JPH0762012A - Catalyst for olefin polymerization and method for polymerizing olefin using the same - Google Patents

Abstract

PURPOSE:To obtain a catalyst for olefin polymerization which is a metallocene- based catalyst capable of polymerizing an olefin in high activity in spite of absence of an organoaluminum oxy compound and has high economic efficiency and to provide a method for olefin polymerization. CONSTITUTION:This catalyst for olefin polymerization comprises [A] a transition metal compound of group IVB containing a ligand having a cyclopentadienyl skeleton and [B] an organoaluminum compound and has a molar ratio of [B] the organoaluminum compound and [A] the transition metal compound calculated as atom of aluminum/transition metal of 1-500. The catalyst for olefin polymerization may comprise [C] a granular carrier besides the components [A] and [B]. Or the catalyst for olefin polymerization may be preliminarily polymerized with a 2-20C olefin. A method for olefin polymerization is carried out by (co)polymerizing an olefin in the presence of the catalyst for olefin polymerization or the preliminarily polymerized catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst and a method for polymerizing olefins using the same, and more particularly to an olefin polymerization catalyst capable of producing an olefin polymer with high polymerization activity and an olefin polymerization catalyst using the same. It relates to a polymerization method.

[0002]

BACKGROUND OF THE INVENTION Conventionally, as a catalyst for producing an olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst or a vanadium compound catalyst containing a solid titanium catalyst component has been used. Vanadium-based catalysts containing components are known. These solid titanium catalyst components or vanadium compound catalyst components are usually used together with an organoaluminum compound as a promoter component.

In recent years, a new Ziegler type olefin polymerization catalyst containing a catalyst component of a Group IV transition metal compound containing a ligand having a cyclopentadienyl skeleton, that is, a metallocene compound catalyst has been proposed. When used with an organoaluminum oxy compound (aluminoxane or alumoxane)
A method for producing an α-olefin copolymer is disclosed in, for example, JP-A-58-19309 and JP-A-60-35005.
JP-A-60-35006, JP-A-60-
It is proposed in Japanese Patent Laid-Open No. 35007, Japanese Patent Laid-Open No. 60-35008, and the like.

It is known that when such a metallocene catalyst is used, an olefin can be polymerized or copolymerized with high activity, and an olefin copolymer having an excellent composition distribution can be produced.

By the way, the metallocene catalyst is usually formed with the metallocene catalyst component and an excess amount of the organoaluminum oxy compound (aluminoxane) with respect to the metallocene catalyst component as described above. Is usually produced by reacting an organoaluminum compound with water, and has a problem that the production process is complicated and expensive.

Polymerization using a metallocene-based catalyst formed of an extremely excess amount of alkylaluminum with respect to the metallocene catalyst component instead of such an organoaluminum oxy compound is also disclosed (Japanese Patent Laid-Open No. 3-197).
No. 513).

The present inventor has studied such metallocene-based catalysts and found that olefin polymerization catalysts formed from a metallocene catalyst component and an organoaluminum compound catalyst component have conventionally been low in olefin polymerization activity. Nevertheless, it has been found that an olefin polymerization catalyst formed from a metallocene catalyst component and a specific amount or less of an organoaluminum compound catalyst component with respect to the metallocene catalyst component can (co) polymerize an olefin with high activity. As a result, the present invention has been completed.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and is a metallocene catalyst capable of polymerizing an olefin with high activity despite containing no organoaluminumoxy compound. Therefore, it is an object of the present invention to provide an olefin polymerization catalyst excellent in economy and a method for olefin polymerization using the catalyst.

[0009]

SUMMARY OF THE INVENTION The catalyst for olefin polymerization according to the present invention is
[A] Includes a ligand having a cyclopentadienyl skeleton
It is composed of a Group IVB transition metal compound and a [B] organoaluminum compound, and the [B] organoaluminum compound and the [A] transition metal compound have an atomic conversion aluminum / transition metal atom ratio of 1 to 500. It is characterized by that. The olefin polymerization catalyst according to the present invention may comprise the catalyst component [A] olefin [B] and a [C] particulate carrier.

