from 10: 1 to 1:10 values in the range from 5: 1 to 1: 5 or from 2: 1 to 1: 2 are set.

The polymerization temperature will generally set in a range of 0 to 200 ° C, with preference at temperatures in the range of 20 to 130 ° C and especially in the range polymerized from 40 to 100 ° C becomes. The carbon monoxide partial pressure is generally in the range from 1 to 300 bar and in particular in the range from 10 to 220 bar. It is advantageous if the total partial pressure of the olefinically unsaturated Compounds under reaction conditions less than the carbon monoxide partial pressure is. In particular, the total partial pressure is the olefinically unsaturated one Compounds under reaction conditions ≤ 50%, ≤ 40%, ≤ 30% or even ≤ 20%, each based on the total pressure. The polymerization reactor is usually before pressing with carbon monoxide by rinsing with carbon monoxide, olefinic unsaturated compounds or inert gas, for example nitrogen or argon. Frequently However, the polymerization is also without prior inertization possible.

In the polymerization process according to the invention average catalyst activities are obtained which are generally ≥ 0.17 kg, often ≥ 0.25 kg and often ≥ 0.5 kg of polymer per gram of complex metal per hour.

Aqueous polymer dispersions are according to the invention get whose about quasi-elastic light scattering (ISO standard 13321) determined number-average Polymer particle diameter in the range up to 1000 nm, often from 100 to 800 nm and often from 200 to 400 nm. Significant is that the polymer particles are usually a narrow, monomodal particle size distribution exhibit.

By means of gel permeation chromatography weight-average with polymethyl methacrylate as standard Molecular weights of the polymers accessible according to the invention are usually in the range of 1000 to 1,000,000, often in the range of 1,500 to 800,000 and often in the range of 2,000 to 600,000.

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

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

Through targeted variation of the olefinic unsaturated According to the invention it is possible for compounds to prepare polymers their glass transition temperature or melting point in the range of -60 to 270 ° C.

The glass transition temperature T _{g means} the limit value of the glass transition temperature, the according to G. Kanig (Kolloid-Zeitschrift & Polymer, vol. 190, p. 1, equation 1), this 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, Bul. 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 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 method according to the invention 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, after the main polymerization reaction is complete in watery Polymer system remaining residual monomers by steam and / or Inert gas stripping can be removed without affecting the polymer properties the one in the watery Detrimentally change the medium present in the polymer.

The aqueous polymer dispersions obtainable according to the invention 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 in the production of adhesives, such as pressure sensitive adhesives, construction adhesives or industrial adhesives, Sealants, plastic plasters and paints, such as for the Paper coating, dispersion paints or for printing inks and varnishes for printing on plastic films and for the production of nonwovens or for the production of protective layers and water vapor barriers, such as for example when priming. These can also be aqueous Polymer dispersions for modifying mineral binders or other plastics are used. It is preferred to set them for paper applications, Paints, textile and leather applications, adhesives, molded foams, sealants, Plastic plasters, carpet back coatings or pharmaceutical applications.

It should also be noted that those obtainable according to the invention aqueous Polymer dispersions in a simple manner to redispersible Polymer powders can be dried (e.g. freeze drying or spray drying). This is especially true when the glass transition temperature of the polymers is ≥ 50 ° C, preferably ≥ 60 ° C, particularly preferably ≥ 70 ° C, very particularly is preferably ≥ 80 ° C and particularly preferably ≥ 90 ° C or ≥ 100 ° C. The Polymer powders are also suitable as binders in adhesives, Sealants, plastic plasters and paints, as well as for production of nonwovens or for modifying mineral binders, like mortar or cement, for example in dry mortar, repair mortar, gypsum mortar, gypsum building materials running floor masses, Plasters and leveling compounds and thermal insulation composite systems. Another use is as modifying additives in others Plastics.

Show due to their manufacture those accessible according to the invention aqueous Polymer dispersions on polymer particles that have no or only very small amounts [optionally, for example, organic hydroxy compound a3)] on organic solvents contain. However, the method according to the invention is present of slightly soluble in water solvents c) carried out so lets there is an odor in the formation of polymer films by selecting high-boiling solvents c) avoid. On the other hand, the optionally used solvents work c) often as a coalescent and favor with it the film formation. Due to the process, those accessible according to the invention show Polymer dispersions Polymer particles with a narrow, monomodal particle size distribution on. The aqueous obtained Polymer dispersions are above stable and even with small amounts of dispersant over weeks and months show during during this time there is usually practically no phase separation, Deposition or coagulation. According to the method according to the invention are also watery Polymer dispersions accessible, whose polymer particles, in addition to the polymer, also contain other additives, such as formulation auxiliaries, antioxidants, light stabilizers, but also contain dyes, pigments and / or waxes. Another Advantage of the method according to the invention is that the additives used, for example the stabilizers used, are already in the particle, which makes the mixing very will be good. this makes possible continue to reduce the number of formulation steps.

