JPH08325332A - Ethylene-alpha-olefin copolymer - Google Patents

Abstract

PURPOSE: To obtain the subject copolymer having broad molecular weight distribution, high melt tension, large die-swell ratio, large n-value and excellent processability and useful for blow molding, etc. CONSTITUTION: The subject copolymer is a copolymer of ethylene and a 3-20C α-olefin, having a melt flow rate of 0.01-200g/10min and a density of 0.880-0.960g/cm<3> , exhibiting >=2 dissolution peaks by temperature-increasing dissolution fractionation wherein at least one of the dissolution peak temperature is >=95 deg.C and at least one of the dissolution peak temperature is <=90 deg.C, and having a die-swell ratio of >=1.5, an n-value of >=1.40 and an Mw/Mn ratio of >=5.0 measured by GPC. The copolymer is produced preferably in the presence of a catalyst obtained e.g. by contacting a silicon oxide and/or aluminum oxide with a compound of the formula Me<1> (OR<1> )p R<2> q X<1> 4-p-q (R<1> and R<2> are each a 1-24C hydrocarbon group; X<1> is a halogen or H; Me<1> is Ti, Zr, etc.; (p) and (q) are each 0-4; p+q is 0-4).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ethylene / α-olefin copolymer having a wide molecular weight distribution and excellent processability. More specifically, it is suitable for hollow molding, injection molding, inflation molding, etc., with a wide molecular weight distribution, a large n value, a large melt tension, and a large die ratio.
The present invention relates to an ethylene / α-olefin copolymer having a narrow composition distribution.

[0002]

2. Description of the Related Art Ethylene / α-olefin copolymers are widely used as various molded resin products. Above all, as a resin for hollow molding or inflation molding, it is desired that the resin has a relatively high molecular weight, a high melt tension, and a high die swell ratio. On the other hand, it is desired that the resin for injection molding has a relatively low molecular weight and a large n value. In any of the applications, it is desirable that the composition distribution is narrow because the strength is high.

Conventionally, in order to produce an ethylene / α-olefin copolymer, an olefin polymerization catalyst, which is generally composed of a titanium or vanadium compound and an organic aluminum compound, a so-called Ziegler catalyst has been used. It is possible to obtain ethylene / α-olefin copolymers with large melt tension, large die swell ratio and large n value by selecting polymerization conditions using this catalyst, but narrow composition distribution. No polymer could be obtained. On the other hand, focusing on the composition distribution, a catalyst composed of a zirconium compound and an aluminoxane, a so-called Kaminsky catalyst, has recently been proposed. Using this catalyst, it is possible to obtain an ethylene / α-olefin copolymer having a narrow composition distribution, but at the same time, the molecular weight distribution becomes narrow and the n value becomes small, resulting in a processability defect.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a wide molecular weight distribution, a large melt tension, a large die swell ratio, a large n value, and a narrow composition distribution. As a result of intensive research aimed at providing an α-olefin copolymer, the present invention has been achieved.

[0005]

That is, the present invention is an ethylene-α-olefin copolymer having 3 to 20 carbon atoms, wherein (A) the melt flow rate is 0.01 to 200 g / 1.
0 min (B) density is 0.880 to 0.960 g / cm ³ (C) There are two or more elution peaks measured by the temperature rising elution fractionation method (TREF), and at least one elution peak temperature is 95 ℃ or more and at least one elution peak temperature is in the range of 90 ℃ or less (D) Diesel ratio is 1.5 or more (E) n value is 1.40 or more (F) Mw measured by GPC / Mn is 5.0 or more, and relates to an ethylene / α-olefin copolymer. By using the ethylene / α-olefin copolymer of the present invention, it is possible to obtain a molded product having excellent processability and excellent performance in hollow molding, inflation molding, injection molding and the like.

The present invention will be described in detail below. The ethylene / α-olefin copolymer of the present invention has a melt flow rate (MFR) of 0.01 to 200 g / 10 mi.
n, preferably 0.02 to 100 g / 10 min,
More preferably, it is 0.03 to 50 g / 10 min. The melt flow rate is JIS K-6760.
(190 ° C, 2.16 kg load).

The ethylene / α-olefin copolymer of the present invention has a density of 0.880 to 0.960 g / cm ³ ,
It is preferably 0.890 to 0.950 g / cm ³ , more preferably 0.900 to 0.940 g / cm ^3.
Is. The density was measured with a density gradient tube using the strand obtained during MFR measurement at 190 ° C. under a load of 2.16 kg. The ethylene / α-olefin copolymer of the present invention has two or more elution peaks measured by the temperature rising elution fractionation method (TREF), and at least two of them have elution peak temperatures of 95 ° C or higher and 90 ° C or lower. , Preferably in the range of 100 ° C or higher and 85 ° C or lower. The temperature rising elution fractionation (TREF) measurement was carried out by dissolving the polymer sample in o-dichlorobenzene to 1 mg / ml, cooling it under slow cooling conditions from 140 ° C to 4 ° C / h, and cooling the polymer layer onto the glass beads. To crystallize. After crystallization was completed up to room temperature, the temperature of the mixture was raised at a rate of 1 ° C / min while flowing o-dichlorobenzene at a flow rate of 1 ml / min, and the eluted components were continuously detected by infrared spectroscopy. . The ethylene / α-olefin copolymer of the present invention has a die swell ratio of 1.5 or more, preferably 1.7 or more, more preferably 2.0 or more. The upper limit is not particularly limited, but is usually about 3.0. The die swell ratio is expressed by the ratio of the outer diameter of the extrudate to the orifice diameter when measuring the MFR, using the same device as the MFR. If the die swell ratio is less than 1.5, the moldability of the hollow molding is reduced, and the object of the present invention cannot be achieved. The ethylene / α-olefin copolymer of the present invention has an n value of 1.40 or more, preferably 1.45 or more,
More preferably, it is 1.50 or more. Although the upper limit is not particularly limited, it is usually about 4.0. The n value is 1.
If it is less than 40, the molding processability in blow molding, inflation molding, injection molding and the like will be deteriorated and the object of the present invention cannot be achieved. The n value is 170 ° C using a Shimadzu flow tester (CFT-500).
Various loads are applied to the sample with a diameter of 2.0 ± 0.01 m
m, length 40.0 ± 0.01 mm, extruded from a die, and calculated the shear rate gradient against shear stress by the following formula.
The value. γ _H : Apparent shear rate of 150 kgf / cm ² (sec ^-1 ) γ _L : Apparent shear rate of 150 kgf / cm ² (sec ^-1 ) τ: Apparent shear stress (dyne / cm ² ) Q: Flow value (Ml / sec) P: load (kg) The ethylene / α-olefin copolymer of the present invention is GPC.
The measured Mw / Mn is 5.0 or more, preferably 6.
It is 0 or more, more preferably 7.0 or more. The upper limit is not particularly limited, but is usually about 50. Mw /
If Mn is less than 5.0, the molding processability is lowered and the object of the present invention cannot be achieved.

The production method of the ethylene / α-olefin copolymer of the present invention as described above is not particularly limited,
It can be obtained by any production method, but as a suitable method, it can be produced by copolymerizing ethylene and α-olefin in the presence of the following various catalysts. Catalyst A: (1) silicon oxide and / or aluminum oxide and (2) general formula Me ¹ (OR ¹ ) p R ² q X ¹ 4-pq
(Wherein R ¹ and R ² are independently a hydrocarbon group having 1 to 24 carbon atoms, X ¹ is a halogen atom or a hydrogen atom, and Me ¹ is T.
i, Zr or Hf, p is 0 ≦ p ≦ 4 and q is 0 ≦ q
≤ 4, p + q is 0 ≤ p + q ≤ 4), and then (3) the general formula Me ² (OR ³ ) m R ⁴ n X ² zmn
(Wherein R ³ and R ⁴ are independently a hydrocarbon group having 1 to 24 carbon atoms, X ² is a halogen atom or a hydrogen atom, Me ² is an element of Group I to III of the periodic table, z Is the valence of Me ² , m is 0 ≦ m ≦ z, n is 0 ≦ n ≦ z, and 1 ≦ m + n ≦ z
And (4) a catalyst obtained by contacting a cyclic organic compound having two or more conjugated double bonds and then (5) contacting a modified organoaluminum compound containing an Al-O-Al bond. Catalyst B: A catalyst obtained by catalytically reacting components (2) to (4), then catalytically reacting component (5), and finally contacting component (1) in catalyst A. Catalyst C: A catalyst obtained by catalytically reacting the components (1) and (5) in the catalyst A, and then sequentially catalytically reacting the components (2), (3) and (4).

