JP3196419B2 - Aluminum oxy compound and polymerization catalyst containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel compound, a polymerization catalyst containing the compound as a component, and a method for producing a polyolefin using the catalyst. More specifically, a novel and useful aluminum oxy compound, a highly active catalyst particularly useful for the polymerization of olefins using the same, and a method for producing a highly active, high molecular weight, highly stereoregular polyolefin using the catalyst About.

[0002]

2. Description of the Related Art It is known that a catalyst system obtained by adding an aluminum oxy compound such as methylaluminoxane as a co-catalyst to a transition metal compound can be used as a catalyst for producing isotactic, syndiotactic polypropylene or polyethylene. . However, a catalyst system containing a transition metal compound and a conventional aluminum oxy compound had an excellent surface in terms of polymerization activity and stereoregularity. (Activity), molecular weight and tacticity of the obtained polymer were not always satisfactory. In addition, it is necessary to use a relatively large amount of an expensive and difficult-to-produce aluminum oxy compound, and the aluminum oxy compound exhibiting polymerization activity must have a degree of polymerization of about 7 to 50, and its range is limited. I was For this reason, there has been a demand for an improved catalyst system which can be used industrially while taking advantage of a catalyst system containing a transition metal compound and an aluminum oxy compound.

[0003]

Accordingly, the present invention is to improve a catalyst system containing a transition metal compound and an aluminum oxy compound as a co-catalyst, to have high productivity,
An object of the present invention is to obtain a catalyst system capable of producing a polymer having a high molecular weight and high stereoregularity, particularly a polyolefin.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have succeeded in obtaining an aluminum oxy compound into which a special group has been introduced. Addition of a transition metal compound as an active site stabilizing agent) or using an organic aluminum compound as a catalyst for olefin polymerization to dramatically increase the activity of polymerization and increase the molecular weight of the polymer Succeeded in imparting high stereoregularity, and completed the present invention. That is, the gist of the present invention is as follows.

[0005]

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[Where R is a hydrocarbon group having 1 to 12 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms, a halogen atom or -X ¹ R ¹ (X ¹ is a group 15 or 16 element. , R ¹ is a halogen atom or a halogen- containing group bonded to X ¹ ), and the polymerization degree n is an integer of 1 or more. When there are a plurality of Rs, each R may be the same or different. However, at least 10% of R is-
X ¹ R ¹ . And (A) (VII) to (X)
A transition metal compound represented by any of the general formulas and (B)
Single weight of olefins composed of the above aluminum compounds
Located case or copolymerization _{^{catalyst, CpM 1 R 5 a R 6}} b R 7 c (VII) CpM 1 R 5 a R 6 b (VIII) (Cp-A e -Cp) M 1 R 5 a R 6 b (IX) M ¹ R ⁵ _a R ⁶ _b R ⁷ _c R ⁸ _d (X) [Cp is a cyclopentadienyl group, a substituted cyclopentadiene
Enyl group, indenyl group, substituted indenyl group, tetrahi
A droindenyl group, a substituted tetrahydroindenyl group,
Indicates Ruoreniru group or a substituted fluorenyl group, M ¹ is Chi
Indicates tan, zirconium or hafnium. R ⁵ ,
R ⁶ , R ⁷ and R ⁸ are each independently a ligand, and A is shared
Shows crosslinking by bonding. a, b, c and d are each German
The letter e is an integer of 0-6, and e is an integer of 0-6. ] , 3rd
In addition, the above components (A) and (B) and (C) a general formula
(XIII) comprising an organic aluminum compound represented by I
Located homopolymerization or copolymerization catalyst of fins _{^{such, R 13 AlQ 3-r (}} XIII) (R 13 represents an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom,
C1-C20 alkoxy group, C6-C20 ant
And r represents an integer of 1 to 3.
You. ) Fourth, in the method for producing a polyolefin using listed in these second or third catalyst. Hereinafter, the contents of the present invention will be described in detail.

The aluminum oxy compound according to the present invention
Is an aluminum alloy having the structure represented by the general formula (I).
Umoxy compound. The general formula according to the present invention
Aluminum oxy compound having a structure represented by (I)
R of the product is a hydrocarbon group having 1 to 12 carbon atoms,
2 oxygen-containing hydrocarbon groups, halogen atoms or -X¹R¹
(X¹Is a Group 15 or 16 element, and R ¹Is X¹Tied to
Electron-withdrawing groups or groups containing electron-withdrawing groups
You. ), When R is plural, each R is the same,
May also be different. Hydrocarbons having 1 to 12 carbon atoms
The basic group is an alkyl group, specifically, a methyl group, an ethyl group
Group, n-propyl group, isopropyl group, n-butyl group,
Isobutyl group, pentyl group, hexyl group, octyl group,
A decyl group, a cyclohexyl group, etc. can be exemplified.
Methyl group, ethyl group, isopropyl group, isobutyl group
preferable. Other hydrocarbon groups include aryl groups,
Examples include a killaryl group and an arylalkyl group. carbon
The oxygen-containing hydrocarbon group of the formulas 1 to 12 is alkoxy
Group, an aryloxy group is preferred, and specifically methoxy
Group, ethoxy group, propoxy group, n-butoxy group,
Nonoxy group, 2,6-dimethylphenoxy group, naphthyl
And a xyl group. Halogen atoms include fluorine and salts
Element.

[0008] X ¹ in -X ¹ R ¹ is at least one element selected from group 15 or 16 element, 15
In group 6, nitrogen and phosphorus are particularly preferable, and in group 16, oxygen and sulfur are particularly preferable.

