JP2000186173A - Elastomer composition and cross-linked elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an elastomer composition and a cross-linked elastomer composition obtained by cross-linking the same, containing an α-olefin-conjugated polyene copolymer having <=3.5 molecular weight distribution (Mw/Mn) measured by a gel permeation chromatography(GPC), and excellent in cross-linked physical property caused by a narrow molecular weight distribution of the copolymer to improve a cross-linking density thereof. SOLUTION: This elastomer composition has 0.1-95 mol% conjugated polyene content and contains 100 pts.wt. α-olefin-conjugated polyene copolymer having <=3.5 extent of molecular weight distribution (Mw/Mn) measured by a gel permeation chromatography(GPC), 5-400 pt.wt. inorganic filler and/or carbon black, and 0.1-20 pts.wt. cross-linking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an elastomer composition and a crosslinked elastomer composition obtained by crosslinking the elastomer composition. More specifically,
The present invention has a molecular weight distribution Mw / Mn of 3. measured by gel permeation chromatography (GPC).
An elastomer composition comprising an α-olefin-conjugated polyene copolymer having a molecular weight distribution of 5 or less, and having a characteristic that the molecular weight distribution of the copolymer is narrow, whereby the crosslink density is improved and the physical properties of the crosslink are excellent. And a crosslinked elastomer composition obtained by crosslinking the same.

[0002]

2. Description of the Related Art Heretofore, as an α-olefin-conjugated polyene copolymer or a method for producing the same, there is known a method for producing an α-olefin-conjugated polyene copolymer using a titanium tetrachloride compound (Japanese Patent Publication No. 49-40632). Ya Tokiko 54
No. -10990) and a stereoregular α-olefin-conjugated polyene copolymer using a metallocene catalyst has been reported (Preprints of the Society of Polymer Science in 1998). Further, as a method for producing an olefin-conjugated polyene copolymer using a metallocene catalyst, synthesis of an ethylene-butadiene copolymer (JP-A-9-316118) is known. Further, the cross-linking properties of the propylene-butadiene alternating copolymer are also disclosed (Japanese Rubber Association, Vol. 49, 1976, JP-B-49-46383, JP-B-50-6217).

However, in the prior art, a crosslinkable elastomer composition containing an α-olefin-conjugated polyene copolymer having a narrow molecular weight distribution as an essential component and a crosslinked elastomer composition derived from the composition are known. I didn't.

[0004]

Under such circumstances, the problem to be solved by the present invention is that the molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC) is 3%. An elastomer composition containing an α-olefin-conjugated polyene copolymer having a molecular weight distribution of not more than 0.5 and having a characteristic that the molecular weight distribution of the copolymer is narrow, whereby the crosslink density is improved and the crosslink properties are excellent. The object of the present invention is to provide a crosslinked elastomer composition obtained by crosslinking a product.

[0005]

That is, the first invention of the present invention is characterized in that the content of the conjugated polyene is from 0.1 to 95 mol% and measured by gel permeation chromatography (GPC). 100 parts by weight of an α-olefin-conjugated polyene copolymer having a molecular weight distribution Mw / Mn of 3.5 or less, 5 to 400 parts by weight of an inorganic filler and / or carbon black, and 0.1 to 20 parts by weight of a crosslinking agent The present invention relates to an elastomer composition containing:

A second aspect of the present invention relates to a crosslinked elastomer composition obtained by crosslinking the elastomer composition of the first aspect.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The α-olefin used in the α-olefin-conjugated polyene copolymer of the present invention includes:
Although not particularly limited, a chain having about 3 to 10 carbon atoms can be suitably used. For example, propylene, 1
-Butene, 3-methyl-1-butene, 4-methyl-1-
Examples thereof include pentene, 1-hexene, 1-octene and 1-decene, and propylene and 1-butene are preferable. Further, these α-olefins may be used singly, or a mixture of a plurality of these α-olefins may be used.

The conjugated polyene used in the α-olefin-conjugated polyene copolymer of the present invention includes 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene and 2-propyl-1,3-butadiene. 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene,
2,3-diethyl-1,3-butadiene, 2-methyl-
1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2, 3-dimethyl-1,3-hexadiene, 2,3-dimethyl-1,3-octadiene, 2,3
-Dimethyl-1,3-decadiene, 2-methyl-1,3
-Cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, 2,3-dimethyl-1,3-cyclohexadiene, 2-chloro-1,3-butadiene , 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene, 2-chloro-1,3-cyclopentadiene, 2-chloro-1, 3
-Cyclohexadiene and the like.

Of these, preferably, the conjugated polyene is a hydrocarbon compound such as 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-
1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2,3-
Dimethyl-1,3-butadiene, 2,3-diethyl-
1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-
1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3
-Dimethyl-1,3-hexadiene, 2,3-dimethyl-1,3-octadiene, 2,3-dimethyl-1,3-
Decadiene, 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3
-Dimethyl-1,3-cyclopentadiene, 2,3-dimethyl-1,3-cyclohexadiene and the like are particularly preferable, and is particularly preferably a branched aliphatic conjugated polyene such as isoprene and 2-ethyl-1,3-butadiene. , 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, 2-hexyl-1,3-butadiene, 2,3
-Dimethyl-1,3-butadiene, 2,3-diethyl-
1,3-butadiene, 2-methyl-1,3-pentadiene, 2-methyl-1,3-hexadiene, 2-methyl-
1,3-octadiene, 2-methyl-1,3-decadiene, 2,3-dimethyl-1,3-pentadiene, 2,3
-Dimethyl-1,3-hexadiene, 2,3-dimethyl-1,3-octadiene, 2,3-dimethyl-1,3-
Decadiene and the like are exemplified. Most preferred is isoprene.

The content of the conjugated polyene in the α-olefin-conjugated polyene copolymer of the present invention is from 0.1 to 95 mol%, preferably from 0.3 to 50 mol%. If the conjugated polyene is too low, vulcanization will not be sufficient. On the other hand, when the amount of the conjugated polyene is too large, the molecular weight may be lowered or the ozone resistance may be lowered.

The α-olefin-conjugated polyene copolymer of the present invention has a peak of 1 J / g or more based on melting of a crystal and a peak of 1 J / g or more based on crystallization as measured by a differential scanning calorimeter (DSC). Preferably does not have any of the above peaks. If these conditions are not satisfied, the resulting composition may have poor physical properties, for example, low-temperature properties. The measurement by the differential scanning calorimeter is performed, for example, by using DSC220C manufactured by Seiko Denshi Kogyo Co., Ltd., and the temperature is raised and lowered at a rate of 10 ° C./min.

In the α-olefin-conjugated polyene copolymer of the present invention, the structure based on the α-olefin is preferably an atactic structure. If it has an isotactic or syndiotactic structure, it may have crystallinity and the α-olefin-conjugated polyene copolymer may have poor low-temperature properties.

The α-olefin-conjugated polyene copolymer of the present invention has a molecular weight distribution Mw / Mn of 3. measured by gel permeation chromatography (GPC).
5 or less, more preferably 1.8 to 3.5,
Most preferably, it is 1.8 to 2.5. If the molecular weight distribution is too wide, problems occur in practical physical properties such as compression set and deterioration in tensile rigidity due to non-uniform crosslinked network structure as physical properties of the crosslinked product obtained by the crosslinking reaction. I do. The molecular weight distribution is determined by gel permeation chromatography (GPC) method (for example, Wa
ters, 150C / GPC device). The elution temperature is 140 ° C., and the column used is, for example, Shodex Packed Column A-80 manufactured by Showa Denko KK
M, a polystyrene (for example, a molecular weight of 68-8, 400,000, manufactured by Tosoh Corporation) is used as a molecular weight standard substance. The obtained polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and the ratio (Mw / Mn) are defined as a molecular weight distribution. The measurement sample is about 5mg of polymer 5ml
Dissolved in o-dichlorobenzene at a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected, the elution solvent flow rate was set to 1.0 ml / min,
Detect with a refractive index detector.

The α-olefin-conjugated polyene copolymer of the present invention preferably has an intrinsic viscosity [η] with a xylene solvent at a temperature of 70 ° C. of at least 0.3, more preferably at least 0.5. If the intrinsic viscosity is too low,
The resulting α-olefin-conjugated polyene copolymer may be poor in cross-linking properties and processability. The intrinsic viscosity [η] is measured in xylene at 70 ° C. using an Ubbelohde viscometer. For the sample, 300 mg was dissolved in 100 ml xylene to prepare a 3 mg / ml solution. Then add the solution to 1
/ 2, 1/3 and 1/5, and each was diluted to 70 ° C (±
(0.1 ° C.) in a constant temperature water bath. The measurement is repeated three times at each concentration, and the obtained values are averaged and used.

The α-olefin-conjugated polyene of the present invention
Weight is the following (A), the following (B) and / or the following
(C) in the presence of an olefin polymerization catalyst comprising
Polymerization of α-olefin and conjugated polyene
It can be manufactured appropriately. (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
Or different. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. )

According to the above-mentioned production method, the amount of the catalyst residue mixed in the polymer is small, and the chlorine content is remarkably reduced as compared with the case where the conventional Ziegler-Natta catalyst is used. This means that the discoloration of the polymer is suppressed, and the effect of expanding the use of the polymer to foods and the like is also exerted.

Hereinafter, the above manufacturing method will be described in more detail.

(A) The transition metal complex will be described.

The transition metal complex (A) has the general formula [I] or [I
I] or [III].

In the general formulas [I], [II] and [III], the transition metal atom represented by M ¹ is a transition of Group 4 of the periodic table of elements (IUPAC revised edition of inorganic chemical nomenclature 1989). A metal element, for example, a titanium atom, a zirconium atom, a hafnium atom, etc. Preferably it is a titanium atom or a zirconium atom.

The atom of Group 16 of the periodic table of the element represented by A in the general formulas [I], [II] and [III] includes, for example, an oxygen atom, a sulfur atom, a selenium atom and the like. Is an oxygen atom.

