JPH11315119A - Ethylene-isoprene random copolymer, elastomer composition and crosslinked elastomer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ethylene-isoprene random copolymer having rapid vulcanizing rate and high vulcanizing density and an elastomer composition using the ethylene-isoprene random copolymer and a crosslinked elastomer composition. SOLUTION: The ethylene-isoprene random copolymer has 1-45 mol.% isoprene content or <=3.5 Q value which is represented by a ratio of number- average molecular weight (Mn) to weight-average molecular weight (Mw). The elastomer composition comprises 100 pts.wt. of the copolymer, 5-400 pts.wt. inorganic filler and/or carbon black and 0.1-20 pts.wt. crosslinking agent. The crosslinked elastomer composition is obtained by crosslinking the elastomer composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an ethylene-isoprene random copolymer, an elastomer composition and a crosslinked elastomer composition. More specifically,
The present invention provides an ethylene-isoprene random copolymer having a high vulcanization rate and a high vulcanization density.
The present invention relates to an elastomer composition and a crosslinked elastomer composition using the ethylene-isoprene random copolymer. The term "random copolymer" used here is an academic expression such as "Kodansha Essential Polymer Science,
21 pages of Seiichi Nakahama et al. "

[0002]

2. Description of the Related Art As a conventional ethylene-isoprene random copolymer, Japanese Patent Publication No. 48-56775 discloses a process for producing an ethylene-isoprene amorphous copolymer using a vanadium chloride compound. Also,
DONG-HOLDE etc. is Et (Ind) ₂ ZrCl ₂
/ A technology using MAO is disclosed (Eur. Pol
ym. J. Vol. 33, no. 4, pp447, 19
97). However, an ethylene-isoprene random copolymer characterized by a high vulcanization rate and a high vulcanization density has not been known.

[0003]

Under such circumstances,
An object of the present invention is to provide an ethylene-isoprene random copolymer having a high vulcanization rate and a high vulcanization density, an elastomer composition using the ethylene-isoprene random copolymer, and crosslinking. The purpose of the present invention is to provide an elastomer composition. In addition,
The high vulcanization rate makes it possible to reduce costs in the vulcanization step or the post-treatment step, and also to reduce the amount of vulcanization accelerator used. In addition, when the vulcanization density is high, there are advantages that a sponge rubber with high foaming and high rigidity can be obtained, low-temperature setability and oil resistance are excellent, high filling is possible and cost reduction is possible. .

[0004]

That is, a first aspect of the present invention is an ethylene-isoprene random copolymer having an isoprene content of 1 to 45 mol%, or a number average molecular weight (Mn) / The present invention relates to an ethylene-isoprene random copolymer having a Q value that is a ratio of weight average molecular weight (Mw) of 3.5 or less.

A second aspect of the present invention is the ethylene-isoprene random copolymer 10 of the first aspect.
0 parts by weight, inorganic filler and / or carbon black 5
The present invention relates to an elastomer composition containing 400 parts by weight and 0.1 to 20 parts by weight of a crosslinking agent.

Further, a third aspect of the present invention relates to a crosslinked elastomer composition obtained by crosslinking the elastomer composition of the second aspect.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION One of the ethylene-isoprene random copolymers of the present invention is an ethylene-isoprene random copolymer having an isoprene content of 1 to 45 mol%, preferably The content is 1.2 to 4
0 mol% of ethylene-isoprene random copolymer. If the content of isoprene is too low, vulcanization is insufficient, while if the content of isoprene is too high, catalytic activity, molecular weight and vulcanization density decrease.

The other copolymer of the ethylene-isoprene random copolymer of the present invention has a number average molecular weight (Mn) /
It is an ethylene-isoprene random copolymer having a Q value, which is a ratio of weight average molecular weight (Mw), of 3.5 or less, preferably 1.8 to 3.5, more preferably 1.8 to 3.5. 2.5. If the Q value is excessive, for example, when the film is used for an application such as a film, problems such as a decrease in strength, an increase in a bleed component, an increase in an extractable component and the like, and a decrease in film density occur. When used as a rubber, there are problems in practical physical properties such as inferior cross-linking physical properties such as compression set and tensile rigidity.

