JP2000143675A - Modified aluminumoxy compound, catalyst component for addition polymerization, catalyst for addition polymerization, production of oleinic polymer, production of alkenyl aromatic hydrocarbon polymer, and copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new aluminumoxy compound useful as an addition polymerization catalyst component used together with a transition metal compound, to provide the use of the aluminumoxy compound, and to provide a copolymer having a high mol.wt. SOLUTION: (1) A modified aluminumoxy compound modified a hydroxyl group- having compound and having a 30 ppm strength M2/10 ppm strength M1 ratio of >=0.60 in 27Al-solid NMR spectrum. (2) an addition polymerization catalyst component comprises the compound. (3) An addition polymerization catalyst component using the catalyst component. (4) A method for producing an olefinic polymer comprises singly polymerizing or copolymerizing an olefin in the presence of the catalyst. (5) A method for producing an alkenyl aromatic hydrocarbon polymer comprises singly polymerizing an alkenyl aromatic hydrocarbon or copolymerizing the alkenyl aromatic hydrocarbon with an olefin. And (6) a copolymer of an alkenyl aromatic hydrocarbon with the olefin has a number-average mol.wt. (Mn) of >=700,000 and a mol.wt. distribution (weight-average mol.wt. Mw/Mn) of 1.85-2.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel modified aluminum oxy compound, a catalyst for addition polymerization containing the modified aluminum oxy compound as a component, and a method for producing a polymer using the catalyst.

[0002]

2. Description of the Related Art A method for producing an olefin polymer using an addition polymerization catalyst comprising a transition metal compound (for example, metallocene or non-metallocene) and an aluminum oxy compound is well known. For example, JP-A-58-
No. 19309 reports a method using bis (cyclopentadienyl) zirconium dichloride and methylaluminoxane. However, in general, in order to obtain an olefin polymer in a high yield, it is necessary to use one transition metal atom.
Aluminum atom 1000 to 10,000 mo per mol
1 and a large amount of an aluminum oxy compound need to be added. As a result, there have been serious problems such as a rise in production cost and a large amount of aluminum atoms remaining in the olefin polymer, which adversely affects the physical properties of the olefin polymer.

[0003] In order to solve these problems, many reports have been made on the reduction of the amount of aluminum oxy compound used. For example, JP-A-60-26060
No. 2 and JP-A-60-130604 report a method in which an aluminum oxy compound and an organic aluminum compound are used in combination with a transition metal compound. JP-A-63-130601 reports a method using a metallocene complex with methylaluminoxane, an aluminum oxy compound in which at least one isobutyl group is bonded to an aluminum atom, and the like. However, even these methods have not sufficiently solved the above-mentioned problems. Furthermore, polymers obtained with these catalysts generally have a low molecular weight, and further improvement is required for practical use.

In recent years, JP-A-6-329714 reports a method in which an aluminum oxy compound having an electron-withdrawing group or a group containing an electron-withdrawing group is used as a catalyst component for addition polymerization. According to this method, a highly active catalyst can be obtained, and when an olefin is polymerized using this catalyst, an olefin polymer having a relatively large molecular weight can be obtained. However, the catalytic activity and the molecular weight of the obtained olefin polymer are not necessarily sufficient. To produce an industrially useful olefin polymer, a new polymerization activity and a new molecular weight of the polymer are realized. The discovery of a novel aluminum oxy compound has been anticipated.

[0005]

In view of the above situation, an object of the present invention, that is, an object of the present invention, is to produce a high-efficiency olefin polymer of high molecular weight by using it together with a transition metal compound. An object of the present invention is to provide a novel aluminum oxy compound useful as a catalyst component for addition polymerization. Further, an addition polymerization catalyst using the novel aluminum oxy compound, a method for producing an olefin polymer and a method for producing an alkenyl aromatic hydrocarbon polymer using the addition polymerization catalyst, and a high molecular weight copolymer Is to provide.

[0006]

Means for Solving the Problems] Specifically, the present invention is modified with a compound having a hydroxyl group, its ²⁷ Al- solid NM
Intensities M1 and 3 at 10 ppm in the R spectrum
The ratio M2 / M1 with the intensity M2 at 0 ppm is 0.60
The modified aluminum oxy compound described above, a catalyst component for addition polymerization comprising the modified aluminum oxy compound, an addition polymerization catalyst using the modified aluminum oxy compound, and homopolymerization or copolymerization of olefins using the addition polymerization catalyst. Method for producing olefin polymer to be polymerized, method for producing alkenyl aromatic hydrocarbon polymer by homopolymerizing alkenyl aromatic hydrocarbon or copolymerizing alkenyl aromatic hydrocarbon and olefin using said catalyst for addition polymerization And a copolymer of an alkenyl aromatic hydrocarbon and an olefin, having a number average molecular weight (Mn) of 70.
Molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of not less than 0000
Is 1.85 to 2.5.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
I do. (A) Modified aluminum oxy compound The modified aluminum oxy compound of the present invention has a hydroxyl group.
Is modified with a compound²⁷Al-solid NMR
Intensities M1 and 30 at 10 ppm in the spectrum
The ratio M2 / M1 to the intensity M2 in ppm is 0.60 or more
The modified aluminum oxy compound above. here
A solid-state NMR spectrum refers to a sample at a magic angle.
Refers to an NMR spectrum measured at high speed. Departure
In the light, the modified aluminum oxy compound or
Luminium oxy compound ²⁷Al-solid NMR
The spectrum is measured as follows.

When the modified aluminum oxy compound or aluminum oxy compound is obtained in the form of a solution or the like, the solvent is first removed by a method such as drying under reduced pressure to dry the modified aluminum oxy compound or aluminum oxy compound. Hereinafter, in the present invention, the denatured modified aluminum oxy compound or aluminum oxy compound may be referred to as a “solid NMR measurement sample”.

In a nitrogen box, a solid-state NMR measurement sample is packed in a predetermined amount in a rotating cell (or spinner, rotor) for solid-state NMR measurement so that stable rotation can be obtained.
A solid-state NMR spectrum of the superconducting magnet at a magnetic field strength of 7.0 T (300 MHz of ¹ H observation magnetic field strength) is measured using a solid-state NMR measurement apparatus in which the cell can be rotated at high speed with nitrogen gas or an inert gas. It is desirable that the cell be rotated at a frequency of 8 kHz or more, preferably 12 to 15 kHz, in the measurement. The chemical shift criterion is such that a peak appearing on the high magnetic field side of activated alumina is 7 ppm. Considering the range in which the peak group to be measured can be measured, the spectral width is 400 pp as the chemical shift width of ²⁷ Al.
m or more, preferably 600 ppm or more and 1000 ppm or less. The pulse width is smaller than the 90 ° pulse width used in the solution ²⁷ Al-NMR spectrum. The pulse interval is a time during which relaxation does not occur. The measurement pulse sequence is a single pulse method without decoupling, for example, HPDEC
A pulse sequence in which the decoupling is turned off by the method can be exemplified. The measurement temperature is usually room temperature (about 20 to 25 ° C)
Perform in. ^In the case of solid state NMR measurement of ²⁷ Al nuclei,
Since the next quadrupole interaction exists, the peak shape and the chemical shift depend on the magnetic field strength. Therefore, it is necessary to measure and compare the ²⁷ Al-solid NMR spectra of a plurality of types of solid NMR measurement samples at the same magnetic field strength.

After completion of the measurement, the Fourier transform of the FID is performed, and in the obtained ²⁷ Al-solid NMR spectrum, the tails of the peak group appearing from about -150 ppm to about 150 ppm in the highest magnetic field and the lowest magnetic field appear in the lowest magnetic field. So that they are almost the same height,
The phase correction and the baseline correction are performed so that the spectrum of the portion where the peak of 150 ppm or less and the peak of 150 ppm or more is not observed is as parallel as possible to the chemical shift axis (horizontal axis). Baseline,
It is drawn between the tail of the highest magnetic field of the peak group and the tail of the peak group appearing at the lowest magnetic field. A perpendicular line is drawn with respect to the chemical shift axis (horizontal axis) at 10 ppm, and the length between the intersection of the perpendicular line and the base line and the intersection of the perpendicular line and the spectrum is defined as the intensity M1 at 10 ppm. A perpendicular line is drawn with respect to the chemical shift axis (horizontal axis) at 30 ppm, and the length between the intersection of the perpendicular line and the base line and the intersection of the perpendicular line and the spectrum is defined as the intensity M2 at 30 ppm. Hereinafter, H in the present invention
1, H2, L1, L2, N1, and N2 are determined in the same manner.

The modified aluminum oxy compound of the present invention has a strength ratio M2 / M1 determined from these values of 0.6.
0 or more, preferably 0.65 or more, and more preferably 0.70 to 1.5.

The modified aluminum oxy compound of the present invention is a modified aluminum oxy compound which satisfies M2 / M1 and is modified with a compound having a hydroxyl group. Such a modified aluminum oxy compound of the present invention comprises (a) ²⁷ A
The ratio H2 / H between the intensity H1 at 10 ppm and the intensity H2 at 30 ppm in the 1-solid NMR spectrum.
An aluminum oxy compound in which 1 is less than 0.35,
It is obtained by reacting (b) water and (c) a compound having a hydroxyl group. This will be described in more detail below.

(A) Aluminum oxy compound The aluminum oxy compound used as a raw material of the modified aluminum oxy compound of the present invention is ²⁷ Al-solid N
In the MR spectrum, the ratio H2 / H1 between the intensity H1 at 10 ppm and the intensity H2 at 30 ppm is 0.3.
It is an aluminum oxy compound smaller than 5.

Examples of the aluminum oxy compound include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane,
Examples thereof include isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane, and methylisobutylaluminoxane. Many of these aluminum oxy compounds are commercially available, and their production methods are well known.

As the aluminum oxy compound (a) used in the present invention, an aluminum oxy compound represented by the following general formula (1) or (2) which is soluble in an aromatic or aliphatic hydrocarbon is preferable. (In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms in each case, a plurality of Rs may be the same or different from each other. Al represents an aluminum atom, and m represents 1 to 5
Represents the number 0. )

Examples of the hydrocarbon group represented by R in the above formula (1) or (2) include an alkyl group, an alkenyl group, an aryl group and an aralkyl group, with an alkyl group being preferred.

Among them, methyl isobutylaluminoxane is particularly preferable, and R in the above general formula (1) or (2) represents a methyl group or an isobutyl group in each case, and the ratio of methyl group to isobutyl group as R is methyl. An aluminum oxy compound having a group: isobutyl group = 5 to 95: 95 to 5 is more preferable, and an aluminum oxy compound having a methyl group: isobutyl group = 10 to 90: 90 to 10 is more preferable.

One of these aluminum oxy compounds may be used alone, or two or more thereof may be used in combination.

(B) Water In producing the modified aluminum oxy compound of the present invention, water is used as the component (b). As such water, distilled water or ion-exchanged water is preferable. Although the details are unknown, in the present invention, it is considered that the molecular weight of the modified aluminum oxy compound is increased by using water (b), and an increase in viscosity and, in some cases, solid precipitation are observed. You.

(C) Compound having a hydroxyl group The compound having a hydroxyl group (c) used in producing the modified aluminum oxy compound of the present invention is a compound having at least one hydroxyl group in a molecule, and an organic compound having a hydroxyl group. Is preferred. More preferred are alcohol compounds, phenol compounds and silanol compounds.

As the alcohol compound here, a compound represented by the following general formula is preferable. CR ¹ R ² R ³ —OH (wherein, R ¹ , R ² and R ³ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and may be the same or different.) As the hydrocarbon group in the above general formula, an alkyl group,
Examples thereof include an aralkyl group and an aryl group. The alkyl group, the aralkyl group, and the aryl group may be substituted with a halogen atom. Preferred are tertiary alcohols and alcohols substituted with halogen atoms, and particularly preferred are tert-butyl alcohol, triphenylmethanol, tricyclohexylmethanol, or 1,1,1,3,3,3-hexafluoroisopropanol. It is.

As the phenol compound, unsubstituted or substituted phenols can be used. Here, examples of the substituent include a halogen atom or an alkyl group, an aralkyl group, an aryl group, a silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a silyloxy group which may be substituted with a halogen atom.

Specific examples of such phenol compounds include 2-methylphenol, 2-ethylphenol,
2-n-butylphenol, 2-isobutylphenol, 2-tert-butylphenol, 2-n-propylphenol, 2-isopropylphenol, 2-phenylphenol, 2-fluorophenol, 2-chlorophenol, 2-bromophenol, etc. 2-substituted phenols; 3-methylphenol, 3-ethylphenol, 3-n-butylphenol, 3-isobutylphenol, 3-tert-butylphenol, 3-n-propylphenol, 3-isopropylphenol, 3-phenylphenol, -3-substituted phenols such as -fluorophenol, 3-chlorophenol, 3-bromophenol; 4-methylphenol, 4-ethylphenol, 4-n-butylphenol, 4-isobutylphenol, 4-tert- 4-substituted phenols such as tylphenol, 4-n-propylphenol, 4-isopropylphenol, 4-phenylphenol, 4-fluorophenol, 4-chlorophenol and 4-bromophenol; 2,6-dimethylphenol, 2, 6-diethylphenol, 2,6-di-n-butylphenol,
2,6-diisobutylphenol, 2,6-di-ter
t-butylphenol, 2,6-di-n-propylphenol, 2,6-di-isopropylphenol, 2,6
2,6-substituted phenols such as diphenylphenol, 2,6-difluorophenol, 2,6-dichlorophenol and 2,6-dibromophenol; 2,4,6-
2, such as trimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,3,5,6-tetrafluorophenol and pentafluorophenol
6, X-substituted phenols (X is one or more numbers selected from 3, 4 and 5); 2,3-substituted phenols such as 2,3-difluorophenol; 2,4-difluorophenols and the like 2,4-substituted phenols; 3,
5-dimethylphenol, 3,5-diethylphenol, 3,5-di-n-butylphenol, 3,5-diisobutylphenol, 3,5-di-tert-butylphenol, 3,5-di-n-propylphenol, 3,
3,5-substituted phenols such as 5-diisopropylphenol, 3,5-diphenylphenol, 3,5-difluorophenol, 3,5-dichlorophenol, 3,5-dibromophenol; catechol, resorcinol, hydroquinone, bisphenol-A And phenols having two or more hydroxyl groups, such as 2,2-thiobis-6-tert-butyl-4-methylphenol. The phenol compound is preferably a halogenated phenol or a phenol having a bulky substituent at the 2,6-position, and particularly preferably pentafluorophenol.