The silicon oxide used as the component (1) in the present invention is silica or silicon and periodic table I.
~ A complex oxide with at least one other metal of Group VIII. The aluminum oxide used as the component (1) in the present invention is a composite oxide of alumina or aluminum and at least another metal of Group I to VIII of the periodic table. Silicon or Aluminum and Periodic Table I to VI
Al ₂ O ₃ .MgO, Al ₂ O ₃ .CaO, and A are typical of complex oxides with at least one other metal of Group II.
l ₂ O ₃ · SiO ₂ , Al ₂ O ₃ · MgO · CaO, Al ₂ O ₃ ·
MgO · SiO ₂ , Al ₂ O ₃ · CuO, Al ₂ O ₃ · Fe ₂ O
Examples thereof include various natural or synthetic multiple oxides such as ₃ , Al ₂ O ₃ .NiO, and SiO ₂ .MgO. Here, the above formula does not represent a molecular formula but represents only a structure, and the structure and component ratio of the multiple oxide used in the present invention are not particularly limited. In addition, as a matter of course, the silicon oxide used in the present invention and /
Alternatively, the aluminum oxide can be used without any problem even if it absorbs a small amount of water, and even if it contains a small amount of impurities. The properties of these silicon oxides and / or aluminum oxides are not particularly limited as long as the object of the present invention is not impaired, but preferably the particle size is 1 to 200 μm, the pore volume is 0.3 ml / g or more, Silica having a surface area of 50 m ² / g or more is desirable. Before use, it is desirable to perform firing treatment at 200 to 800 ° C. in advance by a conventional method.