The molecular weight distribution is measured by gel permeation chromatography (GPC) method (for example,
150C / GPC device). Elution temperature is 140
C., column used is, for example, Shodex manufactured by Showa Denko KK
Packed Column A-80M, the molecular weight standard substance is polystyrene (for example, Tosoh Corporation, molecular weight 6
8-8, 400,000). The obtained polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (M
n), and this ratio (Mw / Mn) is used as the molecular weight distribution.
As a measurement sample, about 5 mg of a polymer is dissolved in 5 ml of o-dichlorobenzene, and the concentration is about 1 mg / ml. Inject 400 μl of the obtained sample solution,
The elution solvent flow rate is 1.0 ml / min, and detection is performed with a refractive index detector.

The ethylene-isoprene random copolymer of the present invention has a feature that the ratio of the content of ethylene and isoprene to the molecular weight distribution from the low molecular weight region to the high molecular weight region is almost uniform and the composition distribution is narrow.

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 obtained ethylene-isoprene random copolymer may be inferior in physical 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 ethylene-isoprene random copolymer of the present invention
The polymer includes the following (A), the following (B) and / or
(C) and an olefin polymerization catalyst.
It can be manufactured appropriately. That is, the catalyst residue in the polymer
Contamination is low, especially chlorine content of conventional Ziegler
It is much lower than when using a Natta catalyst.
You. This reduces discoloration of the polymer and
It also has an effect on the expansion of applications to other ways, and manufactures optimally
Means that. (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 that the effect of expanding the application to food applications and the like is exerted, and that the polymer is produced optimally.

Hereinafter, the above production method will be described in more detail. (A) The transition metal complex will be described. The transition metal complex (A) is represented by the general formula [I], [II] or [III]. In the general formulas [I], [II] and [III], the transition metal atom represented by M ¹ is a periodic table of elements (IUPA).
C, a transition metal element of Group 4 of the inorganic chemical nomenclature revised edition 1989), such as a titanium atom, a zirconium atom, and a hafnium atom. Preferably it is a titanium atom or a zirconium atom. Examples of atoms belonging to Group 16 of the periodic table of the element represented by A in Formulas [I], [II], and [III] include an oxygen atom, a sulfur atom, and a selenium atom, and preferably an oxygen atom It is. Formula [I], [II] or [II
No. 14 of the periodic table of the elements denoted by J in [I]
Examples of group atoms include a carbon atom, a silicon atom, and a germanium atom, and are preferably 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 A 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
- methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl group, eta ⁵ - triethylsilyl indenyl group, eta ^{5-tert-butyldimethylsilyl} indenyl group, eta 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
- propyl fluorenyl group, eta ⁵ - di -n- propyl fluorenyl group, eta ⁵ - isopropyl fluorenyl group, eta 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 N-yl, η ⁵ -n-hexylfluorenyl, η ⁵ -n-octylfluorenyl, η ⁵ -n-decylfluorenyl, η ⁵ -n-dodecylfluorenyl, η ^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 and 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
^{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. All of these aryl groups are a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as 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 substituted silyl group represented by ⁵ or R ⁶ is a silyl group substituted by 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.
Any of these substituted silyl groups is a hydrocarbon group, a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, a methoxy group, an alkoxy group such as an ethoxy group,
An aryloxy group such as a phenoxy group or an aralkyloxy group such as a benzyloxy group may be partially substituted.

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
~ 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 are 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 and 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 aralkyloxy group for ⁵ or R ⁶ is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, a (2-methylphenyl) methoxy group, a (3-methylphenyl) methoxy group, a (4-methylphenyl) methoxy group. 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 an (octylphenyl) methoxy group, a (n-decylphenyl) methoxy group, a (n-tetradecylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy 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, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

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

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
10 to 6 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 arbitrarily combined to form a ring. Preferred R ¹ includes an alkyl group, an aralkyl group, an aryl group and a substituted silyl group. Preferred X ¹ and X ² are each independently a halogen atom,
Examples thereof include an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, and a disubstituted amino group, and more preferable examples include a halogen atom and an alkoxy group. Examples of Group 16 atoms in the periodic table of the element represented by X ³ in Formula [II] or [III] include, for example, an oxygen atom, a sulfur atom, and a selenium atom, and are preferably an oxygen atom.