In the general formulas [I], [II] and [III], examples of atoms belonging to Group 14 of the periodic table of the element represented by J include a carbon atom, a silicon atom, and a germanium atom. Is a carbon atom or a silicon atom.

Examples of the group having a cyclopentadiene-type anion skeleton represented by the substituent Cp ¹ include, for example, η
⁵ - (substituted) cyclopentadienyl group, eta ⁵ - (substituted) indenyl group, eta ⁵ - and the like (substituted) fluorenyl group. Specific examples include, for example, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵
- dimethyl cyclopentadienyl group, eta ⁵ - trimethyl cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - Echirushikuro Bae Ntajieniru group, eta ^5-n-propyl cyclopentadienyl group, eta ⁵ −
Isopropyl cyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group, eta ^{5-sec-butylcyclopentadienyl} group, eta ^{5-tert-Buchirushikuro} Bae Ntajieniru group, eta ^{5-n-Penchirushikuro} Bae Ntajieniru Group, η ⁵ -neopentylcyclopentadienyl group,
η ⁵ -n-hexylcyclopentadienyl group, η ⁵ -n-
Octylcyclopropane Bae Ntajieniru group, eta ⁵ - phenyl cycloalkyl Bae Ntajieniru group, eta ⁵ - Nafuchirushikuro Bae Ntajieniru group, eta ⁵ - trimethylsilylcyclopentadienyl Bae Ntajieniru group, eta ⁵ - triethylsilyl cycloalkyl Bae Ntajieniru group,
eta ^{5-tert-butyldimethylsilyl} cycloalkyl Bae Ntajieniru group, eta ⁵ - indenyl group, eta ⁵ - methylindenyl group, eta ⁵ - dimethyl indenyl group, eta ⁵ - ethyl indenyl group, eta ^5-n-propyl indenyl Nyl group, η ⁵ -isopropylindenyl group, η ⁵ -n-butylindenyl group, η ⁵
-Sec-butylindenyl group,? ⁵ -tert-butylindenyl group,? ^5- n-pentylindenyl group,? ⁵
-Neopentylindenyl group,? ^5- n-hexylindenyl group,? ^5- n-octylindenyl group,? ^5- n-
Decylindenyl group, η ⁵ -phenylindenyl group, η ⁵
-Methylphenylindenyl group,? ⁵ -naphthylindenyl group,? ⁵ -trimethylsilylindenyl group,? ⁵ -triethylsilylindenyl group,? ⁵ -tert-butyldimethylsilylindenyl group,? ⁵ -tetrahydroindenyl group, eta ⁵ - fluorenyl group, eta ⁵ - methyl fluorenyl group, eta ⁵ - dimethyl fluorenyl group, eta ⁵ - ethyl fluorenyl group, eta ⁵ - diethyl fluorenyl group, eta ⁵ -n
-Propylfluorenyl group,? ⁵ -di-n-propylfluorenyl group,? ⁵ -isopropylfluorenyl group,? ⁵
- diisopropyl fluorenyl group, eta ^{5-n-butyl-fluorenyl} group, eta ^{5-sec-butylfluorenyl} group,
η ⁵ -tert-butylfluorenyl group, η ⁵ -di-n-
Butylfluorenyl group, eta ⁵ - di -sec- butyl-fluorenyl group, eta ⁵ - di -tert- butyl-fluorenyl group, eta ^{5-n-pentyl-fluorenyl} group, eta ⁵ - Neopentyl fluorescens alkenyl group, eta ^{5-n-hexyl-fluorenyl} group, eta ^{5-n-octyl-fluorenyl} group, eta ^{5-n-decyl-fluorenyl} group, eta ^{5-n-dodecyl-fluorenyl} group, eta ⁵ - phenyl fluorenyl group, eta ⁵ - di - phenyl fluorenyl group, eta ⁵ - methylphenyl fluorenyl group, eta ⁵ - naphthyl fluorenyl group, eta ⁵ - trimethylsilyl fluorenyl group, eta ⁵ - bis - trimethylsilyl fluorenyl group, eta ⁵ - triethylsilyl fluorenyl group, such as eta ^{5-tert-butyldimethylsilyl-fluorenyl} group and the like, preferably eta ⁵ - cyclopentadienyl group, eta ⁵ - Mechirushiku Pentadienyl, η ⁵ -
tert- butyl cyclopentadienyl group, eta ⁵ - fluorenyl group - tetramethylcyclopentadienyl group, eta ⁵ - indenyl group, or eta ^5.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} halogen atom for ⁵ or R ⁶ , a fluorine atom,
Examples thereof include a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkyl group for ⁵ or R ⁶ has 1 to 1 carbon atoms.
Preferred are 20 alkyl groups, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, amyl, n- Hexyl group,
n-octyl group, n-decyl group, n-dodecyl group, n-
Examples thereof include a pentadecyl group and an n-eicosyl group, and more preferably a methyl group, an ethyl group, an isopropyl group, and a t-group.
tert-butyl or amyl.

Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, a bromomethyl group, and a dibromomethyl group. , Tribromomethyl group, iodomethyl group, diiodomethyl group,
Triiodomethyl, fluoroethyl, difluoroethyl, trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, chloroethyl, dichloroethyl, trichloroethyl, tetrachloroethyl, pentachloroethyl, bromoethyl , Dibromoethyl group, tribromoethyl group, tetrabromoethyl group, pentabromoethyl group, perfluoropropyl group,
Perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluorooctyl, perfluorododecyl, perfluoropentadecyl, perfluoroeicosyl, perchloropropyl, perchlorobutyl, perchloropentyl Group, perchlorohexyl group, perchlorooctyl group, perchlorododecyl group,
Perchloropentadecyl group, perchloroeicosyl group,
Perbromopropyl, perbromobutyl, perbromopentyl, perbromohexyl, perbromooctyl, perbromododecyl, perbromopentadecyl, perbromoeicosyl and the like.

All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyl group for ⁵ or R ⁶ has 7 carbon atoms.
~ 20 aralkyl groups are preferred, for example, benzyl, (2-methylphenyl) methyl, (3-methylphenyl) methyl, (4-methylphenyl) methyl,
(2,3-dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3,4-dimethyl Phenyl) methyl group, (4,6
-Dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3,6-trimethylphenyl) methyl group, (3,4 , 5-trimethylphenyl) methyl group, (2,4,6-trimethylphenyl) methyl group, (2,3,4,5-tetramethylphenyl) methyl group, (2,3,4,6-tetramethylphenyl) ) Methyl, (2,3,5,6-tetramethylphenyl) methyl, (pentamethylphenyl) methyl, (ethylphenyl) methyl, (n-propylphenyl) methyl,
(Isopropylphenyl) methyl group, (n-butylphenyl) methyl group, (sec-butylphenyl) methyl group, (tert-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl)
Methyl group, (n-hexylphenyl) methyl group, (n-
Octylphenyl) methyl group, (n-decylphenyl)
Methyl group, (n-dodecylphenyl) methyl group, (n-
Tetradecylphenyl) methyl group, naphthylmethyl group,
Examples include an anthracenylmethyl group, and more preferably a benzyl group.

All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group; an aryloxy group such as a phenoxy group; It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^{As the} aryl group for ⁵ or R ^6, C ^{6 to} C 6
Preferred are 20 aryl groups such as phenyl, 2
-Tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group,
2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,
3,5-trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group,
3,4,5-trimethylphenyl group, 2,3,4,5-
Tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethylphenyl group, n-
Propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert
-Butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n-octylphenyl group, n-decylphenyl group, n-dodecylphenyl group, n-tetradecylphenyl group, naphthyl group, Examples include an anthracenyl group, and more preferably a phenyl group.

Each of these aryl groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The substituted silyl group represented by ⁵ or R ⁶ is a silyl group substituted with a hydrocarbon group, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. , Sec-butyl group, tert-
Examples thereof include an alkyl group having 1 to 10 carbon atoms such as a butyl group, an isobutyl group, an n-pentyl group, an n-hexyl group and a cyclohexyl group, and an aryl group such as a phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group, dimethylsilyl group, diethylsilyl group, diphenylsilyl group and the like. A disubstituted silyl group having 2 to 20 carbon atoms,
Trimethylsilyl group, triethylsilyl group, tri-n-
Propylsilyl group, triisopropylsilyl group, tri-
n-butylsilyl group, tri-sec-butylsilyl group,
Tri-tert-butylsilyl group, tri-isobutylsilyl group, tert-butyl-dimethylsilyl group, tri-
n-pentylsilyl group, tri-n-hexylsilyl group,
Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a tricyclohexylsilyl group and a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable.

In all of these substituted silyl groups, the hydrocarbon group is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, or an aryloxy group such as a phenoxy group. Alternatively, it may be partially substituted with an aralkyloxy group such as a benzyloxy group.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The alkoxy group for ⁵ or R ⁶ has 1 carbon atom
To 20 alkoxy groups are preferred, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-
Butoxy group, n-pentoxy group, neopentoxy group, n
-Hexoxy group, n-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, and more preferably methoxy group, ethoxy group or tert-butoxy group.

All of these alkoxy groups include halogen atoms such as fluorine, chlorine, bromine and iodine, alkoxy such as methoxy and ethoxy, aryloxy such as phenoxy and benzyloxy. It may be partially substituted with an aralkyloxy group or the like.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
The aralkyloxy group for ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, such as a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, or a (4- Methylphenyl) methoxy group, (2,3-dimethylphenyl)
Methoxy group, (2,4-dimethylphenyl) methoxy group, (2,5-dimethylphenyl) methoxy group, (2
(6-dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl)
A methoxy group, a (2,3,5-trimethylphenyl) methoxy group, a (2,3,6-trimethylphenyl) methoxy group, a (2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include (octylphenyl) methoxy, (n-decylphenyl) methoxy, (n-tetradecylphenyl) methoxy, naphthylmethoxy, and anthracenylmethoxy, and more preferably benzyloxy.

