JP2001302687A - Transition metal compound, catalyst for polymerizing olefin, and method of producing olefin polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a transition metal compound, and to provide a catalyst for polymerizing an olefin, capable of efficiently giving a medium stereoregular olefin polymer having a narrow molecular-weight distribution. SOLUTION: This transition metal compound is expressed by the formula (I) (M is a transition metal belonging to the 3 to 10 groups in the periodic table; R1 to R14 are each H, a halogen, a 1-20C alkyl or the like, and each may be the same to or different from the others; X1 and X2 are each H, a halogen, a 1-20C alkyl or the like, and each may be the same to or different from the other; and A is a divalent crosslinking group, such as a 1-20C divalent hydrocarbon residue). The catalyst for polymerizing the olefin contains the transition metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a transition metal compound,
More specifically, the present invention relates to an olefin polymerization catalyst and a method for producing an olefin polymer, specifically, a novel transition metal compound having an indenyl-based ligand useful as an olefin polymerization catalyst component, an olefin polymerization catalyst containing the transition metal compound, and The present invention relates to a method for producing an olefin polymer using a polymerization catalyst.

[0002]

2. Description of the Related Art Among polyolefins, polypropylene is inexpensive and has excellent physical properties, and is used in a wide range of applications such as packaging films. In packaging film applications, polypropylene has a relatively high melting point, so to improve heat sealing at low temperatures,
Conventionally, it is common to copolymerize propylene with ethylene or an α-olefin having 4 to 20 carbon atoms in the presence of a Ziegler-Natta catalyst composed of a titanium compound or a magnesium compound carrying a titanium compound and an organoaluminum compound. It is being done.

[0003] However, the propylene-α-olefin copolymer packaging film thus obtained is excellent in transparency and scratch resistance as compared with a film made of low-density polyethylene, but has a low temperature. It is known that heat sealability is not sufficient (Japanese Patent No. 268562, Japanese Patent Application Laid-Open No. 9-241439, Japanese Patent Application Laid-Open No. 2-255812). In order to further improve the low-temperature heat sealability, when an attempt is made to increase the α-olefin content in the copolymer, the composition distribution broadens,
In addition, since the molecular weight is reduced, the amount of the solvent-soluble portion is increased, and the blocking resistance is deteriorated. further,
There is also a problem that haze increases and transparency decreases.

On the other hand, it has been reported that a polyolefin having a narrow molecular weight distribution can be obtained by using a metallocene catalyst (J. Polym. Sci., Polym. Che.).
m. Ed. 23, 2117 (1985)). However, at present, a propylene-based polymer excellent in the balance between low-temperature heat sealability and mechanical strength has not been obtained with a metallocene catalyst.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a transition metal compound, a catalyst for olefin polymerization and a process for producing an olefin polymer, which efficiently provide a medium-stereoregular olefin polymer having a narrow molecular weight distribution. Is what you do.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a transition metal compound belonging to Group 3 to 10 of the periodic table having a specific structure, The present inventors have found that the object can be achieved by an olefin polymerization catalyst containing a compound and a method for producing an olefin polymer using the polymerization catalyst, and have completed the present invention based on such findings.

That is, the present invention provides the following transition metal compounds, catalysts for olefin polymerization, and methods for producing olefin polymers. [1] A transition metal compound represented by the following general formula (I).

[0008]

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[Wherein, M represents a transition metal belonging to Groups 3 to 10 of the periodic table. R ^{1 to} R ¹⁴ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a sulfur-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a carbon number. 1
And 20 to 20 phosphorus-containing groups, which may be the same or different from each other, or may be bonded to each other to form a ring. X ¹ and X ² each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, It represents 20 oxygen-containing groups or 1-20 carbon-containing sulfur-containing groups, which may be the same or different. A is a divalent crosslinking group having 1 to 20 carbon atoms.
A divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-,- SO _2- , -N
^{R 15 -, - PR 15 -} , - P (O) R 15 -, - BR 15 -,
Or -AlR ¹⁵ - (provided that, R ¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or carbon atoms 1-2
And 0 represents a halogenated hydrocarbon group. ). [2] (A) The transition metal compound described in the above [1] and (B) (B-1) an aluminum oxy compound, (B-
2) An olefin polymerization catalyst containing an ionic compound that can be converted to a cation by reacting with the transition metal compound and at least one selected from (B-3) Lewis acids.

[3] (A) The transition metal compound described in the above [1] and (B) (B-1) an aluminum oxy compound,
(B-2) An olefin polymerization catalyst containing at least one selected from ionic compounds capable of reacting with the transition metal compound to convert to cations and (B-3) Lewis acids and (C) an organoaluminum compound. .

[4] The olefin polymerization catalyst according to [2] or [3], wherein at least one of the component (A) and the component (B) is supported on a carrier.

[5] The olefin polymerization catalyst according to any one of the above [2] to [4], wherein M in the general formula (I) is a transition metal belonging to Groups 4 to 6 of the periodic table. [6] A method for producing an olefin polymer in which an olefin is polymerized in the presence of the olefin polymerization catalyst according to any one of [2] to [5].

[7] An olefin polymer which polymerizes propylene or propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to any one of the above [2] to [5]. Manufacturing method.

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a transition metal compound as described above, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the catalyst. More specifically, the present invention relates to a transition metal compound that efficiently gives a medium stereoregular olefin polymer having a narrow molecular weight distribution, an olefin polymerization catalyst, and a method for producing an olefin polymer using the catalyst. More specifically, the tacticity is moderate (for example, the tacticity represented by the isotactic pentad fraction is 85 mol% or less, preferably 80 mol% or less), the tackiness is low, and the melting temperature is low. Low, and flexible (having a tensile modulus of 600 to 1,600 MPa, preferably 700
To 1,200 MPa, particularly preferably 800 to 1,10
The present invention relates to a catalyst for olefin polymerization that efficiently provides an olefin polymer excellent in 0 MPa), a method for producing an olefin polymer using the catalyst, and a transition metal compound used for the catalyst.

First, the olefin polymer obtained by the present invention will be described in detail. [Olefin Polymer Obtained by the Present Invention] The olefin polymer obtained by the present invention is not particularly limited, but typically includes a propylene-based polymer described below. <Propylene-based polymer> The propylene-based polymer obtained by the present invention has a heat of fusion ΔH (J / g) and a melting point Tm (° C) measured by a differential scanning calorimeter in a relationship of ΔH ≧ 0.45 × Tm + 22. It is a propylene-based polymer that fills.

When this requirement is satisfied, the balance between the melting temperature and the elastic modulus is excellent, and the balance between the moldability and workability at a low temperature and the mechanical strength is excellent. That is, when the present polymer is used for a film, the balance between the low-temperature heat sealability and the mechanical strength of the obtained film is excellent, which is preferable.

The propylene polymer includes ΔH
(J / g) and Tm (° C.) preferably satisfy the relationship of ΔH ≧ 0.45 × Tm + 25.

Further, as the propylene-based polymer,
Propylene polymers having the properties shown in the following (1), (2) and (3) are more preferred. (1) Melting point Tm (° C) measured by differential scanning calorimeter
Is 110 ≦ Tm ≦ 140, and (2) the half width at the peak top Th (° C.) of the elution curve measured by the temperature rising fractionation method
Satisfies the relationship of Th ≦ 5, and (3) intrinsic viscosity [η] (dl / g) measured in a tetralin solvent at 135 ° C. is 0.5 to 5.

The Tm (° C.) is as follows: 120 ≦ Tm ≦
140 is preferable, and 120 ≦ Tm ≦ 135 is more preferable. [Η] is preferably 0.5 to 4 dl / g, more preferably 1.0 to 3 dl / g. In addition,
The method for measuring the various parameters will be described in detail in Examples.

Further, in addition to the requirements described above, the propylene-based polymer has a molecular weight distribution (Mw / Mn) measured by a gel permeation (GPC) method.
Is preferably 4 or less, more preferably 3.5 or less, and 3 or less.
The following are particularly preferred. If the molecular weight distribution (Mw / Mn) exceeds 4, stickiness may occur. Further, the amount of boiling diethyl ether extracted is preferably 5% by mass or less. If it exceeds 5% by mass, the film may be sticky. The method for measuring the amount of boiling diethyl ether extracted will be described in detail in Examples.
Further, the temperature Tp at the peak position of the elution curve measured by the temperature rising fractionation method is preferably 60 to 95 ° C. Further, the amount of the component eluted in a temperature range of Tp ± 5 ° C. is preferably 70% by mass or more.

