JP2953520B2 - Olefin polymerization catalyst and olefin polymerization method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a catalyst for olefin polymerization and a method for polymerizing olefins using the catalyst. More specifically, the present invention relates to an olefin having excellent polymerization activity and a wide molecular weight distribution (copolymer). The present invention relates to a novel catalyst for olefin polymerization capable of providing a polymer and a method for polymerizing olefins using the catalyst.

TECHNICAL BACKGROUND OF THE INVENTION AND PROBLEMS THEREOF Conventionally, as a catalyst for producing an α-olefin polymer such as an ethylene polymer or an ethylene / α-olefin copolymer, a titanium-based catalyst comprising a titanium compound and an organoaluminum has been known. Have been. However, in general, an olefin polymer obtained by using a titanium catalyst system has a wide molecular weight distribution and a wide composition distribution, and particularly has a poor surface non-adhesiveness and transparency due to a wide composition distribution.

On the other hand, as a new Ziegler type olefin polymerization catalyst, a method for producing an ethylene / α-olefin copolymer using a catalyst comprising a zirconium compound and an aluminoxane has been recently proposed.

The olefin polymer obtained using the above-mentioned new Ziegler-type olefin polymerization catalyst usually has a narrow molecular weight distribution and a narrow composition distribution. Therefore, depending on the application,
An olefin polymer having a wide molecular weight distribution and excellent moldability has been desired.

Also, when an olefin is polymerized or copolymerized in the presence of a transition metal compound catalyst containing a ligand having a cycloalkadienyl skeleton, it is difficult to obtain an olefin polymer having a high molecular weight, and thus an olefin polymer having a high molecular weight is obtained. There has been a demand for the appearance of a transition metal compound catalyst containing a ligand having a cycloalkadienyl skeleton so as to obtain the compound (1).

Object of the Invention The present invention has been made in view of the prior art as described above, and has a good balance of having excellent polymerization activity, wide molecular weight distribution, excellent moldability, and narrow composition distribution. An object of the present invention is to provide an olefin polymerization catalyst capable of obtaining an olefin polymer and a method for polymerizing an olefin using the catalyst.

SUMMARY OF THE INVENTION The catalyst for olefin polymerization according to the present invention comprises: [A] titanium, magnesium and halogen obtained by contacting a liquid phase titanium compound, a liquid phase magnesium compound and, if necessary, an electron donor in a liquid phase. [B] A zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound are supported on a solid titanium catalyst component containing, as an essential component.

 Further, the catalyst for olefin polymerization according to the present invention is characterized in that [I] the solid catalyst component as described above, [II] an organoaluminum compound, and if necessary, [III] an organoaluminum oxy compound. Features.

In the solid catalyst [I] as described above, an olefin may be prepolymerized.

Further, the olefin polymerization method according to the present invention is characterized in that olefin is polymerized or copolymerized in the presence of the above-mentioned olefin polymerization catalyst.

The olefin polymerization catalyst component according to the present invention has excellent polymerization activity and can provide a high molecular weight olefin polymer having a wide molecular weight distribution and excellent moldability.

DETAILED DESCRIPTION OF THE INVENTION Hereinafter, the catalyst for olefin polymerization according to the present invention and a method for polymerizing olefins using the catalyst will be specifically described.

FIG. 1 shows an explanatory diagram of the olefin polymerization catalyst according to the present invention.

In the present invention, the term "polymerization" is sometimes used to mean not only homopolymerization but also copolymerization, and the term "polymer" means not only homopolymer but also copolymer. Sometimes used in

The solid catalyst for olefin polymerization according to the present invention is essentially composed of [A] a titanium compound in a liquid phase, a magnesium compound in a liquid phase, and, if necessary, titanium, magnesium and halogen obtained by contacting an electron donor in a liquid phase. [B] A zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound are supported on a solid titanium catalyst component.

First, [A] a solid titanium catalyst component containing titanium, magnesium and halogen as essential components will be described. This solid titanium catalyst component [A] contains titanium, magnesium and halogen as essential components, and further contains an electron if necessary. Contains donor.

Such a solid titanium catalyst component [A] is prepared by contacting a magnesium compound, a titanium compound and, if necessary, an electron donor.

In the present invention, the titanium compound used for preparing the solid titanium catalyst component [A] includes, for example, Ti (OR)
_g X _4-g (R is a hydrocarbon group, X is a halogen atom, 0 ≦ g ≦
The tetravalent titanium compound represented by 4) can be exemplified. More specifically, titanium tetrahalides such as TiCl ₄ , TiBr ₄ , and TiI ₄ ; Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (OisoC ₄ H ₉ ) Br _3, etc .; trihalogenated alkoxytitanium; Ti (OCH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti ( _{On-C 4 H 9) 2} Cl 2, Ti (OC 2 H 5) 2 dihalogenated dialkoxy titanium, such as _{Br 2; Ti (OCH 3)} 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti (On Monohalogenated trialkoxy titanium such as -C ₄ H ₉ ) ₃ Cl, Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (On-C ₄ H) _{9) 4 Ti (Oiso-C} 4 H 9) 4 Ti (O-2- _ethylhexyl) such as tetra-alkoxy titanium such as ₄ can be cited.

Among these, a halogen-containing titanium compound, particularly a titanium tetrahalide, is preferable, and titanium tetrachloride is more preferably used. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include a reducing magnesium compound and a non-reducing magnesium compound.

Here, examples of the magnesium compound having a reducing property include a magnesium compound having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a reducing magnesium compound include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, diamylmagnesium, dihexylmagnesium, didecylmagnesium, ethylmagnesium chloride, propylmagnesiumchloride, and butyl. Examples thereof include magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butylethoxymagnesium, ethylbutylmagnesium, octylbutylmagnesium, and butylmagnesium halide. These magnesium compounds can be used alone or may form a complex compound with an organic aluminum compound described later. These magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxy magnesium chloride, ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy chloride. Alkoxy magnesium halides such as magnesium and octoxy magnesium chloride; alkoxy magnesium halides such as phenoxy magnesium chloride and methylphenoxy magnesium chloride; alkoxy such as ethoxy magnesium, isopropoxy magnesium, butoxy magnesium, n-octoxy magnesium and 2-ethylhexoxy magnesium Magnesium; allyloximers such as phenoxymagnesium and dimethylphenoxymagnesium Neshiumu; magnesium laurate, such as carboxylic acid salts of magnesium such as magnesium stearate and the like.

The non-reducing magnesium compound may be a compound derived from the above-described reducing magnesium compound or a compound derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound is converted to a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, or the like. What is necessary is just to contact with a compound.

The magnesium compound is a complex compound, a complex compound of the above-mentioned magnesium compound and another metal, or a mixture of another metal compound, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property. You may. Further, a mixture of two or more of the above compounds may be used.

