JP2001163924A - Branched propylene polymer and manufacturing method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymer and a method for obtaining it wherein moldability is improved without loss of excellent mechanical properties of polypropylene. SOLUTION: A propylene polymer is characterized by fulfilling the following conditions (A), (B) and (C) wherein: (A) the ratio of a meso-racemic-racemic-meso chain having 5 chain parts of a propylene unit comprising a head to tail bond measured by 13C-NMR is not more than 9 mole %, (B) the number of long chain branches per 1,000 carbons in a main chain of the polymer is 0.02 to 2, and (C) the weight-average molecular weight Mw measured by gel permeation chromatography is within the range of 50,000 to 1,000,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel propylene polymer having a high isotactic triad fraction and a branched amount of a specific amount of polypropylene. More specifically, the present invention relates to a novel propylene polymer having a long-chain polypropylene branch obtained by copolymerizing propylene using an isotactic propylene polymer having a vinyl group at a terminal as a macromer.

The propylene polymer of the present invention has an unprecedented feature that the moldability is improved without impairing the excellent mechanical properties of polypropylene.

[0003]

2. Description of the Related Art Propylene polymers are rigid, heat-resistant,
It is noted for its excellent moldability, transparency and chemical resistance, and is widely used in various applications such as various industrial materials, various containers, daily necessities, films and fibers.

[0004] In the conventional propylene polymer, since the catalyst has heterogeneity, there is a problem in that the physical properties are reduced due to by-produced polymer having low stereoregularity. On the other hand, the advent of metallocene catalysts has made it possible to obtain homogeneous stereoregular propylene polymers, but on the other hand, the molecular weight distribution is sharp, making molding difficult, and improvements have been desired.

For the purpose of improving the moldability of polypropylene obtained with a metallocene catalyst, attempts have been made to use a plurality of catalysts or to carry out multi-stage polymerization. In addition to the above, there are concerns that sufficient physical properties may not be exhibited due to differences in performance among a plurality of catalysts, and that production costs may increase due to multi-stage polymerization, and further improvement is desired.

[0006]

SUMMARY OF THE INVENTION In view of the above situation, the present invention has been studied with the aim of finding a polymer and a technique for improving moldability without deteriorating physical properties. A novel propylene polymer having a high tic triad fraction and a specific amount of polypropylene and having a branch, specifically, an isotactic propylene polymer having a vinyl group at a terminal is used as a macromer to copolymerize propylene. A propylene polymer having a polypropylene branch obtained by the method, has been found that the moldability is improved without impairing the excellent mechanical properties of polypropylene, and provides such a polymer, and a method for obtaining the same. .

[0007]

The object of the present invention is to solve the problem by finding a propylene polymer having a special structure and a method for producing the same.

The present invention provides a propylene polymer characterized by satisfying the following conditions (A), (B) and (C). (A) the ratio of the meso-racemic-racemic-meso chain of 5 propylene units consisting of head-to-tail bonds measured by ¹³ C-NMR is 9 mol% or less, and (B) the polymer main chain The number of long-chain branches per 1000 carbon atoms is 0.02 to 2, and (C) the weight average molecular weight Mw measured by gel permeation chromatography is in the range of 50,000 to 1,000,000.

Further, the present invention provides the following essential catalyst component (A):
And (B) and, if necessary, propylene in the presence of optional component (C) and / or optional component (D) to produce a branched polypropylene precursor having the structure of the following general formula [2]. The propylene polymer is obtained by polymerizing the product in the presence of the following catalyst components (E) and (B) and, if necessary, an optional component (C) and / or an optional component (D). It is intended to provide a method for producing a polymer.

[0010]

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Catalyst component (A): transition metal compound represented by the following general formula [3]

[0012]

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(In the general formula [3], R ¹ and R ⁴ are each independently a hydrocarbon group having 3 to 10 carbon atoms or a hydrocarbon group having 2 to 2 carbon atoms.
A silicon-containing hydrocarbon group of 18; R ² and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms;
R ³ and R ⁶ each independently represent a divalent saturated or unsaturated hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded. R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon, a nitrogen-containing hydrocarbon, or a phosphorus-containing hydrocarbon. m and n each independently represent an integer of 0 to 20. Q is a bond of two 5-membered rings, at least one of a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and phosphorus An alkylene group having a containing hydrocarbon group, or at least one of 1 to 2 carbon atoms
0 hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a silylene group having a phosphorus-containing hydrocarbon group, or at least one of 1 to 20 carbon atoms. And a germylene group having a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group. X and Y each independently 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, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, It represents a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and M represents a transition metal belonging to Groups 3 to 6 of the periodic table. Catalyst component (B): an aluminum oxy compound, an ionic compound capable of reacting with component (A) to convert component (A) into a cation, a Lewis acid, an ion-exchange layered compound excluding silicate, and One or more substances selected from the group consisting of inorganic silicates Optional component (C): fine particle carrier Optional component (D): organoaluminum compound Catalyst component (E): transition metal compound represented by the following general formula [4]

[0014]

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Wherein A and A ′ are conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Represents a bonding group that crosslinks a child at an arbitrary position, and M represents a periodic table 4 to
X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. (Excluding those included in general formula [3])

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION <A Propylene Polymer> (A) Monomer Chain Structure The propylene polymer according to the present invention has a meso-racemic structure consisting of 5 propylene units consisting of head-to-tail bonds, as measured by ¹³ C-NMR. A racemic-meso chain ratio of 9 mol% or less,
It is preferably at most 7.5 mol%. Note that the meso-racemic-racemic-meso chain is hereinafter referred to as mrrm.

