TW201542293A - Dimerization of olefins - Google Patents

Abstract

The invention relates to a catalyst system for the preparation of dimers by reaction of olefins over a nickel-containing catalyst, to the use of this catalyst and of the catalyst system, and to a process for dimerizing olefins.

Description

Dimerization of olefins

The present invention relates to a catalyst system for preparing a dimer by reacting an olefin containing a nickel-containing catalyst, the catalyst and the use of the catalyst system, and a method of dimerizing a olefin.

Oligomers of low molecular weight olefins (especially dimers of C ₃ -C ₅ olefins) are, for example, intermediates used in the preparation of aldehydes, carboxylic acids and alcohols. The C ₈ olefins derived from linear butenes can be converted to the corresponding sterols by hydroformylation and subsequent hydrogenation, which in turn are used primarily for the manufacture of plasticizers.

The oligomerization of alkenes, especially propylene and butene, is carried out industrially in a homogeneous phase using a solution catalyst or heterogeneously using a solid catalyst or a two-phase catalyst system.

In the case of this heterogeneous catalytic process, oligomerization using acidic catalysts has long been established. In this art, for example, zeolite or phosphoric acid/carriers are used. In this case, a mixture of isomers of branched type olefins is obtained. An example of the acidic catalysis of oligomerization of such olefins is found in WO 92/13818.

For non-acidic heterogeneous catalytic oligomers of olefins having high dimer selectivity, nickel compound/carrier materials are frequently utilized in the art. A catalyst of this type is a fixed bed nickel catalyst used in the OCTOL method of Evonik Industries AG (Hydrocarbon Process., Int. Ed. (1988) 65 (2, Sect. 1, 31-33). Supported nickel catalysts for use are known. What is described in WO 95/14647 is a nickel catalyst for the oligomerization of olefins having a support material consisting of the following components: titanium oxide and / or zirconium oxide, aluminum oxide and silicon oxide and free of a number of alkali metal oxides. using these catalysts, a mixture of linear butenes system to select the rate is less than 75% of C ₈ alkenes to form oligomers.

Homogeneous catalytic schemes are described, for example, by A. Chauvel and G. Lefebvre in Petrochemical Processes, Volume 1, Technip (1989), pages 183 to 187. A homogeneous catalytic process practiced throughout the world is the use of oligomerization of soluble nickel complexes known as the DIMERSOL process (see Yves Chauvin, Helene Olivier, "Applied Homogeneous Catalysis with Organometallic Compounds", edited by Boy Cornils , Wolfgang A. Herrmann, Verlag Chemie, 1996, 258-368).

A disadvantage of the conventional homogeneous catalysis process is that the catalyst leaves the reactor along with the reaction product and the unconverted reactant and must be separated from them. This method requires a post-treatment step and produces a waste stream. Since the product formed by the catalyst is generally not regenerated to obtain an active catalyst, there is also a catalyst cost.

These shortcomings are partially removed with the development of the DIFASOL method. go with. This method is described, for example, in An introduction to Ionic Liquids by Michael Freemantle, Royal Society of Chemistry (2009), pages 248 to 249. Among them, the ionic liquid system is used in combination with an alkyl aluminum chloride as a polar phase. The nickel catalyst used in the solution state in the ionic liquid is separated from the product phase and thus remains in the reactor. However, due to the presence of an acidic center in the ionic liquid, non-insignificant proportions of the reactants are oligomerized via a cation machine and result in the formation of relatively high chain branched product oligomers.

The published patent specification WO 98/47616 discloses a system which greatly prevents the acid catalyzed machine rotation and also allows the product to increase linearity via the use of a buffer base.

It is an object of the present invention to provide an improved catalyst system which results in greater monomer conversion and/or higher dimer selectivity.

Surprisingly, it has been found that the catalyst of claim 1 of the patent application, such as the method of claim 12 and the use of items 14 and 15 of the patent application, meets this purpose.

The subject matter of this patent is a catalyst system comprising a catalyst phase comprising at least one organic halide salt, at least one nickel (II) catalyst, at least one precursor, and at least one buffer.

The organic halide salt in the precursor preferably forms an ionic liquid. The ionic liquid is an organic salt which is liquid at a temperature lower than 100 ° C, and the salt is not in a solution state in a solvent (water).