The transition metal complex represented by the general formula [I] includes, for example, methylene (cyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-ter
t-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert
-Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-trimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-butyl-5-chloro-2- Phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-t
tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyldimethyl Silyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, methylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2)
-Phenoxy) titanium dichloride, methylene (t
tert-butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) 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-butylcyclopentadienyl) (3-trimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methoxy-2-phenoxy)
Titanium dichloride, methylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2
-Phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (tetramethylcyclopentadienyl) (3-tert-butyl-5 -Chloro-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2
-Phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Methylene (trimethylsilylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert -Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3 -T
tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3,5- Dimethyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, methylene (fluorenyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, 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) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-phenyl-2-yl) Phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-tert
-Butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert -Butyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5
-Methyl-2-phenoxy) titanium dichloride,
Isopropylidene (methylcyclopentadienyl) (3
-Phenyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl)
(3-tert-butyldimethylsilyl-5-methyl-
2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-
Phenoxy) titanium dichloride, isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3,5-dimethyl- 2-phenoxy)
Titanium dichloride, isopropylidene (tert
-Butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl)
(3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (te
rt-butylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl- 5
-Methoxy-2-phenoxy) titanium dichloride, isopropylidene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadiene) Enil) (3-
Phenyl-2-phenoxy) titanium dichloride,
Isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5
-Methoxy-2-phenoxy) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3, 5-
Dimethyl-2-phenoxy) titanium dichloride,
Isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl- 5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl)
(3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, isopropylidene (trimethylsilylcyclopentadienyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3,5
-Dimethyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert
-Butyl-2-phenoxy) titanium dichloride,
Isopropylidene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert- Butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl)
(3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-methoxy-2
-Phenoxy) titanium dichloride, isopropylidene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride , Diphenylmethylene (cyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl Dimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3 -Tert-
Butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert- Butyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl- 2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tert
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl)
(3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyldimethyl Silyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) ) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) ( 3-tert
-Butyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, Diphenylmethylene (tetramethylcyclopentadienyl) (3
-Tert-butyldimethylsilyl-5-methyl-2-
Phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5- Methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3,5 −
Dimethyl-2-phenoxy) titanium dichloride,
Diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, Diphenylmethylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, Diphenylmethylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-methoxy-
2-phenoxy) titanium dichloride, diphenylmethylene (trimethylsilylcyclopentadienyl)
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-2 -Phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) ) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-trimethylsilyl-5-methyl-2- Phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, etc., and titanium of these compounds is zirconium or hafnium The compound in which dichloride was changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide, and (cyclopentadienyl) was changed to (dimethylcyclopentadiene) Enyl), (trimethylcyclopentadienyl), (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
J in the general formula [I] such as a compound modified to -methyl-2-phenoxy), (3-tert-butyldimethylsilyl-2-phenoxy), or (3-trimethylsilyl-2-phenoxy) is a carbon atom. Transition metal complex, dimethylsilyl (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-methyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-dimethyl-2-
Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-2)
-Phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3-tert-butyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5
-Di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (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-phenoxy) titanium dichloride, Dimethylsilyl (cyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (Methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl -
2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-
Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) ( 5-methyl-3-phenyl-
2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-
Butyldimethylsilyl-5-methyl-2-phenoxy)
Titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-ter
t-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilyl (methylcyclopentadienyl) (3,5-diamyl-
2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n
-Butylcyclopentadienyl) (3,5-dimethyl-
2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-di-tert
-Butyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (n-butylcyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl ( n-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, dimethylsilyl (n-
Butylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (Tert-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (ter
t-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyldimethyl Cyril-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) ( 3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tert-butylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (2-phenoxy) titanium Dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (Tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert
-Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadiene) Enyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) ) (5-
Methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) )
(3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (3,5-diamyl-2
-Phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopenta Dienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert -Butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-
Chloro-2-phenoxy) titanium dichloride, dimethylsilyl (trimethylsilylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-di-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3-tert-butyl -5-chloro-
2-phenoxy) titanium dichloride, dimethylsilyl (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-2- Phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride Dimethylsilyl (fluorenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride,
Dimethylsilyl (fluorenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-tert
-Butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl) (3-
tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilyl (fluorenyl)
(3,5-Diamyl-2-phenoxy) titanium dichloride, dimethylsilyl (tetramethylcyclopentadienyl) (1-naphthoxy-2-yl) titanium dichloride and the like, and (cyclopentadienyl) of these compounds are (Dimethylcyclopentadienyl), (trimethylcyclopentadienyl), (ethylcyclopentadienyl), (n-propylcyclopentadienyl), (isopropylcyclopentadienyl), (sec-butylcyclopentadienyl) , (Isobutylcyclopentadienyl), (tert-butyldimethylsilylcyclopentadienyl), (phenylcyclopentadienyl),
(Methylindenyl) or a compound in which (phenylindenyl) is changed, (2-phenoxy) is converted to (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy), or (3-tert-butyldimethyl) A compound in which dimethylsilyl is changed to diethylsilyl, diphenylsilyl, or dimethoxysilyl, a compound in which titanium is replaced with zirconium,
Or a compound of the general formula [I] such as a compound in which hafnium has been changed, or a compound in which dichloride has been changed to dibromide, diiodide, bis (dimethylamide), bis (diethylamide), di-n-butoxide or diisopropoxide.
Wherein J is a group 14 atom of the periodic table of elements other than carbon atoms.

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 aluminum compound (B) will be described. As the aluminum compound (B), the following (B1)
And (B3) are at least one aluminum compound. (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.

Specific examples of the organoaluminum compound (B1) represented by the general formula E ¹ _a AlZ _3-a include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum and trihexylaluminum; Dialkylaluminum chlorides such as dimethylaluminum chloride, diethylaluminum chloride, dipropylaluminum chloride, diisobutylaluminum chloride, dihexylaluminum chloride; alkylaluminum dichlorides such as methylaluminum dichloride, ethylaluminum dichloride, propylaluminum dichloride, isobutylaluminum dichloride, 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.

[0032] 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 is 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 or the like) in a suitable organic solvent (benzene or 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 (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified.

The (C) boron compound will be described. As the boron compound (C), (C1) a compound represented by the general formula BQ ¹ Q ²
A boron compound represented by Q ³ , (C2) a general formula G ⁺ (B
^{Q 1 Q 2 Q 3 Q 4} ) - boron compound represented by, (C3) the general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - using either a boron compound represented by be able to.

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).

The general 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, 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.

Specific examples of these combinations include ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, Phenylmethyltetrakis (pentafluorophenyl) borate,
Examples thereof include triphenylmethyltetrakis (3,5-bistrifluoromethylphenyl) borate, and most preferably 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 general formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4) - is a Brønsted acid in the compound represented by (L-
Specific examples of H) ⁺ include trialkyl-substituted ammonium, N, N-dialkylanilinium, dialkylammonium, triarylphosphonium, and the like.
As (BQ ¹ Q ² Q ³ Q ⁴ ) ^{-, the same} as those described above can be mentioned.

Specific combinations thereof include 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 above-mentioned cyclic aluminoxane (B2) and / or 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 from 0.1 to 10,000, preferably from 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 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, in terms of Al atom, 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 ethylene-isoprene random 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 and the like are possible, and both continuous polymerization and batch polymerization are possible. The polymerization temperature is from -70 to 350
Although the range of ° C can be taken, the range of -50 to 220 ° C is particularly preferable, and the range of -20 to 120 ° C is more preferable. The polymerization pressure can range from atmospheric pressure to 350 MPa, preferably from atmospheric pressure to 100 MPa, more preferably from atmospheric pressure to 10 MPa. The polymerization time is generally appropriately determined depending on the type of the catalyst to be used and the reactor, 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.

Next, the elastomer composition of the present invention will be described. The elastomer composition of the present invention is 100 parts by weight of the ethylene-isoprene random copolymer of the present invention,
An elastomer composition containing 5-400 parts by weight of an inorganic filler and / or carbon black and 0.1-20 parts by weight of a crosslinking agent.

Ethylene-isoprene random 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 processability is poor. When the inorganic filler and / or carbon black are used in combination, the amount of the filler is based on the total amount of the filler.

