DE19907999A1 - Process for the polymerization and copolymerization of monoolefins and new palladium complexes therefor - Google Patents

Abstract

According to the invention, monolefins comprising 2 to 12 C atoms can be polymerized to form polymers or copolymers. Said monolefins are polymerized alone or in a mixture as well as with polar monomers such as methylacrylate in the presence of a palladium complex of formula [L1 Pd L2]<+>An<-> and optionally while adding an alkylaluminum compound. In the Pd complex, L1 represents a neutral bidentate N, N'-disubstituted diazadiene ligand, preferably a diazabutadiene ligand; L2 represents an alkoxycycloalkene carbanion with 7 to 8 C annular atoms, preferably a 1-methoxy-cycloocta-4-ene-8 sigma , 4 pi ligand, which is bound to the palladium atom via a sigma bond and whose C=C double bond forms a complexing pi bond to the palladium atom and; An<-> represents an anion of an acid which is non-esterfiable or slightly esterfiable and which is non-coordinating or slightly coordinating. The invention also relates to novel Pd complex catalysts provided for polymerization and copolymerization.

Description

The invention relates to a method for polymerization and Co polymerization of monoolefins in the presence of certain Palladium complexes and suitable new palladium Complexes.

The use of transition metal complexes such as palladium or nickel complexes as catalysts for the polymerization or copolymerization of monoolefins has been described many times. From Italian patent application MI 91A / 2969 it is known by copolymerization of carbon monoxide with monoolefins such as Ethylene polyketones in the presence of cationic Pd complexes to produce, the Pd complexes two bidentate N- or P-containing chelating ligands per Pd atom and two anions of practically non-esterifiable, non-coordinating acids contain. A disadvantage of this method is that it is the user High temperatures and high pressures need to be higher To achieve polymer yields. Similar polyketones by Copoly merization of carbon monoxide and olefinically unsaturated Ver Bonds such as ethylene and especially styrene are according to the EP-A 0728791 in the presence of cationic Pd complexes represents that in addition to a bidentate N- or P-containing chelati ligands a bidentate coordinated anion one a C = C double bond containing compound, its anion a σ bond and its C = C double bond a π bond to the Pd Form atom. A disadvantage of the last manufacturing process of polyketones is that it is based on a combination of the Pd Complex with a liquid halogen-containing compound such as Dichloroethane or chloroform based, d. H. the presence of a halogenated solvent is mandatory.

L. Johnson et al. (J. Amer, Chem. Soc. 1995, 117, pp. 6414-6415) describe cationically activated Pd (II) and Ni (II) complex catalysts which consist of metal dimethyl complexes with a diimine ligand by protonization with in particular H (OEt ₂ ) ₂ ⁺ B (C ₆ F ₅ ) ₄ ^- were produced. The resulting diethyl ether adducts have in the metal complex cation diethyl ether as a ligand and tetrakis-pentafluorophenyl borate anions and polymerize monoolefins such as ethylene, propylene or 1-hexene to give higher molecular weight polymers.

In a later publication, L. Johnson et al. (J. Amer. Chem. Soc. 1996, 118, pp. 267-268) the use of cat ionically activated methyl complexes of Pd (II) for copolymers sation of ethylene or propylene with acrylates, whereby after Formation of cationically activated Pd complexes with ethylene as Ligand or entry of a chelating acrylate ligand itself Form higher molecular weight branched copolymers. From the patent message WO 96/23010 by Johnson et al. is known monoolefine in the presence of transition metals such as Ti, Zr, Sc, V, Cr, Fe, Co, Ni, Pd or rare earth metals, too branched poly polymerize polymer, the metal complexes a two-tough contain some N, N'-disubstituted diazadiene ligands. In the The presence of the metal complexes gave polymerization results hang u. a. heavily on the structure of the over used transition metal complexes. With Pd complexes with diimine ligands that it also had ether or ester adducts in the complex, it was possible, high molecular weight copolymers of ethylene with methyl to produce crylate. A disadvantage of the methods mentioned is that the polymerization-active catalyst centers starting from the Metalldialkyl complex are formed.