R ¹ is required to have a positive Hammett's substituent constant σ, and is specifically selected from at least one of an electron-withdrawing group and a group containing an electron-withdrawing group. Here, examples of the electron-withdrawing group include a halogen atom, a nitro group, a sulfone group, a cyano group, a carbonyl group, and an aldehyde group. Examples of the group containing an electron-withdrawing group include a trihaloalkyl group, a trihaloaryl group, a dihaloaryl group, a monohaloaryl group, a pentakis (trihalo) aryl group, and an ester group. Conventionally used aluminum oxy compounds have the general formula (I
I)

[0010]

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[Where R ⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms or a halogen atom, and the polymerization degree m is an integer of 3 or more. However,
Each R ⁰ may be the same or different. The aluminum oxy compound having the structure represented by the general formula (II), wherein m is 1 or 2,
It has a form in which at least 10% of the group R ⁰ is substituted by a group represented by —X ¹ R ¹ . In this case, an unsubstituted aluminum oxy compound may be present.

As a method for producing the aluminum oxy compound having the structure represented by the above general formula (I), for example, m having the structure represented by the above general formula (II) may be various (50> m ≧ 1). Of the above aluminum oxy compound with a halogenated phenol. As a specific treatment method, a method of contacting the aluminum oxy compound, which is dissolved or suspended in a solvent, with a halogenated phenol in a solution state is used. Examples of the treating agent used here include pentachlorophenol, pentafluorophenol, 3,5-difluorophenol, and 3,5-dichlorophenol.

The content of the group -X ¹ R ¹ of the aluminum oxy compound having the structure represented by the general formula (I) is at least 10% of R regardless of the production method.
And more preferably at least 30%. If the content is less than 10%, for example, even if it is added to the transition metal compound as one component of the polymerization catalyst, the effect according to the object of the present invention cannot be obtained.

On the other hand, the general formula (I) according to the present invention
An aluminum oxy compound having a structure represented by
If n is at least 1, the object is achieved, and there is no particular limitation. Usually, 1 to 50 is preferable, and 1 to 40 is more preferable. In this regard, the conventional general formula (I
In the aluminum oxy compound having the structure shown in I), unless m ≧ 3, especially 20 ≧ m ≧ 7, there is a great difference from the fact that a corresponding effect was not obtained. The fact that the effect is obtained even when the value of n is low makes the production of the aluminum oxy compound having the structure represented by the general formula (I) easier, and for example, as described above, the general formula (II) ),
Production from an aluminum oxy compound having a low polymerization degree is advantageous from the viewpoint of easy availability of raw materials having a low polymerization degree.

Examples of the aluminum oxy compounds having the structures represented by the general formulas (I) and (II) include chain and cyclic aluminoxanes, respectively. The former is represented by the general formulas (III) and (IV), and the latter is represented by the following formulas: It is represented by the general formulas (V) and (VI). However, between the chain aluminoxane and the cyclic aluminoxane, the effect as a catalyst when combined with a transition metal compound or further with an organometallic compound, or (I)
Since there is almost no difference in production efficiency when the aluminum oxy compound having the structure represented by (II) is produced from the aluminum oxy compound having the structure represented by (II),
In the present invention, it is described as an aluminum oxy compound without distinguishing between a chain and a ring.

[00116]

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[Where R is a hydrocarbon having 1 to 12 carbon atoms]
Group, an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms, a halogen atom
Child -X¹R¹(X¹Is a Group 15 or 16 element,
R¹Is X ¹An electron-withdrawing group or an electron-withdrawing group that binds to
It is a group to contain. ), And j represents an integer of 0 or more.
You. When j is 1 or more, even if each R is the same,
It may be. However, at least 10% of R is-
X¹R¹It is. ]

[0018]

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[Where R is a hydrocarbon having 1 to 12 carbon atoms]
Group, an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms, a halogen atom
Child -X¹R¹(X¹Is a Group 15 or 16 element,
R¹Is X ¹An electron-withdrawing group or an electron-withdrawing group that binds to
It is a group to contain. ), And k represents an integer of 1 or more.
You. When a plurality of R are present, each R may be the same or different.
It may be. However, at least 10% of R is -X¹
R¹It is. ]

[0020]

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[Where R ⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms or a halogen atom, and f represents an integer of 2 or more. However, R ⁰ may be the same or different. ]

[0022]

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[Where R ⁰ represents a hydrocarbon group having 1 to 12 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 12 carbon atoms or a halogen atom, and g represents an integer of 3 or more. However, R ⁰ may be the same or different. ]

The first polymerization catalyst proposed in the present invention contains a transition metal compound and the novel aluminum oxy compound. The transition metal compound is not particularly limited, but may be a compound of the Periodic Table 4
Compounds containing Group 10 to 10 elements and elements of the lanthanoid series are particularly preferred. In addition, metallocene containing these elements can be effectively used. Various examples of the transition metal compound include, but are not limited to, the general formula CpM ¹ R ² _a R ³ _b R ⁴ _c (VII) Cp ₂ M ¹ R ² _a R ³ _b (VIII) (Cp-A _e -Cp ) A compound represented by M ¹ R ² _a R ³ _b (IX) or a general formula M ¹ R ² _a R ³ _b R ⁴ _c R ⁵ _d (X) or a derivative thereof is preferable. In the general formulas (VII) to (X), M ¹ represents a transition metal such as titanium, zirconium, hafnium, vanadium, niobium, chromium, etc., and Cp is a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group. , A substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group. R ² , R ³ , R ⁴ and R ⁵ are each independently σ
Ligands such as a binding ligand, a chelating ligand, and a Lewis base are shown. Specific examples of the σ-binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon atom having 1 carbon atom. ~ 20
An alkyl group, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, an acyloxy group having 1 to 20 carbon atoms,
Allyl groups, substituted allyl groups, substituents containing silicon atoms, etc., examples of chelating ligands include acetylacetonate groups and substituted acetylacetonate groups, and examples of Lewis bases include ethers, nitriles, etc. it can. A represents a covalent crosslink. a, b, c and d
Each independently represents an integer of 0 to 4, and e represents an integer of 0 to 6. Two or more of R ² , R ³ , R ⁴ and R ⁵ may combine with each other to form a ring. When the Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In formulas (VIII) and (IX), two Cp's may be the same or different from each other.

