JP2001323009A - CATALYST FOR POLYMERIZING alpha-OLEFIN AND METHOD FOR PRODUCING alpha-OLEFIN POLYMER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst for polymerizing an α-olefin, capable of producing an α-olefin polymer having higher stereoregularity, and further to provide a method for producing the α-olefin polymer having the higher stereoregularity. SOLUTION: This catalyst for polymerizing the α-olefin is obtained by bringing (A) a modified aluminumoxy compound modified with a compound having a hydroxy group, and having >=0.60 ratio M2/M1 of the intensity M2 at 30 ppm to the intensity M1 at 10 ppm in 27Al-solid NMR spectrum thereof, into contact with (B) a transition metal compound having an ability for carrying out a stereoregular polymerization of the α-olefin. The method for producing the α-olefin polymer comprises using the catalyst for polymerizing the α-olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an α-olefin polymerization catalyst classified as a single-site catalyst and a method for producing an α-olefin polymer using the catalyst.

[0002]

2. Description of the Related Art Stereoregular α-olefin polymers have been mainly produced using multi-site catalysts such as conventional solid catalysts, but recently, single-stranded polymers obtained using metallocene complexes having a specific structure have been developed. It is known that a stereoregular α-olefin polymer can be produced even with a site catalyst.

For example, highly stereoregular isotactic propylene using a metallocene complex in which a methyl group is introduced at the 2-position of the indenyl group of the silicon-bridged bisindenyl complex and an isopropyl group, a phenyl group or a naphthyl group is introduced at the 4-position, Production examples of polymers (Organometallics 1994, 13,
954.) and a production example of a highly stereoregular isotactic propylene polymer using a metallocene complex in which two 1-3 substituted η ⁵ -cyclopentadienyl groups are crosslinked (Patent No. 2
No. 587251, Patent No. 2627669, Patent No. 26
No. 68732) is known. It has also been reported that a syndiotactic propylene polymer can be obtained by using a Cs-symmetric metallocene complex such as Me ₂ C (Cp) (Flu) ZrCl ₂ and an aluminum oxy compound (J. Am. Chem. Soc., 1988, 110, 6255.).

[0004]

However, the stereoregularity of the stereoregular α-olefin polymer obtained using these known single-site catalysts cannot be said to be sufficiently high, and the stereoregularity is further improved. desired. In view of the current situation, the problem to be solved by the present invention, that is, an object of the present invention is to provide an α-olefin polymerization catalyst capable of producing an α-olefin polymer having higher stereoregularity, and a higher stereoregularity. An object of the present invention is to provide a method for producing an α-olefin polymer.

[0005]

Means for Solving the Problems The present invention, (A) are modified with a compound having a hydroxyl group, its ²⁷ Al- solid N
In the MR spectrum, the ratio M2 / M1 between the intensity M1 at 10 ppm and the intensity M2 at 30 ppm is 0.6.
The present invention relates to an α-olefin polymerization catalyst obtained by contacting a modified aluminum oxy compound of 0 or more and (B) a transition metal compound having a stereoregular polymerization ability of α-olefin. The present invention also relates to a method for producing an α-olefin polymer using the α-olefin polymerization catalyst.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below.
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 with 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 a solution state 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-state NMR measurement sample”.

[0008] In a nitrogen box, a solid NMR measurement sample is packed in a predetermined amount in a rotating cell (or spinner, rotor) for solid NMR measurement so that stable rotation can be obtained.
Using a solid NMR spectrometer in the high-speed rotation state capable of cells with a nitrogen gas or an inert gas, to measure the solid state NMR spectrum of the magnetic field strength of the superconducting magnet 7.0 T ⁽¹ H observation magnetic field intensity 300 MHz). 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 the measurement is completed, 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 peaks of 150 ppm or less and 150 ppm or more are 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 such aluminum oxy compounds 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 the methyl group to the 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.

These aluminum oxy compounds may be used alone or in combination of two or more.

(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 (b) water, 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 preferably, it is an alcohol compound, a phenol compound or a silanol compound.

As the alcohol compound here, a compound represented by the following general formula is preferable. CR ¹ R ² R ³ —OH (In the formula, 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, and 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 tyl phenol, 4-n-propyl phenol, 4-isopropyl phenol, 4-phenyl phenol, 4-fluoro phenol, 4-chloro phenol, and 4-bromo phenol; 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, 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 compound (c) having a hydroxyl group used in the present invention is more preferably an alcohol compound or a phenol compound, 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) Production of 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.
By reacting an aluminum oxy compound having a molecular weight of 35 or more with (c) a compound having a hydroxyl group,
(A ″) ²⁷ Al-solid NMR spectrum obtained by reacting (a) an aluminum oxy compound with (c) a compound having a hydroxyl group, the intensity N at 10 ppm.
An aluminum oxy compound having a ratio N2 / N1 of 1 to 30 ppm and an intensity N2 of 0.35 or more;
It is obtained by reacting (b) water or simultaneously reacting (a) an aluminum oxy compound, (b) water, and (c) a compound having a hydroxyl group. 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 0.35 or more and less than 0.90, and more preferably 0.35-0.
85. Further, the ratio (L2 / L1) / (H2 / H1) of L2 / L1 to H2 / H1 is preferably 1.5 or more, more preferably 1.5 or more and less than 9.0. The ratio 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 such a reaction is not particularly limited, but the components (a) and (A)
The molar ratio between the 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 the component (c) to (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 after isolation and purification such as recrystallization, but this reaction solution can be used as it is as a catalyst component. Is also possible.

The α-olefin polymerization catalyst of the present invention comprises:
An olefin polymerization catalyst obtained by bringing (A) the above-mentioned modified aluminum oxy compound into contact with (B) a transition metal compound having stereoregular polymerization ability of α-olefin. Hereinafter, the olefin polymerization catalyst of the present invention will be described in more detail.

