JPH09143217A - Olefin polymerization catalyst and method for producing olefin polymer - Google Patents

Abstract

(57) [Summary] (Modified) [PROBLEMS] A catalyst system containing a novel aluminum compound as one of the catalyst components to be combined with a transition metal compound such as a metallocene compound. SOLUTION: (A) General formula R ¹ (X ¹ H _m ) _n (In the formula, R ¹ is an n-valent organic group having 1 to 20 carbon atoms, and X ¹ is 1
Group 5 or group 16 atom, H represents a hydrogen atom. m is 1 or 2, and n is an integer of 2 or more. ) And a compound represented by the general formula R ² _p Al (X ² R ³ _q ) _3-p (wherein R ² is an organic group having 1 to 20 carbon atoms, Al is an aluminum atom, and R ³ is a carbon number. 1 to 20 is an electron-withdrawing group-containing group, X ² is an atom of Group 15 or Group 16, and p is 1
Or 2. q is an aluminum compound obtained by a reaction with an electron-withdrawing group-containing organoaluminum compound represented by 1 or 2) and a transition metal compound of Group 4 to 6 having at least one (B) conjugated five-membered ring ligand. And a catalyst for olefin polymerization comprising an organoaluminum compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an olefin polymerization catalyst. More specifically, the present invention relates to an olefin polymerization catalyst containing a novel aluminum compound as a component and a method for producing an olefin polymer using the catalyst.

[0002]

2. Description of the Related Art A method for producing an olefin polymer by combining a transition metal compound such as a metallocene compound with an aluminoxane is well known (for example, JP-A-58-4).
5205, JP-A-58-19309, JP-A-60-
35007, JP-A-61-130314, JP-A-6-6
2-230802, JP-A-63-142004, JP-A-63-234009, and JP-A-64-51408.
And Japanese Patent Laid-Open No. 64-66214). But,
Since these techniques have low activity per aluminum atom, the production cost is high, and a large amount of aluminum remains in the produced olefin polymer, which adversely affects the physical properties of the polymer.

For the purpose of solving these problems, many proposals have been made for improving aluminoxane (for example, JP-A-60-260602 and JP-A-60-130).
No. 604, JP-A-61-211307, JP-A-63-
89506, JP-A 63-130601, JP-A-6
3-178108, JP-A-63-218707, JP-A-64-9206, JP-A-64-16803, JP-A-1-315407, JP-A-2-22306, JP-A-2-22308, JP-A-2-167307 and JP-A-2-167310). However, although these have some improvement in the polymerization activity, they are insufficient to solve the above problems.

Further, a polymerization catalyst component comprising an aluminoxane compound having two or more kinds of alkyl groups or hydrogen has been proposed (for example, JP-A-2-2470201).
JP-A-2-250886, JP-A-3-13950
3, JP-A-4-46906, JP-A-4-26410.
And JP-A-4-266910). However, even such an aluminoxane compound needs to be used in a large amount in order to exhibit high activity.

On the other hand, as a method not using an aluminoxane compound, there is a method of using an ionic compound or a combination of an ionic compound and an organic aluminum compound as one of the catalyst components (for example, Japanese Patent Publication No. 1-502).
036, JP-A-3-124706, JP-A-3-13
9504, JP-A-3-207703, JP-A-3-2
07704, JP-A-4-253711, JP-A-5-
170826, JP-A-5-247132, and JP-A-5-320240). According to these methods, the polymerization activity per aluminum is improved, and although the problem due to the aluminum remaining in the polymer is solved, in order to dissolve such an ionic compound, toluene or the like as a solvent is dissolved. Since aromatic hydrocarbons must be used, there are many industrial restrictions.

A method using a catalyst system consisting of a transition metal compound and a Lewis acid which reacts with the compound to form a stable ion pair is also disclosed (Japanese Patent Laid-Open No. 5-194).
641). However, the Lewis acid generally used in this catalyst system is a tricoordinated boron compound, and the problem in terms of safety has not always been solved.

In addition, it is disclosed that a compound obtained by reacting a compound having one or more acidic hydroxy groups with a trialkylaluminum is used as a part of a catalyst component for polymerization (special feature). Kaihei 1-10
1303 publication). However, the polymerization activity per aluminum is not necessarily high enough.

It has also been proposed to use a reaction product of a divalent alcohol or a divalent amine with an organoaluminum compound (JP-A-3-62806). However, as a specific embodiment of the invention, the disclosed method involves reacting trialkylaluminum with an approximately equimolar amount of a divalent alcohol or divalent amine. Therefore, it has been reported that when it is combined with a metallocene compound, it exhibits a remarkably low polymerization activity.
Therefore, some improvement is required for industrial use.

