EP1163277A1

EP1163277A1 - Method for the polymerization an copolymerization of monolefins and novel palladium complexes therefor

Info

Publication number: EP1163277A1
Application number: EP00916842A
Authority: EP
Inventors: Andrei Gonioukh; Neil Popham
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-02-25
Filing date: 2000-02-17
Publication date: 2001-12-19
Also published as: DE19907999A1; KR20010102384A; JP2002537451A; WO2000050474A1

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-8σ, 4π ligand, which is bound to the palladium atom via a σ bond and whose C=C double bond forms a complexing π 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

Process for the polymerization and copolymerization of mono-olefins and new palladium complexes therefor

description

The invention relates to a process for the polymerization and copolymerization of monoolefins in the presence of certain palladium complexes and to 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 widely described. It is known from Italian patent application MI 91A / 2969 to prepare polyketones by copolymerization of carbon monoxide with monoolefins such as ethylene in the presence of cationic Pd complexes, the Pd complexes having two bidentate N- or P-containing chelating ligands per Pd atom and two Contain anions of practically non-esterifiable, non-coordinating acids. A disadvantage of this process is that high temperatures and high pressures are required to achieve higher polymer yields. Similar polyketones by copolymerization of carbon monoxide and olefinically unsaturated compounds such as ethylene and in particular styrene are produced according to EP-A 0728791 in the presence of cationic Pd complexes which, in addition to a bidentate N- or P-containing chelating ligand, have a bidentate coordinated ligand Contain an anion of a compound having a C = C double bond, the anion of which forms a σ bond and whose C = C double bond forms a π bond to the Pd atom. A disadvantage of the last process for the production 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, i.e. 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, in particular H (OEt) ₂ ⁺ B (C ₆ F ₅ ) ₄ ". 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 higher molecular weight polymers. In a later publication, L. Johnson et al. (J. Amer. Chem. Soc. 1996, 118, pp.267-268) the use of cationically activated methyl complexes of Pd (II) for the copolymerization of ethylene or propylene with acrylates, wherein after the formation of cationically activated Pd complexes with ethylene as Ligand or entry of a chelating acrylate ligand form higher molecular weight branched copolymers. From patent application WO 96/23010 by Johnson et al. is known to polymerize monoolefins in the presence of transition metals, such as Ti, Zr, Sc, V, Cr, Fe, Co, Ni, Pd or rare earth metals, to give highly branched polymers, the metal complexes comprising a bidentate N, N 'disubstituted diazadiene - Ligands included. The polymerization results achieved in the presence of the metal complexes depend heavily on the structure of the transition metal complexes used. With Pd complexes with diimine ligands, which additionally contained ether or ester adducts in the complex, it was possible to produce higher molecular weight copolymers of ethylene with methyl acrylate. A disadvantage of the methods mentioned is that the polymerization-active catalyst centers are formed starting from the metal dialkyl complex.

Given the known dependence of the product properties of the polymers and copolymers obtained on the specific detail structure of the transition metal complexes used, the task was to investigate the polymerization and copolymerization of monoolefins with polar comonomers using different transition metal complexes.

When this task was carried out, it was surprisingly found that the polymerization of ethylene into 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 a Alkoxy-cycloalkene-carbanion as ligand L ^{2 is} possible.

The present invention relates to a process for the polymerization 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, if appropriate with the addition of an alkyl aluminum compound, the Pd complex having the formula (I),

[L ¹ Pd L ² ] ⁺ On "(I)

wherein L ^{1 is} an uncharged bidentate N, N'-disubstituted diazadiene ligand chelating with the Pd atom,

L ^{2 represents} an alkoxycycloalkene carbanion 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

Anion is an anion of a non- or hardly esterifiable and weak - 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 are chelating with the Pd atom. They include the diimines of the formulas (II), (III) and (IV) which form metal chelates as bidentate ligands.