(B) Transition metal compound capable of stereoregular polymerization of α-olefin The transition metal compound used in the α-olefin polymerization catalyst of the present invention may be an isotactic propylene polymer or a syndiotactic propylene polymer. Stereoregularity α
-There is no particular limitation as long as it is a transition metal compound that can produce an olefin polymer, but the periodic table (IUPAC 1985)
Year) Transition metal compounds having a transition metal atom selected from Groups 4 to 10 and the lanthanoid series are preferred. Examples of such transition metal atoms include titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel, palladium, samarium, and ytterbium. And the like, and a titanium atom, a zirconium atom or a hafnium atom is preferable.

Specific examples of the transition metal compound in which the transition metal atom is a titanium atom include ethylene bis (2-methylcyclopentadienyl) titanium dichloride and ethylene bis (2-n-butylcyclopentadiene). Enyl) titanium dichloride, ethylenebis (3-methylcyclopentadienyl) titanium dichloride, ethylenebis (3-n-butylcyclopentadienyl) titanium dichloride, ethylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride , Ethylene bis (2,4-dimethylcyclopentadienyl) titanium dichloride, ethylene bis (2-ethyl-3-methylcyclopentadienyl) titanium dichloride, ethylene bis (2-ethyl-4-methylcyclopentadienyl) Titanium dichloride, d Lenbis (2-methyl-3-ethylpentadienyl) titanium dichloride, ethylenebis (2-methyl-4-ethylcyclopentadienyl) titanium dichloride, ethylenebis (2,3,4-trimethylcyclopentadienyl) titanium Dichloride, ethylenebis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, ethylenebis {2- (2-furyl) -3,5-dimethylcyclopentadienyl} titanium dichloride, ethylenebis {2- ( 2-furyl)-
4,5-dimethylcyclopentadienyl @ titanium dichloride,

Ethylene bis (indenyl) titanium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) titanium dichloride, ethylene bis (2-
Phenylindenyl) titanium dichloride, ethylenebis (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (methylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (pentamethylcyclopentadienyl) ) (Fluorenyl) titanium dichloride, ethylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (tetramethylpentadienyl) (fluorenyl) titanium dichloride,

Isopropylidenebis (2-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (3-methylcyclopentadienyl) titanium dichloride, Isopropylidenebis (3-n-butylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4-dimethylcyclopentadienyl) titanium dichloride , Isopropylidene bis (2
-Ethyl-3-methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-ethyl-4-
Methylcyclopentadienyl) titanium dichloride, isopropylidenebis (2-methyl-3-ethylpentadienyl) titanium dichloride, isopropylidenebis (2-methyl-4-ethylcyclopentadienyl) titanium dichloride, isopropylidenebis ( 2,3,4-
Trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, isopropylidenebis {2- (2-furyl) -3,5-dimethylcyclopentadienyl} Titanium dichloride, isopropylidenebis {2- (2-furyl) -4,5-dimethylcyclopentadienyl} titanium dichloride,

Isopropylidenebis (indenyl) titanium dichloride, isopropylidenebis (4,5,6,
7-tetrahydroindenyl) titanium dichloride, isopropylidenebis (2-phenylindenyl) titanium dichloride, isopropylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (methylcyclopentadienyl) (fluorenyl) titanium dichloride Isopropylidene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, isopropylidene (tetramethylcyclopentadienyl) (fluorenyl) titanium dichloride,

Dimethylsilylenebis (2-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (3-methylcyclopentadienyl) titanium dichloride, Dimethylsilylenebis (3-n-butylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,3-dimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4-dimethylcyclopentadienyl) titanium dichloride , Dimethylsilylene bis (2
-Ethyl-3-methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-ethyl-4-
Methylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2-methyl-3-ethylpentadienyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-ethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis ( 2,3,4-
Trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis (2,4,5-trimethylcyclopentadienyl) titanium dichloride, dimethylsilylenebis {2- (2-furyl) -3,5-dimethylcyclopentadienyl} Titanium dichloride, dimethylsilylenebis {2- (2-furyl) -4,5-dimethylcyclopentadienyl} titanium dichloride,

Dimethylsilylenebis (indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-
Indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-phenyl-1-indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-
4,5-benzo-indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-naphthyl-1-)
Indenyl) titanium dichloride, dimethylsilylenebis (2-methyl-4-isopropyl-1-indenyl)
Titanium dichloride, dimethylsilylene (2-methyl-
1-indenyl) (2-methyl-4-phenyl-1-indenyl) titanium dichloride, dimethylsilylene (2
-Methyl-1-indenyl) (2-methyl-4-naphthyl-1-indenyl) titanium dichloride, dimethylsilylene (2-methyl-1-indenyl) (2-methyl-
4-isopropyl-1-indenyl) titanium dichloride, dimethylsilylene (2-methyl-4-phenyl-1)
-Indenyl) (2-methyl-4-naphthyl-1-indenyl) titanium dichloride, dimethylsilylene (2-
Methyl-4-phenyl-1-indenyl) (2-methyl-4-isopropyl-1-indenyl) titanium dichloride, dimethylsilylene (2-methyl-4-naphthyl-
1-indenyl) (2-methyl-4-isopropyl-1
-Indenyl) titanium dichloride,

Dimethylsilylenebis (2-ethyl-indenyl) titanium dichloride, dimethylsilylenebis (2-ethyl-4-phenyl-1-indenyl) titanium dichloride, dimethylsilylenebis (2-ethyl-
4,5-benzo-indenyl) titanium dichloride, dimethylsilylenebis (2-ethyl-4-naphthyl-1-)
Indenyl) titanium dichloride, dimethylsilylenebis (2-ethyl-4-isopropyl-1-indenyl)
Titanium dichloride, dimethylsilylene (2-ethyl-
1-indenyl) (2-methyl-4-phenyl-1-indenyl) titanium dichloride, dimethylsilylene (2
-Ethyl-1-indenyl) (2-methyl-4-naphthyl-1-indenyl) titanium dichloride, dimethylsilylene (2-ethyl-1-indenyl) (2-methyl-
4-isopropyl-1-indenyl) titanium dichloride, dimethylsilylene (2-ethyl-4-phenyl-1)
-Indenyl) (2-ethyl-4-naphthyl-1-indenyl) titanium dichloride, dimethylsilylene (2-
Ethyl-4-phenyl-1-indenyl) (2-ethyl-4-isopropyl-1-indenyl) titanium dichloride, dimethylsilylene (2-ethyl-4-naphthyl-
1-indenyl) (2-ethyl-4-isopropyl-1
-Indenyl) titanium dichloride,