The component (2) used in the present invention is as follows:
It is represented by the general formula of. General formula Me ¹ (OR ¹ ) P R ² q X ¹ 4-pq where R ¹ , R ² Individually has 1 to 24 carbon atoms, preferably 1
~ 12, more preferably 1-8 hydrocarbon groups. This
These include methyl, ethyl, propyl and isopropyl groups.
Group, cyclopropyl group, butyl group, isobutyl group, t
ert-butyl group, cyclobutyl group, pentyl group, iso
Pentyl group, neopentyl group, cyclopentyl group, hex
Syl group, isohexyl group, cyclohexyl group, heptyl
Group, alkyl group such as octyl group, vinyl group, allyl group
Such as alkenyl, phenyl, tolyl, xylyl
Group, mesityl group, indenyl group, naphthyl group, etc.
Group, benzyl group, trityl group, phenethyl group, styrene
Ryl group, benzhydryl group, phenylbutyl group, phenyl group
Aralkyl groups such as rupropyl and neophyll
Can be mentioned. These may have branches. Ingredient (1)
Is two or more R ¹ Or R ² If they have carbonized
Hydrogen residues may be the same or different.
Yes. X ¹ Is a halogen source of fluorine, iodine, chlorine or bromine
Child or hydrogen atom, Me ¹ Indicates Zr, Ti or Hf
However, Zr is preferable. p and q are 0 ≦ p
≦ 4, 0 ≦ q ≦ 4, 0 ≦ p + q ≦ 4, preferably 0
<P + q ≦ 4. Compounds that can be used as component (1)
The specific examples of
Traethyl zirconium, tetrapropyl zirconium
System, tetra-n-butylzirconium, tetrapentylzil
Conium, tetraphenylzirconium, tetratolyl
Zirconium, tetrabenzyl zirconium, tetrame
Toxyzirconium, Tetraethoxyzirconium, Te
Trapropoxyzirconium, tetrabutoxyzirconi
Um, tetraphenoxy zirconium, tetratolyl
Xyzirconium, tetrapentyloxyzirconium
, Tetrabenzyloxyzirconium, tetraallyl
Zirconium, tetra neophyll zirconium, trime
Chill monochloro zirconium, triethyl monochloro
Ruconium, tripropyl monochloro zirconium, g
Li-n-butyl monochloro zirconium, tribenzyl mono
Chlorozirconium, dimethyldichlorozirconium,
Diethyldichlorozirconium, di-n-butyldichlorodiene
Ruconium, dibenzyldichlorozirconium, monomer
Tilt trichlorozirconium, monoethyltrichlorodi
Ruconium, mono-n-butyltrichlorozirconium, molybdenum
Nobenzyltrichlorozirconium, tetrachlorozil
Conium, trimethoxy monochloro zirconium, dime
Toxidichlorozirconium, monomethoxytrichloro
Zirconium, tetraethoxyzirconium, trieth
Xymonochloro zirconium, diethoxydichlorozil
Conium, monoethoxytrichlorozirconium, tet
Lysopropoxyzirconium, triisopropoxymo
Nochlorozirconium, diisopropoxydichlorozil
Conium, monoisopropoxytrichlorozirconium
System, tetra-n-butoxy zirconium, tri-n-butoximo
Nochlorozirconium, di-n-butoxydichlorozirconi
Um, mono n-butoxytrichlorozirconium, tetra
Pentoxyzirconium ,. Tripentoxy monochloro
Zirconium, dipentoxydichlorozirconium,
Nopentoxytrichlorozirconium, tetraphenoki
Cizirconium, triphenoxy monochloro zirconium
System, diphenoxydichlorozirconium, monophenoki
Citrichlorozirconium, tetratolyloxylconi
Um, tritolyloxymonochlorozirconium, dito
Ryloxydichlorozirconium, monotolyl oxyto
Lichlorozirconium, tetrabenzyloxyzirconi
Um, tribenzyloxymonochlorozirconium, di
Benzyloxydichlorozirconium, monobenzylo
Xytrichlorozirconium, trimethylmonobromide
Ruconium, triethylmonobromozirconium, tri
Propyl monobromozirconium, tri-n-butyl mono
Bromozirconium, tribenzylmonobromozirconi
Um, dimethyldibromozirconium, diethyldibrom
Mozirconium, di-n-butyldibromozirconium, di
Benzyldibromozirconium, monomethyltribromo
Zirconium, monoethyltribromozirconium,
Non-butyltribromozirconium, monobenzyltri
Bromozirconium, tetrabromozirconium, tri
Methoxymonobromozirconium, dimethoxydibromo
Zirconium, monomethoxytribromozirconium,
Triethoxymonobromozirconium, diethoxydib
Lomozirconium, monoethoxytribromozirconium
System, triisopropoxymonobromozirconium, di
Sopropoxydibromozirconium, monoisopropoxy
Citribromozirconium, tri-n-butoxymonobromo
Zirconium, di-n-butoxydibromozirconium, molybdenum
Non-butoxytribromozirconium, tripentoxy
Monobromozirconium, dipentoxydibromozirco
Ni, monopentoxytribromozirconium, tri
Phenoxymonobromozirconium, diphenoxydib
Lomozirconium, monophenoxytribromozirconi
Um, tritolyloxymonobromozirconium, dito
Ryloxydibromozirconium, monotolyl oxyto
Libromozirconium, tribenzyloxymonobromo
Zirconium, dibenzyloxydibromozirconium
System, monobenzyloxytribromozirconium, tri
Methyl monoiodo zirconium, triethyl monoiodo
Zirconium, tripropyl monoiodo zirconium,
Tri-n-butyl monoiodozirconium, tribenzyl
Monoiodozirconium, dimethyldiiodozirconium
Zirconium, diethyldiiodozirconium, di-n-butyldiio
Zirconium, dibenzyldiiodozirconium,
Nomethyltriiodozirconium, monoethyltriio
Dozirconium, mono n-butyl triiodo zirconium
Aluminum, monobenzyl triiodozirconium, tetrayo
Dozirconium, trimethoxy monoiodo zirconium
Zirconium, dimethoxydiiodozirconium, monomethoxide
Liiodozirconium, triethoxymonoiodozirco
Ni, diethoxydiiodozirconium, monoethoki
Citriiodozirconium, triisopropoxymonoyo
Zirconium dioxide, diisopropoxydiiodozirconi
Um, monoisopropoxytriiodozirconium,
Li-n-butoxy monoiodozirconium, di-n-butoxide
Iodozirconium, mono-n-butoxytriiodozirco
Nitrogen, tripentoxy monoiodo zirconium, dipe
Tonoxydiiodozirconium, monopentoxytolyo
Zirconium, triphenoxymonoiodozirconi
Um, diphenoxydiiodozirconium, monopheno
Xytriiodozirconium, tritolyloxymonoyo
Zirconium, ditolyloxydiiodozirconium
Zirconium, monotolyloxytriiodozirconium, tribe
Zirconyloxymonoiodozirconium, dibenzyloxy
Sidiiodozirconium, monobenzyloxytriio
Dozirconium, tribenzyl monomethoxy zirconium
System, tribenzyl monoethoxy zirconium, triben
Zirl monopropoxy zirconium, tribenzyl monobu
Toxyzirconium, tribenzylmonophenoxydil
Conium, dibenzyldimethoxyzirconium, diben
Zirdiethoxyzirconium, dibenzyldipropoxy
Zirconium, dibenzyldibutoxy zirconium, di
Benzyl diphenoxy zirconium, monobenzyl tri
Methoxyzirconium, monobenzyltriethoxyzil
Conium, monobenzyltripropoxyzirconium,
Monobenzyl tributoxy zirconium, monobenzyl
Triphenoxyzirconium, Trineofil Monometh
Xyzirconium, Trineofil monoethoxy zirco
Titanium, trineophile monopropoxy zirconium,
Trineofil monobutoxy zirconium, trineoff
Ilmonophenoxyzirconium, Dineofildimeth
Xyzirconium, Dineofildiethoxyzirconium
Gum, Dineofildipropoxyzirconium, Dineoff
Zirdibutoxy zirconium, Dineofil diphenoki
Zirconium, mononeophile trimethoxyzirconi
Um, mono neophyll triethoxy zirconium, mono
Neofil tripropoxy zirconium, mononeofi
Rutributoxy zirconium, mononeophile trife
Noxyzirconium, tetramethyltitanium, tetra
Ethyl titanium, tetrapropyl titanium, tetra
n-butyltitanium, tetrapentyltitanium, tet
Laphenyl titanium, tetratolyl titanium, tet
Rabenzyl Titanium, Tetramethoxy Titanium, Te
Traethoxytitanium, tetrapropoxytitanium
System, tetrabutoxytitanium, tetraphenoxytita
Titanium, tetratolyloxytitanium, tetrapenti
Luoxytitanium, tetrabenzyloxytitanium
, Tetraallyl titanium, tetra neophyll titani
Um, trimethyl monochlorotitanium, triethyl moth
Nochlorotitanium, tripropyl monochlorotitanium
System, tri-n-butyl monochlorotitanium, tribenzyl
Monochlorotitanium, dimethyldichlorotitanium,
Diethyldichlorotitanium, di-n-butyldichlorotitanium
, Dibenzyldichlorotitanium, monomethylt
Lichlorotitanium, monoethyltrichlorotitanium
System, mono-n-butyltrichlorotitanium, monobenzyl
Trichlorotitanium, tetramethoxytitanium,
Remethoxy monochlorotitanium, dimethoxydichloro
Titanium, monomethoxytrichlorotitanium, tet
Laethoxytitanium, triethoxymonochlorotani
Um, diethoxydichlorotitanium, monoethoxide
Lichlorotitanium, tetraisopropoxytitanium
System, triisopropoxy monochlorotitanium, diiso
Propoxydichlorotitanium, monoisopropoxide
Lichlorotitanium, tetra-n-butoxytitanium, g
Li-n-butoxy monochlorotitanium, di-n-butoxide
Lolotitanium, mono n-butoxytrichlorotitanium
System, tetrapentoxytitanium, tripentoxymono
Chlorotitanium, dipentoxydichlorotitanium,
Monopentoxytrichlorotitanium, tetraphenoki
Titanium, triphenoxymonochlorotitanium,
Diphenoxydichlorotitanium, monophenoxytri
Chlorotitanium, tetratolyloxytitanium,
Litolyloxy monochlorotitanium, ditolyloxy
Dichlorotitanium, monotolyloxytrichlorotita
Titanium, tetrabenzyloxytitanium, tribenz
Luoxy monochlorotitanium, dibenzyloxydi
Lolotitanium, monobenzyloxytrichlorotitani
Um, trimethylmonobromotitanium, triethylmo
Nobromotitanium, tripropylmonobromotitanium
System, tri-n-butylmonobromotitanium, tribenz
Rumonobromotitanium, dimethyldibromotitanium
System, diethyldibromotitanium, di-n-butyldibromo
Titanium, dibenzyldibromotitanium, monometh
Lutribromotitanium, monoethyltribromotitanium
Um, mono-n-butyltribromotitanium, monobenz
Rutribromotitanium, tetrabromotitanium,
Limethoxymonobromotitanium, dimethoxydibromo
Titanium, monomethoxytribromotitanium, tri
Ethoxymonobromotitanium, diethoxydibromotitanium
Titanium, monoethoxytribromotitanium, triy
Sopropoxy monobromotitanium, diisopropoxy
Dibromotitanium, monoisopropoxytribromoti
Titanium, tri-n-butoxymonobromotitanium, di-n-
Butoxydibromotitanium, mono-n-butoxytribro
Motitanium, tripentoxymonobromotitanium,
Dipentoxydibromotitanium, monopentoxytri
Bromotitanium, triphenoxymonobromotitanium
Diphenoxydibromotitanium, monophenoxy
Tribromotitanium, tritolyloxymonobromoti
Titanium, ditolyloxydibromotitanium, monoto
Ryloxytribromotitanium, tribenzyloxy
Monobromotitanium, dibenzyloxydibromotita
Titanium, monobenzyloxytribromotitanium,
Limethyl monoiodo titanium, triethyl monoiodo
Titanium, tripropyl monoiodo titanium, tri
-n-butyl monoiodo titanium, triberezyl monoyo
Titanium, dimethyldiiodotitanium, diet
Rudioioditanium, di-n-butyldiiodotitanium
Mu, dibenzyldiiodo titanium, monomethyl triio
Titanium, monoethyltriiodotitanium, molybdenum
Non-butyl triiodo titanium, monobenzyl triio
Titanium, Tetraiodotitanium, Trimethoki
Simonoiodo Titanium, Dimethoxydiiodo Titanium
System, monomethoxytriioditanium, triethoxy
Monoiodotitanium, diethoxydiiodotitanium
System, monoethoxytriiodotitanium, triisopro
Poxymonoiodotitanium, diisopropoxydiyo
Dotitanium, monoisopropoxytriiodotitanium
Tri-n-butoxymonoiodotitanium, Di-n-butoki
Sidiiodo titanium, mono n-butoxytriiodo titanium
Nium, tripentoxy monoiodotitanium, dipen
Toxidiiodotitanium, Monopentoxytriiodine
Titanium, triphenoxymonoiodotitanium, di
Phenoxydiiodo titanium, monophenoxytriyo
Titanium, tritolyloxymonoiodotitanium
Mu, ditolyloxydiiodotitanium, monotriluo
Xytriiodotitanium, tribenzyloxymonoyo
Detitanium, dibenzyloxydiiododotitanium
System, monobenzyloxytriiodotitanium, tribe
Benzyl monomethoxytitanium, tribenzyl monoeth
Xytitanium, tribenzyl monopropoxytitanium
System, tribenzyl monobutoxytitanium, tribenz
Lumonophenoxytitanium, dibenzyldimethoxyti
Titanium, dibenzyldiethoxytitanium, dibenz
Rudipropoxytitanium, dibenzyldibutoxytita
Ni, dibenzyldiphenoxytitanium, monoben
Diltrimethoxytitanium, monobenzyltriethoxide
Citanium, monobenzyl tripropoxy titanium
System, monobenzyltributoxytitanium, monobenz
Lutriphenoxytitanium, Trineophyll Monometh
Xytitanium, trineophyll monoethoxy titanium
Trineophile monopropoxy titanium, Trine
Ofilmono Butoxy Titanium, Trineofil Mono
Phenoxy titanium, Dineofil dimethoxy titani
Um, dineofil diethoxytitanium, dineophyll
Rudipropoxytitanium, Dineofildibutoxide
Tanium, Dineofil diphenoxytitanium, Mono
Neofil trimethoxy titanium, mono neofilt
Liethoxytitanium, mononeophyl tripropoxy
Titanium, mononeophyl tributoxytitanium,
Mononeophyl triphenoxy titanium, tetramethy
Ruhafnium, tetraethylhafnium, tetrapropy
Ruhafnium, tetra-n-butylhafnium, tetrapene
Cylhafnium, tetraphenylhafnium, tetrato
Lilhafnium, tetrabenzylhafnium, tetrame
Toxihafnium, tetraethoxyhafnium, tetra
Propoxy hafnium, tetrabucitriiodo titanium
, Toxyhafnium, tetraphenoxyhafnium,
Tetratolyloxy hafnium, tetrapentyloxy
Hafnium, tetrabenzyloxy hafnium, tetra
Allyl hafnium, tetra neophyll hafnium, tri
Methyl monochloro hafnium, triethyl monochloro ha
Funnium, tripropyl monochlorohafnium, tri-n-
Butyl monochlorohafnium, tribenzyl monochloro
Hafnium, dimethyldichlorohafnium, diethyldi
Chlorohafnium, di-n-butyldichlorohafnium, di
Benzyldichlorohafnium, monomethyltrichloroha
Funnium, monoethyltrichlorohafnium, mono n-bu
Titritrichlorohafnium, monobenzyltrichloroha
Funnium, tetramethoxy hafnium, trimethoxymo
Nochlorohafnium, dimethoxydichlorohafnium,
Monomethoxytrichlorohafnium, tetraethoxy ha
Funnium, triethoxy monochlorohafnium, diet
Xydichlorohafnium, monoethoxytrichlorohaf
Nium, tetraisopropoxy hafnium, triisop
Ropoxy monochlorohafnium, diisopropoxydioxy
Lolohafnium, monoisopropoxytrichlorohafni
Um, tetra-n-butoxy hafnium, tri-n-butoximo
Nochlorohafnium, di-n-butoxydichlorohafnium
System, mono-n-butoxytrichlorohafnium, tetrapene
Toxihafnium, tripentoxy monochlorohafuniu
, Dipentoxydichlorohafnium, monopentoxy
Trichlorohafnium, tetraphenoxy hafnium,
Triphenoxy monochlorohafnium, diphenoxydi
Chlorohafnium, monophenoxytrichlorohafnium
Haemnium, tetratolyloxy hafnium, tritolyloxy
Monochlorohafnium, ditolyloxydichlorohafni
Um, monotolyloxytrichlorohafnium, tetra
Benzyloxy hafnium, tribenzyloxy monoc
Lolohafnium, dibenzyloxydichlorohafuniu
System, monobenzyloxytrichlorohafnium, trime
Cylmonobromohafnium, triethylmonobromohaf
, Tripropylmonobromohafnium, tri-n-
Butyl monobromohafnium, tribenzyl monobromo
Hafnium, dimethyldibromohafnium, diethyldi
Bromohafnium, di-n-butyldibromohafnium, di
Benzyl dibromo hafnium, monomethyl tribromo ha
Funnium, monoethyltribromohafnium, mono n-bu
Titritribromohafnium, monobenzyltribromoha
Hunium, tetrabromohafnium, trimethoxymono
Bromohafnium, dimethoxydibromohafnium, mo
Nomethoxytribromohafnium, triethoxymonobu
Lomohafnium, diethoxydibromohafnium, mono
Ethoxytribromohafnium, triisopropoxymo
Nobromohafnium, diisopropoxydibromohafni
Um, monoisopropoxytribromohafnium, tri
n-Butoxymonobromohafnium, di-n-butoxydibroth
Mohafnium, mono n-butoxytribromohafnium,
Tripentoxy monobromohafnium, dipentoxydi
Bromohafnium, monopentoxytribromohafnium
, Triphenoxymonobromohafnium, Dienoxy
Dibromohafnium, monophenoxytribromohafni
Um, tritolyloxymonobromohafnium, ditri
Luoxydibromohafnium, monotolyloxytrib
Lomohafnium, tribenzyloxymonobromohafni
Um, dibenzyloxydibromohafnium, monoben
Ziroxytribromohafnium, trimethylmonoio
Dohafnium, triethylmonoiodohafnium, tri
Propyl monoiodohafnium, tri-n-butyl monoyo
Hafnium, tribenzylmonoiodohafnium,
Dimethyldiiodohafnium, Diethyldiiodohafni
Um, di-n-butyldiiodohafnium, dibenzyldiyo
Hafnium, monomethyltriiodohafnium,
Noethyltriiodohafnium, mono-n-butyltriio
Dohafnium, monobenzyltriiodohafnium, Te
Traiodohafnium, trimethoxymonoiodohafni
Um, dimethoxydiiodohafnium, monomethoxide
Liiodohafnium, triethoxymonoiodohafuniu
, Diethoxydiiodohafnium, monoethoxytri
Iodohafnium, triisopropoxymonoiodohaf
Ni, diisopropoxydiiodohafnium, monoi
Sopropoxytriiodohafnium, tri-n-butoximo
Noiodohafnium, di-n-butoxydiiodohafnium
Mono, n-butoxytriiodohafnium, tripent
Kismonoiodohafnium, dipentoxydiiodohaf
Homonium, monopentoxytriiodohafnium, trif
Enoxymonoiodohafnium, Dienoxydiiodoha
Hunium, monophenoxytriiodohafnium, tri
Trilyloxymonoiodohafnium, ditolyloxydi
Iodohafnium, monotolyloxytriiodohafni
Um, tribenzyloxymonoiodohafnium, jib
Nyloxydiiodohafnium, monobenzyloxy
Triiodohafnium, tribenzyl monomethoxy huff
Ni, tribenzyl monoethoxy hafnium, tribe
Benzyl monopropoxy hafnium, tribenzyl monobu
Toxihafnium, tribenzylmonophenoxyhafni
Um, dibenzyldimethoxyhafnium, dibenzyldi
Ethoxy hafnium, dibenzyl dipropoxy hafnium
Dibenzyldibutoxyhafnium, dibenzyldiph
Enoxy hafnium, monobenzyl trimethoxy hafni
Um, monobenzyltriethoxy hafnium, monoben
Ziltripropoxy hafnium, monobenzyl tributo
Xyhafnium, monobenzyltriphenoxyoxyhafnium
System, trineofil monomethoxy hafnium, trineo
Fill monoethoxy hafnium, Trineofil monop
Ropoxy hafnium, Trineofil monobutoxy haf
Nium, trineophyll monophenoxy hafnium, di
Neofil dimethoxyhafnium, Dineofildieto
Xyhafnium, Dineofildipropoxy Hafuniu
Mu, Dineofil Dibutoxy Hafnium, Dineofil
Diphenoxy hafnium, mononeophyl trimethoxy
Hafnium, mononeophyll triethoxy hafnium,
Mononeophyl tripropoxy hafnium, mononeoff
Filthytoxoxy hafnium, mononeofil trife
Noxy hafnium, zirconium tetrahydride, di
Ruconium Monohydride Trimethoxide, Zirco
Nimonomonohydride Triethoxide, Zirconium
Mumono hydride tripropoxide, zirconium
Monohydride tributoxide, zirconium diha
Idride dimethoxide, zirconium dihydric
Doziethoxide, zirconium dihydride dodipro
Poxide, zirconium dihydride dibutoxia
Z, zirconium trihydride monomethoxide,
Zirconium trihydride monoethoxide, zircon
Konium trihydride monopropoxide, Zirco
Nitritrihydride monobutoxide, Zirconium
Mumono Hydride Trichloride, Zirconium Mono
Hydride tribromide, zirconium monohydrate
Ride triiodide, zirconium monohydrate
Dotrifluoride, zirconium dihydride
Loride, zirconium dihydride dibromide,
Zirconium dihydride diiodide, zirconium
Ummdihydride difluoride, zirconium tri
Hydride Monochloride, Zirconium trihydrate
Ride monobromide, zirconium trihydride
Mono iodide, zirconium trihydride mono
Fluoride, zirconium monohydride trimethy
Le, zirconium monohydride tribenzyl, zircon
Conium monohydride triphenyl, zirconium
Dihydride dimethyl, zirconium dihydride
Dibenzyl, zirconium dihydride diphenyl,
Zirconium trihydride monomethyl, zirconium
Mutrihydride monobenzyl, zirconium triha
Ilide monophenyl, zirconium monohydrate
Dojimetokiside Monochrome Ride, Zirconium Monoha
Hydride Jetoxide Side Monochrome Ride, Zirconiu
Mumono Hydride Dipropoxide Monochrome Ride,
Zirconium monohydride jibtocide monochrome
Ride, zirconium dihydride monomethoxide
Monochrome ride, zirconium dihydride monoeth
Kiside Monochrome Ride, Zirconium Dihydride
Monopropoxide monochloride, zirconium diha
Idride Monobutokiside Monochrome Ride, Zirconi
Ummono hydride dimethoxide monomethyl, dill
Konium Mono Hydride Jetoxide Monovenge
Le, zirconium monohydride dipropoxide
Nophenyl, zirconium dihydride monomethoxa
Idmonomethyl, zirconium dihydride monoeth
Kide monobenzyl, zirconium dihydrido
Nopropoxide monophenyl, zirconium monohigh
Dride Monomethoki Side Monochrome Ride Monovenge
Le, zirconium monohydride monomethoxide
Nochloride monophenyl, zirconium monohydra
Id monomethoxide monochloride monomethyl etc.
is there. Among them, tetramethyl zirconium, tetraethyl
Zirconium, tetrabenzyl zirconium, tetrap
Ropoxy zirconium, tetrabutoxy zirconium, TE
Trachlorozirconium is preferred. These compounds are
It is also possible to use a mixture of two or more kinds.

