Process for producing unsaturated hydrocarbon compound   

Abstract: Disclosed is a method for producing an unsaturated hydrocarbon compound wherein an α-olefin is dimerized by using a catalyst system composed of a metallocene compound (A) and an oxygen-containing organometallic compound modified with a halogen-containing compound (B). By this method, an unsaturated hydrocarbon compound having unsaturated double bonds in a high ratio, in particular the one having a terminal vinylidene group can be produced efficiently.

TECHNICAL FIELD

The present invention relates to an efficient method for producing an unsaturated hydrocarbon compound useful as a lubricant, cleaning agent, additive, its intermediate or the like.

BACKGROUND ART

Dimerization reaction of an α-olefin using a catalyst composed of a combination of a metallocene, an aluminoxane, an organoaluminum compound and the like is publicly known, and examples of such catalyst include a catalyst composed of zirconocene and methylaluminoxane (for example, Patent Document 1), a catalyst composed of zirconocene, alkylaluminoxane, trimethylaluminum (for example, Patent Document 2) and others.

Moreover, oligomerization of an α-olefin is also publicly known, for which a catalyst composed of zirconocene, organoaluminum and borate (for example, Patent Document 3), a catalyst composed of zirconocene, organoaluminum and borane (for example, Patent Document 4), a catalyst composed of zirconocene, methylaluminoxane, and organoaluminum (for example, Patent Document 5), and the like are used.

However, as activity of those catalyst systems are low and a large amount of the catalyst is required, productivity is inferior, and therefore, industrial utilization is difficult.

Furthermore, addition of hydrogen to dimerization and oligomerization reaction systems is not known.

In a polymerization reaction using a metallocene catalyst, hydrogen is added to control the molecular weight of the polymer.

This is to cause chain transfer reaction by the addition of hydrogen, and as a result, terminal groups of the polymer are saturated (for example, Patent Documents 6 and 7).

Therefore, to obtain a polymer having unsaturated double bonds in a high ratio, the addition of hydrogen was considered to be avoided. Patent Document 1: Japanese Examined Patent Publication No. H07-116065 Patent Document 2: Japanese Patent No. 3073234 Patent Document 3: Japanese Publication of Translation of PCT No. 2002-518582 Patent Document 4: Japanese Publication of Translation of PCT No. 2002-522572 Patent Document 5: Japanese Publication of Translation of PCT No. 2002-522575 Patent Document 6: Japanese Patent No. 3058419 Patent Document 7: Japanese Patent No. 3086469

DISCLOSURE OF THE INVENTION

The present invention is to address the above problems, and an object of the present invention is to provide a method for efficiently producing an unsaturated hydrocarbon compound having unsaturated double bonds in a high ratio, particularly a terminal vinylidene group (α-olefin dimer).

The inventors of the present invention have found that, by using an oxygen-containing organometallic compound modified with a halogen-containing compound as a component of the catalyst, an unsaturated hydrocarbon compound having unsaturated terminal double bonds in a high ratio is obtained, and thus accomplished the present invention.

The present invention was completed based on such knowledge.

Namely, the present invention provides the following:

1. A method for producing an unsaturated hydrocarbon compound, wherein an α-olefin is dimerized using a catalyst composed of a metallocene compound (A) and an oxygen-containing organometallic compound modified with a halogen-containing compound (B). 2. The method for producing an unsaturated hydrocarbon compound described in the above 1, wherein the component (B) is an oxygen-containing organometallic compound, represented by the general formula (2) and/or (3), modified with a halogen-containing compound,

in the formula, R8 to R14 each independently represent an alkyl group having 1 to 8 carbon atoms, A1 to A5 each independently represent a metal element of Group 13 in the periodic table. Each of h to k is a number of 0 to 50, and both (h+i) and (j+k) are larger than 1, 3. The method for producing an unsaturated hydrocarbon compound described in the above 1 or 2, wherein the halogen-containing compound is a halogenated alkyl aluminium compound or a halogenated hydrocarbon compound, 4. The method for producing an unsaturated hydrocarbon compound described in the above 3, wherein the halogenated alkyl aluminium compound is represented by the general formula (4),