The substituted cyclopentadienyl group in the above formulas (VII) to (IX) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group; isopropylcyclopentadienyl group; Pentadienyl group; tetramethylcyclopentadienyl group; 1,3-dimethylcyclopentadienyl group;
2,3-trimethylcyclopentadienyl group;
4-trimethylcyclopentadienyl group; pentamethylcyclopentadienyl group; trimethylsilylcyclopentadienyl group and the like. In addition, the above (VII)-
Specific examples of R ^{2 to} R ^{5 in} the formula (X) include, in addition to the above hydrogen atom and oxygen atom, for example, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and a carbon atom having 1 to 2 carbon atoms.
As an alkyl group of 0, methyl, ethyl, n-propyl, isopropyl, n-butyl, octyl, 2
An ethylhexyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group as an alkoxy group having 1 to 20 carbon atoms, a phenyl group, a tolyl group as an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group; , Xylyl group, benzyl group, carbon number 1
A heptadecylcarbonyloxy group as an acyloxy group, a trimethylsilyl group, a (trimethylsilyl) methyl group as a substituent containing a silicon atom, dimethyl ether, diethyl ether, ethers such as tetrahydrofuran as Lewis bases, thioethers such as tetrahydrothiophene, and ethyl as Lewis bases; Esters such as benzoate; acetonitrile; nitriles such as benzonitrile; trimethylamine; triethylamine; tributylamine; N, N-dimethylaniline;
2'-bipyridine; amines such as phenanthroline,
Phosphines such as triethylphosphine; and triphenylphosphine. Further, ethylene; butadiene; 1-pentene; isoprene; pentadiene; linear unsaturated hydrocarbons such as 1-hexene and their derivatives, benzene; toluene; xylene; cycloheptatriene; cyclooctadiene; cyclooctatriene; And cyclic unsaturated hydrocarbons such as octatetraene and derivatives thereof. Examples of the crosslink by the covalent bond of A in the above formula (IX) include, for example, a methylene bridge, a dimethylmethylene bridge, an ethylene bridge,
1′-cyclohexylene bridge, dimethylsilylene bridge,
Examples include dimethylgermylene crosslink and dimethylstannylene crosslink.

Examples of the compound represented by the general formula (VII) include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, and (pentamethylcyclopentadienyl) Tribenzyl zirconium, (pentamethylcyclopentadienyl) trichloro zirconium, (pentamethyl cyclopentadienyl) trimethoxy zirconium, (cyclopentadienyl) trimethyl zirconium, (cyclopentadienyl) triphenyl zirconium, (cyclopentadi (Enyl) tribenzyl zirconium, (cyclopentadienyl) trichloro zirconium, (cyclopentadienyl) trimethoxy zirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium , (Methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) ) Dimethyl (methoxy) zirconium, (dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium, and the like, and the like. In these, a compound in which zirconium is replaced with titanium or hafnium is mentioned.

Examples of the compound represented by the general formula (VIII) include bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, and bis (cyclopentadienyl) diethyl zirconium. Cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydride Zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentameth Lecyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (penta Methylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl)
Examples thereof include (pentamethylcyclopentadienyl) dichlorozirconium, and further, a compound in which zirconium is replaced by titanium or hafnium.

Examples of the compound represented by the general formula (IX) include ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) dichloro zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, and ethylene bis (tetrahydroindenyl). ) Dichlorozirconium, dimethylsilylenebis (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl)
(9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl)
Dimethyl zirconium, diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexalidene (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium , Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-
Trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium, and the like. Compounds can be given by substituting hafnium.

Further, as the compound represented by the general formula (X), for example, tetramethyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrabutoxy zirconium, tetrachloro zirconium, tetrabromo zirconium, butoxy trichloro Zirconium, dibutoxydichlorozirconium, bis (2,5-di-t-butylphenoxy) dimethylzirconium, bis (2,5-di-
t-butylphenoxy) dichlorozirconium, zirconiumbis (acetylacetonate) and the like,
In these, the compound which substituted titanium or hafnium for zirconium is mentioned.

Specific examples of the vanadium compound include vanadium trichloride, vanadyl trichloride,
Vanadium triacetylacetonate, vanadium tetrachloride, vanadium tributoxide, vanadyl dichloride, vanadyl bisacetylacetonate, vanadyl triacetylacetonate, dibenzene vanadium, dicyclopentadienyl vanadium, dicyclopentadienyl vanadium dichloride, cyclopentane Dienyl vanadium dichloride, dicyclopentadienyl methyl vanadium and the like can be mentioned.