In the present invention, the olefin polymerization catalyst may be prepolymerized with an olefin having 2 to 20 carbon atoms. The olefin polymerization method according to the present invention is characterized by (co) polymerizing an olefin in the presence of the above-described olefin polymerization catalyst or prepolymerization catalyst.

Such an olefin polymerization catalyst according to the present invention is formed from a [A] transition metal compound catalyst component (metallocene catalyst component) and a [B] organoaluminum compound catalyst component. It is possible to (co) polymerize an olefin with high activity, even though it does not contain

[0012]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst according to the present invention and the olefin polymerization method using the catalyst will be specifically described below.

In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymerization. May be used to mean coalesce.

FIG. 1 shows the steps for preparing the olefin polymerization catalyst according to the present invention. The olefin polymerization catalyst according to the present invention is formed from a [A] transition metal compound and a [B] organoaluminum compound in a specific amount or less with respect to the [A] transition metal compound.

The olefin polymerization catalyst according to the present invention, together with these catalyst components [A] and [B],
It may be formed from [C] a particulate carrier. First, each component used when preparing the olefin polymerization catalyst according to the present invention will be described.

[A] Transition Metal Compound Catalyst Component [A] Group IVB transition metal compound containing a ligand having a cyclopentadienyl skeleton used in the present invention (hereinafter sometimes referred to as component [A]). ) Is represented by the following formula [I].

ML _x ... [I] [In the formula, M is a transition metal selected from the group consisting of Zr, Ti, Hf, V, Nb, Ta and Cr, and L is a ligand coordinated to the transition metal. And at least one L is a ligand having a cyclopentadienyl skeleton, and L other than the ligand having a cyclopentadienyl skeleton has 1 to 1 carbon atoms.
2 hydrocarbon group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group (where R is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent such as halogen), a halogen atom Alternatively, it is a hydrogen atom, and x is the valence of the transition metal. Examples of the ligand having a cyclopentadienyl skeleton include, for example, a cyclopentadienyl group, a methylcyclopentadienyl group, a dimethylcyclopentadienyl group, a trimethylcyclopentadienyl group,
Tetramethylcyclopentadienyl group, pentamethylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadiene group Examples of alkyl-substituted cyclopentadienyl groups such as enyl group, methylbutylcyclopentadienyl group, hexylcyclopentadienyl group or indenyl group, 4,5,6,7-tetrahydroindenyl group, fluorenyl group, etc. You can These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

Among the ligands which coordinate to these transition metals, an alkyl-substituted cyclopentadienyl group is particularly preferable. When the compound represented by the general formula [I] contains two or more groups having a cyclopentadienyl skeleton, the groups having two cyclopentadienyl skeletons are alkylene such as ethylene and propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene, a silylene group or a dimethylsilylene group, a substituted silylene group such as a diphenylsilylene group or a methylphenylsilylene group, and the like.

Specific examples of the ligand L other than the ligand having a cyclopentadienyl skeleton include the following. Examples of the hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. More specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, and an isopropyl group. Group, butyl group, etc., cycloalkyl group, cyclopentyl group, cyclohexyl group, etc., aryl group, phenyl group, tolyl group, etc., aralkyl group, benzyl group, neophyll group, etc. Are exemplified.

As the alkoxy group, a methoxy group,
Examples thereof include an ethoxy group and a butoxy group, examples of the aryloxy group include a phenoxy group, and examples of the halogen include fluorine, chlorine, bromine, iodine and the like.

Examples of the ligand represented by SO ₃ R include a p-toluenesulfonato group, a methanesulfonato group, and a trifluoromethanesulfonato group. The transition metal compound [A] containing such a ligand having a cyclopentadienyl skeleton is more specifically represented by the following formula [I ′] when the valence of the transition metal atom is 4. .