The present invention is based on the following examples explained.

A. Production of the metal complexes

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

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

Bis (3,5-bis (trifluoromethyl) phenyl) phosphine (7.06 g, 15.41 mmol) was suspended in 60 ml DMSO. After adding an aqueous KOH solution (1.12 g, 20.03 mmol, 1.5 ml H ₂ O), a dark red solution was obtained. After stirring for 30 minutes, 1,3-dibromopropane (1.55 g, 7.71 mmol) was added and the mixture was stirred at room temperature for a further 48 h. The reaction mixture was poured into water. This precipitate was separated and dissolved in ether, washed three times with water, dried over Na ₂ SO ₄ and the solvent removed in vacuo. The residue was washed with n-pentane and dried in vacuo.
Yield: 5 g (68%). ¹ H NMR (CDCl ₃ ): δ 7.88 (s, 4H, para Ar), 7.77 (d, 8H, ortho Ar), 2.35 (t, 4H, -CH ₂ P), 1.61 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCl ₃ ): δ 139.93 (d, ipso Ar), 132.7-132.1 (m, ortho Ar, meta Ar), 123.65 (sept, para Ar), 122.89 ( q, CF ₃ ), 28.86 (vt, - CH ₂ P), 21.92 (t, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ -14.88 (s). ^{1 9} F ^{1 H} NMR _(CDCl3): δ - 63.62 (s). MS (EI, m / z (%)): 743 (100) [M-Ar] ⁺ , 956 (15) [M] ⁺ , 937 (8) [MF] ⁺ .

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

Bis (3,5-bis (trifluoromethyl) phenyl) phosphine (6.34 g, 13.84 mmol) was suspended in DMSO (50 ml) and by adding an aqueous KOH solution (1.01 g, 17.99 mmol , 2 ml water) deprotonated. The dark red solution was stirred for 30 minutes. A solution of 3-chloropropyldiphenylphosphine (3.40 g, 12.94 mmol) in DMSO (15 ml) was added to the mixture and stirred for 24 hours at room temperature and for a further 2 hours at 50 ° C. After cooling, the mixture was poured into 300 ml of water. After adding NaCl, the oil phase was separated off, dissolved in ether and washed three times with water, dried over Na ₂ SO ₄ and the solvent was stripped off. Excess bis (3,5-bis (trifluoromethyl) phenyl) phosphine was removed by vacuum distillation.
Yield: 6.6 g (70%). ¹ H NMR (CDCl ₃ ): δ 7.86 (s, 2H, para Ar), 7.75 (d, 4H, ortho Ar), 7.39-7.32 (m, 4H, Ph), 7.31- 7.27 (m, 6H, Ph), 2.27 (t, 2H, -CH ₂ PAr ₂ ), 2.22 (t, 2H, - CH ₂ PPh ₂ ), 1.59 (m, 2H, CH ₂ ). ¹³ C NMR (CDCl ₃ ): δ 140.65 (d, ipso Ar), 138.00 (d, ipso Ph), 132.8-132.3 (m, ortho Ph, meta Ar, ortho Ar), 123 , 34 (sept, para Ar), 122.99 (q, CF ₃ ), 29.37 (vt, -CH ₂ P '), 28.97 (vt, -CH ₂ P'), 22.15 (vt, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ - 13.84 (s, PAr ₂ ), -17.16 (s, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CDCl ₃ ): δ -63.45 (s). MS (Cl, m / z (%)): 665 (100) [M -F] ⁺ , 685 (89) [MH] ⁺ , 607 (6) [M -Ph] ⁺ , 471 (5) [M - Ar] ⁺ .

A) Diphenyl (3-phosphinopropyl) phosphine

A solution of diisopropyl 3- (diphenylphosphino) propyl phosphonate (23.12 g, 58.8 mmol) in ether (100 ml) slowly became a suspension of LiAlH ₄ (4.5 g, 118 mmol) in ether (150 ml) dosed at 0 ° C. The reaction mixture was stirred for a further 30 min at 0 ° C. and overnight at room temperature. The mixture was then hydrolyzed at 0 ° C. The organic phase was separated and the residue extracted with ether. The combined organic phases were washed with water, dried and freed from the solvent in vacuo. A colorless air sensitive oil was obtained.
Yield: 13.4 g (88%). ¹ H NMR (CDCl ₃ ): δ 7.43-7.38 (m, 4H, Ph), 7.34-7.27 (m, 6H, Ph), 2.64 (dt, 2H, -PH ₂ ), 2.11 (t, 2H, -CH ₂ P _(Ph) ), 1.70-1.57 (m, 4H, -CH ₂ -CH ₂ -P _(prim) ). ¹³ C NMR (CDCl ₃ ): δ 138.57 (d, ipso Ph), 132.65 (d, ortho Ph), 128.52 (s, para Ph), 128.38 (d, meta Ph), 29 , 27 (dd, -CH ₂ -P), 29.02 (dd, -CH ₂ -P '), 15.39 (dd, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ -16.29 (s, PPh ₂ ), -137.97 (s, P _(prim) ). MS (C, m / z (%)): 261 (100) [MH] ⁺ .

