KR20010102384A - Method for the Polymerization an Copolymerization of Monoolefins and Novel Palladium Complexes Therefor - Google Patents

Abstract

According to the present invention, monoolefins having 2 to 12 carbon atoms can be polymerized to form polymers or copolymers. The monoolefin is polymerized with a polar monomer, such as methylacrylate, optionally in the presence of a palladium complex of the formula [L ¹ Pd L ² ] ⁺ An ⁻ , with addition of an alkylaluminum compound, and also alone or in a mixture. In the Pd complex, L ¹ represents a neutral bidentate N, N′-disubstituted diazadiene ligand, preferably a diazabutadiene ligand; L ² is bonded to the palladium atom via σ bond and its C═C double bond forms a π-complexed bond with the palladium atom and has an alkoxycycloalkene carboion ion having cyclic atoms of 7 to 8 carbon atoms, preferably 1- Methoxy-cycloocta-4-ene-8π, 4σ ligand; An ^- represents an anion of a noncoordinating or weakly coordinating acid which does not form esters or forms slightly esters. The present invention also relates to novel Pd complex catalysts for polymerization and copolymerization.

Description

Method for the polymerization and copolymerization of monoolefins, and novel palladium complexes therefor {Method for the Polymerization an Copolymerization of Monoolefins and Novel Palladium Complexes Therefor}

The present invention relates to a process for the polymerization and copolymerization of monoolefins in the presence of certain palladium complexes and to novel palladium complexes suitable for this purpose.

The use of transition metal complexes such as palladium or nickel complexes as catalysts for the polymerization or copolymerization of monoolefins has been described several times. Italian patent application MI 91A / 2969 discloses two cationic N- or P-containing chelate-forming ligands per Pd atom in the presence of a cationic Pd complex comprising two anions of a non-coordinating acid which virtually do not form esters. It is known that polyolefins can be obtained by copolymerizing monoolefins such as ethylene with carbon monoxide. The disadvantage of this method is that high temperatures and high pressures must be used to achieve relatively high polymer yields. According to EP-A 0728791, in addition to the bidentate N- or P-containing chelate forming ligand, there are C═C double bonds and their anions form σ bonds with Pd atoms and their C═C double bonds with Pd atoms Similar polyketones were prepared by copolymerization of carbon monoxide with olefinically unsaturated compounds such as ethylene, in particular styrene, in the presence of cationic Pd complexes containing bidentate anions to form bonds. The disadvantage of this polyketone production method is due to the combination of liquid halogen-containing compounds of the Pd complex, for example dichloroethane or chloroform (ie halogenated solvents are essential).

L. Johnson et al., J. Amer. Chem. Soc. 1995, 117, pp. 6414-6415], the diimine ligand of the metal-dimethyl especially H (OEt _{2) 2} ⁺ B from the complex with (C ₆ F _{5) 4} ^- in using the cationic activity produced by the proton addition reaction Pd (II) and Ni (II ) Catalyst complexes are described. The resulting diethyl ether adduct has a diethyl ether as a ligand and a tetrakis (pentafluorophenyl) borate anion in the metal complex cation, and polymerizes a monoolefin such as ethylene, propylene or 1-hexene to produce a relatively high molecular weight polymer. to provide.

Johnson's later publication, L. Johnson et al., J. Amer. Chem. Soc. 1996, 118, pp. 267-268 describes the use of cationic active methyl complexes of Pd (II) for copolymerization of ethylene or propylene with acrylates, which process forms, or chelates, cationic active Pd complexes having ethylene as a ligand. The insertion of acrylate ligands results in the formation of relatively high molecular weight branched copolymers. In patent application WO 96/23010 to Johnson et al., Monoolefins are polymerized in the presence of transition metals such as Ti, Zr, Sc, V, Cr, Fe, Co, Ni, Pd, or rare earth metals to form highly branched polymers. Wherein the metal complex contains a bidentate N, N'-disubstituted diazadiene ligand. The result of the polymerization reaction achieved in the presence of the metal complex depends in particular on the structure of the transition metal complex used. Relatively high molecular weight copolymers of ethylene and methyl acrylate can be prepared using Pd complexes containing diimine ligands and additionally containing ether or ester adducts in the complex. A disadvantage of the process mentioned is that the polymerization-active catalyst center is formed starting from the metal-dialkyl complex.