Dimethylsilylenebis (2,4,6-trimethyl-1-indenyl) titanium dichloride, dimethylsilylenebis (4,5,6,7-tetrahydroindenyl) titanium dichloride, dimethylsilylene (cyclopentadienyl) ( Fluorenyl) titanium dichloride, dimethylsilylene (methylcyclopentadienyl)
(Fluorenyl) titanium dichloride, dimethylsilylene (n-butylcyclopentadienyl) (fluorenyl) titanium dichloride, dimethylsilylene (tetramethylcyclopentadienyl) (indenyl) titanium dichloride,

(Tert-butylamido) fluorenyl-1,2-ethanediyltitanium dichloride,
(tert-butylamido) fluorenyl-1,2-ethanediyltitanium dimethyl, (tert-butylamido) fluorenyldimethylsilanetitanium dichloride, (tert
-Butylamido) fluorenyldimethylsilanetitanium dimethyl and the like. Further, compounds in which titanium is replaced with zirconium or hafnium in the above titanium compounds can also be exemplified. When the transition metal compound has a racemic form and a meso form, the racemic form is preferable.

Among these transition metal compounds, a transition metal compound represented by the following general formula (I) or a transition metal compound represented by the following general formula (II) is preferable. (Wherein, M is a transition metal atom of Group 4 of the periodic table, L is an η ⁵ -indenyl group or a substituted η ⁵ -indenyl group, and the two Ls may be the same or different. Y is a bridging group connecting two L, and two Xs are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group,
It is an aralkyloxy group, an aryloxy group or a heterocyclic group. )

[0042] (Wherein M is a transition metal atom of Group 4 of the periodic table, and Y ²
Silicon atom, a germanium atom or a tin _{^{atom, (R 2 n -C 5 H}} 4-n) and _{^{(R 2 q -C 5 H 4}} -q) each substituted eta ⁵ - be a cyclopentadienyl group , N and q are each an integer of 1 to 3. Each R ² may be the same or different from each other, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, show an aryloxy group or a heterocyclic group, a substituted eta ⁵ The position and / or type of R ^{2 in} the cyclopentadienyl group is selected such that there is no plane of symmetry containing M. R ³ and X are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group, and R ³ and X are all the same. Or different from each other. )

In the above general formula [I] or [II],
The transition metal atom represented by M is the periodic table of the element (IU
PAC inorganic metal nomenclature, revised edition 1989). Preferably,
It is a titanium atom or a zirconium atom.

In the above general formula [I], L is an η ⁵ -indenyl group or a substituted η ⁵ -indenyl group, and the two Ls may be the same or different. Specific examples of L include η ⁵ -indenyl group, η ⁵ -methylindenyl group, η ⁵ -dimethylindenyl group, η ⁵ -n-propylindenyl group, η ⁵ -isopropylindenyl group,
eta ^5-n-butyl indenyl group, eta ^5-tert-butyl indenyl group, eta ⁵ - phenyl indenyl group, eta ⁵ - methylphenyl indenyl group, eta ⁵ - naphthyl indenyl group, eta ⁵ - trimethylsilyl indenyl And a η ⁵ -tetrahydroindenyl group.

In the above general formula [II], (R ² _n -C ₅
H _4-n ) and (R ² _q -C ₅ H _4-q ) are each substituted η ⁵
-Cyclopentadienyl group, n and q are 1 to 3
Is an integer. Each R ² may be the same or different from each other, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, show an aryloxy group or a heterocyclic group, a substituted eta ⁵ The position and / or type of R ^{2 in} the cyclopentadienyl group is selected such that there is no plane of symmetry containing M.

Examples of the halogen atom here include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom or a bromine atom, and more preferably a chlorine atom.