The ionic liquid preferably has a melting point at 1 bar of not more than 100 ° C, more particularly not more than 80 ° C, more preferably not more than 50 ° C, more particularly not more than 30 ° C.

In a preferred embodiment, the precursor is a Lewis acid or a Lewis acid mixture, more particularly a formula R _n MX _3-n and/or R _m M ₂ X _6-m , wherein R is C _1- C ₆ alkyl, M is aluminum, boron, gallium or iron (III), X is a halogen or an alkoxy group having 1 to 4 carbon atoms, n is 1, 2 or 3, and m is 1, 2 or 3.

In one embodiment, the precursor is Lewis acid. Suitable precursors include AlCl ₃ , Me ₂ Al ₂ Cl ₄ , Me ₄ Al ₂ Cl ₂ , Me ₃ Al, Et ₂ Al ₂ Cl ₄ , Et ₄ Al ₂ Cl ₂ , Et ₃ Al, iPr ₂ Al ₂ Cl ₄ iPr ₄ Al ₂ Cl ₂ , iPr ₃ Al, iBu ₂ Al ₂ Cl ₄ , iBu ₄ Al ₂ Cl ₂ , iBu ₃ Al, Et ₃ Al ₂ Cl ₃ and Et ₂ AlOEt. In a preferred embodiment, the precursor is selected from the group consisting of AlCl ₃ , Me ₂ Al ₂ Cl ₄ , Me ₄ Al ₂ Cl ₂ , Et ₂ Al ₂ Cl ₄ , Et ₄ Al ₂ Cl ₂ , iPr ₂ Al ₂ Cl ₄ , a group consisting of iPr ₄ Al ₂ Cl ₂ , iBu ₂ Al ₂ Cl ₄ , iBu ₄ Al ₂ Cl ₂ , Et ₃ Al ₂ Cl ₃ , Et ₂ AlOEt, and mixtures thereof. In a similar preferred embodiment, the precursor is selected from the group consisting of AlCl ₃ , Me ₂ Al ₂ Cl ₄ , Et ₂ Al ₂ Cl ₄ , iPr ₂ Al ₂ Cl ₄ , iBu ₂ Al ₂ Cl ₄ , Et ₃ Al ₂ Cl _3. A group consisting of Et ₂ AlOEt and mixtures thereof.

In a particularly preferred embodiment, the nickel (II) catalyst is selected from the group consisting of NiZ ₂ L ₂ , NiZ'L ₂ , NiZ ₂ L', NiZ'L', NiY ₂ , NiY', wherein Z is a ligand with a single negative charge, Z' is a ligand with double negative charge, Y is a double-dentate chelating ligand with a single negative charge, and Y' is a tetradentate with double negative charge Ligand, L is a neutral ligand, and L' is a neutral bidentate ligand.

Examples of suitable ligands with a single negative charge are halides (such as fluorides, chlorides, bromides, and iodides), acetates (OAc), third-butoxides (OtBu), ethoxylates ( OEt) and methoxide (OMe).

Suitable ligands with double negative charge are tartrate (tart) and oxalate (ox).

Suitable intermediate ligands include, in particular, substituted trialkylphosphanes such as substituted trimethylphosphine (PMe ₃ ), triethylphosphine (PEt ₃ ), substituted tricycloalkyl a phosphine such as a substituted tricyclohexylphosphane (PCy ₃ ), a substituted triarylphosphine (PAr ₃ ) such as a substituted triphenylphosphinone (TPP), and a substituted benzyl group Phenylphenylphosphine (BMPP), the neutral ligand is preferably trimethylphosphine.

Suitable neutral chelating ligands are, for example, ethylenediamine (en), acetoacetone (acac), 8-hydroxyquinoline, 2,2'-bipyridyl (bpy), 1,10-morpholine (phen , 1,2-bis(diphenylphosphino)ethane (dppe), 1,2-diaminocyclohexane, bis(diphenylphosphino)methane (dppm), 1,3-double ( Diphenylphosphino)propane (dppp) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP).

Preferred neutral chelating ligands are bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)methane (dppm), 1,3-bis(diphenylphosphino)propane (dppp) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP).