It has been disclosed that a reaction product of an alkylboronic acid and an organoaluminum compound is used as a catalyst component for olefin polymerization (JP-A-6-
Nos. 172438 and 6-172439).
As a result, although the activity per aluminum is slightly improved, there is a problem that the amount of aluminum used is not necessarily small and the amount of boron compound used is large.

More recently, it has been proposed to use an aluminum compound containing an electron-withdrawing group or an electron-withdrawing group-containing group as a catalyst component for olefin polymerization (JP-A-6-329713). With this proposal,
Although the polymerization activity per aluminum in ethylene polymerization is improved, the molecular weight of the copolymer is not necessarily high when ethylene / α-olefin copolymerization is performed,
Improvements are needed to produce ethylene / α-olefin copolymers that are highly industrially useful.

[0011]

Under the present circumstances,
The problem to be solved by the present invention is one of catalyst components to be combined with a transition metal compound such as a metallocene compound,
A catalyst system containing a novel aluminum compound, comprising:
It is an object of the present invention to provide a catalyst system capable of producing a highly active and high molecular weight olefin polymer and copolymer.

[0012]

Means for Solving the Problems As a result of diligent studies on such problems, the present inventors have identified a reaction product of a specific organic compound having two or more active hydrogens and a specific aluminum compound having an electron-withdrawing group. The present invention has been accomplished by finding out as an organic metal component for an olefin polymerization catalyst.

That is, the present invention provides (A) the general formula R ¹ (X ¹
H _m ) _n (In the formula, R ¹ is an n-valent organic group having 1 to 20 carbon atoms, and X ¹ is an atom of Group 15 or Group 16.
Represents a hydrogen atom. m is 1 or 2 depending on the valence of X ¹ . n is an integer of 2 or more. ) And a compound represented by the general formula R ² _p Al (X ² R ³ _q ) _3-p (wherein R ² is an organic group having 1 to 20 carbon atoms, Al is an aluminum atom, and R ³ is a carbon number. 1 to 20 is an electron-withdrawing group-containing group, X ² is an atom of Group 15 or Group 16, and p is 1
Or 2. q is depending on the valence of X ² 1 or 2
It is. And an aluminum compound obtained by reaction with an electron-withdrawing group-containing organoaluminum compound represented by the formula (4), and (B) at least one conjugated five-membered ring ligand
~ Olefin polymerization catalyst comprising a Group 6 transition metal compound,
And further (C) the general formula R ¹² _d AlY _3-d (where R
¹² is a hydrocarbon group having 1 to 8 carbon atoms, Y is hydrogen and / or
Or halogen. a represents the integer of 0-3. And a catalyst for olefin polymerization comprising an organoaluminum compound represented by the formula (1), and a method for producing an olefin polymer using the catalyst.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the compound represented by the general formula R ¹ (X ¹ H _m ) _{n according} to the present invention, R ¹ is an n-valent organic group having 1 to 20 carbon atoms, and n is an integer of 2 or more. n is preferably an integer of 2 or more and 4 or less, and more preferably n is 2. When n is 2, a specific example of R ¹ is an ethylene group,
Examples thereof include alkylene groups such as acetylene groups, phenylene groups, and substituted phenylene groups. Preferred are a phenylene group and a substituted phenylene group.

X ¹ is a group 15 or group 16 atom,
Specifically, the group 15 atom includes a nitrogen atom and a phosphorus atom, and the group 16 atom includes an oxygen atom and a sulfur atom. Of these, a nitrogen atom and an oxygen atom are preferable, and an oxygen atom is more preferable.

Specific examples of the compound represented by the general formula R ¹ (X ¹ H _m ) _n include alkylene diols such as ethylene glycol and propylene glycol; hydroquinone, resorcinol, catechol, 4-methylcatechol, 4- t-butylcatechol, 2,2'-bi
Arylene diols such as 1-naphthol; ethylenediamine, propylenediamine, butanediamine, 1,
Alkylenediamines such as 3-cyclopentanediamine; Allylenediamines such as 1,4-naphthalenediamine; Erythritols such as pentaerythritol and dipentaerythritol; and the like are preferable, and diols are preferable, and ethylene is particularly preferable. Glycol, 4-
t-butylcatechol, 4-methylcatechol, 2,
Examples thereof include diols such as 2'-bi-1-naphthol. Of these, 4-t-butylcatechol is most preferable.

The general formula R ² _p Al (X ²
R ² in R ³ _q) an electron-withdrawing group-containing organoaluminum compound represented by the _3-p is an organic group having 1 to 20 carbon atoms, for example, an alkyl group, an aryl group, an aralkyl group or the like. Specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a benzyl group. However, a methyl group, an ethyl group, an isobutyl group and the like are preferable.