R ¹ _a R ² _b R ³ _c R ⁴ _d M ... [I '] [In the formula [I'], M is the same transition metal atom as in the formula [I], and R ¹ is cyclopentadienyl. A group (ligand) having a skeleton, wherein R ² , R ³ and R ⁴ are a group having a cyclopentadienyl skeleton, an alkyl group, a cycloalkyl group,
Aryl group, aralkyl group, alkoxy group, aryloxy group, trialkylsilyl group, SO ₃ R group, SO ₂ R group,
It is a halogen atom or a hydrogen atom, a is an integer of 1 or more, and a + b + c + d = 4. In the present invention, in the above formula [I ′], at least two of R ¹ , R ² , R ³ and R ⁴ , for example, R ¹ and R ² are groups (ligands) having a cyclopentadienyl skeleton. Metallocene compounds are preferably used.

These cyclopentadienyl skeleton-containing groups are alkylene groups such as ethylene and propylene, substituted alkylene groups such as isopropylidene and diphenylmethylene, silylene groups or substituted silylene groups such as dimethylsilylene, diphenylsilylene and methylphenylsilylene groups. It may be bound via a group or the like.

R ³ and R ⁴ are groups having a cyclopentadienyl skeleton, alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkoxy groups, aryloxy groups, trialkylsilyl groups, SO ₃ R groups, SO ₂ R group, halogen atom or hydrogen atom.

Specific examples of transition metal compounds in which M is zirconium will be shown below. Bis (indenyl) zirconium dichloride, bis (indenyl)
Zirconium dibromide, bis (indenyl) zirconium bis (p-toluenesulfonato) bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (fluorenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dichloride, ethylene Bis (indenyl) zirconium dibromide, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium, ethylenebis (indenyl) methylzirconium monochloride, ethylenebis (indenyl) zirconium bis (methanesulfonate), ethylenebis ( Indenyl) zirconium bis (p-toluene sulfonate), ethylene bis (indenyl) zirconium bis (trifluoromethane sulfonate), ethylene bis (yne Denyl) zirconium bis (p-toluenesulfinato), ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl)
-Fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-methylcyclopentadienyl) zirconium dichloride, dimethylsilylene bis (cyclopentadienyl) zirconium dichloride,
Dimethylsilylenebis (methylcyclopentadienyl)
Zirconium dichloride, dimethylsilylene bis (dimethylcyclopentadienyl) zirconium dichloride,
Dimethyl silylene bis (trimethylcyclopentadienyl) zirconium dichloride, dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (2-methylindenyl) zirconium dichloride, dimethyl silylene bis (2-methyl, 4-isopropylindenyl) zirconium Dichloride, dimethylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium bis (trifluoromethanesulfonate), dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) Zirconium dichloride, dimethylsilylene (cyclopentadienyl-fluorenyl) zirconium dichloride,
Diphenylsilylenebis (indenyl) zirconium dichloride, diphenylsilylenebis (2-methyl, 4-isopropylindenyl) zirconium dichloride, diphenylsilylenebis (2,4,7-trimethylindenyl) zirconium dichloride, methylphenylsilylenebis (indenyl) Zirconium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) zirconium dibromide, bis (cyclopentadienyl) methylzirconium monochloride, bis (cyclopentadienyl) ethylzirconium monochloride, bis ( Cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium monochloride, bis (cyclopentadienyl) ben Zirconium monochloride,
Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) methylzirconium monohydride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) (Enyl) dibenzyl zirconium, bis (cyclopentadienyl) zirconium methoxy chloride, bis (cyclopentadienyl) zirconium ethoxy chloride, bis (cyclopentadienyl) zirconium bis (methanesulfonato), bis (cyclopentadienyl)
Zirconium bis (p-toluenesulfonato), bis (cyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (cyclopentadienyl) zirconium bis (p-toluenesulfinato), bis (methylcyclopentadiene) (Enyl) zirconium dichloride,
Bis (dimethylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium ethoxy chloride, bis (dimethylcyclopentadienyl) zirconium bis (trifluoromethanesulfonato), bis (ethylcyclopentadienyl) zirconium dichloride , Bis (methylethylcyclopentadienyl) zirconium dichloride, bis (propylcyclopentadienyl) zirconium dichloride, bis (methylpropylcyclopentadienyl) zirconium dichloride, bis (butylcyclopentadienyl) zirconium dichloride, bis (methyl Butylcyclopentadienyl) zirconium dichloride, bis (methylbutylcyclopentadienyl) zirconium bis (methanesulfonate), bis ( Trimethyl cyclopentadienyl)
Zirconium dichloride, bis (tetramethylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dichloride, bis (hexylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride.