It is an object of the present invention, given the well-known fact that the product properties of the resulting polymers and copolymers depend on the specific microstructure of the transition metal complex used, the polymerization and copolymerization of monoolefins and polar comonomers using various transition complexes. Would like to develop.

The inventors have found that this object is achieved by copolymerizing ethylene with a polar comonomer, such as methyl acrylate, in the presence of a cationic active Pd complex having alkoxycycloalkene carboanions as ligand L ¹ and ligand L ² as chelated diimines. It has been found that this can be achieved by obtaining topographic polyethylene or copolymers.

The present invention relates to monoolefins having 2 to 12 carbon atoms or mixtures thereof and optionally olefins, with or without the addition of an alkylaluminum compound in the presence of a Pd chelate complex of formula (I) having an N, N'-disubstituted diazadiene ligand Methods of polymerization and copolymerization with unsaturated polar monomers are provided.

^{[L 1 Pd L 2] +} An -

Where

L ¹ is an uncharged bidentate N, N'-disubstituted diazadiene ligand that forms chelate with palladium,

L ² is an alkoxycycloalkene carboion having 7 to 8 carbon atoms, which is bonded to a palladium atom via σ-bond and its C═C double bond forms a π-complex with the palladium atom,

An ⁻ is an anion of a weakly coordinating or noncoordinating acid that does not substantially form an ester.

Suitable ligands L ¹ for cationic active Pd complexes are the corresponding bidentate N, N′-disubstituted diazadiene ligands that chelate with Pd atoms described in patent application WO 96/23010. These include diamines of the formula: which act as bidentate ligands that form metal chelates.

(I) (II) (IV)

Where

R ¹ and R ² are the same or different and each is a substituted or unsubstituted hydrocarbon radical, or a substituted or unsubstituted heteroaromatic radical,

R ³ and R ⁴ are the same or different and each is a hydrogen atom, a substituted or unsubstituted hydrocarbon radical, or R ³ and R ⁴ together form a substituted or unsubstituted divalent hydrocarbon radical,

R ⁵ and R ⁸ are the same or different and each is a substituted or unsubstituted hydrocarbon radical or a substituted or unsubstituted heteroaromatic radical,

R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and each is a hydrogen atom or a substituted or unsubstituted hydrocarbon radical, or R ⁹ and R ¹⁰ together are a substituted or unsubstituted divalent hydrocarbon radical,

R ¹¹ and R ¹² are the same or different and each is a substituted or unsubstituted hydrocarbon radical,

R ¹³ and R ¹⁴ are the same or different and each is a hydrogen atom, a substituted or unsubstituted hydrocarbon radical, or together form a substituted or unsubstituted divalent hydrocarbon radical.

Among the diazadienes coordination with Pd atoms in a bidentate manner, the N, N'-disubstituted diazabutadienes of the formula (II) are preferred, the larger and bulkier substituents R ¹ and / or R of two N atoms ² , for example substituted or unsubstituted aromatic or substituted or unsubstituted heteroaromatic radicals are preferred. Suitable substituents R ¹ and R ^2, which may be the same or different, are substituted phenyl radicals, in particular phenyl radicals substituted by C ₁ -C ₈ -alkyl groups in the 2,4 and / or 6 positions, for example 2 -Methylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl, 2-tert-butylphenyl, 2,6-diethylphenyl or 2,6-diisopropylphenyl. Still other suitable substituents R ¹ and R ² are other heteroaromatic radicals containing hetero atoms, in particular S-, O- and / or N-atoms, near the 2-pyrimidyl and C atoms bonded to the imino-N atoms. to be.