The propylene polymer may be a homopolymer of propylene, or a copolymer of propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms (hereinafter referred to as propylene copolymer). Union). As the α-olefin having 4 to 20 carbon atoms, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples thereof include octadecene and 1-eicosene, and in the present invention, one or more of these may be used.

In the case of a propylene homopolymer, the isotactic pendad fraction [mmmm] is preferably from 65 to 85 mol%, more preferably from 70 to 80 mol%. The isotactic pendad fraction is described by A. Zambelli et al.
romolecules, 6 , 925 (1973) ", means the isotactic fraction in pentad units in a polypropylene molecular chain measured by the signal of the methyl group in the ¹³ C nuclear magnetic resonance spectrum. ¹³ C
The measurement of the nuclear magnetic resonance spectrum is described by A. Samberg (A.
Zambellli) et al.
les, 8 , 687 (1975) ", according to the following apparatus and conditions according to the assignment of peaks.

Apparatus: JNM-EX40 manufactured by JEOL Ltd.
Type 0 ¹³ C-NMR apparatus Method: Proton complete decoupling method Concentration: 220 mg / mL Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C. Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10,000 times On the other hand, in the case of a propylene-based copolymer, the content of comonomer other than propylene is preferably 1.0 mol% or less, in addition to the above requirements. The propylene-based copolymer has a stereoregularity index expressed by an isotactic triad fraction [mm] of a propylene portion of 80.
It is preferably from about 92 mol%. The larger this value is, the higher the stereoregularity is, and if it is less than 80 mol%, the elasticity is too low and the moldability may be poor. On the other hand, if it exceeds 92 mol%, it may become hard and not soft. [Mm] is ¹³ C-NMR
It is determined by measuring the spectrum in the same manner as in the above [mmmm]. Details will be described in Examples. Further, the propylene-based copolymer preferably has a random structure.

In general, in the polymerization of propylene, the carbon atom on the methylene side of the propylene monomer is bonded to the active site of the catalyst, and the propylene monomer is coordinated and polymerized in the same manner in the so-called 1,2-insertion. Is usually performed, but rarely, 2,1 insertion or 1,3 insertion (also referred to as abnormal insertion) may occur. The propylene-based polymer preferably has a small amount of the 2,1 or 1,3 insertion. The ratio of these insertions is expressed by the following relational expression (1) [(m−2,1) + (r−2,1) + (1,3)] ≦ 5.0 (%) (1) [Wherein (m-2,1) is the meso-2,1 insertion content (%) measured by ¹³ C-NMR, and (r-2,1) is the ¹³ C-N
Racemic-2,1 insertion content (%) measured by MR,
(1,3) indicates the 1,3 insertion content (%) measured by ¹³ C-NMR. Is preferable, and the relational expression (2) [(m−2,1) + (r−2,1) + (1,3)] ≦ 1.0 (%) (2) Satisfaction is more preferable. In particular, those satisfying the relational expression (3) [(m−2, 1) + (r−2, 1) + (1, 3)] ≦ 0.1 (%) (3) are most preferable. This relational expression (1)
If not, the crystallinity may be reduced more than expected, which may cause stickiness.

(M-2,1), (r-2,1) and (1,3) are reported by Grassi et al. (Macromo).
lucules, 21 , p. 617 (1988)) and a report by Busico et al. (Macromolecule).
s, 27 , p. ¹³ C based on the 7538 (1994))
-It is each insertion content obtained by determining the assignment of the peak of the NMR spectrum and calculating from the integrated intensity of each peak. That is,
(M−2,1) is Pα, γthre that appears around 17.2 ppm with respect to the integrated intensity in the entire methyl carbon region.
It is the meso-2,1 insertion content (%) calculated from the ratio of the integrated intensity of the peak attributed to o. (R-2,1) is
15.0p for integrated intensity in all methyl carbon region
It is the racemic-2,1 insertion content (%) calculated from the ratio of the integrated intensity of peaks belonging to Pα and γthreo appearing near pm. (1,3) is the value of T which appears around 31.0 ppm relative to the integrated intensity in the entire methine carbon region.
1,3 insertion content (%) calculated from the ratio of the integrated intensities of the peaks belonging to β, γ.

Further, as the propylene-based polymer,
Is¹³In the measurement of the C-NMR spectrum,
Attributable to the end of the molecular chain (n-butyl group) derived from
Those in which a peak is not substantially observed are more preferable. This
Regarding the molecular chain end derived from the 2,1 insertion of Jun,
gling et al. (J. Polym. Sci .: Pa.
rtA: Po1ym. Chem. ,33, P1305
(1995)) ¹³Of the C-NMR spectrum
Of the peaks, and from the integrated intensity of each peak,
Calculate the prevalence. In addition, isotactic polypropylene
The peak appearing at around 18.9 ppm was n-butyl
At the unsubstituted methyl group carbon. Also, abnormal insertion
Or regarding molecular chain end measurement¹³C-NMR measurement
What is necessary is just to carry out with the said apparatus and conditions.

Since the olefin polymer obtained by the present invention has the above-mentioned properties, it has good moldability and workability at low temperatures (for example, low-temperature heat sealing properties), embossing and heat sealing, stretched films, blow molding. It is also excellent in secondary workability, such as a laminated film, a heat sealant, a stretched film, a resin modifier for softness, and a blow molded article.

Next, the transition metal compound of the present invention, a catalyst for olefin polymerization, and a method for producing an olefin polymer using the catalyst will be described in detail below. Transition metal compound The transition metal compound of the present invention is a transition metal compound represented by the following general formula (I).

[0029]

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[Wherein, M represents a transition metal belonging to Groups 3 to 10 of the periodic table. R ^{1 to} R ¹⁴ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, a sulfur-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a carbon number. 1
And 20 to 20 phosphorus-containing groups, which may be the same or different from each other, or may be bonded to each other to form a ring. X ¹ and X ² each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, It represents 20 oxygen-containing groups or 1-20 carbon-containing sulfur-containing groups, which may be the same or different. A is a divalent crosslinking group having 1 to 20 carbon atoms.
A divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-,- SO _2- , -N
^{R 15 -, - PR 15 -} , - P (O) R 15 -, - BR 15 -,
Or -AlR ¹⁵ - (provided that, R ¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or carbon atoms 1-2
And 0 represents a halogenated hydrocarbon group. ). M in the general formula (I) represents a metal element belonging to Groups 3 to 10 of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, vanadium, chromium, iron, cobalt,
Or nickel. As M, a metal element belonging to Groups 4 to 6 of the periodic table is preferable because the activity becomes high.
Among them, titanium, zirconium and hafnium are particularly preferred.