In the above example, the di-substituted cyclopentadienyl ring includes 1,2- and 1,3-substituted compounds, and the tri-substituted compound is 1,2,3- and 1,2,4-substituted compounds. Including the body. Alkyl groups such as propyl and butyl are n-, i-, sec-, tert-
Including isomers such as.

It is also possible to use a compound in which zirconium is replaced with titanium, hafnium, vanadium, niobium, tantalum or chromium in the zirconium compound as described above.

These compounds may be used alone,
You may use it in combination of 2 or more type. It may be diluted with a hydrocarbon or a halogenated hydrocarbon before use. In the present invention, a zirconocene compound having a central metal atom of zirconium and having a ligand containing at least two cyclopentadienyl skeletons is preferably used as the transition metal compound [A].

[B] Organoaluminum Compound Catalyst Component In the present invention, an organoaluminum compound represented by the following formula [II] is used as the [B] organoaluminum compound.

[0030] In ^{_{R a n AlX 3-n ...}} [II] formula, R ^a is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen atom or a hydrogen atom, n represents 1 to 3.

Examples of such a hydrocarbon group having 1 to 12 carbon atoms include an alkyl group, a cycloalkyl group or an aryl group. Specific examples include a methyl group, an ethyl group, an n-propyl group and an isopropyl group. Group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like. As such an organoaluminum compound, the following compounds are specifically used.

Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri 2-
Trialkylaluminums such as ethylhexylaluminum, alkenylaluminums such as isoprenylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride, dialkylaluminum halides such as dimethylaluminum bromide, methylaluminum sesquichloride, ethylaluminum sesqui Alkyl aluminum sesquihalides such as chloride, isopropylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, alkylaluminum dichloride, ethylaluminum dichloride, isopropylaluminium dichloride, ethylaluminum dibromide, etc. Umujiharaido, diethylaluminum hydride, and alkyl aluminum hydride such as diisobutyl aluminum hydride.

A compound represented by the following formula [II '] can also be used as the [B] organoaluminum compound. During ^{_{R a n AlY 3-n ...}} [II '] formula, R ^a is the same as R ^a in the formula [II], n is 1 to 2, Y is -OR ^b group, -OSiR ^c ₃ units, -O
AlR ^d ₂ group, -NR ^e ₂ group, -SiR ^f ₃ group or -N
(R ^g ) AlR ^h ₂ group.

R^b, R^c, R^dAnd R^hIs a methyl group,
Ethyl group, isopropyl group, isobutyl group, cyclohexyl
Syl group, phenyl group, etc., R^eIs a hydrogen atom,
Group, ethyl group, isopropyl group, phenyl group, trime
Such as a tylsilyl group, R ^fAnd R^gIs a methyl group,
For example, an ethyl group.

Specific examples of such an organoaluminum compound include the following compounds. (i) R ^a _n Al (OR ^b ) _3-n For example, dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide, etc. (ii) R ^a _n Al (OSiR ^c ₃ ) _3-n For example, Et ₂ Al (OSiMe ₃ ), (iso-Bu) ₂ Al (O
SiMe _3), such as _{(iso-Bu) 2 Al (} OSiEt 3).

(Iii) R ^a _n Al (OAl R ^d ₂ ) _3-n For example, Et ₂ AlOAlEt ₂ (iso-Bu) ₂ AlOAl (iso-Bu) _{2 and the} like.

[0037] _{^{(iv) R a n Al (}} NR e 2) 3-n for _{example, Me 2 AlNEt 2, Et 2} AlNHMe, Me 2 Al
NHEt, Et ₂ AlN (Me ₃ Si) ₂ , (iso-Bu) ₂ AlN
(Me ₃ Si) ₂ etc.