The component (3) is represented by the following general formula. Formula Me ² in ^{(OR 3) m R 4 n} X 2 zmn formula, Me ² is the Periodic Table I~III group, preferably I~
A group II element is shown, and examples of such an element include lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R
³ and R ⁴ each have 1 to 24 carbon atoms, preferably 1 to 1 carbon atoms
2, more preferably 1 to 8 hydrocarbon groups, and the hydrocarbon residue may be branched or unbranched, or may be a cyclic chain. Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, Alkyl group such as todecyl group, cycloalkyl group, alkenyl group such as vinyl group, allyl group, phenyl group, tolyl group, aryl group such as xylyl group, benzyl group, phenethyl group, styryl group, neofil group, benzhydryl group, phenyl Examples thereof include aralkyl groups such as butyl group and phenylpropyl group. When component (2) has more than one R ³ or R ⁴ , the hydrocarbon residues can be the same or different. X ² is a halogen atom of fluorine, iodine, chlorine and bromine or a hydrogen atom. However, when X ² is a hydrogen atom, Me ² is limited to a group III element of the periodic table exemplified by boron, aluminum and the like. z represents the valence of Me ² , usually z is 1 to 3, m is 0 <m ≦ z, and n is 0 <n ≦ z.
It is a number in the range of 0 <m + n ≦ z. Specific examples of the compound that can be used as the component (3) include methyllithium, ethyllithium, n-propyllithium, isopropyllithium, n-butyllithium, t-butyllithium, pentyllithium, octyllithium, phenyllithium, 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 magnesium chloride, Ethyl 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 , Phenyl mug Nitrosium bromide, phenyl magnesium iodide, benzyl 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, trimethylboron, triethylboron, tri-n-propylboron, triisopropylboron, tri-n-butylboron, tri-t -Butylboron, tripentylboron, trioctylboron, triphenylboron, tribenzylboron, trimethylaluminum, triethylaluminum, diethylaluminium chloride, diethylaluminum bromide, diethylaluminum fluoride, diethylaluminium iodide, ethylaluminum dichloride, ethylaluminium dichloride Bromide, ethyl aluminum difluoride, ethyl aluminum diiodide, tripropiroaluminum, dipropyl al Minium chloride, dipropyl aluminum bromide, dipropyl aluminum fluoride, dipropyl aluminum iodide, propyl aluminum dichloride, propiro 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 sesquichloride, n-butyl aluminum sesquibromide, isopropyl aluminum dichloride, isopropyl aluminum dibromide, isopropyl aluminum difluoride, isopropyl aluminum diiodide, 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 sec-butyl aluminum, di sec-butyl aluminum chloride, Di sec-butyl Aluminum bromide, di
sec-Butyl aluminum fluoride, di-sec-butyl aluminum iodide, sec-butyl aluminum dichloride, sec-butyl aluminum dibromide, sec-
Butyl aluminum difluoride, sec-butyl aluminum diiodide, tri tert-butyl aluminum, di tert-butyl aluminum chloride, di tert-
Butyl aluminum bromide, di-tert-butyl aluminum fluoride, di-tert-butyl aluminum iodide, tert-butyl aluminum dichloride, te
rt-Butyl aluminum dibromide, tert-butyl aluminum difluoride, tert-butyl aluminum diiodide, triisobutyl aluminum, diisobutyl aluminum chloride, diisobutyl aluminum bromide, diisobutyl aluminum fluoride, diisobutyl aluminum iodide, isobutyl aluminum dichloride, isobutyl Aluminum dibromide, isobutyl aluminum difluoride, isobutyl aluminum diiodide, trihexyl aluminum, dihexyl aluminum chloride, dihexyl aluminum bromide, dihexyl aluminum fluoride, 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,
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, tridecyl aluminum, aluminum hydride , Dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisopropyl aluminum hydride, dibutyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, dicyclohexyl aluminum hydride, methyl aluminum dihydride, ethyl aluminium Minium dihydride, propyl aluminum dihydride, isopropyl aluminum dihydride, butyl aluminum dihydride, isobutyl aluminum dihydride, hexyl aluminum dihydride, cyclohexyl aluminum dihydride, borane, dimethylboron hydride, diethylboron hydride, methylboron dihydride, ethylboron dihydrate Examples include hydride and diborane. Among them, trimethylaluminum, triethylaluminum, diethylaluminum chloride, tripropyroaluminum, triisopropylaluminum, tributylaluminum, tri-sec-butylaluminum, tritert-butylaluminum, triisobutylaluminum, trihexylaluminum, tripentylaluminum, diisobutylaluminum hydride, Tridecylaluminum is preferred. Also,
These compounds can be used as a mixture of two or more kinds. And the like.