Among these, a magnesium compound having no reducing property is preferable, and a halogen-containing magnesium compound is particularly preferable. Among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

In preparing the solid titanium catalyst component [A], it is preferable to use an electron donor, and examples of the electron donor include alcohols, amines, amides, ethers, ketones, esters, nitriles, and phosphines. , Stippins, arsines, phosphoramides, thioethers,
Examples thereof include thioesters, acid anhydrides, acid halides, aldehydes, alcoholates, alkoxy (aryloxy) silanes, and organic acids. Of these, alcohols, amines, ethers, esters, acid anhydrides, alkoxy (aryloxy) silanes, and organic acids are preferably used.

The solid titanium catalyst component [A] can be produced by bringing a magnesium compound as described above (or a metal magnesium, a titanium compound and an electron donor as necessary) into contact. A known method for preparing a highly active titanium catalyst component from a magnesium compound, a titanium compound, and, if necessary, an electron donor can be employed. May be contacted in the presence of a reaction reagent of

The production method of these solid titanium catalyst components will be briefly described below by giving several examples.

In the method for producing the solid titanium catalyst component [A] described below, an example using an electron donor will be described.
This electron donor need not necessarily be used.

(1) A method of reacting a magnesium compound or a complex compound comprising a magnesium compound and an electron donor with a titanium compound in a liquid phase. In this reaction, each component may be pretreated with an electron donor and / or a reaction auxiliary such as an organoaluminum compound or a halogen-containing silicon compound. In this method, the electron donor is used at least once.

(2) a liquid magnesium compound having no reducing property;
A method of reacting a liquid titanium compound in the presence of an electron donor to precipitate a solid magnesium-titanium composite.

(3) A method in which a titanium compound is further reacted with the reaction product obtained in (2).

(4) The reaction product obtained in (1) or (2)
A method in which an electron donor and a titanium compound are further reacted.

(5) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound or an aromatic hydrocarbon.

(6) A method in which a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium is reacted with an electron donor, a titanium compound and / or a halogen-containing hydrocarbon.

(7) magnesium compound and alkoxytitanium and / or
Or a method in which a catalyst component in a hydrocarbon solution containing at least an electron donor such as an alcohol or an ether is reacted with a halogen-containing compound such as a titanium compound and / or a halogen-containing silicon compound.

Among the methods for preparing the solid titanium catalyst component [A] described in the above (1) to (7), the methods (1) to (4) are preferably used.

The amount of each of the above components used in preparing the solid titanium catalyst component [A] varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of the electron donor is about 0.01 to 1 mol per mol of the magnesium compound. In an amount of 20 moles, preferably 0.05-10 moles, the titanium compound is about 0.01-500
It is preferably used in an amount of 0.05 to 300 moles.

The solid titanium catalyst component thus obtained contains magnesium, titanium, halogen and, if necessary, an electron donor as essential components.

In this solid titanium catalyst component [A], the halogen / titanium (atomic ratio) is about 4 to 200, preferably about 5 to 100.
Wherein the electron donor / titanium (molar ratio) is about 0.1 to 5
0, preferably about 0.2 to about 25, and magnesium / titanium (atomic ratio) of about 1 to 100, preferably about 2 to 50.

The solid titanium catalyst component [A] contains a magnesium halide having a small crystal size as compared with a commercially available magnesium halide, and usually has a specific surface area of about 10 m ² / g.
Or more, preferably about 30 to 1000 m ² / g, more preferably about 50
~800m is a ² / g. The solid titanium catalyst component [A] does not substantially change its composition by washing with hexane since the above components are combined to form a catalyst component.

The method for preparing such a highly active solid titanium catalyst component [A] is described in, for example, JP-A-50-108385,
JP-A-50-126590, JP-A-51-20297, JP-A-51-28189
No. 51-64586, No. 51-2885, No. 51
No. 136625, No. 52-87489, No. 52-100596, No. 52-147688, No. 52-104593, No. 53
No. 2580, No. 53-40093, No. 53-40094, No. 53-43094, No. 55-135102, No. 55-1
No. 35103, No. 55-152710, No. 56-811,
JP-A-56-11908, JP-A-56-18606, JP-A-58-83006
JP-A-58-138705, JP-A-58-138706,
Nos. 58-138707, 58-138708 and 58-138709
JP-A-58-138710, JP-A-58-138715,
Nos. 60-23404, 60-195108, 61-21109, 61-37802, and 61-37803.

The transition metal compound containing a ligand having a [B] cycloalkadienyl skeleton used in the present invention has the following formula: ML _x (where M is a transition metal and L is a ligand coordinated to the transition metal) Wherein at least one L is a ligand having a cycloalkadienyl skeleton, and when at least two ligands having a cycloalkadienyl skeleton are included, at least two cycloalkadienyls The ligand having a skeleton may be bonded through an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group, and L other than the ligand having a cycloalkadienyl skeleton has 1 to 12 carbon atoms. A hydrocarbon group, an alkoxy group, an aryloxy group, a halogen or hydrogen, and x is a valence of a transition metal.)

 In the above formula, M is zirconium.

As the ligand having a cycloalkadienyl skeleton,
For example, alkyl-substituted cyclopentane such as cyclopentadienyl group, methylcyclopentadienyl group, ethylcyclopentadienyl group, n-butylcyclopentadienyl group, dimethylcyclopentadienyl group and pentamethylcyclopentadienyl group Examples thereof include a dienyl group, an indenyl group, and a fluorenyl group.

The ligand having a cycloalkadienyl skeleton as described above may be coordinated to two or more transition metals. In this case, the ligand having at least two cycloalkadienyl skeletons is They may be bonded via an alkylene group, a substituted alkylene group, a silylene group, or a substituted silylene group. Examples of the alkylene group include a methylene group, an ethylene group,
Examples of the substituted alkylene group include a propylene group and the like. Examples of the substituted alkylene group include an isopropylidene group. Examples of the substituted silylene group include a dimethylsilylene group and a diphenylsilylene group.

The ligand other than the ligand having a cycloalkadienyl skeleton is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group, an aryloxy group, a halogen or hydrogen.

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. Specifically, examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , An isopropyl group, a butyl group, and the like.Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.Examples of the aryl group include a phenyl group and a tolyl group.Examples of the aralkyl group include a benzyl group, A neofil group is exemplified.

Examples of the alkoxy group include a methoxy group, an ethoxy group, and a butoxy group. Examples of the aryloxy group include a phenoxy group.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

Hereinafter, specific examples of the transition metal compound containing a ligand having a cycloalkadienyl skeleton in which M is zirconium will be described.

Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium monobromide monohydride, bis (cyclopentadienyl) methylzirconium hydride, bis (cyclopentadienyl) ethylzirconium hydride, bis ( Cyclopentadienyl) phenyl zirconium hydride, bis (cyclopentadienyl) benzyl zirconium hydride, bis (cyclopentadienyl) neopentyl zirconium hydride, bis (methylcyclopentadienyl) zirconium monochloride hydride, bis (indenyl) zirconium Monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (cyclopentadienyl) ) Zirconium dibromide, bis (cyclopentadienyl) methyl zirconium monochloride, bis (cyclopentadienyl) ethyl zirconium monochloride, bis (cyclopentadienyl) cyclohexyl zirconium monochloride, bis (cyclopentadienyl) phenyl zirconium Monochloride, bis (cyclopentadienyl) benzylzirconium monochloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (dimethylcyclopentadienyl) zirconium dichloride bis (n-butylcyclopentadienyl) zirconium dichloride bis ( Indenyl) zirconium dichloride, bis (indenyl) zirconium dibromide, bis (cyclopentadienyl) zirconium dimethyl, bis (cyclohexyl) Pentadienyl) zirconium diphenyl, bis (cyclopentadienyl) zirconium dibenzyl, bis (cyclopentadienyl) zirconium methoxychloride, bis (cyclopentadienyl) zirconium ethoxycyclolide, bis (methylcyclopentadienyl) zirconium ethoxychloride, Bis (cyclopentadienyl) zirconium phenoxycyclolide, bis (fluorenyl) zirconium dichloride, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) diphenylzirconium monochloride, ethylenebis (indenyl) methyl Zirconium monochloride, ethylenebis (indenyl) ethyl zirconium monochloride, ethyl Bis (indenyl) methylzirconium monobromide, ethylenebis (indenyl) zirconium dichloride, ethylenebis (indenyl) zirconium dibromide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) dimethylzirconium, ethylenebis (4 , 5,6,7-Tetrahydro-1-indenyl) methylzirconium monochloride, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7-tetrahydro -1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium dichloride , Echire Bis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methoxy-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7- Dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethoxy-1-indenyl)
Zirconium dichloride.

Dimethylsilylenebis (cyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium dichloride dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, isopropyldenbis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienylfur (Oenyl) zirconium dichloride.

The [C] organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane,
Further, it may be a benzene-insoluble organic aluminum oxy compound found by the present inventors.

The aluminoxane as described above can be produced, for example, by the following method.

(1) Compounds containing water of adsorption or salts containing water of crystallization, such as hydrated magnesium chloride, hydrated copper sulfate, hydrated aluminum sulfate, hydrated nickel sulfate, hydrated cerous chloride A method of adding an organoaluminum compound such as a trialkylaluminum to a suspension of a hydrocarbon medium of Example 1 and reacting the suspension to recover a hydrocarbon solution.

(2) A method in which an organic aluminum compound such as trialkylaluminum is directly allowed to act on water, ice or steam in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran to recover as a hydrocarbon solution.

The aluminoxane may contain a small amount of an organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in the solvent.

Specific examples of the organoaluminum compound used when producing the solution of aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, trin-butylaluminum, triisobutylaluminum, and trisec-. Trialkyl aluminum such as butyl aluminum, tri-tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl aluminum, tricyclohexyl aluminum, tricyclooctyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide ,
Dialkyl aluminum halides such as diisobutyl aluminum chloride, diethyl aluminum hydride, dialkyl aluminum hydrides such as diisobutyl aluminum hydride, dimethyl aluminum methoxide, dialkyl aluminum alkoxides such as diethyl aluminum ethoxide, and dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. Can be

Of these, trialkyl aluminum is particularly preferred.

Further, as the organoaluminum compound, isoform represented by the general formula (iC ₄ H ₉ ) _x A _y (C ₅ H ₁₀ ) _z (x, y, z are positive numbers and z ≧ 2x) Prenyl aluminum can also be used.

The above-mentioned organoaluminum compounds are used alone or in combination.

Solvents used in the solution of aluminoxane include:
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane, cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, etc. Petroleum fractions such as alicyclic hydrocarbons, gasoline, kerosene and light oil, or hydrocarbon solvents such as the above aromatic hydrocarbons, aliphatic hydrocarbons and halides of alicyclic hydrocarbons, especially chlorinated compounds and brominated compounds. No. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbons are particularly preferred.

The benzene-insoluble organoaluminum oxy compound used in the present invention is soluble in benzene at 60 ° C.
The component is 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of A atom, and is insoluble or hardly soluble in benzene.

The solubility of such an organoaluminum oxy compound in benzene is determined by suspending the organoaluminum oxy compound corresponding to 100 milligram atoms of A in 100 ml of benzene, mixing the mixture at 60 ° C. with stirring for 6 hours, and adding a jacket. Using a G-5 glass filter, hot filtration was performed at 60 ° C., and the solid part separated on the filter was washed four times with 50 ml of benzene at 60 ° C., and then the total amount of A atoms in the filtrate was measured. It is determined by measuring the abundance (x mmol) (x%).

Analysis of the benzene-insoluble organoaluminum oxy compound as described above by infrared spectroscopy (IR) shows that
1220cm absorbance at around ^-1 (D _1220), the ratio of the absorbance at around _{^{1260cm -1 (D 1260) (D}} 1260 / D 1220) , the
0.09 or less, preferably 0.08 or less, particularly preferably 0.04 to 0.07
Is desirably within the range.

The infrared spectroscopic analysis of the organic aluminum oxy compound is performed as follows.

First, in a nitrogen box, the organoaluminum oxy compound and Nujol are ground in an agate pestle to form a paste.

Next, the paste-like sample is sandwiched between KBr plates, and an IR spectrum is measured by IR-810 manufactured by JASCO Corporation under a nitrogen atmosphere.

Of the organoaluminum oxy compound used in the present invention
The IR spectrum is shown in FIG.

From the IR spectrum thus obtained, D ₁₂₆₀ / D
_The value of D ₁₂₆₀ / D ₁₂₂₀ is obtained as follows.

(B) 1280 cm ^-1 bear maximum point in the vicinity of and around 1240 cm ^-1, which is the baseline L _1.

(B) the transmittance (T%) at the absorption minimum point near 1260 cm ^-1 ,
A vertical line with wavenumber axis (horizontal axis) from the minimum point, reads the transmittance of intersection of the perpendicular line and the baseline _{L 1 (T 0%),} 1260cm -1 vicinity of absorbance (D ₁₂₆₀ = log T ₀ / T).

(C) Similarly knot the maximum point in the vicinity of 1280 cm _-1 and near 1180 cm ^-1, which is the baseline L _2.

(D) Transmittance at the minimum absorption point near 1220 cm ^-1 (T '%)
From this minimum point, a perpendicular is drawn to the wave number axis (horizontal axis), and the transmittance (T ′) at the intersection of this perpendicular and the baseline L ₂ is drawn.
₀ %) and absorbance near ₁₂₂₀ cm ^-1 (D ₁₂₂₀ = log)
T ′ ₀ / T ′) is calculated.

(E) D ₁₂₆₀ / D ₁₂₂₀ is calculated from these values.

