JP3124087B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method of polymerizing or copolymerizing an olefin in the presence of a specific catalyst to obtain a copolymer having a relatively wide molecular weight distribution, a copolymer having a narrow composition distribution, and having a low molecular weight. The present invention relates to a method for producing a polyolefin having high tackiness and low tackiness.

[0002]

BACKGROUND OF THE INVENTION Polyolefins, especially ethylene polymers or ethylene α-
The use of a catalyst comprising a zirconium compound (typically a metallocene compound) and an aluminoxane in producing an olefin copolymer is disclosed in Japanese Patent Application Laid-Open No. 58-19309.
It is known in Japanese Patent Publication No. Although this technique has an advantage that an ethylene-based copolymer can be produced at a high yield, the copolymer has a drawback that the molecular weight distribution is narrow, the composition distribution is narrow, and the molecular weight is low.

Focusing solely on increasing the molecular weight of the produced polymer, it is possible to increase the molecular weight to some extent by selecting a transition metal compound of metallocene, which is one of the components of the catalyst. For example, JP-A-63-234005 uses a transition metal compound having a 2,3- and 4-substituted cyclopentadienyl group, and JP-A-2-22307 discloses at least two bridged compounds. Proposals have been made to increase the molecular weight of each produced polymer by using a hafnium compound having a ligand bonded to a conjugated cycloalkadienyl group.

[0004] However, the above catalyst components are
The synthesis route is complicated, the operation is complicated, and when hafnium is used as the transition metal species, the yield of the obtained polymer is reduced. Furthermore, the above-mentioned conventional catalyst systems are often soluble in the reaction system, and when used in slurry polymerization and gas phase polymerization, the resulting polymer has a problem that the bulk density is extremely small and the granular properties are inferior. .

[0005]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned drawbacks of the prior art, and as a result, have found that a novel catalyst system having a completely different structure from the conventional catalyst system is used. As a result, they have found that a polyolefin suitable for the intended purpose, that is, a polyolefin having a high molecular weight, a relatively wide molecular weight distribution, a narrow composition distribution, and excellent granular properties can be produced in high yield.

Namely, the manufacturing method of polyolefin according to the present invention, a) (1) General formula ^{_{Me 1 (OR ') p R}} 1 q X 1 compound represented by the _4-pq (wherein, R ¹ and R 'Is a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, Me ¹ is Zr, Ti
Or Hf, p is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4 ,
p + q is 0 ≦ p + q ≦ 4 . ), (2) a compound represented by the general formula Me ² R ² _m X ² _Zm (wherein R
² is a hydrocarbon group having 1 to 24 carbon atoms, X ² is an alkoxy group or a halogen atom having 1 to 12 carbon atoms, Me ² Periodic Table I
Group I and III elements (excluding Al) are shown, z is the valence of Me ² , and m is 0 <m ≦ 3. ), (3) carbon, hydrogen, oxygen, silicon, halo
From the configuration element selected from the group consisting of a plasminogen atom
Becomes, Chi lifting conjugated double bonds two or more carbon atoms constituting the ring
The catalyst component obtained by allowing numbers contacting a 5 or 7 to 24 ring at least one organic <br/> machine cyclic compounds that Yusuke, and (4) to each other inorganic carriers and / or particulate polymer carrier And b) polymerizing or copolymerizing the olefin in the presence of a catalyst consisting of an organoaluminum compound and a modified organoaluminum compound containing an Al-O-Al bond obtained by the reaction of water.

The catalyst used in the process of the present invention has a high activity per transition metal, and the polyolefin obtained has a high molecular weight and a relatively wide molecular weight distribution. In addition, the composition distribution is narrow, the surface tackiness is extremely low, and the bulky density is high, and the uniform particle properties are good.

The catalyst used in the present invention is as described above.
Catalyst components obtained by bringing the components (1) to (4) into contact with each other
And a modified organoaluminum having an Al-O-Al bond
It is composed of a compound, and details thereof are as follows.Catalyst component Component (1) used for preparing the catalyst component has a general formulaMe
¹ (OR ') _p R ¹ _q X ¹ _4-pq It is represented by Where R¹Is
C1-24, preferably 1-12, more preferably 1
~ 8 hydrocarbon residues, including methyl
, Ethyl, propyl, butyl, pentyl,
Hexyl group, alkyl group such as octyl group, vinyl group,
Alkenyl groups such as allyl group, phenyl group, tolyl group,
Aryl group such as xylyl group, benzyl group, phenethyl
Groups, styryl groups, aralkyl groups such as neophyl groups, etc.
Is included.R ′ has 1 to 24 carbon atoms, preferably
1 to 12, more preferably 1 to 8 hydrocarbon residues
Which include methyl, ethyl, propyl
Group, butyl group, pentyl group, hexyl group, octyl group
Any alkenyl such as alkyl, vinyl, allyl
Aryl such as phenyl, tolyl, and xylyl groups
Group, benzyl group, phenethyl group, styryl group, neophyl group
And an aralkyl group such as an aryl group.X¹Is
Halogen atom of iodine, iodine, chlorine and bromine, Me¹Is
It represents Ti, Zr or Hf, and is preferably Zr.
p is 0 ≦ p ≦ 4, q is 0 ≦ q ≦ 4, p + q is 0 ≦ p + q
≦ 4, preferably p + q is 0 <p + q ≦ 4.

Specific examples of the compound which can be used as the component (1) include tetramethyl zirconium, tetraethyl zirconium, tetrapropyl zirconium, and tetrapropyl zirconium.
n-butyl zirconium, tetrapentyl zirconium,
Tetraphenyl zirconium, tetratolyl zirconium, tetrabenzyl zirconium, tetramethoxy zirconium, tetraethoxy zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, tetraphenoxy zirconium, tetratolyloxy zirconium, tetrapentyloxy zirconium, tetrabenzyloxy zirconium, tetraallyl zirconium , Tetraneophylzirconium, trimethylmonochlororhosiliconium, triethylmonochlororhosiliconium, tripropylmonochlororhosiliconium, tri-n-butylmonochlororhosiliconium, tribenzylmonochlororhosiliconium, dimethyldichlorozirconium, diethyldichlorozirconium, din-butyldichlorozirconium, dibenzyldichloro Zirconium, monomethyltrichlorozirconium, monoethyltrichlorozirconium, mono-n-butyltrichlorozirconium, monobenzyltrichlorozirconium, tetrachlorozirconium, trimethoxymonochlorodisilconium,

Dimethoxydichlorozirconium, monomethoxytrichlorozirconium, tetraethoxyzirconium, triethoxymonochlorodisilconium, diethoxydichlorozirconium, monoethoxytrichlorozirconium, tetraisopropoxyzirconium, triisopropoxymonochlororodiconium, diisopropoxydichlorozirconium, monoiso Propoxytrichlorozirconium, tetra-n-butoxyzirconium, tri-n-butoxymonochlorodisilconium, di-n-butoxydichlorozirconium, mono-n-butoxytrichlorozirconium, tetrapentoxyzirconium,. Tripentoxy monochlorodisilconium, dipentoxy dichloro zirconium, monopentoxy trichloro zirconium,
Tetraphenoxyzirconium, triphenoxymonochlororodiconium, diphenoxydichlorozirconium, monophenoxytrichlorozirconium, tetratolyloxylkonium, tolyloxymonochlororhodicirconium, ditolyloxydichlorozirconium, monotolyloxytrichlorozirconium, tetrabenzyloxyzirconium, tribenzyl Oxymonochlorodisilconium, dibenzyloxydichlorozirconium, monobenzyloxytrichlorozirconium,