As the component (4), a cyclic organic compound having two or more conjugated double bonds is used. For example, two or more, preferably 2 to 4, more preferably 2 to 4 conjugated double bonds are used. Have one or two or more rings having three,
A cyclic hydrocarbon compound having a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially 1 to
A cyclic hydrocarbon compound substituted with 6 hydrocarbon groups (typically, an alkyl group having 1 to 12 carbon atoms or an aralkyl group); 2 or more, preferably 2 to 4 conjugated double bonds,
More preferably, an organosilicon compound having a cyclic hydrocarbon group having 1 or 2 or more rings having 2 to 3 and having a total carbon number of 4 to 24, preferably 4 to 12; Also included are organosilicon compounds partially substituted with 1 to 6 hydrocarbon residues; and also alkali metal salts (sodium salts, lithium salts, etc.) of these compounds. Particularly preferably, one having a cyclopentadiene structure in any of the molecules is desirable. A preferable example of the cyclic hydrocarbon compound is a compound represented by the following general formula.

Embedded image In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each hydrogen or a hydrocarbon residue having 1 to 10 carbon atoms, and further R ⁵ , R ⁶ , R ⁷ and R ⁸ are Any two may together form a cyclic hydrocarbon group. As the hydrocarbon residue, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, alkyl group such as octyl group, aryl group such as phenyl group, methoxy group, ethoxy group, As a skeleton of a cyclic hydrocarbon group in the case where an alkoxy group such as a propoxy group, an aryloxy group such as a phenoxy group, an aralkyl group such as a benzyl group, or any two of them jointly form a cyclic hydrocarbon group. Include cycloheptatriene, aryl and condensed rings thereof. As the compound represented by Chemical formula 1, preferred are cyclopentadiene, indene, azulene, or alkyl or aryl of these having 1 to 10 carbon atoms,
Examples thereof include aralkyl, alkoxy or aryloxy substituted derivatives. Further, the compound represented by Chemical formula 1 is an alkylene group (its carbon number is usually 2 to 8, preferably 2 to 3).
A compound bonded (crosslinked) via is also preferably used.