R15nAlX13-n  (4)

in the formula, R15 represents a hydrocarbyl group having 1 to 20 carbon atoms or an organometalloid group, X1 represents a halogen atom, and n satisfies the relation 0<n<3. 5. The method for producing an unsaturated hydrocarbon compound described in the above 3, wherein the halogenated hydrocarbon compound is a compound in which hydrogen atoms in a hydrocarbon group having 1 to 20 carbon atoms are substituted with 1 to 4 halogen atoms, 6. The method for producing an unsaturated hydrocarbon compound described in any of the above 1 to 5, wherein the component (A) is a compound represented by the general formula (1),

Qa(C5H5-a-bR1b)(C5H5-a-cR2c)M1XY  (1)

in the formula, Q represents a connecting group for crosslinking two conjugated 5-membered ring ligands (C5H5-a-bR1b) and (C5H5-a-xR2c). R1 and R2 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group and may be the same or different from each other when plural groups are present, or may form a ring structure by bonding with each other. The symbol a is 0, 1 or 2. The symbols b and c each are an integer of 0 to 5 when a=0, an integer of 0 to 4 when a=1, and an integer of 0 to 3 when a=2. M1 represents a transition metal of Group 4 in the periodic table. X and Y each represent a covalent bond ligand or an ionic bond ligand, and may be bonded with each other. 7. The method for producing an unsaturated hydrocarbon compound described in the above 6, wherein M1 represents zirconium. 8. The method for producing an unsaturated hydrocarbon compound described in any of the above 1 to 7, wherein an α-olefin is dimerized in the presence of hydrogen, and 9. The method for producing an unsaturated hydrocarbon compound described in any of the above 1 to 8, wherein the ratio of unsaturated double bonds contained in the unsaturated hydrocarbon compound is 80 mol % or more.

According to the present invention, an unsaturated hydrocarbon compound having unsaturated double bonds in a high ratio, particularly a terminal vinylidene group may be economically produced in a high yield and high selectivity by using a catalyst containing a metallocene compound (A) and an oxygen-containing organometallic compound modified with a halogen-containing compound (B).

The present invention relates to a process for producing an unsaturated hydrocarbon compound by dimerization of an α-olefin using a catalyst composed of a metallocene compound (A) and an oxygen-containing organometallic compound modified with a halogen-containing compound (B).

The following compounds may be preferably used as a component of the catalyst of the present invention.

Metallocene Compound (A)

In the present invention, although various metallocene compounds may be used, preferably a transition metal compound of Group 4 in the periodic table is used.

The transition metal compound of Group 4 in the periodic table is represented by the general formula (1),

Qa(C5H5-a-bR1b)(C5H5-a-cR2c)M1XY  (1)

where Q represents a connecting group for crosslinking two conjugated 5-membered ring ligands (C5H5-a-bR1b) and (C5H5-a-cR2c). R1 and R2 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group, and may be the same or different from each other when plural groups are present, or may form a ring structure by bonding with each other. The symbol a is 0, 1 or 2. The symbols b and c each are an integer of 0 to 5 when a=0, an integer of 0 to 4 when a=1, and an integer of 0 to 3 when a=2. M1 represents a transition metal of Group 4 in the periodic table. X and Y each represent a covalent bond ligand or an ionic bond ligand, and may be bonded with each other.