(II) (III) (IV)

The following represent:

in formula (II):

R ¹ and R ² , the same or different, are an optionally substituted one

Hydrocarbon radical or an optionally substituted heteroaromatic radical,

R ³ and R ⁴ , identical or different, represent a hydrogen atom, an optionally substituted hydrocarbon radical or R ³ and R ⁴ together form 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, represent a hydrogen atom or an optionally substituted hydrocarbon radical or R ⁹ and R ¹⁰ together form a divalent optionally substituted hydrocarbon radical;

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 radicals. Suitable substituents R ¹ and R ² , which can be the same or different, are substituted phenyl radicals and in particular in the 2,4 and / or 6-position Ci-Cs-alkyl-substituted phenyl radicals such as 2-methylphenyl, 4-methylphenyl, 2, 4, 6 -Trimethylphenyl, 2-tert. Butylphenyl, 2, 6-diethylphenyl or 2, 6-diisopropylphenyl. Also suitable are 2-pyrimidyl and other heteroaromatic radicals which contain heteroatoms, in particular S, O and / or N atoms, bound in a heteroaromatic in the vicinity of the C atom bound to the imino N atom.

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 divalent optionally substituted aromatic radicals such as 1,8-naphthylene. The preparation of the neutral N, N'-disubstituted diazadiene ligands L ¹ is known and can be carried out, for example, by reactions of appropriately 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 alkoxycycloalkenecarbanions 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 carbanions, in which the alkoxy group can in particular contain 1 to 8 carbon atoms, but preferably represents methoxy, can be prepared 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- (l-methoxy-cycloocta-4-en-8σ, 4π) -μ, μ '- dichloropalladium (formula (VI)), starting from a cycloocadiene-Pd complex (V), shows equation below and is described in Example 7.

(V) (VI)

By reaction with the neutral diazadiene ligands L1, as shown in Examples 8 to 11, the obtained

L2-dichloro-Pd complexes (V) can be converted into the [Ll Pd L2] ⁺ An "catalyst complexes used according to the invention, for example one of the formula (VII):

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

Anions which can be used are anions of a non-esterifiable or weakly or non-coordinating acid which is not or hardly esterifiable and which in particular has a pk _a value of less than 3 and preferably less than 2, but not hydrogen halides. Suitable anions are known to the person skilled in the art and are often bulky in structure. Examples of suitable anions are tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, p-toluenesulfonate, trifluoromethanesulfonate, tetraphenylborate, tetrakis [3,5-bis- (trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate - Orphosphate, hexafluoroantimonate, tetrafluoroborate, tetrakis [3,5-bis- (trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate are preferred. Regarding coordination, please refer to the literature, e.g. W. 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 selected palladium complexes of formula (I), in which

a) L ^{1 represents} 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 Ci-Cs hydrocarbon radical and

R ³ and R ⁴ , the same or different, represent a hydrogen atom or a Ci-Cis hydrocarbon residue, preferably an alkyl residue, or R ³ and R ⁴ together form a divalent hydrocarbon residue with up to 18 C atoms and in particular 2 to 12 C. -Atoms represent

b) L ² an l -CC ₈ alkoxy-cycloocta-4-en-8σ, 4π ligand, and

c) An "represent an anion of a hardly or preferably non-esterifiable and weakly or preferably non-coordinating acid, as indicated, and An ^~ preferably tetrafluoroborate, tetrakis [3, 5-bis (tri-fluoromethyl) phenyl] borate, tetrakis (penta - fluorophenyl) borate, hexafluorophosphate or hexafluoroantimonate. Suitable olefins as monomers or comonomers are aliphatic and cycloaliphatic monoolefins having 2 to 12 carbon atoms, these containing an olefinic C = C double bond which is not part of an aromatic ring system. Mono-olefins which are hydrocarbons are preferred. Preferred mono-olefins for homopolymerization are mono-olefins with 2 to 6 carbon atoms, in particular ethylene, propylene and cyclopentene.

Olefinically unsaturated polar monomers as comonomers are, above all, monoolefinic monomers with C = 0 groups, which, according to their structure, are capable of complexing with the cationically activated Pd atom. Acrylic acid, methacrylic acid, their esters and vinyl ketones, of which alkyl esters of methacrylic acid and in particular acrylic acid are particularly suitable, may be mentioned. Of these, methyl acrylate is particularly preferred.

In many cases it has proven to be advantageous to use the Pd complexes used according to the invention with the addition of alkyl aluminum compounds in which at least one alkyl group having 1 to 25 C atoms is bonded to an aluminum atom. Halogen or oxygen atoms or, for example, alkoxy groups can also be bound to the aluminum atom in the alkylaluminum compounds. Examples of suitable aluminum compounds are triisobutyl 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 by isobu 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, if appropriate, an alkylaluminum compound with the monomers, preferably in the presence of an organic diluent or solvent, organic hydrocarbons having proven to be very suitable as organic diluents, in particular aromatic hydrocarbons such as benzene or Toluene. The polymerization temperature is generally from -20 to +300 and in particular from +10 to + 150 ° C. In particular, polymerization temperatures between +20 and + 120 ° C are used. The process can be carried out under slight negative pressure, normal pressure to high pressure. In general, the pressure during the polymerization is 0.1 to 3000, in particular 1 to 150 bar. Suitable polymerization reactors are, for example, autoclaves and stirred kettles which allow the corresponding application of pressure. The process can be carried out batchwise or continuously. The polymerization time is also determined by the polymerization temperature and can be up to 10 hours to achieve satisfactory yields. The polymerization is expediently terminated by adding hydrogen chloride in alcohol such as methanol. After washing the dilution or solvent phase with water and filtering, for example with the aid of an aluminum oxide column, it is advantageous to separate and dry the polymer or polymer mixture by evaporating the solvent or diluent.

The results obtained by the process according to the invention are shown in Table 1 and are sometimes surprising. In the homopolymerization of ethylene, relatively low molecular weight polymers with a highly branched structure are obtained. By copolymerizing ethylene with 1-hexene, the molecular weight of the copolymers obtained can be greatly increased compared to the ethylene homopolymer. The copolymerization of ethylene with methyl acrylate led to low molecular weight polymers with a relatively broad molecular weight distribution.

The available copolymers with polar comonomers can e.g. as a viscosity index improver in mineral oil, as a dispersing flow improver in diesel fuel, as a plasticizer for plastics or as a lubricant. The olefin polymers and copolymers can also advantageously be processed with other elastomeric or thermoplastic polymers to give polymer blends which, depending on the choice of the polymers, have good toughness or stickiness.

The following examples are intended to explain the invention further, but not to limit it. Unless otherwise stated, parts and percentages are by weight. The stated number and weight average molecular weights of the polymers were determined by gel permeation chromatography (GPC) using an HDPE standard. The structure (branches) of the polymers obtained were determined by NMR spectroscopy. In this connection, reference is made to the articles by DE Axelson et al, Macromolecules 12 (1979) 41-52; T. Usami et al. Macromolecules 17 (1984) 1757-1761 and JV 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 40% aqueous solution) were added dropwise. After stirring for 8 hours, a lemon-yellow suspension 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). iH-NMR analysis (in CDC1 ₃ ): ä 1.2 (24H, isopropyl CH ₃ ), 2.9 (4H, isopropyl), 7.2 (6H aromat.), 8.K2H, = 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 (wench - thyglyoxal) were 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 CDC1 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 using 2, 6-dimethylphenylamine as the amine. 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. ⁱ H-NMR analysis (in CDC1 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 used as the amine 2,6-diethylphenylamine. 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 using 2, 6-diethylphenylamine as the amine. The yield was 42.3% of theory.

Example 7

Synthesis of the intermediate product di (1-methoxy-cyclo-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) Cl2] (7 mmol) (COD = cyclooctadiene) in methanol and the resulting mixture was stirred at room temperature for 50 minutes, changing the color the suspension turned 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. Elemental 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-dimethyldiazabutadynyl] - [l-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 in accordance with Example 7 was suspended in 70 ml of methanol. 1.29 g (3.2 mmol) of the in accordance with Example 2 prepared 1, 4-di (2, 6-diisopropylphenyl) -2, 3-dimethyldiazabutadiene, the molar ratio of palladium to diazabutadiene ver- bond 1: 1.2. After stirring for about 3 hours, 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. Soon a crystalline sediment had formed, which was filtered off after 30 minutes, washed with diethyl ether and dried under vacuum. The yield was 73.7% of theory. ¹ H-NMR analysis (in CDC1 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 Catalyst 2P1-1:

[1,4-Di (2,6-diisopropylphenyl) -2, 3-dimethyldiazabutadienyl] - [l-methoxycycloocta-4-en-8σ, 4π] palladium tetrakis (pentafluorophenyl) borate.

The procedure was essentially the same as in Example 8, but using dimethylanilinium tetrahis (pentafluorophenyl) borate instead of ammonium hexafluorophosphate as the activator. The yield was 93.6% of theory.

Example 10

Synthesis of catalyst 1P1-1:

[1, -Di (2, 6-diisopropylphenyl) diazabutadienyl] - [1-methoxycycloocta-4-en-8σ, 4π] palladium tetrakis (pentafluorophenyl) borate.

The procedure was essentially as in Example 9, but the 1, 4-di (2, 6-diisopropylphenyl) diazabutadiene prepared according to Example 1 was used as ligand L1. The yield was 88.0% of the

Theory.

Example 11 Synthesis of Catalyst 6P1-1:

[1,4-di (2,6-diethylphenyl) -2, 3-dimethyl-diazabuta- dienyl] - [l-methoxy-cycloocta-4-en-8σ, 4π] palladium tetrakis (pentafluorophenyl) borate.

The procedure was essentially as in Example 9, but the ligand 1 used was the 1, -di (2, 6-diethylphenyl) -2, 3-dimethyl-diazabutadiene prepared according to Example 6. The yield was 97.5% of theory.

Example 12 (Polymerization Experiment Pi;

300 ml of dry toluene were placed in a 500 ml four-necked flask and 20 mmol of triisobutylaluminum and 2.83 mmol of the catalyst 1P1-1 prepared according to Example 10 were added. Ethylene was blown through the solution without pressure at a throughput of 40 liters per hour and a polymerization temperature of 55 ° C. was set. After 7 hours the polymerization was stopped by adding hydrogen chloride in methanol and the mixture was separated in a separatory funnel. The toluene phase was washed with water and then dried. After filtration through a neutral alumina column, the polymer was separated by evaporation of the toluene (7 ° C, 1 mbar, 3 hours) and analyzed. The result is shown in Table 1.

Example 13 (Polymerization Test P2)

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

Example 14 (Polymerization Test P3)

The procedure was essentially as in Example 12 (polymerisation test P1), but the catalyst 2P1-2 was used as the palladium complex catalyst. The test result is shown in Table 1.

Example 15 (Polymerization Test P4)

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

Example 16 (Polymerization Test P5)

150 ml of dry toluene and 150 ml of dry 1-hexene were placed in a 500 ml four-necked flask. After the addition of 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1, ethyl len with a throughput of 40 liters per hour without pressure through the solution, and set a polymerization temperature of 55 ° C. After a further 7 hours, the polymerization was terminated by adding hydrogen chloride in methanol. The resulting mixture was separated in a separatory funnel, the toluene phase washed with water and dried. After filtration through a neutral alumina column, the polymer was separated by evaporating the toluene (75 ° C; 0.1 mbar, 3 hours). The test result is shown in Table 1.

10

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

150 ml of dry toluene and 150 ml of dry 1-decene were placed in a 500 ml four-necked flask. After adding

15 20 mmoles of triisobutylaluminum and 2.83 mmoles of catalyst 2P1-1 were blown through the solution without pressure at a rate of 40 liters per hour. A polymerization temperature of 55 ° C. was then set and polymerization was carried out for 7 hours. Thereafter, the polymerization was carried out by adding hydrogen chloride

20 canceled in methanol. After separating the mixture in one

Separating funnel, the toluene phase was washed with water and then dried. After filtration through a neutral alumina column, the polymer was separated by evaporating the toluene (75 ° C; 0.1 mbar; 3 hours). The test result shows

25 Table 1.

Example 18 (Polymerization Test P7)

300 ml of dry toluene 30 were placed in a 500 ml four-necked flask and 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1 were added. Then propylene was passed through the solution at a throughput of 40 liters per hour without pressure, which was set to 55 ° C. After 7 hours the polymerization was terminated by adding hydrogen chloride in methanol 35 and the resulting mixture was separated in a separatory funnel. The toluene phase was washed with water and dried. After filtration through a neutral alumina column, the polymer was isolated by evaporating the toluene (75 ° C; 0.1 mbar; 3 hours). The test result is shown in Table 1.

40

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

300 ml of dry toluene was placed in a 500 ml four-necked flask and 20 mmol of triisobutylaluminum and 2.83 mmol 45 of the catalyst 2P1-1 were added. Then 1-butene was blown through the solution at a throughput of 40 liters per hour without pressure and a polymerization temperature of 55 ° C. was set. 7 hours later, the polymerization was stopped by adding hydrogen chloride in methanol. The resulting mixture was separated in a separatory funnel and the toluene phase was washed with water, dried and filtered through a neutral alumina column. The polymer was separated by evaporating the toluene (75 ° C; 0.1 mbar; 3 hours). The test result is shown in Table 1.

Example 20 (Polymerization Test P9)

120 ml of dry toluene and 3 g of methyl acrylate were placed in a 500 ml four-necked flask and 0.27 mmol of the catalyst 2P1-1 was added to the mixture. Ethylene was then blown through the mixture at a throughput of 40 liters per hour without pressure, a polymerization temperature of 54-56 ° C. having been set. After 7 hours the polymerization was stopped by adding hydrogen chloride in methanol. After filtration through a neutral alumina column, the polymer was separated by evaporating the toluene (75 ° C; 0.1 mbar; 3 hours). The test result is shown in Table 1.

Example 21 (Polymerization Test P10)

350 ml of dry cyclopentene were placed in a 500 ml four-necked flask and 4.9 mmol of triisobutylaluminum and 0.49 mmol of catalyst 2P1-1 were added. The polymerization was carried out at 55 ° C., the polymer precipitating out as a white powder. After 7 hours the polymerization was stopped by adding hydrogen chloride in methanol. The polymer was filtered off, washed with water and dried in a vacuum cabinet. It had a melting point of 250 ° C (DSC analysis).

Table 1

Results of the polymerisation experiments

The polymers of Ex. 15, 16 and 19 had on side groups:

Ex. 15 44.7 methyl; 29.2 ethyl; 12.0 butyl; 26.8 ≥hexyl; Ex. 16 62.0 methyl; 10.1 ethyl; 18.9 butyl; 15.5 ≥ hexyl; Ex. 19 62.7 methyl; 66.3 ethyl; 9.0 ≥ Hexyl.

Claims

claims

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 alkylaluminum compound, characterized in that the palladium complex has the formula (I) having,

[L ¹ Pd L ² ] ⁺ On "(I)

wherein Ll is a neutral bidentate palladium chelating, N, N '-disubstituted diazadiene ligand, L2 is an alkoxycycloalkene carbanion with 7 to 8 carbon 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 anion is an anion of a non or hardly esterifiable and weakly or non-coordinating acid.

2. The method according to claim 1, characterized in that mixtures of ethylene are polymerized with esters of acrylic acid and / or methacrylic acid.

3. The method according to claim 1 or 2, characterized in that the polymerization takes place in the presence of an aromatic hydrocarbon.

4. The method according to any one of claims 1 to 3, characterized in that the palladium complex used as ligand radical L2 has a carbanion of an l-alkoxy-cycloocta-4-en-8σ, π.

5. The method according to any one of claims 1 to 4, characterized in that the palladium complex used as ligand Ll 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, are an optionally substituted aromatic radical having 6 to 18 C atoms or optionally substituted heteroaromatic radical having at least one S, O or N heteroatom in the heteroaromatic and having 3 to 18 C -Atoms, R ³ and R ⁴ , the same or different, represent a hydrogen atom, a C ₈ -C ₈ hydrocarbon radical or R ³ and R ⁴ together represent a divalent, optionally substituted hydrocarbon radical having 2 to 18 carbon atoms.

6. The method according to any one of claims 1 to 5, characterized in that the anion is a tetrafluoroborate, tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, pentafluorophosphate or hexa-fluoranti - month anion.

7. Palladium complexes of the formula (I)

[L ¹ Pd L ² ] ⁺ On "(I)

in which L ^{1 represents} an N, N'-disubstituted diaza-butadiene ligand of the formula (II),

R ¹ -N = CR ³ -CR ⁴ = NR ² (II)

wherein R ¹ and R ² , identical or different, a phenyl radical substituted by at least one Ci-Cβ hydrocarbon radical, and R ³ and R ⁴ , identical or different, a hydrogen atom or a Cχ-Ci8 hydrocarbon radical or R ³ and R ^{4 in} common sam represent a divalent hydrocarbon radical with a total of up to 18 carbon atoms,

L ^{2 represents} a 1 -C 8 alkoxy-cycloocta-4-en-8σ, 4π ligand, and anion is 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 anion in formula (I) is a tetrafluoroborate, tetrakis [3, 5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, Hexafluorophosphate or hexafluoro-antimonate anion is.