Given the known dependence of the product properties of the polymers and copolymers held by the specific detail structure of the transition metal complexes used gift, the polymerization and copolymerization of monoolefins with polar comonomers using different To explore transition metal complexes.

When carrying out this task, it was surprisingly found that the polymerization of ethylene to form a branched polyethylene and the copolymerization of ethylene also with a polar comonomer such as methyl acrylate in the presence of a cationically activated Pd complex with a chelating diimine ligand L ¹ and one Alkoxy-cycloalkene carbon ion as ligand L ^{2 is} possible.

The present invention relates to a process for the poly merization of monoolefins having 2 to 12 carbon atoms or their mixtures and their copolymerization with an olefinically unsaturated polar comonomer in the presence of a Pd chelate complex with an N, N'-disubstituted diazadiene ligand , optionally with the addition of an alkyl aluminum compound, the Pd complex having the formula (I),

[L ¹ Pd L ² ] ⁺ An ^- (I)

wherein
L ^{1 is} an uncharged bidentate N, N'-disubstituted diazadiene ligand chelating with the Pd atom,
L ^{2 represents} an alkoxycycloalkene carbon ion with 7 to 8 C atoms in the ring, which is connected to the Pd atom by a σ bond and whose C = C double bond forms a complexing π bond to the Pd atom, and
An ^{- represents} an anion of a non- or hardly esterifiable and weakly or non-coordinating acid.

Suitable ligands L ^{1 of} the cationically activated Pd complex are the corresponding bidentate N, N'-disubstituted diazadiene ligands listed in patent application WO 96/23010, which chelate with the Pd atom. They include the diimines of the formulas (II), (III) and (IV) which form metal chelates as bidentate ligands.

The following represent:
in formula (II):
R ¹ and R ² , identical or different, an optionally substituted hydrocarbon radical or an optionally substituted heteroaromatic radical,
R ³ and R ^{4 are the} same or different, a hydrogen atom, an optionally substituted hydrocarbon radical or R ³ and R ⁴ together a divalent optionally substituted hydrocarbon radical;
in formula (III):
R ⁵ and R ⁸ , identical or different, are an optionally substituted hydrocarbon residue or optionally substituted heteroaromatic residue,
R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each, the same or different, a hydrogen atom or an optionally substituted hydrocarbon residue or R ⁹ and R ¹⁰ together form a divalent optionally substituted hydrocarbon residue;
in formula (IV):
R ¹¹ and R ¹² , the same or different, are an optionally substituted hydrocarbon radical,
R ¹³ and R ¹⁴ , the same or different, represent a hydrogen atom, an optionally substituted hydrocarbon radical or together a divalent optionally substituted hydrocarbon radical.

Of the diazadienes coordinating with Pd atoms, the N, N'-disubstituted diazabutadienes of the formula (II) are preferred, and of these, in turn, those which have larger bulky substituents R ¹ and / or R ² on the two N atoms, such as optionally substituted aromatic or optionally substituted heteroaromatic residues. Suitable substituents R ¹ and R ² , which may be the same or different, are substituted phenyl radicals and in particular in the 2, 4 and / or 6-position C ₁ -C ₈ alkyl-substituted phenyl radicals, such as 2-methylphenyl, 4-methylphenyl, 2 , 4,6-trimethylphenyl, 2-tert. Butylphenyl, 2,6-diethylphenyl or 2,6-diisopropyl phenyl. Also suitable are 2-pyrimidyl and other heteroaromatic radicals which, in the vicinity of the carbon atom bonded to the imino N atom, contain heteroatoms, in particular S, O and / or N atoms, bound in a heteroaromatic.

Of the substituents R ¹ , R ² , R ⁵ and R ^6, those in which the C atoms bonded to the imino N atoms are linked to at least two further C atoms have proven very successful. Particularly preferred substituents R ¹ , R ² , R ⁵ and R ⁶ are 2,6-diethylphenyl and 2,6-diisopropylphenyl.