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 ethylene-isoprene random 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'disinnamyliden-1,
6-hexanediamine, 4,4'-methylenebis (cyclohexylamine) carbamate, 4,4'-methylenebis- (2-chloroaniline) and the like,
Specific examples of the resin crosslinking agent include an alkylphenol-formaldehyde resin, a 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-butylperoxy Shioisobutre-
Tert-butyl peroxy 2-ethylhexanoate,
Tertiary butyl peroxy benzoate, tertiary butyl peroxy isopropyl carbonate, tertiary butyl peroxy allyl carbonate, acrylic cross-linking agents, and other cross-linking agents include ethylene glycol dimethacrylate , Trimethylolpropane trimethacrylate, polyfunctional methacrylate monomer, polyvalent alcohol methacrylate, N, N'-m-phenylenebismaleimide, ammonium benzoate, silica filler-containing monomer, 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-nitropropyl) -1,6-hexanediamine, isocyanuric acid, thiadiazole derivative, cationic activator, special mixed vulcanizing agent, high-purity industrial soap and the like can be mentioned. In addition, these crosslinking agents are arbitrarily selected according to use. The amount of the cross-linking agent used is also arbitrarily selected depending on the required cross-linking speed, required properties of the cross-linked product, and the like. 1-2
0 parts by weight, preferably 0.2 to 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.

The elastomer composition of the present invention can be mixed with various additives known in the art (Handbook of Rubber and Plastic Compounds Revised 2nd Edition, edited by Rubber-Digest Co., Ltd.) as necessary. Examples of such additives include vulcanization accelerators, vulcanization accelerators, activators, scorch inhibitors, antioxidants, antioxidants, antiozonants, ultraviolet absorbers, light stabilizers, Kneading accelerator, tackifier, plasticizer, rubber softener, rubber reinforcing agent, filler, reinforcing agent, foaming agent, foaming aid, lubricant, slip agent, internal mold release agent, anti-fog agent, flame retardant, kneading Antistatic agent for coloring, coloring agent, coupling agent,
Preservatives, fungicides and the like are exemplified. Specific examples of each additive described in the publicly known document (Handbook of Rubber / Plastic Compounding Chemicals Revised 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 accelerator / 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-antioxidant-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, 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. or,
These additives are usually mixed with a Brabender, a Banbury mixer, a kneader, an open roll or the like before the crosslinking reaction to obtain the elastomer rubber composition of the present invention.

The elastomer rubber composition of the present invention is formed 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 formed vulcanized rubber composition. Vulcanization is usually performed at a temperature of 120 ° C. or higher, preferably 130 to 200 ° C., and pressure and atmospheric pressure.
Primary vulcanization under heating of 15 MPa for about 1 to 60 minutes, and if necessary at a temperature of 130 to 200 ° C. for 1 to 20 hours,
Secondary vulcanization.

The ethylene-isoprene random copolymer, elastomer composition and crosslinked elastomer composition of the present invention can be blended with a resin or another rubber.
Examples include 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-propylene-non-conjugated diene copolymer rubber, ethylene-α-olefin-non-conjugated diene 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 It may be performed with rubber, chlorosulfonated polyethylene, silicon rubber, urethane rubber, natural rubber, or the like. If necessary, a crosslinking reaction can be carried out by adding a crosslinking agent such as peroxide or sulfur.
Further, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a lubricant, an antistatic agent, a pigment, a filler, and a flame retardant may be added.

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 ethylene-isoprene random copolymer, elastomer composition and crosslinked elastomer composition of the present invention have the characteristics as described in the above-mentioned various places, and are used as modifiers for various resins, automotive parts, It can be optimally used in the fields of electric parts use, industrial parts use, building materials use and the like.

[0057]

EXAMPLES [I] Measurement method The measurement was performed as follows. (1) Intrinsic viscosity [η] This was carried out 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. (2) Molecular weight distribution Gel permeation chromatography (GPC) method (W
aters company, 150C / GPC apparatus). The elution temperature is 140 ° C and the column used is Showa Denko S
Odex Packed Column A-80M, molecular weight standard substance is polystyrene (manufactured by Tosoh Corporation, molecular weight 68
-8,400,000). The obtained polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (M
n) and the ratio (Mw / Mn) is defined as the molecular weight distribution. As a measurement sample, about 5 mg of a polymer is dissolved in 5 ml of o-dichlorobenzene, and the concentration is 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. (3) GPC-IR Measurement Gel Permission Chromatography (CFCT-150A Apparatus, Dia Instruments Co., Ltd.) / Fourier Transform Infrared Spectroscopy (Nicolet Co., Ltd., Mag,
na550 FTIR apparatus). Elution temperature is 14
0 ° C, column used is UT-806 manufactured by Showa Denko KK
Using two of M, 100 mg of the polymer was dissolved in 25 ml of o-dichlorobenzene, and 0.8 ml of the obtained sample solution was injected. The resulting solution is then placed in an FT-IR device and
The absorption peak based on the CH stretching vibration at 82 cm-1 is analyzed. (4) Density Determined according to JIS K-6760 (23 ° C value). (5) Iodine value The isoprene content (mol%) was determined by titration, and the value was calculated from the value. (6) Structure of isoprene contained in the copolymer Calculated from the area intensity of each assigned signal in the nuclear magnetic resonance spectrum. trans-1,4 1.62-1.65 (3H) cis-1,4 1.71-1.73 (3H) 1,2,4.90 (2H) 3,4 4.81 (2H) trans1. 4 + cis1.4.24 (2H)