The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula. (Cp) r SiR ¹⁰ _s X ³ _4-rs where Cp represents the cyclohydrocarbon group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R ¹⁰ Is an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, pentyl group, hexyl group, octyl group; alkenyl group such as vinyl group, allyl group; methoxy group, ethoxy group, Alkoxy groups such as propoxy group, butoxy group; aryl groups such as phenyl group, tolyl group, xylyl group; aryloxy groups such as phenoxy group; benzyl group, phenethyl group, styryl group,
As exemplified by an aralkyl group such as a neophyll group,
A hydrocarbon residue having 1 to 24 carbon atoms, preferably 1 to 12 or hydrogen, wherein R ¹⁰ is not only n- but also iso-, s
It also includes the case of various structural isomer groups such as-, t-, and neo-. X3 represents a halogen atom such as fluorine, iodine, chlorine or bromine, and r and s are 1≤r≤.
4, 0 ≦ s ≦ 3, preferably S = 0, and 1 ≦
r + s ≦ 4.

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, substituted fluorene such as methylfluorene, etc. Tajienirushiran, dicyclopentadienyl silane, tri cyclopentadienyl silane,
Tetracyclopentadienylsilane, monocyclopentadienylmonomethylsilane, monocyclopentadienylmonoethylsilane, monocyclopentadienyldimethylsilane, monocyclopentadienyldiethylsilane, monocyclopentadienyltrimethylsilane, monocyclo Pentadienyltriethylsilane, monocyclopentadienylmonomethoxysilane, monocyclopentadienylmonoethoxysilane, monocyclopentadienylmonophenoxysilane, dicyclopentadienylmonomethylsilane, dicyclopentadienylmonoethylsilane, Dicyclopentadienyldimethylsilane, Dicyclopentadienyldiethylsilane, Dicyclopentadienylmethylethylsilane, Dicyclopentadienyldipropylsilane, Dicyclopente Dienylethylpropylsilane, dicyclopentadienyldiphenylsilane, dicyclopentadienylphenylmethylsilane, dicyclopentadienylmonomethoxysilane, dicyclopentadienylmonoethoxysilane, tricyclopentadienylmonomethylsilane, tri Cyclopentadienyl monoethylsilane,
Tricyclopentadienyl monomethoxysilane, tricyclopentadienyl monoethoxysilane, 3-methylcyclopentadienylsilane, bis 3-methylcyclopentadienylsilane, 3-methylcyclopentadienylmethylsilane, 1,2 -Dimethylcyclopentadienylsilane, 1,3-
Dimethylcyclopentadienylsilane, 1,2,4-trimethylcyclopentadienylsilane, 1,2,3,4-tetramethylcyclopentadienylsilane, pentamethylcyclopentadienylsilane, monocyclopentadienylmonomethyl Monochlorosilane, monocyclopentadienyl monoethyl monochlorosilane, monocyclopentadienyl monomethyldichlorosilane, monocyclopentadienyl monoethyldichlorosilane, monocyclopentadienyl trichlorosilane, dicyclopentadienylmethylchlorosilane, dicyclo Pentadienylethylchlorosilane, dicyclopentadienyldichlorosilane, dicyclopentadienyl monomethoxymonochlorosilane, dicyclopentadienylmonoethoxymonochlorosilane, tricyclopentadienylmonoc Rosilane, monoindenylsilane, diindenylsilane, triindenylsilane, tetraindenylsilane, monoindenylmonomethylsilane, monoindenylmonoethylsilane, monoindenyldimethylsilane, monoindenyldiethylsilane, monoindenyl Trimethylsilane, monoindenyltriethylsilane, monoindenylmonomethoxysilane, monoindenylmonoethoxysilane, monoindenylmonophenoxysilane, diindenylmonomethylsilane, diindenylmonoethylsilane, diindenyldimethylsilane, di Indenyldiethylsilane, diindenylmethylethylsilane, diindenyldipropylsilane, diindenylethylpropylsilane, diindenyldiephenylsilane, diindenylphenylmethylsilane , Diindenylmonomethoxysilane, diindenylmonoethoxysilane, triindenylmonomethylsilane, triindenylmonoethylsilane, triindenylmonomethoxysilane, triindenylmonoethoxysilane, 3-methylindenylsilane, bis 3-methylindenylsilane, 3-methylindenylmethylsilane, 1,2-dimethylindenylsilane, 1,3-dimethylindenylsilane, 1,2,4-trimethylindenylsilane, 1,2,3, 4-tetramethylindenylsilane, pentamethylindenylsilane monoindenylmonomethylmonochlorosilane, monoindenylmonoethylmonochlorosilane, monoindenylmonomethyldichlorosilane, monoindenylmonoethyldichlorosilane, monoindenyltrichlorosilane, di Indenyl monomethoxy monochloro Examples include silane, diindenyl monoethoxy monochlorosilane, and triindenyl monochlorosilane.

Any one of the above-mentioned compounds may be an alkylene group (the carbon number of which is usually 2-8, preferably 2
A compound bound via 3) can also be used as the component (3) of the present invention. For example, bisindenylethane, bis (4,5,6,7-tetrahydro-1-indenyl) ethane, 1,3
-Propandinylbisindene, 1,3-Propandinylbis (4,5,6,7-tetrahydro) indene, Propylenebis (1-indene), Isopropyl (1-indenyl) cyclopentadiene, Diphenylmethylene (9-fluorenyl ) Cyclopentadiene, isopropylcyclopentadienyl-1-fluorene and the like are all components of the present invention.
It is a compound that can be used as (4). Among them, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, t-butylcyclopentadiene, 1,3-dimethylcyclopentadiene, 1,2,4-trimethylcyclopentadiene, pentamethylcyclopentadiene, indene,
4-Methyl-1-indene, 4,7-dimethylindene, diindenyldimethylsilane and bisindenylethane are preferred.

A modified organoaluminum compound is used as the component (5) of the present invention. Such compounds include
The molecule contains an Al-O-Al bond, and the number of bonds is usually 1 to 100, preferably 1 to 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 for the preparation of the modified organoaluminum compound has the general formula R ¹¹ _c AlX _3-c (wherein R ¹¹ has 1 carbon atom).
To 18, preferably 1 to 12 hydrocarbon groups such as alkyl groups, alkenyl groups, aryl groups and aralkyl groups, X represents a hydrogen atom or a halogen atom, and c represents an integer of 1 ≦ c ≦ 3). Although any of the above compounds can be used, trialkylaluminum is preferably used. The alkyl group of trialkylaluminum may be any of methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group, etc. Is particularly preferable. The reaction ratio between water and the organoaluminum compound (water / Al molar ratio) was 0.
25/1 to 1.2 / 1, particularly preferably 0.5 / 1 to 1/1, and the reaction temperature is usually -70 to 100 ° C.
It is preferably in the range of -20 to 20 ° C. 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. Among these modified organoaluminum compounds, those obtained by reacting alkylaluminum with water are usually called aluminoxane, and methylaluminoxane (or a substance substantially consisting of methylaluminoxane) is particularly preferable. Of course, in the present invention, 2
Combinations of more than one modified organoaluminum compound can also be used.

In preparing the above-mentioned catalyst, the method of contacting each component is not particularly limited, but usually in an inert atmosphere of nitrogen or argon, generally, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene (usually carbon 6-12), in the presence of liquid inert hydrocarbons such as aliphatic or alicyclic hydrocarbons (usually 5-12) such as heptane, hexane, decane, dodecane, cyclohexane,
A method of contacting each component with or without stirring is adopted. This contact is usually at a temperature of -100 ° C to 200 ° C, preferably -50 ° C to 100 ° C for 30 minutes to 50 ° C.
It is desirable that the time is 1 hour to 24 hours. After the contact reaction, it is desirable to finally remove the solvent to obtain a solid catalyst. The method of removing the solvent is
Usually, it is carried out at a temperature of 20 ° C. to 150 ° C., preferably 30 ° C. to 80 ° C. with nitrogen blowing or reduced pressure.