Each of these aralkyloxy groups is
Partially substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group. You may.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The aryloxy group for ⁵ or R ⁶ is preferably an aryloxy group having 6 to 20 carbon atoms, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3- Dimethylphenoxy group, 2,4-dimethylphenoxy group, 2,5
-Dimethylphenoxy group, 2,6-dimethylphenoxy group, 3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6-trimethylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2,3,5,6-tetramethylphenoxy group, pentamethylphenoxy Group, ethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy Group, n-tetradecylphenoxy group, naphthoxy group, anthracenoxy group and the like.

Each of these aryloxy groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group and an ethoxy group;
An aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

The substituents X ¹ , X ² , R ¹ , R ² , R ³ , R ⁴ , R
^The disubstituted amino group in ⁵ or R ⁶ is an amino group substituted with two hydrocarbon groups, and examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, isobutyl group, n-pentyl group, n
A hexyl group, a cyclohexyl group or the like having 1 to 1 carbon atoms
6-1 carbon atoms such as an alkyl group and a phenyl group
And an aralkyl group having 7 to 10 carbon atoms. Examples of such a disubstituted amino group substituted with a hydrocarbon group having 1 to 10 carbon atoms include a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, Di-sec-butylamino group, di-tert-butylamino group, di-isobutylamino group, tert-butylisopropylamino group, di-n-hexylamino group, di-n-octylamino group, di-n-decylamino Groups, a diphenylamino group, a bistrimethylsilylamino group, a bis-tert-butyldimethylsilylamino group and the like, and preferably a dimethylamino group or a diethylamino group. Each of these disubstituted amino groups is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyl group such as a benzyloxy group. Part may be substituted with an oxy group or the like.

The substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R
⁶ may be optionally bonded to form a ring.

Preferred examples of R ¹ include an alkyl group, an aralkyl group, an aryl group and a substituted silyl group.

Preferred X ¹ and X ² each independently include a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group and a disubstituted amino group, and more preferably a halogen atom and An alkoxy group can be mentioned.

In the general formula [II] or [III], the atoms of Group 16 of the periodic table of the element represented by X ³ include:
For example, an oxygen atom, a sulfur atom, a selenium atom and the like can be mentioned, and an oxygen atom is preferable.