Trimethyl monobromo zirconium, triethyl monobromo zirconium, tripropyl monobromo zirconium, tri-n-butyl monobromo zirconium, tribenzyl monobromo zirconium, dimethyl dibromo zirconium, diethyl dibromo zirconium,
Di-n-butyl dibromo zirconium, dibenzyl dibromo zirconium, monomethyl tribromo zirconium, monoethyl tribromo zirconium, mono n-butyl tribromo zirconium, monobenzyl tribromo zirconium, tetrabromo zirconium, trimethoxy monobromo zirconium, dimethoxy dibromo zirconium , Monomethoxytribromozirconium, triethoxymonobromozirconium, diethoxydibromozirconium, monoethoxytribromozirconium, triisopropoxymonobromozirconium, diisopropoxydibromozirconium, monoisopropoxytribromozirconium, tri-n-butoxymonobromo zirconium,
Di-n-butoxydibromozirconium, mono-n-butoxytribromozirconium, tripentoxymonobromozirconium, dipentoxydibromozirconium, monopentoxytribromozirconium, triphenoxymonobromozirconium, dienoxydibromozirconium, monophenoxytri Bromozirconium, tolyloxymonobromozirconium, ditolyloxydibromozirconium, monotolyloxytribromozirconium, tribenzyloxymonobromozirconium,
Dibenzyloxydibromozirconium, monobenzyloxytribromozirconium,

Trimethyl monoiodo zirconium, triethyl monoiodo zirconium, tripropyl monoiodo zirconium, tri-n-butyl monoiodo zirconium, tribenzyl monoiodo zirconium, dimethyl diiodo zirconium, diethyl diiodo zirconium,
Di-n-butyl diiodo zirconium, dibenzyl diiodo zirconium, monomethyl triiodo zirconium, monoethyl triiodo zirconium, mono n-butyl triiodo zirconium, monobenzyl triiodo zirconium, tetraiodo zirconium, trimethoxy monoiodo zirconium, dimethoxy Diiodo zirconium, monomethoxytriiodo zirconium, triethoxy monoiodo zirconium, diethoxy diiodo zirconium, monoethoxy triiodo zirconium, triisopropoxy monoiodo zirconium, diisopropoxy diiodo zirconium, monoisopropoxy triiodo zirconium, triiso zirconium zirconium n-butoxymonoiodo,
Di-n-butoxydiiodo zirconium, mono-n-butoxytriiodo zirconium, tripentoxy monoiodo zirconium, dipentoxy diiodo zirconium, monopentoxy triiodo zirconium, triphenoxy monoiodo zirconium, diphenoxy diiodo zirconium, mono Phenoxy triiodo zirconium, tolyloxy monoiodo zirconium, ditolyloxy diiodo zirconium, monotolyloxy triiodo zirconium, tribenzyloxy monoiodo zirconium,
Dibenzyloxydiiodo zirconium, monobenzyloxytriiodo zirconium,

[0013] Tetramethyltitanium, tetraethyltitanium, tetrapropyltitanium, tetran-butyltitanium, tetrapentyltitanium, tetraphenyltitanium, tetratolyltitanium, tetrabenzyltitanium, tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxy Titanium, tetraphenoxytitanium, tetratolyloxytitanium, tetrapentyloxytitanium, tetrabenzyloxytitanium, tetraallyl titanium, tetraneofil titanium, trimethyl monochlorotitanium, triethyl monochlorotitanium, tripropyl monochlorotitanium, tri-n-butyl monochlorotitanium, Tribenzyl monochlorotitanium, dimethyl Dichlorotitanium, diethyldichlorotitanium, di-n-butyldichlorotitanium, dibenzyldichlorotitanium, monomethyltrichlorotitanium, monoethyltrichlorotitanium, monon-butyltrichlorotitanium, monobenzyltrichlorotitanium, tetramethoxytitanium, trimethoxymonochlorotitanium, dimethoxy Dichlorotitanium, monomethoxytrichlorotitanium, tetraethoxytitanium, triethoxymonochlorotitanium, diethoxydichlorotitanium, monoethoxytrichlorotitanium,

Tetraisopropoxytitanium, triisopropoxymonochlorotitanium, diisopropoxydichlorotitanium, monoisopropoxytrichlorotitanium, tetra-n-butoxytitanium, tri-n-butoxymonochlorotitanium, di-n-butoxydichlorotitanium, mono-n-butoxy Trichlorotitanium, tetrapentoxytitanium, tripentoxymonochlorotitanium, dipentoxydichlorotitanium, monopentoxytrichlorotitanium, tetraphenoxytitanium, triphenoxymonochlorotitanium, diphenoxydichlorotitanium, monophenoxytrichlorotitanium, tetratolyloxytitanium, Tolyloxyl monochlorotitanium, ditolyloxydichlorotitanium, monotolyl Carboxymethyl trichloro titanium, tetra-benzyloxy titanium, tri-benzyloxy-monochloro titanium, di-benzyloxy dichlorotitanium, mono benzyloxy trichlorotitanium, trimethyl monobromo titanium, triethyl monobromo titanium, tripropylamine monobromo titanium, tri -n
-Butyl monobromotitanium, tribenzylmonobromotitanium, dimethyldibromotitanium, diethyldibromotitanium, di-n-butyldibromotitanium,
Dibenzyldibromotitanium, monomethyltribromotitanium, monoethyltribromotitanium, mono-n-
Butyltribromotitanium, monobenzyltribromotitanium, tetrabromotitanium, trimethoxymonobromotitanium, dimethoxydibromotitanium,
Monomethoxytribromotitanium,

Triethoxymonobromotitanium, diethoxydibromotitanium, monoethoxytribromotitanium, triisopropoxymonobromotitanium,
Diisopropoxydibromotitanium, monoisopropoxytribromotitanium, tri-n-butoxymonobromotitanium, di-n-butoxydibromotitanium, mono-n-
Butoxytribromotitanium, tripentoxymonobromotitanium, dipentoxydibromotitanium, monopentoxytribromotitanium, triphenoxymonobromotitanium, diphenoxydibromotitanium, monophenoxytribromotitanium, tritolyloxymonobromotitanium, Tolyloxydibromotitanium, monotolyloxytribromotitanium,
Tribenzyloxymonobromotitanium, dibenzyloxydibromotitanium, monobenzyloxytribromotitanium, trimethylmonoiodotitanium, triethylmonoiodotitanium, tripropylmonoiodotitanium, tri-n-butylmonoiodotitanium,
Triberesyl monoiodo titanium, dimethyl diiodo titanium, diethyl diiodo titanium, di-n-butyl diiodo titanium, dibenzyl diiodo titanium,
Monomethyltriiodotitanium, monoethyltriiodotitanium, mono-n-butyltriiodotitanium, monobenzyltriiodotitanium, tetraiodotitanium, trimethoxymonoiodotitanium,

