JPH06199926A - Catalytic component for polymerization of olefins and production of polyolefin - Google Patents

Abstract

PURPOSE:To provide a catalytic component capable of producing an olefin polymer in high efficiency having a high molecular weight, a relatively wide molecular weight distribution and, in the case of a copolymer, a narrow composition distribution. CONSTITUTION:This catalytic component can be produced by bringing (1) an inorganic carrier and/or a granular polymer carrier, (2) a compound of formula Me<1>R<1>nX<1>4-n [R<1> is a hydrocarbon residue. X<1> is a halogen atom. Me<1> exhibits Zr, Ti or Hf and n satisfies 0<=n<=4], (3) a compound of formula Me<2>R<2>mX<2>2-m [R<2> is a hydrocarbon residue. X<2> is a halogen atom. Me2 is an element belonging to I to III group in the periodic table. Z shows the valence number of Me<2> and m satisfies 0<=m<=Z], (4) an organic cyclic compound having two or more conjugated double bonds and (5) a modified organoaluminum compound containing Al-O-Al bond and having one or more branched chain alkyl groups bonded to Al atom into contact with each other.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is used for polymerizing or copolymerizing olefins, and has a high molecular weight and a relatively wide molecular weight distribution. The present invention relates to a catalyst component capable of increasing efficiency of an olefin polymer or copolymer having a narrow distribution. The present invention also relates to a method for producing an olefin polymer or copolymer having good particle properties using this catalyst component.

[0002]

2. Description of the Related Art In producing a polyolefin, particularly an ethylene polymer or an ethylene / α-olefin copolymer, a catalyst comprising, for example, a zirconium compound (typically a zirconocene compound) and an aluminoxane is used. It is used in JP-A-58
It is known as shown in No. 19309. In such a conventional technique, an ethylene-based polymer can be produced in a certain yield, and the obtained copolymer has a narrow molecular weight distribution and a narrow composition distribution.

However, in order to obtain a polymer in a high yield using such a catalyst system, the amount of aluminoxane used as a promoter for the transition metal such as zirconium must be increased. Further, since aluminoxane, especially methylaluminoxane, is expensive, there is a drawback that the cost for producing the catalyst becomes high. From the above, it has been desired to reduce the use ratio of aluminoxane to the catalyst component. In order to improve this point, JP-A-60-2808
No. 02, JP-A-63-218707 and the like have been proposed, but the effect is not yet sufficient. Further, the above-mentioned conventional catalyst system is often soluble in the reaction system, and when it is used for slurry polymerization or gas phase polymerization, the resulting polymer has a problem that the bulk density is low and the granular properties are inferior.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies to solve the above-mentioned drawbacks of the prior art, the present inventors have used a novel catalyst system having a completely different constitution from the conventional catalyst system, Good granular properties, high yield and high molecular weight even if the ratio of aluminoxane to transition metal used is low,
We have found a catalyst component capable of producing an olefin polymer having a relatively wide molecular weight distribution and a narrow composition distribution.

That is, the present invention is, firstly, (1) an inorganic carrier and / or a particulate polymer carrier, (2) a compound represented by the general formula Me ¹ R ¹ _n X ¹ _4-n (wherein R ¹
Is a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, Me ¹ is Zr, Ti or Hf, and n is 0 ≦ n.
≦ 4. ), (3) the general formula _{^{Me 2 R 2 m X 2 z}} -m
(Wherein R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X ² is a halogen atom, and Me ² is a periodic table I to
Group III element, z is the valence of Me ² , and m is 0 ≦ m ≦
z. ), (4) an organic cyclic compound having two or more conjugated double bonds, and (5) an Al-O-Al bond obtained by the reaction of an organoaluminum compound and water,
And a catalyst component for olefin polymerization obtained by bringing a modified organoaluminum compound in which at least one branched-chain alkyl group is bonded to an aluminum atom into contact with each other, and the present invention secondly relates to a) (1) Inorganic carrier and / or particulate polymer carrier, (2) General formula Me
Compound represented by ¹ R ¹ _n X ¹ _4-n (wherein, R ¹ is a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, M ¹
e ¹ represents Zr, Ti or Hf, and n is 0 ≦ n ≦ 4. ), (3) a compound represented by the general formula Me ² R ² _m X ² _zm (wherein R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X ² is a halogen atom, and Me ² is a cycle). Tables I-III
Group element, z represents the valence of Me ² , and m is 0 ≦ m ≦ z. ), (4) an organic cyclic compound having two or more conjugated double bonds, and (5) an Al-O-Al bond obtained by the reaction of an organoaluminum compound and water, and containing at least one aluminum atom. A component obtained by bringing modified organoaluminum compounds having a branched alkyl group bonded to each other into contact with each other; and b) a modified organoaluminum compound containing an Al-O-Al bond obtained by reacting an organoaluminum compound with water. The present invention relates to a method for producing an olefin polymer, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst.

The catalyst component used in the method of the present invention has high activity per transition metal even when the ratio of aluminoxane to transition metal used is low, and the obtained polyolefin has a high molecular weight and a relatively wide molecular weight distribution. In addition, its molecular weight distribution can be freely controlled, especially ethylene / α-olefin copolymers have a narrow composition distribution, very little surface tackiness, high bulk density, and good particle properties such as small particle shape distribution. Is. Hereinafter, the present invention will be described in detail.

The olefin polymerization catalyst component of the present invention is
As described above, (1) an inorganic carrier and / or a particulate polymer carrier, (2) a compound represented by the general formula Me ¹ R ¹ _n X ¹ _4-n , (3) a general formula Me ² R ² _m X ² _z. A compound represented by _-m , (4) an organic cyclic compound having two or more conjugated double bonds, and (5) an Al-O-Al bond obtained by reacting an organoaluminum compound with water, and aluminum It is obtained by bringing into contact with each other modified organoaluminum compounds having at least one branched chain alkyl group attached to the atom. First, the inorganic carrier and / or the particulate polymer carrier as the component (1) will be described.

The inorganic carrier used in the present invention may be in any shape such as powder, granules, flakes, foil or fibrous as long as it retains its original shape at the stage of preparing the catalyst of the present invention. Although there is no problem, the maximum length of any shape is usually 5 to 200 μm, preferably 10 to 100 μm. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m ² / g and a pore volume of 0.0.
It is preferably in the range of 5 to ³ cm ³ .

As the inorganic carrier of the present invention, a carbonaceous material, a metal, a metal oxide, a metal chloride, a metal carbonate or a mixture thereof can be used, and these are usually 200 to 90.
It is used by firing at 0 ° C. in air or in an inert gas such as nitrogen or argon.

Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. Further, as the metal oxide, the periodic table I to VI is used.
Group II single oxides or complex oxides may be mentioned, for example, SiO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , T.
iO ₂ , ZrO ₂ , Fe ₂ O ₃ , SiO ₂ · Al
₂ O ₃ , Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, A
l ₂ O ₃ · MgO · CaO, Al ₂ O ₃ · MgO · Si
O ₂ , Al ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ ,
Examples thereof include Al ₂ O ₃ .NiO and SiO ₂ .MgO. In addition, the above formula represented by an oxide is not a molecular formula but represents only a composition, that is, the structure and the component ratio of the multiple oxide used in the present invention are not particularly limited. Further, the metal oxide used in the present invention may adsorb a small amount of water, or may contain a small amount of impurities.

As the metal chloride, for example, chlorides of alkali metals and alkaline earth metals are preferable, and specifically, MgCl ₂ , CaCl _{2 and the} like are particularly preferable. The metal carbonate is preferably an alkali metal or alkaline earth metal carbonate, and specific examples thereof include magnesium carbonate, calcium carbonate and barium carbonate. Examples of the carbonaceous material include carbon black and activated carbon. Although any of the above inorganic carriers can be preferably used in the present invention, it is particularly preferable to use a metal oxide.

On the other hand, as the particulate polymer carrier, either a thermoplastic resin or a thermosetting resin can be used as long as it does not melt and remains solid during catalyst preparation and polymerization reaction. The particle size is usually 5-2000μ
m, preferably in the range of 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can exist as a solid substance at the time of catalyst preparation and polymerization reaction, and can be arbitrarily selected from low molecular weight to ultra high molecular weight. Although it can be used, and it depends on the kind of the polymer, a polymer having a molecular weight of 1,000 to 3,000,000 is usually desirable. Specifically, a particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly 1
-Various polyolefins (preferably having 2 to 12 carbon atoms) represented by butene, polyester, polyamide,
In addition to polyvinyl chloride, polymethylmethacrylate, polymethylacrylate, polystyrene, polynorbornene,
Various natural polymers and mixtures thereof can be used as the polymeric carrier.

Of course, the above-mentioned inorganic carrier and particulate polymer carrier can be used as they are as the component (1) of the present invention, but as a pretreatment, these carriers are used as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-aluminum. -Organylaluminum compounds such as hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylmonoethoxyaluminum, and triethoxyaluminum, or modified organoaluminum compounds containing Al-O-Al bonds (this compound will be described later),
Alternatively, it can be used as the component (1) after being contacted with a silane compound or the like.

As for the inorganic carrier, it further contains an active hydrogen-containing compound such as alcohol and aldehyde, an electron-donating compound such as ester and ether, and an alkoxide group such as tetraalkoxysilicate, tetraalkoxyaluminum and transition metal tetraalkoxide. A method of contacting a compound or the like in advance and then using it as the component (1) is also preferably used.

As such a preliminary contact treatment method, aromatic hydrocarbons (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, etc., heptane, in an inert atmosphere such as nitrogen or argon are usually used. Compound for pretreatment of carrier in the presence of liquid inert hydrocarbon such as aliphatic or alicyclic hydrocarbon (usually having 5 to 12 carbon atoms) such as hexane, decane, dodecane, cyclohexane, with or without stirring The method of contacting with is mentioned. It is desirable that this contact be performed at a temperature of usually -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C for 30 minutes to 50 hours, preferably 1 hour to 24 hours.

In this catalytic reaction, a solvent in which the above-mentioned pretreatment compound is soluble, that is, benzene, toluene,
It is preferable to carry out in an aromatic hydrocarbon such as xylene or ethylbenzene (usually having a carbon number of 6 to 12). In this case, after the catalytic reaction, this is used as it is without preparing the solvent to prepare the catalyst component of the present invention. Can be used for Further, in the contact reaction product, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or sparingly soluble (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, decane, dodecane, cyclohexane). (Aliphatic or alicyclic hydrocarbon, etc.) is added and component (1) is precipitated as a solid component and dried, or part or all of the aromatic hydrocarbon that is the solvent during the pretreatment is dried. After removal by means such as the above, the component (1) can be taken out as a solid component.

The ratio of the inorganic carrier and / or particulate polymer carrier to be subjected to the pretreatment and the pretreatment compound is as follows.
There is no particular limitation as long as the object of the present invention is not impaired, but it is usually selected in the range of 1 to 10000 mmol, preferably 5 to 1500 mmol (however, Al atom concentration in the modified aluminum compound) per 1 g of the carrier. .

Next, the general formula Me ¹ R ¹ _n X ^{1 of the} component (2) is used.
_The compound represented by _4-n will be described. In such formula, R ¹ has 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms.
2, more preferably 1 to 8 hydrocarbon residues, and examples of such a hydrocarbon residue include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and octyl group. Groups, vinyl groups, alkenyl groups such as allyl groups, phenyl groups, tolyl groups, aryl groups such as xylyl groups, benzyl groups, phenethyl groups, styryl groups, hydrocarbon groups such as aralkyl groups such as neophyll groups, and the like, Oxygen-containing hydrocarbon groups such as methoxy group, ethoxy group, propoxy group, butoxy group, alkoxy group such as pentyloxy group, phenoxy group, aryloxy group such as tolyloxy group, aralkyloxy group such as benzyloxy group, etc. Is mentioned. X ¹ is a halogen atom of fluorine, iodine, chlorine and bromine, Me
¹ represents Zr, Ti or Hf, preferably Zr. n is 0 ≦ n ≦ 4, preferably 0 <n ≦ 4.