Very suitable radicals R ³ and R ⁴ are hydrogen atoms, alkyl radicals with preferably 1 to 4 carbon atoms such as the methyl radical, alkylene radicals such as butylene or 2-ethylbutylene and also divalent aromatic radicals, such as substituted, such as 1,8-naphthylene.

The preparation of the neutral N, N'-disubstituted diazadiene ligand L ¹ is known and can, for. B. by reactions of accordingly structured amines with glyoxal or 1,2-diketones. Examples of the production of preferred ligands L ¹ are given in Examples 1 to 6.

Ligands L ² are alkoxycycloalkene carbon ions chelating with Pd metal with 7 to 8 C atoms in the ring, which are connected to the Pd atom by a σ bond and whose C = C double bond forms a complexing π bond to the Pd Form atom. The alkoxy derivatives of the cycloalkene carbon ions, in which the alkoxy group can contain in particular 1 to 8 carbon atoms, but preferably methoxy, can in a manner known per se from in particular the cyclooctadiene or norbornadiene-Pd complexes by addition of alcohol in Presence of alkali. A suitable synthesis of the di- (1-methoxy-cycloocta-4-en-8σ, 4π) -µ, µ'-dichloropalladium (formula (VI)), starting from a cycloocta diene-Pd complex (V), shows equation below and is described in Example 7.

By reaction with the neutral diazadiene ligands L1, as shown in Examples 8 to 11, the L2-dichloro-Pd complexes (V) obtained can be converted into the [L1 Pd L2] ⁺ an ^- catalyst complexes used according to the invention, e.g. B. one of the formula (VII) can be converted:

The synthesis avoids the sensitive R-Pd-R intermediates and thus leads to high yields of stable Pd catalyst complex.

Suitable anions An ^- are anions have little or no esterifiable and weak or non-coordinating acid, in particular a pk _a of less than 3 and preferably less than 2, has questioned, but not hydrogen halides. Suitable anions are known to the person skilled in the art and are often bulky in structure. In games of suitable anions An ^- are tetrafluoroborate, hexafluoro phosphate, hexafluoroantimonate, p-toluenesulfonate, trifluoromethane sulfonate, tetraphenyl borate, tetrakis [3,5-bis (trifluoromethyl) phe nyl] borate and tetrakis (pentafluorophenyl) borate, of which orphosphat Hexaflu, Hexafluoroantimonate, tetrafluoroborate, tetra kis [3,5-bis- (trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate are preferred. Regarding coordination, please refer to the literature, e.g. BW Beck et al. Chem. Rev. 88 (1988) 1405-1421, and SH Strauss, Chem. Rev. 93 (1993) 927-942.

Another object of the present invention are new from selected palladium complexes of formula (I), in which

• a) L ^{1 is} a neutral N, N'-disubstituted diazabutadiene ligand of the formula (II) in which
  R ¹ and R ² , identical or different, are a phenyl radical substituted by at least one C ₁ -C ₈ hydrocarbon radical and
  R ³ and R ⁴ , the same or different, represent a hydrogen atom or a C ₁ -C ₁₈ hydrocarbon radical, preferably an alkyl radical, or R ³ and R ⁴ together form a divalent carbon hydrogen radical with up to 18 C atoms and in particular 2 to 12 Represent carbon atoms,
• b) L ^{2 is} a 1-C ₁ -C ₈ alkoxy-cycloocta-4-en-8σ, 4π ligand, and
• c) An ^- an anion of a hardly or preferably non-esterifiable and weakly or preferably non-coordinating acid, as indicated, and An ^- preferably tetrafluoroborate, tetrais [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (penta fluorophenyl) Borate, hexafluorophosphate or hexafluoroantimonate means.