In the case of catalyst A, the use ratio of the components (1) to (5) of the present invention is such that the component (2) is usually at a transition metal concentration (Me ¹ ) of 0.1 g per 1 g of the component ( ¹ ). 001-5
It is desirable to use it in a proportion of 0 mmol, preferably 0.01 to 5 mmol, and more preferably 0.02 to 0.5. Further, the component (3) is usually added in an amount of 0.01 to 100 mol, preferably 0.1 to 50 mol, and more preferably 1 to 10 mol, relative to 1 mol of the component (2). 4) is usually 0.01 to 1
00 moles, preferably 0.1 to 50 moles, more preferably 1 to 10 moles, component (5) is usually 1 to 10,000, preferably 10
It is desirable to select at a ratio of up to 1,000. Catalyst B
And C, the component (2) is usually added in an amount of 0.001 to 5 ^per 1 g of the component (1) at a transition metal concentration (Me ¹ ).
It is desirable to use it in a proportion of 0 mmol, preferably 0.01 to 5 mmol, and more preferably 0.02 to 0.5. In addition, the amount of the component (3) is usually 0.01 to 6 mol, preferably 0.1 to 4 mol, and more preferably 0.5 to 3 mol based on 1 mol of the component (2).
The amount of the component (4) is usually 0.01 to 4 mol, preferably 0.1 to 3 mol, more preferably 0.5 to
The amount of the component (5) is usually 1 to 10,000, preferably 10 to 1,0 per mol of the component (2) at a ratio of 2 mol.
It is desirable to select the ratio of 00. To obtain the polyolefin of the present invention using the above catalyst, slurry polymerization, solution polymerization or gas phase polymerization can be carried out. Particularly, it can be suitably obtained by gas phase polymerization. That is, all the reactions are carried out in the presence or absence of an inactive hydrocarbon with oxygen and water being substantially cut off. The olefin polymerization conditions are a temperature of 20 to 120 ° C., preferably 50 to 110 ° C., and a pressure of normal pressure to 70 kg.
/ Cm ² , preferably 2 to 60 kg / cm ² . The molecular weight can be adjusted to some extent by changing the polymerization conditions such as the polymerization temperature and the molar ratio of the catalyst, but it is effectively performed by adding hydrogen to the polymerization system. Of course, there is no problem even if two or more different stages of polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature are used. It can be carried out without any problem even if a component for removing water, so-called scavenging, is added to the polymerization system. Examples of such scavenging include organoaluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, the above-mentioned modified organoaluminum compound, and modified organoaluminum containing a branched alkyl. Further, a promoter component may be further added to the polymerization system for polymerization, and the promoter component typically includes the modified organoaluminum compound. Before the main polymerization, the olefins may be contacted with each other in advance to carry out the prepolymerization, and then the prepolymerization catalyst may be used for the main polymerization.

Α used for obtaining the copolymer of the present invention
-The olefin has 3 to 20 carbon atoms, preferably 3 to 1 carbon atoms
2, more preferably 3-8 alpha-olefins are preferred. The α-olefin content in the ethylene / α-olefin copolymer is usually 0.1 to 20 mol%, preferably 0.5 to 10 mol%.

[0020]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but prior to that, preparation of modified organoaluminum compounds used in the Examples and Comparative Examples will be described. <Preparation of modified organoaluminum compound (methylaluminoxane)> 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 toluene 5 was added.
Suspended with 0 ml. Then, 150 ml of a trimethylaluminum solution having a concentration of 1 mmol / ml was added dropwise to the above suspension under the temperature condition of 0 ° C., and 25 ° C. after the addition was completed.
The temperature was raised to, and the reaction was carried out at that temperature for 24 hours. After a while
The reaction product was filtered, and toluene in the liquid containing the reaction product was removed to obtain white crystalline methylalumoxane (MAO) 4
g was obtained.

Example 1 (1) Preparation of solid catalyst To a 300 ml three-necked flask (A) equipped with an electromagnetic induction stirrer, 150 ml of purified toluene and 0.33 g of tetrapropoxyzirconium were added under nitrogen and stirred for 15 minutes to dissolve therein. 25 g of silica (Fuji Davison # 952) was added, and the mixture was stirred at room temperature for 1 hour. 10 with another electromagnetic induction stirrer
20 ml of purified toluene was added to a 0 ml three-necked flask (B) under nitrogen, 10 ml of triisobutylaluminum (TIBA 1 mmol / ml toluene solution) and 1.2 g of indene were added thereto, and the mixture was stirred at room temperature for 1 hour. The three-necked flask (A) was cooled to 0 ° C., and the solution in the three-necked flask (B) was added dropwise thereto over 1 hour.
The temperature was raised to ° C and the reaction was carried out for 2 hours. After cooling to room temperature, a toluene solution of methylaluminoxane (MAO) (concentration 1m
(mol / ml) 100 ml, and the mixture was stirred at room temperature for 30 minutes. After that, toluene was removed by nitrogen blowing at 40 ° C. to obtain a solid catalyst. (2) Polymerization A 3 L stainless steel autoclave equipped with a stirrer was sufficiently dried and then replaced with nitrogen gas. 75
The temperature was raised to 0 ° C and 0.5 ml of a hexane solution of triethylaluminum (1 mmol / ml) was added to remove impurities.
The mixture was added and stirred for 30 minutes. Next, a mixed gas of ethylene and 1-butene (1-butene / ethylene molar ratio = 0.09) was supplied at a gauge pressure up to 7 kgf / cm ² . 150 mg of the above solid catalyst was sampled in a catalyst supply pipe (capacity 1 ml) partitioned by a ball valve attached to the flange of the autoclave, and the ball valve was opened immediately after pressurizing with ethylene of 9.5 kgf / cm ² to the autoclave. Was supplied to initiate polymerization. While continuously feeding the mixed gas of ethylene and butene-1 (butene-1 / ethylene molar ratio = 0.08), while maintaining the total pressure at 9.5Kgf / cm ^{2 2}
Polymerization was carried out for a period of time. After the polymerization was completed, unreacted gas was discharged to obtain 24 g of a white polymer. Catalyst efficiency is 58 Kg / g
It was Zr. The MFR of the obtained polymer was 2.3 g /
10 minutes, density 0.932 g / cm ³ , TREF 9
There were elution peaks at 7 ° C and 82 ° C, the die swell ratio was 2.2, the n value was 1.51, and the Mw / Mn was 5.9. Moreover, this copolymer was excellent in moldability.

Example 2 (1) Preparation of solid catalyst To a 300 ml three-necked flask (A) equipped with an electromagnetic induction stirrer, 150 ml of purified toluene and 0.38 g of tetrabutoxyzirconium were added under nitrogen and stirred for 15 minutes to dissolve therein. 25 g of silica (Fuji Davison # 952) was added, and the mixture was stirred at room temperature for 1 hour. 10 with another electromagnetic induction stirrer
To a 0 ml three-necked flask (B), 20 ml of purified toluene was added under nitrogen, and trihexyl aluminum (T
8 ml of HA 1 mmol / ml toluene solution) and 0.96 g of indene were added, and the mixture was stirred at room temperature for 1 hour. After cooling the three-necked flask (A) to 0 ° C. and dropping the solution in the three-necked flask (B) over 1 hour, 120 ° C.
The temperature was raised to 2, and the reaction was performed for 2 hours. After cooling to room temperature, a toluene solution of methylaluminoxane (MAO) (concentration 1 mm
ol / ml) was added and the mixture was stirred at room temperature for 30 minutes. After that, toluene was removed by nitrogen blowing at 40 ° C. to obtain a solid catalyst. (2) Polymerization Polymerization was performed under the same conditions as in Example 1 using the same polymerization apparatus as in Example 1 to obtain 28 g of a white polymer. The catalyst efficiency was 67 Kg / gZr. MF of the obtained polymer
R is 1.9 g / 10 minutes, density is 0.928 g / cm ³ ,
TREF has elution peaks at 96 ° C and 81 ° C, the die swell ratio is 2.1, and the n value is 1.52, Mw / Mn.
Was 6.0. Moreover, this copolymer was excellent in moldability.