Substituents R ¹ , R ² , R ⁵ and R ^{6 which} have been found to be very useful are those in which a C atom bonded to an imino-N atom is bonded to at least two other carbon atoms. Particularly preferred substituents R ¹ , R ² , R ⁵ and R ⁶ are 2,6-diethylphenyl and 2,6-diisopropylphenyl.

Very useful radicals R ³ and R ⁴ are hydrogen atoms, preferably alkyl radicals having 1 to 4 carbon atoms, for example methyl radicals, alkylene radicals such as butylene or 2-ethylbutylene and also divalent substitutions or unsubstituted Ring aromatic radicals such as 1,8-naphthylene.

The preparation of uncharged N, N'-disubstituted diazadiene ligands L ¹ is known and can be carried out, for example, by reaction of suitably configured amines with glyoxal or 1,2-diketone. Preferred examples of the preparation of the ligand L ¹ are shown in Examples 1 to 6 below.

Ligand L ² forms a chelate with Pd and has 7 or 8 carbon atoms in the ring and is bonded to the Pd atom via σ bond and its C═C double bond forms a π-complex with the Pd atom It is an anion. Alkoxy derivatives of (preferably methoxy) cycloalkene carboion ions, in which the number of carbon atoms of the alkoxy group may in particular be from 1 to 8, are known to the cyclooctadiene- or norbornadi by known methods, in particular by the addition of alcohols in the presence of alkali It can be prepared from the N-Pd complex. A suitable synthesis of di (1-methoxycyclooct-4-ene-8σ, 4π) -μ, μ'-dichloropalladium (formula VI) starting from cyclooctadiene-Pd complex (V) is shown in the following scheme And described in Example 7 below.

L obtained as described in Examples 8-11 below²-Dichloro-Pd complex (V) to uncharged diazadiene ligand L^OneReacted with the [L]^OnePd L²]⁺An^-It may be converted to a catalyst complex (eg, formula VII).

This synthesis yields high yields of stable Pd catalyst complexes by preventing unstable R-Pd-R intermediates.

Possible anions An ⁻ are, in particular, weakly coordinating or noncoordinating acids which do not form esters or in fact form esters other than hydrogen halides, having _a pK _a of less than 3, preferably less than 2. Suitable anions are known to those skilled in the art and often have a bulky structure. Examples of suitable anions An ⁻ include tetrafluoroborate, hexafluorophosphate, hexafluoroantimonate, p-toluenesulfonate, trifluoromethanesulfonate, tetraphenylborate, tetrakis [3,5-bis ( Trifluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate, among others hexafluorophosphate, hexafluoroantimonate, tetrafluoroborate, tetrakis [3,5-bis (tri Fluoromethyl) phenyl] borate and tetrakis (pentafluorophenyl) borate are preferred. For coordination capacity see, for example, W. Beck et al. Chem. Rev. 88 (1988) 1405-1421 and SH Strauss, Chem. Rev. 93 (1993) 927-942.

The present invention also provides novel specific palladium complexes of formula I, wherein

a) L ¹ is a formula II wherein R ¹ and R ² are the same or different and each is a phenyl radical substituted with one or more C ₁ -C ₈ -hydrocarbon radicals, R ³ and R ⁴ are the same or different and each is 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 hydrocarbon radical having 18 or less carbon atoms, preferably 2 to 12 carbon atoms), N'-disubstituted diazabutadiene ligand,

b) L ² is 1-C ₁ -C ₈ -alkoxycyclooct-4-ene-8σ, 4π ligand,

c) An ⁻ is an anion of a weakly coordinating acid, preferably a non-coordinating acid, which does not form esters or substantially does not form esters as indicated above, and An ⁻ is preferably tetrafluoroborate, tetrakis [3,5- Bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate or hexafluoroantimonate.