Suitable olefins as monomers or comonomers are aliphatic and cycloaliphatic monoolefins having 2 to 12 carbon atoms, where these contain an olefinic C = C double bond that does not Is part of an aromatic ring system. Mono is preferred olefins, which are hydrocarbons. Preferred mono Olefins for homopolymerization are monoolefins with 2 to 6 carbon atoms, especially ethylene, propylene and cyclopentene.

Olefinically unsaturated polar monomers as comonomers are available all monoolefinic monomers with C = O groupings, which according to their structure with the cationically activated Pd atom Complex formation are capable. Acrylic acid, meth acrylic acid, its esters and vinyl ketones, of which alkyl esters the methacrylic acid and especially acrylic acid particularly ge are suitable. Of these, methyl acrylate in particular is particularly useful prefers.

In many cases it has proven to be advantageous to use the Pd complexes according to the invention with the addition of alkyl aluminum compounds in which at least one alkyl group having 1 to 25 carbon atoms is bonded to an aluminum atom. In the alkyl aluminum compounds halogen or Sau erstoffatome or z. B. alkoxy groups on the aluminum atom be the. Examples of suitable aluminum compounds are triiso butyl aluminum, diethyl aluminum chloride, ethyl aluminum dichloride, methylaluminoxane (an oligomer of the formula [MeAlO] _n with Me = methyl and n preferably 5 to 30 or a modified methylaluminoxane in which about 20 to 30 mol% of the methyl groups pass through The amount of alkyl aluminum compounds added is advantageously about 5 to 15 moles per mole of Pd complex catalyst used.

Based on the amount of Pd complex compounds used, the monomers and comonomers are used in a large excess for the polymerization with the organometallic catalysts. For example, the amount of catalyst can be in the range from 10 ^-7 to 10 ^-3 gram atom of palladium per mole of ethylenically / olefinically unsaturated compound (monomer or monomer + comonomer).

The polymerization process according to the invention is carried out by Contacting the Pd complex and possibly an alkyl aluminum compound with the monomers, preferably in the presence of a organic diluent or solvent, where as organic diluents organic hydrocarbons as have proven very suitable, especially aromatic coals Hydrogen such as benzene or toluene.  

The polymerization temperature is generally from -20 to +300 and especially at +10 to + 150 ° C. In particular, be Polymerization temperatures between +20 and + 120 ° C applied. The The process can be carried out with slight negative pressure, normal pressure to high pressure be carried out. Generally the pressure on the poly is merization 0.1 to 3000, in particular 1 to 150 bar. Suitable Polymerization reactors are e.g. B. autoclaves and stirred kettles, the allow the appropriate printing application. The procedure can be exercised discontinuously or continuously. The poly The polymerization time depends on the polymerization temperature determined and can achieve satisfactory yields up to Amount to 10 hours. The polymerization is expediently carried out by Addition of hydrogen chloride in alcohol such as methanol stopped. After washing the dilution or solvent phase with water and filtering e.g. B. using an alumina column advantageous to evaporate the polymer or polymer mixture separate and dry the solvent or diluent.

The results obtained by the method according to the invention shows Table 1 and are sometimes surprising. So at Homopolymerization of ethylene relatively low molecular weight polymers preserved with a highly branched structure. By copolymerization of ethylene with 1-hexene, the molecular weight of the copolymers obtained over the ethylene homopolymer increase sharply. The copolymerization of ethylene with methyl acrylate led to low molecular weight polymers with a relative broad molecular weight distribution.

The available copolymers with polar comonomers can e.g. B. as a viscosity index improver in mineral oil as a dispersion flow improvers of diesel fuel, as plasticizers of plastics or as a lubricant. The Ole Fin polymers and copolymers can also be used advantageously other elastomeric or thermoplastic polymers to polymer Process blends that, depending on the choice of polymers, have good toughness or stickiness.