Dimethoxydiiodotitanium, monomethoxytriiodotitanium, triethoxymonoiodotitanium, diethoxydiiodotitanium, monoethoxytriiodotitanium, triisopropoxymonoiodotitanium, diisopropoxydiioditanium,
Monoisopropoxy triiodo titanium, tri n-butoxy monoiodo titanium, di n-butoxy diiodo titanium, mono n-butoxy triiodo titanium, tripentoxy monoiodo titanium, dipentoxy diiodo titanium, monopentoxy triiodine Titanium, triphenoxy monoiodo titanium, diphenoxy diiodo titanium, monophenoxy triiodo titanium, tolyloxy monoiodo titanium, ditolyloxy diiodo titanium, monotolyloxy triiodo titanium, tribenzyloxy monoiodo titanium, dibenzyl Oxydiiodo titanium, monobenzyloxytetramethyl hafnium, tetraethyl hafnium, tetrapropyl hafnium, tetra n-butyl hafnium, tetrapentyl Funium, tetraphenylhafnium, tetratolylhafnium, tetrabenzylhafnium, tetramethoxyhafnium, tetraethoxyhafnium, tetrapropoxyhafnium, tetrabucitriiodotitanium, toxichafnium, tetraphenoxyhafnium, tetratolyloxyhafnium, tetrapentyloxyhafnium, tetra Benzyloxyhafnium, tetraallylhafnium, tetraneophylhafnium,

Trimethylmonochlorohafnium, triethylmonochlorohafnium, tripropylmonochlorohafnium, trin-butylmonochlorohafnium, tribenzylmonochlorohafnium, dimethyldichlorohafnium, diethyldichlorohafnium, din-butyldichlorohafnium, dibenzyldichlorohafnium, monomethyltrichlorohafnium Hafnium, monoethyltrichlorohafnium, mono-n-butyltrichlorohafnium, monobenzyltrichlorohafnium, tetramethoxyhafnium, trimethoxymonochlorohafnium, dimethoxydichlorohafnium, monomethoxytrichlorohafnium, tetraethoxyhafnium, triethoxymonochlorohafnium, diethoxydichlorohafnium , Monoethoxytrichlorohafni Arm, tetraisopropoxy hafnium, triisopropoxy monochlorosilane hafnium,
Diisopropoxydichlorohafnium, monoisopropoxytrichlorohafnium, tetra-n-butoxyhafnium, tri-n-butoxymonochlorohafnium, di-n-butoxydichlorohafnium, mono-n-butoxytrichlorohafnium, tetrapentoxyhafnium, tripentoxymonochlorohafnium, Dipentoxydichlorohafnium, monopentoxytrichlorohafnium, tetraphenoxyhafnium, triphenoxymonochlorohafnium, diphenoxydichlorohafnium, monophenoxytrichlorohafnium,

Tetratolyloxyhafnium, tolyloxymonochlorohafnium, ditolyloxydichlorohafnium, monotolyloxytrichlorohafnium, tetrabenzyloxyhafnium, tribenzyloxymonochlorohafnium, dibenzyloxydichlorohafnium, monobenzyloxytrichlorohafnium, trimethyl Monobromohafnium, triethylmonobromohafnium, tripropylmonobromohafnium, tri-n-butylmonobromohafnium, triberezyl monobromohafnium, dimethyldibromohafnium, diethyldibromohafnium, di-n-butyldibromohafnium, dibenzyldibromohafnium , Monomethyltribromohafnium, monoethyltribromohafnium, mono-n-butyltribro Hafnium, monobenzyltribromohafnium, tetrabromohafnium, trimethoxymonobromohafnium, dimethoxydibromohafnium, monomethoxytribromohafnium, triethoxymonobromohafnium, diethoxydibromohafnium, monoethoxytribromohafnium, triisopropoxymonobromo Hafnium, diisopropoxydibromohafnium, monoisopropoxytribromohafnium, tri-n-butoxymonobromohafnium, di-n-
Butoxydibromohafnium, mono-n-butoxytribromohafnium, tripentoxymonobromohafnium,
Dipentoxydibromohafnium, monopentoxytribromohafnium, triphenoxymonobromohafnium, dienoxydibromohafnium, monophenoxytribromohafnium, tolyloxymonobromohafnium, ditolyloxydibromohafnium, monotolyloxytribromohafnium , Tribenzyloxymonobromohafnium,

Dibenzyloxydibromohafnium, monobenzyloxytribromohafnium, trimethylmonoiodohafnium, triethylmonoiodohafnium, tripropylmonoiodohafnium, tri-n-butylmonoiodohafnium, tribenzylmonoiodohafnium, dimethyldiiodo Hafnium, diethyldiiodohafnium, di-n-butyldiiodohafnium, dibenzyldiiodohafnium, monomethyltriiodohafnium, monoethyltriiodohafnium, mono-n-butyltriiodohafnium, monobenzyltriiodohafnium, tetraiodohafnium, Trimethoxymonoiodohafnium, Dimethoxydiiodohafnium, Monomethoxytriiodohafnium, Triethoxymonoiodohafnium, Diethoxy Diiodo hafnium, monoethoxy triiodo hafnium, triisopropoxy mono iodo hafnium, diisopropoxy di-iodo hafnium, mono-isopropoxy-triiodo hafnium, tri n-
Butoxymonoiodohafnium, di-n-butoxydiiodohafnium, monon-butoxytriiodohafnium, tripentoxymonoiodohafnium, dipentoxydiiodohafnium, monopentoxytriiodohafnium, triphenoxymonoiodohafnium, dienoki Sidiiodohafnium, monophenoxytriiodohafnium, tolyloxymonoiodohafnium, ditolyloxydiiodohafnium, monotolyloxytriiodohafnium, tribenzyloxymonoiodohafnium, dibenzyloxydiiodohafnium, monobenzyloxytriiodo And hafnium. Among them, tetramethyl zirconium, tetraethyl zirconium, tetrabenzyl zirconium, tetrapropoxy zirconium, tetrabutoxy zirconium, and tetrachloro zirconium are preferable, and two or more kinds can be used in combination.

The component (2) is represented by the general formula Me ² R ² _m X ² _{Z -m} . In the formula, R ² has 1 to 24 carbon atoms, preferably 1 to 12,
More preferably, they represent 1 to 8 hydrocarbon groups, and examples of such hydrocarbon groups include methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, decyl, and dodecyl. And alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as benzyl group, phenethyl group and styryl group. X ² has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms.
Or a halogen atom of fluorine, iodine, chlorine and bromine. When X ² is an alkoxy group, examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Me
² represents a group II or III element (excluding Al) of the periodic table, and z
Is the valence of Me ² , and m is a number in the range of 0 <m ≦ 3.