The compounds represented by these general formulas are as follows:
Specifically, tetramethyl zirconium, tetraethyl zirconium, tetrapropyl zirconium, tetra n
-Butyl zirconium, tetrapentyl zirconium,
Tetraphenylzirconium, tetratolylzirconium, tetrabenzylzirconium, tetraallylzirconium, tetraneophyllzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrapropoxyzirconium, tetrabutoxyzirconium, tetrapentyloxyzirconium, tetraphenoxyzirconium, tetratolyloxyzirconium ,
Tetrabenzyloxyzirconium, tetraallyloxyzirconium, tetraneophylloxyzirconium, trimethyl monochloro zirconium, triethyl monochloro zirconium, tripropyl monochloro zirconium, tri-n-butyl monochloro zirconium, tripentyl monochloro zirconium, triphenyl monochloro zirconium, tritolyl monochloro zirconium , Tribenzyl monochloro zirconium, triallyl monochloro zirconium, trineophyl monochloro zirconium, dimethyldichloro zirconium, diethyl dichloro zirconium, dipropyl dichloro zirconium, di n-butyl dichloro zirconium, dipentyl dichloro zirconium, diphenyl dichloro zirconium, ditolyl dichloro di Conium, dibenzyldichlorozirconium, diallyldichlorozirconium, dineofildichlorozirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, monopropyltrichlorozirconium, mono-n-butyltrichlorozirconium, monopentyltrichlorozirconium, monophenyltrichlorozirconium, monotolyl Trichlorozirconium, monobenzyltrichlorozirconium, monoallyltrichlorozirconium, mononeophile trichlorozirconium, tetrachlorozirconium, trimethoxymonochlorozirconium, dimethoxydichlorozirconium, monomethoxytrichlorozirconium, triethoxymonochlorozirconium, diethoxydichlorozirconium, mono Toxyltrichlorozirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, monopropoxytrichlorozirconium, tri-n-butoxymonochlorozirconium, di-n-butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tripentyloxymonochlorozirconium, dipentyloxydichlorozirconium , Monopentyloxytrichlorozirconium, triphenoxymonochlorozirconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium, tritolyloxymonochlorozirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tribenzyloxymonochlorozirconium, dibenzyloxydichlorozirconium Lorozirconium, monobenzyloxytrichlorozirconium, triallyloxymonochlorozirconium, diallyloxydichlorozirconium, monoallyloxytrichlorozirconium, trineophyloxymonochlorozirconium, dineofiloxydichlorozirconium, mononeophylloxytrichlorozirconium, tetrabromozirconium , Trimethylmonobromozirconium, triethylmonobromozirconium, tripropylmonobromozirconium, tri-n-
Butylmonobromozirconium, tripentylmonobromozirconium, triphenylmonobromozirconium, tritolylmonobromozirconium, tribenzylmonobromozirconium, triallylmonobromozirconium, trineophylmonobromozirconium, dimethyldibromozirconium, diethyldibromozirconium, di Propyldibromozirconium, di-n-butyldibromozirconium, dipentyldibromozirconium, diphenyldibromozirconium, ditolyldibromozirconium, dibenzyldibromozirconium, diallyldibromozirconium, dineofildibromozirconium, monomethyltribromozirconium, monoethyltribromozirconium, Monopropyltribromozirconium, n-butyltribromozirconium, monopentyltribromozirconium, monophenyltribromozirconium, monotolyltribromozirconium, monobenzyltribromozirconium, monoallyltribromozirconium, mononeophyltribromozirconium, tetrabromozirconium, trimethoxy Monobromozirconium, dimethoxydibromozirconium, monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, tripropoxymonobromozirconium, dipropoxydibromozirconium, monopropoxytribromozirconium, tri-n -Butoxymonobromozirconium, di-n-butoxydibromozirconium , Mono-n-butoxytribromozirconium, tripentyloxymonobromozirconium, dipentyloxydibromozirconium, monopentyloxytribromozirconium, triphenoxymonobromozirconium, diphenoxydibromozirconium, monophenoxytribromozirconium, tritolyloxymonobromo Zirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium, tribenzyloxymonobromozirconium, dibenzyloxydibromozirconium, monobenzyloxytribromozirconium, triallyloxymonobromozirconium, diallyloxydibromozirconium, monoallyloxy Tribromozirconium, trineophylloxy monobromozirconi Um, dineofiloxydibromozirconium, mononeophylloxytribromozirconium, tetraiodozirconium, trimethylmonoiodozirconium, triethylmonoiodozirconium, tripropylmonoiodozirconium, tri-n-butylmonoiodozirconium, tripentylmonoiodozirconium , Triphenyl monoiodo zirconium, tritolyl monoiodo zirconium, tribenzyl monoiodo zirconium, triallyl monoiodo zirconium, trineophyll monoiodo zirconium, dimethyldiiodo zirconium, diethyl diiodo zirconium, dipropyl diiodo zirconium, di n- Butyl diiodo zirconium, dipentyl diiodo zirconium, diphenyl diiodo zirconium, dito Distearate iodo zirconium, dibenzyl iodo zirconium, diallyl diiodo zirconium, di neophyl diiodo zirconium,
Monomethyl triiodo zirconium, monoethyl triiodo zirconium, monopropyl triiodo zirconium, mono n-butyl triiodo zirconium, monopentyl triiodo zirconium, monophenyl triiodo zirconium, monotolyl triiodo zirconium, monobenzyl triiodo zirconium, tetra Iodozirconium, trimethoxymonoiodozirconium, dimethoxydiiodozirconium, monomethoxytriiodozirconium, triethoxymonoiodozirconium,
Diethoxydiiodozirconium, monoethoxytriiodozirconium, tripropoxymonoiodozirconium, dipropoxydiiodozirconium, monopropoxytriiodozirconium, tri-n-butoxymonoiodozirconium, di-n-butoxydiiodozirconium, mono-n-butoxy. Triiodozirconium, tripentyloxymonoiodozirconium, dipentyloxydiiodozirconium, monopentyloxytriiodozirconium, triphenoxymonoiodozirconium, diphenoxydiiodozirconium, monophenoxytriiodozirconium, tritolyloxymonoiodozirconium, di Tolyloxydiiodozirconium, monotolyloxytriiodozirconium, tribenzyloxymonoyo Dozirconium, dibenzyloxydiiodozirconium, monobenzyloxytriiodozirconium, triallyloxymonoiodozirconium, diallyloxydiiodozirconium, monoallyloxytriiodozirconium, trineophylloxymonoiodozirconium, dineofiloxydi Iodozirconium, mononeophyloxytriiodozirconium, tribenzylmonomethoxyzirconium, tribenzylmonoethoxyzirconium, tribenzylmonopropoxyzirconium, tribenzylmonobutoxyzirconium, tribenzylmonopentyloxyzirconium, tribenzylmonophenoxyzirconium, tribenzyl Monotolyloxy zirconium, tribenzyl monobenzyloxy zirconium, Revenge monoallyl oxy zirconium tribenzyl mono neophyl oxy zirconium dibenzyl dimethoxy zirconium, dibenzyl diethoxy zirconium, dibenzyl propoxy zirconium dibenzyl dibutoxy zirconium dibenzyl dipentyl oxyzirconium,
Dibenzyldiphenoxyzirconium, dibenzylditolyloxyzirconium, dibenzyldibenzyloxyzirconium, dibenzyldiallyloxyzirconium, dibenzyldineophyloxyzirconium, monobenzyltrimethoxyzirconium, monobenzyltriethoxyzirconium, monobenzyltripropoxy Zirconium, monobenzyl tributoxy zirconium,
Monobenzyltripentyloxyzirconium, monobenzyltriphenoxyzirconium, monobenzyltritolyloxyzirconium, monobenzyltribenzyloxyzirconium, monobenzyltriallyloxyzirconium, monobenzyltrineophyloxyzirconium, trineophyllmonomethoxyzirconium, tri Neofil monoethoxy zirconium, trineofil monopropoxy zirconium, trineofil monobutoxy zirconium, trineofil monophenoxy zirconium, dineofil dimethoxyzirconium, dineofil diethoxyzirconium, dineofil dipropoxy zirconium, dineofil Dipoxy Zirconium, Dineofil Diphenoxy Zirconium, Mononeofil trime Alkoxy zirconium, mono neophyl triethoxy zirconium, mono neophyl tripropoxy zirconium, mono neophyl tributoxyzirconium, mono- neophyl triphenodioxazine shea zirconium, trimethoxy (trimethylsilylmethyl) zirconium,
Triethoxy (trimethylsilylmethyl) zirconium, tripropoxy (trimethylsilylmethyl) zirconium, tributoxy (trimethylsilylmethyl) zirconium,

Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetra-n-butyltitanium, tetrapentyltitanium, tetraphenyltitanium, tetratolyltitanium, tetrabenzyltitanium, tetraallyltitanium, tetraneofiltitanium, tetramethoxytitanium, tetra Ethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetrapentyloxytitanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrabenzyloxytitanium, tetraallyloxytitanium, tetraneophylloxytitanium, trimethylmonochlorotitanium, triethylmonochlorotitanium, tri Propyl monochlorotitanium, tri-n- Till monochlorotitanium, tribenzyl monochlorotitanium, dimethyldichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, mono-n-butyltrichlorotitanium, monobenzyltrichlorotitanium, Tetrachlorotitanium, trimethoxymonochlorotitanium, dimethoxydichlorotitanium, monomethoxytrichlorotitanium, triethoxymonochlorotitanium, diethoxydichlorotitanium, monoethoxytrichlorotitanium, tripropoxymonochlorotitanium, dipropoxydichlorotitanium, monopropoxytrichlorotitanium, trin -Butoxy monochloroti Chloride, di-n
-Butoxydichlorotitanium, mono-n-butoxytrichlorotitanium, tripentyloxymonochlorotitanium, dipentyloxydichlorotitanium, monopentyloxytrichlorotitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium,
Monophenoxytrichlorotitanium, tritolyloxymonochlorotitanium, ditolyloxydichlorotitanium, monotolyloxytrichlorotitanium, tribenzyloxymonochlorotitanium, dibenzyloxydichlorotitanium, monobenzyloxytrichlorotitanium, tetrabromotitanium, trimethylmonobromotitanium, Triethyl monobromotitanium,
Tripropylmonobromotitanium, tri-n-butylmonobromotitanium, tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium, dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium , Mono-n-butyltribromotitanium, monobenzyltribromotitanium, tetrabromotitanium, trimethoxymonobromotitanium, dimethoxydibromotitanium, monomethoxytribromotitanium, triethoxymonobromotitanium, diethoxydibromotitanium, monoethoxytribromo Titanium, tripropoxymonobromotitanium, dipropoxydibromotitanium, monopropoxytribro Titanium, tri-n-butoxymonobromotitanium, di-n-butoxydibromotitanium, mono-n-butoxytribromotitanium, tripentyloxymonobromotitanium, dipentyloxydibromotitanium, monopentyloxytribromotitanium, triphenoxymonobromotitanium, Diphenoxydibromotitanium, monophenoxytribromotitanium, tritolyloxymonobromotitanium,
Ditryloxydibromotitanium, monotolyloxytribromotitanium, tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium, monobenzyloxytribromotitanium, tetraiodotitanium, trimethylmonoiodotitanium, triethylmonoiodotitanium, tripropylmonotitanium Iodotitanium, tri-n-butylmonoiodotitanium, tribenzylmonoiodotitanium, dimethyldiiodotitanium, diethyldiiodotitanium, di-n-butyldiiodotitanium, dibenzyldiiodotitanium, monomethyltriiodotitanium, monoethyltriiodo Titanium, mono-n-butyltriiodotitanium, monobenzyltriiodotitanium, tetraiodotitanium, trimethoxy Monoiodotitanium, Dimexidiiodotitanium, Monomethoxytriiodotitanium, Triethoxymonoiodotitanium, Diethoxydiiodotitanium, Monoethoxytriiodotitanium, Tripropoxymonoiodotitanium, Dipropoxydiiodotitanium, Monopropoxytriiodo Titanium, tri-n-butoxymonoiodotitanium, di-n
-Butoxydiiodotitanium, mono-n-butoxytriiodotitanium, tripentyloxymonoiodotitanium, dipentyloxydiiodotitanium, monopentyloxytriiodotitanium, triphenoxymonoiodotitanium, diphenoxydiiodotitanium, monophenoxytriiodo Titanium, tritolyloxymonoiodotitanium, ditolyloxydiiodotitanium, monotolyloxytriiodotitanium,
Tribenzyloxymonoiodotitanium, dibenzyloxydiiodotitanium, monobenzyloxytriiodotitanium, tribenzylmonomethoxytitanium, tribenzylmonoethoxytitanium, tribenzylmonopropoxytitanium, tribenzylmonobutoxytitanium, tribenzylmonophenoxytitanium , Dibenzyldimethoxytitanium, dibenzyldiethoxytitanium, dibenzylpropoxytitanium,
Dibenzyldibutoxytitanium, dibenzyldiphenoxytitanium, monobenzyltrimethoxytitanium, monobenzyltriethoxytitanium, monobenzyltripropoxytitanium, monobenzyltributoxytitanium, monobenzyltriphenoxytitanium, trineophil monomethoxytitanium, tri Neofil monoethoxytitanium, Trineofil monopropoxytitanium, Trineofil monobutoxytitanium, Trineofil monophenoxytitanium, Dineofil dimethoxytitanium, Dineofil diethoxytitanium, Dineofil dipropoxytitanium, Dineofil Dibutoxytitanium, dineofil diphenoxytitanium, mononeophyll trimethoxytitanium, mononeoff Le triethoxy titanium,
Mononeophyll tripropoxytitanium, mononeophyll tributoxytitanium, mononeophyll triphenoxytitanium, trimethoxy (trimethylsilylmethyl) titanium, triethoxy (trimethylsilylmethyl) titanium, tripropoxy (trimethylsilylmethyl) titanium, tributoxy (trimethylsilylmethyl) titanium,

Tetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrapentyl hafnium, tetraphenyl hafnium, tetratolyl hafnium, tetrabenzyl hafnium, tetraallyl hafnium, tetraneophyll hafnium, tetramethoxy hafnium, tetra Ethoxyhafnium, tetrapropoxyhafnium, tetrabutoxyhafnium, tetrapentyloxyhafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrabenzyloxyhafnium, tetraallyloxyhafnium, tetraneophiloxyhafnium, trimethylmonochlorohafnium, triethylmonochlorohafnium, tri Propyl monochlorohafnium, tri n- Till monochlorohafnium, tribenzyl monochlorohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, di-n-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium, monoethyltrichlorohafnium, mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium, Tetrachlorohafnium, trimethoxymonochlorohafnium, dimethoxydichlorohafnium, monomethoxytrichlorohafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium, monoethoxytrichlorohafnium, tripropoxymonochlorohafnium, dipropoxydichlorohafnium, monopropoxytrichlorohafnium, trin -Butoxy Monochrome Chloride, di-n
-Butoxydichlorohafnium, mono-n-butoxytrichlorohafnium, tripentyloxymonochlorohafnium, dipentyloxydichlorohafnium, monopentyloxytrichlorohafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium, tritolyloxymonochlorohafnium, Ditolyloxydichlorohafnium, monotolyloxytrichlorohafnium,
Tribenzyloxy monochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, tetrabromohafnium, trimethylmonobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, tri-n-butylmonobromohafnium, tribenzylmonobromo Hafnium, dimethyldibromohafnium, diethyldibromohafnium, di-n-butyldibromohafnium, dibenzyldibromohafnium, monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribromohafnium, monobenzyltribromohafnium, tetrabromohafnium , Trimethoxymonobromohafnium, dimethoxydibromohafnium, monomethoxytrib Mohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, tripropoxymonobromohafnium, dipropoxydibromohafnium, monopropoxytribromohafnium, tri-n-butoxymonobromohafnium, di-n-butoxydibromohafnium , Mono-n-butoxytribromohafnium, tripentyloxymonobromohafnium, dipentyloxydibromohafnium, monopentyloxytribromohafnium, triphenoxymonobromohafnium, dienoxydibromohafnium, monophenoxytribromohafnium, tolyloxymonomono. Bromohafnium,
Ditolyloxydibromohafnium, monotolyloxytribromohafnium, tribenzyloxymonobromohafnium, dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, tetraiodohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmono Iodohafnium, tri-n-butylmonoiodohafnium, tribenzylmonoiodohafnium, dimethyldiiodohafnium, diethyldiiodohafnium, di-n-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodo Hafnium, mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium, trimethoxy Monoiodohafnium, dimethoxydiiodohafnium, monomethoxytriiodohafnium, triethoxymonoiodohafnium, diethoxydiiodohafnium, monoethoxytriiodohafnium, tripropoxymonoiodohafnium, dipropoxydiiodohafnium, monopropoxytriiodohafnium , Tri-n-butoxymonoiodohafnium, di-n
-Butoxydiiodohafnium, mono-n-butoxytriiodohafnium, tripentyloxymonoiodohafnium, dipentyloxydiiodohafnium, monopentyloxytriiodohafnium, triphenoxymonoiodohafnium, diphenoxydiiodohafnium, monophenoxytriiodo Hafnium, tritolyloxymonoiodohafnium, ditolyloxydiiodohafnium, monotolyloxytriiodohafnium,
Tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodohafnium, tribenzylmonomethoxyhafnium, tribenzylmonoethoxyhafnium, tribenzylmonopropoxyhafnium, tribenzylmonobutoxyhafnium, tribenzylmonophenoxyhafnium , Dibenzyldimethoxyhafnium, dibenzyldiethoxyhafnium, dibenzyldipropoxyhafnium, dibenzyldibutoxyhafnium, dibenzyldiphenoxyhafnium, monobenzyltrimethoxyhafnium, monobenzyltriethoxyhafnium, monobenzyltripropoxyhafnium, monobenzyl Tributoxy hafnium, monobenzyl triphenoxy hafnium, trineophyll mono Toxihafnium, Trineophyll monoethoxy hafnium, Trineophyll monopropoxy hafnium, Trineofil monobutoxy hafnium, Trineophyll monophenoxy hafnium, Dineofil dimethoxy hafnium, Dineofil diethoxy hafnium, Dineofil dipropoxy hafnium , Dineofildibutoxyhafnium, Dineofildiphenoxyhafnium, Mononeophile trimethoxyhafnium, Mononeophile triethoxyhafnium,
Mononeophyll tripropoxy hafnium, mononeophyll tributoxy hafnium, mononeophyll triphenoxy hafnium, trimethoxy (trimethylsilylmethyl) hafnium, triethoxy (trimethylsilylmethyl) hafnium, tripropoxy (trimethylsilylmethyl) hafnium, tributoxy (trimethylsilylmethyl) hafnium, And so on. Of course, in these compounds listed as the specific examples of the above component (2), the R ¹ is not only n- but also iso-, s-, t.
It also includes cases in which various structural isomer groups such as-and neo- are included. Among these specific compounds, tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, tetrabutoxyzirconium, tetrabutoxytitanium and tetrabutoxyhafnium are preferable. Particularly preferred are Zr (OR) ₄ compounds such as tetrapropoxyzirconium and tetrabutoxyzirconium. These compounds are 2
It is also possible to use a mixture of two or more species.

Next, the general formula Me ² R ² _m X ^{2 of the} component (3) is used.
_The compound represented by zm will be described. In such compounds, R ² has 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms.
And more preferably a hydrocarbon residue of 1 to 8, and examples of such a hydrocarbon residue include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a pentyl group. , Hexyl group, octyl group,
For alkyl groups such as decyl group, todecyl group, alkenyl groups such as vinyl group, allyl group, aryl groups such as phenyl group, tolyl group, xylyl group, aralkyl groups such as benzyl group, phenethyl group, styryl group, neofil group, etc. Examples include hydrocarbon groups, alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, and pentyloxy, aryloxy groups such as phenoxy, tolyloxy, and aralkyloxy groups such as benzyloxy. And oxygen-containing hydrocarbon groups.
X ² is a halogen atom such as fluorine, iodine, chlorine and bromine. Me ² represents a Group I to III element of the periodic table,
Examples of such elements include lithium, sodium, potassium, magnesium, calcium, zinc, boron and aluminum. z represents the valence of Me ² , usually z is 1 to 3, and m is 0 <m ≦ z,
It is preferably a number in the range of 0 <m <z. Specific examples of the compound represented by this general formula include methyl lithium, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, t-butyl lithium, pentyl lithium, octyl lithium, phenyl lithium and benzyl. Lithium, dimethyl magnesium, diethyl magnesium, di-n-propyl magnesium, di-isopropyl magnesium, di-n-butyl magnesium, di-t-butyl magnesium, dipentyl magnesium, dioctyl magnesium, diphenyl magnesium, dibenzyl magnesium, methyl magnesium chloride, ethyl magnesium chloride, n-propyl magnesium chloride, isopropyl magnesium chloride, n-butyl magnesium chloride, t-butyl magne Umium chloride, pentyl magnesium chloride, octyl magnesium chloride, phenyl magnesium chloride, benzyl magnesium chloride, methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, ethyl magnesium iodide, n-propyl magnesium bromide, n-propyl magnesium iodide, Isopropyl magnesium bromide, isopropyl magnesium iodide, n-butyl magnesium bromide, n-butyl magnesium iodide, t
-Butyl magnesium bromide, t-butyl magnesium iodide, pentyl magnesium bromide,
Pentyl magnesium iodide, octyl magnesium bromide, octyl magnesium iodide,
Phenylmagnesium bromide, phenylmagnesium iodide, benzylmagnesium bromide, benzylmagnesium iodide,

Dimethyl zinc, diethyl zinc, di-n-propyl zinc, di-isopropyl zinc, di-n-butyl zinc, di-t-butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, dibenzyl zinc, trimethylboron, triethylboron, trin -Propylboron, triisopropylboron, tri-n-butylboron, trit-butylboron, tripentylboron, trioctylboron, triphenylboron, tribenzylboron,

Trimethyl aluminum, triethyl aluminum, trioctyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide,
Diethyl aluminum fluoride, diethyl aluminum iodide, ethyl aluminum dichloride,
Ethyl aluminum dibromide, ethyl aluminum difluoride, ethyl aluminum diiodide,
Tripropyloaluminum, dipropyl aluminum chloride, dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide, propyl aluminum dichloride,
Propyro aluminum dibromide, propyl aluminum difluoride, propyl aluminum diiodide, triisopropyl aluminum, diisopropyl aluminum chloride, diisopropyl aluminum bromide, diisopropyl aluminum fluoride, diisopropyl aluminum iodide, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, Propyl aluminum sesquichloride, propyl aluminum sesquibromide, n-butyl aluminum sesquibromide, n-butyl aluminum sesquibromide, isopropyl aluminum dichloride, isopropyl aluminum dibromide, isopropyl aluminum difluoride, isopropyl aluminum diai Iodide, tributyl aluminum, dibutyl aluminum chloride, dibutyl aluminum bromide, dibutyl aluminum fluoride, dibutyl aluminum iodide, butyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum difluoride, butyl aluminum diiodide, tri s- butyl aluminum,
Di-s-butyl aluminum chloride, di-s-butyl aluminum bromide, di-s-butyl aluminum fluoride, di-s-butyl aluminum iodide, s
-Butyl aluminum dichloride, s-butyl aluminum dibromide, s-butyl aluminum difluoride, s-butyl aluminum diiodide, tri-t-butyl aluminum, di-t-butyl aluminum chloride, di-t-butyl aluminum bromide, di-t
-Butyl aluminum fluoride, di-t-butyl aluminum iodide, t-butyl aluminum dichloride, t-butyl aluminum dibromide, t-butyl aluminum difluoride, t-butyl aluminum diiodide, triisobutyl aluminum, diisobutyl aluminum chloride , Diisobutylaluminum bromide, diisobutylaluminum fluoride, diisobutylaluminum iodide, isobutylaluminum dichloride, isobutylaluminum dibromide, isobutylaluminum difluoride, isobutylaluminium diiodide, trihexylaluminum, dihexylaluminum chloride, dihexylaluminum bromide, dihexylaluminum Fluo Id, dihexyl aluminum iodide, hexyl aluminum dichloride, hexyl aluminum dibromide, hexyl aluminum difluoride, hexyl aluminum diiodide,
Tripentyl aluminum, dipentyl aluminum chloride, dipentyl aluminum bromide, dipentyl aluminum fluoride, dipentyl aluminum iodide, pentyl aluminum dichloride,
Pentyl aluminum dibromide, pentyl aluminum difluoride and pentyl aluminum diiodide,

Methyl aluminum methoxide, methyl aluminum ethoxide, methyl aluminum propoxide, methyl aluminum butoxide, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, dimethyl aluminum propoxide, dimethyl aluminum butoxide, ethyl aluminum methoxide, ethyl aluminum ethoxide. , Ethyl aluminum propoxide, ethyl aluminum butoxide, diethyl aluminum methoxide, diethyl aluminum ethoxide,
Diethyl aluminum propoxide, diethyl aluminum butoxide, propyl aluminum methoxide, propyl aluminum ethoxide, propyl aluminum propoxide, propyl aluminum butoxide, dipropyl aluminum methoxide, dipropyl aluminum ethoxide, dipropyl aluminum propoxide,
Examples thereof include dipropyl aluminum butoxide, butyl aluminum methoxide, butyl aluminum ethoxide, butyl aluminum propoxide, butyl aluminum butoxide, dibutyl aluminum methoxide, dibutyl aluminum ethoxide, dibutyl aluminum propoxide, dibutyl aluminum butoxide. Of course, in these compounds exemplified as the above-mentioned component (3), the case where R ² is not only n- but also various structural isomer groups such as iso-, s-, t-, neo- is included. Is what you are doing.