The alkyl group may have 1 to 1 carbon atoms.
Preferred are 20 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl,
sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, neopentyl group, amyl group, n-
Hexyl group, n-octyl group, n-decyl group, n-dodecyl group, n-pentadecyl group, n-eicosyl group and the like, more preferably methyl group, ethyl group, isopropyl group, tert-butyl group, isobutyl Or an amyl group. Any of these alkyl groups may be substituted with a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom include a fluoromethyl group, a trifluoromethyl group, a chloromethyl group, a trichloromethyl group, a fluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, Examples include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, a perchloropropyl group, a perchlorobutyl group, a perbromopropyl group, and the like. All of these alkyl groups may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The aralkyl group may have 7 to 2 carbon atoms.
An aralkyl group of 0 is preferred, for example, a benzyl group, (2
-Methylphenyl) methyl group, (3-methylphenyl)
Methyl group, (4-methylphenyl) methyl group, (2,3
-Dimethylphenyl) methyl group, (2,4-dimethylphenyl) methyl group, (2,5-dimethylphenyl) methyl group, (2,6-dimethylphenyl) methyl group, (3
(4-dimethylphenyl) methyl group, (3,5-dimethylphenyl) methyl group, (2,3,4-trimethylphenyl) methyl group, (2,3,5-trimethylphenyl) methyl group, (2,3 6-trimethylphenyl) methyl group, (3,4,5-trimethylphenyl) methyl group,
(2,4,6-trimethylphenyl) methyl group, (2,4
3,4,5-tetramethylphenyl) methyl group, (2,
3,4,6-tetramethylphenyl) methyl group, (2,
3,5,6-tetramethylphenyl) methyl group, (pentamethylphenyl) methyl group, (ethylphenyl) methyl group, (n-propylphenyl) methyl group, (isopropylphenyl) methyl group, (n-butylphenyl) Methyl group, (sec-butylphenyl) methyl group, (ter
t-butylphenyl) methyl group, (n-pentylphenyl) methyl group, (neopentylphenyl) methyl group,
(N-hexylphenyl) methyl group, (n-octylphenyl) methyl group, (n-decylphenyl) methyl group,
Examples thereof include a (n-dodecylphenyl) methyl group, a naphthylmethyl group and an anthracenylmethyl group, and more preferably a benzyl group. All of these aralkyl groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aryl group may have 6 to 20 carbon atoms.
Are preferred, for example, phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5-xylyl, 2,6
-Xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 2,3,5-
Trimethylphenyl group, 2,3,6-trimethylphenyl group, 2,4,6-trimethylphenyl group, 3,4,5
-Trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2,3,5,6-tetramethylphenyl group, pentamethylphenyl group, ethyl Phenyl group, n-propylphenyl group, isopropylphenyl group, n-butylphenyl group, sec-butylphenyl group, tert-butylphenyl group, n-pentylphenyl group, neopentylphenyl group, n-hexylphenyl group, n- Examples include an octylphenyl group, an n-decylphenyl group, an n-dodecylphenyl group, an n-tetradecylphenyl group, a naphthyl group, and an anthracenyl group, and a phenyl group is more preferable. All of these aryl groups are a fluorine atom,
Halogen atoms such as chlorine atom, bromine atom and iodine atom,
It may be partially substituted with an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The substituted silyl group is a silyl group substituted by a hydrocarbon group. Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a sec- An alkyl group having 1 to 10 carbon atoms such as -butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group and cyclohexyl group; and an aryl group such as phenyl group. Examples of the substituted silyl group having 1 to 20 carbon atoms include mono-substituted silyl groups having 1 to 20 carbon atoms such as methylsilyl group, ethylsilyl group and phenylsilyl group.
Disubstituted silyl group having 2 to 20 carbon atoms such as dimethylsilyl group, diethylsilyl group, diphenylsilyl group, trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, triisopropylsilyl group, tri-n-
Butylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, triisobutylsilyl group, tert-butyldimethylsilyl group, tri-n-pentylsilyl group, tri-n-hexylsilyl group, tricyclohexylsilyl group, Examples thereof include a trisubstituted silyl group having 3 to 20 carbon atoms such as a triphenylsilyl group, and a trimethylsilyl group, a tert-butyldimethylsilyl group, or a triphenylsilyl group is preferable. All of these substituted silyl groups have a hydrocarbon group such as a fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or a benzyloxy group. May be partially substituted with an aralkyloxy group such as a group.

As the alkoxy group, one having 1 to 2 carbon atoms
An alkoxy group of 0 is preferable, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group , N-octoxy group, n-dodesoxy group, n-pentadeoxy group, n-icosoxy group and the like, more preferably methoxy group, ethoxy group, isopropoxy group and tert-butoxy group. All of these alkoxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group and an aralkyloxy group such as a benzyloxy group. May be partially substituted.

The aralkyloxy group is preferably an aralkyloxy group having 7 to 20 carbon atoms, for example, a benzyloxy group, a (2-methylphenyl) methoxy group,
(3-methylphenyl) methoxy group, (4-methylphenyl) methoxy group, (2,3-dimethylphenyl) methoxy group, (2,4-dimethylphenyl) methoxy group,
(2,5-dimethylphenyl) methoxy group, (2,6-
(Dimethylphenyl) methoxy group, (3,4-dimethylphenyl) methoxy group, (3,5-dimethylphenyl) methoxy group, (2,3,4-trimethylphenyl) methoxy group, (2,3,5-trimethylphenyl) A) methoxy group, a (2,3,6-trimethylphenyl) methoxy group,
(2,4,5-trimethylphenyl) methoxy group,
A (2,4,6-trimethylphenyl) methoxy group,
(3,4,5-trimethylphenyl) methoxy group,
(2,3,4,5-tetramethylphenyl) methoxy, (2,3,4,6-tetramethylphenyl) methoxy, (2,3,5,6-tetramethylphenyl) methoxy, (penta (Methylphenyl) methoxy group, (ethylphenyl) methoxy group, (n-propylphenyl) methoxy group, (isopropylphenyl) methoxy group, (n
-Butylphenyl) methoxy group, (sec-butylphenyl) methoxy group, (tert-butylphenyl) methoxy group, (n-hexylphenyl) methoxy group, (n-
Examples thereof include an octylphenyl) methoxy group, an (n-decylphenyl) methoxy group, a naphthylmethoxy group, and an anthracenylmethoxy group, and more preferably a benzyloxy group. All of these aralkyloxy groups include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

The aryloxy group has 6 carbon atoms.
To 20 aryloxy groups, for example, phenoxy, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2,5 -Dimethylphenoxy group, 2,6-dimethylphenoxy group,
3,4-dimethylphenoxy group, 3,5-dimethylphenoxy group, 2-tert-butyl-3-methylphenoxy group, 2-tert-butyl-4-methylphenoxy group, 2-tert-butyl-5-methylphenoxy group Group,
2-tert-butyl-6-methylphenoxy group, 2,
3,4-trimethylphenoxy group, 2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group, 2,4,6
-Trimethylphenoxy group, 2-tert-butyl-
3,4-dimethylphenoxy group, 2-tert-butyl-3,5-dimethylphenoxy group, 2-tert-butyl-3,6-dimethylphenoxy group, 2,6-di-te
rt-butyl-3-methylphenoxy group, 2-tert
-Butyl-4,5-dimethylphenoxy group, 2,6-di-tert-butyl-4-methylphenoxy group, 3,
4,5-trimethylphenoxy group, 2,3,4,5-tetramethylphenoxy group, 2-tert-butyl-3,
4,5-trimethylphenoxy group, 2,3,4,6-tetramethylphenoxy group, 2-tert-butyl-3,
4,6-trimethylphenoxy group, 2,6-di-ter
t-butyl-3,4-dimethylphenoxy group, 2,3
5,6-tetramethylphenoxy group, 2-tert-butyl-3,5,6-trimethylphenoxy group, 2,6-
Di-tert-butyl-3,5-dimethylphenoxy group, pentamethylphenoxy group, ethylphenoxy group,
n-propylphenoxy group, isopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-hexylphenoxy group, n-octylphenoxy group, n-decylphenoxy group, n-tetradecyl Examples include a phenoxy group, a naphthoxy group, and an anthracenoxy group. All of these aryloxy groups are a fluorine atom, a chlorine atom,
A part thereof may be substituted with a halogen atom such as a bromine atom or an iodine atom, an alkoxy group such as a methoxy group or an ethoxy group, an aryloxy group such as a phenoxy group, or an aralkyloxy group such as a benzyloxy group.