Compounds usable as component (2)
Is di-methyl magnesium, diethyl magnesium, di-n- propyl magnesium, magnesium diisopropyl, di-n- butyl magnesium, di-t- butyl magnesium, dipentyl magnesium, methyl magnesium chloride, isopropyl magnesium chloride, n-
Propyl magnesium chloride, n-butyl magnesium chloride, t-butyl magnesium 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, isopropyl magnesium bromide, isopropyl magnesium iodide, n-propyl magnesium bromide, n - propyl magnesium iodide, n- butyl magnesium bromide, n- butylmagnesium iodide, pentyl magnesium bromide, pentyl magnesium iodide, octyl magnesium bromide, Ok Ji Le magnesium iodide, phenyl magnesium bromide, phenyl magnesium iodide Benzyl magnesium bromide, benzyl magnesium iodide, dimethyl zinc, diethyl zinc, di-n-propyl zinc, diisopropyl zinc, di-n-butyl zinc, di-t-butyl zinc, dipentyl zinc, dioctyl zinc, diphenyl zinc, dibenzyl zinc, trimethyl boron , Triethyl boron, tri n
-Propyl boron, triisopropyl boron, tri n-
Preferred examples include butyl boron, tri-t-butyl boron, tripentyl boron, trioctyl boron, triphenyl boron, tribenzyl boron and the like.

Component (3) includes a carbon atom, a hydrogen atom, oxygen
From the group consisting of atoms, silicon atoms and halogen atoms
Consists construction element selected, the conjugated double bonds at least two <br/> lifting Chi, the ring number of carbon atoms constituting the ring is 5 or 7 to 24
An organic cyclic compound having at least one is used. Such organic cyclic compounds have 4 to 2 carbon atoms per molecule.
4, preferably 4 to 12, and includes a cyclic hydrocarbon compound having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds.
~ 24 aralkylene, cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene,
This includes substituted fluorene, cycloheptatriene, substituted cycloheptatriene, cyclooctatetraene, substituted cyclooctatetraene, and the like. The substituent of each of the above-mentioned substituted compounds may be, for example, an alkyl group having 1 to 12 carbon atoms, an aralkyl group or the like.

Accordingly, specific compounds of component (3) include cyclopentadiene, methylcyclopentadiene,
Ethylcyclopentadiene, t-butylcyclopentadiene, hexylcyclopentadiene, octylcyclopentadiene, 1,2-dimethylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, 1,2,3, 4-tetramethylcyclopentadiene,
Pentamethylcyclopentadiene, indene, 4-methyl
-1- indene, 4,7-dimethylindene, 4,5,6,7-tetrahydroindene, fluorene, methylfluorene, cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, methylcyclooctatetraene, etc. No.

In addition, a compound in which any one of the above compounds is bonded via an alkylene group (the number of carbon atoms of which is usually 2 to 8, preferably 2 to 3) can also be used when preparing the catalyst component of the present invention. Can be used as component (3) of
Specific examples of such compounds include, for example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3-propanedinylbisindene,
3-propanedinyl bis (4,5,6,7-tetrahydro) indene, propylene bis (1-indene), isopropyl (1-indenyl) cyclopentadiene, diphenylmethylene (9-fluorenyl) cyclopentadiene, isopropylcyclopentadiene Enyl-1-fluorene and the like.

[0025] Further, as components of the present invention (3), the general formula (Cp) a compound represented by ^{_{r SiR 3 s X 3 4-}} rs can also be used. In the formula, Cp represents a cyclopendienyl group, and R ³ represents a hydrocarbon group having 1 to 24, preferably 1 to 12 carbon atoms. Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group, a tolyl group, and a xylyl group. And aralkyl groups such as a benzyl group, a phenethyl group, a styryl group, and a neophyl group. X ³ represents a halogen atom of fluorine, iodine, chlorine and bromine, and r and s are numbers in the range of 0 <r ≦ 4 and 0 ≦ s ≦ 3.

[0026] To illustrate the general formula ^{_{(Cp) r SiR 3 s X}} 3 compound represented by _4-rs, monocyclopentadienyl silane, dicyclopentadienyl silane, tri cyclopentadienyl silane, tetra cyclopentadiene Enylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclopentadienyldimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane, monocyclopentadienyltriethyl Silane, monocyclopentadienyl monomethoxysilane, monocyclopentadienyl monoethoxysilane, monocyclopentadienyl monophenoxysilane, monocyclopentadienyl monomethyl monochlorosilane, monocyclopentadienyl monoethylmo Nochlorosilane, monocyclopentadienyl monomethyldichlorosilane, monocyclopentadienyl monoethyldichlorosilane, monocyclopentadienyltrichlorosilane, dicyclopentadienyldimethylsilane, dicyclopentadienyldiethylsilane, dicyclopentadi Enylmethylethylsilane,

Dicyclopentadienyldipropylsilane, dicyclopentadienylethylpropylsilane, dicyclopentadienyldiphenylsilane, dicyclopentadienylmethylphenylsilane, dicyclopentadienylmethylchlorosilane, dicyclopentadisilane Enylethylchlorosilane, dicyclopentadienyldichlorosilane, dicyclopentadienylmonomethoxysilane, dicyclopentadienylmonoethoxysilane, dicyclopentadienylmonomethoxymonochlorosilane, dicyclopentadienylmonoethoxymonochlorosilane, Tricyclopentadienylmonomethylsilane, tricyclopentadienylmonoethylsilane, tricyclopentadienylmonomethoxysilane, tricyclopentadienylmonoethoxysilane, Such as cyclopentadienyl monochloro silane.

Furthermore, as the component of the present invention (3), the general formula ^{_{(Ind) t SiR 4 u X}} 4 compounds represented by _^4-tu can be used. Wherein Ind represents an indenyl group, R
⁴ represents a hydrogen atom or a hydrocarbon group having 1 to 24, preferably 1 to 12 carbon atoms. Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and an octyl group, an alkenyl group such as a vinyl group and an allyl group, a phenyl group, a tolyl group, and a xylyl group. And aralkyl groups such as a benzyl group, a phenethyl group, a styryl group, and a neophyl group. X ⁴ represents a halogen atom of fluorine, iodine, chlorine and bromine, and t and u are 0 <t ≦ 4, 0 ≦ u
It is a number in the range of ≦ 3.

[0029] To illustrate the general formula ^{_{(Ind) t SiR 4 u X}} 4 specific compounds represented by the _^4-tu, mono indenyl silane, di indenyl silane, tri indenyl silane, tetra indenyl silane, Monoinde Nylmonomethylsilane, monoindenylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyltrimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, mono Indenylmonophenoxysilane, monoindenylmonomethylmonochlorosilane, monoindenylmonoethylmonochlorosilane, monoindenylmonomethyldichlorosilane, monoindenylmonoethyldichlorosilane, monoindenyltrichlorosilane,

Bisindenyldimethylsilane, bisindenyldiethylsilane, bisindenylmethylethylsilane, bisindenyldipropylsilane, bisindenyldiphenylsilane, bisindenylmethylphenylsilane, bisindenylmethylchlorosilane, bisindenylmethylsilane Nilethylchlorosilane, bisindenyldichlorosilane, bisindenylmonomethoxysilane, bisindenylmonoethoxysilane, bisindenylmonomethoxymonochlorosilane, bisindenylmonoethoxymonochlorosilane, triindenylmonomethylsilane, triindenylmono Ethyl silane, triindenyl monomethoxy silane, triindenyl monoethoxy silane, triindenyl monochlorosilane, etc.