As the component (4), an organic cyclic compound having two or more conjugated double bonds is used. The component (4) has two or more conjugated double bonds, preferably 2 to 4 and more preferably 2 to 3 and has a total carbon number of 4 to 24, preferably 4 to 12 Hydrogen compound; Cyclic hydrocarbon compound in which the cyclic hydrocarbon compound is partially substituted with a hydrocarbon group having 1 to 6 carbons (typically, an alkyl group having 1 to 12 carbon atoms or an aralkyl group); Two or more bonds, preferably 2 to 4, more preferably 2 to
An organosilicon compound having 3 cyclic carbon groups having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group being partially substituted with 1 to 6 hydrocarbon residues. Also included are alkali metal salts of these compounds (sodium salt, lithium salt, etc.). Incidentally, the organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. (Cp) _r SiR ³ _s X ³ _4-rs

Here, Cp is a cyclopentadienyl group,
Substituted cyclopentadienyl group, indenyl group, shows the cyclic hydrocarbon group exemplified by the substituted indenyl group,
R ³ is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group or an octyl group; an alkenyl group such as a vinyl group or an allyl group; a methoxy group, Alkoxy groups such as ethoxy group, propoxy group, butoxy group; phenyl group,
Aryl groups such as tolyl group and xylyl group; aryloxy groups such as phenoxy group; benzyl group, phenethyl group,
It represents a hydrocarbon residue or hydrogen having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, as exemplified by an aralkyl group such as a styryl group and a neophyll group, and R ³ represents not only n- but also i.
It also includes cases in which various structural isomer groups such as so-, s-, t-, and neo- are included. X ³ represents a halogen atom such as fluorine, iodine, chlorine or bromine, and r and s
Is a number in the range of 0 <r ≦ 4 and 0 ≦ s ≦ 3.

Therefore, specific examples of the organic cyclic hydrocarbon compound usable as the component (4) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2
-Substituted cyclopentadiene such as dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3,4-tetramethylcyclopentadiene, pentamethylcyclopentadiene, indene, 4- Substituted indene such as methyl-1-indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene, cycloheptatriene, substituted cycloheptatriene such as methylcycloheptatriene, cyclooctatetraene, methyl Substituted cyclooctatetraene such as cyclooctatetraene, azulene, methylazulene, ethylazulene, fluorene, cyclopolyene having 7 to 24 carbon atoms such as substituted fluorene such as methylfluorene, or a substituted cyclopolyene,

Monocyclopentadienylsilane, dicyclopentadienylsilane, tricyclopentadienylsilane, tetracyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclo Pentadienyldimethylsilane, Monocyclopentadienyldiethylsilane, Monocyclopentadienyltrimethylsilane, Monocyclopentadienyltriethylsilane, Monocyclopentadienylmonomethoxysilane, Monocyclopentadienylmonoethoxysilane, Monocyclo Pentadienylmonophenoxysilane, Monocyclopentadienylmonomethylmonochlorosilane, Monocyclopentadienylmonoethylmonochlorosilane, Monocyclopentadienylmonomethyldichlorosilane Silane, monocyclopentadienyl monoethyldichlorosilane, monocyclopentadienyl trichlorosilane, dicyclopentadienyl monomethylsilane, dicyclopentadienyl monoethylsilane, dicyclopentadienyl dimethylsilane, dicyclopentadienyl Diethylsilane, dicyclopentadienylmethylethylsilane, dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane,
Dicyclopentadienyldiphenylsilane, Dicyclopentadienylphenylmethylsilane, Dicyclopentadienylmethylchlorosilane, Dicyclopentadienylethylchlorosilane, Dicyclopentadienyldichlorosilane, Dicyclopentadienylmonomethoxy Silane, dicyclopentadienyl monoethoxysilane, dicyclopentadienyl monomethoxy monochlorosilane, dicyclopentadienyl monoethoxy monochlorosilane, tricyclopentadienyl monomethylsilane, tricyclopentadienyl monoethylsilane, tricyclo Pentadienyl monomethoxysilane, tricyclopentadienyl monoethoxysilane, tricyclopentadienyl monochlorosilane, 3-methylcyclopentadienylsilane, bis-3-methylcyclo 1,3-dimethylcyclopentadienylmethylsilane, 1,2-dimethylcyclopentadienylsilane, 1,3-dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3,4-totetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane,

Monoindenylsilane, diindenylsilane, triindenylsilane, tetraindenylsilane,
Monoindenylmonomethylsilane, monoindenylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane , Monoindenylmonophenoxysilane, monoindenylmonomethylmonochlorosilane, monoindenylmonoethylmonochlorosilane, monoindenylmonomethyldichlorosilane, monoindenylmonoethyldichlorosilane, monoindenyltrichlorosilane, diindenylmonomethylsilane, Diindenyl monoethylsilane, diindenyldimethylsilane, diindenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, Indenyl ethylpropyl silane,
Diindenyldiephenylsilane, diindenylphenylmethylsilane, diindenylmethylchlorosilane, diindenylethylchlorosilane, diindenyldichlorosilane, diindenylmonomethoxysilane, diindenylmonoethoxysilane, diindenylmonosilane Methoxymonochlorosilane, diindenylmonoethoxymonochlorosilane, triindenylmonomethylsilane, triindenylmonoethylsilane, triindenylmonomethoxysilane, triindenylmonoethoxysilane, triindenylmonochlorosilane, 3-methylindenyl Silane, bis-3-methylindenylsilane, 3-methylindenylmethylsilane, 1,2-dimethylindenylsilane,
1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3,4-tetramethylindenylsilane, pentamethylindenylsilane, and the like. Preferred are cyclopentadiene, substituted cyclopentadiene, indene, substituted indene and the like.

Further, any one of the above-mentioned compounds may have an alkylene group (the carbon number thereof is usually 2 to 8, preferably 2 to
A compound bound via 3) can also be used as the component (4) of the present invention. For example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl)
Ethane, 1,3-propanedienylbisindene, 1,
3-propanedienylbis (4,5,6,7-tetrahydro) indene, propylenebis (1-indene),
Isopropyl (1-indenyl) cyclopentadiene,
Examples thereof include diphenylmethylene (9-fluorenyl) cyclopentadiene and isopropylcyclopentadienyl-1-fluorene.

Al-O- used as the component (5)
At least 1 in an aluminum atom, including an Al bond
The modified organoaluminum compound having a branched alkyl group bonded thereto is usually obtained by reacting an organoaluminum compound having a branched alkyl group with water. Such organoaluminum compounds are preferably represented by the general formula _{R a R 'b AlX 3-} a-b. Where R
Represents a branched chain alkyl group having 3 to 18 carbon atoms, preferably 3 to 12, and examples of the branched alkyl group include isopropyl group, isobutyl group, 2-methylbutylaluminum, 3-methylbutyl group, 2-methylpentyl group, 3-
Examples thereof include a methylpentyl group, a 4-methylpentyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylhexyl group and a 2-ethylhexyl group. Also,
R'represents a hydrocarbon group such as a linear alkyl group having 1 to 18 carbon atoms, preferably 1 to 12 groups, an alkenyl group, an aryl group, an aralkyl group, and the like. Examples of the hydrocarbon group include a methyl group, an ethyl group, Examples thereof include propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, vinyl group, allyl group, phenyl group, tolyl group, xylyl group, benzyl group, phenethyl group, styryl group and neophyll group. In the formula, X represents a hydrogen atom or a halogen atom such as fluorine, bromine or chlorine, and a and b are 0 <a ≦.
3, 0 ≦ b <3 is satisfied, preferably a + b = 3, and more preferably a = 3.

As such an organoaluminum compound,
Specifically, triisopropylaluminum, triisobutylaluminum, tri-2-methylbutylaluminum, tri-3-methylbutylaluminum, tri2-methylpentylaluminum, tri-3-methylpentylaluminum, tri4-methylpentylaluminum, tri-2. -Methylhexylaluminum, tri3-methylhexylaluminum, tri4-methylhexylaluminum, tri2-ethylhexylaluminum, diisopropylmonomethylaluminum, diisopropylmonoethylaluminum, diisopropylmonoisobutylaluminum, diisopropylmononormalbutylaluminum, diisopropylmonophenylaluminum, Diisopropyl monobenzyl aluminum, diisopropyl aluminum hide Id, diisopropyl monochlorobenzene aluminum, diisopropyl monobromo aluminum,
Diisopropyl monoiodo aluminum, diisopropyl monofluoro aluminum, isopropyl dimethyl aluminum, isopropyl diethyl aluminum, isopropyl diisobutyl aluminum, isopropyl dinormal butyl aluminum, isopropyl diphenyl aluminum, isopropyl dibenzyl aluminum, isopropyl dihydride, isopropyl dichloro aluminum, isopropyl dibromo aluminum, isopropyl Diiodo aluminum, isopropyl difluoro aluminum, diisobutyl monomethyl aluminum,
Diisobutyl monoethyl aluminum, diisobutyl mononormal propyl aluminum, diisobutyl mononormal butyl aluminum, diisobutyl monophenyl aluminum, diisobutyl monobenzyl aluminum, diisobutyl aluminum hydride, diisobutyl monochloroaluminum, diisobutyl monobromoaluminum, diisobutyl monoiodo aluminum,
Diisobutyl monofluoro aluminum, isobutyl dimethyl aluminum, isobutyl diethyl aluminum, isobutyl dinormal butyl aluminum, isobutyl diphenyl aluminum, isobutyl dibenzyl aluminum, isobutyl dihydride, isobutyl dichloro aluminum, isobutyl dibromo aluminum, isobutyl diiodo aluminum, isobutyl difluoro aluminum, di 2-methylbutylmonomethylaluminum, di2-methylbutylmonoethylaluminum, di2-methylbutylmonochloroaluminum, di2
-Methyl butyl monophenyl aluminum, 2-methyl butyl dimethyl aluminum, 2-methyl butyl diethyl aluminum, 2-methyl butyl dichloro aluminum, etc. are mentioned. Trialkylaluminum is preferably used as the organoaluminum compound having a branched alkyl mentioned above.

As mentioned above, the modified organoaluminum compound used in the present invention is usually obtained by reacting the above-mentioned organoaluminum compound with water. The water is not particularly limited, but ordinary water can be used. First, it includes various crystal waters contained in copper sulfate hydrate, aluminum sulfate hydrate and the like, and components capable of generating water in the reaction system. In the modified organoaluminum compound, 1 to 100, preferably 1 to 50 A's are usually contained in one molecule.
It has an l-O-Al bond and is usually represented by the following general formula.

[0035] In the formula, R represents the above-mentioned branched chain alkyl group,
R ′, R ″, R ″ ″ are the above-mentioned straight chain alkyl groups,
It represents a hydrocarbon group, a hydrogen atom, a halogen atom (chlorine, fluorine, bromine, etc.) exemplified by an alkenyl group, an aryl group, an aralkyl group and the like, and R ″ and R ″ ″ are bonded to each other to form a ring (alkylene group). Groups, etc.) may be formed.
Further, p is usually 1 ≦ p ≦ 100, preferably 2 ≦ p ≦ 5.
0 and q are 0 ≦ q ≦ 100, preferably 0 ≦ p ≦ 50.

The reaction between the organoaluminum compound and water is
It is usually carried out in an inert hydrocarbon, and examples of such an inert hydrocarbon include aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene. Particularly preferred are aliphatic hydrocarbons. The reaction ratio between water and organic aluminum (water (H ₂ O) / Al molar ratio) is usually 0.1 / 1 to 2.0 / 1, preferably 0.25 / 1 to
1.5 / 1, more preferably 0.5 / 1 to 1.25 /
1, the reaction temperature is usually -70 to 100 ° C, preferably -20 to 20 ° C, and the reaction time is usually 5
The range of minutes to 24 hours, preferably 1 to 5 hours is desirable.