The transition metal complex represented by the general formula [I]
For example, methylene (cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dik
Chloride, methylene (cyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichlora
Id, methylene (cyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium
Dichloride, methylene (cyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichlori
De, methylene (cyclopentadienyl) (3-tert
-Butyldimethylsilyl-5-methyl-2-phenoxy
C) Titanium dichloride, methylene (cyclopentane
Dienyl) (3-trimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, methylene
Lopentadienyl) (3-tert-butyl-5-methoate
(Xy-2-phenoxy) titanium dichloride, methyl
Len (cyclopentadienyl) (3-tert-butyl
-5-chloro-2-phenoxy) titanium dichlori
De, methylene (methylcyclopentadienyl) (3,5
-Dimethyl-2-phenoxy) titanium dichlori
De, methylene (methylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichlora
Id, methylene (methylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) tita
Dichloride, methylene (methylcyclopentadi
Enyl) (3-phenyl-2-phenoxy) titanium
Dichloride, methylene (methylcyclopentadienyl
) (3-tert-butyldimethylsilyl-5-methyl)
Ru-2-phenoxy) titanium dichloride, methyle
(Methylcyclopentadienyl) (3-trimethyl
Ryl-5-methyl-2-phenoxy) titanium dichloro
Ride, methylene (methylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, methylene (methylcyclopen
Tadienyl) (3-tert-butyl-5-chloro-2
-Phenoxy) titanium dichloride, methylene (t
tert-butylcyclopentadienyl) (3,5-dimethyl
Tyl-2-phenoxy) titanium dichloride, methyl
Len (tert-butylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloro
Ride, methylene (tert-butylcyclopentadie
Nyl) (3-tert-butyl-5-methyl-2-fe
Noxy) titanium dichloride, methylene (tert
-Butylcyclopentadienyl) (3-phenyl-2-
Phenoxy) titanium dichloride, methylene (te
rt-butylcyclopentadienyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, methylene (tert-butyl
Cyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride,
Tylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, methylene (tert-butyl
Cyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride,
Tylene (tetramethylcyclopentadienyl) (3,5
-Dimethyl-2-phenoxy) titanium dichlori
De, methylene (tetramethylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium
Dichloride, methylene (tetramethylcyclopentadi
Enyl) (3-tert-butyl-5-methyl-2-f
Enoxy) titanium dichloride, methylene (tetra
Methylcyclopentadienyl) (3-phenyl-2-f
Enoxy) titanium dichloride, methylene (tetra
Methylcyclopentadienyl) (3-tert-butyl
Dimethylsilyl-5-methyl-2-phenoxy) titani
Um dichloride, methylene (tetramethylcyclopen
Tadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, methylene (
Tramethylcyclopentadienyl) (3-tert-butyl
Tyl-5-methoxy-2-phenoxy) titaniumdic
Chloride, methylene (tetramethylcyclopentadienyl
) (3-tert-butyl-5-chloro-2-pheno)
Xy) titanium dichloride, methylene (trimethyl
Silylcyclopentadienyl) (3,5-dimethyl-2
-Phenoxy) titanium dichloride, methylene (t)
Trimethylsilylcyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Methylene (trimethylsilylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy
Si) titanium dichloride, methylene (trimethylsi
Rylcyclopentadienyl) (3-phenyl-2-fe
Nonoxy) titanium dichloride, methylene (trimethyi)
Lucylylcyclopentadienyl) (3-tert-butyl)
Dimethylsilyl-5-methyl-2-phenoxy) tita
Dichloride, methylene (trimethylsilylcyclyl)
Lopentadienyl) (3-trimethylsilyl-5-methyl
Ru-2-phenoxy) titanium dichloride, methyle
(Trimethylsilylcyclopentadienyl) (3-t
tert-butyl-5-methoxy-2-phenoxy) tita
Dichloride, methylene (trimethylsilylcyclyl)
Lopentadienyl) (3-tert-butyl-5-chloro
B-2-phenoxy) titanium dichloride, methyle
(Fluorenyl) (3,5-dimethyl-2-phenoxy)
B) Titanium dichloride, methylene (fluorenyl)
) (3-tert-butyl-2-phenoxy) titani
Um dichloride, methylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titani
Um dichloride, methylene (fluorenyl) (3-F
Enyl-2-phenoxy) titanium dichloride,
Tylene (fluorenyl) (3-tert-butyl dimethyl
Lucylyl-5-methyl-2-phenoxy) titaniumdi
Chloride, methylene (fluorenyl) (3-trimethyl
Lucylyl-5-methyl-2-phenoxy) titaniumdi
Chloride, methylene (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium
Dichloride, methylene (fluorenyl) (3-ter
t-butyl-5-chloro-2-phenoxy) titanium
Dichloride, isopropylidene (cyclopentadienyl
) (3,5-dimethyl-2-phenoxy) titanium
Dichloride, isopropylidene (cyclopentadienyl
) (3-tert-butyl-2-phenoxy) titani
Um dichloride, isopropylidene (cyclopentadi
Enyl) (3-tert-butyl-5-methyl-2-f
Enoxy) titanium dichloride, isopropylidene
(Cyclopentadienyl) (3-phenyl-2-pheno
Xy) titanium dichloride, isopropylidene (Si
Clopentadienyl) (3-tert-butyldimethyl
Silyl-5-methyl-2-phenoxy) titaniumdic
Lolide, isopropylidene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoki
B) Titanium dichloride, isopropylidene (sic)
Lopentadienyl) (3-tert-butyl-5-methoate
(Xy-2-phenoxy) titanium dichloride, iso
Propylidene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titaniumdi
Chloride, isopropylidene (methylcyclopentadi
Enyl) (3,5-dimethyl-2-phenoxy) titani
Um dichloride, isopropylidene (methylcyclope
Antadienyl) (3-tert-butyl-2-phenoxy)
B) Titanium dichloride, isopropylidene (meth
Rucyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichlori
Do, isopropylidene (methylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropyl
Ridene (methylcyclopentadienyl) (3-trimethyl
Lucylyl-5-methyl-2-phenoxy) titaniumdi
Chloride, isopropylidene (methylcyclopentadi
Enyl) (3-tert-butyl-5-methoxy-2-
Phenoxy) titanium dichloride, isopropylide
(Methylcyclopentadienyl) (3-tert-butyl
Tyl-5-chloro-2-phenoxy) titanium dichloro
Ride, isopropylidene (tert-butylcyclope)
Antadienyl) (3,5-dimethyl-2-phenoxy)
Titanium dichloride, isopropylidene (tert
-Butylcyclopentadienyl) (3-tert-butyl)
Ru-2-phenoxy) titanium dichloride, isop
Lopylidene (tert-butylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy
C) Titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, isopropyl
Lidene (tert-butylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, isopropylide
(Tert-butylcyclopentadienyl) (3-t
Limethylsilyl-5-methyl-2-phenoxy) titani
Um dichloride, isopropylidene (tert-butyl
Rucyclopentadienyl) (3-tert-butyl-5
-Methoxy-2-phenoxy) titanium dichlorai
Do, isopropylidene (tert-butylcyclopentane
Dienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, isopropylide
(Tetramethylcyclopentadienyl) (3,5-di
Methyl-2-phenoxy) titanium dichloride, i
Sopropylidene (tetramethylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium
Dichloride, isopropylidene (tetramethylcyclo
Pentadienyl) (3-tert-butyl-5-methyl
-2-phenoxy) titanium dichloride, isopro
Pyridene (tetramethylcyclopentadienyl) (3-
Phenyl-2-phenoxy) titanium dichloride,
Isopropylidene (tetramethylcyclopentadienyl
) (3-tert-butyldimethylsilyl-5-methyl)
Ru-2-phenoxy) titanium dichloride, isop
Lopylidene (tetramethylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) thio
Titanium dichloride, isopropylidene (tetramethyl
Rucyclopentadienyl) (3-tert-butyl-5
-Methoxy-2-phenoxy) titanium dichlorai
Do, isopropylidene (tetramethylcyclopentadie
Nyl) (3-tert-butyl-5-chloro-2-fe
Noxy) titanium dichloride, isopropylidene
(Trimethylsilylcyclopentadienyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Isopropylidene (trimethylsilylcyclopentadie
Nyl) (3-tert-butyl-2-phenoxy) tita
Dichloride, isopropylidene (trimethyl
Rylcyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichlori
, Isopropylidene (trimethylsilylcyclopenta
Dienyl) (3-phenyl-2-phenoxy) titanium
Mudichloride, isopropylidene (trimethylsilyl
Cyclopentadienyl) (3-tert-butyldimethyi)
Lucylyl-5-methyl-2-phenoxy) titaniumdi
Chloride, isopropylidene (trimethylsilylcyclyl)
Lopentadienyl) (3-trimethylsilyl-5-methyl
Ru-2-phenoxy) titanium dichloride, isop
Lopylidene (trimethylsilylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy
C) Titanium dichloride, isopropylidene (tri)
Methylsilylcyclopentadienyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dik
Chloride, isopropylidene (fluorenyl) (3,5
-Dimethyl-2-phenoxy) titanium dichlori
De, isopropylidene (fluorenyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl
Tyl-5-methyl-2-phenoxy) titanium dichloro
Ride, isopropylidene (fluorenyl) (3-Fe
Nyl-2-phenoxy) titanium dichloride, iso
Propylidene (fluorenyl) (3-tert-butyl
Dimethylsilyl-5-methyl-2-phenoxy) titani
Um dichloride, isopropylidene (fluorenyl)
(3-trimethylsilyl-5-methyl-2-phenoki
C) Titanium dichloride, isopropylidene (full
Olenyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropyl
Den (fluorenyl) (3-tert-butyl-5-c
(Rolo-2-phenoxy) titanium dichloride, diph
Phenylmethylene (cyclopentadienyl) (3,5-di
Methyl-2-phenoxy) titanium dichloride, di
Phenylmethylene (cyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichlori
Do, diphenylmethylene (cyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (cyclope
Antadienyl) (3-phenyl-2-phenoxy) tita
Dichloride, diphenylmethylene (cyclopen
Tadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichlori
Do, diphenylmethylene (cyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (cyclope
Antadienyl) (3-tert-butyl-5-methoxy
-2-phenoxy) titanium dichloride, diphenyi
Lmethylene (cyclopentadienyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dik
Chloride, diphenylmethylene (methylcyclopentadi
Enyl) (3,5-dimethyl-2-phenoxy) titani
Um dichloride, diphenylmethylene (methylcyclo
Pentadienyl) (3-tert-butyl-2-pheno
Xy) titanium dichloride, diphenylmethylene
(Methylcyclopentadienyl) (3-tert-butyl)
Ru-5-methyl-2-phenoxy) titanium dichlora
Id, diphenylmethylene (methylcyclopentadienyl
) (3-phenyl-2-phenoxy) titanium
Chloride, diphenylmethylene (methylcyclopentadi
Enyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, di
Phenylmethylene (methylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (methyl
Clopentadienyl) (3-tert-butyl-5-meth
Toxi-2-phenoxy) titanium dichloride, di
Phenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (tert
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, diphenyl
Methylene (tert-butylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium
Dichloride, diphenylmethylene (tert-butyl
Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, di
Phenylmethylene (tert-butylcyclopentadie
Nyl) (3-phenyl-2-phenoxy) titaniumdi
Chloride, diphenylmethylene (tert-butyl
Clopentadienyl) (3-tert-butyldimethyl
Silyl-5-methyl-2-phenoxy) titaniumdic
Chloride, diphenylmethylene (tert-butylcyclyl)
Lopentadienyl) (3-trimethylsilyl-5-methyl
Ru-2-phenoxy) titanium dichloride, dife
Nylmethylene (tert-butylcyclopentadienyl
) (3-tert-butyl-5-methoxy-2-fe)
Noxy) titanium dichloride, diphenylmethylene
(Tert-butylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium
Mudichloride, diphenylmethylene (tetramethyl
Clopentadienyl) (3,5-dimethyl-2-pheno
Xy) titanium dichloride, diphenylmethylene
(Tetramethylcyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (tetramethylcyclopentadiene
) (3-tert-butyl-5-methyl-2-pheno)
Xy) titanium dichloride, diphenylmethylene
(Tetramethylcyclopentadienyl) (3-phenyl
-2-phenoxy) titanium dichloride, diphenyi
Lmethylene (tetramethylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, diphenylmethyl
Len (tetramethylcyclopentadienyl) (3-tri
Methylsilyl-5-methyl-2-phenoxy) titanium
Mudichloride, diphenylmethylene (tetramethyl
Clopentadienyl) (3-tert-butyl-5-meth
Toxi-2-phenoxy) titanium dichloride, di
Phenylmethylene (tetramethylcyclopentadienyl
) (3-tert-butyl-5-chloro-2-pheno)
Xy) titanium dichloride, diphenylmethylene
(Trimethylsilylcyclopentadienyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (trimethylsilylcyclopentadi
Enyl) (3-tert-butyl-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (trimethyl
Lucylylcyclopentadienyl) (3-tert-butyl)
Ru-5-methyl-2-phenoxy) titanium dichlora
Id, diphenylmethylene (trimethylsilylcyclope
Antadienyl) (3-phenyl-2-phenoxy) tita
Dichloride, diphenylmethylene (trimethyl
Silylcyclopentadienyl) (3-tert-butyl
Dimethylsilyl-5-methyl-2-phenoxy) titani
Um dichloride, diphenylmethylene (trimethyl
Rylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichlori
Do, diphenylmethylene (trimethylsilylcyclopen
Tadienyl) (3-tert-butyl-5-methoxy-
2-phenoxy) titanium dichloride, diphenyl
Methylene (trimethylsilylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy
C) Titanium dichloride, diphenylmethylene (
Fluorenyl) (3,5-dimethyl-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (fluore
Nyl) (3-tert-butyl-2-phenoxy) tita
Dichloride, diphenylmethylene (fluorenyl)
) (3-tert-butyl-5-methyl-2-pheno)
Xy) titanium dichloride, diphenylmethylene
(Fluorenyl) (3-phenyl-2-phenoxy) thio
Titanium dichloride, diphenylmethylene (fluore
Nil) (3-tert-butyldimethylsilyl-5-
Tyl-2-phenoxy) titanium dichloride, diph
Phenylmethylene (fluorenyl) (3-trimethylsilyl
Ru-5-methyl-2-phenoxy) titanium dichlora
Id, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titani
Um dichloride, diphenylmethylene (fluorenyl)
) (3-tert-butyl-5-chloro-2-pheno)
Xy) titanium dichloride and these compounds
Change titanium to zirconium or hafnium
Dichloride to dibromide, diiodide
, Bis (dimethylamide), bis (diethylamido)
), Di-n-butoxide or diisopropoxide
The modified compound, (cyclopentadienyl)
Rucyclopentadienyl), (trimethylcyclopenta
Dienyl), (n-butylcyclopentadienyl),
(Tert-butyldimethylsilylcyclopentadienyl
) Or a compound changed to (indenyl), (3,5
-Dimethyl-2-phenoxy) to (2-phenoxy),
(3-methyl-2-phenoxy), (3,5-di-te)
rt-butyl-2-phenoxy), (3-phenyl-5
-Methyl-2-phenoxy), (3-tert-butyl
Dimethylsilyl-2-phenoxy) or (3-trime
Tylsilyl-2-phenoxy)
Transition gold wherein J in the general formula [I] is a carbon atom
Genus complex and dimethylsilyl (cyclopentadienyl)
) (2-phenoxy) titanium dichloride, dime
Tylsilyl (cyclopentadienyl) (3-methyl-2
-Phenoxy) titanium dichloride, dimethylsilicone
(Cyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilyl
(Cyclopentadienyl) (3-tert-butyl-2
-Phenoxy) titanium dichloride, dimethylsilicone
(Cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichlori
Dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium
Dichloride, dimethylsilyl (cyclopentadienyl
) (5-methyl-3-phenyl-2-phenoxy) thio
Titanium dichloride, dimethylsilyl (cyclopentane
Dienyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (cyclopentadienyl) (5-methyl
-3-trimethylsilyl-2-phenoxy) titanium
Dichloride, dimethylsilyl (cyclopentadienyl
) (3-tert-butyl-5-methoxy-2-fe)
Nonoxy) titanium dichloride, dimethylsilyl (Si
Clopentadienyl) (3-tert-butyl-5-c
(Rolo-2-phenoxy) titanium dichloride, dime
Tylsilyl (cyclopentadienyl) (3,5-diamido)
Ru-2-phenoxy) titanium dichloride, dimethyi
Lucylyl (methylcyclopentadienyl) (2-pheno
Xy) titanium dichloride, dimethylsilyl (methyl
Rucyclopentadienyl) (3-methyl-2-phenoxy)
Si) titanium dichloride, dimethylsilyl (methyl
Cyclopentadienyl) (3,5-dimethyl-2-fe
Nonoxy) titanium dichloride, dimethylsilyl (meth
Tylcyclopentadienyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, dimethyl
Ryl (methylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium
Chloride, dimethylsilyl (methylcyclopentadienyl
) (3,5-di-tert-butyl-2-phenoxy)
Si) titanium dichloride, dimethylsilyl (methyl
Cyclopentadienyl) (5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethyl
Ryl (methylcyclopentadienyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (methylcyclyl
Lopentadienyl) (5-methyl-3-trimethylsilyl
Ru-2-phenoxy) titanium dichloride, dimethyi
Lucylyl (methylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium
Mudichloride, dimethylsilyl (methylcyclopenta
Dienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilyl
(Methylcyclopentadienyl) (3,5-diamyl-
2-phenoxy) titanium dichloride, dimethyl
Ryl (n-butylcyclopentadienyl) (2-pheno
Xy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-methyl-2-fe
Noxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, dimethyl
Ryl (n-butylcyclopentadienyl) (3-ter
t-butyl-2-phenoxy) titanium dichlori
Do, dimethylsilyl (n-butylcyclopentadienyl
) (3-tert-butyl-5-methyl-2-pheno)
Xy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (n-butylcyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titani
Um dichloride, dimethylsilyl (n-butylcyclo
Pentadienyl) (3-tert-butyldimethylsilyl
Ru-5-methyl-2-phenoxy) titanium dichlora
Id, dimethylsilyl (n-butylcyclopentadienyl
) (5-methyl-3-trimethylsilyl-2-pheno)
Xy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-tert-butyl
-5-methoxy-2-phenoxy) titanium dichlora
Id, dimethylsilyl (n-butylcyclopentadienyl
) (3-tert-butyl-5-chloro-2-pheno)
Xy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilicone
(Tert-butylcyclopentadienyl) (2-f
Enoxy) titanium dichloride, dimethylsilyl
(Tert-butylcyclopentadienyl) (3-methyl
Ru-2-phenoxy) titanium dichloride, dimethyi
Lucylyl (tert-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dik
Chloride, dimethylsilyl (tert-butylcyclope)
Antadienyl) (3-tert-butyl-2-phenoxy)
B) titanium dichloride, dimethylsilyl (ter)
t-butylcyclopentadienyl) (3-tert-butyl
Tyl-5-methyl-2-phenoxy) titanium dichloro
Ride, dimethylsilyl (tert-butylcyclopen
Tadienyl) (3,5-di-tert-butyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Tert-butylcyclopentadienyl) (5-methyl
Ru-3-phenyl-2-phenoxy) titanium dichloro
Ride, dimethylsilyl (tert-butylcyclopen
Tadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichlori
De, dimethylsilyl (tert-butylcyclopentadi
Enyl) (5-methyl-3-trimethylsilyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Tert-butylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titani
Um dichloride, dimethylsilyl (tert-butyl
Cyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, di
Methylsilyl (tert-butylcyclopentadienyl
(3) (3,5-Diamyl-2-phenoxy) titanium
Dichloride, dimethylsilyl (tetramethylcyclope
Nantadienyl) (2-phenoxy) titanium dichlora
Id, dimethylsilyl (tetramethylcyclopentadie
Nyl) (3-methyl-2-phenoxy) titanium
Chloride, dimethylsilyl (tetramethylcyclopenta
Dienyl) (3,5-dimethyl-2-phenoxy) tita
Dichloride, dimethylsilyl (tetramethylsilyl)
Clopentadienyl) (3-tert-butyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titaniumdi
Chloride, dimethylsilyl (tetramethylcyclopen
Tadienyl) (3,5-di-tert-butyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Tetramethylcyclopentadienyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichlori
Do, dimethylsilyl (tetramethylcyclopentadienyl
) (3-tert-butyldimethylsilyl-5-methyl)
Ru-2-phenoxy) titanium dichloride, dimethyi
Lucylyl (tetramethylcyclopentadienyl) (5-
Methyl-3-trimethylsilyl-2-phenoxy) tita
Dichloride, dimethylsilyl (tetramethylsilyl)
Clopentadienyl) (3-tert-butyl-5-meth
Toxi-2-phenoxy) titanium dichloride, di
Methylsilyl (tetramethylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy
Si) titanium dichloride, dimethylsilyl (tetra
Methylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilicone
(Trimethylsilylcyclopentadienyl) (2-f
Enoxy) titanium dichloride, dimethylsilyl
(Trimethylsilylcyclopentadienyl) (3-methyl
Ru-2-phenoxy) titanium dichloride, dimethyi
Lucyl (trimethylsilylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dik
Chloride, dimethylsilyl (trimethylsilylcyclope
Antadienyl) (3-tert-butyl-2-phenoxy)
Si) titanium dichloride, dimethylsilyl (trime
Tylsilylcyclopentadienyl) (3-tert-butyl
Tyl-5-methyl-2-phenoxy) titanium dichloro
Ride, dimethylsilyl (trimethylsilylcyclopen
Tadienyl) (3,5-di-tert-butyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Trimethylsilylcyclopentadienyl) (5-methyl
Ru-3-phenyl-2-phenoxy) titanium dichloro
Ride, dimethylsilyl (trimethylsilylcyclopen
Tadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichlori
Dimethylsilyl (trimethylsilylcyclopentadi
Enyl) (5-methyl-3-trimethylsilyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titani
Um dichloride, dimethylsilyl (trimethylsilyl)
Cyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, di
Methylsilyl (trimethylsilylcyclopentadienyl
(3) (3,5-Diamyl-2-phenoxy) titanium
Dichloride, dimethylsilyl (indenyl) (2-F
Enoxy) titanium dichloride, dimethylsilyl
(Indenyl) (3-methyl-2-phenoxy) titani
Um dichloride, dimethylsilyl (indenyl)
(3,5-dimethyl-2-phenoxy) titanium dik
Chloride, dimethylsilyl (indenyl) (3-ter
t-butyl-2-phenoxy) titanium dichlori
Do, dimethylsilyl (indenyl) (3-tert-
Tyl-5-methyl-2-phenoxy) titanium dichloro
Ride, dimethylsilyl (indenyl) (3,5-di-
tert-butyl-2-phenoxy) titanium dichloro
Ride, dimethylsilyl (indenyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichlori
Do, dimethylsilyl (indenyl) (3-tert-
Tyldimethylsilyl-5-methyl-2-phenoxy) thio
Thanium dichloride, dimethylsilyl (indenyl)
(5-methyl-3-trimethylsilyl-2-phenoxy
C) titanium dichloride, dimethylsilyl (indene
Nyl) (3-tert-butyl-5-methoxy-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Indenyl) (3-tert-butyl-5-chloro-
2-phenoxy) titanium dichloride, dimethyl
Ryl (indenyl) (3,5-diamyl-2-phenoxy)
Si) titanium dichloride, dimethylsilyl (fluoro)
Lenyl) (2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (3-methyl-2-f
Enoxy) titanium dichloride, dimethylsilyl
(Fluorenyl) (3,5-dimethyl-2-phenoxy)
Si) titanium dichloride, dimethylsilyl (fluoro)
Lenyl) (3-tert-butyl-2-phenoxy) thio
Titanium dichloride, dimethylsilyl (fluorenyl
) (3-tert-butyl-5-methyl-2-pheno)
Xy) titanium dichloride, dimethylsilyl (full
Olenyl) (3,5-di-tert-butyl-2-fe
Nonoxy) titanium dichloride, dimethylsilyl
Fluorenyl) (5-methyl-3-phenyl-2-pheno
Xy) titanium dichloride, dimethylsilyl (full
Olenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (5-methyl-3-to
Limethylsilyl-2-phenoxy) titanium dichlora
Id, dimethylsilyl (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium
Dichloride, dimethylsilyl (fluorenyl) (3-
tert-butyl-5-chloro-2-phenoxy) tita
Dichloride, dimethylsilyl (fluorenyl)
(3,5-Diamyl-2-phenoxy) titanium dik
Chloride, dimethylsilyl (tetramethylcyclopenta
Dienyl) (1-naphthoxy-2-yl) titanium dichloride
And the compounds (cyclopentadienyl)
) To (dimethylcyclopentadienyl), (trimethyl
Lecyclopentadienyl), (ethylcyclopentadiene)
Yl), (n-propylcyclopentadienyl), (a
Isopropylcyclopentadienyl), (sec-butyl
Cyclopentadienyl), (isobutylcyclopentadi)
Enyl), (tert-butyldimethylsilylcyclope)
Antadienyl), (phenylcyclopentadienyl),
(Methylindenyl) or (phenylindenyl)
The modified compound, (2-phenoxy) is replaced with (3-phenyl
2-phenoxy), (3-trimethylsilyl-2-fe
Nonoxy) or (3-tert-butyldimethylsilyl)
-2-Phenoxy), dimethylsilyl
Is diethylsilyl, diphenylsilyl, or dimethoxy
Compound converted to silyl, titanium to zirconium,
Or dichloride, a compound changed to hafnium
Lomide, diiodide, bis (dimethylamide),
(Diethylamide), di-n-butoxide,
General formula [I] such as a compound converted to sopropoxide
J in group 14 of the periodic table of elements other than carbon atoms
The transition metal complex which is an atom of is mentioned.