The heterocyclic group is a group having a heterocyclic ring.
A group having an 8-membered heterocyclic ring is preferable, and a group having a 4- to 8-membered aromatic heterocyclic ring is more preferable. As the hetero atom contained in the hetero ring, a nitrogen atom, an oxygen atom or a sulfur atom is preferable. Specific examples of such a heterocyclic group include, for example, an indolyl group, a furyl group, a thienyl group, a pyridyl group,
Examples thereof include a piperidyl group, a quinolyl group, and an isoquinolyl group, and a specific example of such a heterocyclic group is more preferably a furyl group. All of these heterocyclic groups are a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group and an ethoxy group, an aryloxy group such as a phenoxy group, and an aralkyloxy group such as a benzyloxy group. It may be partially substituted with a group or the like.

R ² is preferably an alkyl group or a heterocyclic group. n and q are each an integer of 1 to 3.

Having such R ² , the position and / or type of R ² in the substituted η ⁵ -cyclopentadienyl group is selected such that there is no plane of symmetry containing M (R ² _n -C
₅ H _{4 -n)} or _{^{(R 2 q -C 5 H 4}} -q As), for example 2
-Methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-propylcyclopentadienyl group, 2-isopropylcyclopentadienyl group, 2-
n-butylcyclopentadienyl group, 2-isobutylcyclopentadienyl group, 2-tert-butylcyclopentadienyl group, 2-n-hexylcyclopentadienyl group, 3-methylcyclopentadienyl group, 3 -Ethylcyclopentadienyl group, 3-n-propylcyclopentadienyl group, 3-isopropylcyclopentadienyl group, 3-n-butylcyclopentadienyl group, 3-isobutylcyclopentadienyl group, 3- tert-butylcyclopentadienyl group, 3-n-hexylcyclopentadienyl group,

2,3-dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3
-Di-n-propylcyclopentadienyl group, 2,3-
Diisopropylcyclopentadienyl group, 2,3-di-
n-butylcyclopentadienyl group, 2,3-diisobutylcyclopentadienyl group, 2,3-di-tert-
Butylcyclopentadienyl group, 2,3-di-n-hexylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2,4-diethylcyclopentadienyl group, 2,4-di- n-propylcyclopentadienyl group, 2,4-diisopropylcyclopentadienyl group, 2,4-di-n-butylcyclopentadienyl group,
2,4-diisobutylcyclopentadienyl group, 2,4
-Di-tert-butylcyclopentadienyl group, 2,
4-di-n-hexylcyclopentadienyl group, 3,5
-Dimethylcyclopentadienyl group, 3,5-diethylcyclopentadienyl group, 3,5-di-n-propylcyclopentadienyl group, 3,5-diisopropylcyclopentadienyl group, 3,5-di -N-butylcyclopentadienyl group, 3,5-diisobutylcyclopentadienyl group, 3,5-di-tert-butylcyclopentadienyl group, 3,5-di-n-hexylcyclopentadienyl group ,

2-ethyl-3-methylcyclopentadienyl group, 2-methyl-3-ethylcyclopentadienyl group, 2-methyl-3-n-propylcyclopentadienyl group, 2-methyl-3- Isopropylcyclopentadienyl group, 2-ethyl-3-isopropylcyclopentadienyl group, 2-methyl-3-n-butylcyclopentadienyl group, 2-methyl-3-isobutylcyclopentadienyl group, 2- Methyl-3-tert-butylcyclopentadienyl group, 2-methyl-3-n-hexylcyclopentadienyl group, 2-ethyl-4-methylcyclopentadienyl group, 2-methyl-4-ethylcyclopenta Dienyl group, 2-methyl-4-n-propylcyclopentadienyl group, 2-methyl-4-isopropylcyclopentadienyl group, 2 Ethyl-4-isopropylcyclopentadienyl group, 2-methyl-4-n-butylcyclopentadienyl group, 2-methyl-4-isobutylcyclopentadienyl group, 2-methyl-4-tert-butylcyclopenta Dienyl group, 2-methyl-4-n-hexylcyclopentadienyl group 3-ethyl-5-methylcyclopentadienyl group, 3-methyl-5-ethylcyclopentadienyl group, 3-methyl-5 n-propylcyclopentadienyl group, 3-methyl-5-isopropylcyclopentadienyl group, 3-ethyl-5-isopropylcyclopentadienyl group, 3-methyl-5-n-butylcyclopentadienyl group, 3-methyl-5-isobutylcyclopentadienyl group, 3-methyl-5-tert-butylcyclopentadienyl group, 5-n-hexylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,4,5-trimethylcyclopentadienyl group, 2- (2-furyl) -3,5 -Dimethylcyclopentadienyl group, 2- (2-furyl)-
4,5-dimethylcyclopentadienyl group and the like.