Specific examples of Q include:

(1) Alkylene group having 1 to 20 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, isopropylene group, methylphenyl methylene group, diphenyl methylene group, cyclohexylene group and the like, cycloalkylene group, or cycloalkylene group having side chain lower alkyl or phenyl-substituted cycloalkylene group. (2) Silylene group such as silylene group, dimethylsilylene group, methylphenyl silylene group, diphenylsilylene group, disilylene group, tetramethyldisilylene group and the like, oligo silylene group, or oligo silylene group having side chain lower alkyl or phenyl-substituted oligo silylene group. (3) Hydrocarbon containing germanium, phosphorus, nitrogen, boron or aluminum group [lower alkyl group, phenyl group, hydrocarbyloxy group (preferably lower alkoxy group) and the like] such as (CH3)2Ge group, (C6H5)2Ge group, (CH3)P group, (C6H5)P group, (C4H9)N group, (C6H5)N group, (CH3)B group, (C4H9)B group, (C6H5)B group, (C6H5)Al group, (CH3O)Al group, and the like.

Among them, alkylene group and silylene group are preferable.

Furthermore, (C5H5-a-bR1b) and (C5H5-a-cR2c) each represent a conjugated 5-membered ring ligand. R1 and R2 each represent a hydrocarbon group, a halogen atom, an alkoxy group, a silicon-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a nitrogen-containing hydrocarbon group or a boron-containing hydrocarbon group. The symbol a is 0, 1 or 2.

The symbols b and c each are an integer of 0 to 5 when a=0, an integer of 0 to 4 when a=1, and an integer of 0 to 3 when a=2.

As the hydrocarbon group mentioned above, those having 1 to 20 carbon atoms are preferable, and those having 1 to 12 carbon atoms are particularly preferable.

The hydrocarbon group as a monovalent group, may be bonded to a cyclopentadienyl group that is a conjugated 5-membered ring group, or when plural groups are present, two of them may be bonded with each other to form a ring structure together with a part of cyclopentadienyl group.

Namely, representative examples of conjugated 5-membered ring ligand include substituted or unsubstituted cyclopentadienyl group, indenyl group and fluorenyl group.

As the halogen atom, chlorine, bromine, iodine and fluorine atoms are cited, and as alkoxy group, those having 1 to 12 carbon atoms are cited preferably.

Examples of silicon-containing hydrocarbon group include —Si(R3)(R4)(R5) (where R3, R4 and R5 each represent a hydrocarbon group having 1 to 24 carbon atoms) and the like, examples of the phosphorous-containing hydrocarbon group, nitrogen-containing hydrocarbon group and boron-containing hydrocarbon group include, respectively, —P(R6)(R7), —N(R6)(R7), —B(R6)(R7) and the like, where R6 and R7 each represent a hydrocarbon group having 1 to 18 carbon atoms.

When plural R1s and R2s are present, they may be the same or different from each other.

Furthermore, in a compound represented by the general formula (1), conjugated 5-membered ring ligands (C5H5-a-bR1b) and (C5H5-a-cR2c) may be the same or different from each other.

M1 represents a transition metal element of Group 4 in the periodic table, and specific examples include titanium, zirconium, hafnium, of which zirconium is most preferable.

X and Y each represent a covalent bonding ligand or an ionic bonding ligand. Specific examples include hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, amino group, a phosphorous-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (such as diphenyl phosphine group) or silicon-containing hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms (such as trimethylsilyl group), hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, or halogen-containing boron compound (such as B(C6H5)4, BF4).

Among those groups, hydrogen atom, halogen atom, hydrocarbon group and alkoxy group are preferable.

X and Y may be the same or different from each other.

Specific examples of a compound represented by the above general formula (1) include compounds described in the following (a) to (f):