According to the present invention, the modified organoaluminum compound having a branched alkyl group bonded thereto is one component of the catalyst component, and the olefin is polymerized or co-polymerized in the presence of the catalyst composed of the catalyst component and the modified organoaluminum compound. Be polymerized. The proportion of the modified organoaluminum compound having a branched chain alkyl bonded is such that the atomic ratio of aluminum in the modified organoaluminum compound having a branched chain alkyl bonded to the transition metal in the catalyst component is 1 to 100,00.
It is selected to be 0, preferably 5 to 1,000.

As described above, the catalyst component used in the production method of the present invention is (1) an inorganic carrier and / or a particulate polymer carrier (component (1)), (2) a general formula Me ¹ R ¹
a compound represented by _n X ¹⁴ _-n (component (2)), (3)
Formula _{^{Me 2 R 2 m X 2 z}} -m compound represented by (component (3)), (4) an organic cyclic compound having conjugated double bonds two or more (component (4)) and (5) Al A modified organoaluminum compound containing an —O—Al bond and having at least one branched alkyl group bonded to an aluminum atom (component (5)) is brought into contact with each other.
The order of contacting these components is not particularly limited.

Therefore, as the method of contacting the above components (1) to (5), first, the components (1) to (5) are simultaneously contacted, and the components (1) to (4) are simultaneously contacted, and then, Method of contacting component (5), method of contacting component (1), component (2), component (4) at the same time, then method of contacting component (3) and then component (5), component (1) and ( 2) is first contacted, then the component (3) and then the component (4) and then the component (5) are contacted, the component (1) and the component (2) are contacted first, and then the components (3) to (5). Method of contacting simultaneously with the above, components (1) and (4) are first contacted, then component (2) and then component (3) and then component (5), component (1) and component (4) is first contacted, then components (2), (3) and Method in which (5) is contacted at the same time, components (1) and (5) are contacted first, then component (2), then component (3) and then component (4) are contacted, component (1) ) And component (5) are contacted first, and then component (2)-
Method in which (4) is contacted at the same time, component (1), component (2), component (4) are simultaneously contacted, and then component (3) is followed by contact with component (5), component Method of contacting (2) and (3) first, then component (1) and then component (4) and then component (5), contacting components (2) and (4) first, then component (3) and then component (3) Method of contacting the component (1) and then the component (5), first contacting the components (2) and (4),
Component (3), then component (5), followed by contacting component (1), components (2) and (4) are contacted first, then component (1) and then component (5), then component (3)
, The components (2) and (5) are contacted first, then the component (1) and then the component (3) and then the component (4) are contacted in advance.
A method of contacting component (1) after contacting (5),
Method of contacting components (2) to (4) in advance, then contacting component (1) and then component (5), after contacting components (3) and (4) in advance, then component (1) and then component (2) After that, a method of contacting the component (5), in which the components (2) and (4) are contacted in advance, the component (1) is contacted, and then the contact product of the components (3) and (5) is contacted. Method of contacting, components (3) and (5) are contacted in advance, then component (1) and then component (2) and then component (4) are contacted, one of component (1) and component (4) Part, and then contacting the rest of component (2), component (4), contact product of component (3), component (5), contacting part of component (1) and component (5) Then, a method of contacting the rest of the components (2), (3), (4) and (5) Examples thereof include a method of contacting components (2) to (5) in advance and then contacting component (1), and components (2) and (4) are contacted first, and then component (3). Then, the method of contacting the component (1) and then the component (5), the components (2) and (4)
First, followed by contacting component (3), then component (5) and then component (1), first contacting components (2) and (4), then component (1), then component (5), then component (5) The method of contacting (3) is preferable.

The method of contacting these five components is not particularly limited, but is usually an aromatic hydrocarbon (usually having a carbon number of 6 to 6) such as benzene, toluene, xylene, ethylbenzene in an inert atmosphere such as nitrogen or argon. 12),
Aliphatic or alicyclic hydrocarbons such as heptane, hexane, decane, dodecane, cyclohexane (usually 5 carbon atoms)
The method of contacting each component with or without stirring in the presence of a liquid inert hydrocarbon such as the above (12) is used. This contact is generally -100 ° C to 200 ° C, preferably -5 ° C.
It is desirable to carry out at a temperature of 0 ° C. to 100 ° C. for 30 minutes to 50 hours, preferably 1 hour to 24 hours. When a particulate polymer carrier is used as the component (1), it goes without saying that the catalytic reaction is carried out under the condition that the polymer remains substantially solid.

In contacting the components (1) to (5), as described above, an aromatic hydrocarbon solvent in which a certain component is soluble and an aliphatic or alicyclic ring in which the certain component is insoluble or sparingly soluble. Any of the group hydrocarbon solvents can be used. When the contact reaction between the components is carried out stepwise, the soluble aromatic hydrocarbon solvent used in the preceding step may be used as it is as a solvent for the catalytic reaction in the subsequent step without removing it. In addition, after the contact reaction of the first stage using a soluble solvent,
Liquid inert hydrocarbons in which certain components are insoluble or sparingly soluble (for example, aliphatic or alicyclic hydrocarbons such as pentane, hexane, decane, dodecane, cyclohexane) are added to give the desired product as a solid. After the recovery, or after the aromatic hydrocarbon solvent is partially or wholly removed by a means such as drying to take out the desired product as a solid, the subsequent catalytic reaction of the desired product is performed as described above. It can also be carried out using any of the inert hydrocarbon solvents. In the present invention, the contact reaction of each component may be carried out multiple times.

The ratio of the components (2) to (5) used in the present invention is usually 0.
01 to 100 mol, preferably 0.1 to 50 mol, more preferably 1 to 20 mol, component (4) is usually 0.01 to 100 mol, preferably 0.1 to 50 mol,
More preferably in the range of 1 to 20 mol, the component (5) is usually 0.01 to 100,000 mol, preferably 0.1 to 100 mol.
It is desirable to select in the range of 5000 mol, more preferably 1 to 1000 mol, and 100 g of component (1)
Against the atomic ratio of aluminum to component (2) a transition metal concentration ^{(Me 1) (Al / Me} 1) is usually 0.
It is desirable to be 1 to 10,000, preferably 10 to 1,000.

The catalyst component of the present invention obtained by bringing the components (1) to (5) into contact with each other as described above is usually combined with a promoter component to form a catalyst useful for the polymerization or copolymerization of olefins. Become. The promoter component includes
Any promoter can be used as long as it does not impair the purpose of the present invention and the performance of the catalyst component, but a modified organoaluminum compound as shown below is typically used.

Modified Organoaluminum Compound The modified organoaluminum compound preferably used in the present invention has an Al—O—Al bond in its molecule, and the number of bonds is usually 1 to 100, preferably 1. It is desirable that the number is ~ 50. Such a modified organoaluminum compound is usually a product obtained by reacting an organoaluminum compound with water. The reaction of organoaluminum with water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene, alicyclic hydrocarbons and aromatic hydrocarbons can be used. It is preferred to use group hydrocarbons.

The organoaluminum compound used to prepare the modified organoaluminum compound has the general formula R ⁴ _c AlX
_3-c (In the formula, R ⁴ has 1 to 18 carbon atoms, preferably 1 to
12 are hydrocarbon groups such as an alkyl group, an alkenyl group, an aryl group and an aralkyl group, X is a hydrogen atom or a halogen atom, and c is an integer of 1 ≦ c ≦ 3). Although possible, preferably trialkylaluminum is used. The alkyl group of trialkylaluminum includes a methyl group, an ethyl group, a propyl group,
Any of an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an octyl group, a decyl group and a dodecyl group may be used, but a methyl group is particularly preferable.

The reaction ratio of water to the organoaluminum compound (water / Al molar ratio) is preferably 0.25 / 1 to 1.2 / 1, and particularly preferably 0.5 / 1 to 1/1. The reaction temperature is usually -70 to 100 ° C, preferably -20 to 20 ° C.
Is in the range. The reaction time is usually selected in the range of 5 to 24 hours, preferably 10 to 5 hours. As water required for the reaction, not only mere water but also water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like and components capable of generating water in the reaction system can be used.

According to the present invention, olefins are homopolymerized or copolymerized in the presence of a catalyst composed of the above catalyst component and a promoter component exemplified by a modified organoaluminum compound. In this case, the catalyst component and the modified organoaluminum compound can be separately or previously mixed and supplied into the polymerization reaction system. In the case of premixing, not only a method of simply contacting the catalyst component with the modified organoaluminum, but also a step of contacting (mixing) each raw material component during preparation of the catalyst component may be performed. In any case, the use ratio of the catalyst component and the modified organoaluminum compound is such that the atomic ratio of aluminum in the modified organoaluminum compound to the transition metal in the catalyst component is 1 to 100,000, preferably 5
˜1,000, more preferably 50 to 100.

The olefins referred to in the present invention include α-olefins, cyclic olefins, dienes, trienes and styrene analogs. The α-olefins include those having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically, ethylene, propylene, butene-1,
Hexene-1,4-methylpentene-1 and the like are exemplified. The α-olefins can be homopolymerized by using the catalyst component of the present invention, and also two or more kinds of α-olefins can be copolymerized. The copolymerization is alternating copolymerization, random copolymerization. It does not matter whether it is polymerization or block copolymerization.

For the copolymerization of α-olefins, ethylene and propylene, ethylene and butene-1, ethylene and hexene-1, ethylene and 4-methylpentene-1, such as ethylene and carbon number 3 to 12, preferably. Is 3 to 8
-When copolymerizing with an olefin, propylene and butene-1, propylene and 4-methylpentene-1, propylene and 4-methylbutene-1, propylene and hexene-
1, such as propylene and octene-1, the case of copolymerizing propylene with an α-olefin having 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms is included. When copolymerizing ethylene or propylene with other α-olefin, the other α
-The amount of the olefin can be arbitrarily selected in the range of 90 mol% or less of all the monomers, but in the case of the ethylene copolymer, it is generally 40 mol% or less, preferably 30 mol% or less, It is preferably 20 mol% or less, and in the case of a propylene copolymer, it is selected in the range of 1 to 90 mol%, preferably 5 to 90 mol%, more preferably 10 to 70 mol%.

The cyclic olefin has 3 to 2 carbon atoms.
4, preferably 3 to 18 can be used in the present invention, for example cyclopentene, cyclobutene,
Cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, dicyclopentadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl- 2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-trimethyl-2-norbornene, ethylidene norbornene and the like are included. The cyclic olefin is usually copolymerized with the above-mentioned α-olefin, and in this case, the amount of the cyclic olefin is 50 mol% or less of the copolymer, usually 1 to 50 mol%, preferably 2 to 50 mol. It is in the range of%.

The dienes and trienes usable in the present invention can be represented by the following general formula. It is a chain polyene. _{CH 2 CH (CH) n (} CHCH 2) m , where, m is 1 or 2, n is 0 to 20, preferably 2 to
The number of 20 is shown. Specifically, butadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 1,13-tetradecadiene, 2,6-dimethyl-
1,5-Hebutadiene, 2-methyl-2,7-octadiene, 2,7-dimethyl-2,6-octadiene, 1,
Examples include 5,9-decatriene and the like. When a chain diene or triene is used in the present invention, it is usually the above α
-It is customary to copolymerize with an olefin, but the content of chain diene and / or triene in the copolymer is
Generally, 0.1 to 50 mol%, preferably 0.2 to 10
It is in the range of mol%.

Styrene analogs which can be used in the present invention are styrene and styrene derivatives, and examples of the derivatives include t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene and 1,1-diphenyl. Examples thereof include ethylene, N, N-dimethyl-p-aminoethylstyrene and N, N-diethyl-p-aminoethylstyrene. The catalyst component of the present invention can also be suitably used in the case where a homopolymer or copolymer of olefins is further polymerized with a polar monomer to modify the homopolymer or copolymer. Examples of polar monomers include unsaturated carboxylic acid esters such as methyl acrylate, methyl methacrylate, butyl methacrylate, dimethyl maleate, diethyl maleate, monomethyl maleate, diethyl fumarate, and dimethyl itaconate. it can. The polar monomer content of the modified copolymer is usually 0.1 to 10 mol%, preferably 0.2 to
It is in the range of 2 mol%.