As the transition metal complex represented by the general formula [II], for example, μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (cyclopentadiene) Enyl) (2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene ( Cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {isopropylidene (methylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (methyl) Cyclopentadienyl) (2-
Phenoxy) titanium methoxide {, μ-oxobis} isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} isopropylidene (methylcyclopentadienyl) (3-te
rt-butyl-5-methyl-2-phenoxy) titanium methoxide, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethylcyclo) Pentadienyl) (2
-Phenoxy) titanium methoxide {, μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {isopropylidene (tetramethyl) Cyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide}, μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (cyclopentane) Dienyl) (2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (cyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium chloride {, μ-oxobis} dimethylsilylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium chloride｝, μ-
Oxobis {dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium methoxide},
μ-oxobis {dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2)
-Phenoxy) titanium chloride｝, μ-oxobis ｛dimethylsilylene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide {, μ-oxobis} dimethylsilylene (tetramethylcyclopentadienyl) (2
-Phenoxy) titanium chloride {, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium methoxide}, μ
-Oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride}, μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-
Phenoxy) titanium methoxide, and the like.

Examples of the transition metal complex represented by the general formula [III] include di-μ-oxobis {isopropylidene (cyclopentadienyl) (2-phenoxy) titanium} and di-μ-oxobis {isopropylidene ( Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis} isopropylidene (methylcyclopentadienyl)
(2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {isopropylidene (Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium {, di-μ-oxobis {dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis} dimethylsilylene (cyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl)
(2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (methylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium}, di-μ-oxobis {dimethylsilylene (Tetramethylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium}, and the like.