FIG. 3 shows the IR spectrum of a conventionally known benzene-soluble organic aluminum oxy compound. As can be seen from FIG. 3, the benzene-soluble organoaluminum oxy compound has a D ₁₂₆₀ / D ₁₂₂₀ value of about 0.10 to 0.13.
The benzene-insoluble organoaluminum oxy compound used in the present invention is clearly different from the conventionally known benzene-soluble organoaluminum oxy compound in the D ₁₂₆₀ / D ₁₂₂₀ value.

The benzene-insoluble organoaluminum oxy compound as described above is [Wherein, R ¹ is a hydrocarbon group having 1 to 12 carbon atoms].

In the above alkyloxyaluminum unit, R ¹
Is specifically exemplified by methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl, octyl, decyl, cyclohexyl, cyclooctyl, etc. it can. Of these, a methyl group and an ethyl group are preferable, and a methyl group is particularly preferable.

This benzene-insoluble organoaluminum oxy compound has the formula In addition to the alkyloxyaluminum unit represented by Wherein R ¹ is the same as above, and R ² is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. , Hydroxyl, halogen or hydrogen, R ¹ and R ²
Represents different groups from each other]. In that case, the alkyloxyaluminum unit Is preferably an organoaluminum oxy compound having an alkyloxyaluminum unit containing at least 30 mol%, preferably at least 50 mol%, particularly preferably at least 70 mol%.

Next, a method for producing the benzene-insoluble organic aluminum oxy compound as described above will be specifically described.

This benzene-insoluble organoaluminum oxy compound is obtained by contacting a solution of aluminoxane with water or an active hydrogen-containing compound.

Examples of the active hydrogen-containing compound include alcohols such as methanol, ethanol, n-propanol and isopropal, diols such as ethylene glycol and hydroquinone, and organic acids such as acetic acid and propionic acid. Of these, alcohols and diols are preferred, and alcohols are particularly preferred.

The water or active hydrogen-containing compound to be brought into contact with the solution of aluminoxane is dissolved or dispersed in a hydrocarbon solvent such as benzene, toluene, or hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or steam or It can be used in a solid state. Also, as water, magnesium chloride,
Water of crystallization of salts such as magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate and cerous chloride, or water adsorbed on inorganic compounds or polymers such as silica, alumina and aluminum hydroxide may be used. it can.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out in a solvent such as a hydrocarbon solvent. Examples of the solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, cyclopentane and cyclohexane. , Cyclooctane, alicyclic hydrocarbons such as methylcyclohexane, hydrocarbon solvents such as gasoline, kerosene, petroleum fractions such as light oil, and the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, halides of alicyclic hydrocarbons And halogenated hydrocarbons such as chlorinated products and brominated products, and ethers such as ethyl ether and tetrahydrofuran. Among these media, aromatic hydrocarbons are particularly preferred.

Water or an active hydrogen-containing compound used in the catalytic reaction is 0.1 to 0.1% of the A atom in the solution of aluminoxane.
５5 mol, preferably 0.2-3 mol. The concentration in the reaction system is usually 1 in terms of aluminum atoms.
The concentration is preferably in the range of × 10 ^{-3 to} 5 gram atoms / preferably 1 × 10 ^{-2 to} 3 gram atoms /, and the concentration of water in the reaction system is usually 2 × 10 ^{-4 to} 5 mol / preferably. Is 2
It is desirable that the concentration be from × 10 ^{-3 to} 3 mol /.

The contact of the aluminoxane solution with water or an active hydrogen-containing compound may be carried out specifically as follows.

(1) A method in which a solution of aluminoxane is brought into contact with water or a hydrocarbon solvent containing an active hydrogen-containing compound.

(2) A method of bringing aluminoxane and vapor into contact with each other by, for example, sucking water or a vapor of an active hydrogen-containing compound into a solution of aluminoxane.

(3) A method in which a solution of aluminoxane is brought into direct contact with water, ice or an active hydrogen-containing compound.

(4) Aluminoxane solution is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a water of crystallization or a hydrocarbon suspension of a compound to which an active hydrogen-containing compound is adsorbed. And contacting the water with the adsorbed water or water of crystallization.

The aluminoxane solution as described above may contain other components as long as the reaction between the aluminoxane and water or the active hydrogen-containing compound is not adversely affected.

The contact reaction between the solution of aluminoxane and water or an active hydrogen-containing compound is usually carried out at -50 to 150 ° C, preferably at 0 to 1 ° C.
The reaction is carried out at a temperature of 20 ° C, more preferably 20 to 100 ° C.
The reaction time varies greatly depending on the reaction temperature,
Usually, it is about 0.5 to 300 hours, preferably about 1 to 150 hours.

The benzene-insoluble organoaluminum oxy compound can also be obtained directly by bringing the above-mentioned organoaluminum into contact with water. In this case, water is used in such an amount that the amount of the organic aluminum atoms dissolved in the reaction system is 20% or less based on all the organic aluminum atoms.

Water to be brought into contact with the organoaluminum compound can be used by dissolving or dispersing it in a hydrocarbon solvent such as benzene, toluene, and hexane, an ether solvent such as tetrahydrofuran, an amine solvent such as triethylamine, or in the form of steam or ice. . In addition, water such as water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate, and cerium chloride, or inorganic compounds such as silica, alumina and aluminum hydroxide or polymers are adsorbed. Adsorbed water or the like can also be used.

The contact reaction between the organoaluminum compound and water is usually
Performed in a hydrocarbon solvent. Examples of the hydrocarbon solvent used in this case include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane; and cyclopentane. , Cyclohexane, cyclooctane, alicyclic hydrocarbons such as methylcyclohexane, petroleum fractions such as gasoline, kerosene, and gas oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, especially chlorinated products And hydrocarbon solvents such as bromides. In addition, ethers such as ethyl ether tetrahydrofuran can be used. Of these media, aromatic hydrocarbons are particularly preferred.

The concentration of the organic aluminum compound in the reaction system is usually 1 × 10 ^{−3 to} 5 g atom /
Preferably, the concentration is in the range of 1 × 10 ^{-2 to} 3 g atom /, and the concentration of water in the reaction system is usually 1 × 10 ^-2.
The concentration is preferably ^{-3 to} 5 mol / preferably 1 × 10 ^{-2 to} 3 mol /. At this time, the amount of the organic aluminum atoms dissolved in the reaction system is desirably 20% or less, preferably 10% or less, more preferably 0 to 5% based on all the organic aluminum atoms.

The contact between the organoaluminum compound and water may be specifically performed as follows.

(1) A method of contacting a hydrocarbon solution of organoaluminum with a hydrocarbon solvent containing water (2) A method of contacting organoaluminum with steam by blowing steam into the hydrocarbon solution of organoaluminum .

(3) A method in which a hydrocarbon solution of an organic aluminum is mixed with a hydrocarbon suspension of a compound containing adsorbed water or a compound containing water of crystallization, and the organic aluminum is brought into contact with the adsorbed water or the water of crystallization.

