JP2004292543A - Catalyst for olefin dimerization and method for producing olefin dimer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a catalyst for olefin dimerization for providing an olefin dimer in high selectivity and to provide a method for producing an olefin dimer using the catalyst. <P>SOLUTION: The catalyst for olefin dimerization is obtained by bringing (i) a metal compound represented by general formula [1]: MX<SB>n</SB>[M is a metal atom of the group 7 of the periodic table of the elements; n is an integer of 2 or 3; X is a chelate type anionic ligand in which a coordination atom is an oxygen atom] into contact with an organoaluminum compound represented by formula [2]: E<SB>2</SB>AlY (E is an hydrocarbon group; each E may be the same or different; Y is a halogen atom). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an olefin dimerization catalyst and a method for producing an olefin dimer using the catalyst.
[0002]
[Prior art]
As a catalyst having a Group 7 metal atom used for synthesis of an olefin dimer such as synthesis of 1-butene by a dimerization reaction of ethylene, for example, a catalyst comprising manganese dichloride and ethylaluminum dichloride is known. (For example, refer to Patent Document 1).
[0003]
[Patent Document 1]
JP-B-48-19601 [0004]
[Problems to be solved by the invention]
However, when an olefin is reacted using the above-mentioned manganese compound catalyst, a trimer or the like may be formed as a by-product other than the dimer, and the dimer selectivity is not sufficiently satisfactory.
Under such circumstances, an object of the present invention is to provide an olefin dimerization catalyst capable of obtaining an olefin dimer with a high selectivity, and a method for producing an olefin dimer using the catalyst.
[0005]
[Means for Solving the Problems]
That is, the first aspect of the present invention relates to an olefin dimerization catalyst obtained by contacting the following components (i) and (ii).
(I) Metal compound MX _n [1] represented by the following formula [1]
M: a metal atom of Group 7 of the periodic table of the elements.
n: an integer of 2 or 3.
X: chelating anionic ligand in which the coordinating atom is an oxygen atom (ii) an organoaluminum compound E ₂ AlY [2] represented by the following formula [2]
E: hydrocarbon group. However, each E may be the same or different.
Y: halogen atom
The second aspect of the present invention relates to a method for producing an olefin dimer using the above olefin dimerization catalyst.
[0007]
BEST MODE FOR CARRYING OUT THE INVENTION
Component (i) of the present invention is a metal compound represented by the following formula [1].
MX _n [1]
M: a metal atom of Group 7 of the periodic table of the elements.
n: an integer of 2 or 3.
X: chelating type anionic ligand in which the coordinating atom is an oxygen atom
M in the formula [1] represents a metal atom of Group 7 of the Periodic Table of the Elements (IUPAC revised version of the inorganic chemical nomenclature 1989), preferably a manganese atom, a technetium atom or a rhenium atom, particularly preferably a manganese atom. Is an atom.
[0009]
N in the formula [1] is an integer of 2 or 3, and is preferably 3.
[0010]
X in the formula [1] represents a chelating anionic ligand in which the coordinating atom is an oxygen atom, and specifically, acetate, ethanoate, propionate, n-butanoate, isobutanoate, n-pentanoate, and isopentanoate Carboxylate compounds such as ate, neopentanoate, n-hexanoate, 2-ethylhexanoate, benzoate, acetylacetonate, heptandionate, 2,6-dimethylheptanedionate, 2,2,6,6- Dionate compounds such as tetramethylheptane dionate, 1,3-diphenylpropanedionate, and hexafluoroacetylacetonate, and the like, preferably acetate, 2-ethylhexanoate, acetylacetonate, 2,2,6,6 -Tetramethylheptanedione DOO, 1,3-diphenyl propane dionate or hexafluoroacetylacetonate, more preferably acetate, acetylacetonate or 2,2,6,6 tetramethylheptanedionate.
[0011]
Specific examples of the compound represented by the formula [1] include tris (acetate) manganese, tris (ethanoate) manganese, tris (propionate) manganese, tris (n-butanoate) manganese, tris (isobutanoate) manganese, and tris (n -Pentanoate) manganese, tris (isopentanoate) manganese, tris (neopentanoate) manganese, tris (n-hexanoate) manganese, tris (2-ethylhexanoate) manganese, tris (benzoate) manganese, tris ( Acetylacetonate) manganese, tris (heptanedionate) manganese, tris (2,6-dimethylheptanedionate) manganese, tris (2,2,6,6-tetramethylheptanedionate) manganese, tris (1,3 -Diphenylpro Njioneto) manganese, tris (hexafluoroacetylacetonate) compound of MX ₃ type such as manganese;
[0012]
Bis (acetate) manganese, bis (ethanoate) manganese, bis (propionate) manganese, bis (n-butanoate) manganese, bis (isobutanoate) manganese, bis (n-pentanoate) manganese, bis (isopentanoate) manganese, bis (Neopentanoate) manganese, bis (n-hexanoate) manganese, bis (2-ethylhexanoate) manganese, bis (benzoate) manganese, bis (acetylacetonate) manganese, bis (heptanedionate) manganese, bis (2,6-dimethylheptanedionate) manganese, bis (2,2,6,6-tetramethylheptanedionate) manganese, bis (1,3-diphenylpropanedionate) manganese, bis (hexafluoroacetylacetonate) )manga MX ₂ type compounds and the like such.
[0013]
As specific examples of the compound represented by the formula [1], preferably, tris (acetate) manganese, tris (2-ethylhexanoate) manganese, tris (acetylacetonate) manganese, tris (2,2,6) 6-tetramethylheptanedionate) manganese, tris (1,3-diphenylpropanedionate) manganese, or tris (hexafluoroacetylacetonate) manganese, more preferably tris (acetate) manganese, tris (acetylacetonate) ) Manganese or tris (2,2,6,6-tetramethylheptanedionate) manganese.
[0014]
The method for synthesizing the metal compound represented by the formula [1] of the component (i) is not particularly limited, but is produced, for example, by the method described in West German Patent Specification No. 2420775.
[0015]
The component (ii) of the present invention is an organoaluminum compound represented by the following formula [2].
E ₂ AlY [2]
E: hydrocarbon group. However, each E may be the same or different.
Y: halogen atom
Examples of the hydrocarbon group represented by E in the formula [2] include an alkyl group, an aralkyl group, and an aryl group, and are preferably a hydrocarbon group having 1 to 8 carbon atoms, and more preferably 1 to 8 carbon atoms. To E-8, and each E may be the same or different from each other.
[0017]
Y in the formula [2] is a halogen atom, and includes a fluorine atom, a chlorine atom and the like, and is preferably a chlorine atom.
[0018]
Specific examples of the compound represented by the formula [2] include dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, di-n-hexylaluminum chloride, and dioctylaluminum chloride. , Preferably diethylaluminum chloride. The organoaluminum compound represented by the formula [2] is used alone or in combination of two or more.
[0019]
The olefin dimerization catalyst of the present invention is obtained by bringing component (i) into contact with component (ii).
[0020]
The component (i) and the component (ii) may be brought into contact with each other by any means as long as the component (i) and the component (ii) come into contact with each other to form an olefin dimerization catalyst. Or a method in which the component (i) and the component (ii) are mixed and contacted without dilution, or a method in which the component (i) and the component (ii) are separately supplied to a reaction vessel and brought into contact in the reaction vessel. Here, the component (i) and the component (ii) may be used by combining a plurality of types of compounds, respectively, and some of them may be used by mixing them in advance, or may be separately polymerized. It may be supplied to a tank and used.
[0021]
As the ratio of the amount of the contact treatment between the component (i) and the component (ii), [the number of moles of the component (ii)] / [the number of moles of the group 7 metal atom contained in the component (i)] is preferably 0.1. It is 1 to 10000, more preferably 500 to 5000.
[0022]
When the component (i) and the component (ii) are used in a solution state, a suspension state in a solvent or a slurry state, the concentration of each component is determined by conditions such as the performance of an apparatus for supplying each component to the olefin dimerization reactor. Is selected as appropriate. Generally, the concentration of the component (i) is usually 0.001 to 200 mmol / l, more preferably 0.001 to 100 mmol / l, in terms of the molar concentration of the Group 7 metal atom contained in the component (i). And more preferably 0.05 to 50 mmol / l. The concentration of the component (ii) is usually 0.01 to 5000 mmol / liter, more preferably 0.1 to 2500 mmol / liter, and further preferably 0.1 to 2000 mmol / liter.
[0023]
The method for producing an olefin dimer using the olefin dimerization catalyst of the present invention is not particularly limited. For example, a fixed bed reaction method, a gas phase reaction method, a solution reaction method using an appropriate solvent, a slurry reaction method Any method can be used. When a solvent is used, various solvents can be used provided that they do not deactivate the catalyst. Examples of such a solvent include aliphatic hydrocarbons such as butane, pentane, hexane, heptane, and octane; benzene, and toluene. And aromatic hydrocarbons such as methylene dichloride, chlorobenzene and the like. In these production methods, either a continuous reaction or a batch reaction may be used.