Suitable olefins as monomers or comonomers are aliphatic and cycloaliphatic monoolefins with olefinic C═C double bonds having 2 to 12 carbon atoms and which are not part of the aromatic system. Preference is given to monoolefins which are hydrocarbons. Preferred monoolefins for homopolymerization are monoolefins having 2 to 6 carbon atoms, in particular ethylene, propylene and cyclopentene.

Olefinically unsaturated polar monomers as comonomers are, in particular, monoolefinic monomers having C═O groups which can complex with cationic active Pd atoms, depending on their structure. Examples that may be mentioned are acrylic acid, methacrylic acid, esters thereof and also vinyl ketones, among which alkyl esters of methacrylic acid, in particular acrylic acid are particularly preferred. Among them, methyl acrylate is particularly preferred.

The inventors have found that the Pd complex used according to the invention is advantageous when it is often used with the addition of alkylaluminum compounds in which at least one alkyl group having 1 to 25 carbon atoms is bonded to an aluminum atom. In the alkylaluminum compound, a halogen atom or an oxygen atom (for example, an oxygen atom of an alkoxy group) may be bonded to an aluminum atom. Examples of suitable aluminum compounds include triisobutylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxanes (oligomers of the formula [MeAlO] _n where Me = methyl and n is preferably 5 to 30), or There is a modified methylaluminoxane in which about 20 to 30 mol% of methyl groups are substituted with isobutyl groups. The amount of the alkylaluminum compound added is advantageously 5 to 15 mol per mol of the Pd complex catalyst used.

Based on the amount of Pd complex used, monomers and co-monomers are used in excess in the polymerization with the organometallic catalyst. For example, the catalytic amount is 10 ^-7 to 10 ^-3 g of palladium atoms per mol of ethylenic / olefinically unsaturated compound (monomer or monomer + comonomer).

The polymerization process of the invention is carried out by contacting the Pd complex with the alkylaluminum compound, if desired, with the monomer, preferably in the presence of an organic diluent or solvent. Organic diluents that have been found to be very useful are organic hydrocarbons, in particular aromatic hydrocarbons such as benzene or toluene.

The polymerization temperature is generally in the range of -20 ° C to + 300 ° C, in particular + 10 ° C to + 150 ° C. Particular preference is given to using polymerization temperatures in the range from + 20 ° C to + 120 ° C. This method can be carried out at a pressure slightly below atmospheric pressure, atmospheric to high pressure. In general, the pressure in the polymerization is in the range from 0.1 to 3000 bar, in particular from 1 to 150 bar. Suitable polymerization reactors are, for example, autoclaves and stirred vessels which can use appropriate pressures. This method can be carried out batchwise or continuously. The polymerization time to achieve a satisfactory yield, determined in part by the polymerization temperature, may be up to 10 hours. The polymerization reaction is conveniently stopped by the addition of hydrogen chloride in alcohols such as methanol. It is advantageous to wash the diluent or solvent phase with water, for example using an aluminum oxide column and then to evaporate the solvent or diluent to separate the polymer or polymer mixture and to dry the polymer.

The results obtained in the process of the invention are shown in Table 1 below, some of which are surprising. For example, relatively low molecular weight polymers with strong branched structures have been obtained in homopolymerization of ethylene. Copolymerization of ethylene with 1-hexene can cause the molecular weight of the copolymer obtained to be significantly increased over ethylene homopolymers. Copolymerization of ethylene with methyl acrylate provides a low molecular weight polymer with a relatively broad molecular weight distribution.

Copolymers obtainable with polar comonomers can be used, for example, as viscosity index improvers for mineral oils, as dispersive flow improvers for diesel fuels, as plasticizers for polymers, or as lubricants. Olefin polymers and copolymers can be processed with other elastomeric or thermoplastic polymers to produce polymer blends with good toughness and tack, depending on the choice of the polymer.