(V) R ^a _n Al (SiR ^f ₃ ) _3-n For example, (iso-Bu) ₂ AlSiMe _{3 and the} like. (vi) R ^a _n Al [N (R ^g ) -Al R ^h ₂ ] _3-n For example, Et ₂ AlN (Me) -AlEt ₂ , (iso-Bu) ₂ A
1N (Et) Al (iso-Bu) _{2 and the} like.

Further, as the organoaluminum compound [B], a complex alkyl compound of a group I metal represented by the following general formula and aluminum can be used. M ¹ AlR ^j ₄ (wherein M ¹ is Li, Na, K, and R ^j has 1 carbon atom)
~ 15 hydrocarbon groups. ) Specifically, LiAl (C
₂ H ₅ ) ₄ , LiAl (C ₇ H ₁₅ ) _{4 and the} like.

A compound of a Group II metal represented by the following general formula and aluminum can also be used. R ^k R ^l M ² (In the formula, R ^k and R ^l are a hydrocarbon group having 1 to 15 carbon atoms or a halogen atom and may be the same or different from each other, but they are not halogen. (M ² is Mg, Zn, Cd) Specifically, diethyl zinc,
Diethyl magnesium, butyl ethyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, etc. are mentioned.

Of these, trialkyl aluminum, dialkyl aluminum halide, dialkyl aluminum hydride, dialkyl aluminum alkoxide and the like are preferably used.

These compounds can be used alone or in combination of two or more kinds. [C] Particulate Carrier Specific examples of the [C] particulate carrier used in the present invention include SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , MgO, and Zr.
O ₂ , CaO, TiO ₂ , ZnO, Zn ₂ O, Sn ₂ O,
BaO, ThO, V ₂ O ₅ , Cr ₂ O _3, etc., or a mixture thereof such as SiO ₂ —MgO, SiO ₂ —
_{Al 2 O 3, SiO 2 -TiO} 2, SiO 2 -V 2 O 5,
Inorganic carriers such as SiO ₂ —Cr ₂ O ₃ and SiO ₂ —TiO ₂ —MgO, and homopolymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, and 4-methyl-1-pentene. Resins such as a copolymer formed from these as a main component, a homopolymer of vinylcyclohexane or styrene, or a copolymer formed from any of these as a main component may be used.

The particulate carrier [C] used in the present invention is
Usually, the particle size is 10 to 300 μm, preferably 20 to 20
A granular or fine particle solid having a size of 0 μm is preferable, and a porous body is more preferable.

Olefin Polymerization Catalyst The olefin polymerization catalyst according to the present invention comprises the above catalyst components [A] transition metal compound and [B] organoaluminum compound. The organoaluminum compound has an atomic conversion molar ratio (aluminum atom in [B] / transition metal atom in [A]) of 1 to 1 of the [A] transition metal compound.
It is present in an amount of 500, preferably 10-250.

The olefin polymerization catalyst containing the [A] transition metal compound and the [B] organoaluminum compound in such amounts can be olefin polymerized with high polymerization activity.

The olefin polymerization catalyst according to the present invention may be formed from a [C] particulate carrier together with a [A] transition metal compound and a [B] organoaluminum compound. The catalyst components are contacted in any order. Specifically, for example, the [A] transition metal compound and the [B] organoaluminum compound may be directly contacted with each other before the polymerization and then added to the polymerization system. At this time, [A] and [B]
May be added after being supported on the [C] particulate carrier.

The transition metal compound [A] and the organoaluminum compound [B] may be added to the polymerization system simultaneously or separately. At this time, [A] and / or [B]
May be supported on the [C] particulate carrier.

When the [C] particulate carrier is used in forming the olefin polymerization catalyst, the [A] transition metal compound is usually used in an amount of 0.0 per 1 g of the [C] particulate carrier.
It is used in an amount of 05 to 0.5 mmol, preferably 0.05 to 0.5 mmol.

The olefin polymerization catalyst according to the present invention may be prepared by preliminarily polymerizing the above olefin polymerization catalyst with an olefin having 2 to 20 carbon atoms as will be described later in the olefin polymerization (main polymerization). .