The polymerization reaction can be carried out by slurry polymerization, solution polymerization or gas phase polymerization in the presence of the catalyst component and promoter component described above. In particular, slurry polymerization or gas phase polymerization is preferable, and in a state where oxygen, water and the like are substantially cut off, hexane, aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene, toluene and xylene, cyclohexane,
The olefin is polymerized in the presence or absence of an inert hydrocarbon solvent selected from alicyclic hydrocarbons such as methylcyclohexane. The polymerization conditions at this time are a temperature of 20 to 2
00 ° C., preferably 50 to 100 ° C., pressure normal pressure to 70 k
It is usually in the range of g / cm ² G, preferably atmospheric pressure to 20 kg / cm ² G, and the polymerization time is usually 5 minutes to 10 hours, preferably 5 minutes to 5 hours.

The molecular weight of the produced polymer can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but the addition of hydrogen to the polymerization reaction system allows the molecular weight to be adjusted more effectively. It can be carried out. Further, it can be carried out without any trouble even if a component for the purpose of removing water, so-called scavenging, is added to the polymerization system. Examples of such scavenging include organoaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, the above-mentioned modified organoaluminum compound, and modified organoaluminum containing branched alkyl. Are exemplified. Different polymerization conditions such as hydrogen concentration, monomer amount, polymerization pressure, polymerization temperature, etc. 2
It can also be applied to a multi-stage polymerization system of multiple stages or more without any problem.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The physical properties of the polymers obtained in Examples and Comparative Examples were measured by the following methods. Melt Index (MI) ASTM D 1238-57T 190 ° C, 2.16
It was measured based on the kg load. The density was measured according to ASTM D 1505-68. Melting point measurement by differential scanning calorimeter (DSC) Using a DSC-20 type melting point measuring device manufactured by Seiko Denshi, the sample (5 mg) was held at 180 ° C for 3 minutes, and then cooled to 0 ° C at 10 ° C / minute. The melting point was measured by holding at 0 ° C. for 10 minutes and then raising the temperature at 10 ° C./minute. Preparation of Modified Organoaluminum Compound A modified organoaluminum compound (methylaluminoxane) used as a promoter in the following Examples and Comparative Examples was prepared as follows. 13 g of copper sulfate pentahydrate was placed in a three-necked flask with a capacity of 300 ml equipped with an electromagnetic induction stirrer and suspended with 50 ml of toluene. Next, 150 ml of a solution of trimethylaluminum having a concentration of 1 mmol / ml was added dropwise to the above suspension at a temperature of 0 ° C. over 2 hours, and the temperature was raised to 25 ° C. at the end of the dropping, and the temperature was adjusted to 24
Reacted for hours. After that, the reaction product was filtered, and toluene in the liquid containing the reaction product was removed to obtain 4 g of white crystalline methylaluminoxane (hereinafter referred to as MAO).

Example 1 (1) Preparation of isobutylaluminoxane (hereinafter referred to as IBAO) solution 150 ml of purified hexane in a 300 ml flask under nitrogen
Was added, and a stock solution of triisobutylaluminum 51 was added.
ml was added. The system was then kept at 0 ° C. and 50 μl of water was added dropwise. After the dropping was completed, the system was stirred at 0 ° C. for 2 hours. Then the system was brought to room temperature and stirred for a further 5 hours, then 1 ml /
Purified hexane was added to the solution to make a mol solution. The analysis results of the obtained isobutylaluminoxane are as follows. Molecular weight (benzene freezing point depression method) 1513 (2) Preparation of transition metal catalyst component Purified toluene 150 ml in a 300 ml flask under nitrogen
Then, tetrabutoxy zirconium (hereinafter referred to as Zr
(Represented by OnBu) ₄ ) 3.85 g and indene 11.6
g and stirred at room temperature for 30 minutes, then the system was kept at 0 ° C. and triethylaluminum (hereinafter referred to as AlEt ₃ ) 11.6.
g was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (assumed to be). The concentration of this solution is 0.056 mmol / ml as Zr. Si baked in a 50 ml flask at 600 ° C. for 5 hours
O ₂ (manufactured by Fuji Devison, grade # 952, surface area 3
00m ² / g) 1g, and further purified toluene 10m
1 was added. After that, 4 ml of the above-mentioned solution was sampled and stirred at room temperature for 1 hour. Then 1.3 above
The ml slurry was placed in another 50 ml flask, 8 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (3) Contact of catalyst component with promoter Subsequently, 15.3 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. After that, the solvent was removed and the catalyst was obtained (). (4) Polymerization A 3 liter capacity stainless steel autoclave equipped with a stirrer was purged with nitrogen, and dried salt 2
00 g was added, 1.8 mg of Zr of the catalyst prepared above was added, and the mixture was heated to 60 ° C. under stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was introduced so as to be 9 kgf / cm ² to start polymerization, and a mixed gas of ethylene and butene-1 (butene- While continuously supplying a 1 / ethylene molar ratio of 0.05), polymerization was carried out for 2 hours while maintaining the total pressure at 9 kgf / cm ² . After the completion of the polymerization, the mixture was cooled and sodium chloride was removed to obtain 94 g of a white polymer. The amount of transition metal supported was 2 wt% and the MAO / Zr ratio was 100. Table 1 shows the results of the polymerization and the physical properties of the obtained polymer.
Described in.

Example 2 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
And then tetrapropoxyzirconium (hereinafter Z
r (OnPr) ₄ ) 3.27 g and indene 9.3
g and stirred at room temperature for 30 minutes, then the system was kept at 0 ° C and Al
4.6 g of Et ₃ was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (referred to as). The concentration of this solution is 0.06 mmol as Zr /
ml. In a 50 ml flask under nitrogen at 600 ° C 5
Sintered for ₂ hours (Fuji Davison, grade #
952, surface area 300 m ² / g) 1 g was added, and further purified toluene 10 ml was added. Then 2m of the above solution
1 was taken and stirred at room temperature for 1 hour. Then, the above 1.7 ml slurry was placed in another 50 ml flask under nitrogen, 5 ml of the hexane solution of isobutylaluminoxane of (1) in Example 1 was added, and the mixture was stirred at room temperature for 1 hour.
After stirring for a time, a catalyst component was obtained. (2) Contact of catalyst component with promoter Subsequently, 1 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. After that, the solvent was removed to obtain a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
1wt%, transition metal addition amount is 1.6mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 3 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.27 g of Zr (OnPr) ₄ and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes, and then 0
While maintaining the system at 0 ° C., 4.6 of AlEt ₃ was dropped, and after completion of the dropping, the system was stirred at room temperature for 2 hours to prepare a transition metal catalyst component (assumed to be). The concentration of this solution is 0.06 mmol / ml as Zr. 6 in a 50 ml flask
SiO ₂ baked at 00 ° C. for 5 hours (manufactured by Fuji Devison,
# 952) 1 g was added, and 10 ml of purified toluene and a toluene solution of methylaluminoxane (concentration 1 mm
ol / ml) was added and the mixture was stirred at room temperature for 2 hours. Then, 2 ml of the above solution was collected under nitrogen and stirred at room temperature for 1 hour. Then, 1.8 ml of the above slurry was placed in another 50 ml flask, and
4.4 ml of a hexane solution of the used isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 0.73 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
1 wt%, transition metal addition amount is 1.3 mg, MAO / Zr
The ratio was 50. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 4 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.27 g of Zr (OnPr) ₄ and trimethylcyclopentadienylsilane (hereinafter referred to as CpSiMe ₃
11 g) and after stirring at room temperature for 30 minutes, the system is kept at 0 ° C. and 9.1 g of AlEt ₃ is added dropwise. After completion of the dropping, the system is stirred at room temperature for 2 hours to prepare a transition metal catalyst component. Was prepared. The concentration of this solution is Zr.
It is 057 mmol / ml. 60 in a 50 ml flask
SiO ₂ baked at 0 ° C. for 5 hours (manufactured by Fuji Devison, #
952) 1 g was added, and further 10 ml of purified toluene and a toluene solution of methylaluminoxane (concentration 1 mmo
(1 / ml) was added and the mixture was stirred at room temperature for 2 hours.
Then, 3 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then, 2 ml of the above slurry was placed in another 50 ml flask, and 6.4 ml of the hexane solution of isobutylaluminoxane used in Example 1 was added,
After stirring at room temperature for 1 hour, a catalyst component was obtained. (2) Contact of catalyst component with promoter Subsequently, 1 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
55 wt%, transition metal addition amount is 1.9 mg, MAO / Z
The r ratio was 50. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 5 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.27 g of Zr (OnPr) ₄ and 11.6 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and the system was kept at 0 ° C. to maintain diethyl aluminum ethoxide (hereinafter referred to as AlEt).
₂ (OEt)) was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (assumed to be). The concentration of this solution is 0.0 as Zr.
It is 51 mmol / ml. MgC in a 50 ml flask
l ₂ and triethoxyaluminum (hereinafter Al (OEt)
₃ ) of the co-ground product (into a stainless steel pot with an internal volume of 400 ml containing 25 1/2 inch diameter stainless steel balls), anhydrous magnesium chloride 1
(0 g and 3.8 g of triethoxyaluminum were added and subjected to pole milling for 16 hours at room temperature in a nitrogen atmosphere)
1 g was added, further 10 ml of purified toluene was added, and the mixture was stirred at room temperature for 2 hours. Then 3.2 ml of the above solution
Was collected and stirred at room temperature for 1 hour. Then, 1.5 ml of the above slurry was placed in another 50 ml flask, 5.6 ml of the hexane solution of isobutylaluminoxane used in Example 1 was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 1.9 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
5 wt%, transition metal addition amount is 1.7 mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 6 (1) Preparation of transition metal catalyst component The same transition metal catalyst component as in Example 5 was used. 5 ml of purified toluene and 0.3 ml of the above solution were placed in a 50 ml flask, and 5.0 ml of a hexane solution of isobutylaluminoxane used in Example 1 was added,
After stirring at room temperature for 1 hour, a catalyst component was obtained. Then, a methylaluminoxane solution with a concentration of 1 mmol / ml 1.6
ml was added, and the mixture was stirred at room temperature for 1 hour. 5
Polyethylene powder (Ligna Ro Density Polyethylene MFR 1.0 g / 10 m in a 0 ml flask)
in, bulk density 0.30 g / cc, particle size 500 μm, melting point 121 ° C.) 1 g, and the total amount was added. Then, the mixture was stirred and the solvent was removed to prepare a catalyst. (2) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 0.
15 wt%, transition metal addition amount is 1.5 mg, MAO / Z
The r ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 7 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.85 g of Zr (OnBu) ₄ and 10.3 g of bisindenylethane were added, and the mixture was stirred at room temperature for 30 minutes,
While maintaining the system at 0 ° C., 9.1 g of AlEt ₃ was added dropwise, and after completion of the addition, the system was stirred at room temperature for 2 hours to prepare a transition metal catalyst component (assumed to be). The concentration of this solution is 0.061 mmol / ml as Zr. To a 50 ml flask was added 1 g of SiO ₂ (# 952, manufactured by Fuji Devison Co., Ltd.) that had been calcined at 600 ° C. for 5 hours, and purified toluene 10 was added.
ml and 3 ml of a toluene solution of trimethylaluminum (concentration 1 mmol / ml) were added, and the mixture was stirred at room temperature for 2 hours. Then, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then, 1 ml of the above slurry was placed in another 50 ml flask, and the hexane solution of isobutylaluminoxane used in Example 1 was 8.5 m.
1 was added and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 2.9 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported is 2.
2 wt%, transition metal addition amount is 1.3 mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 8 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.0 g of tripropoxymonochlorozirconium (hereinafter referred to as Zr (OnPr) ₃ Cl) and 5.3 g of cyclopentadiene were added, and the mixture was stirred at room temperature for 30 minutes, and then 0
While maintaining the system at ℃, 9.6 g of diethylaluminum chloride (hereinafter referred to as AlEt ₂ Cl) was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component. ). The concentration of this solution is 0.060 mmol / ml as Zr. To a 50 ml flask, 1 g of Al ₂ O ₃ (catalyst chemical conversion surface area 300 m ² / g, average particle size 60 μm) calcined at 400 ° C. for 5 hours was added,
Further 10 ml of purified toluene and 2 ml of the above solution
Was collected and stirred at room temperature for 1 hour. Then, 2 ml of the above slurry was placed in another 50 ml flask, 3.7 ml of the hexane solution of isobutylaluminoxane used in Example 1 was added, and the mixture was stirred at room temperature for 1 hour,
A catalyst component was obtained. (2) Contact of catalyst component with promoter Subsequently, 1.9 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
1 wt%, transition metal addition amount is 1.7 mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 9 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.27 g of Zr (OnPr) ₄ and 4.7 g of indene were added, and after stirring at room temperature for 30 minutes, the system was kept at 0 ° C. and 9.1 g of AlEt ₃ was added dropwise over 30 minutes. The rear system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (referred to as). The concentration of this solution is 0.059 mmol / ml as Zr. 1 g of Mg (CO ₃ ) ₂ calcined at 150 ° C. for 2 hours was added to a 50 ml flask, and further 10 ml of purified toluene and 3 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml).
Was added and the mixture was stirred at room temperature for 2 hours. Then, 3 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then, 2 ml of the above slurry was placed in another 50 ml flask, 11 ml of a hexane solution of isobutylaluminoxane used in Example 1 was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 2.2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
6 wt%, transition metal addition amount is 2.0 mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 10 (1) Preparation of transition metal catalyst component The transition metal catalyst component of Example 9 was used. 5
SiO baked in a 0 ml flask at 600 ° C for 5 hours
₂ (Fuji Devison Co. # 952) 1 g was added, and further purified toluene 10 ml and isobutylaluminoxane hexane solution (concentration 1 mmol / ml) 5 ml were added, and the mixture was stirred at room temperature for 2 hours. Then the above solution 2.
5 ml was sampled and stirred at room temperature for 1 hour.
Then, 2 ml of the above slurry was placed in another 50 ml flask, 1.6 ml of a hexane solution of isobutylaluminoxane used in Example 1 was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 1.6 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
3 wt%, transition metal addition amount is 1.5 mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 11 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 3.27 g of Zr (OnPr) ₄ and 4.7 g of indene were added, and the mixture was stirred at room temperature for 30 minutes, and then the system was maintained at 0 ° C. to maintain n-butylmagnesium chloride (hereinafter referred to as nBuM).
ether solution of gCl (concentration 2 mmol / m
l) 40 μl was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (assumed to be). The concentration of this solution is 0.063 mmol as Zr
/ Ml. To a 50 ml flask, 1 g of SiO ₂ (# 952 manufactured by Fuji Devison Co., Ltd.) calcined at 600 ° C. for 5 hours was added, and further 10 ml of purified toluene and 3 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml).
Was added and the mixture was stirred at room temperature for 2 hours. Then, 1.9 ml of the above-mentioned solution was collected and stirred at room temperature for 1 hour. Then, 2 ml of the above slurry was placed in another 50 ml flask, and isopropylaluminoxane (hereinafter referred to as IP
4.9 ml of a hexane solution of rAO) was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 1.64 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst.