The following examples illustrate the invention but do not limit the invention. Unless indicated otherwise, parts and percentages are by weight. The number average molecular weight and weight average molecular weight of the polymers were determined by gel permeation chromatography (GPC) using HDPE standards. The structure (branch type) of the obtained polymer was determined by NMR spectroscopy. In the present application, D. E. Axelson et al., Macromolecules 12 (1979) 41-52; 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% concentration solution) was mixed with 300 ml of methanol and treated with 1 ml of formic acid. Then 21.76 g of 40% strength glyoxal (150 mmol as 40% concentration aqueous solution) was added dropwise. Stir for 8 hours to give a lemon yellow suspension which was filtered and the solid washed with 200 ml of cold methanol. The product obtained was dried under reduced pressure. The yield was 32.8% (18.5 g) of theoretical values. ¹ H-NMR analysis (in CDCl ₃ ): δ1.2 (24H, isopropyl CH ₃ ), 2.9 (4H, isopropyl), 7.2 (6H aromatic), 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% concentration solution) were mixed with 100 ml of methanol and then treated with 1 ml of formic acid. Then 4.2 ml (45.14 mmol, 99% strength solution) of biacetyl (dimethylglyoxal) was added dropwise. After stirring for 8 hours a lemon yellow suspension was obtained which was filtered and the solid was washed with 200 ml of methanol. The product obtained was dried under reduced pressure. The yield was 82.4% of the theoretical value. ¹ H-NMR analysis (in CDCl ₃ ): δ1.2 (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

This process was essentially the same as in Example 1, but 2,6-dimethylphenylamine was used as the amine. The yield was 10.3% of the theoretical value.

<Example 4>

Synthesis of Ligand 1-4: 1,4-di (2,6-dimethylphenyl) -2,3-dimethyldiazabutadiene

This process was essentially the same as in Example 2, but 2,6-dimethylphenylamine was used as the amine. The yield was 51.7% of the theoretical value. ¹ H-NMR analysis (in CDCl ₃ ): δ 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

This process was essentially the same as in Example 1, but 2,6-diethylphenylamine was used as the amine. The yield was 23.0% of the theoretical value.

<Example 6>

Synthesis of Ligand 1-6: 1,4-di (2,6-diethylphenyl) -2,3-dimethyldiazabutadiene

This process was essentially the same as in Example 2, but 2,6-diethylphenylamine was used as the amine. The yield was 42.3% of the theoretical value.

<Example 7>

Synthesis of Intermediate Di (1-methoxycyclooct-4-ene-8σ-4π) -μ, μ'-dichloropalladium

0.8 g of anhydrous sodium carbonate (7.5 mmol) was added to a yellow suspension of [Pd (COD) Cl ₂ ] (7 mmol) (COD = cyclooctadiene) in methanol, the resulting mixture was stirred at room temperature for 50 minutes, and the suspension The color of white became white. The product was filtered off and washed with cold methanol and diethyl ether. The product was dried under reduced pressure and the yield was 84% of theory. Elemental analysis yielded the following values:

C: 38%; H: 5.3%; Cl: 13.0% (Theoretical value: C: 37.7%; H: 4.7%; Cl: 12.8%).

<Example 8>

Synthesis of Catalyst 2P1-2: [(1,4-di (2,6-diisopropylphenyl) -2,3-dimethyldiazabutadienyl] [1-methoxycyclooct-4-ene-8σ- 4π] palladium hexafluorophosphate

0.75 g (1.33 mmol) of solid [Pd (COD-OCH ₃ ) Cl] ₂ prepared as described in Example 7 were suspended in 70 ml of methanol. 1.29 g (3.2 mmol) of 1,4-di (2,6-diisopropylphenyl) -2,3-dimethyldiazabutadiene prepared as described in Example 2 were added to the suspension. The molar ratio of palladium to diazabutadiene was 1: 1.2. After stirring for about 3 hours, a yellow solution formed. A solution of 0.52 g (3.2 mmol) of ammonium hexafluorophosphate in 5 ml of methanol was added dropwise to the resulting solution. A crystalline precipitate formed soon after, filtered after 30 minutes, washed with diethyl ether and dried under reduced pressure. The yield was 73.7% of the theoretical value. ¹ H-NMR analysis (in CDCl ₃ ) gave the following:

1.1 ppm 3H d isopropyl methyl

1.21 ppm 3H d isopropyl methyl

1.39 ppm 3H d isopropyl methyl

1.37 ppm 3H d isopropyl methyl

1.45 ppm 12H d isopropyl methyl

CH _{2 in} 1.30 ppm 8H dd 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] [1-methoxycyclooct-4-ene-8σ, 4π] palladium tetrakis (pentafluor Rophenyl) borate

This process was essentially the same as in Example 8, but dimethylanilinium tetrakis (pentafluorophenyl) borate was used as the activator instead of ammonium hexafluorophosphate. The yield was 93.6% of the theoretical value.

<Example 10>

Synthesis of Catalyst 1P1-1:

[1,4-di (2,6-diisopropylphenyl) diazabidienyl] [1-methoxycyclooct-4-ene-8σ, 4π] palladium tetrakis (pentafluorophenyl) borate

This process was essentially the same as in Example 9, but 1,4-di (2,6-diisopropylphenyl) diazabutadiene prepared as described in Example 1 was used as ligand L ¹ . The yield was 88.0% of the theoretical value.

<Example 11>

Synthesis of Catalyst 6P1-1:

[1,4-di (2,6-diethylphenyl) -2,3-dimethyldiazabutadiethyl] [1-methoxycyclooct-4-ene-8σ, 4π] palladium tetrakis (pentafluorophenyl Baud rate

This process was essentially the same as in Example 9, but using 1,4-di (2,6-diethylphenyl) -2,3-dimethyldiazabutadiene prepared as described in Example 6 as ligand L ¹ It was. The yield was 97.5% of the theoretical value.

<Example 12 (polymerization experiment P1)>

300 ml of anhydrous toluene were placed in a 500 ml 4-neck flask and 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 1P1-1 prepared as described in Example 10 were added. Under atmospheric pressure, ethylene was blown through the solution at a flow rate of 40 l / h and the polymerization temperature was set at 55 ° C. After 7 hours, the polymerization reaction was stopped by adding hydrogen chloride in methanol and the mixture was separated in a separating funnel. The toluene phase was washed with water and then dried. After filtration through a neutral aluminum oxide column, toluene was evaporated (7 ° C., 1 mbar, 3 hours) to separate and analyze the polymer. The results are shown in Table 1 below.

<Example 13 (Polymerization Experiment P2)>

This process was essentially the same as in Example 12, but the catalyst used was Catalyst 6P1-1, prepared as described in Example 11. The results are shown in Table 1 below.

<Example 14 (polymerization experiment P3)>

This process was essentially the same as in Example 12 (polymerization experiment P1), but the palladium catalyst complex used was 2P1-2. The experimental results are shown in Table 1 below.

<Example 15 (Polymerization Experiment P4)>

This process was essentially the same as in Example 12, but the catalyst used was Catalyst 2P1-1, prepared as described in Example 9. The experimental results are shown in Table 1 below.

<Example 16 (polymerization experiment P5)>

150 ml of anhydrous toluene and 150 ml of anhydrous 1-hexene were placed in a 500 ml four-neck flask. After addition of 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1, ethylene was blown through the solution under atmospheric pressure at a flow rate of 40 l / h and the polymerization temperature was set at 55 ° C. After 7 hours, the polymerization was stopped by the addition of hydrogen chloride in methanol. The resulting mixture was separated in a separating funnel and the toluene phase was washed with water and then dried. After filtration through a neutral aluminum oxide column, toluene was evaporated (75 ° C., 0.1 mbar, 3 hours) to separate and analyze the polymer. The experimental results are shown in Table 1 below.

Example 17 Polymerization Experiment P6 (Ethylene / 1-Deken)

150 ml of anhydrous toluene and 150 ml of anhydrous 1-deken were placed in a 500 ml four-neck flask. After addition of 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1, ethylene was blown through the solution under atmospheric pressure at a flow rate of 40 l / h. The polymerization temperature was then set to 55 ° C. and the polymerization reaction was carried out for 7 hours. Thereafter, hydrogen chloride in methanol was added to stop the polymerization reaction. The mixture was separated in a separating funnel and the toluene phase was washed with water and then dried. After filtration through a neutral aluminum oxide column, toluene was evaporated (75 ° C., 0.1 mbar, 3 hours) to separate and analyze the polymer. The experimental results are shown in Table 1 below.

<Example 18 (polymerization experiment P7)>

300 ml of anhydrous toluene were placed in a 500 ml 4-neck flask and 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1 were added. Propylene was then blown at a flow rate of 40 l / h under atmospheric pressure through a solution having a temperature set to 55 ° C. After 7 hours, the polymerization reaction was stopped by addition of hydrogen chloride in methanol, and the resulting mixture was separated in a separating funnel. The toluene phase was washed with water and then dried. After filtration through a neutral aluminum oxide column, toluene was evaporated (75 ° C., 0.1 mbar, 3 hours) to separate and analyze the polymer. The experimental results are shown in Table 1 below.

Example 19 (polymerization experiment P8) (1-butene)

300 ml of anhydrous toluene were placed in a 500 ml 4-neck flask, to which 20 mmol of triisobutylaluminum and 2.83 mmol of catalyst 2P1-1 were added. Subsequently, 1-butene was blown at a flow rate of 40 l / h under atmospheric pressure through a solution having a temperature set at 55 ° C. After 7 hours, the polymerization reaction was stopped by addition of hydrogen chloride in methanol. The resulting mixture was separated in a separating funnel, the toluene phase was washed with water and then dried and filtered through a neutral aluminum oxide column. Toluene was evaporated (75 ° C., 0.1 mbar, 3 hours) to separate the polymer. The experimental results are shown in Table 1 below.

<Example 20 (polymerization experiment P9)>

120 ml of anhydrous toluene and 3 g of methyl acrylate were placed in a 500 ml 4-neck flask and 0.27 mmol of catalyst 2P1-1 was added to the mixture. Ethylene propylene was blown at a flow rate of 40 l / h under atmospheric pressure through a mixture having a polymerization temperature set at 54 to 55 ° C. After 7 hours, the polymerization reaction was stopped by addition of hydrogen chloride in methanol. After filtration through a neutral aluminum oxide column, toluene was evaporated (75 ° C., 0.1 mbar, 3 hours) to separate the polymer. The experimental results are shown in Table 1 below.

<Example 21 (Polymerization Experiment P10)>

350 ml of anhydrous cyclopentene were placed in a 500 ml 4-neck flask, and 4.9 mmol of triisobutylaluminum and 0.49 mmol of catalyst 2P1-1 were added. The polymerization reaction was carried out at 55 ° C., and the polymer precipitated out as a white powder. After 7 hours, the polymerization reaction was stopped by addition of hydrogen chloride in methanol. The polymer was filtered off, washed with water and dried under reduced pressure. Its melting point was 250 ° C. (DSC analysis).