(a) Transition metal compound having two conjugated 5-membered ring ligands without having a crosslinking bonding group, such as bis(cyclopentadienyl)zirconium dichloride, bis(methylcyclopentadienyl)zirconium dichloride, bis(1,3-dimethylcyclopentadienyl) zirconium dichloride, bis(1,2,4-trimethylcyclopentadienyl)zirconium dichloride, bis(tetramethylcyclopentadienyl)zirconium dichloride, bis(pentamethyl cyclopentadienyl)zirconium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(trimethylsilylcyclopentadienyl)zirconium dichloride, bis[bis(trimethylsilyl)cyclopentadienyl]zirconium dichloride, bis(trimethylsilyl methyl cyclopentadienyl)zirconium dichloride, bis(indenyl)zirconium dichloride, bis(1,2,3-trimethylindenyl)zirconium dichloride, bis(1,2,3-trimethyl tetrahydro indenyl)zirconium dichloride, bis(fluorenyl)zirconium dichloride, bis(9-methylfluorenyl)zirconium dichloride, bis(9-methyloctahydrofluorenyl)zirconium dichloride, bis(cyclopentadienyl)zirconium chlorohydride, bis(cyclopentadienyl)methyl zirconium chloride, bis(cyclopentadienyl)ethyl zirconium chloride, bis(cyclopentadienyl)methoxy zirconium chloride, bis(cyclopentadienyl)phenyl zirconium chloride, bis(cyclopentadienyl)dimethyl zirconium, bis(cyclopentadienyl)diphenyl zirconium, bis(cyclopentadienyl)dineopentyl zirconium, bis(cyclopentadienyl)dihydrozirconium, bis(cyclopentadienyl)dimethoxyzirconium, (cyclopentadienyl)(pentamethylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(indenyl)zirconium dichloride, (cyclopentadienyl)(fluorenyl) zirconium dichloride, and the like, (b) Transition metal compound having two conjugated 5-membered ring ligands crosslinked by an alkylene group such as methylenebis(cyclopentadienyl)zirconium dichloride, ethylenebis(cyclopentadienyl)zirconium dichloride, 1,3-propylene bis(cyclopentadienyl)zirconium dichloride, 1,4-butylenebis(cyclopentadienyl)zirconium dichloride, isopropylidenebis(cyclopentadienyl)zirconium dichloride, rac-methylenebis(indenyl)ziroconium dichloride, meso-methylenebis(indenyl) zirconium dichloride, rac-ethylenebis(indenyl)zirconium dichloride, meso-ethylene bis(indenyl)zirconium dichloride, ethylenebis(fluorenyl)zirconium dichloride, rac-1,3-propylenebis(indenyl)zirconium dichloride, meso-1,3-propylene bis(indenyl)zirconium dichloride, rac-1,4-butylenebis(indenyl)zirconium dichloride, meso-1,4-butylenebis(indenyl)zirconium dichloride, rac-ethylene bis(4,5,6,7-tetrahydro indenyl)zirconium dichloride, meso-ethylene bis(4,5,6,7-tetrahydro indenyl)zirconium dichloride, rac-ethylenebis(2-methylindenyl)zirconium dichloride, meso-ethylene bis(2-methylindenyl)zirconium dichloride, rac-ethylenebis(2,3-dimethylindenyl) zirconium dichloride, meso-ethylenebis(2,3-dimethylindenyl)zirconium dichloride, ethylene(2,4-dimethylcyclopentadienyl)(3′,5′-dimethyl cyclopentadienyl)zirconium dichloride, ethylene(2-methyl-4-tert-butylcyclopentadienyl)(3′-tert-butyl-5′-methyl cyclopentadienyl)zirconium dichloride, ethylene(2,3,5-trimethyl cyclopentadienyl) (2′,4′,5′-trimethylcyclopentadienyl)zirconium dichloride, ethylene bis(tetramethyl cyclopentadienyl)zirconium dichloride, methylene(cyclopentadienyl)(3,4-dimethyl cyclopentadienyl)zirconium dichloride, methylene(cyclopentadienyl)(trimethyl cyclopentadienyl)zirconium