Next, specific examples of the chromium compound include tetramethylchromium, tetra (t-butoxy) chromium, bis (cyclopentadienyl) chromium, hydridetricarbonyl (cyclopentadienyl) chromium, and hexacarbonyl (cyclohexane). Examples thereof include (pentadienyl) chromium, bis (benzene) chromium, tricarbonyltris (triphenylphosphonate) chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, and chromium tris (acetylacetonate). further,
In the general formula (VIII), two substituted or unsubstituted conjugated cyclopentadienyl groups (at least one of which is a substituted cyclopentadienyl group) is one of the groups in the periodic table.
A group 4 transition metal compound having a ligand as a multiple coordinating compound bonded to each other via an element selected from group 4 can be preferably used. Such compounds include, for example, those represented by the general formula (XI)

[0032]

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Compounds represented by the following or derivatives thereof
be able to. Y in the general formula (XI)¹Is carbon, kei
Element, germanium or tin atom, R⁶ _t-C_FiveH_4-tPassing
And R⁶ _u-C_FiveH_4-uAre each substituted cyclopentadie.
The nyl group, t and u represent an integer of 1 to 4. Where R⁶
Represents a hydrogen atom, a silyl group or a hydrocarbon group,
They may be one or different. Also at least one piece
One of the cyclopentadienyl groups has Y¹Bound to
R on at least one carbon next to the carbon⁶Exists.
R⁷Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or carbon
An aryl group, an alkylaryl group, or
It represents an arylalkyl group. M^TwoIs titanium, zirconium
Or hafnium atom, X^TwoIs hydrogen atom, halogen
Atom, alkyl group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
An aryl group, an alkylaryl group or an aryl group
It represents an alkyl group or an alkoxy group having 1 to 20 carbon atoms. X
^TwoMay be the same or different from each other, and R⁷Also
They may be the same or different.

The substituted cyclopentadienyl group in the above formula (XI) includes, for example, methylcyclopentadienyl group; ethylcyclopentadienyl group; isopropylcyclopentadienyl group; 1,2-dimethylcyclopentadienyl 1,3-dimethylcyclopentadienyl group; 1,2,3-trimethylcyclopentadienyl group;
1,2,4-trimethylcyclopentadienyl group and the like. Specific examples of X ² include a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom as a halogen atom, a methyl group as an alkyl group having 1 to 20 carbon atoms,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, octyl group, 2-ethylhexyl group, having 1 to 1 carbon atoms
20 alkoxy groups such as methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group and carbon number of 6 to 2;
A phenyl group, a tolyl group, a xylyl group as an aryl group, an alkylaryl group or an arylalkyl group of 0,
And a benzyl group. Specific examples of R ⁷ include a methyl group, an ethyl group, a phenyl group, a tolyl group, a xylyl group, and a benzyl group.

Specific examples of the compound represented by the general formula (XI) include dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) zirconium dichloride and dimethylsilylenebis (2,3,5-trimethyl Cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) hafnium dichloride and the like. Furthermore, the general formula (XII)

[0036]

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The compounds represented by the following formulas are also included. The general formula
In the compound (XII), Cp is cyclopentadienyl
Group, substituted cyclopentadienyl group, indenyl group, substituted
Indenyl group, tetrahydroindenyl group, substituted tetra
Hydroindenyl, fluorenyl or substituted fluor
Cyclic unsaturated hydrocarbon group such as an n-yl group or chain unsaturated carbon
Shows a hydrogen group. M^ThreeIs titanium, zirconium or hafni
X^ThreeIs hydrogen atom, halogen atom, carbon
An alkyl group having 1 to 20 carbon atoms and an aryl group having 6 to 20 carbon atoms
Group, alkylaryl group or arylalkyl group or
Represents an alkoxy group having 1 to 20 carbon atoms. Z is Si
R⁸ _Two, CR⁸ _Two, SiR⁸ _TwoSiR⁸ _Two, CR⁸ _TwoCR⁸ _Two, CR
⁸ _TwoCR⁸ _TwoCR⁸ _Two, CR⁸= CR⁸, CR⁸ _TwoSiR⁸ _TwoOr
GeR⁸ _TwoAnd Y ^TwoIs -N (R⁹)-, -O-, -S-
Or -P (R⁹)-. R above⁸Is a hydrogen atom or 2
Alkyl, aryl, silyl with up to 0 non-hydrogen atoms
, Alkyl halides, aryl halides and
A group selected from these combinations,⁹Has 1 to 1 carbon atoms
An alkyl group of 10 or an aryl group having 6 to 10 carbon atoms
Any or one or more R⁸And up to 30
May form a fused ring system of non-hydrogen atoms. w is 1 or
2 is shown.

Specific examples of the compound represented by the general formula (XII) include (tert-butylamide) (tetramethyl-
[eta] ⁵ -cyclopentadienyl) -1,2-ethanediylzirconium dichloride; (tert-butylamide) (tetramethyl- [eta] ⁵ -cyclopentadienyl) -1,2-
Ethanediyl titanium dichloride; (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl) -1,2-
Ethanediylzirconium dichloride; (methylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
1,2-ethanediyltitanium dichloride; (ethylamide) (tetramethyl-η ⁵ -cyclopentadienyl)-
Methylene titanium dichloride; (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl)
Silane titanium dichloride; (tert-butylamido) dimethyl (tetramethyl-eta ⁵ - cyclopentadienyl) silane zirconium dibenzyl; (benzylamide) dimethyl - (tetramethyl-eta ⁵ - cyclopentadienyl)
Silane titanium dichloride; (phenyl phosphide) dimethyl (tetramethyl-η ⁵ -cyclopentadienyl) silane zirconium dibenzyl and the like.