The general formula R ² _P Al (X ² R ³ _q )
R ³ in the electron-withdrawing group-containing organoaluminum compound represented by _3-p is an electron-withdrawing group-containing group having 1 to 20 carbon atoms. As such an electron-withdrawing group, a halogen atom,
Examples thereof include a nitro group, a sulfone group, a cyano group and a carbonyl group, and a halogen atom is preferable. More preferably, it is a fluorine atom.

R ³ is specifically a trihaloalkyl group,
Examples thereof include pentahaloaryl group, pentakis (trihaloalkyl) aryl group, trihaloaryl group, dihaloaryl group, monohaloaryl group, and the like, and preferable examples include trihaloalkyl group, pentahaloaryl group, pentakis (trihaloalkyl) aryl group, and the like. It is a haloalkyl group or a perhaloaryl group. As a specific example,
Pentafluorophenyl group, pentachlorophenyl group,
A pentabromophenyl group etc. are illustrated. Among the halogen atoms, a fluorine atom is most preferable, and a perfluoroalkyl group such as a trifluoromethyl group and a trifluoroethyl group or a perfluoroaryl group such as a pentafluorophenyl group is preferable. Particularly preferred as a specific example is a pentafluorophenyl group.

The general formula _{^{R 2 P Al (X 2 R}} 3 q) X 2 in the electron withdrawing group-containing organoaluminum compound represented by the _3-p is 15 or Group 16 atom, and specific examples include, Nitrogen atoms and phosphorus atoms are 1 as group 15 atoms
Examples of the atom of Group 6 include an oxygen atom and a sulfur atom, and
Selected independently of ¹ . Of these, a nitrogen atom and an oxygen atom are preferable. More preferably, it is an oxygen atom.

In the electron-withdrawing group-containing organoaluminum compound represented by the general formula R ² _P Al (X ² R ³ _q ) _3-p , q is 1 or 2 depending on the valence of X ² . X ²
Is 2 when X is a group 15 atom, and is 1 when X ² is a group 16 atom. p is 1 or 2.

The above general formula R ² _P Al (X ² R ³
_q ) Specific examples of the electron withdrawing group-containing organoaluminum compound represented by _3-p include bis (trifluoromethoxy) aluminum methyl, bis (trifluoromethoxy) aluminum ethyl, bis (trifluoromethoxy) aluminum butyl, Bis (trifluoroethoxy) aluminum methyl, bis (trifluoroethoxy) aluminum ethyl, bis (trifluoroethoxy) aluminum butyl, bis (trichloromethoxy)
Aluminum methyl, bis (trichloromethoxy) aluminum ethyl, bis (trichloromethoxy) aluminum butyl, bis (hexafluoropropoxy) aluminum methyl, bis (hexafluoropropoxy) aluminum ethyl, bis (hexafluoropropoxy) aluminum butyl, bis (hexachloropropoxy) ) Aluminum methyl, bis (hexachloropropoxy) aluminum ethyl, bis (hexachloropropoxy) aluminum butyl, bis (trifluorophenoxy) aluminum methyl, bis (trifluorophenoxy) aluminum ethyl, bis (trifluorophenoxy) aluminum butyl, bis (trichloro) Phenoxy) aluminum methyl, bis (trichlorophenoxy) aluminum ethyl, bi (Trichlorophenoxy) aluminum butyl, bis (tribromophenoxy) aluminum methyl, bis (tribromophenoxy) aluminum ethyl, bis (tribromophenoxy) aluminum butyl, bis (pentafluorophenoxy) aluminum methyl, bis (pentafluorophenoxy) aluminum Ethyl, bis (pentafluorophenoxy) aluminum butyl, bis (pentachlorophenoxy) aluminum methyl, bis (pentachlorophenoxy) aluminum ethyl, bis (pentachlorophenoxy) aluminum butyl, bis (pentabromophenoxy) aluminum methyl, bis (penta Bromophenoxy) aluminum ethyl, bis (pentabromophenoxy) aluminum butyl, bis (trifluorophenyl) Noxy) aluminum methyl, bis (trifluoromethylphenoxy) aluminum ethyl, bis (trifluoromethylphenoxy) aluminum butyl, bis (trichloromethylphenoxy) aluminum methyl, bis (trichloromethylphenoxy) aluminum ethyl, bis (trichloromethylphenoxy) aluminum Butyl, bis (trifluoroethylamino) aluminum methyl, bis (trifluoroethylamino) aluminum ethyl, bis (trifluoroethylamino) aluminum butyl, bis (pentafluoroanilino) aluminum methyl, bis (pentafluoroanilino) aluminum Ethyl, bis (pentafluoroanilino) aluminum butyl, bis (pentachloroanilino) aluminum methyl, bis (pen Tachloroanilino) aluminum ethyl, bis (pentachloroanilino) aluminum butyl, bis (trifluoromethylanilino) aluminum methyl, bis (trifluoromethylanilino) aluminum ethyl, bis (trifluoromethylanilino) aluminum butyl,
Bis (trichloromethylanilino) aluminum methyl, bis (trichloromethylanilino) aluminum ethyl, bis (trichloromethylanilino) aluminum butyl, trifluoromethoxyaluminum dimethyl,
Examples thereof include trifluoromethoxyaluminum diethyl, pentafluorophenoxydimethyl, pentafluorophenoxydibutyl and the like, preferably bis (pentafluorophenoxy) aluminum methyl, bis (pentafluorophenoxy) aluminum ethyl, and bis (pentafluorophenoxy) aluminum butyl. To be