The transition metal complex represented by the general formula [I] can be produced, for example, by the method described in WO 97/03992. The transition metal complex represented by the general formula [II] or [III] can be produced by reacting the transition metal complex represented by the general formula [I] with one or two equivalents of water.

The (B) aluminum compound will be described.

The aluminum compound (B) is at least one aluminum compound selected from the following (B1) to (B3). (B1) the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B2) general formula {-Al (E ²⁾ -O-} cyclic aluminoxane (B3) having a structure represented by _b the formula E ³ ｛-Al (E ³ ) -O-｝ _c AlE ³
Linear aluminoxane having a structure represented by ₂ (provided that E ¹ , E ² , and E ³ are each a hydrocarbon group, and all E ¹ , all E ^2, and all E ³ are the same; Z represents a hydrogen atom or a halogen atom, and all Z may be the same or different, a is a number satisfying 0 <a ≦ 3, and b is 2 or more. And c represents an integer of 1 or more.)

As the hydrocarbon group for E ¹ , E ² or E ³ , a hydrocarbon group having 1 to 8 carbon atoms is preferable, and an alkyl group is more preferable.

[0052] As specific examples of the general formula E ¹ _a AlZ organoaluminum compound represented by the _3-a (B1), trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisobutyl aluminum, trialkyl aluminum such as tri-hexyl aluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride and dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride and hexylaluminum dichloride Dimethylal Examples thereof include dialkylaluminum hydrides such as minium hydride, diethylaluminum hydride, dipropylaluminum hydride, diisobutylaluminum hydride, and dihexylaluminum hydride.

Preferably, it is a trialkylaluminum, and more preferably, triethylaluminum or triisobutylaluminum.

[0054] In the general formula {-Al (E ²⁾ -O-} cyclic aluminoxane having the structure represented by _b (B2), the general formula ^{E 3 {-Al (E 3)} -O-} c AlE 3 2 In a linear aluminoxane (B3) having the structure shown,
Specific examples of E ² and E ³ include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group,
Examples thereof include an alkyl group such as an isobutyl group, a normal pentyl group, and a neopentyl group. b is an integer of 2 or more, and c is an integer of 1 or more. Preferably, E ²
And E ³ is a methyl group or an isobutyl group, and b is 2
-40 and c are 1-40.

The above aluminoxane can be made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum) in a suitable organic solvent (benzene, aliphatic hydrocarbon, or the like) is brought into contact with water. In addition, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt containing crystallization water (for example, copper sulfate hydrate or the like) can be exemplified.

The (C) boron compound will be described.

Examples of the boron compound (C) include (C1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ and (C2)
A boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , (C3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^-
Any of the boron compounds represented by the following formulas can be used.

General formula BQ¹Q^TwoQ^ThreeBoration represented by
In the compound (C1), B is boron in a trivalent valence state
Atom, Q¹~ Q^ThreeRepresents a halogen atom, a hydrocarbon group,
A hydrogenated hydrocarbon group, a substituted silyl group, an alkoxy group or
Disubstituted amino groups, which are the same or different
May be. Q¹~ Q^ThreeIs preferably a halogen atom,
A hydrocarbon group containing 1-20 carbon atoms, 1-20
Halogenated hydrocarbon groups containing carbon atoms, from 1 to 20 carbon atoms
Substituted silyl groups containing 1 to 20 carbon atoms
An alkoxy group or an amino containing 2 to 20 carbon atoms
And more preferred Q¹~ Q^ThreeIs a halogen atom, 1 to
A hydrocarbon group containing 20 carbon atoms, or 1-20
It is a halogenated hydrocarbon group containing a carbon atom. More preferred
Or Q ¹~ Q^FourIs at least one fluorine source
A fluorinated hydrocarbon group having 1 to 20 carbon atoms containing
And particularly preferably Q¹~ Q^FourIs at least 1 each
Fluorinated carbon atoms having 6 to 20 carbon atoms containing two fluorine atoms
It is a reel group.

Specific examples of the compound (C1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (C2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic or organic cation, and B is boron in a trivalent valence state. an atom, Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above (C1).

[0061] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

As specific combinations of these, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate and the like can be mentioned, and most preferred is triphenylmethyltetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound represented (C3), L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is boron atom in the trivalent valence state ,
Q ¹ to Q ⁴ are the same as Q ¹ to Q ³ in the above Lewis acid (C1).

The compound represented by the general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— is a Bronsted acid (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same as described above.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Examples thereof include tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the copolymerization, the transition metal complex (A)
And an olefin polymerization catalyst comprising the above (B) and / or the above (C). When an olefin polymerization catalyst comprising two components (A) and (B) is used, the cyclic aluminoxane (B2) and / or the linear aluminoxane (B3) are preferred as (B). Another preferred embodiment of the olefin polymerization catalyst is an olefin polymerization catalyst comprising the above (A), (B) and (C). In this case, the (B) may be the aforementioned (B1) ) Easy to use.

The amount of each component used is usually such that the molar ratio of (B) / (A) is 0.1 to 10000, preferably 5 to 200.
It is desirable to use each component so that the molar ratio of 0, (C) / (A) is 0.01 to 100, preferably 0.5 to 10.

The concentration when each component is used in a solution state or a suspension state in a solvent is appropriately selected depending on conditions such as the performance of a device for supplying each component to the polymerization reactor. , Usually at 0.01 to 500 μmol / g,
More preferably, 0.05 to 100 μmol / g, still more preferably, 0.05 to 50 μmol / g, (B)
Usually, 0.01 to 10000 μmol /
g, more preferably 0.1 to 5000 μmol /
g, more preferably 0.1 to 2000 μmol / g,
(C) is usually from 0.01 to 500 μmol / g, preferably from 0.05 to 200 μmol / g, and more preferably from 0.05 to 100 μmol / g. desirable.

The transition metal complex represented by the compound (A) and the compound (B), or further the compound (C) can be charged and used in an arbitrary order during the polymerization, and can be used. A reactant obtained by previously contacting the combination may be used.

To produce the α-olefin-conjugated polyene copolymer of the present invention, for example, butane, pentane,
Solvent polymerization using aliphatic hydrocarbons such as hexane, heptane and octane, aromatic hydrocarbons such as benzene and toluene, or halogenated hydrocarbons such as methylene dichloride as a solvent, slurry polymerization, and gas polymerization in gaseous monomers Phase polymerization or the like is possible, and both continuous polymerization and batch polymerization are possible. The polymerization temperature is -50 to 200
Although it can take the range of ° C, especially, the range of -20 to 100 ° C is preferable, and the polymerization pressure is preferably atmospheric pressure to 100 MPa. The polymerization time is generally appropriately determined depending on the type of the catalyst used and the reaction apparatus, but can range from 1 minute to 20 hours. Further, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.
The elastomer composition of the present invention contains 100 parts by weight of the above-mentioned α-olefin-conjugated polyene copolymer, 5-400 parts by weight of an inorganic filler and / or carbon black, and 0.1-20 parts by weight of a crosslinking agent. A composition.

Α-olefin-conjugated polyene copolymer 1
The content of the inorganic filler and / or carbon black per 100 parts by weight is 5 to 400 parts by weight, preferably 1 to 400 parts by weight.
0 to 200 parts by weight. If the content is too small, a sufficient reinforcing effect cannot be obtained, while if the content is too large, the viscosity of the composition increases and the processability is poor. The amount of the above filler is based on the total amount of the inorganic filler and carbon black when the inorganic filler and / or carbon black is used in combination.

Specific examples of the inorganic filler include glass flake, kaolin, clay, silica, glass balloon, glass beads, mica, talc, calcium carbonate, titanium oxide, potassium titanate whisker, barium sulfate, shirasu balloon, Aerosil and the like. Can be exemplified.

The crosslinking agent that can be used in the α-olefin-conjugated polyene copolymer composition can be arbitrarily selected from one or more of various crosslinking agents depending on the application. Examples of such a crosslinking agent include a sulfur-based crosslinking agent, an inorganic crosslinking agent, a polyamine crosslinking agent, a resin crosslinking agent, a sulfur compound-based crosslinking agent, an oxime-nitrosamine-based crosslinking agent, an organic peroxide-based crosslinking agent, and other crosslinking agents. can give. Specific examples of such a cross-linking agent include specific examples of sulfur-based cross-linking agents such as powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, and non-contaminating sulfur donors. Specific examples of the polyamine crosslinking agent include selenium, tellurium, magnesium oxide, lithium (lead monoxide), zinc white, and the like. Specific examples of the polyamine crosslinking agent include hexamethylenediamine, triethylenetetramine, and tetraethylene. Pentamine, hexamethylenediaminecarbamate, N, N 'disinnamylidene-1,
6-hexanediamine, 4,4'-methylenebis (cyclohexylamine) carbamate, 4,4'-methylenebis- (2-chloroaniline) and the like,
Specific examples of the resin crosslinking agent include alkylphenol-formaldehyde resin, melamine-formaldehyde condensate,
Examples include triazine formaldehyde condensate, sulfurized-P-tert-butylphenol resin, alkylphenol sulfide resin, hexamethoxymethylmelamine resin, and the like. Specific examples of the sulfur compound-based crosslinking agent include sulfur monochloride, Examples thereof include sulfur chloride, morpholine disulfide, alkylphenol disulfide, polymer polysulfide, and a vulcanization accelerator containing sulfur. Specific examples of the oxime-nitrosamine-based crosslinking agent include p-quinone dioxime, p, p'-Dibenzoylquinone dioxime, tetrachloro-p-benzoquinone, poly-p-dinitrosobenzene, and the like. Specific examples of the organic peroxide-based crosslinking agent include tert-butyl hydroperoxide. Oxide, 1,
1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane 2,5-dihydroperoxide, di-tert-butyl Peroxide, dicumyl peroxide, tert-butylcumyl peroxide, 1,1-bis (tert-butylperoxy) cyclododecane, 2,2-bis (tert-butylperoxy) octane, 1,1-di-tert-butyl Tributylperoxycyclohexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5- (tert-butylperoxy) hexyne-3,1,3-bis ( Tert-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (benzo Ilperoxy) hexane,
1,1-bis (tert-butylperoxy) -3,3,5-
Trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, m-toluyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl Peroxyisobutre
Tert-butyl peroxy 2-ethylhexanoate,
Tertiary butyl peroxybenzoate, tertiary butyl peroxyisopropyl carbonate, tertiary butyl peroxyallyl carbonate, acrylic cross-linking agents, and other cross-linking agents include ethylene glycol dimethacrylate , Trimethylolpropane trimethacrylate, polyfunctional methacrylate monomer, polyvalent alcohol methacrylate, acrylate, N, N'-m-phenylenedimaleimide, ammonium benzoate, silica-based filler Containing monomers, triallyl isocyanurate,
Metal-containing monomer, zinc methacrylate, magnesium methacrylate, zinc dimethacrylate, magnesium dimethacrylate, 2,4,6-trimercapto-S-triazine, N, N'-bis (2-methyl-2-nitro (Propyl) -1,6-hexanediamine, isocyanuric acid, thiadiazol derivatives, cationic activators, special mixed vulcanizing agents, high-purity industrial soaps and the like. In addition,
These crosslinking agents are arbitrarily selected according to the application. The amount of the cross-linking agent used is also arbitrarily selected according to the required cross-linking speed, required properties of the cross-linked product, etc. 0.1 to 20 parts by weight, preferably 0.2 to 20 parts by weight.
10 parts by weight. If the content is too small, the crosslinking may hardly proceed, while if the content is too large, the physical properties of the vulcanized product may be impaired.