The second polymerization catalyst proposed in the present invention comprises (A) a transition metal compound, (B) the novel aluminum oxy compound, and (C) an organoaluminum compound. Examples of the organoaluminum compound include a compound represented by the general formula (XIII) R ¹⁰ _r AlQ _3-r (XIII) (wherein R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms, Q is a hydrogen atom, and an alkoxy group having 1 to 20 carbon atoms) , C6-20
Wherein r is an integer of 1 to 3).

Specific examples of the compound represented by the general formula (XIII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride,
Examples thereof include diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more.

Next, the use ratio of each catalyst component in the present invention will be described. When (A) a transition metal compound and (B) an aluminum oxy compound are used as the catalyst components, (A) :( B) is preferably from 1: 1 to 1: 5,000 (as an aluminum atom), 1-1: 10
00 is more preferable, but in terms of activity, economy and post-treatment,
In particular, 1: 1 to 1: 600 is preferable. When the above (A), (B) and (C) organoaluminum compounds are used as the catalyst components, (A) :( B) is preferably in the above range, but (A) :( C) is 1: 1. ~ 1: 10,000
Is preferred, and 1: 5 to 1: 2,000 is more preferred, and 1:10 to 1: 1000 is particularly preferred.

In the present invention, at least the catalyst component
One can be used by supporting it on a suitable carrier. The charge
There is no particular limitation on the type of body, inorganic oxide carrier,
Use any other inorganic or organic carrier
Can be formed, but in particular, inorganic oxide carrier or other
Organic carriers are preferred. As the inorganic oxide carrier, specifically,
Is SiO_Two, Al_TwoO_Three, MgO, ZrO_Two, TiO
_Two, Fe_TwoO_Three, B_TwoO_Three, CaO, ZnO, BaO,
ThO_TwoAnd mixtures thereof, such as silica alumina and zeolite.
Olite, ferrite, glass fiber, smectite
And the like. Among them, especially SiO 2_Two,
Al _TwoO_ThreeIs preferred. Incidentally, the inorganic oxide carrier,
It may contain a small amount of carbonate, nitrate, sulfate and the like.
On the other hand, as a carrier other than the above, MgCl_Two, Mg (OC
_TwoH_Five)_TwoSuch as magnesium compounds
General formula MgR¹¹ _XX^Four _yA magnesium compound represented by
Examples thereof include complex salts. Where R¹¹Is charcoal
Alkyl having 1 to 20 carbon atoms and alkoxy having 1 to 20 carbon atoms
A cyclo group or an aryl group having 6 to 20 carbon atoms, X^FourIs halogen
X represents an atom or an alkyl group having 1 to 20 carbon atoms;
An integer of 2 and y is an integer of 0 to 2 and x + y = 2
You. Each R¹¹And each X^FourMay be the same or different
It may be. Use of the above carrier in the present invention
In this case, the preferred carrier is MgCl _Two, MgC
l (OC_TwoH_Five), Mg (OC_TwoH_Five)_Two, SiO_Two, Al
_TwoO_ThreeAnd so on. In addition, as an organic carrier, polystyrene
Ren, polyethylene, polypropylene, substituted polystyrene
Polymers such as carbon and polyarylate, starch and carbon
And the like.

The properties of the carrier vary depending on its type and production method, but the average particle size is usually 1 to 300 μm, preferably 10 to 300 μm.
２００200 μm, more preferably 20-100 μm. If the particle size is too small, the fine powder of the polymer will increase. Conversely, if the particle size is too large, the coarse particles of the polymer will increase, causing a decrease in bulk density and clogging of the hopper. The specific surface area of the carrier is usually 1 to 1000 m ² / g, preferably 50 to 1000 m ² / g.
500 m ² / g, pore volume is usually 0.1-5 cm ³ / g,
Preferably it is 0.3 to ³ cm ³ / g. If either the specific surface area or the pore volume deviates from the above range, the catalytic activity may decrease. The specific surface area and pore volume are
For example, it can be determined from the volume of nitrogen gas adsorbed according to the BET method (see Journal of the American Chemical Society, Vol. 60, p. 309 (1983)). Further, the carrier is usually 1
It is desirable to use by baking at 50 to 1000 ° C, preferably 200 to 800 ° C.

When the catalyst component is supported on the carrier,
When it is composed of (A) a transition metal compound and (B) an aluminoxy compound, at least one, preferably both, of (A) and (B) are used, and both (A), (B) and (C) When it is made of an aluminum compound, it is desirable to support at least one of them, preferably all the components. The method of supporting at least one of the component (A), the component (B) and the component (C) on the carrier is not particularly limited.
A method of mixing at least one of the components (B) and (C) with a carrier, treating the carrier with the component (C) (or treating with a halogen-containing silicon compound when the component (C) is not used), A method of mixing with at least one of the component (A) and the component (B) in an active solvent, a carrier and the component (A) and / or the component (B) and the component (C) (or silicon when the component (C) is not used) Compound) with
After supporting the component (A) or the component (B) on a carrier,
A method of mixing the component (B) or the component (A), a method of mixing the contact reactant of the component (A) and the component (B) with a carrier,
At the time of the contact reaction between the component (A) and the component (B), a method in which a carrier coexists may be used. In addition, in the above or the above-mentioned reaction or mixing, the component (C) may be added.