Example 3 (1) Preparation of solid catalyst To a 300 ml three-necked flask (A) equipped with an electromagnetic induction stirrer, 150 ml of purified toluene and 0.82 g of tetrapropoxyzirconium were added under nitrogen and stirred for 15 minutes to dissolve therein. 25 g of silica (Fuji Davison # 952) was added, and the mixture was stirred at room temperature for 1 hour. 10 with another electromagnetic induction stirrer
20 ml of purified toluene was added to a 0 ml three-necked flask (B) under nitrogen, and triethylaluminum (TE) was added thereto.
6 ml of A 1 mmol / ml toluene solution) and 0.5 g of indene were added, and the mixture was stirred at room temperature for 1 hour. Cool the three-necked flask (A) to 0 ° C, and place the three-necked flask (B) there.
The solution in was added dropwise over 1 hour, then heated to 120 ° C. and reacted for 2 hours. After cooling to room temperature, a toluene solution of methylaluminoxane (MAO) (concentration 1 mmol /
250 ml) was added, and the mixture was stirred at room temperature for 30 minutes. After that, toluene was removed by nitrogen blowing at 40 ° C. to obtain a solid catalyst. (2) Polymerization Polymerization was performed under the same conditions as in Example 1 using the same polymerization apparatus as in Example 1 to obtain 21 g of a white polymer. The catalyst efficiency was 50 Kg / gZr. MF of the obtained polymer
R is 2.5 g / 10 min, density is 0.926 g / cm ³ ,
TREF has elution peaks at 97 ° C and 80 ° C, the die swell ratio is 1.8, the n value is 1.48, and the Mw / Mn is
Was 5.6. Moreover, this copolymer was excellent in moldability.

Example 4 (1) Preparation of Solid Catalyst In a 500 ml three-necked flask equipped with an electromagnetic induction stirrer, 50 ml of purified toluene under nitrogen, 1.0 g of tetrabutoxyzirconium, 0.3 g of indene and trihexylaluminum (THA 1 mmol / ml toluene solution) ) 5m
1 was added and the mixture was reacted at 120 ° C. for 2 hours. After cooling to room temperature, 250 ml of a toluene solution of methylaluminoxane (MAO) (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Silica (Fuji Davidson # 95
2) 25 g was added and stirred at room temperature for 1 hour. Then 40 ° C
Toluene was removed by nitrogen blowing to obtain a solid catalyst. (2) Polymerization Polymerization was performed using the same polymerization apparatus as in Example 1 under the same conditions as in Example 1 to obtain 15 g of a white polymer. The catalyst efficiency was 36 Kg / gZr. MF of the obtained polymer
R is 0.5 g / 10 min, density is 0.925 g / cm ³ ,
TREF has elution peaks at 103 ° C, 97 ° C and 80 ° C, the die swell ratio is 2.2, and the n value is 1.53.
Mw / Mn was 7.5. Moreover, this copolymer was excellent in moldability.

Example 5 (1) Preparation of solid catalyst In a 500 ml three-necked flask equipped with an electromagnetic induction stirrer, 50 ml of purified toluene, 1.0 g of tetrabutoxyzirconium, 1.0 g of indene and trihexylaluminum (THA 1 mmol / ml toluene solution) ) 1
2.5 ml was added and reacted at 120 ° C. for 2 hours. After cooling to room temperature, 250 ml of a toluene solution of methylaluminoxane (MAO) (concentration 1 mmol / ml) was added,
The mixture was stirred at room temperature for 30 minutes. Silica there (Fuji Davidson #
952) 25 g was added and the mixture was stirred at room temperature for 1 hour. Then 4
Toluene was removed by nitrogen blowing at 0 ° C to obtain a solid catalyst. (2) Polymerization Polymerization was carried out under the same conditions as in Example 1 using the same polymerization apparatus as in Example 1 to obtain 17 g of white polymer. The catalyst efficiency was 41 Kg / gZr. MF of the obtained polymer
R is 0.8 g / 10 minutes, density is 0.928 g / cm ³ ,
TREF has elution peaks at 104 ° C, 97 ° C and 82 ° C, a die swell ratio of 2.0, an n value of 1.50,
Mw / Mn was 7.1. Moreover, this copolymer was excellent in moldability.

Example 6 (1) Preparation of solid catalyst To a 300 ml three-necked flask (A) equipped with an electromagnetic induction stirrer, 25 g of silica (Fuji Davison # 952) was added under nitrogen, and a toluene solution of methylaluminoxane (concentration: 1 mmol / ml) was added thereto. ) 250 ml was added, and the mixture was stirred at room temperature for 30 minutes. To another 100 ml three-necked flask (B) equipped with an electromagnetic induction stirrer, 20 ml of purified toluene was added under nitrogen, and tetrapropoxyzirconium 0.82 g, indene 0.3 g, triethylaluminum (TEA) 0.6 were added.
g was added, the temperature was raised to 120 ° C., and the reaction was performed for 2 hours. The three-necked flask (A) was cooled to 0 ° C., and the solution in the three-necked flask (B) was added dropwise thereto over 1 hour, and then the mixture was allowed to stand at room temperature for 2 hours.
Allowed to react for hours. After that, toluene was removed by nitrogen blowing at 40 ° C. to obtain a solid catalyst. (2) Polymerization Polymerization was performed under the same conditions as in Example 1 using the same polymerization apparatus as in Example 1 to obtain 16 g of white polymer. The catalyst efficiency was 38 Kg / gZr. MF of the obtained polymer
R is 0.7 g / 10 min, density is 0.925 g / cm ³ ,
TREF has elution peaks at 101 ° C, 96 ° C and 80 ° C, a die swell ratio of 2.0 and an n value of 1.52.
Mw / Mn was 6.8. Moreover, this copolymer was excellent in moldability.

Example 7 (1) Preparation of solid catalyst To a 300 ml three-necked flask (A) equipped with an electromagnetic induction stirrer, 25 g of silica (Fuji Davison # 952) was added under nitrogen, and a toluene solution of methylaluminoxane (concentration: 1 mmol / ml) was added thereto. ) 250 ml was added, and the mixture was stirred at room temperature for 30 minutes. To another 100 ml three-necked flask (B) equipped with an electromagnetic induction stirrer, 20 ml of purified toluene was added under nitrogen, and tetrapropoxyzirconium 0.82 g, indene 0.6 g, triethylaluminum (TEA) 1.1 was added.
g was added, the temperature was raised to 120 ° C., and the reaction was performed for 2 hours. The three-necked flask (A) was cooled to 0 ° C., and the solution in the three-necked flask (B) was added dropwise thereto over 1 hour, and then the mixture was allowed to stand at room temperature for 2 hours.
Allowed to react for hours. After that, toluene was removed by nitrogen blowing at 40 ° C. to obtain a solid catalyst. (2) Polymerization Polymerization was carried out under the same conditions as in Example 1 using the same polymerization apparatus as in Example 1 to obtain 18 g of white polymer. The catalyst efficiency was 43 Kg / gZr. MF of the obtained polymer
R is 1.0 g / 10 min, density is 0.926 g / cm ³ ,
TREF has elution peaks at 100 ° C, 95 ° C and 80 ° C, the die swell ratio is 1.9, the n value is 1.48,
Mw / Mn was 6.5. Moreover, this copolymer was excellent in moldability.

Comparative Example 1 (1) Preparation of Solid Catalyst 50 ml of purified toluene, 0.38 g of tetrabutoxyzirconium, 0.93 g of indene, and trihexylaluminum (THA 1 mmol / ml toluene solution in a 500 ml three-necked flask equipped with an electromagnetic induction stirrer). )
8 ml was added and reacted at 120 ° C. for 2 hours. After cooling to room temperature, 100 ml of a toluene solution of methylaluminoxane (concentration 1 mmol / ml) was added, and the mixture was stirred at room temperature for 30 minutes. Silica (Fuji Davison # 952) 25
g was added and the mixture was stirred at room temperature for 1 hour. After that, toluene was removed by nitrogen blowing at 40 ° C. to obtain a solid catalyst. (2) Polymerization Polymerization was performed under the same conditions as in Example 1 using the same polymerization apparatus as in Example 1 to obtain 31 g of a white polymer. The catalyst efficiency was 74 Kg / gZr. MF of the obtained polymer
R is 3.3 g / 10 min, density is 0.921 g / cm ³ ,
TREF has elution peaks at 94 ° C and 80 ° C, the die swell ratio is 1.2, and the n value is 1.34, Mw / Mn.
Was 3.0.

Claims (1)

[Claims] 1. A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (A) the melt flow rate is 0.01 to 200 g / 1.
0 min (B) density is 0.880 to 0.960 g / cm ³ (C) There are two or more elution peaks measured by the temperature rising elution fractionation method (TREF), and at least one elution peak temperature is 95 ℃ or more and at least one elution peak temperature is in the range of 90 ℃ or less (D) Diesel ratio is 1.5 or more (E) n value is 1.40 or more (F) Mw measured by GPC / Mn is 5.0 or more, ethylene / alpha-olefin copolymer characterized by the above-mentioned.