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

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

General Regulation for the preparation of asymmetric ligands

[3- (Dibromo) phosphino) propyl] (diphenyl) phosphonium bromide prepared according to B) was cooled to -78 ° C. The Solid was in pre-cooled solvent suspended (THF in case 1e and diethyl ether at 1 c, 1 d, 1f). A previously filtered aryl magnesium bromide solution in THF was slowly added this suspension dosed at -78 ° C.

After 15 minutes, it was left Warm the mixture to room temperature and stirred 12 hours after. Subsequently the mixture was hydrolyzed and neutralized. After extractive The ligands were worked up with only minor impurities, easy to remove after conversion to the palladium complexes were. If desired, the pure one can also be obtained from these palladium complexes Ligand are released with sodium cyanide.

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

Diphenyl (3-phosphinopropyl) phosphine (2.19 g, 8.41 mmol, 80 ml CCl ₄ ) was brominated (2.69 g bromine, 16.83 mmol, 10 ml CCl ₄ ) and suspended in diethyl ether (100 ml) , The product was quenched with 3,5-dimethylphenyl magnesium bromide (made from 5-bromo-m-xylene (4.68 g, 25.24 mmol, 20 ml THF) and Mg (0.77 g, 31.56 mmol, 20 ml THF )) implemented. After the hydrolysis, the mixture was worked up extractively with dichloromethane. After purification by column chromatography on silica gel with dichloromethane, an oily product was obtained.
Yield: 0.9 g (38%). ¹ H NMR (CDCl ₃ ): δ 7.38-7.33 (m, 4H, Ph), 7.30-7.26 (m, 6H, Ph), 6.98 (br d, 4H, ortho Ar ), 6.91 (br s, 2H, para Ar), 2.25 (s, 12H, CH ₃ ), 2.21-2.12 (m, 4H, -CH ₂ P), 1.60 (m , 2H, -CH ₂ -). ¹³ C NMR (CDCl ₃ ): δ 138.69 (d, ipso), 138.31 (d, ipso '), 137.66 (d, meta Ar), 132.65 (d, ortho Ph), 130, 35 (d, ortho Ar), 129.04 (s, para Ar), 128.42 (s, para Ph), 128.32 (d, meta Ph), 29.87-29.40 (m, -CH ₂ -P, -CH ₂ -P '), 22.55 (vt, -CH ₂ -), 21.27 (s -CH ₃ ). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ -16.74 (s), -16.96 (s). MS (CI, m / z (%)): 469 (100) [MH] ⁺ , 391 (15) [M -Ph] ⁺ , 363 (8) [M -Ar] ⁺ . Anal. calculated for C ₃₁ H ₃₄ P ₂ : C, 79.46; H, 7.31. found: C, 79.21; H, 7.17.

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

Diphenyl (3-phosphinopropyl) phosphine (4.40 g, 16.91 mmol, 180 ml CCl ₄ ) was brominated (5.40 g bromine, 33.81 mmol, 20 ml CCl ₄ ) and suspended in 200 ml ether. The product was quenched with 3,5-difluorophenyl magnesium bromide (made from 1-bromo-3,5-difluorobenzene (9.80 g, 50.72 mmol, 20 ml THF)) and Mg (1.55 g, 63.39 mmol, 20 ml THF)) implemented. The organic phase was worked up in water extractively with ether. The product thus obtained was extracted several times with pentane. After removal of the solvent and purification on silica gel (dichloromethane), the product was obtained.
Yield: 2.1 g (42%). ¹ H NMR (CDCl ₃ ): δ 7.40-7.34 (m, 4H, Ph), 7.32-7.28 (m, 6H, Ph), 6.83 (m, 4H, ortho Ar) , 6.75 (tt, 2H, para Ar), 2.19 (t, 2H, -CH ₂ P), 2.13 (t, 2H, - CH ₂ P '), 1.56 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCl ₃ ): δ 162.89 (ddd, meta Ar), 142.05 (dt, ipso Ar), 138.21 (d, ipso Ph), 132.63 (d, ortho Ph), 128 , 67 (s, para Ph), 128.44 (d, meta Ph), 115.03 (vsex, ortho Ar), 104.63 (t, para Ar), 29.44 (vt, -CH ₂ -P ), 29.07 (vt, -CH ₂ -P '), 22.01 (vt, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): 12.42 (s, PAr ₂ ), -17.17 (s, PPh ₂ ). ^{1 9} F ^{1 H} NMR _(CDCl3): δ -109.01 (s). MS (Cl, m / z (%)): 485 (100) [MH] ⁺ , 371 (49) [M -Ar] ⁺ , 407 (9) [M -Ph ^{] +} .