The following examples are intended to explain the invention further but not limit it. If not stated otherwise, parts and percentages are by weight. The specified Number and weight average of the molecular weights of the polymers were determined by gel permeation chromatography (GPC) Use of an HDPE standard. The structure (ramifications) of the polymers obtained were determined by NMR spectroscopy. In connection with this, the articles by D. E. Axelson et al. Macromolecules 12: 41-52 (1979); T. Usami et al. Macromolecules  17 (1984) 1757-1761 and J.V. Prasad et al., Eur. Polym. J. 27 (1991) 251-254.

example 1 Synthesis of ligand 1-1 1,4-di (2,6-diisopropylphenyl) diazabutadiene

62.86 ml of 2,6-diisopropylaniline (300 mmol, 90% solution) were added to 300 ml of methanol and then 1 ml of formic acid. Then 21.76 g of 40% glyoxal (150 mmol as a 40% aqueous solution) were added dropwise. After stirring for 8 hours, a lemon yellow suspension was formed, which was filtered off and washed with 200 ml of cold methanol. The resulting product was dried under vacuum. The yield was 32.8% of theory (18.5 g). ¹ H-NMR analysis (in CDCl ₃ ): ä 1.2 (24H, isopropyl CH ₃ ), 2.9 (4H, isopropyl), 7.2 (6H aromat.), 8.1 (2H, = CH-CH =).

Example 2 Synthesis of ligand 1-2 1,4-di (2,6-diisopropylphenyl) -2,3-dimethyldiazabutadiene

20 ml of 2,6-diisopropylphenylamine (95.44 mmol, 90% solution) were added to 100 ml of methanol and then 1 ml of formic acid. Then 4.2 ml (45.14 mmol, 99% solution) of biacetyl (dime thyglyoxal) was added dropwise. After stirring for 8 hours, a lemon yellow suspension was formed which was filtered off and washed with 200 ml of methanol. The resulting product was dried under vacuum. The yield was 82.4% of theory. ¹ H NMR analysis (in CDCl ₃ ): σ 1.2 (24H, isopropyl CH ₃ ), 2.06 (6H, 2,3-dimethyl), 2.7 (4H, isopropyl CH), 7.2 (6H aromatic).

Example 3 Synthesis of ligand 1-3 1,4-di (2,6-dimethylphenyl) diazabutadiene

The procedure was essentially as in Example 1, but as Amine 2,6-dimethylphenylamine used. The yield was 10.3% of theory.

Example 4 Synthesis of ligand 1-4 1,4-di (2,6-dimethylphenyl) -2,3-dimethyldiazabutadiene

The procedure was essentially as in Example 2, but 2,6-dimethylphenylamine was used as the amine. The yield was 51.7% of theory. ¹ H NMR analysis (in CDCl ₃ ): σ 2.06 (18 H), 6.93 (2H, para-aromatic), 7.08 (4H, meta-aromatic).

Example 5 Synthesis of ligand 1-5 1,4-di (2,6-diethylphenyl) diazabutadiene

The procedure was essentially as in Example 1, but as Amine 2,6-diethylphenylamine used. The yield was 23.0% of theory.

Example 6 Synthesis of ligand 1-6 1,4-di (2,6-diethylphenyl) -2,3-dimethyldiazabutadiene

The procedure was essentially as in Example 2, but as Amine 2,6-diethylphenylamine used. The yield was 42.3% of theory.

Example 7 Synthesis of the intermediate Di (1-methoxy-cy cloocta-4-en-8σ-4π) -µ, µ'-dichloro-palladium

0.8 g of dry sodium carbonate (7.5 mmol) was added to the yellow suspension of [Pd (COD) Cl ₂ ] (7 mmol) (COD = cyclooctadiene) in methanol and the resulting mixture was stirred at room temperature for 50 minutes, the color of the suspension became white. The product was filtered off and washed with cold methanol and diethyl ether. The product dried under vacuum was obtained in a yield of 84% of theory. The elementary analysis gave the values:
C: 38%; H: 5.3%; Cl: 13.0% (theoretical values: C: 37.7%; H: 4.7%; Cl: 12.8%).