In the above general formula (I), Y is two L
Is a cross-linking group. As the bridging group, 14th of the Periodic Table of the Elements (IUPAC revised version of inorganic chemical nomenclature 1989) can be used.
And a divalent crosslinking group containing a group atom, and preferably a divalent crosslinking group containing a carbon atom, a silicon atom, a germanium atom or a tin atom. More preferably, 2
The two L-bonding atoms are a carbon atom, a silicon atom, a germanium atom and / or a tin atom, and more preferably, the two L-bonding atoms are a carbon atom, a silicon atom, and a germanium atom. And / or a divalent bridging group having a minimum number of atoms of 3 or less between two L-bonding atoms (including a single L-bonding atom). is there. In particular,
Methylene group, ethylene group, propylene group, dimethylmethylene group (isopropylidene group), diphenylmethylene group, tetramethylethylene group, silylene group, dimethylsilylene group, diethylsilylene group, diphenylsilylene group, tetramethyldisilylene group, dimethoxysilylene And methylene group, ethylene group, dimethylmethylene group (isopropylidene group), dimethylsilylene group, diethylsilylene group and diphenylsilylene group.

In the above formula [II], Y ² is a carbon atom, a silicon atom, a germanium atom or a tin atom, preferably a carbon atom or a silicon atom.

In the above general formula [I] or [II],
R ³ and X are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxy group, an aryloxy group or a heterocyclic group, and R ³ and X are all the same. Or different from each other. The halogen atom, the alkyl group, the aralkyl group, the aryl group, the substituted silyl group, the alkoxy group, the aralkyloxy group, the aryloxy group, and the heterocyclic group are the same as those already described as R ² .

R ³ is preferably a hydrogen atom or an alkyl group. X is preferably a halogen atom,
It is an alkyl group, an aralkyl group or an alkoxy group.

In the present invention, these transition metal compounds may be used alone or in combination of two or more. Further, as the α-olefin polymerization catalyst of the present invention, an organoaluminum compound may be further used together. That is, the α-olefin polymerization catalyst of the present invention includes (A) the modified aluminum oxy compound described above,
(B) a transition metal compound having the ability of stereoregular polymerization of an α-olefin; and (C) an olefin polymerization catalyst obtained by contacting an organoaluminum compound.

(C) Organoaluminum Compound As the organoaluminum compound (C), a known organoaluminum compound can be used. Preferred are organoaluminum compounds represented by the following general formula (III). R _c AlY ⁹ _3-c (III) (where R represents a hydrocarbon group having 1 to 8 carbon atoms, Y ⁹ represents a hydrogen atom and / or a halogen atom, and c represents 0 <c ≦ 3) Represents a satisfactory number.)

In the general formula (III) representing an organoaluminum compound, R is preferably an alkyl group, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, an isobutyl group, a normal hexyl group,
Examples thereof include a 2-methylhexyl group and a normal octyl group, preferably a methyl group, an ethyl group, a normal butyl group, an isobutyl group, and a normal hexyl group. Also,
Specific examples of the case where Y ⁹ is a halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom,
Preferably it is a chlorine atom.

Specific examples of the organoaluminum compound represented by the general formula (III) include trimethylaluminum, triethylaluminum, trinormal propylaluminum, 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.

[Α-Olefin Polymerization] The α-olefin polymerization catalyst of the present invention is obtained by contacting (A) the above-mentioned modified aluminum oxy compound and (B) the above-mentioned transition metal compound, or further comprises (C) ) An α-olefin polymerization catalyst obtained by contacting the above-mentioned organoaluminum compound. The contact here means the catalyst component (A)
And (B) or the catalyst components (A) to (C) are in contact with each other to form a catalyst. Any catalyst may be used. The catalyst components may be diluted with a solvent in advance or mixed without dilution. A method of bringing them into contact, a method of separately supplying them to a polymerization tank and bringing them into contact in the polymerization tank, and the like can be adopted. When the catalyst components (A) to (C) are used, those obtained by previously contacting any two of the components and the remaining one component are separately supplied to a polymerization tank and brought into contact in the polymerization tank. You may.

The use ratio (molar ratio) of each catalyst component in the present invention is not particularly limited, but component (A) a modified aluminum oxy compound (mol number in terms of Al atom) and component (B) a transition metal The molar ratio of the compounds is usually (A):
A molar ratio in the range (B) = 1: 1 to 10000: 1 is employed, preferably a molar ratio in the range of 1: 1 to 5000: 1. When the component (C) organoaluminum compound is used, the amount used is usually (B) :( C) = 1: 0.1 to
A molar ratio in the range of 1: 10000 is employed, preferably 1: 1 to 1: 5000, more preferably 1: 1 to 1:
The molar ratio is in the range of 1000.

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 / L, preferably 0 to 100 mol / L, respectively, as calculated as 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 10 mmol / L in terms of transition metal 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 a solution is dissolved in a hydrocarbon solvent, or a method in which each component is supplied in a slurry state in which the components are suspended 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 Examples include bulk polymerization for carrying out polymerization, gas phase polymerization for gaseous monomers, and a high-pressure method in a supercritical fluid state under high temperature and high pressure. As a polymerization method, either a batch type or a continuous type is possible.

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.

As the monomer used in the polymerization, an α-olefin having 3 to 20 carbon atoms is preferable, and two or more monomers can be used at the same time. Specific examples of these include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 5-methyl-2-pentene, 1-
Hexene, 1-heptene, 1-octene, 1-nonene,
Examples thereof include 1-decene and vinylcyclohexane, and preferably propylene and / or 1-butene, and particularly preferably propylene. The method for producing an α-olefin polymer of the present invention is a method for producing such a polymer of α-olefin, and includes a homopolymer of α-olefin and α-olefin.
It is suitable as a method for producing a copolymer of an olefin and ethylene, a cyclic olefin, a diolefin or the like. Specific examples of such a cyclic olefin include norbornene, and specific examples of the diolefin include 1,3-butadiene, 1,4-heptadiene, 1,5-hexadiene,
Examples include 1,7-octadiene, 5-ethylidene-2-norbornene, and the like.

The α-olefin polymerization catalyst of the present invention can produce an α-olefin having a more excellent stereoregularity.
It is a catalyst for olefin polymerization, suitable as a catalyst for isotactic stereoregular α-olefin polymerization, and particularly suitable as a catalyst for isotactic stereoregular propylene polymerization. The method for producing an α-olefin polymer of the present invention is also suitable as a method for producing an isotactic stereoregular α-olefin polymer, and particularly suitable as a method for producing an isotactic stereoregular propylene polymer.