Preparation of Isopropylaluminoxane Solution Purified hexane 150 ml in 300 ml flask under nitrogen
And then stock solution of triisopropylaluminum 3
1.2 g was added. Then, the system is kept at 0 ° C., and 50 μl
Water was added dropwise. After the dropping was completed, the system was stirred at 0 ° C. for 2 hours. The system is then brought to room temperature and stirred for a further 5 hours, then 1
Purified hexane was added to make a ml / mol solution. The results of analysis of the obtained isopropylaluminoxane are as follows. Molecular weight (benzene freezing point depression method) 1150 (3) Polymerization The same as in Example 1. The amount of transition metal supported was 1.
1 wt%, transition metal addition amount is 1.5 mg, MAO / Zr
The ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 12 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, tetrabutoxy titanium (hereinafter Ti (On
Bu) ₄ ) and 3.40 g of cyclopentadiene.
After adding 3 g and stirring at room temperature for 30 minutes, the system was kept at 0 ° C. and 40 μl of an ether solution of phenylmagnesium chloride (hereinafter referred to as PhMgCl) (concentration 2 mmol / ml).
Was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours,
A transition metal catalyst component was (and is) prepared. The concentration Ti of this solution is 0.063 mmol / ml. Fifty
1 ml of SiO ₂ (# 952 manufactured by Fuji Devison Co., Ltd.) calcined at 600 ° C. for 5 hours was added to a ml flask, 10 ml of purified toluene and 3 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) were added, and the mixture was allowed to stand at room temperature for 2 hours.
I stirred the time. Then, 6.6 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then take 1.5 ml of the above slurry in another 50 ml flask,
11 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 11 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported is 2.
0 wt%, transition metal addition amount is 1.5 mg, MAO / Ti
The ratio was 500. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 13 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
And then tetrapropoxy hafnium (hereinafter Hf
(OnPr) ₄ ) (4.1 g) and cyclopentadiene (5.3 g) were added, and the mixture was stirred at room temperature for 30 minutes, and the system was kept at 0 ° C. to maintain benzyl magnesium chloride (hereinafter BzMgCl).
Represented by) in an ether solution (concentration 2 mmol / ml) 40
μl was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (referred to as). The concentration of this solution is 0.065 mmol / ml as Hf. Si baked in a 50 ml flask at 600 ° C. for 5 hours
1 g of O ₂ (# 952 manufactured by Fuji Devison Co., Ltd.) was added, and further 10 ml of purified toluene and 5 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) were added,
The mixture was stirred at room temperature for 2 hours. Then 0.9m of the above solution
1 was taken and stirred at room temperature for 1 hour. Then, 2.4 ml of the above-mentioned slurry was placed in another 50 ml flask, and a hexane solution of isobutylaluminoxane was added.
2 ml was added and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 4.2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
0 wt%, transition metal addition amount is 1.5 mg, MAO / Hf
The ratio was 500. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 14 (1) Preparation of tetrabenzylzirconium (hereinafter represented by ZrBz ₄ ) 500 ml of a diethyl ether solution containing 70 g of benzylmagnesium chloride at 0 ° C. was placed in a 1 liter flask under nitrogen, and then ZrCl _{4 was} added. 30 g
Was added. The mixture was stirred for 2 hours while raising the temperature to room temperature. Next, 300 ml of decalin was added, and the mixture was stirred at room temperature for 1 hour. The produced MgCl ₂ was isolated, and the resulting decalin solution was heated to 50 ° C. to remove ether. From the obtained decalin solution, ZrBz
₄ 32 g was obtained. (2) Preparation of transition metal catalyst component Purified toluene 150 ml in 300 ml flask under nitrogen
And then 4.5g of ZrBz ₄ and 9.3g of indene.
Was added and stirred at room temperature for 30 minutes, then the system was kept at 0 ° C and AlE was added.
4.6 g of t ₃ was added dropwise, and after completion of the addition, the system was brought to room temperature and 2
The mixture was stirred for a period of time to prepare a transition metal catalyst component. The concentration of this solution is 0.061 mmol as Zr
/ Ml. To a 50 ml flask, 1 g of SiO ₂ (# 952 manufactured by Fuji Devison Co., Ltd.) calcined at 600 ° C. for 5 hours was added, and further 10 ml of purified toluene and 3 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml).
Was added and the mixture was stirred at room temperature for 2 hours. Then, 2.7 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then, 1.8 ml of the above slurry was added to another 50 m
In a 1-liter flask, 9.3 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 3.7 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
5 wt%, transition metal addition amount is 1.7 mg, MAO / Zr
The ratio was 200. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 15 (1) Preparation of transition metal catalyst component 150 ml of purified toluene in a 300 ml flask under nitrogen
Then, 2.3 g of ZrCl ₄ and 4.65 of indene were added.
g and stirred at room temperature for 30 minutes, then the system was kept at 0 ° C and Al
9.1 g of Et ₃ was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (referred to as). The concentration of this solution is 0.060 mmol as Zr
/ Ml. To a 50 ml flask, 1 g of SiO ₂ (# 952 manufactured by Fuji Devison Co., Ltd.) calcined at 600 ° C. for 5 hours was added, and further 10 ml of purified toluene and 5 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml).
Was added and the mixture was stirred at room temperature for 2 hours. Then, 1.8 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then 3.2 ml of the above slurry was added to another 50 m
In a 1-liter flask, 10.4 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour to obtain a catalyst component. (2) Contact of catalyst component with promoter Subsequently, 4.2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and the mixture was stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst. (3) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported was 1.
0 wt%, transition metal addition amount is 1.9 mg, MAO / Zr
The ratio was 200. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 16 Ethylene homopolymerization was carried out under the same conditions as in Example 1 except that only ethylene was used instead of the mixed gas of ethylene and butene-1. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 17 Homopolymerization of propylene was carried out under the same conditions as in Example 7 except that only propylene was used instead of the mixed gas of ethylene and butene-1. However, the polymerization temperature was 50 ° C. and the polymerization pressure was 7 kgf / cm ^2, and the polymerization was carried out for 1 hour. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 18 (1) Preparation of Transition Metal Catalyst Component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, and then 2.6 g of monoisopropoxytrichlorozirconium and 11.
After adding 6 g and stirring at room temperature for 30 minutes, 11.6 g of triethylaluminum was added dropwise while maintaining the system at 0 ° C. After completion of the addition, the system was stirred at room temperature for 2 hours to prepare a transition metal catalyst component ( And). The concentration of this solution is 0.057 mmol / ml as Zr. Separately, 2 g of SiO ₂ (Fuji Davison Grade # 952) calcined at 600 ° C. for 5 hours was added to a 50 ml flask, and further 10 ml of purified toluene was added. Thereafter, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour to obtain a catalyst component (assumed to be). Then add 1.3 ml of the above slurry to another 50 m
10 ml of a hexane solution of isobutylaluminoxane was added to the flask. (2) Contact of catalyst component with promoter Further, 2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was replaced with nitrogen, 200 g of dried salt was added thereto, and the Zr of the catalyst prepared in (2) was 1.6.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After the completion of the polymerization, the mixture was cooled and sodium chloride was removed to obtain 78 g of a white polymer. The amount of transition metal supported is 1
The wt% and MAO / Zr ratio were 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 19 (1) Preparation of transition metal catalyst component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, and then 2.8 g of diisopropoxydichlorozirconium and 11.6 g of indene.
Was added and stirred at room temperature for 30 minutes, 11.6 g of triethylaluminum was added dropwise while maintaining the system at 0 ° C., and after completion of the addition, the system was stirred at room temperature for 2 hours to prepare a transition metal catalyst component (and To). The concentration of this solution is 0.0 as Zr.
57 mmol / ml. Separately 6 in a 50 ml flask
SiO ₂ (manufactured by Fuji Devison Co., Ltd.) baked at 00 ° C. for 5 hours
Grade # 952) 2g was added and further purified toluene 1
0 ml was added. After that, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then, 1.3 ml of the above slurry was placed in another 50 ml flask, and 10 ml of a hexane solution of isobutylaluminoxane was added. (2) Contact of catalyst component with promoter Further, 2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added thereto, and the Zr of the catalyst prepared in (2) was 1.5.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After completion of the polymerization, the mixture was cooled and the sodium chloride was removed to obtain 76 g of a white polymer. The amount of transition metal supported is 1
The wt% and MAO / Zr ratio were 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 20 (1) Preparation of transition metal catalyst component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, and then 3.85 g of tetrabutoxyzirconium and 2.3 g of indene were added and the mixture was kept at room temperature for 30 minutes. After stirring, the system was kept at 0 ° C. and the normal butyl lithium (concentration 2 mol / liter) ether solution 20 m
l was added dropwise, and after the addition was completed, the system was brought to room temperature and stirred for 2 hours to prepare a transition metal catalyst component (referred to as). The concentration of this solution is 0.056 mmol / ml as Zr. Separately, 2 g of SiO ₂ (Fuji Davison Grade # 952) which was baked in a 50 ml flask at 600 ° C. for 5 hours.
Was added, and further 10 ml of purified toluene was added. Thereafter, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour to obtain a catalyst component (assumed to be). Then, 1.3 ml of the above slurry was placed in another 50 ml flask, and 10 ml of a hexane solution of isobutylaluminoxane was added. (2) Contact of catalyst component with promoter Further, 2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L capacity stainless steel autoclave equipped with a stirrer was replaced with nitrogen, 200 g of dried salt was added thereto, and Zr of the catalyst prepared in (2) was 1.7.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After the completion of the polymerization, the mixture was cooled and the sodium chloride was removed to obtain 91 g of a white polymer. The amount of transition metal supported (on silica) was 1 wt% and the MAO / Zr ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Example 21 (1) Preparation of transition metal catalyst component (a) Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then 3.85 g of tetrabutoxyzirconium and 2.3 g of indene were added at room temperature. Stir for 30 minutes below. The concentration of this solution is 0.064 mmol / ml as Zr. (B) S baked in a 50 ml flask at 600 ° C. for 5 hours
₂ g of io ₂ (Fuji Davison grade # 952) was added, and further 10 ml of purified toluene and a toluene solution of methylaluminoxane (concentration 1 mmol / ml) 6 m
1 was added, and the mixture was stirred at room temperature for 2 hours. Then, above (a)
4 ml of the above solution was added and the mixture was stirred at room temperature for 1 hour. (C) 2 ml of the above (b) slurry in a 50 ml flask
Then, 12 ml of a hexane solution of isobutylaluminoxane was added, and 27.
5 mg was added dropwise. (2) Contact of catalyst component with promoter Further, 2.4 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. After that, the solvent was not removed and used as a catalyst. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 1 liter of purified hexane was added thereto, and 1.3 mg of the catalyst Zr was added.
The system was heated to 60 ° C. and ethylene was added at 9 kgf / cm ²
Polymerization is started by adhering to G so that the total pressure is 9 kg.
Polymerization was carried out for 2 hours while maintaining f / cm ² G. After the polymerization was completed, the excess gas was discharged, the contents were cooled and the contents were taken out to obtain 38 g of a white polymer. The amount of transition metal supported was 1.1 wt% and the MAO / Zr ratio was 100. Table 1 shows the results of the polymerization and the physical properties of the obtained polymer.
Described in.

Comparative Example 1 (1) Preparation of Transition Metal Catalyst Component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, then 3.85 g of tetrabutoxyzirconium and 11.6 g of indene were added, and the mixture was kept at room temperature for 30 minutes. After stirring, 11.6 g of triethylaluminum was added dropwise while maintaining the system at 0 ° C., and after completion of the addition, the system was stirred at room temperature for 2 hours to prepare a transition metal catalyst component. The concentration of this solution is 0.056 mmo1 / ml as Zr. Then, 1.3 ml of the above solution was placed in a 50 ml flask, 36 ml of isobutylaluminoxane having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 1 hour. (2) Contact of catalyst component with promoter Then, 7.3 ml of methylaluminoxane solution was added and stirred at room temperature for 2 hours. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, and Zr of the catalyst prepared in (2) was 1.4.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After completion of the polymerization, the mixture was cooled and the sodium chloride was removed to obtain 100 g of a white polymer. The MAO / Zr ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Comparative Example 2 (1) Preparation of catalyst component Under nitrogen, 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and then indene 11.
6 g and 11.6 g of triethylaluminum were added, and the mixture was stirred at room temperature for 30 minutes. Then, 36 ml of isobutylaluminoxane having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 1 hour.
Stir for hours. Then, the methylaluminoxane solution was added.
3 ml was added and the mixture was stirred at room temperature for 2 hours. Separately, 1 g of SiO ₂ (manufactured by Fuji Devison Co., grade # 952) baked at 600 ° C. for 5 hours was added to a 50 ml flask, and further 10 ml of purified toluene was added. Then, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour. (2) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added thereto, 1.3 ml of the catalyst solution prepared in (1) was added, and the mixture was stirred at 60 ° C. Heated to. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After the polymerization was completed, the solution was cooled and the sodium chloride was removed, but no polymer was formed. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Comparative Example 3 (1) Preparation of Transition Metal Catalyst Component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, then 3.85 g of tetrabutoxyzirconium was added, and the mixture was stirred at room temperature for 30 minutes, then 0.
11.6 g of triethylaluminum with the system kept at ℃
Was added dropwise, and after completion of the addition, the system was brought to room temperature and stirred for 2 hours,
A transition metal catalyst component was prepared. The concentration of this solution is 0.060 mmol / ml as Zr. Separately, 2 g of SiO ₂ (manufactured by Fuji Devison, grade # 952) baked at 600 ° C. for 5 hours was added to a 50 ml flask, and further 10 ml of purified toluene was added. Then, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour. Then the above slurry 1.3
Then, ml was placed in another 50 ml flask, 11 ml of a hexane solution of isobutylfluminoxane was added, and the mixture was stirred at room temperature for 1 hour. (2) Contact between catalyst component and promoter Then, a methylaluminoxane solution 2.2 having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L capacity stainless steel autoclave equipped with a stirrer was replaced with nitrogen, 200 g of dried salt was added thereto, and Zr of the catalyst prepared in (2) was 1.7.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After the polymerization was completed, the solution was cooled and the sodium chloride was removed, but no polymer was formed. The amount of transition metal supported was 1.1 wt% and the MAO / Zr ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Comparative Example 4 (1) Preparation of Transition Metal Catalyst Component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, 3.85 g of tetrabutoxyzirconium and 11.6 g of indene were added, and the mixture was kept at room temperature for 2 hours. The mixture was stirred to prepare a transition metal catalyst component. The concentration of this solution is 0.061 mmol / ml as Zr. Separately, SiO ₂ (manufactured by Fuji Devison Co., grade # 952) 2 baked in a 50 ml flask at 600 ° C. for 5 hours
g, and 10 ml of purified toluene was further added. Thereafter, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour to form a slurry. Then add 1.3 ml of the above slurry to another 50 ml
11 ml of a hexane solution of isobutylfluminoxane was added to the flask, and the mixture was stirred at room temperature for 1 hour. (2) Contact of catalyst component with promoter Subsequently, 2.2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, and Zr of the catalyst prepared in (2) was 1.4.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After completion of the polymerization, the mixture was cooled and the sodium chloride was removed to obtain 34 g of a white polymer. The amount of transition metal supported was 1.1 wt% and the MAO / Zr ratio was 100. Table 1 shows the results of the polymerization and the physical properties of the obtained polymer.
Described in.

Comparative Example 5 (1) Preparation of Transition Metal Catalyst Component 150 ml of purified toluene was added to a 300 ml three-necked flask equipped with an electromagnetic induction stirrer under nitrogen, then 3.85 g of tetrabutoxyzirconium and 11.6 g of indene were added, and the mixture was kept at room temperature for 30 minutes. After stirring, 11.6 g of triethylaluminum was added dropwise while maintaining the system at 0 ° C., and after completion of the addition, the system was stirred at room temperature for 2 hours to prepare a transition metal catalyst component. The concentration of this solution is 0.056 mmol / ml as Zr. Separately, SiO ₂ (manufactured by Fuji Devison Co., grade # 952) 2 baked in a 50 ml flask at 600 ° C. for 5 hours
g, and 10 ml of purified toluene was further added. Then, 4 ml of the above solution was sampled and stirred at room temperature for 1 hour. (2) Contact of catalyst component with promoter Subsequently, 1.3 ml of the above slurry was placed in another 50 ml flask, 2 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added, and the mixture was stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added thereto, and the Zr of the catalyst prepared in (2) was 1.5.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After completion of the polymerization, the mixture was cooled and the sodium chloride was removed to obtain 47 g of a white polymer. The amount of transition metal supported is 1
The wt% and MAO / Zr ratio were 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Comparative Example 6 (1) Preparation of Transition Metal Catalyst Component The transition metal catalyst component of Example 1 was used. Si baked in a 50 ml flask at 600 ° C. for 5 hours
1 g of O ₂ (# 952 manufactured by Fuji Devison Co., Ltd.) was added, 10 ml of purified toluene was further added, and the mixture was stirred at room temperature for 2 hours. Then, 2 ml of the above solution was sampled and stirred at room temperature for 1 hour. After that, the solvent was removed to prepare a catalyst (
And). Then, 2 ml of the above slurry was placed in another 50 ml flask, 9.3 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour.
After that, the solvent was removed to prepare a catalyst. (2) Polymerization The same procedure as in Example 1 was performed. The amount of transition metal supported is 2.
0 wt% and the amount of transition metal added were 1.8 mg. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Comparative Example 7 (1) Preparation of transition metal catalyst component SiO ₂ baked in a 50 ml flask at 600 ° C. for 5 hours
(Fuji Davison Grade # 952) 2g,
Further, 11 ml of a solution of zirconocene dichloride (concentration 0.02 mol / liter) dissolved in toluene was added, and the mixture was stirred for 2 hours. Then, 1 ml of the above slurry was placed in another 50 ml flask, 10 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour. (2) Contact of catalyst component with promoter Then, 2.0 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. Then, the solvent was removed to obtain a catalyst. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added, and Zr of the catalyst prepared in (2) was 1.4.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added). Polymerization was carried out for 2 hours while continuously supplying a molar ratio of −1 / ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G. After the completion of the polymerization, the mixture was cooled and the sodium chloride was removed to obtain 18 g of a white polymer. The amount of transition metal supported is 1
The wt% and MAO / Zr ratio were 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

Comparative Example 8 (1) Preparation of Transition Metal Catalyst Component Solution 1 of zirconocene dichloride (concentration 0.02 mol / liter) dissolved in toluene in a 50 ml flask.
10 ml of a hexane solution of isobutylaluminoxane was added, and the mixture was stirred at room temperature for 1 hour. (2) Contact of catalyst component with promoter Then, 2.0 ml of a methylaluminoxane solution having a concentration of 1 mmol / ml was added and stirred at room temperature for 2 hours. (3) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was purged with nitrogen, 200 g of dried salt was added thereto, and the Zr of the catalyst prepared in (2) was 1.5.
mg was added and heated to 60 ° C. with stirring. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio of 0.25) was introduced so as to be 9 kgf / cm ² G to start polymerization, and a mixed gas of ethylene and butene-1 (butene was added. Polymerization was carried out while continuously supplying (1/1 mole ratio of ethylene of 0.05) and maintaining the total pressure at 9 kgf / cm ² G, but a block was formed. The MAO / Zr ratio was 100. The results of the polymerization and the physical properties of the obtained polymer are shown in Table 1.

[0086]

[Table 1]

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[Procedure amendment]

[Submission date] July 20, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a flow chart showing steps for producing a catalyst of the present invention.
Is.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Satoshi Mori 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Nippon Petroleum Co., Ltd. Central Technology Research Institute

Claims (2)

[Claims] (1) An inorganic carrier and / or a particulate polymer carrier, (2) a compound represented by the general formula Me ¹ R ¹ _n X ¹ _4-n (wherein R ¹ has 1 to 24 carbon atoms). Hydrocarbon residue, X ¹ is a halogen atom, Me ¹ is Zr, Ti or Hf,
n is 0 ≦ n ≦ 4. ), (3) A compound represented by the general formula Me ² R ² _m X ² _zm (wherein R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X ² is a halogen atom, and Me ² is a cycle). Table I-III group elements, z
Represents the valence of Me ² , and m is 0 ≦ m ≦ z. ), (4) an organic cyclic compound having two or more conjugated double bonds, and (5) an Al-O-Al bond obtained by reacting an organoaluminum compound with water, and containing at least one aluminum atom. A catalyst component for olefin polymerization obtained by bringing modified organoaluminum compounds having a branched alkyl group bonded to each other. 2. A) (1) an inorganic carrier and / or a particulate polymer carrier, (2) a compound represented by the general formula Me ¹ R ¹ _n X ¹ _4-n (wherein R ¹ has ¹ carbon atom). A hydrocarbon residue of -24, X ¹ is a halogen atom, Me ¹ is Zr, Ti or Hf,
n is 0 ≦ n ≦ 4. ), (3) A compound represented by the general formula Me ² R ² _m X ² _zm (wherein R ² is a hydrocarbon residue having 1 to 24 carbon atoms, X ² is a halogen atom, and Me ² is a cycle). Table I-III group elements, z
Represents the valence of Me ² , and m is 0 ≦ m ≦ z. ), (4) an organic cyclic compound having two or more conjugated double bonds, and (5) an Al-O-Al bond obtained by reacting an organoaluminum compound with water, and containing at least one aluminum atom. A component obtained by bringing modified organoaluminum compounds having a branched alkyl group bonded to each other into contact with each other; and b) a modified organoaluminum compound containing an Al-O-Al bond obtained by reacting an organoaluminum compound with water. A method for producing an olefin polymer, which comprises polymerizing or copolymerizing olefins in the presence of a catalyst.