dichloride, methylene(cyclopentadienyl)(tetramethyl cyclopentadienyl)zirconium dichloride, isopropylidene(cyclopentadienyl) (3,4-dimethylcyclopentadienyl)zirconium dichloride, isopropylidene(cyclopentadienyl) (tetramethylcyclopentadienyl)zirconium dichloride, isopropylidene(cyclopentadienyl) (3-methylindenyl)zirconium dichloride, isopropylidene(cyclopentadienyl)(fluoreyl) zirconium dichloride, isopropylidene(2-methylcyclopentadienyl)(fluorenyl)zirconium dichloride, isopropylidene(2,5-dimethylcyclopentadienyl) (3,4-dimethylcyclopentadienyl)zirconium dichloride, isopropylidene (2,5-dimethylcyclopentadienyl)(fluorenyl)zirconium dichloride, ethylene(cyclopentadienyl)(2,4-dimethylcyclopentadienyl)zirconium dichloride, ethylene(cyclopentadienyl)(fluorenyl)zirconium dichloride, ethylene (2,5-dimethyl cyclopentadienyl)(fluorenyl)zirconium dichloride, ethylene(2,5-diethyl cyclopentadienyl)(fluorenyl)zirconium dichloride, diphenylmethylene (cyclopentadienyl)(3,4-diethylcyclopentadienyl)zirconium dichloride, diphenyl methylene(cyclopentadienyl)(3,4-diethylcyclopentadienyl)zirconium dichloride, cyclohexylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride, cyclohexylidene (2,5-dimethylcyclopentadienyl)(3′,4′-dimethylcyclopentadienyl)zirconium dichloride, and the like, (c) Transition metal compound having two conjugated 5-membered ring ligands crosslinked by a silylene group such as dimethylsilylene bis(cyclopentadienyl)zirconium dichloride, phenylmethylsilylene bis(cyclopentadienyl)zirconium dichloride, diphenylsilylene bis(cyclopentadienyl)zirconium dichloride, tetramethyl disilylene bis(cyclopentadienyl)zirconium dichloride, dimethyl silylene (cyclopentadienyl) (tetramethylcyclopentadienyl)zirconium dichloride, and the like, (d) Transition metal compound having two conjugated 5-membered ring ligands which are crosslinked by a hydrocarbon group containing germanium, aluminum, boron, phosphorous or nitrogen such as dimethylgermylenebis(cyclopentadienyl)zirconium dichloride, methylalumilenebis(cyclopentadienyl)zirconium dichloride, phenylalumilenebis(cyclopentadienyl)zirconium dichloride, phenylphosphilene bis(cyclopentadienyl)zirconium dichloride, ethylborenebis(cyclopentadienyl)zirconium dichloride, phenylamylenebis(cyclopentadienyl)zirconium chloride, and the like. (e) Transition metal compound having two conjugated 5-membered ring ligands doubly crosslinked with each other such as (1,1′-dimethylsilylene)(2,2′-isopropylidene) bis(cyclopentadienyl)zirconium dichloride, (1,1′-ethylene)(2,2′-ethylene) bis(cyclopentadienyl)zirconium dichloride, (1,1′-dimethylsilylene)(2,2′-dimethylsilylene)bis(cyclopentadienyl)zirconium dichloride, (1,2′-dimethyl-silylene)(2,1′-ethylene)bis(indenyl)zirconium dichloride, (1,1′-dimethylsilylene)(2,2′-ethylene)bis(indenyl)zirconium dichloride, (1,1′-ethylene) (2,2′-dimethylsilylene)bis(indenyl)zirconium dichloride, (1,1′-dimethylsilylene)(2,2′-cyclo-hexylidene)bis(indenyl)zirconium dichloride, and the like, (f) Furthermore, a compound described in the above (a) to (e) wherein chlorine atom is replaced with bromine atom, iodine atom, hydrogen atom, methyl group, phenyl group, and the centered metal of the above compounds, zirconium, is replaced with titanium or hafnium.