(4) A method in which ice is brought into contact with a hydrocarbon solution of an organic aluminum.

The organic aluminum hydrocarbon solution as described above may contain other components as long as the reaction between the organic aluminum and water is not adversely affected.

The contact reaction between the organoaluminum compound and water is usually
100-150 ° C, preferably -70-100 ° C, more preferably -5
It is performed at a temperature of 0 to 80 ° C. The reaction time varies greatly depending on the reaction temperature, but is usually about 1 to 200 hours, preferably about 2 to 100 hours.

The solid catalyst component for olefin polymerization according to the present invention comprises a zirconium compound containing a ligand having a [B] cycloalkadienyl skeleton and a [C] organoaluminum on the above-mentioned [A] solid titanium catalyst component. An oxy compound is supported, but [A] a zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound on a solid titanium catalyst component. Can be performed as follows.

(1) A method in which [A] a solid titanium catalyst component, [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton, and [C] an organoaluminum oxy compound are mixed and contacted in a hydrocarbon solvent.

At this time, [A], [B] and [C] may be mixed simultaneously, or after mixing two components, another one component may be mixed.

(2) A method of evaporating a hydrocarbon solvent from the suspension obtained in (1).

(3) A method of co-milling the components [A], [B] and [C].

(4) A method of coexisting a hydrocarbon solvent or a halogenated hydrocarbon solvent when performing (3).

Of the above methods, the methods (1) and (2) are preferable, and the method (1) is particularly preferable. For example, when the components [A], [B] and [C] are mixed in a hydrocarbon solvent, the concentration of the component [A] is usually 0.1 to 200 milligram atoms / preferably 1 to 200 milligram atoms / titanium atom. 5050 mg atom /, 0.1 to 50 mmol /, preferably 1 to 30 mmol / in the component [B],
In the component [C], 1 in terms of aluminum atom
It is used in the range of 50005000 mg atom /, preferably 510001000 mg atom /. The reaction temperature is usually
The temperature is in the range of 50 to 100 ° C., preferably -20 to 50 ° C., and the time required for the reaction varies depending on the reaction temperature.
It is 2 to 50 hours, preferably 0.5 to 20 hours.

[A] On a solid titanium catalyst component, [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton has an atomic ratio of transition metal to titanium (transition metal / Ti).
Is desirably supported in an amount such that it is 0.02 to 10, preferably 0.05 to 5.

The organic aluminum oxy compound has an atomic ratio of aluminum to transition metal (A / transition metal) of 10 to 500,
It is desirable to be carried in an amount that is preferably 20 to 200.

The first olefin polymerization catalyst according to the present invention is obtained by contacting the above-mentioned [A] liquid-phase titanium compound, liquid-phase magnesium compound and, if necessary, an electron donor in a liquid phase, with titanium. From a solid catalyst comprising [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound on a solid titanium catalyst component containing magnesium and halogen as essential components. Has become. That is, this olefin polymerization solid catalyst can be used as it is as an olefin polymerization catalyst.

Next, the second olefin polymerization catalyst according to the present invention will be described.

 This olefin polymerization catalyst is formed from [I] the solid catalyst as described above, and [II] an organoaluminum compound.

Such [II] organoaluminum compounds include:
For example, R _n ⁶ AX _3-n (wherein, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms, X is a halogen or hydrogen, and n is 1 to 3
3) is used.

In the above formula, R ⁶ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group. Group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Specific examples of such an organoaluminum compound include the following compounds.

Trimethyl aluminum, triethyl aluminum,
Trialkyl aluminums such as triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum and tri 2-ethylhexyl aluminum.

Alkenyl aluminum such as isoprenyl aluminum.

Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diisopropylaluminum chloride, diisobutylaluminum chloride and dimethylaluminum bromide.

Alkyl aluminum sesquichlorides such as methyl aluminum sesquichloride, ethyl aluminium sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide;

Alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride and ethylaluminum dibromide;

Alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum ^{_{compound, R 6 n AY 3-n}} ( wherein R ⁶ is as defined above, Y is -OR ⁷ group, -OSiR ⁸ ₃ group,
-OAr ⁹ ₂ group, -NR ¹⁰ ₂ group, -SiR ¹¹ ₃ group or Wherein n is 1-2, R ⁷ , R ⁸ , R ⁹ and R ¹³ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ¹⁰ is hydrogen,
Examples include a methyl group, an ethyl group, an isopropyl group, a phenyl group, and a trimethylsilyl group, and R ¹¹ and R ¹² are a methyl group, an ethyl group, and the like. ) Can also be used.

As such an organoaluminum compound, specifically, the following compounds are used.

^{(I) R 6n A (OR} 7) 3-n dimethylaluminum methoxide, diethylaluminum ethoxide and diisobutylaluminum _{^{methoxide, (ii) R 6 n A}} (OSiR 8 3) 3-n Et 2 A (OSiMe 3 _{) (iso-Bu) 2 A} (OSiMe 3) (iso-Bu) , etc. _{2 A (OSiEt 3), (} iii) R 6n A (OAR 9 2) 3-n Et 2 AOAEt 2 (iso-Bu) 2 AOA such as _{(iso-Bu) 2, (} iv) R 6n A (NR 10 2) 3-n Me 2 ANEt 2 Et 2 ANHMe Me 2 ANHEt Et 2 AN (Me 3 Si) 2 (iso-Bu) 2 AN (Me etc. _{3 Si) 2,} etc. ^{(v) R 6n A (SiR} 11 3) 3-n (iso-Bu) 2 ASiMe 3, Organoaluminum compounds mentioned above, R ⁶ ₃ A
_{^{, R 6 n A (OR 7}} ) 3-n, it can be mentioned organoaluminum compounds represented by _{^{R 6 n A (OAR 9 2}} ) 3-n suitable examples, in particular R ⁶ is isoalkyl group, Those having n = 2 are preferred. These organoaluminum compounds are 2
A mixture of two or more species can be used.

Next, the third olefin polymerization catalyst according to the present invention will be described.

 The olefin polymerization catalyst is formed from [I] the solid catalyst as described above, and [III] an organoaluminum oxy compound.

As the [III] organoaluminum oxy compound, the same organoaluminum oxy compound as used in preparing the above [I] solid catalyst is used.

Further, the fourth olefin polymerization catalyst according to the present invention will be described.

This olefin polymerization catalyst is formed from: [I] the solid catalyst as described above, [II] the organic aluminum compound as described above, and [III] the organic aluminum oxy compound as described above.

The first prepolymerization catalyst according to the present invention will be described. This prepolymerization catalyst comprises [A] a zirconium compound containing a ligand having a cycloalkadienyl skeleton on a solid titanium catalyst component, and [B] C] An olefin is preliminarily polymerized on a solid catalyst for olefin polymerization in which an organic aluminum oxy compound is supported.