R ^{1 to} R ¹⁴ are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms,
Represents an oxygen-containing group having 1 to 20 carbon atoms, a sulfur-containing group having 1 to 20 carbon atoms, a nitrogen-containing group having 1 to 20 carbon atoms, or a phosphorus-containing group having 1 to 20 carbon atoms. May be combined with each other to form a ring. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom. Specific examples of the hydrocarbon group having 1 to 20 carbon atoms include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group and an octyl group, a vinyl group, a propenyl group, and a cycloalkyl group. Alkenyl group such as hexenyl group; arylalkyl group such as benzyl group, phenylethyl group, phenylpropyl group; phenyl group, tolyl group, dimethylphenyl group, trimethylphenyl group, ethylphenyl group, propylphenyl group, biphenyl group, naphthyl group And aryl groups such as methylnaphthyl group, anthracenyl group and phenanthonyl group. Among them, methyl group, ethyl group,
An alkyl group such as a propyl group and an aryl group such as a phenyl group are preferred. Examples of the halogenated hydrocarbon group having 1 to 20 carbon atoms include a halogenated hydrocarbon group in which a halogen atom is substituted for the hydrocarbon group. Of these, halogenated alkyl groups such as a trifluoromethyl group and a trichloromethyl group are preferable. Examples of the silicon-containing group having 1 to 20 carbon atoms include monohydrocarbon-substituted silyl groups such as methylsilyl group and phenylsilyl group; dihydrocarbon-substituted silyl groups such as dimethylsilyl group and diphenylsilyl group; trimethylsilyl group, triethylsilyl group; Tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methylphenyldisilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbon-substituted silyl groups; carbonization of trimethylsilyl ether groups and the like A silyl ether group of a hydrogen-substituted silyl group; a silicon-substituted alkyl group such as a trimethylsilylmethyl group; a silicon-substituted aryl group such as a trimethylsilylphenyl group. Among them, a trimethylsilyl group, a phenethyldimethylsilyl group and the like are preferable. Examples of the oxygen-containing group having 1 to 20 carbon atoms include methoxy group, ethoxy group, propyloxy group, butoxy group, hexyloxy group, cyclohexyloxy group, alkyloxy group such as octyloxy group, vinyloxy group, propenyloxy group, Alkenyloxy groups such as cyclohexenyloxy group; arylalkyloxy groups such as benzyloxy group, phenylethyloxy group and phenylpropyloxy group; phenoxy group, tolyloxy group, dimethylphenyloxy group, trimethylphenyloxy group, and ethylphenyloxy group ,
And aryloxy groups such as a propylphenyloxy group, a biphenyloxy group, a naphthyloxy group, a methylnaphthyloxy group, an anthracenyloxy group, and a phenanthonyloxy group. Examples of the sulfur-containing group having 1 to 20 carbon atoms include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, a hexyl sulfide group, a cyclohexyl sulfide group, an alkyl sulfide group such as an octyl sulfide group, and a vinyl sulfide group. Alkenyl sulfide groups such as propenyl sulfide group and cyclohexenyl sulfide group; arylalkyl sulfide groups such as benzyl sulfide group, phenylethyl sulfide group and phenyl propyl sulfide group; phenyl sulfide group, tolyl sulfide group, dimethyl phenyl sulfide group and trimethyl phenyl sulfide Group, ethylphenyl sulfide group, propylphenyl sulfide group, biphenyl sulfide group, naphthyl sulfide group, methyl naphthyl sulfide Group, anthracenyl Nils sulfide group, an aryl sulfide groups such as phenanthridine Nils sulfide group. 1-20 carbon atoms
Examples of the nitrogen-containing group include an alkylamino group such as a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a dicyclohexylamino group, and a methylethylamino group, a divinylamino group, a dipropenylamino group, and a dicyclohexenyl. An alkenylamino group such as an amino group; an arylalkylamino group such as a dibenzylamino group, a phenylethylamino group and a phenylpropylamino group; and an arylamino group such as a diphenylamino group and a dinaphthylamino group. Examples of the phosphorus-containing group having 1 to 20 carbon atoms include a phenylphosphine group. R ^{1 to} R ^{14 each} represent a hydrogen atom or a carbon atom
Twenty hydrocarbon groups are preferred.

X ¹ and X ² each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
0 represents a halogenated hydrocarbon group, a silicon-containing group having 1 to 20 carbon atoms, an oxygen-containing group having 1 to 20 carbon atoms, and a sulfur-containing group having 1 to 20 carbon atoms. Is also good. X ¹ and X ^{2 each} include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms, and 1 to 2 carbon atoms.
Examples of the oxygen-containing group having 0 and the sulfur-containing group having 1 to 20 carbon atoms include the same as those exemplified for R ^{1 to} R ¹⁴ .

A is a divalent crosslinking group having 1 to 1 carbon atoms.
20, a divalent hydrocarbon group, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, -O-, -CO-, -S-, -SO ₂ -,
^{-NR 15 -, - PR 15 -} , - P (O) R 15 -, - BR 15
— Or —AlR ¹⁵ — (where R ¹⁵ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
And 0 represents a halogenated hydrocarbon group. ). Carbon number 1
Examples of the divalent hydrocarbon group of -20 include methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, and 1,2-cyclohexylene. Examples of the divalent halogenated hydrocarbon group having 1 to 20 carbon atoms include those in which a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom are bonded as the halogen atom to the divalent hydrocarbon group having 1 to 20 carbon atoms. No. As the divalent silicon-containing group,
Examples include dimethylsilylene and tetramethyldisilylene. Examples of the divalent germanium-containing group include dimethylgermylene and the like. Other specifics include:
Methyl Helsingborg isopropylidene (CH ₃ -B =), methylaluminoxane isopropylidene (CH ₃ -Al =), phenylphosphonic Philippines Den (Ph
-P =), phenylphosphoridene (PhPO =), 1,
2-phenylene, vinylene (-CH = CH-), vinylidene (CH ₂ = C =), methylimide, oxygen (-O
-), Sulfur (-S-) and the like. Incidentally, the halogen atom in R ^15, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, R ¹ ~
Similar to those exemplified in R ¹⁴ can be mentioned.
As A, methylene, ethylene, ethylidene and isopropylidene are preferable among these in view of attaining the object of the present invention.

As a specific example of the transition metal compound represented by the general formula (I), dimethylsilylene (1- (2-methyl-4,5-benzoindene) may be mentioned as an example of Group 4 of the periodic table. Yl)) (2-indenyl) zirconium dichloride, dimethylsilylene (1- (2-ethyl-4,5-benzoindenyl)) (2-indenyl) zirconium dichloride, dimethylsilylene (1- (2-butyl-4,
5-benzoindenyl)) (2-indenyl) zirconium dichloride, dimethylsilylene (1- (2-methyl-4,5-benzoindenyl)) (2-4,7-dimethylindenyl) zirconium dichloride, dimethylsilylene (1- (2-ethyl-4,5-benzoindenyl)) (2-4,7-dimethylindenyl) zirconium dichloride, diphenylsilylene (1- (2-methyl-4,5-benzoindenyl)) (2-indenyl) zirconium dichloride, diphenylsilylene (1- (2
-Ethyl-4,5-benzoindenyl)) (2-indenyl) zirconium dichloride, diphenylsilylenesilylene (1- (2-butyl-4,5-benzoindenyl)) (2-indenyl) zirconium dichloride, diphenylsilylene (1- (2-methyl-4,5-benzoindenyl)) (2-4,7-dimethylindenyl) zirconium dichloride, diphenylsilylene (1- (2
-Ethyl-4,5-benzoindenyl)) (2-4,7
-Dimethylindenyl) zirconium dichloride, or a transition metal compound in which zirconium in the above compound is changed to titanium or hafnium. 2. Olefin polymerization catalyst The olefin polymerization catalyst of the present invention comprises (A) a transition metal compound represented by the general formula (I), (B) (B-1) an aluminum oxy compound, and (B-2) a transition metal compound described above. An olefin polymerization catalyst containing at least one selected from an ionic compound capable of reacting and converting to a cation and a (B-3) Lewis acid and, if necessary, an (C) organoaluminum compound.

Hereinafter, each component will be described. (A) Component The (A) component is the above-mentioned transition metal compound. (B) component (B) component is (B-1) aluminum oxy compound,
It is at least one selected from (B-2) an ionic compound that can be converted to a cation by reacting with the transition metal compound and (B-3) a Lewis acid.

The aluminum oxy compound of the component (B-1) is represented by the general formula (II):

[0037]

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(Wherein R ¹⁶ is an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, w represents an average degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁶ may be the same or different. Aluminoxane represented by the general formula (III):

[0039]

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(Wherein, R ¹⁶ and w are the same as those of the above general formula (II)
Same as in I). ) Can be mentioned. Specific examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and the like. Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be performed according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminum with a tetraalkyldialuminoxane, and further reacting water.

The aluminoxane may be insoluble in a hydrocarbon solvent or may be soluble in a hydrocarbon solvent. Preferably, it is soluble in a hydrocarbon solvent and the residual organoaluminum compound measured by ¹ H-NMR is 10% by mass or less. More preferably, the residual organoaluminum compound is 3 to 5% by mass or less, particularly preferably 2 to 4% by mass. The use of such an aluminoxane is preferable because the ratio of the aluminoxane supported on the carrier (also referred to as a supporting ratio) increases. Since it is soluble in a hydrocarbon solvent, there is also an advantage that unsupported aluminoxane can be recycled and reused. Furthermore, since the properties of the aluminoxane are stable, there is an advantage that no special treatment is required for use. Further, the average particle size and the particle size distribution (generically referred to as morphology) of the polyolefin obtained by polymerization are improved, which is preferable. If the residual organoaluminum compound exceeds 10% by mass, the loading rate may decrease, and the polymerization activity may decrease.