As the monomer to be prepolymerized, olefins used in the polymerization are preferable among them. Further, these olefins can be polymerized or copolymerized.

In the present invention, when forming the prepolymerization catalyst, olefin is added in an amount of 0.1 per 1 g of the [C] fine particle carrier.
It is desirable to pre-polymerize in an amount of ˜500 g, preferably 0.5 to 50 g.

The prepolymerization can be carried out by either liquid phase polymerization such as suspension polymerization or gas phase polymerization. When the preliminary polymerization is carried out by the liquid phase polymerization method, the same polymerization solvent as the polymerization solvent used in the main polymerization as described later can be used. Also, the olefin itself can be used as the solvent.

In the preliminary polymerization, the [A] transition metal compound is usually added in an amount of 0.0001 to 1 per liter of the polymerization volume.
In an amount of 0 mmol, preferably 0.001 to 1 mmol, the [B] organoaluminum compound is converted into an atomic conversion (Al / transition metal) with respect to the amount of the [A] transition metal compound.
It is used in a molar ratio of 1 to 500, preferably 10 to 250.

The temperature of the prepolymerization is usually -50 to 150.
° C., preferably 0 to 100 ° C., the polymerization pressure is usually atmospheric pressure to 100 kg / cm ^2, preferably atmospheric pressure to 50 kg /
It is cm ² .

Preliminary polymerization can be carried out by any of batch, semi-continuous and continuous methods. In the present invention, the olefin polymerization catalyst or the prepolymerization catalyst may contain other components useful for olefin polymerization in addition to the above-mentioned components.

The olefin polymerization catalyst (or prepolymerization catalyst) according to the present invention can polymerize olefins with excellent polymerization activity. Olefin polymerization method In the olefin polymerization method according to the present invention, in the presence of an olefin polymerization catalyst or a prepolymerization catalyst as described above,
The olefin is polymerized or copolymerized.

As the olefin used in the present invention,
Examples of the α-olefin having 2 to 20 carbon atoms include, specifically, ethylene, propylene, 1-butene, 1-pentene, 1-
Hexene, 3-methyl-1-butene, 3-methyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1- Examples include hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene.

Further, aromatic vinyl compounds such as styrene, substituted styrenes, allylbenzene, substituted allylbenzenes, vinylnaphthalene, substituted vinylnaphthalene, allylnaphthalene and substituted allylnaphthalene, vinylcyclopentane, substituted vinylcyclopentanes. , Vinylcyclohexane, substituted vinylcyclohexanes, vinylcycloheptane, substituted vinylcycloheptanes, alicyclic vinyl compounds such as allyl norbornane, allyltrimethylsilane, allyltriethylsilane, 4-trimethylsilyl-1-butene, 6-trimethylsilyl-1 -Hexene, 8-trimethylsilyl-1-octene, 10-trimethylsilyl-1-
Silane unsaturated compounds such as decene, cyclopentene,
Cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene Such as cyclic olefins, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-
Propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7- Conjugate or non-conjugate of dienes such as ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, isoprene and butadiene. A conjugated diene or the like can also be used.

Of these, ethylene, propylene, 1-
Butene, 4-methyl-1-pentene, 3-methyl-1-butene and the like are preferable. These may be used alone or in combination.

During the polymerization, the [A] transition metal compound is
Converted to a transition metal atom, usually 0.0001 to 10.0 mmol, preferably 0.00 per 1 liter of polymerization volume.
Used in an amount of 1 to 1 mmol.

The organoaluminum compound [B] is usually used in an amount of 0.0001 to 5000 mmol, preferably 0.001 to 1000 mmol, per liter of polymerization volume. Atomic conversion molar ratio (aluminum atom in [B] /
The transition metal atom in [A] is used in an amount of 1 to 500, preferably 10 to 250.