(B) Oxygen-Containing Organometallic Compound Modified with a Halogen-Containing Compound

The oxygen-containing organometallic compound modified with a halogen-containing compound used in the present invention is obtained by modifying the oxygen-containing organometallic compound (b1) with a halogen-containing compound (b2).

Examples of the halogen-containing compound (b2) include, as described later, a halogenated alkylaluminum compound (b3), and a halogenated hydrocarbon compound (b4).

For preparation of the component (B), the halogen-containing compound (b2), namely, the halogenated alkylaluminum compound (b3) or the halogenated hydrocarbon compound (b4) may be used alone or in a combination of two or more with the oxygen-containing organometallic compound (b1).

Oxygen-Containing Organometallic Compound (b1)

The oxygen-containing organometallic compound preferably used in the present invention is represented by the general formula (2) and/or (3):

where R8 to R14 each independently represent an alkyl group having 1 to 8 carbon atoms, A1 to A5 each independently represent a metal element of Group 13 in the periodic table. The symbols h to k each are an integer of 0 to 50, and both (h+i) and (j+k) are larger than 1.

The alkyl groups R8 to R14 having 1 to 8 carbon atoms in the oxygen-containing organometallic compound represented by the general formula (2) and (3) include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups. The metal elements represented by A1 to A5 belonging to Group 13 in the periodic table include boron, aluminum, gallium, indium, and thallium.

Among those metal elements, boron and aluminum are particularly preferable.

Further, the value of h to k is preferably in the range of 1 to 20, and particularly preferably 1 to 5.

The compounds represented by the general formulas (2) and (3) include alumoxanes such as straight chain or cyclic tetramethyl dialumoxane, tetraisobutyldialumoxane, methyl alumoxane, ethyl alumoxane, butyl alumoxane, isobutylalumoxane and the like; boroxanes such as trimethyl boroxane and methyl boroxane and the like.

Among those compounds, alumoxanes are preferable, particularly methyl alumoxane are preferable.

Halogen-Containing Compound (b2)

The halogen-containing compound used in the present invention includes halogenated alkylaluminium compound (b3) and/or halogenated hydrocarbon compound (b4).

Preferable halogenated alkylaluminum compound is represented by the general formula (4):

R15nAlX13-n  (4)

where R15 represents a hydrocarbyl group having 1 to 20 carbon atoms or an organometalloid group, X1 represents a halogen atom, and n satisfies the relation 0<n<3.

Preferable examples of hydrocarbyl group and organometalloid group of R15 in the compound represented by the general formula (4) include methyl group, ethyl group, propyl group, isopropyl group, various butyl groups, various aryl groups, various hydrocarbyl silyl group and the like.

Moreover, n in the formula is preferably 1, 1.5 or 2, more preferably 2.

Examples for n=1 include methylaluminum dichloride, ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, tert-butyl aluminum dichloride and the like.

Examples for n=1.5 include methylaluminum sesquichloride, ethylaluminum sesquichloride, n-propylaluminum sesquichloride, n-butylaluminum sesquichloride, iso-butylaluminum sesquichloride, tert-butylaluminum sesquichloride and the like.

Examples for n=2 include dimethylaluminum chloride, diethylaluminum chloride, di-n-propylaluminum chloride, di-n-butylaluminum chloride, di-isobutylaluminum chloride, di-tert-butylaluminum chloride and the like.

In the present invention, those compounds may be used alone or in a combination of two or more.

Halogenated Hydrocarbon Compound (b4)

The halogenated hydrocarbon compound used in the present invention is preferably a compound in which hydrogen atoms in a hydrocarbon group having 1 to 20 carbon atoms are substituted with 1 to 4 halogen atoms.

Preferable examples of hydrocarbon group having 1 to 20 carbon atoms include alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 5 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and aralkyl group having 7 to 20 carbon atoms.

Examples of the halogenated hydrocarbon compound include methyl chloride, ethyl chloride, propyl chloride, butyl chloride, pentyl chloride, octyl chloride, phenyl chloride, benzyl chloride, naphthyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, ethyl bromide, propyl bromide, butyl bromide, pentyl bromide, octyl bromide, phenyl bromide, benzyl bromide, naphthyl bromide, methylene bromide, bromoform, carbon tetrabromide, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, pentyl iodide, octyl iodide, phenyl iodide, benzyl iodide, naphthyl iodide, methylene iodide, iodoform, carbon tetraiodide and the like.