As the component (4) of the present invention, an inorganic carrier and / or a particulate polymer carrier is used. In the inorganic carrier, in the stage of preparing the catalyst of the present invention, as long as the original shape is maintained, powdery, granular, flake,
Any shape such as a foil shape or a fibrous shape may be used, but the maximum length is usually 5 to 200 μm regardless of the shape.
m, preferably in the range of 10 to 100 μm. Further, the inorganic carrier is preferably porous,
Normally, the surface area of 50~1000 m ² / g, a pore volume of 0.05
It is in the range of 3 cm ³ . As the inorganic carrier of the present invention, carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof can be used.
It is used by firing at 0 to 900 ° C in air or in an inert gas such as nitrogen or argon.

Suitable metals that can be used for the inorganic carrier include, for example, iron, aluminium, nickel and the like. In addition, as metal oxides, Periodic Tables I to VI
Group II single or double oxides, for example, S
iO ₂ , Al ₂ O ₃ , MgO, CaO, B ₂ O ₃ , Ti
O ₂ , ZrO ₂ , Fe ₂ O ₃ , SiO ₂ .Al ₂ O ₃ ,
Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, Al ₂ O ₃
・ MgO ・ CaO, Al ₂ O ₃・ MgO ・ SiO ₂ , A
l ₂ O ₃ .CuO, Al ₂ O ₃ .Fe ₂ O ₃ , Al ₂ O
_3. NiO, SiO ₂ • MgO and the like. It should be noted that the above-described formula expressed by an oxide represents not a molecular formula but a composition only, that is, the structure and component ratio of the double oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may adsorb a small amount of water, or may contain a small amount of impurities.

The metal chloride is preferably, for example, an alkali metal or alkaline earth metal chloride.
MgCl ₂ , CaCl _{2 and the} like are particularly preferred. As the metal carbonate, an alkali metal or an alkaline earth metal carbonate is preferable.Specifically, magnesium carbonate, calcium carbonate,
Barium carbonate and the like can be mentioned. Examples of the carbonaceous material include carbon black and activated carbon. Although any of the above inorganic carriers can be suitably used in the present invention, the use of metal oxides is particularly preferred.

On the other hand, as the particle polymer carrier, any of a thermoplastic resin and a thermosetting resin can be used as long as they maintain a solid state without melting or the like at the time of catalyst preparation and polymerization reaction. The particle size is usually 5 to 2000 μm, preferably 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 at the time of polymerization reaction, from low molecular weight to ultrahigh molecular weight. Can be used arbitrarily.
Specifically, a particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer,
Various polyolefins (preferably having 2 to 12 carbon atoms) represented by poly 1-butene, polyester, polyamide, polyvinyl chloride, polymethyl methacrylate, polymethyl methacrylate, polystyrene, polynorbornene, and various natural Polymers and mixtures thereof can be used as polymer carriers.

The above-mentioned inorganic carrier and particulate polymer carrier can of course be used as they are as component (4) of the present invention, but as a pretreatment, these carriers are treated with trimethylaluminum, triethylaluminum, triisobutylaluminum, -Such as organoaluminum compounds such as hexylaluminum, dimethylaluminum chloride, diethylaluminum chloride, diethylmonoethoxyaluminum, modified organoaluminum compounds containing Al-O-Al bonds (this compound will be described later), or silane compounds. After the contact treatment, it can be used as the component (4).
Further speaking of inorganic carriers, this is alcohol,
An active hydrogen-containing compound such as an aldehyde, an electron-donating compound such as an ester or an ether, an alkoxide group-containing compound such as a tetraalkoxysilicate, a tetraalkoxyaluminum, or a transition metal tetraalkoxide. The method used is also preferably used.

As the contact treatment method, an aromatic hydrocarbon (generally having 6 to 12 carbon atoms) such as benzene, toluene, xylene, ethylbenzene, heptane, hexane, decane, or the like is generally used in an inert atmosphere such as nitrogen or argon. A method in which a carrier is contacted with a compound for pretreatment under stirring or non-stirring in the presence of a liquid inert hydrocarbon such as an aliphatic or alicyclic hydrocarbon (generally having 5 to 12 carbon atoms) such as dodecane and cyclohexane. Is mentioned. This contact is carried out 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. This contact reaction is preferably carried out in a solvent in which the above-mentioned compound for pretreatment is soluble, that is, in an aromatic hydrocarbon (usually having 6 to 12 carbon atoms) such as benzene, toluene, xylene and ethylbenzene. In this case, after the contact reaction, the solvent can be directly used for preparing the catalyst component of the present invention without removing the solvent. Further, a liquid inert hydrocarbon in which the pretreatment compound is insoluble or hardly soluble in the contact reaction product (for example, when the pretreatment compound is a modified organoaluminum compound, pentane, hexane, decane, dodecane, cyclohexane Such as an aliphatic or alicyclic hydrocarbon), and the component (4) is precipitated as a solid component and dried, or a part or all of the aromatic hydrocarbon which is a solvent solvent at the time of the pretreatment is added. After removal by a means such as drying, the component (4) can be taken out as a solid component.

The ratio between the inorganic carrier and / or the particulate polymer carrier to be subjected to the pretreatment and the pretreatment compound is not particularly limited as long as the object of the present invention is not impaired.
Usually, it is selected within a range of 1 to 10,000 mmol, preferably 5 to 1500 mmol (Al atom concentration in a modified aluminum compound) per 100 g of the carrier.

As described above, the catalyst component used in the present invention is prepared by bringing components (1) to (4) into contact with each other, but the order of contact of these components is not particularly limited. Absent. Therefore, as the contact method of the above (1) to (4), (A) a method of simultaneously contacting the components (1) to (4), (B) a method of simultaneously contacting the components (1) to (3), and then ( (4) Method of contacting (C) Contacting components (2) to (4) at the same time, and then contacting (1) (D) Contacting components (1), (3) and (4) simultaneously, Incidentally
Method of contacting (2) (E) Contact components (1), (2) and (4) simultaneously, and then
(3) Method of contacting (3) (F) Contact components (1) and (2) first, and then
Method of contacting component (4) after contacting (3) (G) Contacting components (1) and (2) first, then component
Method of contacting component (3) after contacting (4) (H) Contact components (1) and (3) first, then
Method of contacting component (4) after contacting (2) (I) Contacting components (1) and (3) first, then component
(4) Contacting component (2) after contacting (4) (J) Contacting components (1) and (4) first, then component
Method of contacting component (3) after contacting (2) (K) Contact components (1) and (4) first, and then
(3) Method of contacting component (2) after contacting (3) (L) Contact components (2) and (3) first, and then
(1) Contacting component (4) after contacting (1) (M) Contacting components (2) and (3) first, then component
(4) Method of contacting component (1) after contacting (N) (N) Contact components (2) and (4) first, then
(1) Contacting component (3) after contacting (1) (O) Contact components (2) and (4) first, then
Method of contacting component (1) after contacting (3) (P) Contact components (3) and (4) first, then
Method of contacting component (2) after contacting (1) (Q) Contact components (3) and (4) first, then
(2) Contacting component (1) after contacting (2) (R) Contact components (1) and (4) first, then
(2) Contacting component (3) after contacting (2) (S) Contact components (1) and (4) first, then
(3) and then contacting the component (2). Of these, the methods (A), (B), (F), (H) and (I) are preferred.