In a preferred embodiment, the neutral ligand L or L' is a phosphine, more preferably a trialkylphosphane. Suitable phosphanes are, in particular, selected from tricyclohexylphosphanes which may be substituted, trimethylphosphine, triethylphosphine, substituted triarylphosphines such as substituted triphenylphosphinones (TPP) ), benzylmethylphenylphosphine (BMPP), bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)methane (dppm), 1,3-bis(diphenylphosphine) Group of propane (dppp) and 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl (BINAP).

Other monodentate phosphatas suitable as ligand L are primary phosphines such as R ⁴ PH ₂ , secondary phosphanes such as R ⁴ R ⁵ PH and tertiary phosphanes such as R ⁴ R ⁵ R ⁶ P.

R ⁴ , R ⁵ and R ⁶ may independently of each other be a linear, cyclic or branched alkyl group, a linear, cyclic or branched alkenyl group, a linear, cyclic or branched alkynyl group, an aryl group, or Benzyl. The alkyl, alkenyl, alkynyl, aryl and/or benzylic groups may be substituted. The alkyl, alkenyl and/or alkynyl groups of the secondary and tertiary phosphanes can be closed to form a ring. In a preferred embodiment, the alkyl, alkenyl and/or alkynyl group has from 1 to 10 carbon atoms, more preferably from 1 to 7 carbon atoms, and even more preferably from 1 to 5 carbon atoms. In another preferred embodiment, the aryl or benzyl group has from 6 to 9 carbon atoms. Suitable substituents include alkyl, alkenyl, alkynyl, aryl or benzyl groups which are similar to R ⁴ , R ⁵ and R ⁶ .

In a preferred embodiment, the nickel (II) catalyst has two phosphine ligands L (preferably trimethylphosphine) and two halide ligands (preferably chloride). More preferably, the Ni(II) catalyst is NiCl ₂ (PMe ₃ ) ₂ .

In a preferred embodiment, the organic halide salt is selected from a halogenated imidazole which may be substituted (such as 1-butyl-3-methylimidazolium halide (halogenated BMIM)), which may be substituted with a halogenated pyridyl which may be substituted a halogenated pyrrolidine, a substituted halogenated hydrazine, a substituted halogenated urea, a substituted halogenated thiourea, a substituted halogenated piperidine, a substituted halogenated phenanthroline, a substituted ammonium halide, A group of substituted ruthenium halides, and mixtures thereof. More preferably, the organic halide salt is selected from the group consisting of a replaceable imidazolium chloride, a substituted pyridine chloride, a substituted ammonium chloride, and mixtures thereof.

Preferred substituents are selected from linear, cyclic or branched alkyl groups having from 1 to 16, preferably from 1 to 10, more preferably from 1 to 7, more particularly from 1 to 6 carbon atoms. The alkyl group may be substituted.

The buffering agent is preferably a mixture of a Lewis basic compound or a Lewis base. In a particular embodiment, the Lewis base is a base having at least one element of Group 15 of the Periodic Table (Lotus base of Group 15 of the Periodic Table). Suitable Lewis bases of Group 15 of the Periodic Table are particularly selected from the group consisting of nitrogen bases, phosphorous bases, arsenic bases, strontium bases and strontium bases. In a preferred embodiment, the Lewis base is selected from the group consisting of primary amines such as R ¹ NH ₂ , secondary amines such as R ¹ R ² NH, tertiary amines such as R ¹ R ² R ³ N, first order phosphorus Alkane such as R ¹ PH ₂ , a secondary phosphane such as R ¹ R ² PH, a tertiary phosphane such as R ¹ R ² R ³ P.

R ¹ , R ² and R ³ may independently of each other be a linear, cyclic or branched alkyl group, a linear, cyclic or branched alkenyl group, a linear, cyclic or branched alkynyl group, an aryl group, or Benzyl groups, which may have heteroatoms such as N, O and S and/or may be N, O and S. The alkyl, alkenyl and/or alkynyl groups of the secondary and tertiary amines or phosphins can be closed to form a ring. In a more specific embodiment, the alkyl, alkenyl and/or alkynyl group has from 1 to 10 carbon atoms, more preferably from 1 to 7 carbon atoms, and most preferably from 1 to 5 carbon atoms. In another preferred embodiment, the aryl or benzyl group has from 6 to 9 carbon atoms. Suitable substituents include definitions of R ^1, R ² and R ³ are similar to the alkyl group, alkenyl group, an alkynyl group, an aryl group or a benzyl group, include halogen such as -F, -Cl, -Br and -I.