If necessary, various additives known in the art (Handbook of Rubber and Plastic Compound Revision, Second Edition, edited by Rubber Digest Co.) can be added to the elastomer composition of the present invention, if necessary. Examples of such additives include:
Vulcanization accelerator, vulcanization accelerator, activator, scorch inhibitor,
Antioxidants, antioxidants, antiozonants, ultraviolet absorbers, light stabilizers, mastication accelerators, tackifiers, plasticizers,
Rubber softener, rubber reinforcing agent, filler, reinforcing agent, foaming agent, foaming aid, lubricant, slip agent, internal release agent, antifogging agent, flame retardant, antistatic agent for kneading, coloring agent, coupling Agent,
Preservatives, fungicides and the like are exemplified. Specific examples of each additive described in known documents (Handbook of Rubber and Plastic Compounding Revision, Second Edition, Rubber Digest Co., Ltd.)
Alternatively, a part of the classification is listed. First, specific examples of the vulcanization accelerator include guanidine, aldehyde-ammonia, aldehyde-amine, thiazole, sulfamine amide, thiourea, thiuram, dithiocarbamate, and xanthate. Specific examples of the vulcanization accelerating aid-activator include compounds such as metal oxides, metal carbonates, fatty acids and derivatives thereof, and amines.
Specific examples of the antioxidant include an organic acid and a nitroso compound, and specific examples of the antioxidant-the antioxidant-the antiozonant include naphthylamine-based, diphenylamine-based,
p-phenylenediamine, quinoline, hydroquinone derivatives, monophenol, bis, trisphenol, thiobisphenol, hindered phenol,
Phosphite esters, waxes, copper damage inhibitors, etc. are specific examples of ultraviolet absorbers and light stabilizers, and salicylic acid derivatives, benzophenones, benzotriazoles, hindered amines, etc. are pulverizing accelerators. Specific examples of the tackifier include a mixture of pentachlorothiophenol and an active additive, a zinc salt of pentachlorothiophenol, and mixed diall disulfide.As specific examples of the tackifier, cumarone-indene resin, Phenol / formaldehyde resin, xylene, formaldehyde resin, polyterpene resin, petroleum hydrocarbon resin, rosin acid ester, etc. Specific examples of the plasticizer include phthalic acid derivatives, isophthalic acid derivatives, tetrahydrophthalic acid derivatives, adipic acid Derivatives, azelaic acid derivatives, sebacic acid derivatives, dodecane-2-acid derivatives, maleic acid Conductor, fumaric acid derivatives, trimellitic acid derivatives, pyromellitic acid derivatives, citric acid derivatives,
Itaconic acid derivatives, oleic acid derivatives, ricinoleic acid derivatives, stearic acid derivatives, other fatty acid derivatives, sulfonic acid derivatives, phosphoric acid derivatives, glutaric acid derivatives, monoester plasticizers, glycol derivatives, glycerin derivatives, Paraffin derivative, epoxy derivative, polyester, polyether, poly-α-methylstyrene, low molecular weight polystyrene, liquid polychloroprene, depolymerized rubber,
Etc., as specific examples of the rubber softener, mineral oil softener,
Vegetable oil-based softeners, sub- (factis), fatty acids and fatty acid salts, etc. are specific examples of rubber reinforcing agents. Carbon black, inorganic reinforcing agents, and organic reinforcing agents are specific examples of fillers and reinforcing agents. Are inorganic fillers, organic fillers, and plastic reinforcing agents; specific examples of foaming agents and foaming aids include inorganic foaming agents, nitroso compounds, azo compounds, sulfonyl hydrazides, etc .; Specific examples of mold agents, anti-fog agents and flame retardants include paraffins and hydrocarbon resins, fatty acids, fatty acid amides, fatty acid esters, fatty acid alcohols, and partial esters of fatty acids and polyhydric alcohols.
Specific examples of the kneading antistatic agent include cationic activators, quaternary ammonium salts, and stearoamidopropyldimethyl-β-hydroxyethylammonium. Specific examples of the coloring agent include inorganic pigments and organic pigments. , Organic fluorescent pigments, pearl foil, etc., as specific examples of the coupling agent,
Examples thereof include silane-based, aluminum-based, and titanate-based coupling agents. The amount of these additives depends on
There is no particular limitation because it is appropriately prepared according to the purpose. The elastomer composition of the present invention can be obtained by preliminarily mixing these additives with a Brabender, a Banbury mixer, a kneader, an open roll or the like before the crosslinking reaction. .

The elastomer rubber composition of the present invention is molded into an intended shape by an extruder, a calender roll or a press according to the purpose, and is subjected to a vulcanization step to obtain a molded vulcanized rubber composition. The vulcanization is usually performed at a temperature of 120 ° C. or higher, preferably at a temperature of 130 to 200 ° C. for about 1 to 60 minutes, and as necessary, at a temperature of 130 to 200 ° C. for 1 to 20 hours. .

The α-olefin-conjugated polyene copolymer, elastomer composition and crosslinked elastomer composition of the present invention can be blended with a resin or another rubber.
For example, high-density polyethylene, medium-density polyethylene, low-density polyethylene, polyethylene resins such as LLDPE (linear low-density polyethylene), polypropylene resins, poly-4-methyl-pentene-1, polystyrene,
Polyester, polyamide, polyphenylene ether,
Polyolefin resin, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-non-conjugated polyene copolymer rubber, polybutadiene, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, Styrene-butadiene random copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, partially hydrogenated styrene-butadiene random copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene Block copolymer rubber, polyacrylonitrile rubber, acrylonitrile-butadiene copolymer rubber, partially hydrogenated acrylonitrile-butadiene copolymer rubber, butyl rubber, chloroprene rubber, fluorine rubber, chlorosulfonated polyethylene, silicone rubber Rubber, urethane rubber, natural rubber, or the like.

As a method for obtaining a blend of the elastomer rubber composition of the present invention and a resin or another rubber, each component is
Examples of the method include melt kneading using a twin-screw extruder, a Banbury mixer, or the like.

The α-olefin-conjugated polyene copolymer elastomer composition and the crosslinked elastomer composition of the present invention have the characteristics described in the above-mentioned various places, and are used as modifiers for various resins, automobile parts and the like. It can be optimally used in fields such as applications, electrical components, industrial components, and building materials.

[0079]

The present invention will be described in more detail with reference to the following examples, which are for illustrative purposes only and should not be construed as limiting the present invention. The measurement was performed as follows. [I] Measured Conjugated Polyene Content of Copolymer The iodine value was determined by a titration method, and the conjugated polyene content (mol%) (wt%) was calculated from the value. Differential scanning calorimeter (DSC) measurement Differential scanning calorimeter (DSC220 manufactured by Seiko Instruments Inc. )
Using C), the measurement was performed at a rate of 10 ° C./min in both the temperature raising and constant temperature processes. Intrinsic viscosity [η] The measurement was performed in xylene at 70 ° C. using an Ubbelohde viscometer.
Sample dissolved 300mg in 100ml xylene,
A 3 mg / ml solution was prepared. The solution was further diluted with 1 /
It was diluted to 2, 1/3 and 1/5, and each was diluted to 70 ° C (±
(0.1 ° C.) in a constant temperature water bath. The measurement was repeated three times at each concentration, and the obtained values were averaged and used. The molecular weight distribution was measured by gel permeation chromatography (GPC) method (Waters, 150C / GPC apparatus). The elution temperature was 140 ° C, and the column used was Shodex Packed Column A-80 manufactured by Showa Denko KK
M and polystyrene (Molecular weight 68-8, 400,000, manufactured by Tosoh Corporation) were used as the molecular weight standard substance. The obtained polystyrene-equivalent weight average molecular weight (Mw), number average molecular weight (Mn), and the ratio (Mw / Mn) are defined as a molecular weight distribution. The measurement sample was prepared by adding about 5 mg of polymer to 5 ml of o-
Dissolve in dichlorobenzene to a concentration of about 1 mg / ml. 400 μl of the obtained sample solution was injected. The elution solvent flow rate was 1.0 ml / min, and detection was performed with a refractive index detector.