When a prepolymerization catalyst is used as the olefin polymerization catalyst, the prepolymerization catalyst is usually converted to a transition metal atom in the catalyst in an amount of 0.0001 to 10.0 mmol per 1 liter of polymerization volume. , Preferably 0.0
Used in an amount of 001 to 0.1 mmol. If necessary, the [A] transition metal compound and / or [B] organoaluminum compound may be added together with the prepolymerization catalyst.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as suspension polymerization or a gas phase polymerization method.
When the polymerization is carried out by a liquid phase polymerization method, as a polymerization solvent, propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, cyclopentane, cyclohexane, methylcyclopentane And the like, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene, and dichloromethane can be used. These may be used alone or in combination. Further, the polymerized olefin itself can be used as the solvent.

In the present invention, the olefin polymerization temperature is usually -50 to 150 ° C, preferably 0 to 100 ° C. The polymerization pressure is usually from normal pressure to 100 kg / cm ² , preferably from normal pressure to 50 kg / cm ² .

Polymerization can be carried out by any of batch, semi-continuous and continuous methods. Further, the polymerization can be carried out in two or more stages under different reaction conditions. The molecular weight of the obtained olefin polymer can be adjusted by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.

[0066]

The olefin polymerization catalyst according to the present invention is
Olefin can be polymerized with excellent polymerization activity without using an organic aluminooxy compound.

In the olefin polymerization method according to the present invention, an olefin is polymerized in the presence of such an olefin polymerization catalyst, and an olefin polymer can be produced in a high yield.

[0068]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Intrinsic viscosity ([η]) [dl / g]: 135 ° C.
It was measured in decalin. Reduced specific viscosity (RSV) [dl / g]: Measured by dissolving it in decalin at 135 ° C at a concentration of 0.1 g / dl.

Ethylene content (mol%): Determined by IR spectrum. Melting point (Tm): measured using a Perkin-Elmer DSC-7 type device. Approximately 5 mg of sample is packed in aluminum pan,
The temperature was increased from 0 ° C./min to 200 ° C., held at 200 ° C. for 5 minutes, lowered to room temperature at 20 ° C./min, and then increased from 10 ° C./min.

[0071]

Example 1 The glass polymerization vessel was replaced with nitrogen, 1000 ml of toluene was added, and the mixture was heated to 75 ° C. and ethylene (100
Liter / hr) was introduced to fully saturate the solvent.

Triisobutylaluminum (0.4 mmol in terms of aluminum atoms) and ethylenebisindenyl zirconium dichloride (0.005 mmol in terms of zirconium atoms) were added to this polymerization vessel (A
1 / Zr = 80) to start the polymerization.

After polymerizing for 1 hour, a small amount of isobutyl alcohol was added to stop the polymerization, and the reaction product was poured into a large amount of methanol to precipitate the whole amount of the polymer. Then, hydrochloric acid was added and the mixture was filtered through a glass filter. The polymer was vacuum dried at 80 ° C. for 10 hours, and then polyethylene (PE) 38.5 was used.
g was obtained.

The polymerization activity per 1 mmol of zirconium was 7680 g, and the intrinsic viscosity [η] of the obtained polyethylene was 2.25 dl / g.

[0075]

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that triisobutylaluminum was used in an amount of 4.25 mmol which was 850 times that of zirconium, but a trace amount of polyethylene was used. I only got it.

[0076]

Example 2 Polymerization was carried out in the same manner as in Example 1 except that tridecylaluminum was used instead of triisobutylaluminum to obtain 8.40 g of polyethylene.

The polymerization activity per 1 mmol of zirconium was 1680 g, and the intrinsic viscosity [η] of the obtained polyethylene was 2.36 dl / g.

[0078]

Example 3 Polymerization was carried out in the same manner as in Example 1 except that 1,3-dimethylcyclopentadienyl zirconium dichloride was used instead of ethylenebisindenyl zirconium dichloride. 3.4 g of polyethylene was obtained.

The polymerization activity per 1 mmol of zirconium was 680 g.

[0080]

Example 4 The glass polymerization vessel was replaced with nitrogen, 1000 ml of toluene was added, and the mixture was heated to 50 ° C., ethylene (80 liters / hr) and propylene (120 liters / hr).
Was introduced to fully saturate the solvent.