Example 8 Synthesis of the catalyst 2P1-2 [(1,4-Di (2,6-diisopropylphenyl) -2,3-dimethyldiazabutadi nyl] - [1-methoxy-cycloocta-4-en-8σ, 4π] palladium hexafluorophosph Has

0.75 g (1.33 mmol) of the solid [Pd (COD-OCH ₃ Cl] ₂ ) prepared according to Example 7 was suspended in 70 ml of methanol, and 1.29 g (3.2 mmol) of the according to Example were suspended 2 prepared 1,4-di (2,6-diisopropylphenyl) -2,3-dimethyldiazabutadiene added, the molar ratio of palladium to diazabutadiene compound being 1: 1.2, and after about 3 hours of stirring a yellow solution was formed. A solution of 0.52 g (3.2 mmol) of ammonium hexafluorophosphate in 5 ml of methanol was added dropwise to the solution obtained, and soon a crystalline sediment had formed, which was filtered off after 30 minutes, washed with diethyl ether and dried under vacuum was 73.7% of theory and ¹ H-NMR analysis (in CDCl ₃ ) showed:

1.1 ppm 3H d isopropylmethyl
1.21 ppm 3H d isopropylmethyl
1.39 ppm 3H d isopropylmethyl
1.37 ppm 3H d isopropylmethyl
1.45 ppm 12H d isopropylmethyl
1.30 ppm 8H dd CH ₂ in COD 'ligand
2.39 ppm 8H s methyl backbone
2.43 ppm 3H s COD'-methoxy
2.50 ppm 3H s methyl backbone
4.81 ppm 1H m COD 'double bond
5.30 ppm 1H m COD 'double bond
3.02 ppm 4H isopropyl CH
1.83 ppm 1H COD '(* HC-Pd)
2.10 ppm 1H COD '(* HC-methoxy)

Example 9 Synthesis of the catalyst 2P1-1 [1,4-Di (2,6-diisopropylphenyl) -2,3-dimethyldiazabuta dienyl] - [1-methoxy-cycloocta-4-en-8σ, 4π] palladium tetrakis (penta fluorophenyl) borate

The procedure was essentially as in Example 8, but as Activator instead of ammonium hexafluorophosphate dimethylanilinium-te trakis (pentafluorophenyl) borate is used. The yield was 93.6% of theory.

Example 10 Synthesis of catalyst 1P1-1 [1,4-di (2,6-diisopropylphenyl) diazabutadienyl] - [1-methoxy cycloocta-4-en-8σ, 4π] palladium tetrakis (pentafluorophenyl) borate

The procedure was essentially as in Example 9, but as Ligand L1 is the 1,4-di (2,6-diisopro pylphenyl) diazabutadiene used. The yield was 88.0% of the Theory.

Example 11 Synthesis of catalyst 6P1-1 [1,4-Di (2,6-diethylphenyl) -2,3-dimethyldiazabuta  dienyl] - [1-methoxy-cycloocta-4-en-8σ, 4π] palladium tetrakis (penta fluorophenyl) borate

The procedure was essentially as in Example 9, but as Ligand 1 the 1,4-di (2,6-diethylphe nyl) -2,3-dimethyl-diazabutadiene used. The yield was 97.5% of theory.

Example 12 (Polymerization Test P1)

300 ml of dry toluene was placed in a 500 ml four-necked flask submitted and 20 mmol of triisobutylaluminum and 2.83 mmol of the ge 1P1-1 catalyst prepared according to Example 10 was added, Ethylene was depressurized with a throughput of 40 liters per Blown for an hour through the solution and a polymerization tempera of 55 ° C. After 7 hours the polymerization canceled by adding hydrogen chloride in methanol and the Mix in the separating funnel separately. The toluene phase was with Washed water and then dried. After filtration through the polymer was made a neutral alumina column by Ver evaporate the toluene (7 ° C, 1 mbar, 3 hours) and ana lysed. The result is shown in Table 1.