Result of polymerization experiment Example 12 13 14 15 16 17 18 19 20 Polymerization experiment P1 P2 P3 P4 P5 P6 P7 P8 P9 Pd Catalyst 1P1-1 6P1-1 2P1-2 2P1-1 2P1-1 2P1-1 2P1-1 2P1-1 2P1-1 Monomer Ethylene Ethylene Ethylene Ethylene Ethylene + 1-hexene Ethylene + 1-deken Propylene 1-butene Ethylene + Methyl Acrylate M _n kg / mol 3500 9200 11200 20000 43600 16900 2400 4270 3000 M _w kg / mol 7400 18410 28000 39300 78000 66000 40500 7300 10000 M _n / M _w 2.10 2.00 2.50 1.96 1.79 3.90 1.69 1.71 3.33 ₃ CH total (1/1000 C) 98.3 115.0 118.2 122.7 106.5 80.0 210.0 138.0 The polymers of Examples 15, 16 and 19 have the following side chain groups: Example 15: 44.7 methyl; 29.2 ethyl; 12.0 butyl; 26.8 ≧ hexyl; Example 16: 62.0 methyl; 10.1 ethyl; 18.9 butyl; 15.5 ≧ hexyl; Example 19: 62.7 methyl; 66.3 ethyl; 9.0≥hexyl.

Claims (8)

A process for the polymerization and copolymerization with monoolefins having 2 to 12 carbon atoms or mixtures thereof and optionally olefinically unsaturated polar monomers, with or without the addition of an alkylaluminum compound in the presence of a palladium complex of formula (I). <Formula I> [L^OnePd L²]⁺An^- Where L ¹ is an uncharged bidentate N, N'-disubstituted diazadiene ligand that forms chelate with palladium, L ² is an alkoxycycloalkene carboion having 7 to 8 carbon atoms, which is bonded to a palladium atom via σ-bond and its C═C double bond forms a π-complex with the palladium atom, An ⁻ is an anion of a weakly coordinating or noncoordinating acid which does not form esters or substantially forms esters. The process of claim 1 wherein the mixture of ethylene is polymerized with esters of acrylic acid and / or methacrylic acid. The process according to claim 1 or 2, wherein the polymerization is carried out in the presence of an aromatic hydrocarbon. The method according to any one of claims 1 to 3, wherein the ligand L ² in the palladium complex used is a carboion ion of 1-alkoxycyclooct-4-ene-8σ, 4π. The method according to any one of claims 1 to 4, wherein the ligand L ¹ in the palladium complex used is a diazabutadiene ligand of formula II. R ¹ -N = CR ³ -CR ⁴ = NR ² Where R ¹ and R ² are the same or different and each has a substituted or unsubstituted aromatic radical having 6 to 18 carbon atoms, or a substituted or unsubstituted carbon atom having 3 to 18 carbon atoms, having at least one S-, O- or N-heteroatom of a heteroaromatic; Ring heteroaromatic radicals, R ³ and R ⁴ are the same or different and are each a hydrogen atom, a C ₁ -C ₁₈ -hydrocarbon radical, or R ³ and R ⁴ together form a substituted or unsubstituted divalent hydrocarbon radical having 2 to 18 carbon atoms. The anion An ⁻ is tetrafluoroborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate according to any one of claims 1 to 5. , Pentafluorophosphate or hexafluoroantimonate anion. Palladium complex of formula (I) <Formula I> [L^OnePd L²]⁺An^- Where L ¹ is an N, N'-disubstituted diazabutadiene ligand of Formula II <Formula II> R ¹ -N + CR ³ -CR ⁴ = NR ² Wherein R ¹ and R ² are the same or different and each is a phenyl radical substituted with one or more C ₁ -C ₈ -hydrocarbon radicals; R ³ and R ⁴ are the same or different and each is a hydrogen atom, C ₁ -C ₁₈ A hydrocarbon radical, or R ³ and R ⁴ together form a divalent hydrocarbon radical having up to 18 carbon atoms, L ² is a 1-C ₁ -C ₈ -alkoxycyclooct-4-ene-8σ, 4π ligand, An ⁻ is an anion of a weak coordinating or uncoordinating acid that does not form esters or substantially does not form esters. The compound of claim 7, wherein the anion An ⁻ of formula I is tetrafluoroborate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate, tetrakis (pentafluorophenyl) borate, hexafluorophosphate Or hexafluoroantimonate anion.