As a method of obtaining such an aluminoxane, for example, a method of evaporating a solvent of an aluminoxane solution by heating and reducing the pressure under reduced pressure to dryness (also referred to as a dry-up method) may be mentioned. In the dry-up method, the evaporation of the solvent by heating and decompression is preferably 80 ° C. or lower, more preferably 60 ° C. or lower.

As a method for removing components insoluble in the hydrocarbon solvent from the aluminoxane, for example, a method in which the components insoluble in the hydrocarbon solvent are spontaneously precipitated and then separated by decantation is used. Alternatively, a method of separation by an operation such as centrifugation may be used. Thereafter, it is preferable to filter the recovered soluble components using a G5 glass filter or the like under a nitrogen stream, since insoluble components are sufficiently removed. The gel component of the aluminoxane thus obtained may increase with time, but is preferably used within 48 hours after preparation, particularly preferably immediately after preparation. The ratio of the aluminoxane and the hydrocarbon solvent is not particularly limited,
It is preferable to use such a concentration that the aluminum atom in the aluminoxane is 0.5 to 10 mol per 1 liter of the hydrocarbon solvent.

The hydrocarbon solvent includes
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene, cymene and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, octadecane and cycloaliphatic rings such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane And petroleum fractions such as formula hydrocarbons, naphtha, kerosene, and light gas oil.

These aluminoxanes may be used alone or in combination of two or more. On the other hand, (B
As the component -2), any compound can be used as long as it is an ionic compound that can be converted into a cation by reacting with the transition metal compound. Particularly, from the viewpoint that a polymerization active site can be efficiently formed, The following general formulas (IV), (V) ([L ¹ -R ¹⁸ ] ^{h +} ) _a ([Z] ^- ) _b ... (IV) ([L ² ] ^{h +} ) _a ([Z] ^- ) _b · · · (V) (except, L ^{2 is, M 2, R 19 R 20} M 3, R 21 3 C or R ²²
M is ^3. [In the formulas (IV) and (V), L ¹ is a Lewis base and [Z] ⁻
Is a non-coordinating anion [Z ^{1] -} or [Z ^{2] -,} wherein [Z ^{1] -} anion in which a plurality of groups are bonded to the element, i.e. ^{[M 4 G 1 G 2 ··· G} f (Where M ⁴ represents an element of Groups 5 to 15 of the periodic table, preferably an element of Groups 13 to 15 of the periodic table. G ^{1 to} G ^f represent a hydrogen atom, a halogen atom, and a carbon number of 1 to 20, respectively) An alkyl group, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, and an alkylaryl having 7 to 40 carbon atoms Group, an arylalkyl group having 7 to 40 carbon atoms, a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a hydrocarbon group containing 2 to 20 carbon atoms containing a hetero atom two or more of .G ¹ ~G ^f showing the can to form a ring Which may be .f represents an integer of [(valence of central metal M ⁴⁾ +1]), [Z ^{2] -.} The logarithm of the reciprocal of the acid dissociation constant (pK _a) of -10 or less Bronsted A conjugate base of an acid alone or a combination of a Bronsted acid and a Lewis acid, or a conjugate base generally defined as a super strong acid is shown. Further, a Lewis base may be coordinated. Also, R ¹⁸ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, alkylaryl group or arylalkyl group having 7 to 40 carbon atoms of 7 to 40 carbon atoms, R ¹⁹ And R ²⁰ are a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, respectively, and R ²¹ is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 40 carbon atoms. Or an arylalkyl group having 7 to 40 carbon atoms. R ²² represents a macrocyclic ligand such as tetraphenylporphyrin and phthalocyanine. h is [L ¹ -R ¹⁸ ],
In the ionic valence of [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (h × a). M ² is the first to the ^first in the periodic table.
Containing elements of groups 3, 11 to 13, and 17;
³ represents an element in Groups 7 to 12 of the periodic table. ] Can be suitably used.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁷ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹⁸ and R ²⁰ include cyclopentadienyl group, methylcyclopentane Examples thereof include a dienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Specific examples of R ²¹ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group, and specific examples of R ²² include a tetraphenylporphyrin, phthalocyanine, allyl, and methallyl. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, F
e, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ⁵ G ¹ G ^2.
··· G ^f ], as specific examples of M ⁵ , B, Al, S
i, P, As, Sb and the like, preferably B and Al. Specific examples of G ¹ , G ^{2 to} G ^f include dimethylamino and diethylamino as dialkylamino groups, methoxy, ethoxy, n-butoxy, phenoxy and the like as alkoxy or aryloxy groups. Methyl group, ethyl group, n-
Propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t-butylphenyl, 3,5-dimethylphenyl For example, fluorine, chlorine, bromine, iodine as a halogen atom, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,
5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group,
Pentamethylantimony, trimethylsilyl, trimethylgermyl, diphenylarsine, organic metalloid groups such as bis (trimethylsilyl) methyl group,
Examples include a dicyclohexylantimony group and diphenylboron.

Further, a non-coordinating anion, ie, pKa
-10 or less Brønsted acid alone or
Conjugate base [Z^Two]^-Concrete
Examples include the trifluoromethanesulfonate anion (C
F_ThreeSO_Three)^-, Bis (trifluoromethanesulfonyl)
Methyl anion, bis (trifluoromethanesulfonate
Le) benzyl anion, bis (trifluoromethanesulfur)
Phonyl) amide, perchlorate anion (ClO_Four)^-,bird
Fluoroacetate anion (CF_ThreeCO_Two)^-, Hexafluo
Loantimony anion (SbF₆)^-, Fluorosulfone
Acid anio (FSO _Three)^-, Chlorosulfonic acid anion
(ClSO_Three)^-, Fluorosulfonic acid anion / 5-f
Antimony nitride (FSO_Three/ SbF_Five)^-, Fluorosul
Phosphate anion / 5-arsenic fluoride (FSO_Three/ AsF_Five)
^-, Trifluoromethanesulfonic acid / 5-antifluoride
Mon (CF_ThreeSO_Three/ SbF_Five)^-And the like
You.

Specific examples of the component compound (B-2) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, and tetraphenylborate. Methyl (tri-n-butyl) ammonium, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, tetraphenylborate Methylpyridinium, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) Triethylammonium, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Tetraethylammonium, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate,
Methylanilinium tetrakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Benzylpyridinium, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), tetrakis ( Pentafluorophenyl) triphenylphosphonium borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate dimethyl Anilinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocene tetrakis (pentafluorophenyl) borate ), Decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Sodium, manganese tetraphenylporphyrin, tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate Hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and the like of silver trifluoromethanesulfonate. As the component (B-2), an ionic compound represented by the above general formula (5) is preferable.

As the component (B-2), an ionic compound which can be converted into a cation by reacting with the transition metal compound of the component (A) may be used alone or in combination of two or more. Is also good.

The Lewis acid of the component (B-3) is not particularly limited, and may be an organic compound or a solid inorganic compound. Organic compounds include boron compounds and aluminum compounds, and inorganic compounds include magnesium compounds,
Aluminum compounds and the like are preferably used because they can form active sites efficiently. Examples of the aluminum compound include bis (2,6-di-t-butyl-4-methylphenoxy) aluminum methyl, (1,1-bi-2-
Naphthoxy) aluminum methyl and the like; magnesium compounds such as magnesium chloride and diethoxymagnesium; aluminum compounds such as aluminum oxide and aluminum chloride; and boron compounds such as triphenylboron and tris (pentafluorophenyl) boron. Tris [3,5-bis (trifluoromethyl) phenyl] boron, tris [(4-fluoromethyl) phenyl] boron, trimethylboron, triethylboron, tri-n-butylboron, tris (fluoromethyl)
Boron, tris (pentafluoroethyl) boron, tris (nonafluorobutyl) boron, tris (2,4,6-trifluorophenyl) boron, tris (3,5-difluoro) boron, tris [3,5-bis ( Trifluoromethyl) phenyl] boron, bis (pentafluorophenyl)
Fluoroboron, diphenylfluoroboron, bis (pentafluorophenyl) chloroboron, dimethylfluoroboron, diethylfluoroboron, di-n-butylfluoroboron, pentafluorophenyldifluoroboron, phenyldifluoroboron, pentafluorophenyldichloroboron, methyldifluoro Boron, ethyldifluoroboron, n
-Butyldifluoroboron and the like.