The method of contacting these four components is not particularly limited, but is generally an aromatic hydrocarbon such as benzene, toluene, xylene and ethylbenzene (generally having 6 to 6 carbon atoms) in an inert atmosphere such as nitrogen or argon. 12), aliphatic or alicyclic hydrocarbons such as heptane, hexane, decane, dodecane and cyclohexane (normally having 5 to 5 carbon atoms)
A method of contacting each component with or without stirring in the presence of a liquid inert hydrocarbon such as 12) is employed. This contact is usually performed at -100 ° C to 200 ° C, preferably at -50 ° C to 100 ° C.
At a temperature of 30 minutes to 50 hours, preferably 1 hour to 24 hours. When a particulate polymer carrier is used as the component (4), it is a matter of course that the contact reaction is carried out under the condition that the polymer is kept substantially solid.

When the components (1) to (4) are brought into contact, as described above, an aromatic hydrocarbon solvent in which certain components are soluble
Any of insoluble or hardly soluble aliphatic or alicyclic hydrocarbon solvents can be used.
It is desirable to use an aromatic hydrocarbon in which (1) to (3) are soluble as a solvent. Then, when the contact reaction between the components is performed stepwise, without removing the soluble aromatic hydrocarbon solvent used in the previous step at all, it may be used as it is in the solvent for the subsequent contact reaction. Good. In addition, after the previous contact reaction using a soluble solvent, a liquid inert hydrocarbon in which certain components are insoluble or hardly soluble (for example, aliphatic or alicyclic hydrocarbons such as pentane, hexane, decane, dodecane, and cyclohexane) ) To collect the desired product as a solid, or after once removing a desired product as a solid by removing some or all of the aromatic hydrocarbon solvent by drying or the like, The subsequent catalytic reaction of this desired product can also be carried out using any of the above-mentioned inert hydrocarbon solvents.
In the present invention, the contact reaction of each component is not prevented from being performed a plurality of times.

After the components are brought into contact in an inert hydrocarbon solvent, the components can be directly used for polymerization without removing the solvent, and the catalyst component of the present invention can be converted from the contact reaction product by an appropriate means. After being taken out as a solid, it can be subjected to polymerization. Component (1) to component (4) of the present invention is used in an amount of component (2) per mole of component (1), usually 0.0.
Component (3) is generally used in an amount of from 0.01 to 100 mol, preferably from 0.1 to 10 mol, more preferably from 1 to 5 mol, in the range of from 1 to 100 mol, preferably from 0.1 to 10 mol, more preferably from 1 to 10 mol.
It is desirable to select in a molar ratio, and the component (4) 100
g, component (1) is usually 0.01 to
It is desirable to use 500 mmol, preferably 0.05 to 200 mmol, more preferably 0.1 to 20 mmol. The catalyst component used in the present invention has an atomic ratio of aluminum to transition metal (Me ¹ ) (Al / M
e ¹ ) is usually from 0.1 to 2,000, preferably from 15 to 1,000.

Modified Organoaluminum Compound The modified organoaluminum compound used in the present invention is a reaction product of an organoaluminum compound and water, and contains 1 to 100, preferably 1 to 100 in the molecule.
It contains 50 Al-O-Al bonds. The reaction between the organoaluminum and water is usually performed in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic and aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and xylene can be used, but aliphatic and aromatic hydrocarbons are preferred.

The above-mentioned organoaluminum compound has the general formula R _n AlX _3-n (R is a group having 1 to 18 carbon atoms, preferably 1 to
To X 12 are a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, and an aralkyl group; X represents a hydrogen atom or a halogen atom; and n represents an integer of 1 ≦ n ≦ 3). Preferably, a trialkylaluminum is used. The alkyl group of the trialkylaluminum may be any of a methyl group, an ethyl group, a propyl group, 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. Is particularly preferred.

The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is preferably from 0.25 / 1 to 1.2 / 1, particularly preferably from 0.5 / 1 to 1/1. The reaction temperature is usually -70 to 100C, preferably -20 to 20C.
Range. The reaction time is selected in the range of usually 5 to 24 hours, preferably 10 to 5 hours. As the water required for the reaction, water of crystallization contained in copper sulfate hydrate, aluminum sulfate hydrate and the like can also be used.

According to the present invention, the olefin is polymerized or copolymerized in the presence of the catalyst comprising the above-mentioned catalyst component and the modified organoaluminum compound, but the catalyst component and the modified organoaluminum compound are mixed separately or in advance. And fed into the polymerization reaction system. 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 10.
It is selected to be in the range of 0.000, preferably 5 to 1,000.

The method of the present invention can be applied to the production of various olefin polymers and olefin copolymers. Among them, α-olefins having 2 to 12 carbon atoms, for example, ethylene, propylene, 1-butene , 1-hexene, 4-methylpentene-1, etc., when homopolymerized, ethylene and propylene, ethylene and 1
-Ethylene and carbon number 3-1 such as butene, ethylene and 1-hexene, ethylene and 4-methylpentene-1.
It is suitably used when copolymerizing the α-olefin of No. 2, when copolymerizing propylene with 1-butene, or when copolymerizing ethylene with two or more other α-olefins.

For the purpose of modifying the olefin polymer, a diene compound such as butadiene, 1,4-hexadiene, ethylidene norbornene or dicyclopentadiene may be used as a copolymer component. The method of the invention can be applied.

The comonomer content in the copolymerization can be arbitrarily selected, and ethylene and α having 3 to 12 carbon atoms can be selected.
When the olefin is copolymerized with the olefin, the α-olefin content in the ethylene / α-olefin copolymer is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less. It is desirable to do.

The polymerization reaction can be performed by slurry polymerization, solution polymerization, or gas phase polymerization in the presence of the above-mentioned specific catalyst. In particular, slurry polymerization or gas phase polymerization is preferable, and hexane,
In the presence or absence of an inert hydrocarbon solvent selected from aliphatic hydrocarbons such as heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, olefins Is polymerized. The polymerization conditions at this time are as follows:
℃, preferably 50 ℃ ~ 100 ℃, pressure normal pressure ~ 70 kg /
cm ² G, preferably normal 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 molecular weight can be more effectively adjusted by adding hydrogen to the polymerization reaction system. It can be carried out. Further, the method of the present invention is not limited to a polymerization mode, and can be applied to a multi-stage polymerization mode having two or more stages having different hydrogen concentrations and polymerization temperatures without any trouble.

[0051]

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) Measured based on ASTM D 1238-57T. The density was measured according to ASTM D 1505-68.

Measurement of melting point by differential scanning calorimeter (DSC)
Using a DSC-20 melting point measuring apparatus manufactured by SEIKO ELECTRONICS CORPORATION, a sample (5 mg) is kept at 180 ° C. for 3 minutes, then cooled at 10 ° C./min to 0 ° C., and kept at 0 ° C. for 10 minutes. The melting point was measured by raising the temperature at 10 ° C./min.