The pre-polymerization is 0.1 to 5 per g of the olefin polymerization catalyst.
The reaction is carried out by prepolymerizing an α-olefin in an amount of 00 g, preferably 0.3 to 300 g, particularly preferably 1 to 100 g.

In the prepolymerization, a catalyst having a considerably higher concentration than the catalyst concentration in the system in the main polymerization can be used.

In the prepolymerization, the solid catalyst [I] is usually used in an amount of about 0.01 to 20 in terms of titanium atom per inert hydrocarbon medium.
It is desirable to use a concentration of 0 milligram atoms, preferably about 0.1 to 100 milligram atoms, particularly preferably 1 to 50 milligram atoms. At this time, if necessary, an organic aluminum compound [II] and / or an organic aluminum oxy compound [III] may be used.

The prepolymerization is preferably carried out under mild conditions by adding an olefin and the above-mentioned catalyst component to an inert hydrocarbon medium.

As the inert hydrocarbon medium used at this time, specifically, aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; hydrocarbons under halogen such as ethylene chloride and chlorobenzene, and mixtures thereof. The olefin itself can be pre-polymerized in a solvent or can be pre-polymerized in a substantially solvent-free state.

The olefin used in the prepolymerization may be the same as or different from the olefin used in the main polymerization described below, and specifically, ethylene is preferable.

The reaction temperature during the prepolymerization is usually about -20 to + 100 ° C,
Preferably about -20 to + 80 ° C, more preferably 0 to +50
It is desirable to be in the range of ° C.

In the prepolymerization, a molecular weight regulator such as hydrogen can be used. Such molecular weight regulators are
It is desirable to use the polymer in an amount such that the intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 135 ° C. is about 0.2 dl / g or more, preferably about 0.5 to 10 dl / g.

As described above, the prepolymerization is desirably carried out so as to produce about 0.1 to 500 g, preferably about 0.3 to 300 g, particularly preferably 1 to 100 g of polymer per 1 g of the solid catalyst component [I]. If the prepolymerization amount is too large, the production efficiency of the olefin polymer may decrease.

Next, the fifth olefin polymerization catalyst according to the present invention will be described.

 This olefin polymerization catalyst is formed from the above-mentioned prepolymerization catalyst and [II] an organic aluminum oxy compound.

The sixth olefin polymerization catalyst according to the present invention will be described. This olefin polymerization catalyst is formed from the above-mentioned prepolymerization catalyst and [III] an organic aluminum oxy compound.

Still further, the seventh olefin polymerization catalyst according to the present invention will be described. The olefin polymerization catalyst comprises a prepolymerization catalyst as described above, [II] an organic aluminum oxy compound, and [III] an organic aluminum compound. Is formed.

In the olefin polymerization method according to the present invention, an olefin polymer is obtained by polymerizing or copolymerizing an olefin in the presence of an olefin polymerization catalyst as described above.

Examples of the olefin that can be polymerized with such an olefin polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms, such as propylene and 1-olefin.
Butene, 1-pentene, 1-hexene, 4-methyl-1
-Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene,
Examples thereof include tetracyclododecene and 2-methyl 1,4,5,8-dimetano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.

Further, styrene, vinylcyclohexane, diene and the like can be used.

In the present invention, the polymerization can be carried out by either a liquid phase polymerization method such as solution polymerization or suspension polymerization or a gas phase polymerization method.

The polymerization temperature of the olefin using such an olefin polymerization catalyst is usually -50 to 200 ° C, preferably 0 to 150 ° C.
C., the polymerization pressure is usually from normal pressure to 100 kg / c.
m ² , preferably normal pressure to 50 kg / cm ² , and the polymerization reaction can be carried out by any of a batch system, a semi-continuous system, and a continuous system. Further, the polymerization can be performed in two or more stages under different reaction conditions. The molecular weight of the resulting olefin polymer can be adjusted by the presence of hydrogen in the polymerization system or by changing the polymerization temperature.

When olefin polymerization is carried out using the olefin polymerization catalyst as described above, the solid catalyst [I] generally contains 10 ^-8 to 10 ^-3 gram atoms of titanium atom per reaction volume.
Preferably 10 ^-7 to 10 ^-4 gram atom and comprising such an amount, the addition transition metal atom is usually 10 ^-8 to 10 ^-3 gram atom of the transition metal compound containing a ligand having a cycloalkadienyl skeleton / And preferably in an amount of 10 ^-7 to 10 ^-4 gram atom /, and the organoaluminum oxy compound is usually 10 ^-6 to 10 ^-2 gram atom / in terms of aluminum atom.
Preferably, it is used in an amount such that it becomes 10 ^{-5 to} 3 × 10 ^-3 gram atom /.

The organoaluminum compound [II] is usually 5 × 10 ^{−5 to} 5
It is desirably used in an amount of × 10 ^-2 mol /, preferably 10 ^-4 to 10 ^-2 mol /.

The organoaluminum oxy compound [III] is usually used in an amount of 10 ^{-7 to} 5 × 10 ^-3 gram atoms / preferably 10 ^-6 to 2 × 10 ^-3 gram atoms / in terms of aluminum atoms. Is desirable.

In the whole polymerization system, the ratio of aluminum / total transition metal (atomic ratio) is desirably 10 to 5,000, preferably 20 to 2,000, and further, the organoaluminum oxy compound [II]
The ratio of the organoaluminum compound [III] to A (atomic ratio A) is in the range of 0.1 to 20, preferably 0.2 to 10.

In the present invention, the catalyst for olefin polymerization may contain other components useful for olefin polymerization, in addition to the above components.

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

The molecular weight distribution (w / n) and the composition distribution (amount of n-decane soluble part) in Examples of the present invention were determined as follows.

The w / n value is measured as follows according to "Gel Permeation Chromatography" by Takeuchi and published by Maruzen.

(1) The molecular weight M and its GPC (Gel Permeation Chromatograph) count were measured using standard polystyrene of known molecular weight (Toyo Soda Co., Ltd. monodisperse polystyrene), and the correlation diagram calibration between molecular weight M and EV (Elution Volume) was measured. Create a curve. The concentration at this time is 0.02% by weight.

(2) GPC chromatograph of the sample by GPC measurement,
According to the above (1), a number average molecular weight n and a weight average molecular weight w in terms of polystyrene are calculated to obtain a w / n value.
The sample preparation conditions and GPC measurement conditions at that time are as follows.

[Sample Preparation] (a) A sample is dispensed into an Erlenmeyer flask together with an o-dichlorobenzene solvent so as to have a concentration of 0.1% by weight.

(B) Heat the Erlenmeyer flask to 140 ° C, stir for about 30 minutes, and dissolve.

(C) Apply the filtrate to GPC.

[GPC Measurement Conditions] The measurement was performed under the following conditions.