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

Diphenyl (3-phosphinopropyl) phosphine (2.83 g, 18.87 mmol, 140 ml CCl ₄ ) was brominated (3.47 g bromine, 21.75 mmol, 15 ml CCl ₄ ) and suspended in 120 ml THF. One equivalent of the bromination product was combined with five equivalents of 2- (trifluoromethyl) phenylmagnesium bromide (made from 1-bromo-2- (trifluoromethyl) benzene (12.23 g, 54.35 mmol, 40 ml THF) and Mg (1.65 g, 67.94 mmol, 30 ml THF)) implemented. After hydrolysis, the THF was removed in vacuo. The solid was filtered, washed with water and taken up in acetone. The acetone extract was evaporated to dryness and taken up in dichloromethane. After drying and concentration, the residue was washed with pentane and diethyl ether and purified by column chromatography (silica gel / dichloromethane).
Yield: 2.2 g (38%). ¹ H NMR (CDCl ₃ ): δ 7.71-7.65 (m, 2H, aroma), 7.45-7.32 (m, 10H, aroma), 7.30-7.25 (m , 6H, aroma), 2.24-2.12 (m, 4H, -CH ₂ P), 1.62 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCl ₃ ): δ 138.26 (d, ipso Ph), 136.84 (d, ipso Ar), 134.12 (qd, CCF ₃ ), 133.19 (s, Ar), 132, 64 (d, ortho Ph), 131.46 (s, Ar), 128.74 (s, Ar), 128.57 (s, para Ph), 128.40 (d, meta Ph), 126.67 ( br, m, Ar), 124.15 (q, CF ₃ ), 30.19 (vt, -CH ₂ P), 29.57 (vt, -CH ₂ P '), 22.40 (dd, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ -17.28 (s, PPh ₂ ), -26.70 (sept, PAr ₂ ). ¹⁹ F { ¹ H} NMR (CDCl ₃ ): δ -57.66 (d). MS (Cl, m / z (%)): 594 (100) [MH] ⁺ , 529 (57) [M -F] ⁺ , 403 (37) [M -Ar] ⁺ .

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

Diphenyl (3-phosphinopropyl) phosphine (4.18 g, 16.05 mmol, 180 ml CCl ₄ ) was brominated (5.13 g bromine, 32.1 mmol, 20 ml CCl ₄ ) and suspended in 200 ml diethyl ether. The product was quenched with 2,4,6-trifluorophenyl magnesium bromide (made from 1-bromo-2,4,6-trifluorobenzene (10.16 g, 48.15 mmol, in 30 ml THF)) and Mg (1.47 g, 60 , 18 mmol, in 20 ml of THF)). After the pH had been adjusted to 8, the organic phase was worked up in aqueous extractive fashion with ether. The product was purified by column chromatography (silica gel / dichloromethane).
Yield: 3.8 g (51%). ¹ H NMR (CDCl ₃ ): δ 7.39-7.33 (m, 4H, Ph), 7.31-7.27 (m, 6H, Ph), 6.58 (m, 4H, meta Ar) , 2.57 (m, 2H, -CH ₂ PAr ₂ ), 2.19 (t, 2H, -CH ₂ PPh ₂ ), 1.54 (m, 2H, -CH ₂ -). ¹³ C NMR (CDCl ₃ ): δ 164.73 (dm, ortho Ar), 163.91 (dm, para Ar), 138.30 (d, ipso Ar), 132.62 (d, ortho Ph), 128 , 53 (s, para Ph), 128.36 (d, meta Ph), 108.7-107.3 (m, ipso Ar), 101.0-100.2 (m, meta Ar), 29.26 (dd, -CH ₂ -PPh ₂ ), 25.31 (m, -CH ₂ -PAr ₂ ), 22.82 (dd, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ - 16.54 (s, PPh ₂ ), -53.12 (quint, PAr ₂ ). ^{1 9} F ^{1 H} NMR _(CDCl3): δ -98.39 (dd, ortho F), -06,30 (t, para F). MS (Cl, m / z (%)): 521 (100) [MH] ⁺ , 389 (26) [M -Ar] ⁺ , 501 (14) [M -F ^{] +} , 443 (8) [M - Ph] ⁺ .

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

A solution of (COD) PdCl ₂ (0.76 g, 2.65 mmol) in CH ₂ Cl ₂ (40 ml) was treated with a solution of the product of 1a) (2.53 g, 2.65 mmol) in CH ₂ Cl ₂ (25 ml) reacted. After stirring for an hour, the bulk of dichloromethane was removed in a stream of argon. After adding pentane, the product precipitated out. After drying in vacuo, a slightly yellow product was obtained.
Yield: 2.9 g (95%). ¹ H NMR (acetone-d ₆ ): δ 8.53 (br d, 8H, ortho Ar), 8.28 (br s, 4H, para Ar), 3.29 (m, 4H, -CH ₂ P) , 2.38 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (acetone-d ₆ ): δ 16.11 (s). ^{1 9} F ^{1 H} NMR (acetone-d _6): δ -62.45 (s). MS (FAB, m / z (%)): 1097 (100) [M - Cl] ⁺ , 1062 (23) [M -2 Cl] ⁺ , 849 (23) (M - 2Cl, Ar] ⁺ . Anal. calculated for C ₃₅ H ₁₈ Cl ₂ F ₂₄ P ₂ Pd: C, 37.08; H, 1.60. Found: C, 36.89; H, 1.66.