In the present invention, those compounds may be used alone or in a combination of two or more.

Preparation of a catalyst of the present invention using the metallocene compound (A), the halogen-containing compound (b2) and the oxygen-containing organometallic compound (b1) is preferably conducted under atmosphere of an inert gas such as nitrogen.

In the preparation of the oxygen-containing organometallic compound (b1) modified with the halogen-containing compound (b2), (B), modification reaction of the oxygen-containing organometallic compound (b1) by the halogen-containing compound (b2) may be conducted by contacting the component (b1) and the component (b2) in advance, but, as the modification reaction proceeds quickly, a catalyst having sufficiently high activity can be obtained by contacting the component (b1) and the component (b2) in the presence of an α-olefin.

The catalyst components prepared in advance in a catalyst preparation vessel may be used, or alternatively, the catalyst components prepared in a reactor used for the dimerization reaction of the α-olefin may be also used for the reaction.

When the catalyst is prepared in a reactor, temperature is preferably adjusted to be lower than the temperature for dimerization reaction of the α-olefin, for example, in the range of −30 to 200° C., preferably 0 to 150° C.

In the dimerization reaction of the present invention, presence of hydrogen increases the yield of the desired unsaturated hydrocarbon compound.

Hydrogen may be introduced into the component (A), the component (b1) and the component (b2) from the beginning without using an inert gas such as nitrogen, or alternatively, may be introduced after the component (A), the component (b1) and the component (b2) are mixed and contacted with α-olefin.

The mixing ratio of the oxygen-containing organometallic compound (b1) to the halogenated alkylaluminum compound (b3), in terms of component (b1)/component (b3) [molar ratio] is normally 0.01 to 10 equivalent, preferably 0.05 to 5 equivalent and more preferably 0.1 to 3 equivalent per metal atom.

If the above ratio is smaller than 0.01 equivalent, the catalyst activity may decrease, if larger than 10 equivalent, a saturated dimer of the α-olefin may be formed, and the ratio of the desired unsaturated groups in the unsaturated hydrocarbon compound may decrease, or the yield may decrease.

The mixing ratio of the oxygen-containing organometallic compound (b1) to the halogenated hydrocarbon compound (b4) in terms of component (b1)/component (b4) [molar ratio] is normally 0.01 to 20 equivalent, preferably 0.05 to 10 equivalent and more preferably 0.1 to 5 equivalent per metal atom.

If the above ratio is smaller than 0.01 equivalent, the catalyst activity may decrease, if the ratio exceeds 20 equivalent, the yield of the desired unsaturated hydrocarbon compound may decrease.

Further, in the case where the component (b1) is modified by the component (b3) and the component (b4), the mixing ratio in terms of the component (b1)/[components (b3)+(b4)] (molar ratio) is normally 0.01 to 20 equivalent, preferably 0.05 to 10 equivalent, and more preferably 0.1 to 5 equivalent per metal atom.

The mixing ratio of the transition metal compound (A) to the oxygen-containing organometallic compound (b1) in terms of the component (A)/the component (b1) [molar ratio] is normally 1/1 to 1/1000 and preferably 1/2 to 1/100.

If the above ratio is smaller than 1/1, the catalyst activity may not be realized, if the ratio exceeds 1/1000, a high molecular weight polymer of the α-olefin may be formed, and the yield of the desired unsaturated hydrocarbon compound may decrease, or a saturated dimer of the α-olefin may be formed, and the ratio of unsaturated groups in the unsaturated hydrocarbon compound may decrease.

The mixing ratio of the transition metal compound (A) to the halogenated alkylaluminum compound (b3) in terms of the component (A)/the component (b3) [molar ratio] is normally 1/0.5 to 1/100, preferably 1/1 to 1/20, and the mixing ratio of the transition metal compound (A) to the halogenated hydrocarbon compound (b4) in terms of the component (A)/the component (b4) [molar ratio] is normally 1/0.5 to 1/200, and preferably 1/1 to 1/50.