(B) Equipment Waters (150C-ALC / GPC) (b) Caram Toyo Soda (GMH type) (c) Sample volume 400μ (d) Temperature 140 ° C (e) Flow rate 1ml / min The amount of n-decane soluble part during polymerization (the smaller the soluble part, the narrower the composition distribution) is measured by adding about 3 g of the copolymer to 450 ml of n-decane, dissolving at 145 ° C, and then to 23 ° C. After cooling, filtration was performed to remove the n-decane-insoluble portion, and the n-decane-soluble portion was recovered from the filtrate.

 The MFR was measured at 190 ° C. under a load of 2.16 kg.

Example 1 (Preparation of [A] solid titanium catalyst component) 5.1 g of commercially available anhydrous magnesium chloride and 194 ml of decane were mixed with 400 g of
into a 1 ml glass flask and stir ethanol 1
8.8 ml was added dropwise over 10 minutes. After the addition, the mixture was stirred at room temperature for 1 hour. Thereafter, 17.5 ml of diethylaluminum chloride diluted with 20 ml of decane was added dropwise over 1 hour. At this time, the temperature in the system was maintained at 35 to 40 ° C. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour. Continue to add 70.6 ml of titanium tetrachloride
The mixture was added dropwise over 30 minutes, and then the temperature was raised to 80 ° C and the mixture was stirred at 80 ° C for 2 hours.

The reaction product was filtered through a jacketed glass filter kept at 80 ° C., and washed several times with decane to obtain 4.8% by weight of titanium, 14% by weight of magnesium, 57% by weight of chlorine, 2.2% by weight of aluminum, A solid titanium catalyst component having 9.7% by weight of ethoxy groups was obtained.

(Preparation of [C] organoaluminum oxy compound) A ₂ (SO ₄ ) was placed in a 400 ml flask sufficiently purged with nitrogen.
₃ · 14H was charged with ₂ O 37.1 g and toluene 133 ml, cooled to -5 ° C., it was added dropwise over 1 hour trimethylaluminum 47.9ml diluted with toluene 152 ml. Then 0-5 ° C
After reacting for 1 hour, the temperature was raised to 40 ° C over 3 hours,
The reaction was further carried out at 72 ° C for 72 hours. After the reaction, solid-liquid separation was performed by filtration, and toluene was removed from the filtrate to obtain an organic aluminum oxy compound as a white solid.

([I] Preparation of solid catalyst) The catalyst component [A] prepared above was added to a 200 ml glass flask sufficiently purged with nitrogen in terms of titanium atom in an amount of 0.5%.
Milligram atom, organoaluminum oxy compound [C]
7.3 ml of a toluene solution (A = 2.73 mol /), 10.5 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr = 0.038 mol /) and 32.2 ml of toluene were added, and the mixture was stirred at 30 ° C. for 1 hour. afterwards,
The toluene was removed under reduced pressure using an evaporator.
The solid part thus obtained was washed several times with hexane to obtain a solid catalyst. The ratio of zirconium to titanium atoms (Zr / Ti) in this solid catalyst was 0.72.

Example 2 (Polymerization) 600 ml of cyclohexane and 4-methyl-1-pentene
Then, the system was heated to 70 ° C. Thereafter, the organoaluminum oxy compound was converted to aluminum atoms by 1 milligram atom and the solid catalyst component [I] prepared in Example 1 was converted to titanium atoms by 2.0 × 10 ^-4 milligram atoms by pressure injection with ethylene. The polymerization was started. The polymerization was carried out at 80 ° C. for 40 minutes at a total pressure of 8 kg / cm ² G while continuously supplying ethylene. As a result, ethylene 4-methyl-1- having an MFR of 1.05 g / 10 min, a density of 0.912 g / cm ³ , a decane-soluble portion of 0.69% by weight, and a w / n of 4.5 was used. 52.0 g of a pentene copolymer was obtained.

Example 3 (Polymerization) In the polymerization of Example 2, 1 mmol of triisobutylaluminum was used instead of the organoaluminum oxy compound, and the solid catalyst component [I] was 1.4 × 1 in terms of titanium atom.
The same procedure was performed except that 0-3 milligram atoms were used, and the MFR was 0.
4 g of an ethylene / 4-methyl-1-pentene copolymer having a density of 0.912 g / cm ³ , a decane-soluble portion of 0.10% by weight, and a w / n of 13.6. I got

Example 4 ([III] Preparation of benzene-insoluble organoaluminum oxy compound) A toluene solution (A = 2.73 mol /) of a benzene-insoluble organoaluminum oxy compound prepared in the example in a 200-ml glass flask sufficiently purged with nitrogen (A = 2.73 mol /) , finely ground _{A 2 (SO 4) 3 ·} 14H 2 O (60 mesh pass product)
1.69 g and 63.4 ml of toluene were mixed and stirred at 80 ° C. for 7 hours to obtain a benzene-insoluble organoaluminum compound. The solubility of this compound in benzene at 60 ° C. was 0.3% by weight.

(Polymerization) Instead of the organoaluminum oxy compound used in the polymerization of Example 2, the above-mentioned benzene-insoluble organoaluminum oxy compound was 0.1 mg atom in terms of aluminum atom and 1 mmol of triisobutylaluminum, and [I] the solid catalyst component was titanium atom. 4.2 × 1
MFR was 0.13, except that ^0-4 mg atoms were used.
g / 10 minutes, the density is 0.904 g / cm ³ , the decane-soluble part amount is 0.35% by weight, and the w / n is 6.1. I got

Example 5 ([A] Preparation of solid titanium catalyst component) 4.8 g of commercially available anhydrous magnesium chloride, 23.1 ml of 2-ethylhexyl alcohol and 27 ml of decane were subjected to a heating reaction at 140 ° C for 3 hours to obtain a homogeneous solution containing magnesium chloride. Obtained. 200 ml of decane was added to this solution, and a decane solution of triethylaluminum (A = 1.0 mol /
) 52 ml was added dropwise over 30 minutes and then allowed to react for 1 hour. Subsequently, the temperature was raised to 80 ° C. over 1 hour, and the reaction was further performed at that temperature for 1 hour. After completion of the reaction, a decane solution of diethylaluminum chloride at 80 ° C. (A = 1 mol /)
60 ml was added dropwise over 30 minutes, and the mixture was reacted for 1 hour. After completion of the reaction, a solid portion was separated by filtration. The solid component thus obtained was resuspended in 200 ml of decane, and 3.75 ml of a decane solution of 2-ethylhexoxytitanium trichloride (Ti = 1 mol /) was added thereto, followed by reaction at 80 ° C. for 1 hour. Done. Thereafter, the mixture was filtered and washed to obtain 1.3% by weight of titanium, 11% by weight of magnesium, 33% by weight of chlorine, 2.4% by weight of aluminum, and 2-ethylhexoxy group 4
A solid titanium catalyst component containing 5% by weight was obtained.