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

A solution of the product from 1b) (2.16 g, 3.16 mmol in CH ₂ Cl ₂ (20 ml) became a solution of (COD) PdCl ₂ (0.9 g, 3.16 mmol) in CH ₂ Cl ₂ (60 After stirring for one hour, the reaction mixture was concentrated in vacuo and the product was eliminated by adding pentane, and after drying in vacuo a pale yellow product was obtained.
Yield: 2.6 g (96%). ¹ H NMR (CDCl ₃ ): δ 8.13 (br d, 4H, ortho Ar), 7.96 (br s, 2H, para Ar), 7.71 (m, 4H, Ph), 7.47 ( m, 2H, Ph) 7.37 (m, 4H, Ph), 2.64-2.48 (m, 4H, - CH ₂ P), 2.09 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ 13.33 (d), 13.02 (d). ^{1 9} F ^{1 H} NMR _(CDCl3): δ -63.38 (s). MS (FAB, m / z (%)): 827 (100) [M -Cl] ⁺ , 790 (18) [M -2 Cl] ⁺ , 749 (12) [M -Cl, Ph] ⁺ , 577 ( 9) [M -2 Cl, Ar] ⁺ . Anal. calculated for C ₃₁ H ₂₂ Cl ₂ F ₁₂ P ₂ Pd: C, 43.21; H, 2.57. found: C, 43.01; H, 2.57.

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

To a solution of (COD) PdCl ₂ (0.46 g, 1.60 mmol) in CH ₂ Cl ₂ (40 ml) was added a solution of the product from 1c) (0.75 g, 1.60 mmol) in CH ₂ Cl ₂ (20 ml) added and stirred for one hour. The reaction mixture was concentrated in vacuo and the product was eliminated by adding pentane. After washing with ether and pentane and drying in vacuo, the product was obtained as a pale yellow solid.
Yield: 1.0 g (94%). ¹ H NMR (CDCl ₃ ): δ 7.81-7.74 (m, 4H, Ph), 7.47-7.33 (m, 10H, aroma), 7.04 (br s, 2H, para Ar ), 2.39-2.28 (m, 4H, -CH ₂ P), 2.26 (s, 12H, -CH ₃ ), 1.99 (m, 2H, -CH ₂ -). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ 12.7 (d), 11.4 (d). MS (FAB, m / z (%)): 609 (100) [M -Cl] ⁺ , 574 (20) [M -2Cl] ⁺ , 533 (6) [M -Cl, Ph] ⁺ . Anal. calculated for C ₃₁ HCl ₂ P ₂ Pd: C, 57.65; H, 5.31. found: C, 57.48; H, 5.24.

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

A solution of the product of 1d) (1.96 g, 4.06 mmol) in CH ₂ Cl ₂ (20 ml) became a solution of (COD) PdCl ₂ (1.16 g, 4.06 mmol) in CH ₂ Cl ₂ (80 ml) added. After stirring for one hour, the reaction mixture was concentrated in vacuo and the product was precipitated out by adding pentane. After washing with ether and pentane and drying in vacuo, a microcrystalline solid was obtained.
Yield: 2.6 g (95%). ¹ H NMR (DMSO-d ₆ ): δ 7.76 (m, 4H, aroma), 7.57-7.44 (m, 12H, aroma), 2.83 (m, 2H, -CH ₂ P) , 2.72 (m, 2H, -CH ₂ P '), 1.78 (m, 2H, -CH ₂ -). ³¹ P {1H} NMR (DMSO-d ₆ ): δ 16.5 (br), 13.3 (br). ¹⁹ F { ¹ H} NMR (DMSO-d ₆ ): δ -107.5 (s). MS (FAB, m / z (%)): 625 (100) [M -Cl] ⁺ , 589 (37) [M -2Cl] ⁺ , 547 (26) [M -Cl, Ph] ⁺ . Anal. calculated for C ₂₁ H ₂₂ Cl ₂ F ₄ P ₂ Pd: C, 49.01; H, 3.35. found: C, 48.79; H, 3.48.