The supported or unsupported catalyst thus obtained may be subjected to polymerization by removing the solvent used for the preparation once and removing it as a solid, and then subjecting it to polymerization. It may be used for polymerization as it is without performing. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system.
For example, at least one of the components (A) and (B), a carrier and, if necessary, the component (C) are added, and an olefin such as ethylene is added at normal pressure to 20 kg / cm ² ,
A method in which prepolymerization is performed at 20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

Next, the preferred use ratio of each catalyst component and carrier will be described. When the catalyst according to the present invention is used with the component (A), (B) or (C) supported on a carrier, the use ratio (weight ratio) between each component and the carrier is preferably 1: 1, respectively. The ratio is from 5 to 1: 10000, more preferably from 1:10 to 1: 500. (A), (B)
Alternatively, when the use ratio of the component (C) and the carrier is outside the above range, the activity may be reduced. The average particle size of the polymerization catalyst of the present invention thus prepared, supported on a carrier, is usually 2 to 200 μm, preferably 10 to 150 μm.
m, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 1000 m ² / g, preferably 50 to ⁵ m ² / g.
00 m ² / g. If the average particle size is less than 2 μm, the fine powder of the polymer may increase, and if it exceeds 200 μm, the coarse particles of the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease,
If it exceeds 1000 m ² / g, the bulk density of the polymer may decrease. By supporting on a carrier in this way, a polymer having an industrially advantageous range of bulk density and excellent particle size distribution can be obtained.

According to the method for producing a polymer of the present invention, homopolymerization of olefins or copolymerization of olefins with other olefins and / or other monomers using the polymerization catalyst described above ( That is, copolymerization with different olefins, copolymerization of olefins with other monomers, or copolymerization of different olefins with other monomers can be suitably performed. The olefin is not particularly limited, but is preferably an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, -Dodecene, 1
-Tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. Also,
The other olefins described above may be appropriately selected from the above olefins.

In the present invention, the above olefins may be used alone or in combination of two or more. When copolymerizing two or more olefins, the above olefins can be arbitrarily combined. In this case, for example, when propylene and ethylene, or ethylene and an α-olefin having 3 to 10 carbon atoms are copolymerized, the copolymerization ratio of propylene and ethylene or ethylene and an α-olefin having 3 to 10 carbon atoms may be used. Polymerization ratio (molar ratio)
Is usually 99.9: 0.1 to 0.1: 99.9, preferably 99.9.
5: 0.5 to 75.0: 25.0. In the present invention, the above-mentioned olefins and other monomers may be copolymerized. Examples of other monomers used in this case include styrene, p-methylstyrene, isopropylstyrene, and t-styrene. Vinyl aromatic compounds such as butylstyrene, chain diolefins such as butadiene, isoprene and 1,5-hexadiene, norbornene,
5,8-Dimethano-1,2,3,4,4a, 5,8,8
Cyclic olefins such as a-octahydronaphthalene and 2-norbornene, cyclic diolefins such as norbornadiene, 5-ethylidene norbornene, 5-vinylnorbornene and dicyclopentadiene, and unsaturated esters such as ethyl acrylate and methyl methacrylate , Β-
Lactones such as propiolactone, β-butyrolactone, γ-butyrolactone, ε-caprolactam, lactams such as δ-valerolactam, epoxypropane,
Epoxides such as 1,2-epoxybutane can be exemplified. In addition, the polymerization catalyst of the present invention can be used not only for the polymerization of the olefins but also for the polymerization of other olefins.

In the present invention, the polymerization method is not particularly limited.
Slurry polymerization method, gas phase polymerization method, bulk polymerization method, solution weight
Any method such as a legal method or a suspension polymerization method may be used.
However, a slurry polymerization method and a gas phase polymerization method are particularly preferred. polymerization
Regarding the conditions, the polymerization temperature is usually −100 to 250 ° C.,
Preferably -50 to 230C, more preferably 0 to 20
0 ° C. Also, the ratio of the catalyst used to the reactants
Is preferably the raw material monomer / component (A) (molar ratio)
1 to 10 ⁸, Especially 100 to 10^FivePreferably
New Further, the polymerization time is usually 5 minutes to 10 hours,
The force is preferably normal pressure to 200 kg / cm^TwoG, especially preferred
Or normal pressure ~ 100kg / cm^TwoG. Minute of polymer
As for the method of adjusting the amount of catalyst, the type of each catalyst component, the amount used,
Selection of the polymerization temperature, and polymerization in the presence of hydrogen, etc.
You. When using a polymerization solvent, for example, benzene, toluene
Aromatic hydrocarbons such as xylene, xylene and ethylbenzene,
Cyclopentane, cyclohexane, methylcyclohexa
Alicyclic hydrocarbons such as pentane, hexane, hepta
, Octane and other aliphatic hydrocarbons, chloroform, di
Use halogenated hydrocarbons such as chloromethane.
Can be. These solvents may be used alone.
Alternatively, two or more kinds may be combined. Also, α-
A monomer such as an olefin may be used as the solvent.
In addition, depending on the polymerization method, it can be carried out without a solvent.
The molecular weight of the polymer thus obtained is particularly limited.
Although it is not a thing, intrinsic viscosity [η] (135 ° C decalin
Is 0.1 deciliter / g or more, preferably
0.2 to 20 deciliters / g, especially 0.3 to 15 deciliters
Torr / g is preferred.

In the present invention, preliminary polymerization can be carried out using the polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited,
A known method can be used. The olefin used in the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, α having 3 to 20 carbon atoms.
Olefins, or mixtures thereof, and the like, but it is advantageous to use the same olefins as those used in the polymerization. The prepolymerization temperature is usually -20 to 200C, preferably -10 to 1C.
The temperature is 30 ° C, more preferably 0 to 80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity of the prepolymerized product [η] (135
C. (measured in decalin) at 0.2 deciliters / g or more, especially 0.5 deciliters / g or more.
The amount of the prepolymerized product per 1 mmol is 1 to 10
It is desirable to adjust the conditions so as to be 000 g, especially 10 to 1000 g.