[II] Preparation of polymerization catalyst (1) Synthesis of transition metal complex (dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride) ) Synthesis of 1-bromo-3-tert-butyl-5-methyl-2-phenol 20.1 g of 2-tert-butyl-4-methylphenol in a 500 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere. 123 mmol) in 150 ml of toluene, followed by 25.9 ml of tert-butylamine.
(18.0 g, 246 mmol) was added. The solution was cooled to -70 ° C, and 10.5 ml of bromine (32.6 ml) was added thereto.
g, 204 mmol). This solution was kept at -70 ° C and stirred for 2 hours. Thereafter, the temperature was raised to room temperature, and 100 ml of 10% diluted hydrochloric acid was added each time, followed by washing three times. The organic layer obtained after washing is dried using anhydrous sodium sulfate, the solvent is removed using an evaporator, and then purified using a silica gel column, and 1-bromo-3-tert-butyl as a colorless oil is obtained. 18.4 g (75.7 mmol) of -5-methyl-2-phenol was obtained. The yield was 62%.

(B) Synthesis of 1-bromo-3-tert-butyl-2-methoxy-5-methylbenzene In a 100 ml four-necked flask equipped with a stirrer under a nitrogen atmosphere, 1 -Bromo-3-ter
13.9 g of t-butyl-5-methyl-2-phenol
(57.2 mmol) was dissolved in 40 ml of acetonitrile, followed by 3.8 g (67.9 mmol) of potassium hydroxide.
l) was added. Further, 17.8 ml of methyl iodide (4
0.6 g, 286 mmol) was added and stirring continued for 12 hours. Thereafter, the solvent was removed by an evaporator, and 40 ml of hexane was added to the residue to extract hexane-soluble components.
The extraction was repeated three times. The solvent was removed from the extract, and 1-bromo-3-tert-butyl- as a pale yellow oil was obtained.
13.8 g of 2-methoxy-5-methylbenzene (5
3.7 mmol). The yield was 94%.

(C) Synthesis of (3-tret-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane Tetrahydrofuran (31.5 ml), hexane (13
9 ml) and 1-bromo-3-t synthesized in (2) above.
To a solution of tert-butyl-2-methoxy-5-methylbenzene (45 g) was added at −40 ° C. a 1.6 mol / l hexane solution of n-butyllithium (115
ml) was added dropwise over 20 minutes. The obtained mixture was -4
After incubating at 0 ° C for 1 hour, tetrahydrofuran (3
1.5 ml) was added dropwise. Dichlorodimethylsilane (1
31 g) and hexane (306 ml) at −40 ° C., the mixture obtained above was added dropwise. The resulting mixture was allowed to warm to room temperature over 2 hours and then at room temperature for 1 hour.
Stir for 2 hours. The solvent and excess dichlorodimethylsilane were distilled off from the reaction mixture under reduced pressure, hexane-soluble components were extracted from the residue using hexane, and the solvent was distilled off from the resulting hexane solution to give a pale yellow oil. (3-te
41.9 g of rt-butyl-2-methoxy-5-methylphenyl) chlorodimethylsilane were obtained. The yield is 84
%Met.

(D) Synthesis of (3-tert-butyl-2-methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (3-tert-butyl-2-silane) synthesized in the above (c). (Methoxy-5-methylphenyl) chlorodimethylsilane (5.24 g) and tetrahydrofuran (50 ml) were added to a solution of lithium tetramethylcyclopentadienyl (2.73 g) at -35 ° C at -35 ° C for 2 hours. Then, the mixture was heated to room temperature, and further stirred at room temperature for 10 hours. The solvent was distilled off from the obtained reaction mixture under reduced pressure, and the hexane-soluble component was extracted from the residue with hexane.The solvent was distilled off from the obtained hexane solution under reduced pressure to give a yellow oil. (3-tert-butyl-2-methoxy-5
-Methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane 6.69 g was obtained. The yield is 97
%Met.