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

A solution of (COD) PdCl ₂ (1.96 g, 6.87 mmol) in CH ₂ Cl ₂ (120 ml) was mixed with a solution of the bisphosphine from Example 1e) (3.77 g, 6.87 mmol) CH ₂ Cl ₂ (40 ml) was added. After stirring for one hour, the reaction mixture was concentrated in vacuo and the product was eliminated by adding pentane. After washing with ether and pentane and drying in vacuo, the product was obtained as a solid.
Yield: 4.8 g (96%). ¹ H NMR (C ₂ D ₂ Cl ₄ ): δ 9.41 (m, 1H, Ar) 7.82-7.32 (m, 16H, aroma), 7.02 (m, 1H, Ar), 2nd , 80-2.62 (m, 2H), 2.30-2.04 (m, 3H), 1.71-1.50 (m, 1H). ³¹ P { ¹ H} NMR (C ₂ D ₂ Cl ₄ ): δ 37.14 (m, PAr ₂ ), 12.47 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (C ₂ D ₂ Cl ₄ ): δ - 54.27 (s), -54.37 (d). MS (FAB, m / z (%)): 689 (100) [M -Cl] ⁺ , 653 (48) [M -2Cl] ⁺ , 611 (7) [M -Cl, Ph] ⁺ .

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

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

Sodium iodide (3.04 g, 20.3 mmol) was added to a solution of the dichloro complex of Example 2e) (3.68 g, 5.07 mmol) in DMSO (80 ml) and the mixture was stirred at room temperature for 48 hours. Subsequently, aqueous extractive (dichloromethane) was worked up. The product thus obtained was purified by chromatography on silica gel (dichloromethane) and excreted with pentane as a red-orange solid.
Yield: 3.27 g (71%). ¹ H NMR (CDCl ₃ ): δ 9.58 (m, 1H, Ar), 7.91-7.34 (m, 16H, aroma), 7.09 (m, 1H, Ar), 2.90- 2.71 (m, 2H), 2.34-2.17 (m, 2H), 2.17-2.04 (m, 1H), 1.91-1.70 (m, 1H). ³¹ P { ¹ H} NMR (CDCl ₃ ): δ 23.06 (m, PAr ₂ ), -0.40 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CDCl ₃ ): δ -54.7 (s), -55.55 (d). MS (FAB, m / z (%)): 781 (100) [M -I] ⁺ , 653 (44) [M-I, HI] ⁺ . Anal. calculated for C ₂₉ H ₂₄ F ₆ I ₂ P ₂ Pd: C, 38.33; H, 2.66. found: C, 38.21; H, 2.54.

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

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

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

AgBF ₄ (0.61 g, 3.12 mmol) was added to a solution of the product of Example 2a) (1.77 g, 1.56 mmol) in acetonitrile (80 ml). After stirring for two hours, the mixture was filtered and concentrated in vacuo. After filtration and further concentration, the product fell after the addition of ether. The solid was washed with ether and pentane and dried in vacuo.
Yield: 1.4 g (68%). ¹ H NMR (acetone-d ₆ ): δ 8.55 (d, 8H, ortho Ar), 8.44 (s, 4H, para Ar), 3.58 (m, 4H, -CH ₂ P), 2.71 (m, 2N, -CH ₂ -), 2.09 (s, 6H, CH ₃ CN). ³¹ P { ¹ H} NMR (acetone-d ₆ ): δ 18.57 (s). ¹⁹ F { ¹ H} NMR (acetone-d ₆ ): δ -62.32 (s, CF ₃ ), -148.16 (s, BF ₄ ). MS (FAB, m / z (%)): 1061 (25) [M -2CH ₃ CN, 2BF ₄ ] ⁺ , 605 (100) [M - 2CH ₃ CN, 2BF ₄ , PAr ₂ ] ⁺ .

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

The product of Example 2b (1.12 g, 1.30 mmol) was dissolved in acetonitrile (70 ml) and AgBF ₄ (0.51 g, 2.50 mmol) was added. After stirring for two hours, the mixture was filtered and concentrated to dryness in vacuo. The residue was extracted with dichloromethane, the extract was concentrated and filtered. After adding pentane, the product was obtained as a solid.
Yield: 1.1 g (81%). ¹ H NMR (CD ₃ CN): δ 8.28 (s, 2H, para Ar), 8.11 (d, 4H, ortho Ar), 7.68-7.59 (m, 6H, Ph), 7 , 56-7.49 (m, 4H, Ph), 2.98-2.85 (m, 4H, -CH ₂ P), 2.30 (m, 2H, -CH ₂ -), 1.95 ( s, CH ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 14.3 (d), 14.1 (d). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -62.1 (s, CF ₃ ), -150.1 (s, BF ₄ ). MS (FAB, m / z (%)): 790 (100) [M - 2CH ₃ CN, 2BF ₄ ] ⁺ .