Hereinafter, the present invention will be described in detail with reference to examples.

【Example】

Example 1 [Preparation of aluminum oxy compound (I)] 1.6 g (27.2 mmol in terms of aluminum atom) of methylaluminoxane (degree of polymerization n = 25) was dissolved in 100 ml of toluene. On the other hand, 5.0 g of pentafluorophenol
(27.2 mmol) was dissolved in 80 ml of toluene, and 0 ° C. was added to the toluene solution of methylaluminoxane.
After the completion of the dropwise addition, the reaction was carried out at room temperature for 24 hours.
After the completion of the reaction, the resultant was washed with toluene, dried, and 5.8 g of a white-brown solid component of aluminum oxy compound (I) was obtained. ²⁷
The chemical shift of Al-NMR appears when a part of the methyl group is replaced by another group by treating methylaluminoxane with pentafluorophenol. After the treatment (FIG. 2), it can be seen that it has shifted to the high magnetic field side,
It can be seen that the above substitution reaction has occurred.

[Polymerization] In a 1-liter stainless steel autoclave, 400 ml of dehydrated toluene, 0.4 mmol of trimethylaluminum, dimethylsilylene (2,
2.0 micromoles of 4-dimethylcyclopentadienyl) zirconium dichloride and aluminum oxy compound
(I) 0.4 mmol (in terms of aluminum atom) was placed in this order, propylene pressure was 3.0 kg / cm ² , and polymerization temperature was 50.
Polymerization was carried out at 30 ° C. for 30 minutes. Thereafter, deashed and washed with a hydrochloric acid / methanol solution, and dried under reduced pressure at 70 ° C. for 2 hours. Table 1 shows the results. In addition, the measurement conditions of each physical property are as follows. Hereinafter, in each of Examples and Comparative Examples, the measurement was performed under the same conditions. (a) (mmmm)%: by ¹³ C-NMR. However, equipment: JEOL GX-270 Measurement conditions: 100 MHz, 120 ° C. Solvent: 1,2,4-trichlorobenzene / d ₆ -benzene mixed solvent (b) Mw and Mn: GPC. However, an apparatus: ALC / GPC 150C, manufactured by Waters Column: TSK HM + GMH6 × 2, manufactured by Tosoh Corporation Solvent: 1,2,4-trichlorobenzene Temperature: 135 ° C. (c) Melting point (Tm): By DSC. However, heating rate: 10 ° C / min (d) [η]: solvent is decalin, 135 ° C

Comparative Example 1 [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

Example 2 [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

Example 3 [Preparation of Aluminum Oxy Compound (II)] 1.24 g (in terms of aluminum atom) of isobutylaluminoxane (n = 25) was dissolved in 100 ml of toluene. On the other hand, 2.06 g (12.4 mmol) of pentafluorophenol was dissolved in 80 ml of toluene, and the solution was added dropwise to the above-mentioned solution of isobutylaluminoxane in toluene at 0 ° C. After completion of the addition, the mixture was reacted at room temperature for 24 hours. . After completion of the reaction, the resultant was washed with toluene and dried to obtain 2.04 g of a white aluminum oxy compound (II) solid component. [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

Comparative Example 2 [Polymerization] Polymerization of a polymer was carried out in the same manner as in Example 1 except for the conditions described in Table 1, but no polymer was obtained. Table 1 shows the results.

Example 4 [Preparation of Aluminum Oxy Compound (III)] 1.5 g of methylaluminoxane (25.0 mmol in terms of aluminum atom) was dissolved in 100 ml of toluene. On the other hand, 7.0 g (25.0 mmol) of pentachlorophenol
Was dissolved in 80 ml of toluene, and added dropwise to a toluene solution of methylaluminoxane at 0 ° C.
The mixture was reacted for 4 hours, washed with toluene, dried, and then 7.0 g of a white aluminum oxy compound (III) solid component.
I got [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

Example 5 [Preparation of aluminum oxy compound (IV)] 1.29 g of methylaluminoxane (n = 25) (22.0 mmol in terms of aluminum atom) was dissolved in 100 ml of toluene. On the other hand, 2.04 g of pentafluorophenol (1
(1.0 mmol) was dissolved in 80 ml of toluene, added dropwise to a toluene solution of methylaluminoxane at 0 ° C., and allowed to react at room temperature for 24 hours after completion of the dropwise addition. After the completion of the reaction, the resultant was washed with toluene and dried to obtain 2.95 g of a white solid component of an aluminum oxy compound (IV). [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

Examples 6 to 10 and 12 to 14 correspond to Example 1.
Comparative Example 3 was performed in accordance with Comparative Example 1. Table 1 shows the results.