Specific examples of the isotactic stereoregular propylene polymer include a homopolymer of propylene, ethylene and / or an α-olefin having 4 to 12 carbon atoms in such an amount that crystallinity is not lost. And copolymers with comonomers. The amount that does not lose crystallinity depends on the type of comonomer,
For example, in the case of ethylene, the amount of the repeating unit derived from ethylene in the copolymer is usually 10% by weight or less, and in the case of another α-olefin such as 1-butene, the amount of the α-olefin in the copolymer is
The amount of the repeating unit derived from the olefin is usually 30.
% By weight or less. In the case of a copolymer, for example, a random copolymer or a block copolymer is exemplified.

In the present invention, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer.

[0077]

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 the ratio (Mw / M) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
n). The calibration curve was prepared using standard polystyrene. 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

(3) Melting point scanning calorimeter (DSC) (Seiko Electronics Co., Ltd. S
SC-5200) under the following conditions. Temperature rise: -50 ° C to 200 ° C (20 ° C / min) Hold for 5 minutes Cooling: 200 ° C to -50 ° C (20 ° C / min) Hold for 5 minutes Measurement: -50 ° C to 300 ° C (raise at 20 ° C / min) Warm)

(4) ¹³ C-NMR measurement (isotactic pentad fraction (mmmm%)) A 200 mg sample was mixed with 3 ml of o-dichlorobenzene and heavy benzene in a mixed solvent (o-dichloro by volume ratio). (Benzene / heavy benzene = 3/1) and measured using a Brooker AC-250.

[0082] (5) 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. (measured temperature: 20 to 25 ° 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.

Example 1 A 1 liter stainless steel autoclave was replaced with argon, and 300 ml of toluene was added.
After charging, 100 g of propylene was charged. And 4
After the temperature was raised to 0 ° C., a toluene solution of MMAO3A manufactured by Tosoh Akzo Co., Ltd. (Al concentration: 5.6 wt%; hereinafter,
It may be abbreviated as “MMAO”. ) As a molar amount of Al atom and 2.0 mmol of water and 0.2 mmol of water were injected thereinto and mixed by stirring for 10 minutes. Further, 0.4 mmol of pentafluorophenol was introduced thereinto and stirred for 10 minutes. Separately, 5 ml of purified toluene and 1 μmol of dimethylsilylenebis (2-methyl-1-indenyl) zirconium dichloride were stirred and mixed into a 25-ml eggplant-shaped flask purged with argon, and then charged into the autoclave using a syringe. After 1 hour of polymerization, 5 ml of methanol was charged to terminate the polymerization. After purging unreacted propylene, the content of the autoclave was poured into about 1000 ml of acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 2.2 g of polypropylene was obtained. [Η] of the obtained polypropylene was 2.9 dl / g, and Mw /
Mn is 2.0, mmmm% = 96.5%, melting point is 15
3.9 ° C.

Example 2 In Example 1, the amount of pentafluorophenol was changed from 0.4 mmol to 0.6 mmol.
The procedure was the same except for changing to l. As a result, 3.2 g
Of polypropylene was obtained. [Η] of the obtained polypropylene was 3.0 dl / g, Mw / Mn was 1.9, m
mmm% = 96.3%, melting point was 153.8 ° C.

Example 3 The same procedure as in Example 1 was carried out except that the amount of water was changed from 0.2 mmol to 0.4 mmol, and the amount of pentafluorophenol was changed from 0.4 mmol to 0.2 mmol. As a result, 15.9 g of polypropylene was obtained. [Η] of the obtained polypropylene was 2.8 dl / g, Mw / Mn was 2.0, mmm
m% = 95.6%, melting point was 152.7 ° C.

Comparative Example 1 A 1 liter stainless steel autoclave was replaced with argon, and 300 ml of toluene was added.
After charging, 100 g of propylene was charged. And 4
After the temperature was raised to 0 ° C., 2.0 mmol of MMAO was added as a molar amount of Al atoms. On the other hand, 5 ml of purified toluene
and 1 μmol of dimethylsilylenebis (2-methyl-1-indenyl) zirconium dichloride were stirred and mixed, and then charged into the above autoclave using a syringe, polymerization was performed for 1 hour, and then 5 ml of methanol was charged. Stopped. After purging unreacted propylene, the content of the autoclave was poured into about 1000 ml of acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 1.2 g of polypropylene was obtained. [Η] of the obtained polypropylene was 2.5 dl / g, Mw / Mn was 2.0, mmmm% =
93.8%, melting point 152.2 ° C.

Example 4 A 1-liter stainless steel autoclave was replaced with argon, and 300 ml of toluene was added.
After charging, propylene was introduced at 0.3 MPa. After the temperature was raised to 40 ° C., 2.0 mmol of MMAO as a molar amount of Al atoms and 0.2 mmol of water were press-injected.
Stir and mix for 0 minutes. Further, 0.2 mmol of pentafluorophenol was introduced thereinto and stirred for 10 minutes. On the other hand, 5 ml of purified toluene and 0.5 μmol of dimethylsilylenebis (2-methyl-4-naphthyl-1-indenyl) zirconium 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. The mixture was charged into the autoclave, and polymerization was performed for 1 hour. Propylene was continuously supplied during the polymerization so that the propylene pressure was always 0.3 MPa. Thereafter, 5 ml of methanol was added to stop the polymerization. After purging unreacted propylene, the content of the autoclave was poured into about 1000 ml of acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. As a result, 2.0 g of polypropylene was obtained. Mw of the obtained polypropylene is 260 × 10
⁴ , Mw / Mn is 2.0, mmmm% = 98.6%,
Melting point was 161.3 ° C.