Triisobutylaluminum (0.4 mmol in terms of aluminum atom) and ethylenebisindenyl zirconium dichloride (0.005 mmol in terms of zirconium atom) were added to this polymerization vessel (A
1 / Zr = 80) to start the polymerization. After an induction period of about 30 minutes, heat was generated and polymerization was confirmed. Polymerization was continued for another 30 minutes, and a small amount of isobutyl alcohol was added to terminate the polymerization. The reaction product was washed with hydrochloric acid and water and concentrated, and then the polymer was vacuum dried at 130 ° C. for 10 hours, followed by EP.
28 g of R (ethylene / propylene copolymer) was obtained.

The polymerization activity for 1 hour after the addition of the catalyst until the termination was 5900 g per 1 mmol of zirconium. The RSV of the obtained EPR was 1.02 dl / g and the ethylene content was 76 mol%.

[0083]

Example 5 In Example 4, tridecylaluminum was used in place of triisobutylaluminum, and
Polymerization was initiated at ° C. After 48 minutes from the start of the polymerization, a rise in the polymerization temperature was observed, so the polymerization was started. After polymerizing for 33 minutes, the polymerization was terminated with isobutyl alcohol, and post-treatment was carried out in the same manner as in Example 4 to obtain 45.3 g of a polymer.

The RSV of the obtained EPR is 0.92 dl / g
And the ethylene content was 66 mol%.

[0085]

Example 6 The glass polymerization vessel was replaced with nitrogen, 1000 ml of toluene was added, and the mixture was heated to 40 ° C. and propylene (100
Liter / hr) was introduced to fully saturate. On the other hand, dimethylsilylbisindenyl zirconium dichloride (0.0208 mmol in terms of zirconium atom) and triisobutylaluminum (1.68 mmol in terms of aluminum atom) were pre-contacted.

The pre-contact material was introduced into the glass polymerization vessel, and 4
Polymerization was carried out for a time, and the polymerization was stopped with triisobutyl alcohol. The polymerization solution was precipitated in a large amount of methanol, hydrochloric acid was added, the polymer was collected by filtration, and vacuum dried at 80 ° C. for 10 hours to obtain 2.5 g of polypropylene (PP).

The polymerization activity was 27 g per 1 mmol of zirconium. The polypropylene thus obtained had an intrinsic viscosity [η] of 0.73 dl / g and a Tm of 136.1 ° C.

[0088]

Example 7 In Example 6, dimethylsilylbisindenyl zirconium dichloride (0.0118 mmol in terms of zirconium atom) and tridecylaluminum (1.89 mmol in terms of aluminum atom).
Polymerization was performed in the same manner as in Example 6 except that was used.
As a result, 3.6 g of polypropylene was obtained.

The polymerization activity was 34 g per 1 mmol of zirconium. The intrinsic viscosity [η] of the obtained polypropylene is 0.70 dl / g and the Tm is 139.3 ° C.
Met.

[0090]

[Table 1]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst according to the present invention.

Claims (4)

[Claims] 1. A transition metal compound of Group IVB containing a ligand having an [A] cyclopentadienyl skeleton and a [B] organoaluminum compound, wherein the [B] organoaluminum compound and [A] transition The metal compound is 1 in terms of atomic ratio of aluminum / transition metal atom.
The catalyst for olefin polymerization is characterized by being -500. 2. A transition metal compound of group IVB containing a ligand having an [A] cyclopentadienyl skeleton, an organoaluminum compound [B], and a particulate carrier [C], said [B] The organoaluminum compound and the [A] transition metal compound have an aluminum / transition metal atomic conversion molar ratio of 1
The catalyst for olefin polymerization is characterized by being -500. 3. A prepolymerized catalyst, characterized in that the olefin polymerization catalyst according to claim 1 or 2 is preliminarily polymerized with an olefin having 2 to 20 carbon atoms. 4. A method for polymerizing an olefin, which comprises polymerizing or copolymerizing an olefin in the presence of the catalyst for olefin polymerization or the prepolymerization catalyst according to claim 1.