The modified organoaluminum compound (methylalumoxane) used in Examples and Comparative Examples was prepared as follows. That is, 13 g of copper sulfate pentahydrate was placed in a 300 ml three-necked flask equipped with an electromagnetic induction stirrer, and suspended in 50 ml of toluene. Then concentration 1mmo
150 ml of a l / ml solution of tolmethylaluminum
Under a temperature condition of ° C., the suspension was dropped into the suspension over 2 hours, and after completion of the dropping, the temperature was raised to 25 ° C., and the reaction was carried out at that temperature for 24 hours. Thereafter, the reaction product was filtered, and toluene in the liquid containing the reaction product was removed to obtain 4 g of white crystalline methylalumoxane.

First, the catalyst components used in each of the examples and comparative examples were prepared as follows.

Catalyst Component A (1) Pretreatment of Component (4) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then calcined at 460 ° C. for 5 hours. SiO ₂ (Grade # 952, manufactured by Fuji Devison Co., Ltd.) Surface area 300m ² / g) 10g
Was added under a nitrogen atmosphere, and 6 ml of a toluene solution of methylalumoxane (concentration: 2.5 mmol / ml) was further added.
After stirring for an hour, the powder was dried by nitrogen blowing to obtain fluid granules. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then tetrahydrogen of ethyl magnesium chloride (EtMgCl) was added. Furan (THF) solution (concentration 2mol / l) 50ml
And 2.2 g of indene were added and cooled to -60 ° C. Another ten
A solution was prepared by adding 50 ml of toluene, 4.2 g of tetrapropoxyzirconium (Zr (OPr) ₄ ) and 0.8 g of indene to a 0c flask, and the solution was added to the above solution over 20 minutes. After completion of the addition, stirring was continued at -60 ° C for 1 hour, then the mixture was gradually warmed with stirring, raised to 20 ° C over 2 hours, and further reacted at 45 ° C for 3 hours with stirring. (3) Preparation of solid catalyst component (component (1) + component (2) + component (3) + component (4)) 10 g of the carrier obtained in the above (1) was placed under a nitrogen atmosphere in a 300 cc three-necked flask. And add 30 ml of a toluene solution of the transition metal catalyst component prepared in (2).
15 ml was added and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was removed under a nitrogen blow and vacuum to obtain 11 g of a solid catalyst component A.

Catalyst component B (1) Pretreatment of component (4) Same as catalyst component A (1). (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then 9.8 g of triethylboron (Et ₃ B). And 2.5 g of cyclopentadiene, and the mixture was cooled to -60 ° C. another
50 ml of toluene, 4.2 g of Zr (OPr) ₄ and 0.84 g of cyclopentadiene were added to a 100 cc flask to prepare a solution. Thereafter, a transition metal catalyst component was prepared in the same manner as in the case of the catalyst component A (2). (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation of (10) 10 g of the carrier obtained in (1) was placed in a 300 cc three-necked flask under a nitrogen atmosphere, and 35 ml of a toluene solution of the transition metal catalyst component prepared in (2) was added.
15 ml was added and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was removed under nitrogen blowing and vacuum to obtain a solid catalyst component B.

Catalyst component C (1) Component (4) SiO ₂ (manufactured by Fuji Devison, Inc.) calcined at 600 ° C. for 5 hours
Grade # 952, surface area 300 m ² / g) 10 g was used for the carrier without pretreatment. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then a THF solution of n-butylmagnesium chloride ( (Concentration 2 mol / l) 25 ml, and cyclopentadiene 1.7 g
And stirred at room temperature for 30 minutes.
A solution in which Zr (OPr) ₄ was dissolved was added over 20 minutes. Thereafter, the reaction was stirred at 45 ° C. for 3 hours. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
10 g of the carrier obtained in (1) above was placed in a 300 cc three-necked flask under a nitrogen atmosphere, and 29 ml of a toluene solution of the transition metal catalyst component prepared in (2) was added.
15 ml was added and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was removed under nitrogen blowing and vacuum to obtain a solid catalyst component C.

Catalyst component D (1) Pretreatment of component (4) In a 400 ml stainless steel pot containing 25 stainless steel balls having a diameter of 1/2 inch, 10 g of anhydrous magnesium chloride and triethoxy aluminum were added. 3.8 g of (Al (OEt) ₃ ) was added, and ball milling was performed at room temperature under a nitrogen atmosphere for 16 hours. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then 15.7 g of diethyl zinc (Et ₂ Zn) was added. And inden 5.
After adding 9 g and stirring at room temperature for 30 minutes, 4.
A solution of 2 g of Zr (OPr) ₄ was added over 20 minutes. Thereafter, the reaction was stirred at 45 ° C. for 3 hours. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation of (10) 10 g of the carrier obtained in (1) above was placed in a 300 cc three-necked flask under a nitrogen atmosphere, and 27 ml of a toluene solution of the transition metal catalyst component prepared in (2) was added.
15 ml was added and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was removed under nitrogen blowing and vacuum to obtain a solid catalyst component D.

Catalyst component E (1) Pretreatment of component (4) Polyethylene powder (linear low density polyethylene MFR 1.0 g / 10 min, bulk density 0.41 g / cc, particle size 500 μm, vacuum-dried at 60 ° C. for 3 hours) Melting point 121 ° C) 10g
Then, a toluene solution of methylalumoxane (concentration 2.5 mmol /
6 ml) was added to sufficiently disperse the mixture, and the mixture was stirred at room temperature for 1 hour and dried by blowing with nitrogen to obtain fluid granules. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 50 ml of EtMgCl THF solution used in step (2) of catalyst component A
Instead of ethyl magnesium bromide (EtMgBr)
A transition metal catalyst component was prepared according to step (2) of catalyst component A, except that 64 ml of a THF solution (concentration: 2 mol / l) was used. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation of (10) 10 g of the carrier obtained in (1) was placed in a 300 cc three-necked flask under a nitrogen atmosphere, and 38 ml of a toluene solution of the transition metal catalyst component prepared in (2) was added.
15 ml was added and the mixture was stirred at room temperature for 2 hours. Thereafter, the solvent was removed under nitrogen blowing and vacuum to obtain a solid catalyst component E.

Catalyst Component F (1) Pretreatment of Component (4) Instead of SiO ₂ used in Step (1) of Catalyst Component A,
The support was pretreated in the same manner as in the step (1) of the catalyst component A, except that 10 g of Al ₂ O ₃ (surface area: 300 m ² / g, average particle size: 60 μm, manufactured by Catalyst Chemical Co.) calcined at 400 ° C. for 5 hours was used. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then a THF solution of ethyl magnesium chloride (concentration: 2) was added. Mol / l) 64 ml and methylcyclopentadiene 4.0
g, and stirred at room temperature for 30 minutes.
g solution of tetrabutoxyzirconium Zr (OnBt) ₄ was added over 20 minutes. Thereafter, the reaction was stirred at 45 ° C. for 3 hours. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation of) The transition metal catalyst component solution prepared in the above (2) is mixed with the carrier obtained in the above (1) so that the Zr carrying amount is 2.1 wt%, and the solid is prepared in the same manner as in the case of the catalyst component A. Catalyst component F was prepared.