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

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

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

AgBF ₄ (0.92 g, 4.72 mmol) was added to the solution of the product from Example 2d) (1.56 g, 2.36 mmol) in acetonitrile (80 ml). After stirring for twelve hours, working up was carried out analogously to Example 4b).
Yield: 1.6 g (80%). ¹ H NMR (CD ₃ CN, 343 ° K): δ 7.72-7.63 (m, 6H, Ph), 7.58-7.53 (m, 4H, Ph), 7.32-7, 25 (m, 4H, ortho Ar), 7.20 (tt, 2H, para Ar), 2.86-2.77 (m, 4H, - CH ₂ P), 2.29 (m, 2H, -CH ₂ - ), 1.95 (s, CN ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 14.4 (m) 12.7 (m). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -105.5 (s, meta F), -150.0 (s, BF ₄ ). MS (FAB, m / z (%)): 609 (39) [M -2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 590 (100) [M -2CH ₃ CN, 2BF ₄ ] ⁺ .

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

AgBF ₄ (0.43 g, 2.22 mmol) was added to the solution of the product from Example 2e) (1.01 g, 1.11 mmol) in acetonitrile (80 ml). After stirring for two hours, working up was carried out analogously to Example 4b).
Yield: 0.9 g (89%). ¹ H NMR (CD ₃ CN): δ 8.61-8.47 (br, 1H, aroma), 8.07-7.37 (m, 17H, aroma), 3.12-2.94 (br, 2H), 2.71 (br, 2H), 2.53-2.29 (br, 1H), 2.10-1.96 (br, 1H), 1.95 (s, CH ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 31.4 (m, PAr ₂ ), 13.2 (d, PPh ₂ ). ¹⁹ F { ¹ H} NMR (CD ₃ CN): δ -54.1 (s, br, CF ₃ ), -54.4 (s, br, CF ₃ ), -150.4 (s, BF ₄ ) , MS (FAB, m / z (%)): 673 (22) [M -2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 654 (100) [M -2CH ₃ CN, 2BF ₄ ] ⁺ .

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

AgBF ₄ (1.07 g, 5.52 mmol) was added to the suspension of the product from Example 2f) (1.93 g, 2.76 mmol) in acetonitrile (100 ml). After stirring for twelve hours, working up was carried out analogously to Example 4b).
Yield: 1.9 g (76%). ¹ H NMR (CD ₃ CN): δ 7.75-7.65 (m, 6H, Ph), 7.64-7.54 (m, 4H, Ph), 7.03 (m, 4H, Ar) , 2.99 (m, 2H, -CH ₂ P), 2.77 (m, 2H, -CH ₂ P '), 2.32 (m, 2H, -CH ₂ -), 1.95 (s, CH ₃ CN). ³¹ P { ¹ H} NMR (CD ₃ CN): δ 14.4 (d, PPh ₂ ), -19.6 (m, PAr ₂ ). ^{1 9} F ^{1 H} NMR (CD ₃ CN): δ -93.4 (vt, ortho F), -96.0 (t, para F), -150.5 (s, BF _4). MS (FAB, m / z (%)): 645 (20) [M -2CH ₃ CN, BF ₄ , BF ₃ ] ⁺ , 626 (100) [M -2CH ₃ CN, 2BF ₄ ] ⁺ .

B. Examples of polymerization

Example P1

At room temperature, 10 mg of complex 4b were dissolved in 5 g of toluene (99% by weight; from Aldrich) in a Schlenk tube under an argon atmosphere and with stirring, then with 0.5 g of n-hexadecane (99% by weight, from Aldrich ), and 1 g of 10-undecenoic acid (98 wt .-%; Aldrich) and stirred for 5 minutes. The organic complex solution thus obtained was stirred at room temperature and under an argon atmosphere in an aqueous solution consisting of 100 g deionized water and 1.0 g Texapon ^® NSO (Schwefelsäurehalbester sodium salt of n-Dodecanolethoxylat, approximately degree medium ethoxylation: 25; trademark of. Henkel) to form an oil-in-water emulsion. This emulsion was brought into contact with a sonotrode (Sonifier II 450 from Branson) for 10 minutes and then the average droplet size was determined.

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

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

The solids content became general determined by about 1 g of the aqueous Copolymer dispersion in an open aluminum crucible with a Inside diameter of approx. 3 cm in a drying cabinet at 100 ° C and 10 mbar (absolute) was dried to constant weight. For determination of the solids content, two separate measurements were carried out and the corresponding mean is formed.

The coagulum content became general determined by adding about 50 g of the aqueous copolymer dispersion obtained 45 μm filter fabric filtered. The filter cloth was then deionized with 50 ml Rinsed water and at 100 ° C / 1 bar (absolute) dried to constant weight. From the weight difference of the filter fabric before filtration and the filter fabric after The coagulum content was determined by filtration and drying.

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

The determination of the glass transition temperature or the melting point was generally carried out in accordance with DIN 53765 using a DSC820 device, series TA8000 from Mettler-Toledo.

Comparative example

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

After relaxing the steel autoclave to atmospheric pressure a 3% solids dispersion was obtained. It came into being an oligomeric propene / CO copolymer with a weight average molecular weight of 3000 g / mol.