These Lewis acids may be used alone or in combination of two or more. When the (B) compound is used as the (B) catalyst component, the molar ratio of the (A) catalyst component and the (B) catalyst component in the polymerization catalyst of the present invention is preferably 1: 1-1: 100
0000, more preferably 1:10 to 1: 10,000
A range of 0 is desirable. If the ratio is outside this range, the cost of the catalyst per unit weight of polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably from 10: 1 to 1: 100, more preferably from 2: 1 to 1: 1.
A ratio of 1:10 is desirable, and if the ratio is outside the above range, the catalyst cost per unit weight polymer becomes high,
Not practical. The use ratio of the catalyst component (A) to the catalyst component (B-3) is preferably a molar ratio of 10: 1.
１ ： 1: 2,000, more preferably 5: 1１ ： 1: 1,0
00, more preferably in the range of 2: 1 to 1: 500. If the ratio deviates from this range, the catalyst cost per unit weight polymer increases, which is not practical. The catalyst component (B) includes (B-1), (B-2), and (B-
3) and the like can be used alone or in combination of two or more.

The polymerization catalyst of the present invention may contain the above components (A) and (B) as main components, or may contain the components (A), (B) and (C). ) An organic aluminum compound may be contained as a main component.

Here, the organoaluminum compound of the component (C) is represented by the following general formula (VI): R ²³ v AlQ3-v (VI) (wherein R ²³ is an alkyl group having 1 to 10 carbon atoms; Q is a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms.
And v is a real number of 1 to 3).

Specific examples of the compound represented by the general formula (VI) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride,
Examples include diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.

These organoaluminum compounds may be used alone or in combination of two or more. Also,
The molar ratio of the catalyst component (A) to the optional catalyst component (C) is preferably 1: 1 to 1: 2.
0000, more preferably 1: 5 to 1: 2,000,
More preferably, the range is from 1:10 to 1: 1,000. By using the catalyst component (C), the polymerization activity per transition metal can be improved. However, if the amount is too large, especially if it exceeds the above range, the organoaluminum compound will be wasted and the polymer will not be contained in the polymer. If a large amount remains, and if it is small, sufficient catalytic activity cannot be obtained,
May not be preferred.

Further, in the present invention, the above (A)
At least one selected from component (B) and component (B).
It can be used supported on a carrier. Type of the carrier
There is no particular limitation on the inorganic oxide carrier,
Both organic carriers and organic carriers can be used,
In particular, from the viewpoint of morphology control, an inorganic oxide carrier or
Other inorganic carriers are preferred. As an inorganic oxide carrier
Is, specifically, SiO 2_Two, Al_TwoO_Three, MgO, Zr
O_Two, TiO_Two, Fe_TwoO_Three, B_TwoO_Three, CaO, ZnO, B
aO, ThO_TwoAnd mixtures thereof, such as silica aluminum
Na, zeolite, ferrite, glass fiber, etc.
No. Among them, especially SiO 2 _TwoOr Al_TwoO
_ThreeIs preferred. In addition, the inorganic oxide carrier is a small amount of carbon.
Acid salts, nitrates, sulfates and the like may be contained. On the other hand
Other than the above, MgCl_Two, Mg (OC_TwoH_Five) 2
General formula MgR represented by a magnesium compound such as
^{twenty four} _XX^Four _yMagnesium compounds represented by
Can be mentioned. Where R^{twenty four}Has 1 to 20 carbon atoms
An alkyl group, an alkoxy group having 1 to 20 carbon atoms or carbon
An aryl group of the formulas 6 to 20, X^FourIs a halogen atom or carbon
Represents an alkyl group of Formulas 1 to 20, x is 0 to 2, y is 0 to
2 and x + y = 2. Each R^{twenty three}And each X^FourIs
Each may be the same or different. Ma
As organic carriers, polystyrene, styrene-divinyl
Nylbenzene copolymer, polyethylene, polypropylene
Polymers such as polystyrene, substituted polystyrene, polyarylate, etc.
Starch, carbon and the like can be mentioned. The present invention
As the carrier used in the above, MgCl_Two, MgC
l (OC_TwoH_Five), Mg (OC_TwoH_Five)_Two, SiO_Two, Al_Two
O_ThreeAre preferred. The nature of the carrier depends on its type and
The average particle size is usually 1 to 300 μm,
Preferably 10 to 200 μm, more preferably 20 to 1
00 μm. Small particle size increases fines in polymer
When the particle size is large, the coarse particles in the polymer increase and the bulk density increases.
Of the hopper and clogging of the hopper. In addition, the carrier
The specific surface area is usually 1 to 1,000 m^Two/ G, preferably
50-500m^Two/ G, pore volume is usually 0.1-5 cm^Three
/ G, preferably 0.3-3 cm^Three/ G. Specific surface
If either the volume or pore volume deviates from the above range,
The solvent activity may decrease. The specific surface area and pores
For example, the volume of the nitrogen gas adsorbed according to the BET method is
It can be determined from the volume (J. Am. Chem. S.
oc, vol. 60, p. 309 (1983)
See). Further, the carrier is usually 150 to 1,000.
C, preferably fired at 200-800C
Is desirable.

When at least one of the catalyst components is supported on the carrier, at least one of the catalyst components (A) and (B), preferably the catalyst components (A) and (B)
Supporting both catalyst components is morphology control,
It is desirable from the viewpoint of applicability to processes such as gas phase polymerization.

The method of supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, at least one of the components (A) and (B) is mixed with the carrier. After the method and the carrier are treated with an organoaluminum compound or a halogen-containing silicon compound (silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc.), at least the components (A) and (B) are treated in an inert solvent. A method of mixing with one, a method of reacting the carrier with the component (A) or the component (B) or both and an organoaluminum compound or a halogen-containing silicon compound (silicon tetrachloride, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, etc.), After supporting the component (A) or the component (B) on a carrier, ( ) Component or a method of mixing with component (A), a method of mixing a contact reactant of component (A) with component (B) with a carrier, A coexisting method or the like can be used. Also, in the above reaction, and
Organoaluminum compounds can also be added. Here, the organoaluminum compound may be appropriately selected from the aforementioned organoaluminum compounds of the component (C).

In the present invention, the compound (B-
1) The use ratio of the component to the carrier is preferably 1: 0.5 to 1: 1,000, more preferably 1: 1 to 1 by weight.
The ratio of the component (B-1) to the carrier is preferably 1:50 to 1:50 by weight.
The ratio is desirably 100, more preferably 1: 0.1 to 1: 5. (B-3) is preferably 1: 0.
5 to 1: 1,000, more preferably 1: 1 to 1:10
It is desirable to set it to 0. When two or more catalyst components (B) are used as a mixture, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of the component (A) to the carrier is preferably 1: 5 to 1: 10,000, more preferably 1: 1, by weight.
It is desirable to set it to 10 to 1: 2,000.

The component (B) [component (B-1), (B-
If the proportion of the component (2) and the component (B-3)] and the carrier or the proportion of the component (A) and the carrier is outside the above range, the activity may be reduced. The average particle size of the polymerization catalyst thus used in the present invention is usually 2 to 2
00 μm, preferably 10 to 150 μm, particularly preferably 20 to 100 μm, and the specific surface area is usually 20 to 100 μm.
1,000 m ² / g, preferably from 50 to 500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase, and if it exceeds 200 μm, coarse particles in the polymer may increase. Specific surface area is 20m ² /
If the amount is less than 0.1 g, the activity may decrease, and
If it exceeds m ² / g, the bulk density of the polymer may decrease. In this polymerization catalyst, the amount of the transition metal in 100 g of the carrier is usually 0.001 to 1 g, particularly 0.001 to 1 g.
Preferably, it is 0.1 g. If the amount of the transition metal is outside the above range, the activity may be reduced. An olefin polymer having an industrially advantageous high bulk density and an excellent particle size distribution can be obtained by supporting on a carrier in this manner.