Further, as the silanol compound, a compound represented by the following general formula is preferable. SiR ⁴ R ⁵ R ⁶ -OH (wherein, R ^4, R ⁵ and R ⁶ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, may be the same or different.) As the hydrocarbon group in the above general formula, an alkyl group,
Examples thereof include an aralkyl group and an aryl group. The alkyl group, the aralkyl group, and the aryl group may be substituted with a halogen atom. Preferred are tertiary silanols or silanols substituted with halogen atoms, and particularly preferred are triphenylsilanol or tricyclohexylsilanol.

The (c) compound having a hydroxyl group used in the present invention is more preferably an alcohol compound or a phenol compound, and particularly preferably pentafluorophenol, triphenylmethanol, tricyclohexylmethanol or 1,1,1,3. , 3,3-hexafluoroisopropanol. One of these compounds having a hydroxyl group may be used alone, or two or more of them may be used in combination.

(A) Method for Producing Modified Aluminum Oxy Compound The modified aluminum oxy compound of the present invention is, as described above,
(A) 10 pp in ²⁷ Al-solid NMR spectrum
It is obtained by reacting an aluminum oxy compound having a ratio H2 / H1 of the intensity H1 at m and the intensity H2 at 30 ppm of less than 0.35, (b) water, and (c) a compound having a hydroxyl group. Such a reaction is preferably performed in an inert gas atmosphere. The reaction temperature is not particularly limited, but is -80 to 200C, preferably -50 to 120C. Reaction time is from 1 minute to 12
Hours, preferably from 2 minutes to 1 hour. In such a reaction, a solvent may be used, or these compounds may be directly reacted without using a solvent. The solvent used is
Although not particularly limited, aliphatic hydrocarbon solvents,
Alternatively, an aromatic hydrocarbon solvent or the like can be used. Specific examples include hexane, heptane, benzene, toluene and the like.

The modified aluminum oxy compound of the present invention preferably comprises (a) an aluminum oxy compound;
(B) Intensity L1 at 10 ppm in (a ') ²⁷ Al-solid NMR spectrum obtained by reacting with water
And the ratio L2 / L1 of the intensity L2 at 30 ppm to 0.
Obtained by reacting an aluminum oxy compound having 35 or more with (c) a compound having a hydroxyl group, or reacting (a) an aluminum oxy compound with (c) a compound having a hydroxyl group (a ”) ²⁷ Al
The ratio N2 / N1 of the intensity N1 at 10 ppm and the intensity N2 at 30 ppm in the solid-state NMR spectrum
An aluminum oxy compound having 0.35 or more;
(B) Obtained by reacting with water. Alternatively, if (a ′) is available, it can be obtained by reacting (a ′) with (c) a compound having a hydroxyl group.

The ratio L2 / L1 is preferably from 0.35 to less than 0.90, and more preferably from 0.35 to 0.5.
85. The ratio (L2 / L1) / (H2 / H1) of L2 / L1 to H2 / H1 is preferably 1.5 or more, and more preferably 1.5 or more and less than 9.0. N2 / N1 is preferably 0.35 or more.
Less than 60, more preferably 0.35 to 0.58
It is.

The ratio (molar ratio) of each component used in the reaction is not particularly limited, but the components (a) and (A)
The molar ratio between component (b) and the component (b) is usually
A molar ratio of (a) :( b) = 1: 3 to 1: 0.01 can be taken, but preferably 1: 1 to 1: 0.0.
A molar ratio in the range of 5. The molar ratio of the component (a) (the number of moles in terms of Al atom) to the component (c) is usually (a):
The molar ratio (c) can be in the range of 1: 3 to 1: 0.01, but is preferably in the range of 1: 1 to 1: 0.05. Component (a ') (mol number converted to Al atom)
The molar ratio of component (c) to component (a ') :( c) =
The molar ratio can range from 1: 3 to 1: 0.01, but is preferably from 1: 1 to 1: 0.05. The molar ratio of the component (a ″) (the number of moles in terms of Al atom) to the component (b) is usually (a ″) :( b) = 1: 3.
A molar ratio in the range of １ ： 1: 0.01 can be taken,
Preferably, the molar ratio is in the range of 1: 1 to 1: 0.05.

The thus obtained modified aluminum oxy compound of the present invention can be used as a catalyst component for addition polymerization after isolation and purification such as recrystallization.
This reaction solution can be used as it is as a catalyst component for addition polymerization.

The modified aluminum oxy compound of the present invention is useful as a catalyst component for addition polymerization. Specific examples of the addition polymerization catalyst using the modified aluminum oxy compound of the present invention include (A) a modified aluminum oxy compound and (B) an addition polymerization catalyst obtained by contacting a transition metal compound; Aluminum oxy compound,
(B) a transition metal compound, and (C) an addition polymerization catalyst obtained by contacting an organoaluminum compound;
An addition polymerization catalyst obtained by contacting (A) a modified aluminum oxy compound, (B) a transition metal compound, (C) an organoaluminum compound, and a boron compound of any of the following (D1) to (D3). (D1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (D2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (D3) a boron compound represented by the general formula (L −H) ⁺ (BQ ¹
A boron compound represented by Q ² Q ³ Q ⁴ ) ^— (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, A substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, G ⁺ is an inorganic or organic cation, L is a neutral Lewis base,
(LH) ⁺ is a Bronsted acid. Hereinafter, the addition polymerization catalyst of the present invention will be described in more detail.

(B) Transition metal compound The transition metal compound used in the catalyst for addition polymerization of the present invention is not particularly limited as long as it is a transition metal compound having addition polymerization activity. Transition metal compounds having a lanthanoid series transition metal atom are preferred. Examples of such a transition metal compound include a transition metal compound represented by the following general formula (3) and a μ-oxo-type transition metal compound which is a dimer obtained by reacting it with water. L _a MX _b (3) (wherein, M is a transition metal atom of the periodic table 4-10 or the lanthanoid series .L is a group containing a group or a hetero atom having a cyclopentadiene type anion skeleton , A plurality of Ls may be connected directly or via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom, and X is a halogen atom or a group having 1 carbon atom. 20 hydrocarbon groups. A represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8.)

In the general formula (3), which represents a transition metal compound, M is the periodic table (IUPAC 1985) 4-1.
It is a transition metal atom of Group 0 or a lanthanoid series. Specific examples thereof include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, as transition metal atoms.
Nickel, palladium, samarium, ytterbium and the like can be mentioned.

In the general formula (3) representing a transition metal compound, L is a group having a cyclopentadiene-type anion skeleton or a group containing a hetero atom, and a plurality of Ls may be the same or different. Further, a plurality of L are directly or a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom,
It may be linked via a residue containing a sulfur atom or a phosphorus atom.

Examples of the group having a cyclopentadiene-type anion skeleton in L include a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a fluorenyl group and a substituted fluorenyl group. Groups having a cyclopentadiene-type anion skeleton include, for example, η ^5- (substituted) cyclopentadienyl group, η ^5-
(Substituted) indenyl group and η ^5- (substituted) fluorenyl group. Specifically, η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵
-Tert-butylcyclopentadienyl group, η ^5-
1,2-dimethyl cyclopentadienyl group, η ⁵ -1,
3-dimethyl cyclopentadienyl group, η ⁵ -1-te
rt-butyl-2-methylcyclopentadienyl group, η
⁵ -1-tert-butyl-3-methylcyclopentadienyl group, eta ^{5-1-methyl-2-isopropyl-cyclopentadienyl} group, eta ^{5-1-methyl-3-isopropyl-cyclopentadienyl} group, eta ⁵ 1,2,3-trimethyl cyclopentadienyl group, eta ^{5-1,2,4-trimethyl} cyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl enyl, eta ⁵ - indenyl group, η ⁵ -4,5,6,
7-tetrahydroindenyl group, eta ^{5-2-methylindenyl} group, eta ^{5-3-methylindenyl} group, eta ^{5-4-methylindenyl} group, eta ^{5-5-methylindenyl} group, eta ⁵
6-methylindenyl group, eta ^{5-7-methylindenyl} group, η ⁵ -2-tert- butyl indenyl group, eta ⁵ -
3-tert-butyl indenyl group, η ⁵ -4-ter
t- butyl indenyl group, η ⁵ -5-tert- butyl-indenyl group, η ⁵ -6-tert- butyl indenyl group, η ⁵ -7-tert- butyl indenyl group, eta ⁵ -
2,3-dimethyl indenyl group, eta ^{5-4,7-dimethyl-indenyl} group, eta ^{5-2,4,7-trimethyl} indenyl group, eta ^{5-2-methyl-4-isopropylindenyl} group, eta ^5-4,5 benzindenyl group, eta ^{5-2-methyl-4,5-benzindenyl} group, eta ^5-4-phenyl indenyl group, eta ^{5-2-methyl-5-phenyl} indenyl group, eta ⁵ - 2-methyl-4-phenyl-indenyl group, eta ^{5-2-methyl-4-naphthyl} indenyl group, eta ⁵
- fluorenyl group, eta ^{5-2,7-dimethyl} fluorenyl group, eta ^5-2,7-di -tert- butyl-fluorenyl group, and substituted versions thereof, and the like.

Examples of the hetero atom in the group containing a hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom, and a phosphorus atom. Examples of such a group include an alkoxy group, an aryloxy group, a thioalkoxy group and a thioaryl. An oxy group, an alkylamino group, an arylamino group, an alkylphosphino group, an arylphosphino group, or an aromatic or aliphatic heterocyclic group having an oxygen atom, a sulfur atom, a nitrogen atom and / or a phosphorus atom in the ring, a chelate Sex ligand and the like.

Specific examples of the group containing a hetero atom include methoxy, ethoxy, propoxy, butoxy, phenoxy, 2-methylphenoxy, 2,6
-Dimethylphenoxy group, 2,4,6-trimethylphenoxy group, 2-ethylphenoxy group, 4-n-propylphenoxy group, 2-isopropylphenoxy group, 2,6
-Diisopropylphenoxy group, 4-sec-butylphenoxy group, 4-tert-butylphenoxy group, 2,
6-di-sec-butylphenoxy group, 2-tert-
Butyl-4-methylphenoxy group, 2,6-di-ter
t-butylphenoxy group, 4-methoxyphenoxy group,
2,6-dimethoxyphenoxy group, 3,5-dimethoxyphenoxy group, 2-chlorophenoxy group, 4-nitrosophenoxy group, 4-nitrophenoxy group, 2-aminophenoxy group, 3-aminophenoxy group, 4-aminothio Phenoxy group, 2,3,6-trichlorophenoxy group,
2,4,6-trifluorophenoxy group, thiomethoxy group, dimethylamino group, diethylamino group, dipropylamino group, diphenylamino group, isopropylamino group, tert-butylamino group, pyrrolyl group, dimethylphosphino group, 2- (2-oxy-1-propyl) phenoxy group, catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, 1,8-dihydroxynaphthyl group, 1,2-dihydroxynaphthyl group, 2,2′-biphenyldiol Group, 1,1'-bi-
2-naphthol group, 2,2'-dihydroxy-6,6 '
-Dimethylbiphenyl group, 4,4 ', 6,6'-tetra-tert-butyl-2,2'methylenediphenoxy group, 4,4', 6,6'-tetramethyl-2,2'-isobutylyl A dendiphenoxy group and the like can be exemplified.

The term "chelating ligand" as used herein refers to a ligand having a plurality of binding sites, and specific examples thereof include acetylacetonate, diimine, oxazoline,
Bisoxazoline, terpyridine, acylhydrazone,
Examples include diethylenetriamine, triethylenetetramine, porphyrin, crown ether, cryptate and the like.

Groups having a cyclopentadiene-type anion skeleton, groups having a cyclopentadiene-type anion skeleton and a group containing a hetero atom, or groups containing a hetero atom may be directly connected to each other; It may be linked via a residue containing a carbon atom, a silicon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Examples of such a residue include an ethylene group,
Alkylene group such as propylene group, dimethylmethylene group,
A substituted alkylene group such as a diphenylmethylene group, or a silylene group, a dimethylsilylene group, a diphenylsilylene group, a substituted silylene group such as a tetramethyldisilylene group,
And heteroatoms such as nitrogen, oxygen, sulfur, and phosphorus atoms.

X in the general formula (3) representing a transition metal compound is a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of X include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom as a halogen atom, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group as a hydrocarbon group having 1 to 20 carbon atoms. n
-Butyl group, phenyl group, benzyl group and the like.

In the general formula (3) representing a transition metal compound, a represents a number satisfying 0 <a ≦ 8, and b represents a number satisfying 0 <b ≦ 8. a and b are appropriately selected so as to be neutral as a compound in consideration of the valence of the transition metal atom m and the valences of L and X.

Specific examples of the transition metal compound in which the transition metal atom is a titanium atom include bis (cyclopentadienyl) titanium dichloride, bis (methylcyclopentadienyl) titanium dichloride, bis (n-butyl) Cyclopentadienyl) titanium dichloride, bis (dimethylcyclopentadienyl) titanium dichloride, bis (ethylmethylcyclopentadienyl) titanium dichloride, bis (trimethylcyclopentadienyl) titanium dichloride, bis (tetramethylcyclopentadienyl) ) Titanium dichloride, bis (pentamethylcyclopentadienyl) titanium dichloride, bis (indenyl) titanium dichloride, bis (4,5)
6,7-tetrahydroindenyl) titanium dichloride, bis (fluorenyl) titanium dichloride, cyclopentadienyl (pentamethylcyclopentadienyl)
Titanium dichloride, cyclopentadienyl (indenyl) titanium dichloride, cyclopentadienyl (fluorenyl) titanium dichloride, indenyl (fluorenyl) titanium dichloride, pentamethylcyclopentadienyl (indenyl) titanium dichloride, pentamethylcyclopentadienyl (fluorenyl) ) Titanium dichloride,

Ethylene bis (cyclopentadienyl) titanium dichloride, ethylene bis (2-methylcyclopentadienyl) titanium dichloride, ethylene bis (3
-Methylcyclopentadienyl) titanium dichloride,
Ethylene bis (2-n-butylcyclopentadienyl)
Titanium dichloride, ethylenebis (3-n-butylcyclopentadienyl) titanium dichloride, ethylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride , Ethylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (3,4-dimethylcyclopentadienyl) titanium dichloride, ethylenebis (2
3-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,5-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (3 , 5-ethylmethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, ethylene Bis (tetramethylcyclopentadienyl) titanium dichloride, ethylenebis (indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylenebis (2
-Phenylindenyl) titanium dichloride, ethylenebis (2-methylindenyl) titanium dichloride, ethylenebis (2-methyl-4-phenylindenyl) titanium dichloride, ethylenebis (2-methyl-4-naphthylindenyl) titanium Dichloride, ethylenebis (2-methyl-4,5-benzoindenyl) titanium dichloride, ethylenebis (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (pentamethylcyclopentadienyl) titanium dichloride, ethylene (cyclopentane) Dienyl) (indenyl) titanium dichloride, ethylene (methylcyclopentadienyl)
(Indenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, Ethylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (pentamethylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (tetramethylpentane) Dienyl) (fluorenyl) titanium dichloride, ethylene (indenyl) (fluorenyl) titanium dichloride,

Isopropylidenebis (cyclopentadienyl) titanium dichloride, isopropylidenebis (2
-Methylcyclopentadienyl) titanium dichloride,
Isopropylidenebis (3-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-
n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2 , 4-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3
4-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,
5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, isopropylidene Redidenbis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (tetramethylcyclopentadienyl) titanium dichloride, isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (4,5,6 , 7-tetrahydroindenyl) titanium dichloride, isopropylidenebis (2-phenylindenyl) titanium dichloride, isopropylidenebis (2-methylindenyl) titanium dichloride, isopropyl Denbisu (2-methyl-4-phenyl indenyl) titanium dichloride, isopropylidene-bis (2-methyl-4-naphthyl indenyl) titanium dichloride, isopropylidene-bis (2-methyl -
4,5-benzoindenyl) titanium dichloride, isopropylidenebis (fluorenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (tetramethylcyclopentadienyl) titanium dichloride,
Isopropylidene (cyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (indenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (indenyl) dichloride, isopropylidene (tetramethyl) Cyclopentadienyl) (indenyl)
Dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (Tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (indenyl) (fluorenyl) titanium dichloride,

Dimethylsilylenebis (cyclopentadienyl) titanium dichloride, dimethylsilylenebis (2
-Methylcyclopentadienyl) titanium dichloride,
Dimethylsilylenebis (3-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-
n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2 , 4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,5-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3
4-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,
5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3,5-ethylmethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3,4-trimethylcyclopentadienyl) titanium dichloride, dimethyl Silylene bis (2,3,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (tetramethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (4,5,6 , 7-tetrahydroindenyl) titanium dichloride, dimethylsilylenebis (2-phenylindenyl) titanium dichloride, dimethylsilylenebis (2-methylindenyl) titanium dichloride, Renbisu (2-methyl-4-phenyl indenyl) titanium dichloride, dimethylsilylene bis (2-methyl-4-naphthyl indenyl) titanium dichloride, dimethylsilylene bis (2-methyl -
4,5-benzoindenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) (indenyl)
Titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (indenyl) titanium dichloride,
Dimethylsilylene (n-butylcyclopentadienyl)
(Indenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl)
Titanium dichloride, dimethylsilylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (n-
Butylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride,
Dimethylsilylene (indenyl) (fluorenyl) titanium dichloride,

Cyclopentadienyl titanium trichloride, pentamethylcyclopentadienyl titanium trichloride, cyclopentadienyl (dimethylamide) titanium dichloride, cyclopentadienyl (phenoxy)
Titanium dichloride, cyclopentadienyl (2,6-
Dimethylphenyl) titanium dichloride, cyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, cyclopentadienyl (2,6-di-te
rt-butylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-dimethylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2,6-diisopropylphenyl) titanium dichloride, pentamethylcyclopentadienyl (2 , 6
-Di-tert-butylphenyl) titanium dichloride, indenyl (2,6-diisopropylphenyl) titanium dichloride, fluorenyl (2,6-diisopropylphenyl) titanium dichloride,

Methylene (cyclopentadienyl) (3
5-dimethyl-2-phenoxy) titanium dichloride,
Methylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, methylene (cyclopentadienyl) (3-tert-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-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (methylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-
tert-butyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-t
tert-butyl-5-methyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (methylcyclopentadienyl) (3-
tert-butyldimethylsilyl-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-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Methylene (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 (tert-butylcyclopentadienyl) (3-t
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-ter
t-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 (trimethylsilyl) Cyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3-trimethylsilyl-
5-methyl-2-phenoxy) titanium dichloride, methylene (trimethylsilylcyclopentadienyl) (3
-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-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-tert-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-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 (tert-butylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, isopropylidene (ter
t-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 (te
rt-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 (tetramethylcyclopentadienyl) (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 Ridene (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-t
tert-butyl-5-chloro-2-phenoxy) titanium dichloride,

Diphenylmethylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, diphenylmethylene (cyclopentadienyl) (3-tert-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-butyldimethylsilyl-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, diphenyl Methylene (methylcyclopentadienyl) (3-tert-butyl-5-
Methyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-phenyl-2-phenoxy) titanium dichloride, diphenylmethylene (methylcyclopentadienyl) (3-t
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 (te
rt-butylcyclopentadienyl) (3-tert-
Butyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (te
rt-butylcyclopentadienyl) (3-phenyl-
2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-trimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butyl) Cyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (3-tert-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-t
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-te
rt-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-te
rt-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-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, diphenylmethylene (fluorenyl) (3-tert-butyl-5 -Chloro-2
-Phenoxy) titanium dichloride

Dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-methyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethyl Silylene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-di-te
rt-butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (cyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3-
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) ( 3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3
-Tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (cyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (methylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-te
rt-butyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (methylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-di-tert-butyl-2-
Phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-te
rt-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) ) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3-tert-butyl-5-chloro-2-
Phenoxy) titanium dichloride, dimethylsilylene (methylcyclopentadienyl) (3,5-diamyl-
2-phenoxy) titanium dichloride,

Dimethylsilylene (n-butylcyclopentadienyl) (2-phenoxy) titanium dichloride,
Dimethylsilylene (n-butylcyclopentadienyl)
(3-methyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (n-butylcyclopentadienyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene ( n-butylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy)
Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (5-methyl- 3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (n-
Butylcyclopentadienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) Titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (3,5-diamyl-2-
Phenoxy) titanium dichloride,

Dimethylsilylene (tert-butylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- Butylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert
-Butylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert- Butylcyclopentadienyl)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene ( tert-butylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2
-Phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (tert-butyl) Cyclopentadienyl)
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (tetramethylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentane) Dienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) ) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (tetramethylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-phenyl-2-phenoxy) ) Titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-t
tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopenta Dienyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, Dimethylsilylene (tetramethylcyclopentadienyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (trimethylsilylcyclopentadienyl) (2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3,5-di-tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadiene) Enil)
(5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclo) Pentadienyl) (5-methyl-3-trimethylsilyl-2
-Phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-te
rt-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) (3-tert-butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (trimethylsilylcyclopentadienyl) )
(3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (indenyl) (2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-
Dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-di-tert-butyl-
2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-phenyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyldimethylsilyl-5
-Methyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3-tert-butyl-5-methoxy-2-phenoxy) ) Titanium dichloride, dimethylsilylene (indenyl) (3-tert-
Butyl-5-chloro-2-phenoxy) titanium dichloride, dimethylsilylene (indenyl) (3,5-diamyl-2-phenoxy) titanium dichloride,

Dimethylsilylene (fluorenyl) (2-
Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl)
(3,5-dimethyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-ter
t-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-di-
tert-butyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (5-methyl-
3-phenyl-2-phenoxy) titanium dichloride,
Dimethylsilylene (fluorenyl) (3-tert-butyldimethylsilyl-5-methyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl)
(5-methyl-3-trimethylsilyl-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl-5-methoxy-2-phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3-tert-butyl -5-chloro-2
-Phenoxy) titanium dichloride, dimethylsilylene (fluorenyl) (3,5-diamyl-2-phenoxy) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl)) (1-naphthoxy-2-
Yl) titanium dichloride or the like, or (2-phenoxy) of these compounds by converting (3-phenyl-2-phenoxy), (3-trimethylsilyl-2-phenoxy) or (3-tert-butyldimethylsilyl-2-phenoxy) ), A compound in which dimethylsilylene is changed to diethylsilylene, diphenylsilylene, or dimethoxysilylene; a dichloride is difluoride, dibromide, diiodidedimethyl, diethyl, diisopropyl, bis (dimethylamide), bis (dimethylamide), Compounds changed to dimethoxide, diethoxide, di-n-butoxide, diisopropoxide,

(Tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdimethyl, (tert-butylamido) Tetramethylcyclopentadienyl-1,2-ethanediyltitanium dibenzyl, (methylamido) tetramethylcyclopentadienyl-1,2-ethanediyltitanium dichloride, (ethylamido) tetramethylcyclopentadienyl-1,
2-ethanediyltitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dimethyl, (tert-butylamido) tetramethylcyclopentadienyl Dimethylsilanetitanium dibenzyl, (benzylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, (phenylphosphide) tetramethylcyclopentadienyldimethylsilanetitanium dibenzyl,

(Tert-butylamido) indenyl-
1,2-ethanediyl titanium dichloride, (tert
-Butylamido) indenyl-1,2-ethanediyltitanium dimethyl, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) tetrahydroindenyl-1,2-ethanediyltitanium dimethyl, (Tert
-Butylamido) fluorenyl-1,2-ethanediyltitanium dichloride, (tert-butylamido) fluorenyl-1,2-ethanediyltitanium dimethyl, (t
(tert-butylamido) indenyldimethylsilanetitanium dichloride, (tert-butylamido) indenyldimethylsilanetitaniumdimethyl, (tert-butylamido) tetrahydroindenyldimethylsilanetitanium dichloride, (tert-butylamido) tetrahydroindenyldimethylsilanetitaniumdimethyl, ( ter
(t-butylamido) fluorenyldimethylsilanetitanium dichloride, (tert-butylamido) fluorenyldimethylsilanetitanium dimethyl,

(Dimethylaminomethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminoethyl) tetramethylcyclopentadienyltitanium (III) dichloride, (dimethylaminopropyl) tetramethylcyclopentadienyltitanium ( II
I) dichloride, (N-pyrrolidinylethyl) tetramethylcyclopentadienyltitanium dichloride, (B
-Dimethylaminoborabenzene) cyclopentadienyl zirconium dichloride, cyclopentadienyl (9
-Mesityl boraanthracenyl) zirconium dichloride,

2,2'-thiobis (4-methyl-6-t
tert-butylphenoxy) titanium dichloride, 2,
2'-thiobis [4-methyl-6- (1-methylethyl) phenoxy] titanium dichloride, 2,2'-thiobis (4,6-dimethylphenoxy) titanium dichloride, 2,2'-methylenebis (4-methyl- 6-ter
t-butylphenoxy) titanium dichloride, 2,2 ′
-Ethylenebis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2'-sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium dichloride, 2,2 '-(4,4' , 6,
6'-tetra-tert-butyl-1,1'biphenoxy) titanium dichloride 2,2'-thiobis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide, 2,2 '
-Methylenebis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide, 2,2′-ethylenebis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide, 2,2′- Sulfinylbis (4-methyl-6-tert-butylphenoxy) titanium diisopropoxide,

(Di-tert-butyl-1,3-propanediamide) titanium dichloride, (dicyclohexyl-1,3-propanediamide) titanium dichloride,
[Bis (trimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-dimethylphenyl)-
1,3-propanediamide] titanium dichloride, [bis (2,6-diisopropylphenyl) -1,3-propanediamide] titanium dichloride, [bis (2,6-
Di-tert-butylphenyl) -1,3-propanediamide] titanium dichloride,

[Bis (triisopropylsilyl) naphthalenediamide] titanium dichloride, [bis (trimethylsilyl) naphthalenediamide] titanium dichloride,
[Bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dichloride, [bis (tert-butyldimethylsilyl) naphthalenediamide] titanium dibromide, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium trichloride, [hydrotris ( 3,5-Dimethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-dimethylpyrazolyl) borate] titanium triiodide, [hydrotris (3,5-diethylpyrazolyl) borate] titanium trichloride, [hydrotris (3 , 5-Diethylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-diethylpyrazolyl) borate] titanium triiodide, [hydrotris (3,5-di-t
[tert-butylpyrazolyl) borate] titanium trichloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium tribromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] titanium triiotate Dyed,

[Tris (3,5-dimethylpyrazolyl)
[Methyl] titanium trichloride, [tris (3,5-dimethylpyrazolyl) methyl] titanium tribromide,
[Tris (3,5-dimethylpyrazolyl) methyl] titanium triiodide, [tris (3,5-diethylpyrazolyl) methyl] titanium trichloride, [tris (3,5-diethylpyrazolyl) methyl] titanium tribromide, Tris (3,5-diethylpyrazolyl) methyl] titanium triiodide, [tris (3,5-di-tert-butylpyrazolyl) methyl] titanium trichloride, [tris (3,5-di-tert-butylpyrazolyl)] Methyl] titanium tribromide, [tris (3,5-di-tert-butylpyrazolyl) methyl]
Titanium triiodide,

Μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (cyclopentadienyl) (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 (methylcyclopentadienyl)] (2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (methylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene (methyl) Cyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (2-
Phenoxy) titanium chloride], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl)
(2-phenoxy) titanium methoxide], μ-oxobis [isopropylidene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium chloride], μ-oxobis [isopropylidene ( Tetramethylcyclopentadienyl) (3
-Tert-butyl-5-methyl-2-phenoxy) titanium methoxide],

Μ-oxobis [dimethylsilylene (cyclopentadienyl) (2-phenoxy) titanium chloride], μ-oxobis [dimethylsilylene (cyclopentadienyl) (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 (methyl Cyclopentadienyl) (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],

Di-μ-oxobis [isopropylidene (cyclopentadienyl) (2-phenoxy) titanium], 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-ter
t-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-ter
t-butyl-5-methyl-2-phenoxy) titanium] and the like. Further, in the above titanium compound,
Compounds in which a titanium atom is replaced with a zirconium atom or a hafnium atom can also be exemplified.

Specific examples of the transition metal compound in which the transition metal atom is a vanadium atom include vanadium acetylacetonate, vanadium tetrachloride,
Vanadium oxytrichloride and the like can be mentioned. Specific examples of the transition metal compound in which the transition metal atom is a samarium atom include bis (pentamethylcyclopentadienyl) samarium methyltetrahydrofuran. Specific examples of the transition metal compound in which the transition metal atom is an ytterbium atom include bis (pentamethylcyclopentadienyl) ytterbium methyltetrahydrofuran.

Specific examples of the transition metal compound in which the transition metal atom is a nickel atom include 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dimethyloxazoline] nickel dichloride, 2′-methylenebis [(4R) -4-phenyl-5,5′-dimethyloxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-phenyl-5,5′-diethyloxazoline] nickel dichloride, 2,2 ′
-Methylenebis [(4R) -4-phenyl-5,5'-
Diethyloxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-phenyl-5,
5'-di-n-propyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-di-n-propyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)
-4-phenyl-5,5'-diisopropyloxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-diisopropyloxazoline] nickel dibromide, 2,2'-methylenebis [ (4R) -4-phenyl-5,5'-dicyclohexyloxazoline] nickel dichloride,
2'-methylenebis [(4R) -4-phenyl-5,
5'-dicyclohexyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5'-dimethoxyoxazoline] nickel dichloride, 2,2'-methylenebis [(4R) -4-
Phenyl-5,5'-dimethoxyoxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-phenyl-5,5'-diethoxyoxazoline] nickel dichloride, 2,2'-methylenebis [(4
R) -4-phenyl-5,5′-diethoxyoxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5′-diphenyloxazoline] nickel dichloride, 2,2 ′ -Methylenebis [(4R) -4-phenyl-5,5'-diphenyloxazoline] nickel dibromide,

Methylene bis [(4R) -4-methyl-
5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4R )-
4-methyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, methylenebis [(4
R) -4-Methyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, methylenebis [(4R) -4-methyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel Dibromide, methylenebis [(4R) -4-methyl-5,5-di- (4
-Methoxyphenyl) oxazoline] nickel dibromide, methylenebis [spiro {(4R) -4-methyloxazoline-5,1′-cyclobutane}] nickel dibromide, methylenebis [spiro} (4R) -4-methyloxazoline-5 1'-cyclopentane}] nickel dibromide, methylenebis [spiro} (4R) -4
-Methyloxazoline-5,1'-cyclohexane}]
Nickel dibromide, methylene bis [spiro II (4
R) -4-Methyloxazoline-5,1'-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Isopropyl-5,5-dimethyloxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-isopropyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-isopropyl-5,5-di-n-propyloxazoline] nickel dibromide, methylenebis [(4R) -4-isopropyl-5,5-diisopropyloxazoline] nickel dibromide, 2,2′-methylenebis [ (4R) -4-isopropyl-5,5-dicyclohexyloxazoline] nickel dibromide,
2,2′-methylenebis [(4R) -4-isopropyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (2- Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isopropyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide,
2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methylphenyl) oxazoline]
Nickel dibromide, 2,2′-methylenebis [(4
R) -4-Isopropyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-isopropyl-
5,5-di- (3-methoxyphenyl) oxazoline]
Nickel dibromide, 2,2'-methylenebis [(4R) -4-isopropyl-5,5-di- (4-methoxyphenyl) oxazoline] Nickel dibromide, 2,2'-methylenebis [spiro} (4R)- 4-
Isopropyl oxazoline-5,1'-cyclobutane}] nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-isopropyloxazoline-
5,1′-cyclopentane]] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,1′-cyclohexane}]
Nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isopropyloxazoline-5,
1′-cycloheptane}] nickel dibromide,

2,2-methylenebis [(4R) -4-isobutyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Isobutyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4
-Isobutyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2 ′ -Methylenebis [(4R) -4-isobutyl-5,5-dicyclohexyloxazoline] nickel dibromide,
2,2'-methylenebis [(4R) -4-isobutyl-
5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-isobutyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide,
2,2'-methylenebis [(4R) -4-isobutyl-
5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-Isobutyl-5,5-di- (2-methoxyphenyl) oxazoline] nickel dibromide,
2′-methylenebis [(4R) -4-isobutyl-5,
5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R)
-4-isobutyl-5,5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-
Methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cyclobutane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R)-
4-isobutyloxazoline-5,1'-cyclopentane}] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-
5,1′-cyclohexane}] nickel dibromide,
2,2′-methylenebis [spiro {(4R) -4-isobutyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
tert-butyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-tert-Butyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4--4-tert-butyl-5,5-di-n-propyloxazoline] Nickel dibromide, 2,2'-methylenebis [(4R) -4-tert
-Butyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-tert-butyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-dicyclohexyloxazoline] nickel dibromide,
2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di- (2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert- Butyl-5,5-di- (3
-Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert
-Butyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-tert-butyl-5,5-di-
(2-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-t
tert-butyl-5,5-di- (3-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-tert-butyl-5,
5-di- (4-methoxyphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [spiro {(4R) -4-tert-butyloxazoline-5,
1'-cyclobutane}] nickel dibromide, 2,
2'-methylenebis [spiro} (4R) -4-tert
-Butyloxazoline-5,1'-cyclopentane}]
Nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-tert-butyloxazoline-
5,1′-cyclohexane}] nickel dibromide,
2,2'-methylenebis [spiro} (4R) -4-te
rt-butyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Phenyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Phenyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Phenyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-phenyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2 ′ -Methylenebis [(4R) -4-phenyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-phenyl-5,5-di-
(2-Methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-phenyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-phenyl-5,5
-Di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-phenyl-5,5-di- (3-methoxyphenyl)
Oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-phenyl-5,5-di- (4
-Methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [spiro} (4R) -4
-Phenyloxazoline-5,1'-cyclobutane}]
Nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-phenyloxazoline-5,1'-
Cyclopentane}] nickel dibromide, 2,2'-
Methylene bis [spiro {(4R) -4-phenyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R)-
4-phenyloxazoline-5,1′-cycloheptane}] nickel dibromide,

2,2'-methylenebis [(4R) -4-
Benzyl-5,5-dimethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Benzyl-5,5-diethyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-
Benzyl-5,5-di-n-propyloxazoline] nickel dibromide, 2,2′-methylenebis [(4
R) -4-benzyl-5,5-di-isopropyloxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-dicyclohexyloxazoline] nickel dibromide, 2,2 ′ -Methylenebis [(4R) -4-benzyl-5,5-diphenyloxazoline] nickel dibromide, 2,2′-
Methylenebis [(4R) -4-benzyl-5,5-di-
(2-methylphenyl) oxazoline] nickel dibromide, 2,2′-methylenebis [(4R) -4-benzyl-5,5-di- (3-methylphenyl) oxazoline] nickel dibromide, 2,2′- Methylenebis [(4R) -4-benzyl-5,5-di- (4-methylphenyl) oxazoline] nickel dibromide, 2,
2'-methylenebis [(4R) -4-benzyl-5,5
-Di- (2-methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [(4R)-
4-benzyl-5,5-di- (3-methoxyphenyl)
Oxazoline] nickel dibromide, 2,2'-methylenebis [(4R) -4-benzyl-5,5-di- (4
-Methoxyphenyl) oxazoline] nickel dibromide, 2,2'-methylenebis [spiro} (4R) -4
-Benzyloxazoline-5,1'-cyclobutane}]
Nickel dibromide, 2,2'-methylenebis [spiro {(4R) -4-benzyloxazoline-5,1'-
Cyclopentane}] nickel dibromide, 2,2'-
Methylenebis [spiro {(4R) -4-benzyloxazoline-5,1′-cyclohexane}] nickel dibromide, 2,2′-methylenebis [spiro} (4R)-
4-benzyloxazoline-5,1′-cycloheptane}] nickel dibromide, and compounds in which (4R) in the above compounds corresponds to (4S). Examples of the meso-isomers include, for example, (4R) in each of the compounds described above as optically active bisoxazolines, a compound in which one oxazoline skeleton corresponds to (4R) and the other oxazoline skeleton corresponds to (4S). No.

Among the transition metal compounds, specific examples of the compound in which the transition metal atom is a nickel atom include [hydrotris (3,5-dimethylpyrazolyl) borate] nickel chloride and [hydrotris (3,5-dimethylpyrazolyl) borate] Nickel bromide, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-dimethylpyrazolyl) borate] nickel ethyl, [ Hydrotris (3,5-dimethylpyrazolyl)
Borate] nickel allyl, [hydrotris (3,5-
Dimethylpyrazolyl) borate] nickel methallyl,
[Hydrotris (3,5-diethylpyrazolyl) borate] nickel chloride, [hydrotris (3,5-diethylpyrazolyl) borate] nickel bromide,
[Hydrotris (3,5-diethylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-diethylpyrazolyl) borate]
Diethylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-diethylpyrazolyl) borate]
Nickel ethyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickel allyl, [hydrotris (3,5-diethylpyrazolyl) borate] nickel methallyl,

[Hydrotris (3,5-di-tert-
Butylpyrazolyl) borate] nickel chloride,
[Hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel bromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel iodide, [hydrotris (3,5-
Di-tert-butylpyrazolyl) borate] nickel methyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel ethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] nickel allyl, [Hydrotris (3,5-di-
tert-butylpyrazolyl) borate] nickel methallyl, and

Compounds represented by the following structural formulas are exemplified.
Can be(Where R⁷And R⁸Are 2,6-diisopropyl
X, R ⁹And R^TenIs shown in Table 1 below.
Any of the combinations of substituents referred to. ) R⁹
And R^TenTogether form a divalent group (eg, acenaphthene
Group).

[Table 1]

[0094] Further, in the above nickel compounds, compounds in which nickel atoms are replaced with palladium atoms, cobalt atoms, rhodium atoms or ruthenium atoms can also be exemplified.

Specific examples of the transition metal compound in which the transition metal atom is iron include 2,6-bis- [1-
(2,6-dimethylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2,6
-Diisopropylphenylimino) ethyl] pyridine iron dichloride, 2,6-bis- [1- (2-te
[rt-butyl-phenylimino) ethyl] pyridineiron dichloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-dimethylpyrazolyl) borate] iron bromide, [hydrotris (3,5- [Dimethylpyrazolyl) borate] iron iodide, [hydrotris (3,5-dimethylpyrazolyl) borate] iron methyl, [hydrotris (3,5-dimethylpyrazolyl) borate] iron ethyl, [hydrotris (3,5-dimethylpyrazolyl) borate ] Iron allyl, [hydrotris (3,5-dimethylpyrazolyl)
Borate] iron metharyl

[Hydrotris (3,5-diethylpyrazolyl) borate] iron chloride, [hydrotris (3,5-diethylpyrazolyl) borate] iron bromide, [hydrotris (3,5-diethylpyrazolyl) borate] iron iodide, Hydrotris (3,5-diethylpyrazolyl) borate] iron methyl, [hydrotris (3,5-diethylpyrazolyl) borate]
Borate] iron ethyl, [hydrotris (3,5-
Diethylpyrazolyl) borate] iron allyl, [hydrotris (3,5-diethylpyrazolyl) borate]
Iron methallyl [hydrotris (3,5-di-ter
[t-butylpyrazolyl) borate] iron chloride, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron bromide, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron iodide, Hydrotris (3,5
-Di-tert-butylpyrazolyl) borate] iron methyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron ethyl, [hydrotris (3,5-di-tert-butylpyrazolyl) borate] ironallyl , [Hydrotris (3,5-di-tert-butylpyrazolyl) borate] iron methallyl and the like. In the above-mentioned iron compounds, compounds in which an iron atom is replaced with a cobalt atom or a nickel atom can also be exemplified.

These transition metal compounds may be used alone or in combination of two or more.

(C) Organoaluminum compound Component (C) used in the olefin polymerization catalyst of the present invention.
Known organic aluminum compounds can be used as the organic aluminum compound. Preferably, it is an organoaluminum compound represented by the general formula (4). R _c AlY _3-c (4) (where R is a hydrocarbon group having 1 to 8 carbon atoms, Y is a hydrogen atom and / or a halogen atom, and c is 0 <c ≦ 3
Represents a number that satisfies )

R in the general formula (4) representing an organoaluminum compound is preferably an alkyl group, and specific examples include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group,
-Methylhexyl group, normal octyl group and the like, and preferably, methyl group, ethyl group, normal butyl group, isobutyl group and normal hexyl group. Also,
When Y is a halogen atom, specific examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

Specific examples of the organoaluminum compound represented by the general formula (4) include trimethylaluminum, triethylaluminum, trinormal propyl aluminum, trinormal butyl aluminum, triisobutyl aluminum, trinormal hexyl aluminum, and trinormal octyl aluminum. Dialkylaluminum chlorides such as dimethylaluminum chloride, dinormalbutylaluminum chloride, diisobutylaluminum chloride and dinormalhexylaluminum chloride; methylaluminum dichloride, ethylaluminum dichloride, normalpropylaluminum dichloride, normalbutylaluminum dichloride, isobutyl A Alkyl aluminum dichlorides such as minium dichloride and normal hexyl aluminum dichloride; dialkyl aluminum hydrides such as dimethyl aluminum hydride, diethyl aluminum hydride, dinormal propyl aluminum hydride, dinormal butyl aluminum hydride, diisobutyl aluminum hydride, dinormal hexyl aluminum hydride and the like. can do. Of these, preferred are trialkylaluminums, and more preferred are trimethylaluminum, triethylaluminum, trinormalbutylaluminum, triisobutylaluminum and trinormalhexylaluminum. These organoaluminum compounds may be used alone or in combination of two or more.

(D) Boron Compound In the present invention, the boron compound (D) includes (D1)
A boron compound represented by the general formula BQ ¹ Q ² Q ³ , (D
2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^— , (D3) a general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q)
^{4) -} one of boron compound represented by can be used.

In the boron compound (D1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. A substituted hydrocarbon group, a substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, 1 to 20
A halogenated hydrocarbon group containing 1 to 20 carbon atoms, a substituted silyl group containing 1 to 20 carbon atoms, an alkoxy group containing 1 to 20 carbon atoms or an amino group containing 2 to 20 carbon atoms. Q ^{1 to} Q ³ are more preferably a halogen atom, a hydrocarbon group containing 1 to 20 carbon atoms, or 1
Halogenated hydrocarbon groups containing up to 20 carbon atoms. More preferably, Q ^{1 to} Q ⁴ are each a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably, Q ^{1 to} Q ⁴ each have at least one fluorine atom. 6 to 2 carbon atoms including atoms
0 is a fluorinated aryl group.

Specific examples of the compound (D1) 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 (D2) 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. Q ^{1 to} Q ⁴ are Q ^{1 to} Q ³ in the above (D1)
Is the same as

[0105] formula ^{G + (BQ 1 Q 2 Q} 3 Q 4) - Examples of G ⁺ as an inorganic cation in the compound represented by, ferrocenium cation, alkyl-substituted ferrocenium cation, silver Examples of G ^{+ in} which a cation or the like is an organic cation include a triphenylmethyl cation. G ⁺ is preferably a carbenium cation, and particularly preferably a triphenylmethyl cation. ^{(BQ 1 Q 2 Q 3 Q} 4) - as the tetrakis (pentafluorophenyl) borate, tetrakis (2,3,5,6-tetrafluorophenyl) borate, tetrakis (2,3,4,5-tetrafluoro Phenyl) borate, tetrakis (3,4,5-trifluorophenyl) borate, tetrakis (2,3,4-trifluorophenyl) borate, phenyltris (pentafluorophenyl) borate, tetrakis (3,5-bistriborate) Fluoromethylphenyl) borate and the like.

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

The formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} In the boron compound (D3) represented by, 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 (D1).

[0108] 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.

As specific combinations of these, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned, and most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) Phenyl) borate or N, N-
Dimethylanilinium tetrakis (pentafluorophenyl) borate.

The amount ratio (molar ratio) of each catalyst component used in the present invention is not particularly limited, but the component (A) modified aluminum oxy compound (mol number in terms of Al atom) and the component (B) transition metal The molar ratio of the compounds is usually (A):
(B) = 1: 1 to 10,000: 1 molar ratio can be taken, but preferably 1: 1 to 5000: 1. When the component (C) organoaluminum compound is used, the amount used is usually (B) :( C) = 1:
The molar ratio can range from 0.1 to 1: 10000, but is preferably from 1: 1 to 1: 5000, more preferably from 1: 1 to 1: 1000. When the component (D) boron compound is used, the amount used is usually
A molar ratio of (B) :( D) = 1: 0.01 to 1: 100 can be taken, but preferably 1: 0.5 to 1: 0.5.
The molar ratio is in the range of 1:10.

The method for supplying each of the catalyst components to the polymerization tank is not particularly limited, but component (A) is a modified aluminum oxy compound, component (B) is a transition metal compound,
Depending on the case, the component (C) the organoaluminum compound and further the component (D) the boron compound may be supplied in contact with the component in advance, or may be separately charged into the polymerization tank. Any two of the components may be pre-contacted, followed by another or two components.

When each of the catalyst components is used in the form of a solution, the concentration of the component (A) -modified aluminum oxy compound and the component (C) of the organoaluminum compound are usually 0.0001 to 100 mol / liter, preferably 0 to 100 mol / L, respectively, in terms of Al atoms. 0.01 to 10 mol / l. The concentration of the component (B) transition metal compound is usually 0.0001 to 100 mmol / L, preferably 0.01 to 50 mmol / L in terms of transition metal atom. The concentration of the component (D) boron compound is usually 0.001 to 500 mmol / L, preferably 0.01 to 250 mmol / L in terms of boron atoms.

The method for supplying each catalyst component to the reactor is not particularly limited. A method in which each component is supplied in a solid state, a method in which the component is dissolved in a hydrocarbon solvent, or a method in which the components are suspended in a slurry state are exemplified.

The polymerization method is not particularly limited. For example, butane, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, aromatic hydrocarbons such as toluene, or solvent polymerization using a halogenated hydrocarbon such as methylene dichloride as a solvent, or slurry polymerization, in the liquid monomer Bulk polymerization to carry out polymerization,
Examples include a gas phase polymerization carried out in a gaseous monomer, and a high pressure method in a supercritical fluid state under high temperature and high pressure. As the polymerization method, either a batch type or a continuous type can be used.

The polymerization temperature is from -50 ° C to 300 ° C, preferably from -20 ° C to 250 ° C. The polymerization pressure is 0.1 to 30
It is 0 MPa, preferably 0.1 to 200 MPa, more preferably 0.1 to 100 MPa. In general, the polymerization time is appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can range from 1 minute to 20 hours.

The addition polymerization catalyst of the present invention produces a highly active, high molecular weight olefin polymer by homopolymerizing or copolymerizing olefins. As the olefins that can be used, any of olefins having 2 to 20 carbon atoms, diolefins, and the like can be used, and two or more olefins can be used at the same time. Specific examples of these include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene,
-Octene, 1-nonene, 1-decene, vinylcyclohexane, norbornene, 1,3-butadiene, 1,4-
Heptadiene, 1,5-hexadiene, 1,7-octadiene, 5-ethylidene-2-norbornene and the like can be mentioned. The present invention is applicable to homopolymerization or copolymerization of these olefins. Specific examples of the monomers constituting the copolymer include ethylene and propylene, and ethylene and 1-
Examples thereof include butene, ethylene and 1-hexene, and propylene and 1-butene, but the present invention is not limited to these.

As the olefin polymer to which the catalyst for addition polymerization of the present invention is applied, a copolymer of ethylene and an α-olefin (so-called LLDPE, ie, a linear low-density polyethylene) is particularly preferable. As the olefin polymer to which the catalyst for addition polymerization of the present invention is applied, a homopolymer of α-olefin, particularly a homopolymer of 1-butene, is particularly preferable. By using the addition polymerization catalyst of the present invention, an ultrahigh molecular weight α-olefin homopolymer can be obtained.

The catalyst for addition polymerization of the present invention is also suitable for a method for producing an alkenyl aromatic hydrocarbon polymer in which alkenyl aromatic hydrocarbon is homopolymerized or alkenyl aromatic hydrocarbon is copolymerized with olefins. Used.
By using the addition polymerization catalyst of the present invention, a highly active and high molecular weight alkenyl aromatic hydrocarbon polymer, particularly a copolymer of an alkenyl aromatic hydrocarbon and an olefin, having a number average molecular weight (Mn) Producing a copolymer having a molecular weight distribution (Mw / Mn) of not less than 700,000 and represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) of 1.85 to 2.5. Can be. Further, as the copolymer, a copolymer having a number average molecular weight of 750,000 or more can be obtained. Specific examples of such alkenyl aromatic hydrocarbons include p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene, , 5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-
5-ethylstyrene, p-tert-butylstyrene,
alkylstyrenes such as p-sec-butylstyrene;
Alkenylbenzenes such as styrene, 2-phenylpropylene and 2-phenylbutene; bisalkenylbenzenes such as divinylbenzene; vinylnaphthalenes such as 1-vinylnaphthalene and the like can be mentioned. The alkenyl aromatic hydrocarbon used in the present invention is preferably styrene, p-methylstyrene, m-methylstyrene, o-
Methylstyrene, p-tert-butylstyrene, 2-
Phenylpropylene, divinylbenzene, or 1-vinylnaphthalene, particularly preferably styrene. The same olefins as described above are used.

In order to control the molecular weight of the polymer, a chain transfer agent such as hydrogen can be added.

[0120]

The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The properties of the olefin polymer in the examples were measured by the following methods.

(1) Intrinsic viscosity [η] Measured in a tetralin solution at 135 ° C. using an Ubbelohde viscometer.

(2) Molecular weight and molecular weight distribution (Mw / M
n) It was measured by gel permeation chromatography (GPC) under the following conditions. The molecular weight distribution is expressed by a ratio (Mw / M) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
n). The calibration curve was created using standard polystyrene. (2-1) Examples 1-22 and 25 and Comparative Example 1
In the case of ８8: Measuring machine: 150C type manufactured by Millipore Waters Co., Ltd. Column: TSK gel GMH6-HT Measurement temperature: 145 ° C. Solvent: orthodichlorobenzene Measurement concentration: 10 mg / 10 ml (If the molecular weight is particularly high, decrease the concentration.)

(2-2) In the case of Examples 23 and 24 and Comparative Examples 9 and 10 Measuring instrument: 800 series manufactured by JASCO Column: Shodex A806M Measurement temperature: 45 ° C. Solvent: Tetrahydrofuran Measurement concentration: 0.5 mg / ml

(3) Melting point of polymer (in the case of Examples 11 to 18 and 20 to 21 and Comparative Examples 5 to 8) Scanning calorimeter (DSC) (SS manufactured by Seiko Denshi Kogyo KK)
C5000 thermal analysis system) under the following conditions. Temperature rise: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 10 ° C (5 ° C / min), hold for 10 minutes Measurement: Temperature rise from 10 ° C to 160 ° C (5 ° C / minute) )

(4) Glass transition point and melting point of polymer (in the case of Examples 23 and 24 and Comparative Examples 9 and 10) Measured using DSC (SSC-5200 manufactured by Seiko Instruments Inc.) under the following conditions. I asked for it. Temperature rise: 20 ° C to 200 ° C (20 ° C / min), hold for 10 minutes Cooling: 200 ° C to -50 ° C (20 ° C / min), hold for 10 minutes Measurement: -50 ° C to 300 ° C (at 20 ° C / minute) Temperature rising)

(5) α-Olefin unit content in the copolymer: infrared spectrophotometer (F, manufactured by PerkinElmer)
TIR 1600 series), and was obtained from the characteristic absorption of ethylene and α-olefin, and was expressed as the number of short-chain branches per 1000 carbons (SCB).

[0127] (6) ²⁷ Al- solid having a superconducting magnet of the NMR spectrum 7.0 T ⁽¹ H observation frequency 300M
Hz), ASX-300 (WB) manufactured by Bruker, and a probe having a rotating cell diameter of 4 mm was used.
Nitrogen gas was used as the gas for rotation, and the measurement was performed after sufficiently replacing the inside of the housing of the measurement probe. The modified aluminum oxy compound or aluminum oxy compound was dried under reduced pressure to remove the solvent, and then dried. In a nitrogen box, a predetermined amount of the dried sample was packed in a rotating cell having a diameter of 4 mm so that stable rotation could be obtained. The rotation speed of the rotating cell was set to 12 to 14 kHz, and the measurement was performed in a room whose temperature was adjusted to 20 ° C.
degree). The measurement pulse sequence used was a pulse sequence in which decoupling was turned off by the HPDEC method. The pulse width is 0.
At 5 μsec, the pulse width was smaller than the 90 ° pulse width used in the solution ²⁷ Al-NMR spectrum. The pulse interval is 2s
ec. The spectral width was 800 ppm as the chemical shift width of ²⁷ Al. The chemical shift criterion is L
Using activated alumina as a filler for the C column, the peak appearing on the high magnetic field side was set to 7 ppm. After the measurement, FID
Of the obtained ²⁷ Al-solid NM
In the R spectrum, from around -150 ppm to 150
The peaks of the peak group appearing in the vicinity of ppm in the highest magnetic field and the lowest magnetic field in the lowest magnetic field are both substantially equal in height.
In order to make the spectrum of the part where the peak of m or more is not observed as parallel to the chemical shift axis (horizontal axis) as possible,
Phase correction and baseline correction were performed. A reference baseline was drawn as parallel to the chemical shift axis (horizontal axis) as possible between the highest field tail of the peak group spectrum and the tail of the peak group appearing at the lowest field. A perpendicular line was drawn with respect to the chemical shift axis (horizontal axis) at 10 ppm, and the length between the intersection between the perpendicular line and the base line and the intersection of the perpendicular line and the spectrum was measured. A perpendicular line was drawn with respect to the chemical shift axis (horizontal axis) at 30 ppm, and the length between the intersection of the perpendicular line with the baseline and the intersection of the perpendicular line with the spectrum was measured.

Reference Example 1 (Transition metal compound: dimethylsilylene (tetramethylcyclopentadienyl) (3-te
Example of Synthesis of rt-butyl-5-methyl-2-phenoxy) titanium dimethoxide <Compound 1> In a Schlenk tube, 0.131 g (4.1 mmol) of methanol is dissolved in 10 ml of anhydrous ether, and the solution is -78 ° C.
An ether solution of methyl lithium (3.9 ml, 4.1 mmol) having a concentration of 1.05 mol / L was added dropwise. 20
Temperature to ℃ and confirm the end of gas generation,
The formation of lithium methoxide was confirmed, and the mixture was cooled again to -78 ° C. Dimethylsilylene (tetramethylcyclopentadienyl) previously prepared in another Schlenk tube
0.919 g of (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride (2.0 mmol
The suspension of 20 ml of anhydrous ether of l) was transferred to the above reaction solution, and then gradually heated to room temperature. After concentrating the reaction solution, 20 ml of toluene was added, and insolubles were filtered off. The filtrate is concentrated, and dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-
2-phenoxy) titanium dimethoxide was obtained as yellow crystals. (0.86 g, 95%) ¹ H-NMR (270 MHz, C ₆ D ₆ ) δ7.26
(M, 2H), 4.13 (s, 6H), 2.33 (s,
3H), 1.97 (s, 6H), 1.89 (s, 6
H), 1.59 (s, 9H), 0.55 (s, 6H)

Example 1 A 100 ml stainless steel autoclave was replaced with argon, and a toluene solution of MMAO3A manufactured by Tosoh Akzo Co., Ltd. (Al concentration: 5.9 wt%, hereinafter referred to as “MMA
O ". 2.5) (in terms of Al atom) and water (ion-exchanged water; ion-exchanged water was used as water unless otherwise specified in the following Examples).
5 mmol was added and mixed with stirring for 10 minutes. Further, 0.5 mmol of pentafluorophenol (toluene solution: 2 mol / l) was added, and the mixture was stirred for 10 minutes. On the other hand, 1 ml of purified toluene and 2,2'-thiobis [4-methyl-
[6-tert-butylphenoxy] titanium dichloride (0.5 μmol) was stirred and mixed, and then charged into the autoclave using a syringe. After stirring and mixing this catalyst solution at room temperature for 10 minutes, 30 g of 1-butene was charged and polymerization was carried out at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene is purged, and the contents of the autoclave are reduced to about 1%.
It was poured into 0-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 0.
17 g of poly (1-butene) were obtained. The polymerization activity was 1.34 × 10 ⁶ g / mol-Ti · hr. [Η] of the obtained poly (1-butene) was 10.9 dl / g.
And Mw / Mn was 2.0.

Example 2 A 100 ml stainless steel autoclave was purged with argon, and 5 mmol of MMAO in a toluene solution and pentafluorophenol (2 mol of a toluene solution: 2 mol) were used.
/ L) 1 mmol was added and mixed with stirring for 10 minutes. Further, 1 mmol of water was added and the mixture was stirred for 10 minutes. On the other hand, 5 ml of purified toluene and 2,2'-thiobis [4-methyl-
[6-tert-butylphenoxy] titanium dichloride (2.5 μmol) was stirred and mixed, and then charged into the autoclave using a syringe. After stirring and mixing this catalyst solution at room temperature for 10 minutes, 30 g of 1-butene was charged and polymerization was carried out at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene is purged, and the contents of the autoclave are reduced to about 1%.
It was poured into 0-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 0.
61 g of poly (1-butene) were obtained. The polymerization activity was 9.80 × 10 ⁵ g / mol-Ti · hr. [Η] of the obtained poly (1-butene) was 10.2 dl / g.
And Mw / Mn was 2.0.

Comparative Example 1 A 100 ml stainless steel autoclave was replaced with argon, and 5 mmol of a toluene solution of MMAO was introduced. Separately, 5 ml of purified toluene and 2.5 μmol of 2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride were stirred and mixed in an eggplant-shaped flask having an inner volume of 25 ml purged with argon. And charged into the autoclave described above. After stirring and mixing this catalyst solution at room temperature for 10 minutes,
30 g of 1-butene was charged and polymerization was performed at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 0.024 g of poly (1-butene)
was gotten. The polymerization activity is 3.80 × 10 ⁴ g / mol-
Ti · hr. [Η] of the obtained poly (1-butene) was 0.53 dl / g.

Comparative Example 2 A 100 ml stainless steel autoclave was replaced with argon, and 2.5 mmol of MMAO in toluene solution was used.
And 0.5 mmol of water were added and mixed with stirring for 10 minutes.
On the other hand, 1 ml of purified toluene and 0.5 μmol of 2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride were stirred and mixed in an eggplant-shaped flask having an inner volume of 25 ml purged with argon. And charged into the autoclave described above. After stirring and mixing this catalyst solution at room temperature for 10 minutes, 30 g of 1-butene was charged and polymerization was carried out at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours.
As a result, 0.055 g of poly (1-butene) was obtained. The polymerization activity is 4.37 × 10 ⁵ g / mol-Ti · h
r. [Η] of the obtained poly (1-butene) was 5.90 dl / g.

Comparative Example 3 A 100 ml stainless steel autoclave was replaced with argon, and 5 mmol of MMAO in a toluene solution and 5 mol of pentafluorophenol (toluene solution: 2 mol)
/ L) 1 mmol was added and mixed with stirring for 10 minutes. on the other hand,
In an eggplant-shaped flask with an inner volume of 25 ml replaced with argon,
After 5 ml of purified toluene and 2.5 μmol of 2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride were stirred and mixed, the mixture was charged into the autoclave using a syringe. After stirring and mixing the catalyst solution at room temperature for 10 minutes, 1-butene was added to 30 minutes.
g and polymerization was carried out at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 0.23 g of poly (1-butene) was obtained. The polymerization activity was 3.65 × 10 ⁵ g / mol-Ti · hr. [Η] of the obtained polymer was 5.16 dl / g.

Example 3 The same procedure was performed as in Example 1 except that 0.3 mmol of triphenylmethanol was used instead of pentafluorophenol. As a result, 0.14 g of poly (1-
Butene) was obtained. The polymerization activity is 1.11 × 10 ⁶ g /
mol-Ti · hr. [Η] of the obtained poly (1-butene) was 6.0 dl / g, and Mw / Mn was 1.9.

Example 4 The procedure of Example 1 was repeated, except that 0.25 mmol of tricyclohexylmethanol was used instead of pentafluorophenol. As a result, 0.16 g of poly (1-butene) was obtained. The polymerization activity is 1.23 × 1
Was ^{0 6 g / mol-Ti ·} hr. [Η] of the obtained poly (1-butene) was 7.7 dl / g.

Example 5 An experiment was carried out in the same manner as in Example 1 except that 0.5 mmol of 1,1,1,3,3,3-hexafluoroisopropanol was used instead of pentafluorophenol.
As a result, 0.13 g of poly (1-butene) was obtained. The polymerization activity is 1.00 × 10 ⁶ g / mol-Ti · h
r.

Example 6 A 100 ml autoclave made of stainless steel was replaced with argon, and 5 mmol of MMAO in toluene solution and 1 mmol of water were added and mixed with stirring for 10 minutes. Furthermore, pentafluorophenol (toluene solution: 2 mol /
l) was added and stirred for 10 minutes. On the other hand, after 5 ml of purified toluene and 2.5 μmol of (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride were stirred and mixed in an eggplant-shaped flask having an inner volume of 25 ml and replaced with argon, the mixture was stirred using a syringe. It was charged into the autoclave. After stirring and mixing this catalyst solution at room temperature for 10 minutes, 30 g of 1-butene was charged and polymerization was carried out at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 0.18 g of poly (1-butene) was obtained.
The polymerization activity was 2.80 × 10 ⁵ g / mol-Ti · hr. [Η] of the obtained poly (1-butene) was 1.3.
It was 1 dl / g.

Comparative Example 4 A 100 ml autoclave made of stainless steel was replaced with argon, and 10 mmol of MMAO in a toluene solution was charged. On the other hand, 5 ml of purified toluene and (tert
-Butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride (10 μmol) was stirred and mixed, and then charged into the autoclave using a syringe. After stirring and mixing this catalyst solution at room temperature for 10 minutes, 30 g of 1-butene was charged and polymerization was carried out at 40 ° C. for 60 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 0.020 g of poly (1-
Butene) was obtained. The polymerization activity is 2.04 × 10 ³ g /
mol-Ti · hr. [Η] of the obtained poly (1-butene) was 0.50 dl / g.

Example 7 In Example 6, instead of (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, isopropylidene (cyclopentadienyl) (3-tert-butyl-5-methyl-2-methyl) was used. The same procedure was performed except that phenoxy) titanium dichloride was used. As a result, 0.60 g of poly (1-butene)
was gotten. The polymerization activity is 2.39 × 10 ⁵ g / mol-
Ti · hr.

Example 8 In Example 6, pentamethylcyclopentadienyltitanium trichloride was used in place of (tert-butylamido) tetramethylcyclopentadienyldimethylsilanetitanium dichloride, and the polymerization time was 30 minutes. Other than that, the procedure was the same. As a result, 1.07
g of poly (1-butene) were obtained. Polymerization activity is 8.5
It was 8 × 10 ⁵ g / mol-Ti · hr.

Example 9 A 1-liter stainless steel autoclave was replaced with argon, and 200 g of 1-butene was charged. Then, 5 mmol of MMAO in a toluene solution and 1 mmol of water were added, and the mixture was stirred and mixed for 10 minutes. Further, 1 mmol of pentafluorophenol (toluene solution: 2 mol / l) was added and stirred for 10 minutes. On the other hand, 2.5 μmol of purified toluene and 2.5 μmol of (pentamethylcyclopentadienyl) (2,6-diisopropylphenoxy) titanium dichloride were stirred and mixed in an eggplant-shaped flask having an inner volume of 25 ml purged with argon, and then mixed with a syringe. Then, the mixture was charged into the above-mentioned autoclave, and polymerization was carried out at 40 ° C. for 60 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 42.2 g of poly (1-butene) was obtained. The polymerization activity was 1.69 × 10 ⁷ g / mol-Ti · hr. [Η] of the obtained poly (1-butene) is 0.97 d
Mw / Mn was 1.8 at 1 / g.

Example 10 The procedure of Example 9 was repeated, except that the polymerization was performed at 5 ° C. As a result, 36.2 g of poly (1-butene) was obtained. The polymerization activity is 1.45 × 10 ⁷ g / mo.
1-Ti · hr. Poly (1-butene) obtained
[Η] was 3.2 dl / g and Mw / Mn was 1.8.

Example 11 A 0.4 L stainless steel autoclave was replaced with argon, 198 ml of toluene was charged as a solvent, and 2 ml of 1-hexene was charged as an α-olefin.
The temperature was raised to 0 ° C. After heating, ethylene pressure is increased to 0.6 MPa
After the inside of the system was stabilized, 2 mmol of MMAO in toluene solution and 0.4 mmol of water were added, and the mixture was stirred and mixed for 10 minutes. Further, pentafluorophenol (toluene solution: 2 mol / l) was added at 0.4 mmol
and stirred for 10 minutes. On the other hand, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert
1 ml of a 1 mmol / L toluene solution of -butyl-5-methyl-2-phenoxy) titanium dichloride was charged into the autoclave using a syringe, and polymerization was carried out for 60 minutes. Unreacted monomers were purged, and the contents of the autoclave were poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours.
As a result of the polymerization, [η] was 4.45 dl / g, and the melting point was 68.dl / g.
The ethylene-hexene-1 copolymer at 4.degree.
g was obtained. The polymerization activity was 5.93 × 10 ⁶ g / mol-T
i · hr.

Comparative Example 5 A 0.4 liter stainless steel autoclave was replaced with argon, 198 ml of toluene was charged as a solvent, and 2 ml of 1-hexene was charged as an α-olefin.
The temperature was raised to 0 ° C. After heating, ethylene pressure is increased to 0.6 MPa
After the system was stabilized and the inside of the system was stabilized, 2 mmol of MMAO in toluene solution and dimethylsilylene (tetramethylcyclopentadienyl) (3-tert
1 ml of a 1 mmol / L toluene solution of -butyl-5-methyl-2-phenoxy) titanium dichloride was charged into the above autoclave using a syringe, and polymerization was carried out for 60 minutes. Unreacted monomers were purged, and the contents of the autoclave were poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours.
As a result of the polymerization, [η] was 1.21 dl / g and the melting point was 75.
2.16 g of an ethylene-1-hexene copolymer at 6 ° C. and 89.5 ° C. was obtained. The polymerization activity is 2.16 × 10 ⁶ g
/ Mol-Ti · hr.

Comparative Example 6 A 0.4-liter stainless steel autoclave was purged with argon, 198 ml of toluene was charged as a solvent, and 2 ml of 1-hexene was charged as an α-olefin.
The temperature was raised to 0 ° C. After heating, ethylene pressure is increased to 0.6 MPa
After the inside of the system was stabilized, 2 mmol of MMAO in toluene solution and 0.4 mmol of water were added, and the mixture was stirred and mixed for 10 minutes. On the other hand, dimethylsilylene (tetramethylcyclopentadienyl) (3-tert
1 ml of a 1 mmol / L toluene solution of -butyl-5-methyl-2-phenoxy) titanium dichloride was charged into the above autoclave using a syringe, and polymerization was carried out for 60 minutes. Unreacted monomers were purged, and the contents of the autoclave were poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours.
As a result of the polymerization, [η] was 1.54 dl / g, and the melting point was 91.dl / g.
The ethylene-1-hexene copolymer at 5 ° C.
g was obtained. The polymerization activity was 8.40 × 10 ⁵ g / mol-T
i · hr.

Example 12 In Example 11, biscyclopentadienyl titanium dichloride was used in place of dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride in a thickness of 2 μm.
ol was used in the same manner except that ol was used. As a result of polymerization,
9.62 g of an ethylene-1-hexene copolymer having [η] of 2.00 dl / g and a melting point of 119 ° C. was obtained. The polymerization activity was 4.81 × 10 ⁶ g / mol-Ti · hr.

Example 13 In Example 11, (pentamethylcyclopentadienyl) (2) was used instead of dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride. , 6-Diisopropylphenoxy) titanium dichloride in 2 μmo
The same operation was performed except that 1 was used. As a result of polymerization, [η]
Was 2.78 dl / g, and the melting point was 51 ° C., and 12.17 g of an ethylene-1-hexene copolymer having a temperature of 113.8 ° C. was obtained. The polymerization activity was 6.09 × 10 ⁶ g / mol-Ti ·
hr.

Example 14 In Example 11, 2 μmol of dimethylsilylenebisindenylhafnium dichloride was used instead of dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride. Except for what was done, it went in the same way. As a result of polymerization, [η] was 2.25 dl / g, melting point was 71 ° C., and 11
The ethylene-1-hexene copolymer at 2 ° C. was 11.6.
1 g was obtained. The polymerization activity was 5.81 × 10 ⁶ g / mol-
Hf · hr.

Example 15 In Example 11, hydrotris (3,5-dimethylpyrazolyl borate) was used instead of dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dichloride.
5 μmol of titanium trichloride, 10 m of MMAO
mol, 2 mmol of water, 2 mmol of pentafluorophenol, and a polymerization temperature of 80 ° C. As a result of the polymerization, [η] was 1.42 dl.
/ G, 2.61 g of an ethylene-1-hexene copolymer having a melting point of 110.7 ° C was obtained. The polymerization activity is 5.22 ×
Was ^{10 5 g / mol-Ti ·} hr.

Example 16 The procedure of Example 15 was repeated, except that hydrotris (3,5-dimethylpyrazolyl borate) zirconium trichloride was used instead of hydrotris (3,5-dimethylpyrazolyl borate) titanium trichloride. As a result of the polymerization, 9.62 g of an ethylene-1-hexene copolymer having [η] of 1.51 dl / g and a melting point of 123.5 ° C. was obtained. The polymerization activity is 1.92 × 10 ⁶ g / m
ol-Zr · hr.

Example 17 A dropping funnel was attached to a 100 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. Heptane 10 ml as solvent, MMAO3A (Tosoh Akzo, Al
20 mmol of a heptane solution having a concentration of 7.0 wt%) was charged into a flask and stirred. 144 μl of water replaced with nitrogen
(8 mmol) and 10 ml of toluene were charged into a dropping funnel and slowly dropped into the flask. After dropping,
The dropping funnel is washed away with 5 ml of toluene, and 25 to 30
Stirred at 30 ° C. for 30 minutes. Then, 4 ml of pentafluorophenol (toluene solution: 2 mol / l) and 10 ml of toluene were charged into a dropping funnel and dropped at 25 to 30 ° C. After completion of the dropping, the dropping funnel was washed away with 5 ml of toluene, and the mixture was stirred at 25 to 30 ° C for 1 hour. The reaction solution was concentrated under reduced pressure to remove the solvent, and a white solid was obtained (Compound A). After replacing the autoclave type reactor equipped with a stirring blade with an inner volume of 0.4 liter with argon, 185 ml of cyclohexane as a solvent and 15 ml of 1-hexene as an α-olefin were charged, and the reactor was heated to 180 ° C. After the temperature was raised, the mixture was fed while adjusting the ethylene pressure to 2.5 MPa.
6 mg (corresponding to 0.41 mmol in terms of Al atom) and dimethylsilylene (tetramethylcyclopentadienyl) (3-tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (compound 1) and triisobutylaluminum Mixed heptane solution (compound 1
Was 1 μmol / ml, the concentration of triisobutylaluminum was 50 μmol / ml, and the molar ratio of Al atoms to Ti atoms was adjusted to 50. ) (0.5 μmol of compound 1 and 25 μmol of triisobutylaluminum). Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was 2.12 dl / g, and the melting point was 79.5.
1.38 g of an ethylene-1-hexene copolymer at a temperature of 83.1 ° C. was obtained. The polymerization activity per mole of Ti atom was 2.7 × 10 ⁶ g / mol-Ti (8.
1 × 10 ⁷ g / mol-Ti · hr).

Example 18 A dropping funnel was attached to a 200 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. Heptane 12 ml as solvent, MMAO3A (Tosoh Akzo, Al
Heptane solution with a concentration of 7.0 wt%) (in terms of Al atom) 2
0 mmol was charged into the flask and stirred. 72 μl (4 mmol) of water purged with nitrogen and 5 ml of toluene were charged into a dropping funnel and slowly dropped into the flask. After completion of the dropping, the dropping funnel was washed away with 5 ml of toluene,
Stirred at 25-30 ° C. for 30 minutes. Then, pentafluorophenol (toluene solution: 2 mol / l) 8 m
was charged into a dropping funnel at 25 to 30 ° C.
Stirred at 5-30 ° C for 1 hour. A white slurry was obtained.
(Al concentration 0.5 mol / L) (Compound B). After replacing the autoclave type reactor with a stirring blade with an inner volume of 0.4 liter with argon, cyclohexane 185 was used as a solvent.
15 ml of hexene-1 as an α-olefin
The reactor was charged and heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 MPa and the mixture was fed. After the inside of the system was stabilized, 2 ml of the above compound B (corresponding to 1 mmol in terms of Al atom) and dimethylsilylene (tetramethylcyclopentadienyl) ( 3-tert-butyl-
Heptane solution in which 5-methyl-2-phenoxy) titanium dimethoxide (compound 1) and triisobutylaluminum are mixed (concentration of compound 1 is 1 μmol / ml, concentration of triisobutylaluminum is 50 μmol / ml
The molar ratio between Al atoms and Ti atoms was adjusted to 50. )
(I.e., 0.5 μmol of compound 1 and 25 μmol of triisobutylaluminum). 2
Polymerization was performed for minutes. As a result of the polymerization, [η] was 1.59 dl.
/ G, melting point of 73.3 ° C, 84.9 ° C, and Mw / Mn of 1.78.
65 g were obtained. The polymerization activity per mole of Ti atom was 7.3 × 10 ⁶ g / mol-Ti (2.19 ×
10 ⁸ g / mol-Ti · hr).

Example 19 A 1-liter stainless steel autoclave was replaced with argon, 200 ml of toluene was charged, and the temperature was raised to 60 ° C. After the temperature was raised, the ethylene pressure was adjusted to 0.6 MPa, and the mixture was fed.
5 mmol of O and 1 mmol of water were added and mixed with stirring for 10 minutes. 1 mmol of pentafluorophenol
In addition, the mixture was stirred and mixed for 10 minutes. On the other hand, 2,6-bis [1
-(2,6-diisopropylphenylimino) ethyl]
5 ml of a 0.5 mmol / L toluene solution of pyridine iron dichloride was charged into the autoclave using a syringe, and polymerization was carried out for 60 minutes. Unreacted monomers were purged, and the contents of the autoclave were poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result of the polymerization, [η] was 1.57 d.
2.40 g of 1 / g polyethylene was obtained. The polymerization activity was 9.62 × 10 ⁵ g / mol-Fe · hr.

Example 20 A dropping funnel was attached to a 200 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. As a solvent, 10 ml of heptane and 10 ml of MMAO3A (manufactured by Tosoh Akzo Co., Ltd., heptane solution: 2 mol / l) were charged into the flask and stirred. 144 μl of water replaced with nitrogen (8 mmo
l) and 10 ml of toluene were charged into a dropping funnel and slowly dropped into the flask. After dropping, toluene 5m
The dropping funnel was washed away with 1 and stirred at 25 to 30 ° C. for 30 minutes. Then, 4 ml of pentafluorophenol (toluene solution: 2 mol / l) and 10 ml of toluene
Was charged into a dropping funnel and dropped at 25 to 30 ° C. After completion of the dropping, the dropping funnel was washed away with 5 ml of toluene,
Stirred at 25-30 ° C for 1 hour. The reaction solution was concentrated under reduced pressure to remove the solvent, and a white solid was obtained (Compound C). After replacing the autoclave type reactor with a stirring blade with an inner volume of 0.4 liter with argon, cyclohexane 18 was used as a solvent.
5 ml, 15 m of 1-hexene as α-olefin
and the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 MPa, and the mixture was fed. After the system was stabilized, 48.9 mg of the above compound C (corresponding to 0.40 mmol in terms of Al atom) and dimethylsilylene (tetramethylcyclopentane) were added. Dienyl) (3-te
tert-butyl-5-methyl-2-phenoxy) titanium dimethoxide (compound 1) and triisobutylaluminum in a heptane solution (compound 1 at a concentration of 1 μmo
l / ml, the concentration of triisobutylaluminum is 50μ
The molar ratio of Al atoms to Ti atoms was adjusted to 50 at mol / ml. ) In 0.5 ml (i.e., 0.5 μl of compound 1).
mol, triisobutylaluminum 25μmo
l) and a heptane slurry (concentration: 1 μmol / ml) of N, N-dimethylanilinium (tetrakispentafluorophenyl) borate (compound 2) is 1.5 m
l. Polymerization was performed for 2 minutes. As a result of polymerization, [η]
1.06 dl / g, SCB 35.3, Mw 634
00, Mw / Mn 3.4, melting point 75.2 ° C, 83.
6.5 g of an ethylene-1-hexene copolymer at 4 ° C.
Obtained. The polymerization activity per mole of Ti atom was 1.3 × 10 ⁷ g / mol-Ti (3.9 × 10 ⁸ g) per 2 minutes.
/ Mol-Ti · hr).

Example 21 An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, and then 185 ml of cyclohexane as a solvent and 1-hexene as an α-olefin were added.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, the ethylene pressure was adjusted to 2.5 MPa and the mixture was fed. After the inside of the system was stabilized, 0.1 mmol of triisobutylaluminum and 0.2 ml of the compound B slurry prepared in Example 18 (Al atom Heptane solution in which compound 1 and triisobutylaluminum are mixed (concentration of compound 1 is 1 μmol)
/ Ml, the concentration of triisobutylaluminum is 50 μm
The molar ratio of Al atoms to Ti atoms was adjusted to 50 at ol / ml. ) In 0.5 ml (i.e., 0.5 μm
ol, 25 μmol of triisobutylaluminum),
And compound 2 in heptane slurry (concentration is 1 μmol
/ Ml). Polymerization was performed for 2 minutes.
As a result of polymerization, [η] was 1.11 dl / g and SCB was 3
As a result, 3.07 g of an ethylene-1-hexene copolymer having 0.4, Mw of 52100, Mw / Mn of 2.4, and melting points of 80.8 ° C and 92.7 ° C was obtained. The polymerization activity per mole of Ti atom was 6.1 × 10 ⁶ g / mol-
Ti (1.83 × 10 ⁸ g / mol-Ti · hr).

Example 22 A dropping funnel was attached to a 100 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. As a solvent, 8 ml of heptane and 10 ml of MMAO3A (manufactured by Tosoh Akzo Co., Ltd., heptane solution: 2 mol / l) were charged into a flask and stirred. 72 μl (8 mmol) of water replaced with nitrogen
And 5 ml of toluene were charged into a dropping funnel and slowly dropped into the flask. After completion of the dropping, the dropping funnel was washed away with 5 ml of toluene, and stirred at 25 to 30 ° C for 30 minutes. Then, 2 ml of pentafluorophenol (toluene solution: 2 mol / l) was charged into the dropping funnel,
It was added dropwise at ３０30 ° C. The mixture was stirred at 25 to 30 ° C for 2 hours. White slurry (Al concentration is calculated as 0.67mo
1 / l) (Compound D). After replacing the autoclave type reactor equipped with a stirring blade with an inner volume of 0.4 liter with argon, 140 ml of cyclohexane as a solvent and 60 ml of 1-hexene as an α-olefin were charged, and the reactor was heated to 180 ° C. After temperature rise, ethylene pressure is increased to 2.5M
The mixture was fed while adjusting the pressure to Pa, and after the inside of the system was stabilized, 1.5 ml of the compound D slurry (1 equivalent in terms of Al atom) was added.
mmol), 1 ml of a toluene solution of bis (n-butylcyclopentadienyl) zirconium dichloride (concentration is 1 μmol / ml), and Compound 2
3m heptane slurry (concentration is 1μmol / ml)
l. Polymerization was performed for 2 minutes. As a result of the polymerization, 5.7 g of an ethylene-1-hexene copolymer was obtained. Zr atom 1
The polymerization activity per mole was 5.7 × 10 ⁶ per 2 minutes.
g / mol-Zr (1.71 × 10 ⁸ g / mol-Zr)
Hr).

Comparative Example 7 An autoclave-type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, 185 ml of cyclohexane was used as a solvent, and 1-hexene was used as an α-olefin.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, feed was performed while adjusting the ethylene pressure to 2.5 MPa. After the inside of the system was stabilized, 0.2 mmol of triisobutylaluminum, a heptane solution in which compound 1 and triisobutylaluminum were mixed (the concentration of compound 1 was 1 μm
ol / ml, the concentration of triisobutylaluminum is 50
μmol / ml) was added to 0.5 ml (i.e., compound
5 μmol, 25 μmo triisobutylaluminum
l), followed by 1.5 ml of a heptane slurry of compound 2 (slurry concentration, 1 μmol / ml).
Polymerization was performed for 2 minutes. As a result of the polymerization, [η] was 1.04 d
1 / g, SCB 31.7, Mw 56500, Mw /
2.33 g of an ethylene-1-hexene copolymer having Mn of 1.9 and melting points of 78.3 ° C. and 89.9 ° C. was obtained. Ti
The polymerization activity per mole of atom is 4.7 × per 2 minutes.
10 ⁶ g / mol-Ti (1.41 × 10 ⁸ g / mol-Ti)
Ti · hr).