(E) Synthesis of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (3-tert-butyl-2) synthesized in the above (d). -Methoxy-5-methylphenyl) dimethyl (tetramethylcyclopentadienyl) silane (10.04 g), toluene (100 ml) and triethylamine (6.30 g)
A solution of 1.63 mol / l of n-butyllithium in hexane (19.0 m
l) was added dropwise, and then the temperature was raised to room temperature over 2 hours.
Further, the temperature was kept at room temperature for 12 hours. At 0 ° C under nitrogen atmosphere,
A solution of titanium tetrachloride (4.82 g) in toluene (50
ml), the mixture obtained above was added dropwise, and the mixture was heated to room temperature over 1 hour, and then heated and refluxed for 10 hours.
The reaction mixture was filtered, the solvent was distilled off from the filtrate, and the residue was recrystallized from a mixed solvent of toluene and hexane to give orange columnar crystals of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-butyl-5 3.46 g of methyl-2-phenoxy) titanium dichloride were obtained. The yield was 27%. The spectrum data was as follows. ¹ H-NMR (CDCl ₃ ) δ 0.57 (s, 6
H), 1.41 (s, 9H), 2.15 (s, 6H),
2.34 (s, 6H), 2.38 (s, 3H), 7.1
5 (s, 1H), 7.18 (s, 1H) 13 C-NMR (CDCl 3) δ 1.25,14.4
8, 16.28, 22.47, 31.25, 36.2
9, 120.23, 130.62, 131.47, 13
3.86, 135.50, 137.37, 140.8
2, 142.28, 167.74 Mass spectrum (CI, m / e) 458

[III] Polymerization reaction Example 1 A 2 L separable flask reactor equipped with a stirrer, thermometer, dropping funnel and reflux condenser was depressurized, and then nitrogen gas was introduced, and the inside was replaced with nitrogen gas. did. 1 L of dried hexane was introduced into the flask as a polymerization solvent. Here, ethylene (8 L / min) was continuously fed at atmospheric pressure, and the temperature of the solvent was set to 0 ° C. using a thermostatic water bath. Thereto was added isoprene (25 mmol). Then
A hexane solution of TIBA (0.5 mmol / Al) was added to the polymerization solvent. Subsequently, dimethylsilyl (tetramethylcyclopentadienyl) (3-tertiary-5-methyl-
A hexane solution (0.002 mmol / Ti) of 2-phenoxy) titanium dichloride was added to the polymerization solvent, and a toluene solution of trispentafluorophenyl borate (0.01 mmol / B) was added. After stirring for 30 minutes, methanol was added to stop the reaction, and the solvent was recovered to obtain 7.4 g of an ethylene-isoprene random copolymer. The isoprene structure of the obtained ethylene-isoprene random copolymer was determined by ¹ H NMR. As a result, 1,4 bonds were 99 mol% or more.

Examples 2 to 4 The same operation as in Example 1 was performed basically in the same manner. Table 1 shows detailed polymerization conditions and evaluation results of the copolymer.

Example 5 Hexane 80 was placed in an autoclave sufficiently purged with nitrogen.
0 ml was charged and this was cooled to 0 ° C. Thereto was charged 50 mmol of isoprene and 2 g of ethylene. Then
A hexane solution of TIBA (1.5 mmol / Al) was added to the polymerization solvent. Subsequently, dimethylsilyl (tetramethylcyclopentadienyl) (3-tertiary-5-methyl-
A hexane solution (0.005 mmol / Ti) of 2-phenoxy) titanium dichloride was added to the polymerization solvent, and a toluene solution of trispentafluorophenyl borate (0.025 mmol / B) was added. The pressure of ethylene was kept at 0.1 MPa (gauge pressure) during the polymerization. 7
After stirring for one minute, methanol was added to stop the reaction, and the solvent was recovered to obtain 4.8 g of an ethylene-isoprene random copolymer. The isoprene structure of the obtained ethylene-isoprene random copolymer was analyzed by ¹ H NMR.
As a result, 1,4 bonds were 99 mol% or more.