[0024]
The reaction temperature of the olefin dimerization reaction is usually -50 to 200C, preferably -20 to 100C. Further, the reaction pressure is usually 6 MPa or less. The reaction time is appropriately determined depending on the kind of the target olefin dimer and the reaction apparatus, and is usually 1 minute to 20 hours.
[0025]
The olefin used in the method for producing an olefin dimer of the present invention is preferably ethylene. Further, the method for producing an olefin dimer of the present invention is suitable for producing 1-alkenes, particularly 1-butene.
[0026]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
I. Raw material component (i)
Tris (acetylacetonate) manganese (Mn (acac) ₃ ):
Tris (acetylacetonate) manganese (min. 97%) manufactured by STREM was used.
Component (ii)
Diethyl aluminum chloride (DEAC):
A 1.0 mol / l toluene solution manufactured by Tosoh Finechem was used.
Ethyl aluminum dichloride (EADC):
A 1.0 mol / l toluene solution manufactured by Tosoh Finechem was used.
[0027]
The amount of 1-butene formed in the reaction product and the selectivity of the dimerization reaction (the ratio of 1-butene in the product having 4 to 20 carbon atoms) were determined by gas chromatography under the following conditions.
Apparatus: Gas chromatograph made by Hewlett Packard (HP-5890 series II)
Column: DB-1 made by J & W Scientific 60m
Carrier: Nitrogen internal standard: Cyclohexane sample volume: 1 μl
Injection temperature: 230 ° C
Detector temperature: 230 ° C
Column temperature: Raised from 40 ° C to 230 ° C to 8 ° C / min.
[Example 1]
A 0.4-liter autoclave with a stirrer was vacuum-dried and purged with argon. At room temperature, 200 ml of toluene was charged as a solvent. Then, the temperature of the autoclave was raised to 60 ° C., and 2.0 MPa of ethylene was autoclaved. Was charged. Subsequently, 1.0 ml of a toluene solution of DEAC (Al concentration = 1.0 mol / l) (amount of Al = 1.0 mmol) was charged into the autoclave under a nitrogen stream, and then a toluene solution of Mn (acac) ₃ ( The reaction was started by charging 1.0 ml (Mn (acac) ₃ amount = 1.0 μmol) into the autoclave under a nitrogen stream, and the ethylene pressure was adjusted to 2.0 MPa. The reaction was performed for 60 minutes while feeding ethylene so as to be adjusted and adjusting the temperature to 60 ° C. As a result, 5.50 × 10 ⁵ g of 1-butene per 1 mol of Mn complex and traces of polyethylene were obtained, and the dimerization reaction selectivity was 100% by weight.
[0029]
[Comparative Example 1]
The procedure was performed in the same manner as in Example 1 except that 1.0 ml (Al amount = 1.0 mmol) of a toluene solution of EADC (Al concentration = 1.0 mol / l) was used instead of the toluene solution of DEAC. As a result, 1.09 × 10 ⁴ g of 1-butene per 1 mol of Mn complex, 1.05 × 10 ³ g of hexene per Mn complex, and traces of polyethylene were obtained, and the dimerization reaction selectivity was 91%. 0.2% by weight.
[0030]
【The invention's effect】
According to the present invention, an olefin dimerization catalyst capable of obtaining an olefin dimer with a high selectivity and a method for producing an olefin dimer using the catalyst can be provided. The olefin dimerization catalyst of the present invention is suitable for producing 1-alkene, particularly 1-butene, and the olefin dimerization catalyst of the present invention can produce olefin dimer in high yield.

Claims (5)

An olefin dimerization catalyst comprising the following components (i) and (ii):
(I) Metal compound MX _n [1] represented by the following formula [1]
M: a metal atom of Group 7 of the periodic table of the elements.
n: an integer of 2 or 3.
X: chelating anionic ligand in which the coordinating atom is an oxygen atom (ii) an organoaluminum compound E ₂ AlY [2] represented by the following formula [2]
E: hydrocarbon group. However, each E may be the same or different.
Y: halogen atom The olefin dimerization catalyst according to claim 1, wherein X of the component (i) is acetylacetonate, 2,2,6,6-tetramethylheptane dionate or acetate. 3. The olefin dimerization catalyst according to claim 1, wherein the component (ii) is diethylaluminum chloride. A method for producing an olefin dimer using the olefin dimerization catalyst according to claim 1. A method for producing butene using the olefin dimerization catalyst according to claim 1.