The above general formula R^Two _PAl (X^TwoR^Three
_q)_3-pElectron-withdrawing group-containing organoaluminum represented by
The compound is, for example, trialkylaluminum perf
General formula HX such as luorophenol^TwoR^Three _q(In the formula, H
Represents a hydrogen atom, X^Two, R ^ThreeAnd q are as defined above.
You. ) Obtained by treating with a compound represented by
You. Specifically, for example, trimethylaluminum, etc.
Trialkylaluminum as a solution of toluene, etc.
Cool in a bath and add an equimolar amount or 2
After adding a double molar amount of perfluorophenol, etc.,
It can be obtained by stirring at room temperature for 24 hours or more. This
Examples of such perfluorophenols include pentaf
Luorophenol and the like are used.

The aluminum compound according to the present invention includes a compound represented by the general formula R ¹ (X ¹ H _m ) _n and an electron represented by the general formula R ² _P Al (X ² R ³ _q ) _3-p. It is obtained by reaction with an organoaluminum compound containing a suction group. Examples of the reaction method include, for example, an electron-withdrawing group-containing organoaluminum compound represented by the general formula R ² _P Al (X ² R ³ _q ) _3-p obtained by the above-mentioned method, in the aluminum atom. On the other hand, there is a method of reacting with a compound represented by the general formula R ¹ (X ¹ H _m ) _n in an amount having an equimolar amount of X ¹ H group. More specifically, for example, in a hydrocarbon solution in which a reaction product of a trialkylaluminum such as trimethylaluminum and the like, and a perfluorophenol such as pentafluorophenol, which have been previously generated, is dissolved,
Diols dissolved in a hydrocarbon solvent may be added dropwise.
Also in this case, the dropping should be done in an ice bath, and at the room temperature after the dropping, 2
The reaction is preferably completed by stirring for 4 hours or more.

The transition metal compound (B) of the present invention is a Group 4 to 6 transition metal compound having at least one conjugated five-membered ring ligand, and has, for example, the general formula CpMR ⁷ _a R ⁸ _b R ⁹ _c ( 3) Cp ₂ MR ⁷ _a R ⁸ _b (4) (Cp-A ¹ -Cp) MR ⁷ _a R ⁸ _b (5) (Cp-A ² -R ¹⁰ ) MR ⁷ _a R ⁸ _b (6) What is used is used.

In the above general formulas (3) to (6), Cp
Is a cyclopentadienyl group or a substituted cyclopentene
Tadienyl group or cyclopentadienyl skeleton
It is a polycyclic group having. M is the transition of groups 4 to 6 of the periodic table
It is a transfer metal atom. R⁷, R ⁸, And R⁹Each one
Vertically shows a σ-bonding ligand and a chelating ligand. R
^TenIs -N (R¹¹)-, -P (R¹¹)-, -O-, -S-
Is shown. R¹¹Is an alkane having 1 to 20 carbon atoms in each case.
Kill group, aryl group, silyl group, halogenated alkyl group
And a halogenated aryl group. A¹And A^TwoIs shared
Shows a cross-linking group by a bond, alkylene having 1 to 20 carbon atoms
Silylene group having two groups or two alkyl groups having 1 to 10 carbon atoms
And so on. a, b and c are each independently an integer of 0 to 4
Indicates a number.

In the general formulas (3) to (6), when Cp is a substituted cyclopentadienyl group, the substituent is an alkyl group having 1 to 20 carbon atoms and a polycyclopentadienyl skeleton. Examples of the cyclic group include an indenyl group skeleton and a fluorenyl group skeleton. In the case of a compound having two Cp's, they do not necessarily have to be the same and may be different.

Specific examples of the substituted cyclopentadienyl group include, for example, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, a normal propylcyclopentadienyl group, a normal butylcyclopentadienyl group, and an isopropylcyclopentadiene group. Dienyl group, isobutylcyclopentadienyl group, secondary butylcyclopentadienyl group, tertiary butylcyclopentadienyl group, 1,
2-dimethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienyl group, 1,2,4-trimethylcyclopentadienyl group, tetramethylcyclopenta group Examples thereof include a dienyl group and a pentamethylcyclopentadienyl group. Further, specific examples of the polycyclic group having a cyclopentadienyl skeleton include indenyl group, 4,5,6,7-
Examples thereof include a tetrahydroindenyl group and a fluorenyl group.

In the above general formulas (3) to (6), M is a transition metal atom of Groups 4 to 6 of the periodic table, preferably a titanium atom, a zirconium atom or a hafnium atom.

In the above general formulas (3) to (6),
R ⁷ , R ⁸ and R ⁹ each independently represent a σ-bonding ligand and a chelating ligand. Specific examples of the σ-bonding ligand include a hydrogen atom, a halogen atom, and a carbon number of 1 to 20.
Alkyl group, C1-20 alkoxy group, C6-20 aryl group or aralkyl group, C1
~ 20 acyloxy groups, allyl groups, substituted allyl groups,
Each may contain a silyl group or a halogen atom as a substituent. Examples of the chelating ligand include an acetylacetonate group and a substituted acetylacetonate group. In addition, R ⁷ , R ⁸ and R ⁹ may combine with each other to form a ring.

Specific examples of R ⁷ , R ⁸ and R ⁹ include, for example, a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group. , Normal propyl group, isopropyl group, normal butyl group, alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group, aryl group having 6 to 20 carbon atoms or aralkyl group. Examples thereof include a phenyl group, a tolyl group, a xylyl group and a benzyl group. Examples of the acyloxy group having 1 to 20 carbon atoms include a heptadecylcarbonyloxy group.

R ¹⁰ is -N (R ¹¹ )-, -P (R ¹¹ )-,
-O- and -S- are shown. R ¹¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group, a silyl group, a halogenated alkyl group or a halogenated aryl group. R ¹⁰ is -N (R ¹¹ )-
Alternatively, as a specific example in the case of -P (R ¹¹ )-,
Butyramide, phenylamide, perfluorophenylamide, butylphosphide, phenylphosphide,
Examples include perfluorophenyl phosphide.

A ¹ and A ² represent a bridging group by a covalent bond, and examples thereof include an alkylene group having 1 to 20 carbon atoms and a silylene group having two alkyl groups having 1 to 10 carbon atoms. Specific examples are methylene, ethylene, isopropylidene, 1,1.
-Diphenylmethylene, 1,1-cyclohexylene, dimethylsilylene, diphenylsilylene and the like can be mentioned.

Among the compounds represented by the general formula (3), specific examples of the compound in which M is zirconium include, for example, (cyclopentadienyl) trimethylzirconium and (cyclopentadienyl) triphenylzirconium. , (Cyclopentadienyl) tribenzylzirconium, (Cyclopentadienyl) zirconium trichloride, (Cyclopentadienyl) zirconium tribromide, (Cyclopentadienyl) trimethoxyzirconium, (Cyclopentadienyl) triphenoxyzirconium , (Methylcyclopentadienyl) trimethylzirconium, (Methylcyclopentadienyl) triphenylzirconium, (Methylcyclopentadienyl) tribenzylzirconium, (Methylcyclopentadienyl) dil Aluminum trichloride, (methylcyclopentadienyl) zirconium tribromide, (methylcyclocyclopentadienyl) trimethoxyzirconium, (methylcyclopentadienyl) triphenoxyzirconium, (pentamethylcyclocyclopentadienyl) trimethylzirconium, (Pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) zirconium trichloride, (pentamethylcyclopentadienyl) zirconium tribromide, (pentamethylcyclopentadienyl) zirconium tribromide, Methylcyclocyclopentadienyl) trimethoxyzirconium,
The same may be said of (pentamethylcyclopentadienyl) triphenoxyzirconium and the like, as well as compounds in which zirconium is replaced by titanium or hafnium.