Furthermore, when the component (b1) is modified by the component (b3) and the component (b4), the mixing ratio to the component (A) in terms of the component (A)/[components (b3)+(b4)] (molar ratio) is normally 1/0.5 to 1/200 and preferably 1/1 to 1/50.

The amount of added hydrogen is normally 0.1 to 700 kPa, and preferably 0.5 to 100 kPa.

Namely, the molar ratio of hydrogen to the metallocene compound (A) is normally 1/1 to 10000/1, preferably 1/1 to 1000/1, and more preferably 5/1 to 1000/1.

Moreover, the molar ratio of hydrogen to the α-olefin is normally 1/10000 to 1/1, preferably 1/10000 to 1/10, and more preferably 1/2000 to 1/10.

If the amount of added hydrogen is excessive, a saturated dimer of the α-olefin may be formed, and the ratio of unsaturated groups in the unsaturated hydrocarbon compound may decrease.

Although the α-olefin used in the present invention is not particularly limited, examples of preferable α-olefin include propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-butene, 4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene, 1-dococene, 1-tetracocene, 1-hexacocene, 1-octacocene, 1-triacontene, 1-doriacontene, 1-tetracontene, vinylcyclohexane and the like.

In the present invention, the above α-olefins may be used alone or in a combination of two or more.

The unsaturated hydrocarbon compound obtained in the present invention contains normally 80 mol % or more of the unsaturated double bond, particularly the ratio of the terminal vinylidene group is normally 75 mol % or more.

In the present invention, the method for reaction is not limited, and the reaction may be conducted in the absence of a solvent or in the presence of a solvent, and either method may be employed.

With respect to the reaction conditions, the reaction temperature is −100 to 250° C., particularly −50 to 100° C. is preferable.

The ratio of the amount of catalyst to α-olefin in terms of the α-olefin/the metallocene compound (A) (molar ratio) is normally 1000 to 106, and preferably 2000 to 105.

The reaction time is normally 10 minutes to 48 hours.

If a solvent is used in the reaction, examples of the solvent include aromatic hydrocarbon such as benzene, toluene, xylene, ethylbenzene and the like, alicyclic hydrocarbon such as cyclopentane, cyclohexane, methyl cyclohexane and the like, aliphatic hydrocarbon such as pentane, hexane, heptane, octane and the like, halogenated hydrocarbon such as chloroform, dichloromethane and the like.

The above solvent may be used alone or in a combination of two or more.

Moreover, the raw material such as the α-olefin may be used as a solvent.

The present invention is explained in further detail with reference to examples. However, the present invention is by no means restricted by these examples.

In a glass container having a 100 mL internal volume, 1.0 ml of a deuterated benzene (C6D6) solution of methylaluminoxane (MAO) adjusted to 1.0 mol/L was charged at 25° C.

Then, 1.0 ml of a deuterated benzene (C6D6) solution of diethylaluminum chloride (DEAC) adjusted to 1.0 mol/L was added to the above solution and the resultant solution was stirred for 10 minutes.

Subsequently, 1.0 mL of a deuterated benzene (C6D6) solution of bis(cyclopentadienyl)zirconium dichloride (Cp2ZrCl2) adjusted to 0.1 mol/L was added and stirred. The result of 1H-NMR measurement of this catalyst system is shown in Table 1.

TABLE 1 1H-NMR (C6D6) Peak due to catalyst + promoter Peak due to promoter near Zr—H near C5H5 Catalyst system(mol ratio) Chemical Assigned Chemical Assigned Chemical Assigned

Download full PDF for full patent description/claims.




You can also Monitor Keywords and Search for tracking patents relating to this Process for producing unsaturated hydrocarbon compound patent application.
###


Other recent patent applications listed under the agent Idemitsu Kosan Co., Ltd.: