JPH1192407A - Catalyst for trimerizing ethylene and trimerization of ethylene in presence of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject catalyst for efficiently and highly selectively producing 1-hexene useful as a raw material comonomer for linear low density polyethylene from ethylene by including a chromium compound, an alkyl metal compound and a specific sulfur compound. SOLUTION: This catalyst comprises a chromium compound of the formula: CrAm [(m) is an integer of 1-6; A is carbon monoxide or the like), an alkyl compound of the formula: Rp MXq [0<(p)<=3, 0<=(q)<3, (p)+(q) is 1 to 3: M is lithium or the like; R is a 1-10C alkyl; X is H or the like), and a sulfur compound of the formula: R<1> -(Y)h -[R<2> -(Y)I]k -R<3> [(h), (i) are each an integer of 1-8; (k) is an integer of 0-10; R<1> , R<3> are each H or the like; R<2> is a 1-8C alkylene; Y is a group expressed by the formula] or the formula: R<4> -S-M (R<4> is a 1-20C hydrocarbon; M is a 2, 11, 12, 13 or 14 group metal element in the periodic table).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an ethylene trimerization catalyst comprising a chromium compound, an alkyl metal compound and a sulfur compound, and a method for trimerizing ethylene using the catalyst. More specifically, linear low density polyethylene (LL
1-Hexene useful as a raw material comonomer of DPE) can be obtained efficiently and highly selectively, and the catalyst preparation operation and handling are easy, and a method for ethylene trimerization using the same. .

[0002]

2. Description of the Related Art It is known to use a chromium compound as a catalyst in a process for obtaining 1-hexene by trimerizing ethylene. For example, JP-A-62-265237 discloses a catalyst system comprising a chromium compound, polyhydrocarbyl aluminum oxide and a donor ligand. JP-A-6-239920 discloses a catalyst system comprising a chromium compound, a pyrrole-containing compound, a metal alkyl and a halide, and JP-A-9-20692 discloses a reaction product of a chromium salt and a metal amide; A catalyst system comprising an inorganic oxide solid, an alumoxane and an electron donor compound is disclosed.

[0003]

In the ethylene trimerization method using a chromium compound as a catalyst, it is necessary to treat a waste chromium catalyst at the end of the ethylene trimerization reaction, but the chromium compound constituting the catalyst depends on the structure. Produces extremely toxic compounds. Therefore, from the aspect of safety,
Although it is necessary to minimize the amount of chromium metal used, the method described in JP-A-62-265237 has a problem that the activity per chromium is not sufficient and a large amount of chromium compound must be used. Was. There is also a problem that a large amount of polyethylene is produced as a by-product.

Further, the method described in JP-A-6-239920 improves the activity per chromium and suppresses the amount of the chromium compound used. However, in this method, the catalyst preparation operation is complicated, and the pyrrole-containing compound, which is a component of the catalyst, is extremely unstable to air, and thus is easily colored and deteriorated. It was not enough as a typical catalyst. Also,
In the method described in JP-A-9-20692, an inorganic oxide solid is indispensable as one component of the catalyst, so that the catalyst preparation operation such as calcining and drying the inorganic oxide solid becomes complicated, Has a problem that it is difficult to handle the catalyst solution and to introduce the catalyst into the reactor because the slurry solution is used.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an industrially advantageous catalyst system which is easy in catalyst preparation operation and handling, and which is useful as a raw material comonomer of LLDPE. An object of the present invention is to provide a method for trimerizing ethylene, which can efficiently and highly selectively obtain hexene from ethylene.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, a catalyst comprising a chromium compound, an alkyl metal compound and a specific sulfur compound has a difficulty in the preparation and handling of the catalyst. It is easy to find that when the ethylene trimerization reaction is carried out in the presence of this catalyst, it shows very high catalytic activity and high selectivity, and has completed the present invention.

That is, the present invention relates to an ethylene trimerization catalyst comprising a chromium compound, an alkyl metal compound and a sulfur compound, and a method for trimerizing ethylene using the catalyst.

[0008]

Next, the present invention will be described in more detail.

The sulfur compound used in the present invention is represented by the following general formula (1): R ^1- (Y) _h- [R ^2- (Y) _i ] _k -R ³ (1) Is an integer of 1 to 8 and k is an integer of 0 to 10. R ¹ and R ³ are each hydrogen and have 1 to 20 carbon atoms.
Hydrocarbon group, an acyl group having 1 to 10 carbon atoms,
10 alkoxy groups, halogen atoms, and R ¹ and R ³ are selected from the group consisting of cyclic substituents bonded by a carbon-carbon bond. R ² represents an alkylene group having 1 to 8 carbon atoms. Y is

[0010]

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Or

[0012]

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And / or the following general formula (2): R ⁴ -SM (2) (wherein R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms,
Represents an acyl group having from 10 to 10 or a thioacyl group having from 1 to 10 carbon atoms, and M represents a substituent-containing or unsubstituted metal element belonging to Group 1, 2, 11, 12, 13, or 14 of the periodic table) Compound.

In the above general formula (1), the number of carbon atoms is 1 to 2.
Examples of the hydrocarbon group 0 include, but are not particularly limited to, an ethyl group, a propyl group, a butyl group, an allyl group, a neopentyl group, a cyclopentadienyl group, a pentamethylcyclopentadienyl group, and a trimethylsilylmethyl group. Phenyl group, tolyl group or fluorine-containing phenyl group. As the acyl group having 1 to 10 carbon atoms,
Although not particularly limited, examples thereof include an acetyl group, a benzoyl group and a toluoyl group. Carbon number 1
The alkoxy group of Nos. To 10 is not particularly limited, but includes, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a stearyloxy group or a phenoxy group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

In the above general formula (2), the number of carbon atoms is 1 to 2
The hydrocarbon group of 0 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a tolyl group, and a fluorine-containing phenyl group. The acyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include an acetyl group, a benzoyl group and a toluoyl group.
The thioacyl group of 0 is not particularly limited, but examples include a thioacetyl group, a thiobenzoyl group, and a thiotoluoyl group. Further, as M, for example, lithium, sodium, potassium, calcium,
Copper, zinc, aluminum, tin or the like can be used. Although it does not specifically limit as a substituent, For example, an alkyl group and an aryl group are mentioned. Examples of the alkyl group include, but are not particularly limited to, for example, a methyl group,
Ethyl, propyl, butyl, hexyl, octyl, octadecyl, benzyl and the like. The aryl group is not particularly limited, but examples include a phenyl group and a tolyl group.

The sulfur compound represented by the above general formula (1) is not particularly limited, but includes, for example, dimethyl sulfide, diethyl sulfide, di (n-propyl) sulfide, di (i-propyl) sulfide, (N-butyl) sulfide, di (sec-butyl) sulfide, di (t-butyl) sulfide, dihexyl sulfide, dioctyl sulfide, didodecyl sulfide, diethylene sulfide, dipropylene sulfide,
Diallyl sulfide, bis (2-mercaptoethyl) sulfide, diphenyl sulfide, dibenzyl sulfide, bis (pentafluorophenyl) sulfide, ethyl methyl sulfide, t-butyl methyl sulfide, phenyl methyl sulfide, allyl methyl sulfide, 2
-Hydroxyethyl methyl sulfide, 2-chloroethyl methyl sulfide, 2-chloroethyl ethyl sulfide, chloromethyl methyl sulfide, chloromethyl trifluoromethyl sulfide, tris (methylthio) methane, bis (methylthio) methane, bis (phenylthio)
Methane, bis (phenylthio) propane, dimethylene sulfide, trimethylene sulfide, tetramethylene sulfide, pentamethylene sulfide, 1,3-dithiane, 1,4-dithiane, 1,3,5-trithiane, 1,
4,7-trithiacyclononane, 1,4,7-trithiacyclodecane, 1,4,7,10-tetrathiacyclododecane, 1,5,9,13-tetrathiacyclohexadecane, 1,4- Thioxane, cyclohexene sulfide, diacetyl sulfide, dibenzoyl sulfide,
Examples include sulfides such as sulfur dichloride and heterocyclic sulfides such as thiophene, benzothiophene, dibenzothiophene, and thianethrene.

Also, dimethyl disulfide, diethyl disulfide, di (n-propyl) disulfide, di (i
-Propyl) disulfide, di (n-butyl) disulfide, di (t-butyl) disulfide, diallyldisulfide, diphenyldisulfide, bis (2-hydroxyethyl) disulfide, methylpropyldisulfide, 1,2-dithiolane, 1,2- Zithian, 1, 2,
Polysulfides such as 3,5,6-pentathiepane, diacetyl disulfide and dibenzoyl disulfide;
Thiocyanates such as methyl thiocyanate and phenyl thiocyanate; sulfoxides such as dimethyl sulfoxide, dibutyl sulfoxide and diphenyl sulfoxide; dimethyl sulfone, diethyl sulfone, dibutyl sulfone, diphenyl sulfone, di (p-tolyl) sulfone, tetramethylene sulfone, bis (phenyl) Sulfones) sulfones such as methane and dimethyl sulfate, thiol sulfinates such as diphenylthiol sulfinate and ditolylthiol sulfinate, and thiol sulfonates such as phenylbenzenethiol sulfonate and phenylbutylthiol sulfonate. Can be

The sulfur compound represented by the general formula (2) is not particularly limited, but includes, for example, diisobutylaluminum thiomethoxide, diisobutylaluminum thioethoxide, diisobutylaluminum thiopropoxide, diisobutylaluminum thiobutoxide, Diisobutylaluminum thiophenoxide,
Metal thioalkoxides such as diisobutylaluminum pentafluorothiophenoxide, diethylaluminum thiobutoxide, dimethylaluminum thiobutoxide, lithium thiobutoxide, sodium thiobutoxide, potassium thiobutoxide or tributyltin thiobutoxide, diisobutylaluminum thioacetate, diisobutylaluminum thiobenzoate, Metal thiocarboxylates such as diphenyltin bis (thiobenzoate), zinc bis (thiobenzoate), copper bis (thiobenzoate), diisobutylaluminum dithioacetate, diisobutylaluminum dithiobenzoate, diphenyltin bis (dithiobenzoate), zinc bis (dithiobenzoate) ), Metals such as copper bis (dithiobenzoate) Thio carboxylates and the like.

The compound of the general formula (2) used in the present invention may be added as it is as a component of the ethylene trimerization catalyst, or may be directly synthesized in a reaction system. For the method of direct synthesis in the reaction system,
There is no particular limitation, and it can be synthesized by a known method.
For example, (1) a method of contacting sulfur with an alkylaluminum compound which is a component of the ethylene trimerization catalyst of the present invention, (2) a method of contacting an alkylaluminum compound with carbon disulfide, (3) a method of contacting an alkylaluminum compound with mercaptan (4) a method of contacting an alkylaluminum compound with a thiocarboxylic acid,
(5) A method of contacting an alkyl aluminum compound with a dithiocarboxylic acid, and the like. Specifically, T.A. M
ol and E. A. Jeffery, ORGANO
ALUMINIUM COMPOUNDS, p251
(1972), ELSEVIER.

Of these sulfur compounds, sulfides are preferred from the viewpoint of safety and availability, and more preferably di (n-butyl) sulfide, dimethyl sulfide or tetramethylene sulfide is used. The sulfur compounds can be used alone or in combination of two or more.

The amount of the sulfur compound used is chromium compound 1
It is 0.01 to 100,000 equivalents, preferably 0.05 to 10,000 equivalents, and more preferably 0.1 to 2,000 equivalents, per mol. When the amount of the sulfur compound used is less than 0.01 equivalent relative to 1 mole of the chromium compound, a large amount of polyethylene is produced as a by-product. On the other hand, if the amount used exceeds 100,000 equivalents per mole of the chromium compound, the catalytic activity tends to decrease.

The chromium compound used in the present invention is not particularly limited. For example, the following general formula (3) CrA _m (3) (where m is an integer of 1 to 6. Is carbon monoxide, arene, alkene, alkyne, carbene, tropylium cation, nitrogen, nitrile, isonitrile, phosphine, phosphite, sulfide, sulfoxide, alkyl, aryl, alkoxy, thioalkoxy, carboxylate, thiol A carboxylate group, a dithiocarboxylate group, a β-diketonate group, a β-ketoester group, a halogen atom, a hydroxyl group, a nitrate group, a sulfate group, a perchlorate group, and oxygen. The compound represented by is preferably used.

In the above general formula (3), the arene is not particularly limited. For example, benzene, toluene, ethylbenzene, isopropylbenzene, t-butylbenzene, xylene, diisopropylbenzene, dibutylbenzene, trimethylbenzene, Tetramethylbenzene, hexamethylbenzene, triphenylbenzene, benzoic acid, methyl benzoate, ethyl benzoate, dimethyl terephthalate, benzaldehyde, anisaldehyde, chlorobenzene, bromobenzene, iodobenzene, fluorobenzene, phenol, anisole, benzyl alcohol, Phenylacetic acid, ethyl phenylacetate, methoxyphenethyl alcohol, styrene, phenylacetylene, trimethylsilylbenzene, triethoxysilylbenzene, Limethylgermaniumbenzene, trimethylstannylbenzene, triphenylborane, triphenylphosphine, phenylmethylsulfide, acetophenone, tetraphenylcyclopentenone, biphenyl, diphenylethane, diphenylpropane, diphenylbutane, diphenylethylene, diphenylbutadiene, benzophenone, naphthalene , Tetrahydronaphthalene, dihydronaphthalene, acenaphthylene, anthracene, dihydroanthracene, phenanthrene, dihydrophenanthrene, indane, indene,
Fluorene, pyrene, tetralone, benzophenone, benzothiophene, furan or thiophene and the like can be mentioned. Further, a polymer containing an aromatic compound as an arene is also included.

Examples of the alkene include, but are not limited to, ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, butadiene, isoprene, octadiene, and the like. Cyclooctadiene, octatriene, cyclooctatriene, cycloheptatriene, maleic acid, maleic anhydride and the like can be mentioned. As alkyne,
Although not particularly limited, for example, acetylene, phenylacetylene, diphenylacetylene, acetylenedicarboxylic acid diethyl ester and the like can be mentioned. The carbene is not particularly limited, for example,
Methylmethoxycarbene, phenylmethoxycarbene, diphenylcarbene and the like can be mentioned. The tropylium cation is not particularly limited, but includes, for example, tropylium, isopropyltropylium, methoxytropylium and the like. As nitrile,
Although not particularly limited, for example, acetonitrile, benzonitrile and the like can be mentioned. Although it does not specifically limit as isonitrile, For example, cyclohexyl isonitrile, t-butyl isonitrile, etc. are mentioned. Examples of the phosphine include, but are not particularly limited to, for example, trimethylphosphine, triethylphosphine, tributylphosphine, tricyclohexylphosphine, trifluorophosphine, triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, dimethylphosphinoethane, and the like. Can be Although it does not specifically limit as a phosphite, For example, trimethyl phosphite, tributyl phosphite, triphenyl phosphite, etc. are mentioned. Although it does not specifically limit as a sulfide, For example, tetramethylene sulfide etc. are mentioned. Although it does not specifically limit as a sulfoxide, For example, dimethyl sulfoxide, tetramethylene sulfoxide, diphenyl sulfoxide, etc. are mentioned.

Examples of the alkyl group include, but are not limited to, methyl, ethyl, butyl, allyl, neopentyl, cyclopentadienyl, pentamethylcyclopentadienyl, and trimethylsilylmethyl. And the like. The aryl group is not particularly limited, but examples include a phenyl group and a toluyl group. Although it does not specifically limit as an alkoxy group, For example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a stearyloxy group, a phenoxy group, etc. are mentioned. Although it does not specifically limit as a thioalkoxy group, For example, a thiomethoxy group, a thioethoxy group, a thiobutoxy group, a thiophenoxy group, etc. are mentioned. The carboxylate group is not particularly limited, for example, an acetate group, a propionate group,
Butyrate group, neopentanoate group, 2-ethylhexanoate group, oxy-2-ethylhexanoate group,
Examples include an isooctanoate group, a dichloroethylhexanoate group, a laurate group, a stearate group, an oleate group, a benzoate group, and a naphthenate group. Although it does not specifically limit as a thiocarboxylate group, For example, a thioacetate group or a thiobenzoate group is mentioned. Although it does not specifically limit as a dithiocarboxylate group, For example, a dithioacetate group or a dithiobenzoate group is mentioned. β
Examples of the diketonate group include, but are not particularly limited to, acetylacetonate group, trifluoroacetylacetonate group, hexafluoroacetylacetonate group, 2,2,6,6-tetramethyl-3,5- Heptandionate group, 1,3-butanedionate group, 2
-Methyl-1,3-butanedionate group, benzoylacetonate group and the like. The β-ketoester group is not particularly limited, but includes, for example, an acetyl acetate group. As a halogen atom,
Although not particularly limited, for example, fluorine, chlorine,
Bromine or iodine is mentioned.

The chromium compound represented by the above general formula (3) is not particularly limited. For example, hexacarbonyl chromium (0), pentacarbonyl (methylmethoxycarbene) chromium (0), pentacarbonyl (phenyl) Methoxycarbene) chromium (0), pentacarbonyl (diphenylcarbene) chromium (0), pentacarbonyl (triphenylphosphine) chromium (0),
Tetracarbonyl (methylmethoxycarbene) (trimethylphosphine) chromium (0), tetracarbonylbis (ethylene) chromium (0), tricarbonyl (benzene) chromium (0), tricarbonyl (toluene) chromium (0), tricarbonyl ( Ethylbenzene) chromium (0), tricarbonyl (isopropylbenzene) chromium (0), tricarbonyl (t-butylbenzene) chromium (0), tricarbonyl (xylene) chromium (0),
Tricarbonyl (diisopropylbenzene) chromium (0), tricarbonyl (dibutylbenzene) chromium (0), tricarbonyl (trimethylbenzene) chromium (0), tricarbonyl (tetramethylbenzene) chromium (0), tricarbonyl (hexamethyl) Benzene) chromium (0), tricarbonyl (triphenylbenzene)
Chromium (0), tricarbonyl (phenol) chromium (0), tricarbonyl (benzoic acid) chromium (0), tricarbonyl (methyl benzoate) chromium (0), tricarbonyl (ethyl benzoate) chromium (0), Tricarbonyl (dimethyl terephthalate) chromium (0), tricarbonyl (benzaldehyde) chromium (0), tricarbonyl (anisaldehyde) chromium (0), tricarbonyl (chlorobenzene) chromium (0), tricarbonyl (bromobenzene) Chromium (0), tricarbonyl (iodobenzene) chromium (0), tricarbonyl (fluorobenzene) chromium (0), tricarbonyl (anisole) chromium (0), tricarbonyl (benzyl alcohol) chromium (0), tricarbonyl (Phenylacetic acid) chromium (0), trical Nyl (ethyl phenylacetate) chromium (0), tricarbonyl (methoxyphenethyl alcohol) chromium (0), tricarbonyl (styrene) chromium (0), tricarbonyl (phenylacetylene) chromium (0), tricarbonyl (trimethylsilylbenzene) Chromium (0), tricarbonyl (triethoxysilylbenzene) chromium (0), tricarbonyl (trimethylgermanium benzene) chromium (0), tricarbonyl (trimethylstannylbenzene) chromium (0), tricarbonyl [1,4- Bis (tributylstannyl) benzene] chromium (0), tricarbonyl (triphenylborane) chromium (0), tricarbonyl (triphenylphosphine) chromium (0), tricarbonyl (phenylmethylsulfide) chromium (0), trica Bonyl (tetraphenylcyclopentenone) chromium (0), tricarbonyl (biphenyl) chromium (0), tricarbonyl (diphenylethane) chromium (0), tricarbonyl (diphenylpropane) chromium (0), tricarbonyl (diphenylbutane) ) Chromium (0), tricarbonyl (diphenylethylene) chromium (0), tricarbonyl (diphenylbutadiene) chromium (0), tricarbonyl (benzophenone) chromium (0), tricarbonyl (naphthalene) chromium (0), tricarbonyl (Tetrahydronaphthalene) chromium (0), tricarbonyl (dihydronaphthalene) chromium (0), tricarbonyl (acenaphthylene) chromium (0), tricarbonyl (anthracene) chromium (0), tricarbonyl (dihydroanthracene) ROM (0), tricarbonyl (phenanthrene) chromium (0), tricarbonyl (dihydrophenanthrene) chromium (0), tricarbonyl (indane)
Chromium (0), tricarbonyl (indene) chromium (0), tricarbonyl (fluorene) chromium (0),
Tricarbonyl (pyrene) chromium (0), tricarbonyl (tetralone) chromium (0), tricarbonyl (benzophenone) chromium (0), tricarbonyl (benzothiophene) chromium (0), tricarbonyl (thiophene) chromium (0) , Tricarbonyl (cycloheptatriene) chromium (0), tricarbonyl (tropylium)
Chromium tetrafluoroborate, tricarbonyl (isopropyltropylium) chromium tetrafluoroborate, tricarbonyl (methoxytropylium) chromium tetrafluoroborate, tricarbonyltris (acetonitrile) chromium (0), tricarbonyltris (t-
Butylisonitrile) chromium (0), tricarbonyltris (triphenylphosphite) chromium (0), (ethylene) dicarbonyl (hexamethylbenzene) chromium (0), (ethylene) dicarbonyl (trimethylbenzene) chromium (0) , (Ethylene) dicarbonyl (benzene) chromium (0), (ethylene) dicarbonyl (naphthalene) chromium (0), (propylene) dicarbonyl (hexamethylbenzene) chromium (0), (butene) dicarbonyl (trimethylbenzene) ) Chromium (0), (pentene) dicarbonyl (hexamethylbenzene) chromium (0), (hexene) dicarbonyl (trimethylbenzene) chromium (0), (heptene) dicarbonyl (trimethylbenzene) chromium (0), ( Octene) dicarbonyl (trimethylbenze) ) Chromium (0), (nonene) dicarbonyl (benzene) chromium (0), (decene) dicarbonyl (trimethylbenzene) chromium (0), (cyclopentene) dicarbonyl (hexamethylbenzene) chromium (0), (cyclohexene) ) Dicarbonyl (benzene) chromium (0), (cycloheptene) dicarbonyl (hexamethylbenzene) chromium (0), (cyclooctene) dicarbonyl (trimethylbenzene) chromium (0), (butadiene) dicarbonyl (hexamethylbenzene) ) Chromium (0), (Isoprene) dicarbonyl (trimethylbenzene) chromium (0), (octadiene) dicarbonyl (hexamethylbenzene) chromium (0), (cyclooctadiene) dicarbonyl (trimethylbenzene) chromium (0) , (Octatriene) zika Bonyl (trimethylbenzene) chromium (0), (cyclooctatriene) dicarbonyl (trimethylbenzene) chromium (0), (maleic acid) dicarbonyl (trimethylbenzene) chromium (0), (maleic anhydride) dicarbonyl (trimethyl) (Benzene) chromium (0), (acetylene) dicarbonyl (hexamethylbenzene) chromium (0), (phenylacetylene) dicarbonyl (trimethylbenzene) chromium (0), (diphenylacetylene) dicarbonyl (hexamethylbenzene) chromium ( 0), (Acetylenedicarboxylic acid diethyl ester)
Dicarbonyl (trimethylbenzene) chromium (0),
(Acetylenedicarboxylic acid diethyl ester) dicarbonyl (hexamethylbenzene) chromium (0), benzonitrile dicarbonyl (benzene) chromium (0), cyclohexylisonitrile dicarbonyl (benzene) chromium (0), triphenylphosphine dicarbonyl (o) -Methoxyacetophenone) chromium (0), triphenylphosphinedicarbonyl (trimethylbenzene) chromium (0), trimethylphosphinedicarbonyl (trimethylbenzene) chromium (0), triethylphosphinedicarbonyl (benzene) chromium (0), tributylphosphine Dicarbonyl (trimethylbenzene) chromium (0), tricyclohexylphosphine dicarbonyl (trimethylbenzene) chromium (0), trifluorophosphine dicarbonyl (tri Butylbenzene) chromium (0), diphenylmethylphosphinedicarbonyl (hexamethylbenzene) chromium (0), methyldiphenylphosphinedicarbonyl (hexamethylbenzene) chromium (0), dimethylphosphinoethanedicarbonyl (trimethylbenzene) chromium (0) ), Trimethyl phosphite dicarbonyl (hexamethylbenzene) chromium (0), triphenyl phosphite dicarbonyl (hexamethylbenzene) chromium (0), tetramethylene sulfide dicarbonyl (hexamethylbenzene) chromium (0), dimethyl sulfoxide Dicarbonyl (hexamethylbenzene) chromium (0), tetramethylenesulfoxidedicarbonyl (benzene) chromium (0), diphenylsulfoxidedicarbonyl (benzene) chromium (0) [Triphenylphosphine dicarbonylchromium (0)] dimer, bis (benzene) chromium (0), bis (ethylbenzene) chromium (0), bis (hexamethylbenzene) chromium (0), tricarbonyl (cyclopentadienyl) Chromium (I) dimer, dicarbonyl (pentamethylcyclopentadienyl) chromium (I) dimer, hydride tricarbonyl (cyclopentadienyl) chromium (II) and the like.

Further, dimethylchromium (II), trimethylchromium (III), tetramethylchromium (IV), tris (η-allyl) chromium (III), tetrakis (η
-Allyl) dichrome (II), tetrakis (neopentyl) chromium (IV), tetrakis (trimethylsilylmethyl) chromium (IV), bis (cyclopentadienyl)
Chromium (II), bis (pentamethylcyclopentadienyl) chromium (II), tris (π-allyl) chromium (III), tetrakis (π-allyl) chromium (I
V), cyclopentadienyl (benzene) chromium (I), diphenyl (benzene) chromium (II), diphenylchromium (II), tetramethoxychromium (I
V), tetraethoxychrome (IV), tetrapropoxychrome (IV), tetrabutoxychrome (IV), tetraphenoxychrome (IV), chromium (II) bis (acetate), chromium (III) tris (acetate), chromium (II) bis (propionate), chromium (III) tris (propionate), chromium (II
I) Tris (butyrate), chromium (II) bis (2-
Ethyl hexanoate), chromium (III) tris (2
-Ethylhexanoate), chromium (II) bis (isooctaneate), chromium (III) tris (isooctaneate), chromium (III) tris (oxy-2-ethylhexanoate), chromium (III) tris (Dichloroethylhexanoate), chromium (III) tris (neopentanoate), chromium (II) bis (neopentanoate), chromium (III) tris (laurate), chromium (II) bis (laurate), Chrome (I
II) Tris (stearate), chromium (II) bis (stearate), chromium (III) tris (oleate), chromium (II) bis (oleate), chromium (I
II) Tris (benzoate), chromium (II) bis (naphthenate), chromium (III) tris (naphthenate), chromium (II) oxalate, chromium (II)
I) Tris (thioacetate), chromium (III) tris (thiobenzoate), chromium (III) tris (dithioacetate), chromium (III) tris (dithiobenzoate), chromium (II) bis (acetylacetonate), chromium (III) Tris (acetylacetonate), chromium (III) tris (trifluoroacetylacetonate), chromium (III) tris (hexafluoroacetylacetonate), chromium (III) tris (2,2,6,6- Tetramethyl-3,5-heptanedionate), chromium (III) tris (1,3-butanedionate), chromium (III) tris (2-methyl-
1,3-butanedionate), chromium (III) tris (benzoylacetonate), chromium (III) tris (acetyl acetate), chromium (II) fluoride, chromium (III) fluoride, chromium (II) chloride, Chromium (III) chloride, chromium (II) bromide, chromium (II) bromide
I), chromium (II) iodide, chromium iodide (II)
I), chromyl chloride, hydroxychromium dichloride (II
I), chromium (III) nitrate, chromium (III) sulfate,
Examples thereof include chromium (III) perchlorate, chromium (III) oxide, and chromium (VI) oxide.

Also, a reaction product of a chromium salt and a sulfur compound represented by the above general formula (2) can be suitably used.
Chromium salts include chromium (II) fluoride, chromium (III) fluoride, chromium (II) chloride, and chromium (II) chloride.
I), chromium (II) bromide, chromium (III) bromide, chromium (II) iodide, chromium (III) iodide, among which chromium (II) chloride, chromium (II) chloride
I) is preferred. The reaction between the chromium salt and the sulfur compound represented by the general formula (2) is performed in an ether-based solvent such as diethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, and the like. The reaction temperature is-
The reaction is carried out at 78 ° C to 60 ° C, preferably at -20 ° C to 40 ° C, for a reaction time of 10 minutes to 48 hours, preferably for 30 minutes to 10 hours, and the ratio of the sulfur compound to the chromium salt is 1.5. It is preferable to carry out in the range of -3.5. This reaction produces a metal salt as a by-product and precipitates in the reaction system, but the metal salt is removed by filtration. Thereafter, the ether solvent is removed under reduced pressure, and the obtained solid is an aliphatic hydrocarbon such as pentane, hexane, heptane, octane, isooctane, nonane, decane, cyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and decalin. To give a reaction product.

Further, a complex comprising the above chromium compound and an electron donor can also be suitably used. Examples of the electron donor include phosphine, phosphite, phosphine oxide, water, carboxylic anhydride, ester, ether, alcohol, ketone, carbon disulfide, sulfone, thiophene and sulfide. Therefore, as a complex comprising a chromium compound and an electron donor, for example, trichlorotris (triphenylphosphine) chromium (II
I), trichloro [bis (2-diethylphosphinoethyl) -ethylphosphine] chromium (III), trichloro [bis (2-diethylphosphinoethyl) -n-propylphosphine] chromium (III), trichloro [bis (2 -Diethylphosphinoethyl) -cyclohexylphosphine] chromium (III), trichloro [1,1,1
-Tris (diethylphosphinomethyl) ethane] chromium (III), trichloro [tris (2-diethylphosphinoethyl) phosphine] chromium (III), trichlorobis (tributylphosphine) chromium (III) dimer, dichlorodinitrosylbis ( Triphenylphosphine oxide) chromium (II), dichlorobis (triphenylphosphine oxide) chromium (II), trichlorotris (butyl acetate) chromium (III), trichlorotris (ethyl acetate) chromium (III),
Trichlorotris (tetrahydrofuran) chromium (II
I), trichlorotris (dioxane) chromium (II)
I), trichlorotris (iso-propanol) chromium (III), trichlorotris (2-ethylhexanol) chromium (III), triphenyltris (tetrahydrofuran) chromium (III), chromium (III) tris (acetate) anhydride Acetic acid adducts and the like can be mentioned.

Further, a complex comprising the above chromium compound and an electron acceptor can also be suitably used. The electron acceptor is not particularly limited, and examples thereof include trinitrobenzene and tetracyanoethylene. Therefore, as a complex composed of a chromium compound and an electron acceptor, for example, tricarbonyl (benzene) chromium (0) trinitrobenzene, tricarbonyl (toluene) chromium (0) trinitrobenzene, tricarbonyl (trimethylbenzene) chromium ( 0) trinitrobenzene, tricarbonyl (benzene) chromium (0) tetracyanoethylene, tricarbonyl (toluene) chromium (0) tetracyanoethylene, tricarbonyl (xylene) chromium (0) tetracyanoethylene, tricarbonyl (Trimethylbenzene) chromium (0) tetracyanoethylene and tricarbonyl (anisole) chromium (0) tetracyanoethylene.

Of these, a chromium compound containing carbon monoxide is preferably used from the viewpoint of catalytic activity. More preferably, hexacarbonyl chromium (0), tricarbonyl (benzene) chromium (0), tricarbonyl (trimethylbenzene) chromium (0), tricarbonyl (naphthalene) chromium (0), tricarbonyl (tetralin) chromium (0) ), Tricarbonyl (cycloheptatriene) chromium (0). Further, the above chromium compounds can be used alone or in combination of two or more.

The alkyl metal compound used in the present invention is not particularly limited. For example, the following general formula (4) R _p MX _q (4) (where p is 0 <p ≦ 3) , Q is 0 ≦ q <3, and p + q is 1 to 3. M represents lithium, magnesium, zinc, boron or aluminum, and R is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms. One
And X represents at least one selected from the group consisting of a hydrogen atom, an alkoxy group, an aryl group and a halogen atom), and / or an aluminoxane.

In the above general formula (4), the number of carbon atoms is 1 to 1.
The alkyl group of 0 is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, and an octyl group.
The alkoxy group is not particularly limited,
For example, a methoxy group, an ethoxy group, a butoxy group, a phenoxy group, or the like can be given. The aryl group is not particularly limited, but includes, for example, a phenyl group. Although it does not specifically limit as a halogen atom, For example, fluorine, chlorine, bromine, or iodine is mentioned.

In the above general formula (4), M is A
l, when p and q are each 1.5, AlR _1.5 X _1.5
Becomes Although such compounds do not exist in theory, they are usually conventionally expressed as sesqui-forms of Al ₂ R ₃ X ₃ , and these compounds are also included in the present invention.

Examples of the alkyl metal compound represented by the general formula (4) include, for example, methyl lithium, ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, diethyl magnesium, ethyl butyl magnesium , Ethylchloromagnesium, ethylbromomagnesium, dimethylzinc, diethylzinc, dibutylzinc, trimethylborane, triethylborane, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, tricyclohexyl Aluminum, dimethylethylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, diethylaluminum ethoxide, diethyl Rumi bromide phenoxide, dicyclohexyl phenyl aluminum, ethyl aluminum ethoxy chloride, diethylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride, dicyclohexyl aluminum chloride,
Examples include methylaluminum sesquichloride, ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum dichloride, isobutylaluminum dichloride and the like.

The aluminoxane used in the present invention is a hydrolysis product obtained by reacting the above-mentioned alkylaluminum compound with water in a quantitative ratio within a certain range. The method for hydrolyzing the alkylaluminum compound is not particularly limited, and can be synthesized by a known method. For example, (1) a method in which water is brought into contact with an alkylaluminum compound as it is or a dilute solution in an organic solvent, (2) an alkylaluminum compound and magnesium chloride · 6 hydrate, iron sulfate · 7 hydrate, copper sulfate · 5 water A method of reacting with water of crystallization of a metal salt such as a salt is employed. Specifically, it is disclosed in the above-mentioned JP-A-62-265237 and JP-A-62-148491. The molar ratio of the alkylaluminum compound to water when performing the hydrolysis is not particularly limited, but is from 1: 0.001 to 1: 1.
2, preferably 1: 0.01 to 1: 1.1.

Of these, alkylaluminum compounds and aluminoxanes are preferably used in terms of availability and activity, and more preferably triethylaluminum, triisobutylaluminum or isobutylaluminoxane. These alkyl metal compounds can be used alone or in combination of two or more.

The amount of the alkyl metal compound used is 0.1 to 10,000 equivalents per mole of the chromium compound.
Preferably 3-3,000 equivalents, more preferably 5-
2,000 equivalents.

The ethylene trimerization catalyst of the present invention can be prepared by bringing the above-mentioned chromium compound, alkyl metal compound and sulfur compound into contact with the starting materials in a solvent. The contact method is not particularly limited, for example, a chromium compound,
A method in which an alkyl metal compound and a sulfur compound are brought into contact in advance to prepare a catalyst, and then contacted with ethylene to perform a trimerization reaction, a chromium compound, an alkyl metal compound and a sulfur compound in the presence of ethylene as a trimerization reaction raw material. A method is employed in which the catalyst is prepared by contact and a trimerization reaction is started simultaneously with the contact. Specifically, in the former case,
(1) introducing an alkyl metal compound into a solution containing a chromium compound and a sulfur compound; (2) introducing a chromium compound into a solution containing an alkyl metal compound and a sulfur compound; and (3) introducing a chromium compound into a solution containing the alkyl metal compound. And a sulfur compound, and (4) introducing a sulfur compound and an alkyl metal compound into a solution containing a chromium compound.
In the latter case, (1) a chromium compound, an alkyl metal compound, a sulfur compound and ethylene are simultaneously and independently introduced into the reaction system, respectively. (2) A chromium compound, a sulfur compound and ethylene are added to a solution containing the alkyl metal compound. (3) introducing an alkyl metal compound and ethylene into a solution containing a chromium compound and a sulfur compound; (4)
A catalyst can be prepared by a method of introducing a chromium compound and ethylene into a solution containing an alkyl metal compound and a sulfur compound, and (5) introducing an alkyl metal compound, a sulfur compound and ethylene into a solution containing a chromium compound. The order of mixing these raw materials is not particularly limited.

The concentration of the chromium compound in preparing the catalyst is not particularly limited, but is usually used at a concentration of 0.001 to 100 mmol, preferably 0.01 to 10 mmol per liter of the solvent. Is done. If the catalyst concentration is lower than this, sufficient activity cannot be obtained. Conversely, if the catalyst concentration is higher than this, catalyst activity does not increase and it is not economical. As the solvent used here, for example, butane, pentane, hexane, heptane,
Octane, isooctane, nonane, decane, cyclopentane, cyclohexane, methylcyclohexane, cyclooctane, aliphatic hydrocarbons such as decalin, benzene,
Examples include aromatic hydrocarbons such as toluene, xylene, ethylbenzene, cumene, chlorobenzene, and dichlorobenzene, and chlorinated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and dichloroethane. In addition, a reaction product, for example, 1-hexene can be used as a solvent. These solvents can be used alone or in combination of two or more. Here, for the purpose of controlling the chromium compound concentration at the time of preparing the catalyst, it may be concentrated or diluted as needed.

The temperature at which the chromium compound, the alkyl metal compound and the sulfur compound are brought into contact is from -100 to 2
The temperature is 50 ° C, preferably 0 to 200 ° C. The contact time is not particularly limited, and is 0 minute to 24 hours, preferably 0 minute to 2 hours. It is desirable that all operations during contact be performed while avoiding air and moisture. Further, it is preferable that the raw materials and the solvent are sufficiently dried.

The trimerization reaction of ethylene is carried out using the catalyst thus prepared. In the present invention, the use amount of the chromium catalyst is not particularly limited, but usually, the chromium compound is diluted with the above-mentioned solvent, and the chromium compound is contained in an amount of 0.001 μmol to 100 mmol, preferably 0.01 μmol to 1 liter of the trimerization reaction solution. Used at a concentration of 10 mmol. If the catalyst concentration is lower than this, sufficient activity cannot be obtained. Conversely, if the catalyst concentration is higher than this, catalyst activity does not increase and it is not economical.

The temperature of the ethylene trimerization reaction in the present invention is from -100 to 250 ° C., preferably from 0 to 2 ° C.
00 ° C. The reaction pressure is not particularly limited as long as the trimerization reaction system is in an ethylene atmosphere.
3,000 kg / cm ² , preferably 0-30
It is 0 kg / cm ² . The reaction time depends on the temperature and the pressure and cannot be determined unconditionally, but is usually 5 seconds to 6 hours. Further, ethylene may be continuously supplied so as to maintain the above-mentioned pressure, or may be sealed at the above-mentioned pressure at the start of the reaction to cause a reaction. Ethylene as a raw material gas includes a gas inert to the reaction, for example, nitrogen, argon,
Helium or the like may be included. It is desirable that all operations of the trimerization reaction be performed while avoiding air and moisture. Further, it is preferable that ethylene is sufficiently dried.

According to the present invention, it is preferable that the catalyst comprising the chromium compound, the alkyl metal compound and the sulfur compound is further irradiated with light to carry out the ethylene trimerization reaction.
Effects such as a significant improvement in catalytic activity by light irradiation are recognized.

The light used in the present invention is not particularly limited, but includes, for example, ultraviolet light, visible light, and infrared light.
Is preferable, and more preferably, light having a wavelength of 200 to 700 nm is used. Although the illuminance of light is not particularly limited, it is preferable that light is directly emitted from a light source.

Either sunlight or an artificial light source may be used as the light source. However, an artificial light source is desirable because sunlight has low illuminance, is affected by the weather, and cannot be used at night. Examples of artificial light sources include, but are not limited to, deuterium lamps, xenon lamps, tungsten lamps, incandescent lamps, halogen lamps, low-pressure mercury lamps, hollow cathode lamps, metal vapor discharge tubes, metal halide lamps, high-pressure sodium lamps , A thallium lamp, a mercury-thallium lamp, a mercury-lead lamp, an H-type discharge tube, a xenon-mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a flash lamp, and the like.

The irradiation time of light is not particularly limited, but it may be applied to a catalyst system comprising a chromium compound, an alkyl metal compound and a sulfur compound, or may be directly applied to an ethylene trimerization reaction system. Good. Specifically, in the former case, (1) a solution containing a chromium compound is irradiated with light, and then an alkyl metal compound and a sulfur compound are introduced and further brought into contact with ethylene to perform an ethylene trimerization reaction. 2) irradiating a solution containing a chromium compound and an alkyl metal compound with light, and then introducing a sulfur compound and further contacting with ethylene to perform an ethylene trimerization reaction;
(3) Light can be applied to the solution containing the chromium compound, the alkyl metal compound and the sulfur compound by irradiating the solution with light and then contacting the solution with ethylene to perform an ethylene trimerization reaction. In the latter case, (1)
Performing ethylene trimerization reaction while irradiating light in the presence of chromium compound, alkyl metal compound and sulfur compound,
(2) Light can be irradiated by a method of performing a trimerization reaction of ethylene while further irradiating light in the presence of a catalyst comprising a chromium compound, an alkyl metal compound, and a sulfur compound that has been irradiated with light. Note that the light irradiation time is not particularly limited.

This reaction can be carried out in any of a batch system, a semi-continuous system and a continuous system. After the completion of the trimerization reaction, the reaction is stopped by adding a polymerization deactivator such as water, alcohol, or an aqueous solution of sodium hydroxide to the reaction solution. After the deactivated waste chromium catalyst is removed by a known deashing treatment method, for example, extraction with water or an aqueous alkali solution, the generated 1-hexene is separated from the reaction solution by a known extraction method or distillation method. In addition, polyethylene as a by-product is separated and removed at a reaction solution outlet as a residue in a known centrifugation method or distillation separation of 1-hexene.

[0049]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are only for illustrating the outline of the present invention and the present invention is not limited to these Examples. . Example 1 In a Schlenk tube having an internal volume of 200 ml, 5.1 mg of tricarbonyl (1,3,5-trimethylbenzene) chromium (0), 3.2 ml of a 0.125 mol / l triisobutylaluminum / cyclohexane solution,
2.0 ml of a 0.145 mol / liter di (n-butyl) sulfide / cyclohexane solution and 100 ml of dried cyclohexane were added, and mixed and stirred. Ushio's ultra-high pressure mercury lamp (500W) under ethylene atmosphere
Was used to irradiate light from the outside for 10 minutes. The reaction solution was charged into a 300-ml stainless steel pressure-resistant reaction vessel equipped with a thermometer, a catalyst feed tube, and a stirring device.

After the reaction vessel was heated to 80 ° C. and the stirring speed was adjusted to 1,000 rpm, ethylene was introduced into the reaction vessel to start the ethylene trimerization reaction. Ethylene gas was blown in so that the absolute pressure in the reaction vessel became 40 kg / cm ^2. Thereafter, the introduction was continued so as to maintain the pressure, and a reaction was carried out for 5 minutes while maintaining these reaction conditions. After 5 minutes, the reaction was stopped by injecting water into the reaction vessel with nitrogen to deactivate the catalyst.

The reaction vessel was cooled to room temperature and then depressurized. The products contained in the reaction solution and the recovered gas were analyzed by gas chromatography. The solid content contained in the reaction solution was separated by filtration using filter paper, air-dried, and then dried under reduced pressure (1 mmHg, 100 ° C.), and its weight was measured. Table 1 shows the results.

Comparative Example 1 Except that di (n-butyl) sulfide was not used,
The reaction was carried out in the same manner as in Example 1. Table 1 shows the results.

[0053]

[Table 1]

[0054]

According to the present invention, a catalyst comprising a chromium compound, an alkyl metal compound and a sulfur compound can be easily prepared and handled. When ethylene is trimerized in the presence of this catalyst, 1-hexene useful as a raw comonomer of LLDPE can be produced with high catalytic activity and highly selectively.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C07C 2/26 C07C 2/26

Claims (5)

[Claims] 1. A chromium compound, an alkyl metal compound and the following general formula (1): R ^1- (Y) _h- [R ^2- (Y) _i ] _k -R ³ (1) (where h and i are K is an integer of 0 to 10. R ¹ and R ³ are each hydrogen and have 1 to 20 carbon atoms.
Hydrocarbon group, an acyl group having 1 to 10 carbon atoms,
10 alkoxy groups, halogen atoms, and R ¹ and R ³ are selected from the group consisting of cyclic substituents bonded by a carbon-carbon bond. R ² represents an alkylene group having 1 to 8 carbon atoms. Y is Or And / or the following general formula (2) R ⁴ -SM (2) (wherein, R ⁴ is a hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom)
Represents an acyl group having from 10 to 10 or a thioacyl group having from 1 to 10 carbon atoms, and M represents a substituent-containing or unsubstituted metal element belonging to Group 1, 2, 11, 12, 13, or 14 of the periodic table) Ethylene trimerization catalyst comprising sulfur compounds. 2. A chromium compound represented by the following general formula (3): CrA _m (3) wherein m is an integer of 1 to 6. A is carbon monoxide, arene, alkene, alkyne, carbene, tropylium. Cation, nitrogen, nitrile, isonitrile, phosphine, phosphite, sulfide, sulfoxide, alkyl group, aryl group, alkoxy group, thioalkoxy group, carboxylate group, thiocarboxylate group, dithiocarboxylate group, β-diketonate group, β -A ketoester group, a halogen atom, a hydroxyl group, a nitrate group, a sulfate group, a perchlorate group and at least one selected from the group consisting of oxygen). The ethylene trimerization catalyst according to the above. 3. An alkyl metal compound represented by the following general formula (4): R _p MX _q (4) (where p is 0 <p ≦ 3, q is 0 ≦ q <3, and p + q is M is lithium, magnesium, zinc, boron or aluminum, and R is 1 selected from the group consisting of alkyl groups having 1 to 10 carbon atoms.
And X is a compound selected from the group consisting of a hydrogen atom, an alkoxy group, an aryl group, and a halogen atom), and / or an aluminoxane. The ethylene trimerization catalyst according to claim 2. 4. A method for trimerizing ethylene, wherein ethylene is trimerized in the presence of the ethylene trimerization catalyst according to claim 1. Description: 5. The method according to claim 4, wherein the ethylene trimerization catalyst is irradiated with light.