In a particularly preferred embodiment, the Lewis base is a nitrogen base such as pyrrole, a pyrrole derivative (eg, N-methylpyrrole), a pyridine, a pyridine derivative, a quinoline, and a quinoline derivative, and a phosphorus base such as a phosphine. Or a purine base such as BiPh ₃ , more particularly a nitrogen base. In a similar preferred embodiment, the Lewis base is a replaceable N-methylpyrrole.

In a preferred embodiment, the catalyst system comprises a polar phase (which comprises an ionic liquid) and a non-polar phase (which comprises an organic solvent). The organic solvent is preferably non-polar.

In one embodiment, the volume ratio of the organic solvent to the ionic liquid is in the range of 0.5:1 to 10:1, preferably in the range of 1:1 to 5:1 or 2:1 to 3:1.

As the organic solvent, it may be any form of liquid carbon or a hetero atom-substituted hydrocarbon which cannot be used as a reactant. The hydrocarbon or heteroatom-substituted hydrocarbon may be linear or branched. The organic solvent is preferably selected from the group consisting of a linear or branched type alkane which may be substituted, a substituted cycloalkane such as cyclohexane, a substituted aromatic and a mixture thereof. Suitable substituents include alkyl, alkenyl, alkynyl, aryl or benzyl groups which are similar to R ¹ , R ² and R ³ (see above), and also include halogens such as —F, —Cl, —Br and — I. The organic solvent is preferably selected from the group consisting of linear or branched alkyls, alkyl-substituted naphthenes (such as cyclohexane), linear or branched chlorinated alkanes (such as tetrachloroethane). a group of chlorinated naphthenes optionally substituted by alkyl groups, substituted chlorinated or unchlorinated aromatics such as cumene, and mixtures thereof. Very particular is the use of alkanes and naphthenes such as cyclohexane and mixtures thereof. Also preferred are linear or branched chlorinated alkanes (such as tetrachloroethane), optionally substituted by alkyl substituted chlorinated naphthenes, substituted aromatics (such as cumene). . Suitable substituents include alkyl, alkenyl, alkynyl, aryl or benzyl groups which are similar to R ¹ , R ² and R ³ (see above), and also include halogens such as —F, —Cl, —Br and — I.

In a specific embodiment, the volume ratio of the organic solvent to the ionic liquid is in the range of 1:1 to 7:1, preferably in the range of 2:1 to 5:1, and the organic solvent is selected from the group consisting of A substituted linear or branched type alkane, a group of substituted naphthenes such as cyclohexane, and mixtures thereof. Suitable substituents include alkyl, alkenyl, alkynyl, aryl or benzyl groups which are similar to R ¹ , R ² and R ³ (see above).

In another specific embodiment, the volume ratio of the organic solvent to the ionic liquid is in the range of 0 to 2 or 0.5 to 1, and the organic solvent is selected from the group consisting of linear or branched chlorinated alkane (such as four Ethyl chloride), optionally substituted by alkyl substituted chlorinated naphthenes, substituted aromatics such as cumene, and mixtures thereof. Suitable substituents include alkyl, alkenyl, alkynyl, aryl or benzyl groups which are similar to R ¹ , R ² and R ³ (see above), and also include halogens such as —F, —Cl, —Br and — I.

In a preferred embodiment, the molar ratio of the organic halide salt to the precursor is 1:0.4-1.8, more specifically 1:0.5-1.4 and/or the molar ratio of the organic halide salt to the buffer is 1. : 0.1-0.8, more specifically 1:0.15-0.5. In another embodiment, the molar ratio of organic halide salt to buffer is from 1:0.2 to 0.3. In another embodiment, the molar ratio of the organic halide salt to R _n MX _3-n is 1:0.8-1.8, more specifically 1:0.9-1.4 and especially 1:1.0-1.3 or 1:1.1. 1.2. In another embodiment, the molar ratio of the organic halide salt to R _m M ₂ X _6-m is from 1:0.4 to 0.9, more specifically from 1:0.5 to 0.8 and especially from 1:0.6 to 0.7. In a preferred embodiment, the molar ratio of the organic halide salt to the organic solvent is from 1:0.5 to 50, more specifically from 1:5 to 35 and very preferably from 1:10 to 20. In another preferred embodiment, the molar ratio of the organic halide salt to the R _n MX _3-n to buffer to organic solvent is 1:1.1-1.3:0.15-0.3:5-35. In another preferred embodiment, the molar ratio of the organic halide salt to the R _m M ₂ X _6-m to buffer to organic solvent is 1:0.5-0.6:0.15-0.3:5-25.

In one embodiment, the molar ratio of the catalyst to the organic halide salt is in the range of 1:30 to 1:300, preferably in the range of 1:40 to 1:250, more preferably 1:50. : 230 range, more particularly in the range of 1:100-1:200.

In a preferred embodiment, the molar ratio of catalyst to buffer is in the range of 1:2-1:100, preferably in the range of 1:5-1:70, more preferably 1:10-1. In the range of :50, more particularly in the range of 1:25-1:30.

Another subject of the invention is a method of dipolymerizing a olefin comprising The following steps: A) provide the catalyst system of the present invention.

In a specific example, step A) includes sub-steps A1, A2 and A3. In substep A1, the organic halide salt is preferably mixed with the precursor to prepare an ionic liquid. In sub-step A2, the buffer is then added to the ionic liquid. The catalyst is dissolved in the buffered ionic liquid in substep A2. In another optional step, the buffered ionic liquid can be mixed with an organic solvent.

In another embodiment, the buffered ionic liquid is prepared in sub-steps A1 and A2. In substep A3, the catalyst is dissolved in the organic solvent. In another step (A4), the buffered ionic liquid and the organic solvent are mixed.

The reactant used in the present invention may be a C ₂ to C ₁₀ , preferably a C ₃ - C ₅ olefin or a mixture thereof. The mixture comprising the reactants preferably does not substantially comprise other unsaturated compounds or polyunsaturated compounds such as dienes or acetylene derivatives. The olefinic mixture to be used preferably contains less than 5% by mass, more particularly less than 1% by mass, of the branched olefins based on the olefinic moiety.

Suitable alkenes include alpha-olefins, 2-olefins and cycloolefins. The olefin as the reactant is preferably an α-olefin.

Propylene is industrially produced by cracking of the petroleum brain and is an essential chemical that is readily available. C ₅ olefinic portion present in the light oil arising in the refiner or crackers. The technical grade mixture comprising linear C ₄ olefins is the light petroleum fraction produced by the refiner, the C ₄ fraction produced by the FC cracker or steam cracker, the mixture produced by the Fischer-Tropsch synthesis, and the butanes. a mixture produced by dehydrogenation, and a mixture formed by metathesis or produced by other industrial processes.

Mixtures of linear butenes suitable for the process of the invention can be obtained, for example, from the C ₄ portion of a steam cracker. In this case, the butadiene is removed in the first step. This is carried out by extraction or extractive distillation of the butadiene or by selective hydrogenation of the same. In the second case, is obtained substantially free of C ₄ to butadiene portion (raffinate I). In the second step, for example by reaction of isobutylene with methanol is removed from this C ₄ stream to produce methyl tertiary butyl ether (MTBE). Other possibilities are the reaction of isobutene from raffinate I with water to obtain a third butanol or an acid catalyzed oligomerization of the isobutene to obtain diisobutylene. The C ₄ portion (residual liquid II) which does not contain isobutylene today contains the linear butenes and the random butanes as needed. Optionally, in addition, the 1-butene can be separated by distillation. The two parts, one of which has but-1-ene or one of which has but-2-ene, can be used in the process of the invention.

Another possibility for preparing suitable reactants is to carry out hydroisomerization of raffinate I, raffinate II or a hydrocarbon mixture having a similar composition in a reaction column. The product of this procedure may include a mixture of 2-butenes, a small portion of 1-butene and optionally n-butane, and isobutane and isobutylene.

Preferably, as the reactant, it is a pure substance composed of C ₂ to C ₁₀ olefins, more preferably a pure substance composed of C ₃ to C ₅ olefins. In another preferred embodiment, an alkene-containing stream, such as crude butane, is supplied to the process as a mixture containing the reactants. Other suitable reactant containing a mixture of raffinate comprising the I (C ₄ steam cracking portion of the butadiene-free filter) and Raffinate II (butadiene-free C ₄ and the vapor portion containing isobutylene cracker) .

In one embodiment, the degree of dimerization relative to the converted reactant (also referred to as "% relative to the selectivity of the dimerization" is at least 17%, preferably at least 25%, more preferably at least 40%. In a preferred embodiment, the degree of dimerization is at least 60%, more preferably at least 85%, and most preferably at least 90%, more specifically at least 95%. In a particularly preferred embodiment, the degree of dimerization is at least 96. %, more preferably at least 98%, and optimally at least 99%.

In a preferred embodiment, the method of the present invention further comprises the steps of: b) dimerizing an olefin or two or more olefins, more particularly selected from the group consisting of ethylene, n-propene, n-butene, n-pentene, n-hexene The olefin of the group consisting of n-heptene, n-octene, n-decene and n-decene is preferably n-propene, n-butene and n-pentene.

The oligomers produced by the process of the invention are used in applications involving the preparation of aldehydes, alcohols and carboxylic acids. Thus, for example, a dimerization system formed from linear butenes produces a furfural mixture by hydroformylation. Generate a corresponding mixture of carboxylic acids produced by oxidation or by hydrogenation of C ₉ alcohol mixtures. The C ₉ acid mixture useful for producing a lubricant or desiccant. When the precursor of the C ₉ alcohol mixtures in the manufacture of plasticizers (nonyl phthalate in particular).

In a specific embodiment, the dimerization step is in the range of 0 to 30 ° C, preferably in the range of 17 to 25 ° C and at a pressure of 1 to 20 bar, preferably 2 to 3 bar. get on.

In another embodiment, the dimerization step is in the range of 0 to 17 ° C, preferably in the range of 2 to 12 ° C and at a pressure of 1 to 20 bar, preferably 2 to 3 bar. Go on.

Another subject of the invention is the use of the catalyst system of the invention for the dipolymerization of olefins and the use of NiCl ₂ (PMe ₃ ) ₂ for the dipolymerization of olefins.

The following examples are intended to illustrate the invention in more detail.

Examples 1A to 1G Preparation of the ionic liquid

11 g (62.9 mmol) of 1-butyl-3-methylimidazolium chloride was introduced and blended with 139.0 mmol of cyclohexane. AlCl ₃ (10.08 g, 75.6 mmol) was added to the solution at 25 ° C in portions.

Buffer of the ionic liquid

After the cyclohexane supernatant had been removed, 3.79 g (12.3 mmol) of the ionic liquid [BMIM][AlCl ₄ ] prepared was filled into the flask and BiPh ₃ (1.18 g, at 25 ° C, 2.7 millimoles) blended. The mixture was stirred for 1 hour.

1-butene polymerization procedure Example 1A

0.015 grams of NiCl ₂ (PMe ₃ ) ₂ (0.054 mmol) was dissolved in the buffered ionic liquid. The resulting two-phase catalyst solution was transferred to a high pressure autoclave and blended with 1 gram of 1-butene (17.8 mmol). Stir at 25 ° C for 4 hours (750 rpm). The experimental results are listed in Tables 1a and 1b.

Example 1B

0.015 grams of NiCl ₂ (PMe ₃ ) ₂ (0.054 mmol) was dissolved in cyclohexane. The prepared non-polar solution and the buffered ionic liquid were mixed, transferred to a high pressure autoclave and blended with 1 gram of 1-butene (17.8 mmol). Stir at 0 ° C for 4 hours (750 rpm). The experimental results are listed in Tables 1a and 1b.

Example 1C to 1G

0.015 grams of NiCl ₂ (PMe ₃ ) ₂ (0.054 mmol) was dissolved in the non-polar solvent used. The prepared non-polar solution and the buffered ionic liquid were mixed, transferred to a high pressure autoclave and blended with 1 gram of 1-butene (17.8 mmol). Stir at 25 ° C for 4 hours (750 rpm). The experimental results are listed in Tables 1a and 1b.

Examples 2A through 2E Buffer of the ionic liquid

The ionic liquid [BMIM][AlCl ₄ ] prepared according to Example 1A in the amounts listed in Table 2 was filled into the flask and blended with N-methylpyrrole in the amounts indicated in Table 2 at room temperature. . The mixture was stirred for 1 hour.