Example 1 [I] Production and Evaluation of Copolymer In a separable flask reactor having a capacity of 2 liters, a stirrer, a thermometer, a dropping funnel and a reflux condenser were attached to reduce the pressure.
Replace with nitrogen. 1 liter of dried hexane in this flask
Was introduced as a polymerization solvent. Here propylene 5L / m
in was continuously fed at atmospheric pressure, and the solvent temperature was set to 0 ° C. 500 mmol of isoprene is added, and 0.5 mmol of triisobutylaluminum (hereinafter abbreviated as TIBA) is added.
Was added to the polymerization tank, and dimethylsilyl (2,3,4,5-tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride of the following chemical formula was used as a polymerization catalyst. 0.01m
mol was added to the polymerization vessel. Two minutes later, 0.05 mmol of triphenylmethyltetrakis (pentafluorophenyl) borate was added to the polymerization tank to start polymerization.
As a result of polymerization for 20 minutes, 21.8 g of a propylene-isoprene copolymer was obtained. The polymerization conditions are shown in Table 1, and the evaluation results of the copolymer are shown in Table 2.

[II] Preparation and Evaluation of Composition The propylene-isoprene copolymer synthesized in Example 1 was kneaded using an 8-inch open roll with the following composition to obtain an elastomer composition. The elastomer composition was press-vulcanized at 145 ° C. for 30 minutes, and various properties shown in Table 4 were measured as a cross-linking property test. * Blending (parts by weight) polymer: 100, HAF-carbon black: 50, aromatic process oil: 5, antioxidant: 1, zinc oxide: 5, stearic acid: 2, dibenzothiazyl disulfide: 0.8 , Tetramethylthiuram disulfide: 0.3, sulfur: 2 tensile test : Measured using a dumbbell shape No. 6 in accordance with JIS K6251. Permanent elongation test : Measured according to JIS 6301. Compression set test : 70 according to JIS 6262
The compression set after 72 hours at C was measured. Bending test : A bending crack growth test was performed at 30 ° C. according to JIS 6260. Before the measurement, a scratch of 2 mm was made, and the number of flexures required for the scratch to grow to 14 mm was measured. Ozone resistance test : A static ozone deterioration test was performed in accordance with JIS 6259, and a crack generation state at a test time of 76 hours was measured. Abrasion test : Akron abrasion test measurement was performed according to JIS 6264. The measurement conditions were a tilt angle of 25 degrees and a load of 4.5.
Kgf, rotation speed 75 times / min, a ring test piece was used as a test piece.

[0082]

[Table 1]

[0083]

[Table 2]

Description of Tables 1 and 2 * 1 Type of copolymer PI: propylene-isoprene copolymer * 2 (a): triisobutylaluminum * 3 (b): triphenylmethyltetrakis (pentafluorophenyl) borate * 4 (c): dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-
2-phenoxy) titanium dichloride * 5: When none of the peak of 1 J / g or more based on the melting of the crystal and the peak of 1 J / g or more based on the crystallization had, none was described.

[0085]

[Table 3]

A 2 mm thick press sheet was prepared from the copolymer synthesized in Example 1, and a test piece punched out from the press sheet with a JIS dumbbell shape No. 6 was used as a Shimadzu Autograph AG-500E model manufactured by Shimadzu Corporation. Using pulling speed 20
The test was performed at 0 (mm / min).

[0087]

[Table 4]

[0088]

As described above, according to the present invention, gel permeation chromatography (GPC)
It contains an α-olefin-conjugated polyene copolymer having a molecular weight distribution Mw / Mn of 3.5 or less as measured by the above, and the cross-link density is improved due to the narrow molecular weight distribution of the copolymer, resulting in excellent cross-linking properties. And a crosslinked elastomer composition obtained by crosslinking the elastomer composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/00 C08K 3/00 3/04 3/04 5/00 5/00 C08L 9/00 C08L 9 / 00 11/00 11/00 (72) Inventor Hirofumi Johoji Temple 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture F-term (reference) in Sumitomo Chemical Co., Ltd. 4F070 AA12 AA15 AA40 AC11 AC13 AC18 AC20 AC27 AC28 AC39 AC42 AC44 AC45 AC46 AC48 AC50 AC56 AC84 AC85 AC86 AE01 AE08 GA05 GA06 GA10 GB02 GB07 4J002 AC001 AC021 AC091 BB141 BB161 BB171 CC052 CC172 CC182 CC242 CN012 DA036 DA047 DA117 DE077 DE107 DE136 DE157 DE186 DE236 DG017 DG046 DJ006 EG017 DJ0077EGEK DJ0 DJ077 EG DJ0 DJ037 EK057 EK067 EK087 EN037 EN047 EN077 EN117 ES007 ES017 EU027 EU187 EU197 EV077 EV347 FA016 FA066 FA086 FA106 FD016 FD142 FD147 4J028 AA01A AB00A AB01A AC01 A AC10A AC20A AC28A BA02B BB01B BC12B BC15B BC16B BC17B BC25B BC26B EB04 EB05 EB07 EB09 EB10 EB12 EB13 EB14 FA01 FA02 FA04 FA06 FA07 GA04 GA06 GA18 GA19 4J100 AA03P AA04P AA01AQAQ ASAAQA JA43 JA67

Claims (15)

[Claims] 1. α- having a conjugated polyene content of 0.1 to 95 mol% and a molecular weight distribution Mw / Mn measured by gel permeation chromatography (GPC) of 3.5 or less. An elastomer composition containing 100 parts by weight of an olefin-conjugated polyene copolymer, 5-400 parts by weight of an inorganic filler and / or carbon black, and 0.1-20 parts by weight of a crosslinking agent. 2. An α-olefin-conjugated polyene copolymer having a peak of 1 J / g or more based on melting of a crystal and a peak of 1 J / g or more based on crystallization as measured by a differential scanning calorimeter (DSC). The elastomer composition according to claim 1, which is an α-olefin-conjugated polyene copolymer having no peak. 3. The elastomer composition according to claim 1, wherein the α-olefin-based structure of the α-olefin-conjugated polyene copolymer is an atactic structure. 4. The α-olefin-conjugated polyene copolymer having an intrinsic viscosity [η] of 0.3 or more in a xylene solvent at a temperature of 70 ° C. of 0.3 or more. The elastomer composition according to claim 1. 5. The elastomer composition according to claim 1, wherein the conjugated polyene is a hydrocarbon compound. 6. The elastomer composition according to claim 1, wherein the conjugated polyene is a branched aliphatic conjugated polyene. 7. The elastomer composition according to claim 1, wherein the conjugated polyene is isoprene. 8. An α-olefin-conjugated polyene copolymer
Is the following (A), the following (B) and / or the following (C)
Α-oleate in the presence of an olefin polymerization catalyst comprising
Α-olefin obtained by polymerizing fin and conjugated polyene
8. A method according to claim 1, wherein the copolymer is a conjugated polyene copolymer.
The elastomer composition according to claim. (A): transition gold represented by the following general formulas [I] to [III]
At least one of the genus complexes(In the above general formulas [I] to [III], M¹Is
Represents a transition metal atom of Group 4 of the Periodic Table of the Elements, where A is an element
Indicates an atom belonging to Group 16 of the Periodic Table,
Shows the atoms of Group 14 of the Rule. Cp¹Is cyclopentadi
A group having an ene-type anion skeleton is shown. X¹, X^Two,
R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are each independently water
Element atom, halogen atom, alkyl group, aralkyl group,
Reel group, substituted silyl group, alkoxy group, aralkyl group
It represents a xy group, an aryloxy group or a disubstituted amino group.
X^ThreeRepresents an atom belonging to Group 16 of the periodic table of the elements. R¹, R
^Two, R^Three, R^Four, R^FiveAnd R⁶Are optionally linked to form a ring
You may. Two M¹, A, J, Cp¹, X¹, X^Two,
X^Three, R¹, R^Two, R^Three, R^Four, R^FiveAnd R⁶Are the same for each
Or different. (B): at least one selected from the following (B1) to (B3)
(B1) General formula E¹ _aAlZ_3-aOrganic aluminum indicated by
Compound (B2) General formula ｛-Al (E^Two) -O-｝_bIndicated by
Cyclic aluminoxane having a structure (B3) General formula E^Three｛-Al (E^Three) -O-｝_cAlE^Three
_TwoLinear aluminoxane having a structure represented by the following formula (provided that E¹, E^TwoAnd E^ThreeIs a hydrocarbon group
All E¹, All E ^TwoAnd all E^ThreeIs the same
Or different. Z is a hydrogen atom or a halogen atom
Represents a child, and all Z may be the same or different
No. a is a number satisfying 0 <a ≦ 3, b is an integer of 2 or more
And c represents an integer of 1 or more. (C): Boration of any of the following (C1) to (C3)
Compound (C1) General formula BQ¹Q^TwoQ^ThreeBoron compound represented by
Object, (C2) general formula G⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-E represented by
Iodine compound, (C3) General formula (LH)⁺(BQ¹Q^TwoQ^ThreeQ^Four)^-In table
(Where B is a boron atom in a trivalent state, Q
¹~ Q^FourIs a halogen atom, hydrocarbon group, halogenated hydrocarbon
Group, substituted silyl group, alkoxy group or disubstituted amino group
And they may be the same or different.
G⁺Is an inorganic or organic cation, and L is a neutral Lewis
A base, (LH)⁺Is a Bronsted acid
You. ) 9. The elastomer composition according to claim 8, wherein A in the general formula [I], [II] or [III] is an oxygen atom. 10. X ³ in the general formula [II] or [III]
The elastomer composition according to claim 8, wherein is an oxygen atom. 11. The elastomer composition according to claim 8, wherein R ¹ in the general formula [I], [II] or [III] is an alkyl group, an aralkyl group, an aryl group or a substituted silyl group. 12. X ¹ and X ² in the general formulas [I], [II] and [III] each independently represent a halogen atom, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group or a disubstituted amino group. An elastomer composition according to claim 8. 13. The elastomer composition according to claim 8, wherein the compound (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 14. The elastomer composition according to claim 8, wherein the compound (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 15. A crosslinked elastomer composition obtained by crosslinking the elastomer composition according to any one of claims 1 to 14.