Example 13 (Polymerization Test P2)

The procedure was essentially as in Example 12, but as Catalyst the catalyst 6P1-1 produced according to Example 11 used. The result is shown in Table 1.

Example 14 (Polymerization Test P3)

It was carried out essentially as in Example 12 (polymerization ver such P1) process, but as a palladium complex catalyst Catalyst 2P1-2 used. The test result shows Table 1.

Example 15 (Polymerization Test P4)

The procedure was essentially as in Example 12, but as Catalyst the catalyst 2P1-1 produced according to Example 9 used. The test result is shown in Table 1.

Example 16 (Polymerization Test P5)

In a 500 ml four-necked flask, 150 ml of dry toluene and 150 ml of dry 1-hexene presented. After the addition of 20 mmol Triisobutylaluminum and 2.83 mmol catalyst 2P1-1 became Ethy  oil at a throughput of 40 liters per hour without pressure blown the solution and a polymerization temperature of 55 ° C. set. After another 7 hours, the polymerization canceled by adding hydrogen chloride in methanol. The resulting mixture was separated in a separatory funnel, the To luol phase washed with water and dried. After filtration through a neutral alumina column was by evaporation of the toluene (75 ° C; 0.1 mbar, 3 hours) the polymer was removed separates. The test result is shown in Table 1.

Example 17 (Polymerization test P6) (ethylene / 1-decene)

150 ml of dry toluene and 150 ml of dry 1-decene were added submitted to a 500 ml four-necked flask. After adding 20 mmol triisobutyl aluminum and 2.83 mmol catalyst 2P1-1 ethylene was printed at a flow rate of 40 liters per hour blown loose through the solution. It then became a polymer set temperature of 55 ° C and polymerized for 7 hours. Thereafter, the polymerization was carried out by adding hydrogen chloride broken off in methanol. After separating the mixture in one The toluene phase was washed with water in a separating funnel and then dried. After filtration through a neutral aluminum The polymer became nium oxide column by evaporating the toluene (75 ° C; 0.1 mbar; 3 hours). The test result shows Table 1.

Example 18 (Polymerization Test P7)

300 ml of dry toluene were placed in a 500 ml four-necked flask submitted and 20 mmol triisobutylaluminum and 2.83 mmol Kataly sator 2P1-1 added. After that, propylene became one-throughput of 40 liters per hour passed through the solution without pressure, whereby this was set to 55 ° C. After 7 hours the polymeri tion canceled by adding hydrogen chloride in methanol and the resulting mixture is separated in the separatory funnel. The Toluene phase was washed with water and dried. After fil The polymer was fed through a neutral alumina column isolated by evaporating the toluene (75 ° C; 0.1 mbar; 3 hours). The test result is shown in Table 1.

Example 19 (Polymerization Test P8) (1-butene)

300 ml of dry toluene was placed in a 500 ml four-necked flask placed and this 20 mmol of triisobutyl aluminum and 2.83 mmol of the catalyst 2P1-1 added. Then 1-butene became one Throughput of 40 liters per hour without pressure through the solution blow and set a polymerization temperature of 55 ° C.  

7 hours later the polymerization was carried out by adding chlorine hydrogen broken off in methanol. The resulting mixture was separated in the separating funnel and the toluene phase with Washed water, dried and through a neutral aluminum xid column filtered. By evaporating the toluene (75 ° C; 0.1 mbar; 3 hours) the polymer was separated. The test result shows Table 1.

Example 20 (Polymerization Test P9)

120 ml of dry toluene and 3 g of methyl acrylate were mixed in one 500 ml four-necked flask and the mixture 0.27 mmol of Catalyst 2P1-1 added. The mixture then became Ethy blown at a throughput of 40 liters per hour without pressure sen, wherein a polymerization temperature of 54-56 ° C is set had been. After 7 hours the polymerization was by addition canceled by hydrogen chloride in methanol. After filtration the polymer was passed through a neutral alumina column Evaporation of the toluene (75 ° C; 0.1 mbar; 3 hours) separated. The The test result is shown in Table 1.

Example 21 (Polymerization Test P10)

350 ml of dry cyclopen were placed in a 500 ml four-necked flask ten submitted and 4.9 mmol of triisobutylaluminum and 0.49 mmol Catalyst 2P1-1 added. The polymerization was carried out at 55 ° C. the polymer precipitated out as a white powder. After 7 hours the polymerization was carried out by adding hydrogen chloride in Me ethanol canceled. The polymer was filtered off with water washed and dried in a vacuum cabinet. It had one Melting point of 250 ° C (DSC analysis).  

Claims (8)

1. A process for the polymerization of monoolefins having 2 to 12 carbon atoms or their mixtures and their copolymerization with olefinically unsaturated polar monomers in the presence of a palladium complex, optionally with the addition of an alkyl aluminum compound, characterized in that the palladium complex has the formula (I) ,
[L ¹ Pd L ² ] ⁺ An ^- (I)
where L1 is a neutral bidentate palladium chelating N, N'-disubstituted diazadiene ligand,
L2 represents an alkoxycycloalkene carbon ion with 7 to 8 C atoms, which is connected to the palladium atom by a σ bond and whose C = C double bond forms a complexing π bond to the palladium atom, and An ^{- is not} an anion or is hardly esterifiable and weakly or non-coordinating acid. 2. The method according to claim 1, characterized in that Mixtures of ethylene with esters of acrylic acid and / or meth acrylic acid are polymerized. 3. The method according to claim 1 or 2, characterized in that the polymerization in the presence of an aromatic carbon hydrogen takes place. 4. The method according to any one of claims 1 to 3, characterized records that the palladium complex used as a ligand rest L2 is a carbon ion of a 1-alkoxy-cycloocta-4-en-8σ, 4π having. 5. The method according to any one of claims 1 to 4, characterized in that the palladium complex used as ligand L1 has a diazabutadiene of the formula (II)
R ¹ -N = CR ³ -CR ⁴ = NR ² (II)
wherein R ¹ and R ² , the same or different, an optionally substituted aromatic radical having 6 to 18 carbon atoms or optionally substituted heteroaromatic radical having at least one S, O or N heteroatom in the heteroaromatic and having 3 to 18 Carbon atoms,
R ³ and R ⁴ , identical or different, represent a hydrogen atom, a C ₁ -C ₁₈ hydrocarbon radical or R ³ and R ⁴ together represent a divalent, optionally substituted hydrocarbon radical with 2 to 18 C atoms. 6. The method according to any one of claims 1 to 5, characterized in that the anion An ^- a tetrafluoroborate, tetra kis [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (penta fluorophenyl) borate, pentafluorophosphate - or hexa-fluoranti month anion. 7. Palladium complexes of the formula (I)
[L ¹ Pd L ² ] ⁺ An ^- (I)
in which L ^{1 represents} an N, N'-disubstituted diazabutadiene ligand of the formula (II),
R ¹ -N = CR ³ -CR ⁴ = NR ² (II)
wherein R ¹ and R ² , identical or different, are a phenyl radical substituted by at least one C ₁ -C ₈ hydrocarbon radical,
and R ³ and R ⁴ , identical or different, denote a hydrogen atom or a C ₁ -C ₁₆ hydrocarbon radical or R ³ and R ⁴ together denote a divalent hydrocarbon radical with a total of up to 18 C atoms,
L ^{2 is} a 1-C ₁ -C ₈ alkoxy-cycloocta-4-en-8σ, 4π ligand, and
An ^{- represents} an anion of a non or hardly esterifiable and weakly or non-coordinating acid. 8. Palladium complexes according to claim 7, characterized in that the anion An ^- in formula (I) is a tetrafluoroborate, tetra kis [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (penta fluorophenyl) borate, Is hexafluorophosphate or hexafluoro antimonate anion.