Catalyst Component G (1) Pretreatment of Component (4) Instead of the toluene solution of methylalumoxane used in Step (1) of Catalyst Component A, trimethylaluminum (Al
The silica was pretreated according to step (1) of catalyst component A, except that 15 ml of an n-hexane solution (concentration: 1 mmol / ml) of Me ₃ ) was used. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then a solution of ethyl magnesium chloride in THF (concentration: 2) was added. (Mol / l) and 3.4 g of cyclopentadiene were added and stirred at room temperature for 30 minutes, and then a solution of 3.9 tripropoxychlorozirconium (Zr (OPr) ₃ Cl) dissolved in 50 ml of toluene was added over 20 minutes. . Thereafter, the reaction was stirred at 45 ° C. for 3 hours. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation of) The transition metal catalyst component solution prepared in the above (2) was mixed with the carrier obtained in the above (1) such that the Zr carrying amount was 2.0 wt%, and the solid was prepared in the same manner as in the case of the catalyst component A. Catalyst component G was prepared.

Pretreatment of catalyst component H (1) Component (4) Same as step (1) for catalyst component A. (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) 100 ml of purified toluene was added to a 300 cc three-necked flask, and then a THF solution of ethyl magnesium chloride (concentration: 2) was added. (Mol / l) and 6.6 g of bisindenylethane were added, and the mixture was stirred at room temperature for 30 minutes. Then, a solution of tetraethoxyzirconium (Zr (OEt) ₄ ) in 3.5 ml of 50 ml of toluene was added over 20 minutes. . Thereafter, the reaction was stirred at 45 ° C. for 3 hours. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation) The transition metal catalyst component solution prepared in the above (2) was mixed with the carrier obtained in the above (1) so that the Zr carrying amount was 1.9 wt%, and the solid was prepared in the same manner as in the case of the catalyst component A. Catalyst component H was prepared.

Catalyst Component I (1) Pretreatment of Component (4) See Catalyst Component A, Step (1). (2) Preparation of transition metal catalyst component (component (1) + component (2) + component (3)) Biscyclopentadienyldimethylsilane is used instead of bisindenylethane used in step (2) of catalyst component H To
Except that 4.8 g was used. A transition metal catalyst component was prepared in the same manner as in the step (2) for the catalyst component H. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Preparation) The transition metal catalyst component solution prepared in the above (2) was mixed with the carrier obtained in the above (1) so that the Zr carrying amount was 1.9 wt%, and the solid was prepared in the same manner as in the case of the catalyst component A. Catalyst component I was prepared.

Catalyst Components JP (1) Pretreatment of Component (4) See Catalyst Component A, Step (1). (2) Preparation of transition metal catalyst components (component (1) + component (2) + component (3)) Preparation of each transition metal catalyst component having the composition ratio shown in Table 1 using the compound shown in Table 1. did. (3) Solid catalyst component (component (1) + component (2) + component (3) + component (4)
Table 1 shows the solution of each transition metal catalyst component prepared in (2) above.
The catalyst components J to P were prepared in the same manner as the catalyst component A by adding to the carrier obtained in (1) so that the amount of the metal supported became the stated value.

[0065]

[Table 1]

Example 1 A 3-liter stainless steel autoclave equipped with a stirrer was purged with nitrogen, and dried with 200 ml of dried salt.
g, and further add 100 mg of the catalyst component A and a concentration of 1 mmol / ml.
22 ml of methylalumoxane solution
Heated. Then, a mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio 0.25) was charged to 9 kgf / cm ² G to start polymerization, and ethylene and butene-1 were introduced.
-1 while continuously supplying a mixed gas of 1 (butene-1 / ethylene molar ratio 0.05) while maintaining the total pressure at 9 kgf / cm ² G.
Time polymerization was carried out. After completion of the polymerization, excess mixed gas was discharged and cooled, and the content was taken out to obtain 66 g of a white polymer. Table 2 shows the polymerization results and the properties of the produced polymer.

[0067]

[Table 2]

Examples 2 to 16 Polymerization was carried out in the same manner as in Example 1 under the conditions described in Table 1. Table 2 shows the polymerization results and the properties of the produced polymer. Example 17 Ethylene homopolymerization was carried out under the same conditions as in Example 1 except that ethylene was used instead of the mixed gas of ethylene and butene-1 and the catalysts shown in Table 1 were used. Table 2 shows the polymerization results and the properties of the produced polymer.

Example 18 Propylene was used in place of a mixed gas of ethylene and butene-1 and propylene was homopolymerized using the catalysts shown in Table 1. However, the polymerization conditions were a polymerization temperature of 50 ° C. and a polymerization temperature of 50 ° C. A pressure of 7 kgf / cm ² G was employed and polymerization was carried out for 1 hour. Table 2 shows the polymerization results and the properties of the produced polymer.

Comparative Examples 1-3 Polymerization was carried out in the same manner as in Example 1 under the conditions described in Table 1.
Table 2 shows the polymerization results and the properties of the produced polymer.

[0071]

According to the production method of the present invention, the polyolefin obtained has a high molecular weight and a relatively wide molecular weight distribution, and particularly in the case of a copolymer, the composition distribution is narrow and the granular properties are excellent such as a high bulk density. A polyolefin is obtained. In addition, the catalyst used in the present invention has excellent features such as easy preparation.

[0072]

[Brief description of the drawings]

FIG. 1 is a flowchart showing the preparation process of the catalyst used in the present invention.

────────────────────────────────────────────────── ─── Continuation of front page (56) References JP-A-63-22804 (JP, A) JP-A-3-59007 (JP, A) JP-A-5-17515 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (1)

(57) [Claims] (1) (1) (1) General formula Me ¹ (OR ′) _p R ¹ _q X ¹
A compound represented by _4-pq (wherein R ¹ and R ′ are each independently a hydrocarbon residue having 1 to 24 carbon atoms, X ¹ is a halogen atom, Me ¹
Represents Zr, Ti or Hf, p is 0 ≦ p ≦ 4, and q is
0 ≦ q ≦ 4 , and p + q is 0 ≦ p + q ≦ 4 . ), (2) a compound represented by the general formula Me ² R ² _m X ² _Zm (wherein R
² is a hydrocarbon group having 1 to 24 carbon atoms, X ² is an alkoxy group or a halogen atom having 1 to 12 carbon atoms, Me ² Periodic Table I
Group I and III elements (excluding Al) are shown, z is the valence of Me ² , and m is 0 <m ≦ 3. ), (3) carbon, hydrogen, oxygen, silicon, halo
From the configuration element selected from the group consisting of a plasminogen atom
Becomes, Chi lifting conjugated double bonds two or more carbon atoms constituting the ring
The catalyst component obtained by allowing numbers contacting a 5 or 7 to 24 ring at least one organic <br/> machine cyclic compounds that Yusuke, and (4) to each other inorganic carriers and / or particulate polymer carrier And b) a polyolefin characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst comprising an organoaluminum compound and a modified organoaluminum compound containing an Al-O-Al bond obtained by reacting with water. Production method.