JPH08165254A - Olefin dimerization method - Google Patents

Abstract

(57) [Summary] [Structure] (A) Dimerization of olefin in the presence of reaction products of the following components (a), (b), and (c), and (B) halogen-containing Lewis acidic compound. how to. (a) Zero-valent nickel compound, (b) Formula R ¹ ₃ P = CR ² -C (O) R ³ (In the formula, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ are hydrogen. , Carbon number 1
~ 12 hydrocarbon groups. ) Ylide compound represented by
(c) Formulas R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = CR ⁶ R ⁷ (wherein R ⁴ and R ⁵
Is a hydrocarbon group having 1 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen and carbon number
1 to 12 hydrocarbon groups or —SiR ₃ groups are shown. ) At least one phosphorus compound selected from the compounds represented by: [Effect] An olefin dimerization method with high catalytic activity using a nickel-based catalyst is provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for dimerizing olefins using a novel catalyst system.

[0002]

2. Description of the Related Art With the ethylene dimerization catalyst
Then, nickel (divalent) compounds are well known.
Journal of Molecular Catalysis 1994, 90, 24
On page 5-255, NiX₂Or NiX₂L₂(X is anionic
The ligand, L, represents a donor ligand. ) Of ethylene
Quantification reactions have been reported. In this dimerization reaction
Is a halogen-containing Lewis acidic compound such as Et₂AlCl
By sharing such halogen-containing organoaluminum
It is described that the property becomes high. Also, Organometa
llics in Organic Synthesis 2, 1989, pp. 6-9 (Spring
er-Verlag Berlin Heidelberg, H. Werner and G. Erker
) Is a Ni allyl complex η³-C₃H_FiveNiLBr and EtAlCl
₂A catalyst system consisting of is described. In addition, Bulltine
Chemical Society Japan, 1977, Vol. 43, p. 3630,
(O-tolyl) Ni [(C ₆H_Five)
₃P]₂Br and BF₃・ OEt₂The ethylene dimerization catalyst consisting of
It is listed. However, ethylene or α-ole
High activity and extremely high selectivity for fin dimerization
An industrially superior catalyst system is desired.

[0003]

An object of the present invention is to provide a method for dimerizing an olefin having a high catalytic activity using a nickel catalyst.

[0004]

The present invention provides (A) reaction products of the following components (a), (b) and (c), and
(B) A method for dimerizing an olefin in the presence of a halogen-containing Lewis acidic compound. (a) Zero-valent nickel compound, (b) Formula R ¹ ₃ P = CR ² -C (O) R ³
(In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ represent hydrogen, and a hydrocarbon group having 1 to 12 carbon atoms.), (C) Formula R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = CR ⁶ R ⁷ (In the formula, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen, and 1 to 12 carbon atoms. hydrocarbon radical, or -SiR shows a ₃ group.) at least one phosphorus compound selected from the compound represented by the.

The component (A) of the catalyst in the present invention is as follows:
Reaction products of (a), (b) and (c). That is, (a) is a zero-valent nickel compound, (b) is the formula R ¹ ₃ P = CR ² -C (O) R
³ (wherein, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ are hydrogen. Indicating a hydrocarbon group having 1 to 12 carbon atoms) ylide compound represented by, and (c) Formulas R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = C
R ⁶ R ⁷ (in the formula, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁶
And R ⁷ is hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, or —SiR ₃
Indicates a group. ) It is at least 1 type of phosphorus compound selected from the compound shown by these.

The above-mentioned (a) zero-valent nickel compound means a compound in which various ligands are bonded to nickel having an oxidation number of zero by a coordinate bond.

The ligand in this case includes phosphine (eg triphenylphosphine), olefin (eg ethylene, norbornadiene, cyclooctadiene), nitrile (eg acrylonitrile), carbonyl and the like.

Specific examples of the zero-valent nickel compound include:
Bis (1,5-cyclooctadiene) nickel, tetrakis (triphenylphosphine) nickel, bis (triphenylphosphine) (1,5-cyclooctadiene) nickel, nickel (tetracarbonyl), bis (acrylonitrile) nickel, bis (Norbornadiene) nickel can be mentioned.

[0009] As the ylide compound of the above (b), R ¹ ₃ P
= Is a compound represented by ^{CR 2 -C (O) R 3} . R ¹ is a carbon number 1 ~
12 hydrocarbon groups, preferably a phenyl group or a substituted phenyl group. R ² and R ³ are hydrogen and a hydrocarbon group having 1 to 12 carbon atoms. As R ² and R ³ , a monocyclic or polycyclic hydrocarbon group may be formed with two carbon atoms to which R ² and R ³ are bonded.

As a specific example, (C ₆ H ₅ ) ₃ P = CH-C (O) CH ₃ ,
(C ₆ H ₅ ) ₃ P = CH-C (O) (C ₆ H ₅ ), or JP-A-61-2720,
The ylide compounds described in Nos. 122721 and 122722 can be mentioned.