Example 11 Preparation of Aluminum Oxy Compound (V) 10.0 g (0.42 mmol) of anhydrous lithium hydroxide was added to anhydrous anisole 5
The solution was heated to 80 ° C., and 30.0 ml (0.32 mol) of trimethylaluminum was slowly added dropwise to the solution, followed by refluxing for 4 hours to complete the reaction. The reaction solution was filtered at 70 ° C., and the obtained liquid layer was evaporated under vacuum to obtain a white powder. This powder was washed with hexane at 50 ° C. two to three times, dissolved in an excess of toluene, and reprecipitated with hexane again to obtain 30.0 g of lithium dimethyl aluminate.
Next, 4.0 g (0.05 mol) of lithium dimethyl aluminate was suspended in n-pentane, and 4.63 g (0.05 mol) of dimethylaluminum chloride was slowly added dropwise to the n-pentane solution at 0 ° C. Thereafter, the reaction was carried out at 0 ° C. for 2 days. After completion of the reaction, the solvent was distilled off under vacuum to obtain 5.58 g of liquid bisdimethylaluminum oxide. Next, 2.08 g of this bisdimethylaluminum oxide
(16.0 mmol) of a 2% by weight toluene solution was cooled to 0 ° C. and 11.8 g of pentafluorophenol was added to this solution.
(64.0 mmol) was slowly added dropwise, and the obtained solid component was washed with toluene to obtain 1.41 g of a solid dimer MAD as a white aluminum oxy compound (V). [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

Example 15 [Preparation of aluminum oxy compound (VI)] 1.5 g of methylaluminoxane (25.0 mmol in terms of aluminum atom) was dissolved in 100 ml of toluene. On the other hand, 3.3 g (25.0 mmol) of 3,5-difluorophenol was dissolved in 80 ml of toluene, and this was added dropwise to the above-mentioned toluene solution of methylaluminoxane at 0 ° C., followed by reaction at room temperature for 24 hours. I let it. After the completion of the reaction, the resultant was washed with toluene and dried to obtain 3.5 g of a white-brown solid component of aluminum oxy compound (VI). [Polymerization] A polymer was produced in the same manner as in Example 1 except for the conditions described in Table 1. Table 1 shows the results.

[0062]

[Table 1]

Me ₂ SiCp'ZrCl ₂ : dimethylsilylene (2,4 dimethylcyclopentadienyl) zirconium dichloride Cp ₂ ZrCl ₂ : biscyclopentadienyl zirconium dichloride EBIZrCl ₂ : ethynylidenebisindenyl zirconium iPrCpFluZrCl ₂ : isopropy Ridencyclopentadienyl-1-fluorenyl zirconium dichloride MeSiCpMTiCl ₂ : Methylsilylene (methylcyclopentadienyl) titanium dichloride TBZ: Zirconium tetrabutoxide Cp ₂ ZrCl ₂ : Biscyclopentadienyl zirconium dichloride Cp ₂ TiCl ₂ : Biscyclopentadienyl titanium dichloride TMA: Trimethylaluminum MAO: Methylaluminoxane TEA: Triethylaluminum iBAO: Isobutylaluminoxane TIBA: Triisobutylaluminum PFPAO: Pentafluorophenol Ruminokisan PCPAO: pentachlorophenol aluminoxane DFPAO: 3,5- difluorophenol ASS: modified aluminum oxy compound

[0064]

[Table 2]

[0065]

[Table 3]

[0066]

As described above, by providing a novel aluminum oxy compound, a catalyst system particularly useful for olefin polymerization, that is, a highly active catalyst was successfully obtained. It was found that polymerizing olefins gave high-molecular-weight polyolefins having high stereoregularity.

[Brief description of the drawings]

FIG. 1 shows that in Example 1, ²⁷ Al—N before treatment of methylaluminoxane with pentafluorophenol.
MR spectrum diagram

FIG. 2 is a diagram showing a ²⁷ Al-NMR spectrum after treatment in Example 1.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-99134 (JP, A) JP-A-63-288218 (JP, A) JP-A-6-16681 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70 C08G 79/10 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A compound of the general formula (I) [Where R is a hydrocarbon group having 1 to 12 carbon atoms,
12 oxygen-containing hydrocarbon groups, halogen atoms or -X ¹ R
¹ (X ¹ is a Group 15 or 16 element, and R ¹ is a halogen atom or a halogen- containing group bonded to X ¹ ), and the polymerization degree n is an integer of 1 or more. When there are a plurality of Rs, each R may be the same or different. However, at least 10% of R is -X ¹ R ^1. ] An aluminum oxy compound having a structure represented by the following formula: (A) A compound represented by any one of formulas (VII) to (X):
Homopolymerization or copolymerization of a transition metal compound to be formed and an olefin comprising (B) the aluminum compound according to claim 1.
Catalyst for polymerization . _{^{CpM 1 R 5 a R 6 b}} R 7 c (VII) CpM 1 R 5 a R 6 b (VIII) (Cp-A e -Cp) M 1 R 5 a R 6 b (IX) M 1 R 5 a R ⁶ _b R ⁷ _c R ⁸ _d (X) [Cp is a cyclopentadienyl group, substituted cyclopentadienyl
Enyl group, indenyl group, substituted indenyl group, tetrahi
A droindenyl group, a substituted tetrahydroindenyl group,
Indicates Ruoreniru group or a substituted fluorenyl group, M ¹ is Chi
Indicates tan, zirconium or hafnium. R ⁵ ,
R ⁶ , R ⁷ and R ⁸ are each independently a ligand, and A is shared
Shows crosslinking by bonding. a, b, c and d are each German
The letter e is an integer of 0-6, and e is an integer of 0-6. ] 3. A catalyst for homopolymerization or copolymerization of an olefin comprising the components (A) and (B) according to claim 2 and (C) an organoaluminum compound represented by the general formula (XIII).
Medium. R ¹³ AlQ _3-r (XIII) (R ¹³ is an alkyl group having 1 to 10 carbon atoms, Q is a hydrogen atom,
C1-C20 alkoxy group, C6-C20 ant
And r represents an integer of 1 to 3.
You. ) Wherein the presence of a catalyst according to claim 2 or 3, o
A method for producing a polyolefin, comprising homopolymerizing or copolymerizing a olefin .