([I] Preparation of solid catalyst) The catalyst component [A] prepared above was added to a 200 ml glass flask sufficiently purged with nitrogen in terms of titanium atom in an amount of 0.5%.
Milligram atom, organoaluminum oxy compound [C]
Of toluene solution (A = 2.73 mol /), 28.9 ml of a toluene solution of bis (methylcyclopentadienyl) zirconium dichloride (Zr = 0.038 mol /) and 10 ml of toluene were added, and the mixture was stirred at 30 ° C. for 1 hour. afterwards,
The toluene was removed under reduced pressure using an evaporator.
The solid part thus obtained was washed several times with hexane to obtain a solid catalyst. The ratio of zirconium to titanium atoms (Zr / Ti) in this solid catalyst was 2.1.

Example 6 (Preliminary polymerization) 200 ml of hexane, 0.3 mg atom of the solid catalyst (I) prepared in Example 5 and 9.5 mmol of triisobutylaluminum in terms of titanium atom were added to a 400 ml glass flask sufficiently purged with nitrogen. Thereafter, ethylene was preliminarily polymerized at 30 ° C. for 5 hours under normal pressure while supplying ethylene into the system. After the pre-polymerization, hexane was removed by decantation and further washing with hexane to obtain a pre-polymerization catalyst containing 29 g of polyethylene per 1 g of the solid catalyst component (I). Note that the atomic ratio (Zr / Ti) of zirconium to titanium in this prepolymerization catalyst was 1.8.

Example 7 (Polymerization) 150 g of sodium chloride (special grade of Wako Pure Chemical Industries, Ltd.) was charged into a stainless steel autoclave of 2 which had been sufficiently purged with nitrogen, and
It dried under reduced pressure at 1 degreeC for 1 hour. Thereafter, the inside of the system was cooled to 65 ° C., the benzene-soluble organic aluminum oxy compound was 0.7 mg atom in terms of aluminum atom, and the prepolymerized catalyst prepared in Example 6 was 8 × 10 ^{−3 in} terms of titanium atom.
Milligram atoms were added. Thereafter, 1.5 hydrogen was introduced, and ethylene was further introduced at 65 ° C. to start the polymerization at a total pressure of 8 kg / cm ² G. Thereafter, the polymerization was carried out at 80 ° C. for 1 hour while maintaining the total pressure at 8 kg / cm ² G while supplying ethylene. After completion of the polymerization, sodium chloride was removed by washing with water, and the remaining polymer was washed with methanol and then dried under reduced pressure at 80 ° C. overnight. As a result, the bulk specific gravity of 0.38 g / cm ^3, MFR is 0.05 g /
In 10 minutes, 76.5 g of polyethylene having a w / n of 5.7 were obtained.

Example 8 (Polymerization) In the polymerization of Example 7, a mixed gas of ethylene and 1-butene (1-butene content: 5.8 mol%) was used instead of ethylene, and a benzene-soluble organoaluminumoxy compound was 0.6 mg in terms of aluminum atoms. Atoms and prepolymerization catalyst were performed in the same manner except that 1 × 10 ^-2 milligram atoms in terms of titanium atoms were used, hydrogen was introduced at 1.5 kg / cm ² , and polymerization was carried out for 40 minutes, and the bulk specific gravity was 0.37 g / cm. ³ , MFR is 2.90 g / 10 min, density is 0.923 g / cm ³ , decane soluble part amount is 3.2% by weight, w / n is 6.5
92.3 g of an ethylene / 1-butene copolymer was obtained.

Comparative Example 1 (Polymerization) The polymerization was carried out in the same manner as in Example 2 except that the solid catalyst component [I] was not used and bis (methylcyclopentadienyl) zirconium dichloride was used in an amount of 1.5 × 10 ⁻⁴ mmol, and the MFR was 1.60 g. / 10 minutes, the density is 0.912 g / cm ³ , the amount of decane-soluble components at 23 ° C. is 0.2% by weight, w
58.1 g of an ethylene / 4-methyl-1-pentene copolymer having an / n of 3.6 was obtained.

Comparative Example 2 (Polymerization) In the polymerization of Example 2, the solid catalyst component [I] was not used, the titanium catalyst component [A] prepared in Example 1 was used in an amount of 2 × 10 ^-3 milligrams in terms of titanium atoms, and 2 kg of hydrogen was used. / cm ² except for the introduction is a MFR of 1.30 g / 10 min conducted similarly, a density of 0.914 g / cm ^3, 1 is decane-soluble component at 23 ° C.
1.9% by weight ethylene / 4-w / n is 7.3
61.5 g of a methyl-1-pentene copolymer was obtained.

[Brief description of the drawings]

FIG. 1 is an illustration of an olefin polymerization catalyst according to the present invention. FIG. 2 shows the benzene-insoluble aluminum oxy compound.
FIG. 3 shows the IR spectrum of the benzene-soluble aluminum oxy compound.
It is an IR spectrum.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C08F 4/658

Claims (6)

(57) [Claims] [1] A solid containing titanium, magnesium and halogen as essential components, which is obtained by contacting a liquid phase titanium compound, a liquid phase magnesium compound and, if necessary, an electron donor in a liquid phase. An olefin polymerization catalyst comprising: [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton; and [C] an organoaluminum oxy compound, on a titanium catalyst component. 2. [I] [A] contains titanium, magnesium and halogen as essential components obtained by contacting a liquid phase titanium compound, a liquid phase magnesium compound and, if necessary, an electron donor in a liquid phase. A solid catalyst comprising [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound on a solid titanium catalyst component, An olefin polymerization catalyst, which is formed from: 3. [I] [A] containing titanium, magnesium and halogen as essential components obtained by contacting a liquid phase titanium compound, a liquid phase magnesium compound and, if necessary, an electron donor in a liquid phase. A solid catalyst comprising [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound on a solid titanium catalyst component, and [III] an organoaluminum oxy compound And a catalyst for olefin polymerization characterized by being formed from: 4. [I] [A] contains titanium, magnesium and halogen as essential components obtained by bringing a liquid phase titanium compound, a liquid phase magnesium compound and, if necessary, an electron donor into contact with a liquid phase. A solid catalyst comprising [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound on a solid titanium catalyst component, And [III] an organoaluminum oxy compound, and an olefin polymerization catalyst. 5. [I] [A] A titanium compound in a liquid phase, a magnesium compound in a liquid phase, and optionally titanium, magnesium and a halogen obtained by bringing an electron donor into contact with the liquid phase as essential components. An olefin is prepolymerized on a solid catalyst in which [B] a zirconium compound containing a ligand having a cycloalkadienyl skeleton and [C] an organoaluminum oxy compound are supported on a solid titanium catalyst component to be formed. An olefin polymerization catalyst comprising: a prepolymerized olefin polymerization catalyst; and [III] an organoaluminum oxy compound. 6. A method for polymerizing olefins, comprising polymerizing or copolymerizing olefins in the presence of the catalyst for olefin polymerization according to any one of claims 1 to 5.