Among the compounds represented by the general formula (4), specific examples of the compound in which M is zirconium include, for example, bis (cyclopentadienyl) zirconium dichloride and bis (cyclopentadienyl) zirconium. Dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (methylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dibromide, bis (methylcyclopentadienyl) zirconium dimethyl, bis (penta Methylcyclopentadienyl) zirconium dichloride, bis (pentamethylcyclopentadienyl) zirconium dibromide, bis (pentamethylcyclopentadienyl) zirconium dimethyl, bis (indenyl) zirconium Dichloride, bis (indenyl) zirconium dibromide, bis (indenyl) zirconium dimethyl, bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, bis (4,
5,6,7-Tetrahydroindenyl) zirconium dibromide, bis (4,5,6,7-tetrahydroindenyl) zirconium dimethyl, bis (fluorenyl)
Zirconium dichloride, bis (fluorenyl) zirconium dibromide, bis (fluorenyl) zirconium dimethyl, and the like, and compounds in which zirconium is replaced with titanium or hafnium in the same manner are also mentioned.

Among the compounds represented by the general formula (5), specific examples of the compounds in which M is zirconium include, for example, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylene. Bis (indenyl) zirconium dimethyl, ethylenebis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, Dimethyl silylene bis (indenyl) zirconium dichloride, dimethyl silylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, dimethyl silylene (cyclopentadienyl) Fluorenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, and the like. Further, a compound in which zirconium is replaced with titanium or hafnium in the zirconium compound as described above can be similarly exemplified.

Further, among the compounds represented by the general formula (6), specific examples of the compound in which M is titanium include
For example, (tertiary-butylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyltitanium dichloride, (tertiary-butylamido) (tetramethylcyclopentadienyl) dimethylsilanetitanium dichloride, (third -Butylamido) (tetramethylcyclopentadienyl) diphenylsilane titanium dichloride, (phenylamido) (tetramethylcyclopentadienyl) -1,2-ethanediyl titanium dichloride, (phenylamido) (tetramethylcyclopentadienyl) ) Dimethylsilane titanium dichloride, (phenylamido) (tetramethylcyclopentadienyl) diphenylsilane titanium dichloride and the like. Further, a compound in which titanium is replaced with zirconium or hafnium in the above titanium compound can be similarly exemplified.

In the present invention, an olefin polymerization catalyst comprising an aluminum compound (A) and a transition metal compound (B) is further added with an organoaluminum compound (C) represented by the general formula R ¹² _d AlY _3-d. It can be used as a polymerization catalyst.

General formula R ¹² _d AlY _3-d (wherein R ¹² is a hydrocarbon group having 1 to 8 carbon atoms, Y is hydrogen and / or halogen, and a is an integer of 0 to 3. Specific examples of the organoaluminum compound represented by) include trialkylaluminum such as trimethylaluminum, triethylaluminum, trinormalpropylaluminum, triisobutylaluminum, and trinormalhexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, and dinormalpropylaluminum. Dialkyl aluminum chlorides such as chloride, diisobutyl aluminum chloride, dinormal hexyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride,
Examples include alkyl aluminum dichlorides such as normal propyl aluminum dichloride, isobutyl aluminum dichloride, normal hexyl aluminum dichloride, dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, diisobutyl aluminum hydride, dialkyl aluminum hydride such as dinormal hexyl aluminum hydride. can do. These organoaluminum compounds may be used alone or in combination of two or more.

Next, regarding the use ratio (molar ratio) of the catalyst component in the present invention, when only (A) transition metal compound and (B) aluminum compound are used,
(A) :( B) = 1: 1 to 5,000 is preferable, but 1: 1 to 500 is particularly preferable in terms of economy and post-treatment. Further, in addition to the above components, the amount of the organoaluminum compound (C) used may be in the range of (A) :( B), but (A) :( C) is 1: 1 to 1,000. It is preferable, but the range of 1:10 to 1: 200 is particularly preferable.

As the polymerization catalyst, a reaction product obtained by previously contacting the components (A), (B) and (C) with each other may be used, and any two of them may be previously contacted. Alternatively, the reaction product obtained by contacting another component after the reaction may be used.

Regarding the concentration when each catalyst component is used in a solution, the component (A) is 0.0001 to 1 mmol / liter, preferably 0.001 to 0.1 mmol / liter, the component (B) and the component (C). Ingredient is 0.0 in terms of Al atom
001 to 500 mmol / liter, preferably 0.0
In the range of 1 to 50 mmol / l, and (B)
It is desirable to use each component so that the component and the component (C) are in the above ranges in molar ratio with respect to the component (A).

As a method for supplying each catalyst component to the polymerization tank, nitrogen, argon, etc. are dissolved or suspended in a hydrocarbon solvent from which components such as water and oxygen for deactivating the catalyst component are sufficiently removed. There are no particular conditions to be restricted except that the pressure is used to supply the inert gas.

The polymerization method in the present invention is not particularly limited, but for example, aliphatic hydrocarbons such as butane, pentane, hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, or methylene. Solvent polymerization using halogenated hydrocarbon such as chloride as a solvent, or slurry polymerization, bulk polymerization in liquid monomer, gas phase polymerization in gaseous monomer is possible. Either formula is possible.

The polymerization in the present invention is carried out at -50 ° C to
Temperature of 200 ° C., preferably 20 ° C. to 100 ° C., pressure of 0 to 100 kg / cm ² , preferably 0 to 50 kg / c
It is carried out in m ^2.

The olefins used in the present invention are ethylene and / or α-olefins, and the α-olefins are α-olefins having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. For example, propylene, butene-1, 4,
-Methylpentene-1, hexene-1, octene-1,
Vinyl cyclohexane etc. are mentioned. The present invention can be applied to homopolymerization or copolymerization of these olefins. In order to adjust the molecular weight of the polymer, a chain transfer agent such as hydrogen can be added.

[0047]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these.

The properties of the polymers in the examples were measured by the following methods. 1) The α-olefin content was measured by using an infrared spectrophotometer (manufactured by JASCO Corporation) JASCO-302 to measure ethylene and α-olefin content.
It was determined as the number of methyl groups in 1000 carbons by characteristic absorption of olefin. 2) For the intrinsic viscosity [η], use an Ubbelohde viscometer.
It was measured in a tetralin solution at 35 ° C. 3) The melting point was determined from the melting peak temperature of the DSC curve measured under the following conditions using Seiko SSC-5200. Temperature increase: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: 10 ° C to 160 ° C (5 ° C / min)

Example 1 (1) Synthesis of Aluminum Compound 20 ml of a toluene solution of trimethylaluminum (1 mol / liter) was placed in a 100 ml four-necked flask. Further, 20 ml of toluene was added, and the mixture was cooled to 0 ° C in an ice bath. 7.36 g of pentafluorophenol
A solution prepared by dissolving (0.04 mol) in 30 ml of toluene was added dropwise. Gas generation was observed during the dropwise addition. Then, the mixture was reacted at room temperature for 24 hours. During the reaction, the solution became slightly red. After completion of the reaction, concentration, recrystallization, filtration and drying were carried out to obtain 4.3 g of a red-white aluminum compound (I). Next, 4.14 g (0.01 mol) of aluminum compound (I) and 50 ml of toluene were added to a 200 ml four-necked flask, and the mixture was cooled to 0 ° C. in an ice bath. 4-t
-Butylcatechol 0.84 g (0.05 mol) dissolved in 20 ml of toluene was added dropwise. Gas generation was observed during the dropwise addition. Then, the reaction was carried out at room temperature for 24 hours or more. After drying, white-green aluminum compound (II)
was gotten.

(2) Ethylene Polymerization An autoclave equipped with a stirrer and having an internal volume of 400 ml was vacuum dried and replaced with argon, and then 200 m of toluene was used as a solvent.
1 was charged and the temperature of the reactor was raised to 60 ° C. After heating, feed ethylene while adjusting the ethylene pressure to 6 Kg / cm ² ,
After stabilizing the system, trimethylaluminum 0.2mm
was added, followed by 5.0 μmol of bis (cyclopentadienyl) titanium dichloride, and then 0.5 mmol of the above-synthesized aluminum compound (II).
I put it in. Polymerization was carried out for 15 minutes. As a result of the polymerization, 6.5 g of a polymer was obtained, and 1 mol of titanium had an activity of 5.2 × 10 ⁶ g / mol-Ti / hr per hour. [Η] was 4.6 dl / g.

Comparative Example 1 (1) Polymerization of Ethylene 0.2 in Example 1 (2)
Example 1 (2) was repeated except that the mmol was changed to 0.5 mmol and the aluminum compound (II) was not added. As a result of the polymerization, 0.0436 g of a polymer was obtained, and the activity was 4.4 × 10 ⁴ g / mol-Ti / hr.

Comparative Example 2 (1) Polymerization of Ethylene Trimethylaluminum 0.2 in Example 1 (2)
0.1 mmol triisobutylaluminum
In the same manner as in Example 1 (2) except that the aluminum compound (II) was changed to the above-synthesized aluminum compound (I). As a result of the polymerization, 4.8 g of a polymer was obtained, and the activity was 1.9 × 10 ⁶ g / mol-Ti / hr.
[Η] was 4.13 dl / g.

Example 2 (1) Copolymerization of ethylene and 1-hexene Same as Example 1 (2) except that 200 ml of toluene in Example 1 (2) was changed to 170 ml of toluene and 30 ml of 1-hexene. . As a result of the polymerization, an ethylene / 1-hexene copolymer having a 1-hexene content = 12.8, [η] = 2.17 dl / g, and a melting point of 106.7 ° C. was added to titanium 1 mol, 1.0 × per hour. 10 ⁶ g /
mol-Ti / hr was manufactured.