Examples 6 to 12 In Example 5, the operation was basically performed in the same manner. Table 1 shows detailed polymerization conditions and evaluation results of the copolymer.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 5, except that ethylene was not used as a monomer, and only isoprene was added.
As a result, no polymer was formed.

[IV] Preparation and Evaluation of Composition Next, the ethylene-isoprene random copolymer synthesized in Examples 9 and 12 was kneaded using an 8-inch open roll with the following composition, and an elastomer composition was obtained. Obtained.
The vulcanization rate and vulcanization density of the elastomer composition were measured using an oscillating disc rheometer manufactured by Toyo Seiki Co., Ltd.
The measurement was performed at 5 ° C. Formulation (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 The following can be seen from the results. The ethylene-isoprene random copolymer satisfying the conditions of the present invention is commercially available EPDM.
-Compared with ENB or synthetic isoprene rubber, has a vulcanization rate comparable to synthetic isoprene rubber,
Moreover, the vulcanization density was much higher than that of EPDM-ENB or synthetic isoprene rubber.

[0069]

[Table 1]

* 1 Instead of dimethylsilyl (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, isopropylidene (cyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride was used.

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4] * 2 MH: Maximum torque value * 3 ML: Minimum torque value * 4 t'c (90): Optimal vulcanization time

[0074]

[0075]

As described above, according to the present invention, an ethylene-isoprene random copolymer characterized by a high vulcanization rate and a high vulcanization density;
An elastomer composition and a crosslinked elastomer composition using an isoprene random copolymer could be provided.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of a method for producing an ethylene-isoprene random copolymer of the present invention.

FIG. 2 is a view showing an oscillating disc rheometer measurement result of the copolymers of Example 12 and Example 9.

FIG. 3 is a view showing a GPC-IR measurement result of a copolymer of Example 6.

FIG. 4 is a diagram showing a ¹ H NMR measurement result of a copolymer of Example 6.

──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. ⁶ Identification symbol FI // (C08F 210/02 236: 08)

Claims (14)

[Claims] 1. An ethylene-isoprene random copolymer having an isoprene content of 1 to 45 mol%. 2. Ethylene having a Q value of 3.5 or less, which is a ratio of number average molecular weight (Mn) / weight average molecular weight (Mw).
Isoprene random copolymer. 3. Ethylene having an isoprene content of 1 to 45 mol% and a Q value of a ratio of number average molecular weight (Mn) / weight average molecular weight (Mw) of 3.5 or less.
Isoprene random copolymer. 4. The ethylene-isoprene random copolymer according to claim 1, wherein the intrinsic viscosity [η] of the xylene solvent at a temperature of 70 ° C. is 0.3 or more. 5. The following (A), the following (B) and / or
Existence of olefin polymerization catalyst using (C)
Below, obtained by polymerizing α-olefin and conjugated polyene
Ethylene-iso according to one of claims 1 to 4.
Pren random copolymer. (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. ) 6. The ethylene-isoprene random copolymer according to claim 5, wherein A in the general formula [I], [II] or [III] is an oxygen atom. 7. X in the general formula [II] or [III]
6. The ethylene-isoprene random copolymer according to claim 5, wherein ³ is an oxygen atom. 8. The ethylene-isoprene random copolymer according to claim 5, 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. 9. 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. The ethylene of claim 5,
Isoprene random copolymer. 10. The ethylene-isoprene random copolymer according to claim 5, wherein the compound (B) is triethylaluminum, triisobutylaluminum or methylaluminoxane. 11. The ethylene-isoprene random copolymer according to claim 5, wherein the compound (C) is dimethylanilinium tetrakis (pentafluorophenyl) borate or triphenylmethyltetrakis (pentafluorophenyl) borate. 12. In the presence of a catalyst for olefin polymerization comprising (A) according to claim 5, and (B) and (C),
4. A polymerization of an α-olefin and a conjugated polyene.
The ethylene-isoprene random copolymer according to claim 1. 13. The ethylene-isoprene random copolymer according to claim 1, 100 parts by weight, an inorganic filler and / or carbon black 5 to 40.
An elastomer composition containing 0 parts by weight and 0.1 to 20 parts by weight of a crosslinking agent. 14. A crosslinked elastomer composition obtained by crosslinking the elastomer composition according to claim 13.