Comparative Example 8 A dropping funnel was attached to a 200 ml four-necked flask, and after purging with nitrogen, a thermometer was attached. As a solvent, 10 ml of heptane and 10 ml of MMAO3A (manufactured by Tosoh Akzo Co., Ltd., heptane solution: 2 mol / l) were charged into the flask and stirred. 360 μl of water replaced with nitrogen (4 mmo
l) and 5 ml of toluene were charged into a dropping funnel and slowly dropped into the flask. After dropping, 5 ml of toluene
Then, the dropping funnel was washed away and stirred at 25 to 30 ° C. for 30 minutes. The reaction solution was concentrated under reduced pressure to remove the solvent, and a white solid was obtained. (Compound E) An autoclave type reactor equipped with a stirring blade having an inner volume of 0.4 liter was purged with argon, and then 185 ml of cyclohexane as a solvent and 1-hexene as an α-olefin were added.
After charging 5 ml, the reactor was heated to 180 ° C. After the temperature was raised, the mixture was fed while adjusting the ethylene pressure to 2.5 MPa, and after the system was stabilized, 27.6 mg of the above compound E was added.
(Equivalent to 0.43 mmol in terms of Al atom) and a heptane solution in which compound 1 and triisobutylaluminum are mixed (the concentration of compound 1 is 1 μmol / ml, the concentration of triisobutylaluminum is 50 μmol / ml, and A
The molar ratio of 1 atom to Ti atom was adjusted to 50. ) To 0.
5 ml (ie, 0.5 μmol of compound 1 and 25 μmol of triisobutylaluminum), and 1.5 ml of a heptane slurry of compound 2 (concentration: 1 μmol / ml)
ml. Polymerization was performed for 2 minutes. As a result of polymerization,
2.45 g of an ethylene-1-hexene copolymer having [η] of 0.97 dl / g, SCB of 34.5, and melting points of 76.6 ° C. and 83.8 ° C. was obtained. The polymerization activity per mole of Ti atom is 4.9 × 10 ⁶ g / mol-T per 2 minutes.
i (1.47 × 10 ⁸ g / mol-Ti · hr).

Example 23 27 ml of styrene and 83 ml of purified toluene were placed in a 400 ml autoclave purged with argon.
After charging, ethylene was charged at 0.8 MPa. further,
In a 50 ml flask separately purged with argon, a toluene solution of MMAO3A manufactured by Tosoh Akzo Co., Ltd. at room temperature.
[Al concentration 5.9% by weight] 4.4 ml and 14 μl of water were mixed, stirred for 10 minutes, added with 0.8 ml of a toluene solution of pentafluorophenol (2 mol / l), and stirred again for 10 minutes. Then, a solution prepared by dissolving 3.2 mg of isopropylidenebis (indenyl) zirconium dichloride in 6.4 ml of purified toluene was charged, and the reaction solution was stirred at 60 ° C. for 1 hour. Thereafter, the reaction solution was diluted with hydrochloric acid (12N) 5 ml.
And 1000 ml of methanol, and the precipitated white solid was collected by filtration. The solid was washed with methanol and dried under reduced pressure to obtain 25.24 g of a polymer. This polymer had a number average molecular weight of 65,000, a molecular weight distribution (weight average molecular weight / number average molecular weight) of 2.2, and a glass transition point of 2
The melting point was 1 ° C and the melting point was 95 ° C.

Comparative Example 9 The toluene solution of MMAO 4.4 m in Example 23 was used.
l was charged in the same manner as in Example 23, except that it was charged without mixing with water and pentafluorophenol.
25.13 g of a polymer were obtained. The number average molecular weight of this polymer is 58,000, the molecular weight distribution (weight average molecular weight / number average molecular weight) is 2.2, the glass transition point is 20 ° C., and the melting point is 98.
° C.

Example 24 14 μl of water in Example 23 was replaced with 29 μl of water, and 3.2 mg of isopropylidenebis (indenyl) zirconium dichloride dissolved in 6.4 ml of purified toluene was added to (tert-butylamido) tetramethylcyclohexane. The same operation as in Example 23 was carried out except that 2.9 mg of pentadienyldimethylsilanetitanium dichloride was dissolved in 5.8 ml of purified toluene, to obtain 11.36 g of a polymer. The number average molecular weight of this polymer was 798,000, and the molecular weight distribution (weight average molecular weight /
(Number average molecular weight) was 2.0, the glass transition point was -6 ° C, and the melting point was 78 ° C. This polymer was molded by preheating at 180 ° C. for 3 minutes and then hot pressing at 180 ° C. under a pressure of 30 to 50 kg / cm ² for 3 minutes, 50 mm × 50 mm
The × 0.3 mm press sheet had excellent tensile strength.

Comparative Example 10 The toluene solution of MMAO 4.4 m in Example 24 was used.
The same operation as in Example 24 was carried out except that 1 was charged without mixing with water and pentafluorophenol, to obtain 13.04 g of a polymer. The number average molecular weight of this polymer was 67,000, the molecular weight distribution (weight average molecular weight / number average molecular weight) was 2.2, the glass transition point was -6 ° C, and the melting point was 79 ° C.

Example 25 A 100 ml stainless steel autoclave was replaced with argon, and a toluene solution of MMAO 20 mmol was used.
(In terms of Al atom), 11 mmol of water and 4 m of pentafluorophenol (toluene solution: 2 mol / l)
mol were mixed at once and stirred for 10 minutes. Separately, 5 ml of purified toluene and 2.5 μmol of 2,2′-thiobis [4-methyl-6-tert-butylphenoxy] titanium dichloride were stirred and mixed in an eggplant-shaped flask having an inner volume of 25 ml purged with argon. And charged into the autoclave described above. After stirring and mixing this catalyst solution at room temperature for 10 minutes, 30 g of 1-butene was charged and polymerization was carried out at 40 ° C. for 15 minutes. After completion of the reaction, unreacted 1-butene was purged, the content of the autoclave was poured into about 10-fold acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. as a result,
0.65 g of poly (1-butene) was obtained. The polymerization activity was 1.04 × 10 ⁶ g / mol-Ti · hr.
[Η] of the obtained poly (1-butene) was 9.21 dl /
g.

[0164]

According to the present invention, there is provided a novel aluminum oxy compound useful as a catalyst component for addition polymerization, which can produce a high-molecular-weight olefin polymer with high efficiency when used together with a transition metal compound. Furthermore, an addition polymerization catalyst using the novel aluminum oxy compound, a method for producing an olefin polymer and a method for producing an alkenyl aromatic hydrocarbon polymer using the addition polymerization catalyst, and a high molecular weight alkenyl aromatic A copolymer of a hydrocarbon and an olefin is provided.

[Brief description of the drawings]

FIG. 1 is a ²⁷ Al-solid NMR spectrum of a sample obtained by drying MMAO3A (MMAO) manufactured by Tosoh Akzo Co., Ltd. used in Example 1 by drying under reduced pressure. H2 / H obtained from this spectrum
The value of 1 was 0.27.

FIG. 2 is a ²⁷ Al-solid NMR spectrum of a sample obtained by drying a stirred mixture of MMAO and water in Example 1 by drying under reduced pressure. The value of L2 / L1 obtained from this spectrum was 0.75.

FIG. 3 shows a sample obtained by stirring and mixing MMAO and water in Example 1, further adding pentafluorophenol, stirring and mixing, and then drying the mixture under reduced pressure to obtain a ²⁷ Al-solid sample. It is an NMR spectrum. The value of M2 / M1 obtained from this spectrum was 1.26.

FIG. 4 is a ²⁷ Al-solid NMR spectrum of a sample obtained by drying a stirred mixture of MMAO and pentafluorophenol in Example 2 by drying under reduced pressure. N2 / N1 obtained from this spectrum
Was 0.57.

FIG. 5 shows a sample obtained by stirring and mixing MMAO and pentafluorophenol in Example 2, further adding water, stirring and mixing, and then drying under reduced pressure to obtain a ²⁷ Al-solid sample. It is an NMR spectrum. The value of M2 / M1 obtained from this spectrum was 0.70.

Figure 6 is a sample obtained dryness under reduced pressure drying a stirred mixed at a time and MMAO water and pentafluorophenol in Example 25 ²⁷
It is an Al-solid NMR spectrum. The value of M2 / M1 obtained from this spectrum was 1.04.

FIG. 7 is a flowchart for helping the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

Continued on the front page (72) Inventor Tatsuya Miyatake 5-1, Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (72) Inventor Yoshihiki Seki 5-1, Anesaki Beach, Ichihara-shi, Chiba Sumitomo Chemical (72) Inventor Nobuo Oi 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture Within Sumitomo Chemical Co., Ltd. (72) Inventor Takeshi Watanabe 5-1, Anesaki Beach, Ichihara City, Chiba Prefecture, Sumitomo Chemical Co., Ltd.

Claims (19)

[Claims] (1) a modified compound having a hydroxyl group,
10 ppm in its ²⁷ Al-solid NMR spectrum
Wherein the ratio M2 / M1 of the strength M1 at 30 ppm to the strength M2 at 30 ppm is 0.60 or more. 2. An aluminum oxy compound in which (a) the ratio H2 / H1 of the intensity H1 at 10 ppm to the intensity H2 at 30 ppm in the ²⁷ Al-solid NMR spectrum is smaller than 0.35, (b) water, and (c) a hydroxyl group. obtained by reacting a compound having the the ²⁷ a
The ratio M2 / M of the intensity M1 at 10 ppm and the intensity M2 at 30 ppm in the 1-solid NMR spectrum.
1. A modified aluminum oxy compound, wherein 1 is 0.60 or more. 3. An (a ′) aluminum oxy compound having a ratio L2 / L1 of an intensity L1 at 10 ppm and an intensity L2 at 30 ppm L2 / L1 of at least 0.35 in a ²⁷ Al-solid NMR spectrum, and (c) a compound having a hydroxyl group. A modified aluminum oxy compound obtained by reacting 4. A reaction between (a) an aluminum oxy compound having a ratio H2 / H1 of less than 0.35 between intensity H1 at 10 ppm and intensity H2 at 30 ppm in a ²⁷ Al-solid NMR spectrum and (b) water. In the obtained (a ′) ²⁷ Al-solid NMR spectrum, 10
intensity L1 at 30 ppm and intensity L2 at 30 ppm
A modified aluminum oxy compound obtained by reacting an aluminum oxy compound having a ratio L2 / L1 of at least 0.35 with (c) a compound having a hydroxyl group. 5. The modified aluminum oxy compound according to claim 3, wherein L2 / L1 is 0.35 or more and less than 0.90. 6. An aluminum oxy compound in which (a) a ratio H2 / H1 of intensity H1 at 10 ppm to intensity H2 at 30 ppm in the ²⁷ Al-solid NMR spectrum is smaller than 0.35, and (c) a compound having a hydroxyl group. In the (a ″) ²⁷ Al-solid NMR spectrum obtained by the reaction, the intensity N1 at 10 ppm and 30 pp
A modified aluminum oxy compound obtained by reacting (b) water with an aluminum oxy compound having a ratio N2 / N1 to strength N2 at m of 0.35 or more and (b) water. 7. The modified aluminum oxy compound according to claim 6, wherein N2 / N1 is at least 0.35 and less than 0.60. 8. A modified aluminum oxy compound comprising ²⁷ Al
The ratio M2 / M1 of the intensity M1 at 10 ppm and the intensity M2 at 30 ppm in the solid-state NMR spectrum
Is 0.60 or more, the modified aluminum oxy compound according to any one of claims 3 to 7. 9. The method according to claim 1, wherein (a) the aluminum oxy compound is an aluminum oxy compound that is soluble in an aromatic or aliphatic hydrocarbon and represented by the following general formula (1) or (2). The modified aluminum oxy compound according to 2, 4, 5, 6, 7 or 8. (In the formula, R represents a hydrocarbon group having 1 to 20 carbon atoms in each case, a plurality of Rs may be the same or different from each other. Al represents an aluminum atom, and m represents 1 to 5
Represents the number 0. ) 10. The modified aluminum oxy compound according to claim 1, wherein the compound having a hydroxyl group is an alcohol compound, a phenol compound or a silanol compound. 11. A catalyst component for addition polymerization, comprising the modified aluminum oxy compound according to any one of claims 1 to 10. 12. A catalyst for addition polymerization obtained by contacting (A) the modified aluminum oxy compound according to any one of claims 1 to 10 and (B) a transition metal compound. 13. An addition polymerization characterized by contacting (A) the modified aluminum oxy compound according to any one of claims 1 to 10, (B) a transition metal compound, and (C) an organoaluminum compound. Catalyst. 14. A modified aluminum oxy compound according to any one of claims 1 to 10, (B) a transition metal compound, (C) an organoaluminum compound, and the following (D)
1) A catalyst for addition polymerization, which is obtained by contacting any one of the boron compounds of (D3) to (D3). (D1) a boron compound represented by the general formula BQ ¹ Q ² Q ³ , (D2) a boron compound represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ , (D3) a boron compound represented by the general formula (L −H) ⁺ (BQ ¹
A boron compound represented by Q ² Q ³ Q ⁴ ) ^— (where B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ are a halogen atom, a hydrocarbon group, a halogenated hydrocarbon group, A substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different, G ⁺ is an inorganic or organic cation, L is a neutral Lewis base,
(LH) ⁺ is a Bronsted acid. ) 15. A method for producing an olefin polymer, comprising homopolymerizing or copolymerizing an olefin using the catalyst for addition polymerization according to any one of claims 12 to 14. 16. The method according to claim 1, wherein the olefin polymer is a copolymer of ethylene and an α-olefin.
5. The process for producing an olefin polymer according to 5 above 17. The method for producing an olefin polymer according to claim 15, wherein the olefin polymer is a 1-butene homopolymer. 18. An alkenyl aromatic hydrocarbon is homopolymerized or an alkenyl aromatic hydrocarbon is copolymerized with an olefin using the addition polymerization catalyst according to any one of claims 12 to 14. For producing an alkenyl aromatic hydrocarbon polymer. 19. A copolymer of an alkenyl aromatic hydrocarbon and an olefin having a number average molecular weight (Mn) of 70.
Molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of not less than 0000
Is 1.85 to 2.5.