Example P2

Example P1 was repeated with with the exception that 5 g of styrene were used instead of hexadecane. You get a 10% solids dispersion.

Example P3

Example P1 was repeated with with the exception that 10 g of 1-hexene were used instead of hexadecane. You get one Dispersion with 18% solids content. The ratio of olefins in propene / 1-hexene / CO Terpolymer was determined by 13C NMR and is approx. 70 mol% propene and 30 mol% 1-hexene.

Example P4

Example P1 was repeated with except that instead of complex compound 4b, complex 4a was used. You get a 4% solids dispersion.

Claims (16)

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

in which M is a transition metal from Group VIIIB, IB or IIB of the Periodic Table of the Elements, E ¹ and E ² independently of one another an element from Group VA of the Periodic Table of the Elements, Y is C ₁ -C ₅ alkylene which is substituted with hydroxyl, C ₁ -C ₆ -Alkoxy, carboxyl, sulfo, amino, ammonium, phosphono, phosphonato, sufamoyl, amidino, carbamoyl, hydroxysufonyloxy, sulfino and C ₁ -C ₄ alkyl and substituted by oxygen, imino, alkylimino, silylene or mono- or dialkylsilylene can or can have a fused-on cycloaliphatic ring or fused benzene or 1,8-naphthylene, R ¹ C ₁ -C ₂₀ -alkyl which is optionally substituted by hydroxyl, C ₁ -C ₆ -alkoxy, carboxyl, sulfo or aryl, C ₆ -C ₁₄ aryl which is optionally substituted by C ₁ -C ₄ alkyl, hydroxyl, C ₁ -C ₆ alkoxyl, carboxyl, cyano or a radical R ² or C ₃ -C ₁₂ cycloalkyl R ² fluorine, Sulfo, nitro, or perfluorinated C ₁ -C ₁₀ alkyl, R ³ , R ⁴ , R ⁵ and R ⁶ independently of one another W Hydrogen or a radical R ² , L ¹ and L ² independently of one another phosphines (R ⁷ ) _x PH _3-x , amines (R ⁷ ) _x NH _{3– x} or ethers (R ⁷ ) ₂ O with the same or different radicals R ⁷ , alcohols R ⁷ OH, H ₂ O, pyridine compounds C ₅ H _5-x (R ⁷ ) _x N, carbon monoxide, C ₆ -C ₁₂ alkyl nitriles, C ₁ -C ₁₄ aryl nitriles or olefins, where x is an integer from 0 to 3 means amide ions (R ⁷ ) _h NH _2-h , where h is an integer from 0 to 2, C ₁ -C ₆ -alkyl anions, C ₃ -C ₁₄ -cycloalkyl anions, allyl anions, methallyl anions, benzyl anions, Anlanions, carboxylic acid anions, sulfonic acid anions, ketones or diketones, where L ¹ and L ² can be linked to one another by one or more covalent bonds. R ^{1 is} hydrogen, C ₁ -C ₂₀ alkyl, optionally with C ₁ -C ₆ alkoxy, mono - or di- (C ₁ -C ₆ alkyl) amino or C ₆ -C ₄ aryl, C ₃ -C ₁₂ cycloalkyl, or C ₆ -C ₁₄ aryl, An ^- the equivalent of an anion is not coordinating S acid with pKs <4.75 and n is an integer 0, 1, 2, 3 or 4 and b) one or more dispersants. A method according to claim 1, characterized in that in the general formula I the radical R ¹ from the radical of the formula II

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

in which E ¹ , E ² , Y, R ¹ , R ² , R ³ , R ⁴ and R ^{5 have} the meaning given in Claim 1, a dispersant and optionally an acid a2) is carried out. Method according to one of claims 1 to 10, characterized in that that one or more olefins optionally with carbon monoxide in aqueous Medium in the presence of a) one or more metal complexes I b) dispersants and optionally c) low in Water soluble organic solvents, are polymerized, the metal complexes I in a partial or the total amount of the olefinically unsaturated compounds and / or the slightly soluble in water organic solvents c) solved and the partial or total amount of the olefinically unsaturated compounds and / or the slightly soluble in water organic solvents c), which contains the metal complexes I dissolved, in the aqueous medium as disperse Phase with an average droplet diameter ≤ 1000 nm is present. aqueous Dispersions with a head / tail linking fraction of <90% and a particle size of 1 μm, available by a method according to claims 1 to 11th Process for the preparation of polyketones by Isolation from polymer dispersions which have been prepared according to claims 1 to 11. Process for the preparation of polyketones according to claim 13, characterized in that the insulation by means of spray drying happens. Uses of the aqueous dispersions according to claim 12 as a binder for Paper applications, paints, textile and leather applications, Adhesives, molded foams, Sealants, plastic plasters, carpet back coatings or pharmaceutical Applications. Use of the dispersion powder according to claim 13 or 14 as a binder or for modifying mineral Binders.