Comparative Example 2 A 1 liter stainless steel autoclave was replaced with argon, and 300 ml of toluene was added.
After charging, propylene was introduced at 0.3 MPa. After the temperature was raised to 40 ° C., 2.0 mmol of MMAO was introduced as a molar amount of Al atoms. On the other hand, 5 ml of purified toluene and dimethylsilylenebis (2-methyl-4-naphthyl-1-indenyl) zirconium dichloride were placed in an eggplant-shaped flask having an inner volume of 25 ml and purged with argon.
After stirring and mixing 5 μmol, the mixture was charged into the autoclave using a syringe, and polymerization was performed for 1 hour. Propylene always has a propylene pressure of 0.
It was continuously supplied so as to be 3 MPa. Thereafter, 5 ml of methanol was added to stop the polymerization. After purging unreacted propylene, the contents of the autoclave were
It was poured into 00 ml of acidic methanol, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 2 hours. as a result,
1.1 g of polypropylene were obtained. Mw of the obtained polypropylene was 219 × 10 ⁴ , and Mw / Mn was 2.
5, mmmm% = 98.0%, melting point was 160.5 ° C.

[0089]

As described above in detail, according to the present invention, an α-olefin polymerization catalyst capable of producing an α-olefin polymer having high stereoregularity, and production of an α-olefin polymer having high stereoregularity A method is provided. Further, according to the present invention, a highly active α-olefin polymerization catalyst capable of producing an α-olefin polymer having high stereoregularity, and an efficient method for producing an α-olefin polymer having high stereoregularity are also provided. Provided, the industrial value of the present invention is enormous.

[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 shows a sample obtained by drying under reduced pressure a mixture obtained by stirring and mixing MMAO and water in a molar ratio of MMAO (mol number in terms of Al atom): water = 5: 1, and drying the mixture under reduced pressure to dryness. ²⁷
It is an Al-solid NMR spectrum. The value of L2 / L1 obtained from this spectrum was 0.75.

FIG. 3 is a diagram showing an example in which MMAO and water are stirred and mixed at a molar ratio of MMAO (mole number in terms of Al atom): water = 5: 1, and pentafluorophenol is further mixed with MMAO (mole number in terms of Al atom): pentafluoro. It is a ²⁷ Al-solid NMR spectrum of a sample obtained by adding a phenol at a molar ratio of 5: 1, stirring and mixing, and then drying it under reduced pressure to dryness. The value of M2 / M1 obtained from this spectrum was 1.26.

FIG. 4 is a diagram showing an example in which MMAO and pentafluorophenol are added in a molar ratio of MMAO (mole number in terms of Al atom): pentafluorophenol = 5: 1, and the mixture is stirred and dried under reduced pressure to dryness. It is a ²⁷ Al-solid NMR spectrum of the sample obtained by making it. The value of N2 / N1 obtained from this spectrum was 0.57.

FIG. 5 is a flowchart for helping the understanding of the present invention. The 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 F term (reference) 4J028 AA01A AB01A AC01A AC08A AC10A AC26A AC28A BA00A BA01B BB00A BB01B BB02B BC15B BC16B BC17B BC25B BC27B EB04 EB05 EB08 EB09 EB10 EB13 EB16 GA18 EB18 GA19

Claims (8)

[Claims] (1) It is modified with (A) a compound having a hydroxyl group, and its ²⁷ Al-solid NMR spectrum shows 10%.
intensity M1 at 30 ppm and intensity M2 at 30 ppm
An α-olefin obtained by contacting a modified aluminum oxy compound having a ratio M2 / M1 of 0.60 or more with a transition metal compound having stereoregular polymerization ability of (B) an α-olefin. Catalyst for polymerization. 2. The method according to claim 2, wherein (A) the modified aluminum oxy compound is
(A) 10 pp in ²⁷ Al-solid NMR spectrum
a modified aluminum oxy compound obtained by reacting an aluminum oxy compound having a ratio H 2 / H 1 of less than 0.35 between the intensity H 1 at m and the intensity H 2 at 30 ppm, (b) water, and (c) a compound having a hydroxyl group. The α-olefin polymerization catalyst according to claim 1, wherein 3. The α-olefin polymerization catalyst according to claim 1, wherein the compound having a hydroxyl group is an alcohol compound, a phenol compound or a silanol compound. 4. The α-olefin polymerization catalyst according to claim 1, wherein the transition metal compound (B) is a transition metal compound represented by the following general formula (I). . (Wherein, M is a transition metal atom of Group 4 of the periodic table, L is an η ⁵ -indenyl group or a substituted η ⁵ -indenyl group, and the two Ls may be the same or different. Y is a bridging group connecting two L, and two Xs are each independently a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, an alkoxy group,
It is an aralkyloxy group, an aryloxy group or a heterocyclic group. ) (5) The transition metal compound (B) has the following general formula (I)
The α-olefin polymerization catalyst according to any one of claims 1 to 3, which is a transition metal compound represented by I). (Wherein M is a transition metal atom of Group 4 of the periodic table, and Y ²
Silicon atom, a germanium atom or a tin _{^{atom, (R 2 n -C 5 H}} 4-n) and _{^{(R 2 q -C 5 H 4}} -q) each substituted eta ⁵ - be a cyclopentadienyl group , N and q are each an integer of 1 to 3. Each R ² may be the same or different from each other, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, show an aryloxy group or a heterocyclic group, a substituted eta ⁵ The position and / or type of R ^{2 in} the cyclopentadienyl group is selected such that there is no plane of symmetry containing M. R ³ and X are each a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an aryl group, a substituted silyl group, alkoxy group, aralkyloxy group, an aryloxy group or a heterocyclic group, R ³ and X are all the same Or different from each other. ) 6. The α-olefin polymerization catalyst according to claim 1, wherein the α-olefin polymerization catalyst is an isotactic stereoregular α-olefin polymerization catalyst. 7. A method for producing an α-olefin polymer, which comprises using the α-olefin polymerization catalyst according to claim 1. 8. A method for producing an α-olefin polymer according to claim 7, wherein the α-olefin polymer is an isotactic propylene polymer.