The above (c) includes R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵
₃ P = a phosphorus compound represented by CR ⁶ R ⁷ . R ⁴ has 1 to 1 carbon atoms
12 hydrocarbon groups, particularly a phenyl group and a substituted phenyl group are preferable. R ⁵ is a hydrocarbon group having 1 to 12 carbon atoms, and a phenyl group and an isopropyl group are particularly preferable. R ⁶ and R ⁷ are hydrogen, a hydrocarbon group having 1 to 12 carbon atoms, a trialkylsilyl group
(-SiR ₃ ).

Specific examples include triphenylphosphine, triphenylphosphine oxide, triphenylmethylenephosphorane (C ₆ H ₅ ) ₃ P = CH ₂ , and triisopropylmethylenephosphorane (isoC ₃ H ₇ ) ₃ P = CH _2. , (IsoC ₃ H ₇ ) ₃ P = CH (C ₆ H
₅ ) and the like. In the present invention, the proportion of each of the components (a), (b) and (c) used in the synthesis of the component (A) is
Normally, (a) :( b) :( c) = 0.5 to 1.5: 0.5 to 1.5: 0.5 to
1.5 (molar ratio), preferably (a) :( b) :( c) =
0.8-1.2: 0.8-1.2: 0.8-1.2 (molar ratio).

In the present invention, as the component (B), halogen-containing Lewis acidic compounds include halogen-containing organoaluminum and halogen-containing organoboron compounds.

Specific examples of the halogen-containing organic aluminum compound include dimethyl aluminum chloride, methyl aluminum dichloride, diethyl aluminum chloride, ethyl aluminum dichloride, diethyl aluminum bromide, ethyl aluminum dibromide, diethyl aluminum iodide, ethyl aluminum diiodide, Examples thereof include diethoxyaluminum chloride, ethoxyaluminum dichloride, aluminum trifluoride, aluminum trichloride, aluminum tribromide and aluminum triiodide.

Specific examples of the halogen-containing organic boron compound include dimethylboron chloride, methylboron dichloride, diethylboron chloride, ethylboron dichloride, diethylboron bromide, ethylboron dibromide, diethylboron iodide, ethylboron diiodide, diethoxy. Examples thereof include boron chloride, ethoxyboron dichloride, boron trifluoride, boron trichloride, boron tribromide, and boron triiodide.

Two or more kinds of these halogen-containing Lewis acidic compounds may be mixed and used.

In the present invention, the nickel ylide complex can be synthesized in the presence of an inorganic compound or an organic polymer compound and used as a supported catalyst.

As the inorganic compound as the carrier, inorganic oxides, inorganic chlorides and inorganic hydroxides are preferable, and those containing a small amount of carbonates and sulfates can also be adopted. Particularly preferred are inorganic oxides such as silica, alumina, magnesia, titania, zirconia, and calcia. These inorganic oxides have an average particle size of 5 to
Porous fine particles having a particle size of 150 μm and a specific surface area of 2 to 800 m ² / g are preferable, and they can be used after heat treatment at 100 to 800 ° C., for example. As the organic polymer compound, an aromatic ring in the side chain, a substituted aromatic ring, or a hydroxy group, a carboxyl group,
Those having a functional group such as an ester group and a halogen atom are preferable.

As specific examples, α-olefin homopolymers and α-olefin copolymers having the above functional groups by chemical modification of polyethylene, polypropylene, polybutene, or acrylic acid, methacrylic acid, vinyl chloride, vinyl alcohol, styrene, divinyl. Mention may be made of homopolymers or copolymers such as benzene, as well as their chemical modifications. As these organic polymer compounds, spherical fine particles having an average particle diameter of 5 to 250 µ are used.

In the present invention, although not particularly limited,
Olefin can be dimerized by the following method using the above-mentioned dimerization catalyst system. The olefin dimerization is
Usually, it can be carried out in a fluidized bed of a supported catalyst or in a fixed bed reactor under a flow of olefin gas, or in a stirred reactor in an organic solvent. The dimerization condition is, for example, a temperature of 5 to 11
The temperature is 0 ° C and the pressure is normal pressure to 100 kg / cm ² .

Specific examples of the olefin in the present invention include:
Ethylene, propylene, butene-1,4-methylpentene-
1, non-polar olefin such as hexene-1, octene-1,
Examples thereof include olefins having a polar group such as acrylic acid ester and acrylonitrile.

[0022]

In the present invention, it is possible to dimerize an olefin with high activity and high selectivity by combining a nickel ylide complex and a halogen-containing Lewis acidic compound.

[0023]

EXAMPLES Analysis of the products of the dimerization reaction was carried out by gas chromatography (GC). Unicarbon A-400 was used as the column packing for GC analysis, helium gas was passed as the carrier gas, and the column temperature was raised from 50 ° C to 1 ° C / min.