Example 3 (1) Copolymerization of ethylene and 1-hexene The procedure of Example 1 (2) was repeated except that 200 ml of toluene was changed to 170 ml of toluene and 30 ml of 1-hexene, and trimethylaluminum was changed to triisobutylaluminum. Same as Example 1 (2). Polymerization result, 1
-Hexene content 14.1, [η] 1.80 (dl /
g), ethylene / 1-hexene copolymer having a melting point of 107.0 ° C., 1 mol of titanium, 1.5 mol / hour
× 10 ⁶ g / mol-Ti / hr was produced.

Comparative Example 3 (1) Copolymerization of ethylene and 1-hexene 0.2 m of triisobutylaluminum in Example 3
mol to 0.1 mmol, aluminum compound (II)
Example 3 was repeated except that was changed to the aluminum compound (I). As a result of polymerization, 1-hexene content = 15.
6, [η] = 0.80 dl / g, ethylene / 1-hexene copolymer having a melting point of 109.5 ° C.
ol, 7.3 × 10 ⁵ g / mol-Ti / per hour
manufactured by hr.

Example 4 (1) Copolymerization of ethylene / α-olefin Same as Example 2 except that bis (cyclopentadienyl) titanium dichloride in Example 2 was changed to ethylenebis (indenyl) zirconium dichloride. .
As a result of the polymerization, 1-hexene content = 22.9, [η] =
Ethylene / 1.23 dl / g, melting point 99.2 ° C
A 1-hexene copolymer was produced in an amount of 1 mol of titanium and 3.0 × 10 ⁵ g / mol-Ti / hr per hour.

[0057]

INDUSTRIAL APPLICABILITY The olefin polymerization catalyst of the present invention can obtain a polymer having a high polymerization activity and a high molecular weight.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the present invention. The flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Claims (6)

[Claims] (A) General formula R ¹ (X ¹ H _m ) _n (wherein R ¹ is an n-valent organic group having 1 to 20 carbon atoms, and X ¹
Is a Group 15 or Group 16 atom. H represents a hydrogen atom. m is 1 or 2 depending on the valence of X ¹ .
n is an integer of 2 or more. ) And a compound represented by the general formula R ² _p Al (X ² R ³ _q ) _3-p (wherein R ² is an organic group having 1 to 20 carbon atoms, Al is an aluminum atom, and R ³ is a carbon number. 1 to 20 are electron-withdrawing group-containing groups, and X ² is 1
An atom of Group 5 or Group 16. p is 1 or 2. q is 1 or 2 depending on the valence of X ² . ) An aluminum compound obtained by the reaction with an electron-withdrawing group-containing organoaluminum compound and (B) a transition metal compound of Groups 4 to 6 having at least one conjugated five-membered ring ligand. And a catalyst for olefin polymerization. 2. (A) General formula R ¹ (X ¹ H _m ) _n (In the formula, R ¹ is an n-valent organic group having 1 to 20 carbon atoms, and X ¹
Is a Group 15 or Group 16 atom. H represents a hydrogen atom. m is 1 or 2 depending on the valence of X ¹ .
n is an integer of 2 or more. ) And a compound represented by the general formula R ² _p Al (X ² R ³ _q ) _3-p (wherein R ² is an organic group having 1 to 20 carbon atoms, Al is an aluminum atom, and R ³ is a carbon number. 1 to 20 are electron-withdrawing group-containing groups, and X ² is 1
An atom of Group 5 or Group 16. p is 1 or 2. q is 1 or 2 depending on the valence of X ² . ) An aluminum compound obtained by a reaction with an electron-withdrawing group-containing organoaluminum compound, (B) a Group 4 to 6 transition metal compound having at least one conjugated five-membered ring ligand, and (C) General formula R ¹² _d AlY _3-d (however,
R ¹² is a hydrocarbon group having 1 to 8 carbon atoms, and Y is hydrogen and / or halogen. a represents the integer of 0-3. )
An olefin polymerization catalyst comprising an organoaluminum compound represented by: 3. The catalyst for olefin polymerization according to claim 1 or 2, wherein X ¹ is an oxygen atom. 4. The catalyst for olefin polymerization according to claim 1 or 2, wherein the compound represented by the general formula R ¹ (X ¹ H _m ) _n is a diol. 5. The catalyst for olefin polymerization according to claim 1 or 2, wherein R ³ is a perfluoroalkyl group or a perfluoroaryl group. 6. A method for producing an olefin polymer, which comprises polymerizing using the catalyst for olefin polymerization according to claim 1 or 2.