The contact of the component (A), the component (B) and, if necessary, the component (C) and / or the carrier is carried out in an inert gas such as nitrogen, pentane, hexane, heptane, toluene,
It may be performed in a hydrocarbon solvent such as cyclohexane. The contact temperature may range from -30 ° C to the boiling point of the solvent, preferably from -10 ° C to 100 ° C, and the contact time may be generally 30 seconds to 10 hours. After contact, the solid catalyst component may or may not be washed. In contact,
Any of the two different transition metal compounds in the component (A) may be used first, or may be used by mixing them in advance.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be generated by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, the catalyst may be a catalyst obtained by adding at least one of the components (A) and (B), a carrier and, if necessary, the organoaluminum compound of the component (C) and prepolymerizing the olefin.
As the olefin used in the prepolymerization, ethylene and an α-olefin having 3 to 20 carbon atoms, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-
Pentene, 1-hexene, 1-octene, 1-decene,
Examples thereof include 1-dodecene, 1-tetradecene, and styrene. Among them, particularly preferred is a combination with ethylene, propylene or an α-olefin used in the polymerization of ethylene-propylene. As the inert hydrocarbon solvent, specifically, the same inert hydrocarbon solvent as used in the preparation of the solid catalyst component described above can be used. In the case of prepolymerization, it is usually 10 ^-6 in terms of transition metal.
~ 2 × 10 ^-2 mol / l (solvent), preferably 5 ×
It is used in an amount of 10 ^-5 to 10 ^-2 mol / liter (solvent), and the atomic ratio of aluminum to transition metal in an organoaluminum compound such as methylaluminoxane (also referred to as MAO) as transition metal per gram of carrier ( Al / transition metal) is usually 10 to 5,000, preferably 20 to 1,
000. The ratio of the aluminum atom in the organoaluminum compound used as necessary to the aluminum atom in MAO is usually from 0.02 to 3, preferably from 0.05 to 3.
The range is 1.5. Prepolymerization temperature is -20 to 60 ° C,
The temperature is preferably from 0 to 50 ° C., and the prepolymerization time is from 0.1 to 50 ° C.
It is about 5 to 100 hours, preferably about 1 to 50 hours.
In the present invention, a catalyst obtained by prepolymerizing an olefin is preferably used.

Next, a method for homopolymerizing propylene or copolymerizing propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms using the above-described polymerization catalyst will be described.

In this case, the polymerization method is not particularly limited, and may be a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method,
Any method such as a suspension polymerization method may be used, but a slurry polymerization method and a gas phase polymerization method are preferred. Among them, the gas phase polymerization method is particularly preferred.

Regarding the polymerization conditions, the polymerization temperature is usually -1.
00 to 250 ° C, preferably -50 to 200 ° C, more preferably
Preferably it is 0-130 degreeC. In addition,
The ratio of the catalyst used is determined by the ratio of raw material monomer / component (a)
Ratio is preferably 1 to 10. ⁸, Especially 10^Two-10^FiveTona
Preferably. Further, the polymerization time is usually from 5 minutes to 10 minutes.
Time and reaction pressure are preferably normal pressure to 20 MPa · G,
The pressure is preferably normal pressure to 10 MPa · G.

Methods for controlling the molecular weight of the polymer include selection of the type and amount of each catalyst component, the amount of polymerization used, the polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane and octane And halogenated hydrocarbons such as chloroform and dichloromethane. These solvents may be used alone or in a combination of two or more. Further, a monomer such as an α-olefin may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the polymerization, preliminary polymerization can be carried out using the above-mentioned polymerization catalyst. The prepolymerization can be performed by, for example, bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited, and a known method can be used. The olefin used for the prepolymerization is not particularly limited, and may be the same as those exemplified above, for example, ethylene, α-α having 3 to 20 carbon atoms.
Olefin, styrene or a mixture thereof can be mentioned, but it is advantageous to use the same olefin as the olefin used in the polymerization.

The prepolymerization temperature is usually from -20 to 20.
0 ° C, preferably -10 to 130 ° C, more preferably 0 ° C.
８０80 ° C. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Of these, aliphatic hydrocarbons are particularly preferred. Further, the prepolymerization may be performed without a solvent.

In the prepolymerization, the intrinsic viscosity [η] (measured in tetralin at 135 ° C.) of the prepolymerized product was 0.2%.
The amount of the prepolymerized product per deciliter / g or more, especially 0.5 deciliter / g or more and 1 mmol of the transition metal component in the catalyst is 1 to 10,000 g, especially 10 to 10 g.
It is desirable to adjust the conditions so that the weight becomes 1,000 g.

In the copolymerization, the order of addition of the monomers does not matter, but it is preferable to charge the α-olefin before propylene. When using ethylene, it is preferable to charge a mixed gas of propylene and ethylene. The charge ratio of the comonomer is 1 to 10,000,000 mol for 1 mol of the catalyst in the case of α-olefin.
1, preferably 1 to 1,000,000 mol, more preferably 1 to 100,000 mol. In the case of ethylene, the (ethylene / propylene) mol ratio is (0.
01/100) to (99/100), preferably (0.
01/100) to (55/100), and more preferably (0.01 / 100) to (10/100).

The pyropyrene-based polymer obtained by the present invention can be formed into a molded product by using various molding methods. These molded articles are characterized by being excellent in low-temperature processing characteristics (especially low-temperature heat sealability and embossability) in spite of flexibility. Furthermore, it has excellent transparency. Examples of the molded body include films, sheets, fibers, containers, interior materials for automobiles, housing materials for home electric appliances, and the like. Especially, it is suitable for films and sheets. Since the film is excellent in low-temperature heat sealability, it is preferably used as a film for food packaging or an agricultural film (eg, a greenhouse). Since the container is excellent in transparency, it is used for a transparent case, a transparent box, a decorative box and the like.

The molding method of the molded article includes an injection molding method,
Examples include a compression molding method, an injection compression molding method, a gas assist injection molding method, an extrusion molding method, a blow molding method, and a calendar molding method. Examples of the method for forming a film or sheet include a compression molding method, an extrusion molding method, a blow molding method, and a cast molding method.

[0075]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention.

First, a method for evaluating the resin properties and physical properties of the polymer according to the present invention will be described. (1) Measurement of [η] Using a VMR-053 automatic viscometer manufactured by Rigosha Co., Ltd.
It was measured at 135 ° C. in tetralin solvent. (2) Measurement of pentad fraction and abnormal insertion fraction It was measured according to the method described in the detailed description. (3) Measurement of molecular weight distribution (Mw / Mn) Mw / Mn is a value calculated from the mass average molecular weight Mw and the number average molecular weight Mn in terms of polyethylene measured by the GPC method using the following apparatus and conditions. GPC measuring device Column: TOSO GMHHR-H (S) HT Detector: RI detector for liquid chromatogram WATERS 150C Measurement conditions Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C. Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / milliliter Injection amount: 160 microliter Calibration curve: Universal Calibration Analysis program: HT-GPC (Ver. 1.0) (4) DSC measurement Differential scanning calorimeter (Perkin-Elmer, DSC) −
7) Using a 10 mg sample at 230 ° C. in a nitrogen atmosphere for 3
After melting for 1 minute, the temperature was lowered to 0 ° C. at 10 ° C./min, and further held at 0 ° C. for 3 minutes, and then the temperature was increased at 10 ° C./min. The peak top of the maximum peak of the melting endothermic curve obtained at this time was defined as melting point: Tm (° C.). (5) Elevated Temperature Separation Chromatograph The amount (% by mass) of components eluted without being adsorbed by the filler at the TREF column temperature of 25 ° C. in the elution curve was determined as follows. (A) Operation method A sample solution is introduced into a TREF column adjusted to a temperature of 135 ° C., and then gradually cooled to 0 ° C. at a rate of 5 ° C./hour, held for 30 minutes, and the sample is adsorbed on a filler. Thereafter, the column was heated at a rate of 40 ° C./hour to 135 columns.
The temperature was raised to ℃ to obtain an elution curve. The temperature at the peak position of the elution curve was defined as Tp, and the amount of the component eluted in a temperature range of Tp ± 5 ° C. was determined from this. The half width of the peak position of the elution curve was determined as Th (° C.). (B) Apparatus configuration TREF column: Silica gel column (4.6 mm x 150 mm) manufactured by GL Sciences Flow cell: 1 mm optical path length KBr cell manufactured by GL Sciences Pump: SSC-3100 pump manufactured by Senshu Kagaku Valve oven: GL Sciences Model 554 oven (high temperature type) TREF oven: GL Science's two-line temperature controller: Rigaku Corporation REX-C100 temperature controller Detector: Infrared detector for liquid chromatography FOXBORO's MIRAN 1A CVF 10-way valve : Barco electric valve loop: Barco 500 microliter loop (c) Measurement conditions Solvent: o-dichlorobenzene Sample concentration: 7.5 g / liter Injection volume: 500 microliter Pump flow rate: 2.0 ml / min Detection Number: 3.41Myuemu column filler: Chromosorb P (30 to 60 mesh) Column temperature distribution: a within ± 0.2 ° C. (6) Tensile modulus propylene polymer to create a press-molded into test pieces,
It measured by the tensile test based on JISK7113.