1-butene oligomerization procedure Examples 2A and 2D

0.015 grams of NiCl ₂ (PMe ₃ ) ₂ (0.054 mmol) was dissolved in the buffered ionic liquid. The resulting two-phase catalyst solution was transferred to a high pressure autoclave and blended with 1 gram of 1-butene (17.8 mmol). Stir at 25 ° C for 4 hours (750 rpm). The experimental results are listed in Tables 3a and 3b.

Example 2E

0.015 grams of NiCl ₂ (PMe ₃ ) ₂ (0.054 mmol) was dissolved in cyclohexane. The prepared non-polar solution and the buffered ionic liquid were mixed, transferred to a high pressure autoclave and blended with 1 gram of 1-butene (17.8 mmol). Stir at 25 ° C for 4 hours (750 rpm). The experimental results are listed in Tables 3a and 3b.

Claims (15)

A catalyst system comprising a catalyst phase, the catalyst phase comprising at least an organic halide salt, at least one nickel (II) catalyst, at least one precursor, and at least one buffer. For example, in the catalyst system of claim 1, the precursor is R _n MX _3-n or R _m M ₂ X _6-m , wherein R is a C ₁ -C ₆ alkyl group, and M is aluminum, boron, gallium. Or iron (III), X is a halogen or an alkoxy group having 1 to 4 carbon atoms, n is 1, 2 or 3, and m is 1, 2 or 3. The catalyst system of claim 1 or 2, wherein the nickel (II) catalyst is selected from the group consisting of NiZ ₂ L ₂ , NiZ'L ₂ , NiZ ₂ L', NiZ'L', NiY ₂ , NiY' a group consisting of Z being a single negatively charged ligand, Z' being a double negatively charged ligand, Y being a single negatively charged double-dentate ligand, and Y' being a double negative The tetradentate ligand of the charge, L is a neutral ligand, and L' is a neutral bidentate ligand. a catalyst system as in any of the prior patent applications, which The organic halide salt is selected from the group consisting of a halogenated imidazole, a halogenated pyridine, a halogenated pyrrole, a ruthenium halide, a urea halide, a thiourea halide, a halogenated piperidine, a halogenated wover, an ammonium halide, and a ruthenium halide, and a cation of the halogenated salt. It may be substituted, and more preferably an organic halogenated salt or mixture selected from the group consisting of imidazole chloride, pyridine chloride and ammonium chloride, the cation of which may be substituted. A catalyst system according to any one of the preceding claims, which is a mixture of a Lewis base compound or a Lewis base and is preferably selected from the group consisting of nitrogen bases, phosphorous bases, arsenic bases, strontium bases and strontium bases. More preferably, the group is a nitrogen base. The catalyst system of any of the preceding claims, further comprising a non-polar phase, which may comprise an organic solvent. The catalyst system of claim 6 is selected from the group consisting of alkanes, naphthenes, chlorinated alkanes, chlorinated naphthenes, and aromatics, which may be substituted. A catalyst system according to any one of the preceding claims, wherein the molar ratio of the organic halide salt to the precursor is 1:0.4-1.8, more specifically 1:0.5-1.4, and/or the organic halide salt The molar ratio to the buffer is 1:0.1-0.8, more specifically 1:0.15-0.5. The molar ratio of the organic halide salt to R _n MX _3-n is from 1:0.8 to 1.8, more specifically 1:0.9 to 1.4, or the organic halide salt, as in the catalyst system of claim 8 The molar ratio to R _m M ₂ X _6-m is 1:0.4-0.9, more specifically 1:0.5-0.8. For example, the catalyst system of any one of claims 6 to 9 The molar ratio of the organic halide salt to the organic solvent is 1:0.5-50, more specifically 1:5-35. The catalyst system according to any one of the preceding claims, wherein the Ni(II) catalyst is NiCl ₂ (PMe ₃ ) ₂ . A method of dipolymerizing a olefin comprising the steps of: A) providing a catalyst system as set forth in claims 1 to 11. The method of claim 12, comprising the steps of: b) dimerizing an olefin or two or more olefins, more particularly selected from the group consisting of ethylene, n-propene, n-butene, n-pentene, n-hexene, and The olefins in the group consisting of heptene, n-octene, n-decene and n-decene are preferably n-propene, n-butene and n-pentene. A use of a catalyst system as claimed in claims 1 to 11 for dipolymerized alkenes. A use of NiCl ₂ (PMe ₃ ) _{2 for} dipolymerized alkenes.