Example 1 300 ml of a toluene solution of 50 mmol of bis (1,5-cyclooctadiene) nickel was cooled to 0 ° C., 50 mmol of triphenylphosphine and (C ₆ H ₅ ) ₃ P = CH were stirred while stirring. -C (O) (C
450 ml of a toluene solution in which ₆ H ₅ ) was dissolved in 50 mmol was gradually added dropwise, and the mixture was further reacted at 50 ° C. for 2 hours. 10 ° C Toluene 60
Diethylaluminum chloride as a toluene solution in 0.5 ml was added in an amount of 0.50 mmol in terms of Al, and the total pressure was adjusted with ethylene.
The reaction solution (containing 40 μmol as Ni metal) in a glass ampoule was maintained at 24.5 kg / cm ² to start polymerization, and the ethylene dimerization reaction was continued for 10 minutes. Reaction solution
Only butene-1 was detected as a product by GC analysis, and the catalytic activity was 9.8 kg / mM.Ni.10 min.

Example 2 The amount of diethylaluminum chloride used was calculated as Al in an amount of 0.1.
The dimerization reaction of ethylene was carried out in the same manner as in Example 1 except that the amount was changed to 25 mmol. Only butene-1 was detected and the catalytic activity was 9.4 kg / mM.Ni.10 min.

Example 3 300 ml of a toluene solution of 50 mmol of bis (1,5-cyclooctadiene) nickel was cooled to 0 ° C., and triphenylmethylenephosphorane ((C ₆ H ₅ ) ₃ P = CH _{2 was} added thereto with stirring. ) Of 50 mmol and (C ₆ H ₅ ) ₃ P = CH—C (O) (CH ₃ ) of 50 mmol dissolved in toluene solution (450 ml) were gradually added dropwise, and the mixture was further reacted at 50 ° C. for 2 hours. Diethylaluminum chloride was added as a toluene solution in 0.50 mmol of toluene in 600 ml of 50 ° C, 0.50 mmol of Al was added, the total pressure was maintained at 20 kg / cm ² with ethylene, and the above reaction solution (containing 40 μmol of Ni metal) in a glass ampoule was destroyed. Then, the polymerization was started, and the dimerization reaction of ethylene was continued for 10 minutes. Only butene-1 was detected as a product by gas chromatography analysis of the reaction solution, and the catalytic activity was 3.7 kg /
It was mM.Ni.10 min.

Example 4 300 ml of a toluene solution of 50 mmol of bis (1,5-cyclooctadiene) nickel was cooled to 0 ° C. and stirred to obtain 50 mmol of triphenylphosphine oxide, (C ₆ H ₅ ) ₃ P
= CH-C (O) (C ₆ H ₅ ) 50mM toluene solution 450mM
l was gradually added dropwise, and the mixture was further reacted at 50 ° C. for 2 hours. 10 ° C
Add 0.50 mmol of diethylaluminum chloride as a toluene solution in 600 ml of toluene in terms of Al, keep the total pressure at 20 kg / cm ² with ethylene, and destroy the above reaction solution (containing 40 μmol of Ni metal) in a glass ampoule to polymerize. Was started and the dimerization reaction of ethylene was continued for 30 minutes. Only butene-1 was detected as a product by gas chromatography analysis of the reaction solution, and the catalytic activity was 2.3 kg / mM.Ni.30 min.
Met.

Example 5 According to the method described in Example 1 of JP-A-6-12720,
Hexamethyldisilazane is reacted with a yellow solid (melting point 164-170 ° C) obtained by the reaction of 4-naphthoquinone and triphenylphosphine, and further triphenylphosphine oxide and bis (1,5-cyclooctadiene) nickel are added. The reaction was performed by heating to prepare a nickel ylide complex solution. 50 ° C
Diethylaluminum chloride was added to 600 ml of toluene as a toluene solution, 0.5 mmol in terms of Al was added, the total pressure was maintained at 20 kg / cm ² with ethylene, and the reaction solution (containing 40 μmol as Ni metal) in the glass ampoule was destroyed and polymerized. Was started and the ethylene dimerization reaction was continued for 1 hour. Only butene-1 was detected as a product by gas chromatography analysis of the reaction solution, and the catalytic activity was 1.2 kg / mM.Ni.hr.

Claims (1)

[Claims] 1. (A) The following components (a), (b), and (c)
A method for dimerizing an olefin in the presence of the reaction product of 1. and (B) a halogen-containing Lewis acidic compound. (a) Zero-valent nickel compound, (b) Formula R ¹ ₃ P = CR ² -C (O) R ³
(In the formula, R ¹ represents a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ represent hydrogen, and a hydrocarbon group having 1 to 12 carbon atoms.), (C) Formula R ⁴ ₃ P, R ⁴ ₃ PO and R ⁵ ₃ P = CR ⁶ R ⁷ (In the formula, R ⁴ and R ⁵ are hydrocarbon groups having 1 to 12 carbon atoms, R ⁶ and R ⁷ are hydrogen, and 1 to 12 carbon atoms. hydrocarbon radical, or -SiR shows a ₃ group.) at least one phosphorus compound selected from the compound represented by the.