Test piece (No. 2 dumbbell) Thickness: 1 mm Crosshead speed: 50 mm / min Load cell: 100 kg (7) Internal haze A test piece is prepared by press molding a propylene polymer.
It was measured by a test according to JIS K 7105.

Test piece: 15 cm × 15 cm × 1 mm
(Test piece thickness = 1 mm) (8) Measurement of boiling diethyl ether extraction The measurement is performed under the following conditions using a Soxhlet extractor.

Sample: 1 to 2 g Sample shape: powder (pelletized material is crushed,
Extraction solvent: diethyl ether Extraction time: 10 hours Number of extractions: 180 or more Extraction amount calculation method: Calculated by the following formula. [Extraction amount into diethyl ether (g) / prepared powder mass (g)] × 100 [Example 1] [dimethylsilylene (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)] Synthesis of Zirconium Dichloride (1)] Synthesis of 2-methyl-4,5-benzo-1-indanone In a 300 ml three-necked flask equipped with a nitrogen inlet tube, methylene chloride (100 ml) and naphthalene (5 g, 0.039) were added.
mol), 2-bromoisobutyryl bromide (9 g,
0.039 mol). Under a nitrogen stream, aluminum chloride (6 g, 0.047 mol) was slowly charged. One hour later, the reaction solution was poured into cold water (200 ml), and the organic phase was separated using a separating funnel. The organic phase was dried over magnesium sulfate, filtered and the solvent was distilled off to obtain the desired compound (6.4 g) (yield 84).
%).

Synthesis of 2-methyl-4,5-benzoindene 2-methyl-4,5-benzo-1-indanone (6.4
g) was dissolved in methanol (100 ml). Sodium borohydride (1 g, 0.026 mol
l) was charged slowly. 30 minutes later, water (100m
l) and ether (100 ml) were added to perform extraction. The organic phase was separated using a separatory funnel. The organic phase was dried over magnesium sulfate, filtered, and the solvent was distilled off to obtain 2-methyl-4,5-benzoindanol (5.7 g). The obtained 2-methyl-4,5-benzoindanol (5.7 g) was added to toluene (100 m
l), pyridinium p-toluenesulfonic acid (0.5 g) was added, and the mixture was refluxed for 30 minutes using a Dean-Stark apparatus to perform a dehydration reaction. After completion of the reaction, the solvent is distilled off under reduced pressure, and the residue is purified by column (solvent: hexane).
Thus, the target compound (3 g) was obtained (yield 48).
%).

Synthesis of 2-indenyl-dimethylchlorosilane Magnesium powder (1.3 g) and iodine (0.01 g)
g) and dehydrated THF (20 ml) were charged into a 200 ml three-necked flask equipped with a Dimroth tube and a dropping funnel. 2
-Bromoindene (ref: J. Org. Chem. 4)
7 , (4), synthesized according to 705 (1982)) (5.4
g, 27.2 mmol) and dehydrated THF (40 ml)
Was poured into a dropping funnel, and slowly added dropwise to such an extent that the mixture was slightly refluxed under a nitrogen atmosphere. After the completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes. Then, dichlorodimethylsilane (3.7
g, 28.5 mmol) and dehydrated THF (20 ml)
Was put into a dropping funnel, and the solution was added dropwise at -78 ° C. After the addition, the mixture was stirred at room temperature for 8 hours. The solvent was distilled off under reduced pressure, and extracted with dehydrated hexane (100 ml). The solvent was distilled off under reduced pressure to obtain 5.3 g of the target compound (yield: 91%). Synthesis of (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) dimethylsilane In a 200 ml Schlenk purged with nitrogen, 2-methyl-4,
5-benzoindene (1.26 g, 7 mmol) and dehydrated hexane (50 ml) were charged. N-
Butyllithium hexane solution (1.50M, 4.7m
1,7 mmol) at -78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours.
-Lithium benzoindenyl was deposited. After allowing the suspension to stand, the supernatant was removed by decantation. Dehydrated THF (25 ml) was added thereto, the mixture was cooled to -78 ° C, and a previously synthesized 2-indenyl-dimethylchlorosilane (1.46 g, 7 mmol) solution in dehydrated THF (25 ml) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 4 hours. After completion of the reaction, water (50 ml) was added, and the mixture was extracted with ether (200 ml). The extracted solution is separated by a separating funnel, the obtained organic phase is dried over magnesium sulfate, filtered, and the solvent is distilled off to obtain the desired compound (2.2 g).
Was obtained (89% yield).

Dimethylsilylene (2-indenyl) (1
Synthesis of-(2-methyl-4,5-benzoindenyl) zirconium dichloride In 200 ml of Schlenk substituted with nitrogen, previously synthesized (2-indenyl) (1- (2-methyl-4,5-benzoindenyl). )) Dimethylsilane (1.0 g, 2.8 m
mol) and dehydrated hexane (40 ml).
A solution of n-butyllithium in hexane (1.5
OM, 3.7 ml, 5.6 mmol) was added dropwise at -78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours.
-Indenyl) (1- (2-methyl-4,5-benzoindenyl)) dimethylsilanedilithium was deposited. After allowing the suspension to stand, the supernatant was removed by decantation. Thereto was added dehydrated toluene (25 ml),
Cool to −78 ° C. and add zirconium tetrachloride (0.65 g,
(2.8 mmol) in anhydrous toluene (25 ml) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the mixture was filtered through a cannula, the filtrate was concentrated, and dehydrated hexane was added. The resulting precipitate was separated by filtration and dried to obtain 0.2 g of the target compound (yield: 12%). ¹ H NMR (δ ppm / CDCl ₃ ): 8.0-7.0.
(M, 8H), 6.50 (s, 1H), 6.12 (d,
1H), 6.02 (d, 1H), 2.32 (s, 3
H), 1.10 (s, 3H), 0.95 (s, 3H) Example 2 [Dimethylsilylene (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)] Synthesis of Hafnium Dichloride (2)] (2-Indenyl) (1- (2-methyl-4,5-benzoindenyl)) dimethylsilane (1.0 g, 2.0 g) was previously synthesized in nitrogen-substituted 200 ml Schlenk. 8 mmol) and dehydrated hexane (4
0 ml). A solution of n-butyllithium in hexane (1.50 M, 3.7 ml, 5.6 mmol) was added to the solution.
l) was added dropwise at -78 ° C. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours to precipitate (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) dimethylsilanedilithium. After allowing the suspension to stand, the supernatant was removed by decantation. Dehydrated toluene (25 ml) was added thereto, and the mixture was cooled to −78 ° C., and hafnium tetrachloride (0.9 g, 2.8 mmol) in dehydrated toluene (2
5 ml) suspension was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 6 hours. After completion of the reaction, the mixture was filtered through a cannula, the filtrate was concentrated, and dehydrated hexane was added. The resulting precipitate was separated by filtration and dried to obtain 0.2 g of the target compound (yield: 12).
%) ¹ H NMR (δ ppm / CDCl ₃ ): 8.0-7.0
(M, 8H), 6.50 (s, 1H), 6.08 (d,
1H), 5.93 (d, 1H), 2.45 (s, 3
H), 1.12 (s, 3H), 0.99 (s, 3H) [Example 3] Slurry polymerization of propylene using (1) A 1-liter sterylene-less pressure-resistant autoclave equipped with a stirrer was heated to 80 ° C. After heating and drying under reduced pressure, the pressure was returned to the atmospheric pressure with dry nitrogen and cooled to room temperature. Under a stream of dry nitrogen, 400 ml of dry deoxygenated heptane and 0.5 ml of a heptane solution of triisobutyl aluminum (2.0 M) (1.0 M
mmol) and 350 r. p. and stirred for a while. Thereafter, a toluene solution of MAO (2.03M, 0.1.
13 ml, 0.26 mmol) and the heptane slurry (10 μmol / liter, 0.1 ml, 1.0 μmol) of (1) synthesized in Example 1 were quickly charged into the autoclave.

Thereafter, 1200 r. p. The stirring was started at m. Next, propylene was pressurized to a total pressure of 0.7 MPa over 3 minutes, and simultaneously the temperature was raised to 50 ° C. 60
The polymerization was carried out for minutes. After completion of the reaction, methanol 20 ml
Was charged into an autoclave, and unreacted propylene was removed by depressurization. Then, the reaction mixture was poured into 2 liters of methanol to precipitate polypropylene, followed by filtration and drying to obtain polypropylene. About the obtained polymer, the above-mentioned "resin property" was evaluated. The following additives were formulated in the obtained polymer, and extruded and granulated with a short-screw extruder (Model TLC35-20 manufactured by Tsukada Juki Seisakusho) to obtain pellets. The measurement was performed using the pellets in accordance with the above-mentioned “Method for evaluating physical properties”. Table 1 shows the obtained results. <Antioxidant> Irganox 1010: 1,000 ppm manufactured by Ciba Specialty Chemicals and Irgafos 168: 1, manufactured by Ciba Specialty Chemicals
Example 4 Slurry Polymerization of Propylene Using (2) In Example 3, the complex dimethylsilylene (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) zirconium dichloride (1) was used. Example 2 instead of)
Dimethylsilylene (2-indenyl) (1-
(2-Methyl-4,5-benzoindenyl)) The same operation as in Example 3 was carried out except that hafnium dichloride (2) was used. Table 1 shows the obtained results.

Example 5 [Methylaluminoxane (MAO) / silica (Si
Preparation of O ₂ ) Carrier] Toluene (500 ml) was charged into a 500-ml glass container with a dropping funnel sufficiently purged with nitrogen, and calcined under nitrogen atmosphere at 200 ° C. for 3 hours (4.04 g, silica). And stir (40
0r. p. m). Then, at 0 ° C., a MAO / toluene solution (29.8 ml) manufactured by Albemarle was slowly added over 45 minutes. The mixture was further stirred at 0 ° C. for 1 hour, at room temperature for 1 hour, and at 80 ° C. for 4 hours. After the reaction is completed, allow to cool
At the time of cooling to 200 ° C., the supernatant was dissolved in toluene (200 m
The resultant was washed by decantation three times in 1) and three times with heptane (200 ml) to obtain the desired product. Finally, it was stored in Schlenk as a heptane slurry. Al loading amount is UV
It was quantified by a quantitative method. (Aluminum supported amount: 12.06%) [Vapor-phase polymerization of propylene using (1)] Heptane (5 ml) and triisobutylaluminum (2 M,
0.25 ml, 0.5 mmol), and then a heptane slurry of the MAO / SiO ₂ carrier obtained above (in terms of Al: 0.37 mol / l, 6.8 ml,
2.5 mmol) and the heptane slurry of (1) synthesized in Example 1 (10 μmol / ml, 0.5 ml, 5
μmol) and stirred at room temperature for 30 minutes to obtain a catalyst.

A 5-liter autoclave was charged with a polypropylene powder (homo PP 720 μm or more, 100 g) as a catalyst dispersant, and vacuum-dried at 70 ° C. for 20 minutes. After the pressure was restored with nitrogen, the mixture was stirred under a nitrogen stream (20
0r. p. m), while adding triisobutylaluminum (2M, 1.25 ml, 2.5 mmol). 1
After stirring for 5 minutes, the previously prepared MAO / SiO
₂ Supported catalyst was added and stirred for 5 minutes. At this point (50 ° C,
Normal pressure, 200 r. p. m), the reactor temperature was 70 ° C., the propylene pressure was 2.8 MPa · G, and the rotation number was 350 r. p. m
The temperature was raised and the pressure was increased over 30 minutes, and then the gas phase polymerization was performed for 60 minutes. As a result, a powdery polymer having no adhesion to the wall was obtained. Table 1 shows the obtained results. [Comparative Example 1] In Example 3, instead of the complex dimethylsilylene (2-indenyl) (1- (2-methyl-4,5-benzoindenyl)) hafnium dichloride (2), JP-A-7-505418 (1,2′-dimethylsilylene) (2,1 ′) obtained by synthesizing according to the publication and Example 10.
-Dimethylsilylene) (tetrahydroindenyl) ₂ zirconium dichloride was used in the same manner as in Example 3. Table 1 shows the obtained results. The polymerization activity was low.

[0086]

[Table 1]

[0087]

According to the present invention, the molecular weight distribution is narrow and the stereoregularity is moderate (for example, a propylene homopolymer having an isotactic pentad fraction of 85 mol% or less), and has a low stickiness. An olefin polymer having a low melting temperature and excellent flexibility can be efficiently obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 10/06 C08F 10/06 // C07F 7/00 C07F 7/00 AZ 7/12 7/12 V F term (reference) 4H049 VN01 VN06 VN07 VP02 VQ08 VQ12 VQ77 VR12 VR22 VU14 VW01 4H050 AA01 AA03 AB40 4J028 AA01A AA02A AB01A AC00A AC01A AC19A AC27A AC31A AC38A AC41A AC42A AC46ABABACBBABACBBABACB BC25B CA16C CA19C CA24A CA24B CA24C CA25A CA25B CA25C CA26A CA26B CA26C CA27A CA27B CA27C CA28A CA28B CA28C CA29A CA29B CA29C CA36A CA36B CA36C CA44A EC44 DA04 EB EB EB CB EB09 CB CB08C FA01 FA02 FA03 FA04 FA07 FA09 GA04 GA14 GA19 GA21

Claims (7)

[Claims] 1. A transition metal compound represented by the following general formula (I). Embedded image [Wherein, M represents a transition metal belonging to Groups 3 to 10 of the periodic table.
R ^{1 to} R ¹⁴ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group having 1 to 20 carbon atoms,
20 oxygen-containing groups, 1 to 20 carbon-containing sulfur-containing groups, 1 to 20 carbon-containing nitrogen-containing groups, or 1 to 20 carbon-containing phosphorus-containing groups, which may be the same or different from each other Or they may combine with each other to form a ring. X ¹ and X ² each represent a hydrogen atom, a halogen atom,
To 20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, silicon-containing groups having 1 to 20 carbon atoms, 1 to 20 carbon atoms
And a sulfur-containing group having 1 to 20 carbon atoms, which may be the same or different from each other. A
Is a divalent cross-linking group, a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium Containing group,-
O -, - CO -, - S -, - SO 2 -, - NR 15 -, -
^{PR 15 -, - P (O} ) R 15 -, - BR 15 -, or -Al
R ¹⁵ — (where R ¹⁵ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). ] 2. (A) The transition metal compound according to claim 1 and (B) (B-1) an aluminum oxy compound, (B-
2) An olefin polymerization catalyst containing an ionic compound that can be converted to a cation by reacting with the transition metal compound and at least one selected from (B-3) Lewis acids. 3. (A) The transition metal compound according to claim 1 and (B) (B-1) an aluminum oxy compound, (B-
2) An olefin polymerization catalyst containing at least one selected from the group consisting of an ionic compound that can be converted into a cation by reacting with the transition metal compound and (B-3) a Lewis acid, and (C) an organoaluminum compound. 4. The olefin polymerization catalyst according to claim 2, wherein at least one of the component (A) and the component (B) is supported on a carrier. 5. In the general formula (I), M is the fourth of the periodic table.
The olefin polymerization catalyst according to any one of claims 2 to 4, which is a transition metal belonging to Groups 6 to 6. 6. A method for producing an olefin polymer in which an olefin is polymerized in the presence of the olefin polymerization catalyst according to any one of claims 2 to 5. 7. A method for producing an olefin polymer, comprising polymerizing propylene or propylene with ethylene and / or an α-olefin having 4 to 20 carbon atoms in the presence of the olefin polymerization catalyst according to any one of claims 2 to 5.