Here, the method of measuring the ¹³ C-NMR spectrum is as follows. ^{The 13} C-NMR spectrum is 1
50-500 in a sample tube for 0 mmΦ NMR measurement
mg sample was completely dissolved in a solvent obtained by adding about 0.5 ml of deuterated benzene as a lock solvent to about 2.0 ml of o-dichlorobenzene, and then measured at 130 ° C. by a complete proton decoupling method.

Waltz 16 was used for decoupling.
The measurement conditions are flip angle 65 °, pulse interval 5T.
_One or more (T ₁ is the longest value of the spin lattice relaxation times of the methyl group) was selected. Since T ₁ of the methylene group and the methine group is shorter than the methyl group in the propylene polymer, the recovery of the magnetization of all carbons is 99% or more under these measurement conditions. The observation frequency is 124 MHz or more, and the digital resolution is 0.008 ppm or less (that is, the observation frequency 1
(Acquisition time is more than 1 second at 25MH)
Was used.

The chemical shift is set at 21.8 ppm for the third unit of the five propylene units in which the head-to-tail bond and the branching direction of the methyl group are the same, and the chemical shift of the other carbon signals is set to 21.8 ppm. Was used as a reference.

According to this criterion, the signal based on the methyl group of the second unit in five chains of propylene units represented by PPPPP (mmmm) and PPPPP (mmmmr) is 2
In the range of 1.44 to 22.10 ppm, the PPPPP (m
mrr), the signal based on the methyl group of the second unit in the 5 chains of propylene units is 20.94 to 21.1
In the range of 4 ppm, the signal based on the methyl group of the second unit in the five propylene units represented by PPPPP (mrm) appears in the range of 19.70 to 20.04 ppm.

Here, the PPP of 5 chains of propylene unit
The upper limit of [mrrm] indicating the ratio of PP (mrm) is represented by the following equation.

The condition (A) of the invention is that the polymer of the present invention has [mrm] of 9% or less, preferably 7.5% or less.

[Mrrm] = I (mrrm) / {I (mmmm) + I (mmmr) + I (mmrr) + I (mrrm) −I (2,1)} Equation 1 I (2,1) = (１ ／) ) {A + A + A + A} Equation 2 In this equation, I (mmmm), I (mmmr), I
(Mmrr) and I (mrrm) are the integral values of the signal based on the methyl group of the second unit in the five chains of each propylene unit. A, A, A, A are
42.3 ppm, 38.6 p derived from partial structure (I)
pm, 36.0 pp, 35.9 ppm.

[0024]

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[0025]

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The propylene polymer may have a structure in which propylene insertion is reversed in addition to the mm and mr bonds. It is considered that such a partial structure is caused by positional irregularities generated during the polymerization of the propylene polymer. The propylene monomer is usually a 1,2-insertion in which the methylene side is bonded to the catalyst center metal side, but may be a rare 2,1- or 1,3-insertion.

The monomer polymerized by the 2,1-insertion forms a position irregular unit represented by the above partial structure (I) (general formula [8]) in the polymer chain.

The monomer polymerized by the 1,3-insertion forms a position irregular unit represented by the above partial structure (II) (general formula [9]) in the polymer chain.

The mm fraction in the entire polymer chain of the propylene polymer according to the present invention is represented by the following equation. By the way, in the partial structure (II), as a result of 1,3-insertion, one methyl group has been lost by one.

The propylene polymer of the present invention has a partial structure (I) or (II) containing a positionally irregular unit based on 2,1-insertion or 1,3-insertion of propylene of 1.0 or 1.0.
It is preferable to satisfy the condition (D) of being at most mol%.

The numerical values of various definitions are quantified as follows.

[0032]

(Equation 1)

In this formula, ΔICH ₃ indicates the area of all methyl groups (19 to 22 ppm). A, A
, A, A, A, A, A, A and A
Are 42.3 ppm, 35.9 ppm and 38.
6 ppm, 30.6 ppm, 36.0 ppm, 31.5
ppm, 31.0 ppm, 37.2 ppm, 27.4 p
pm, which indicates the abundance ratio of carbon shown in the partial structures (I) and (II).

The ratio of 2,1-inserted propylene and the ratio of 1,3-inserted propylene with respect to the total propylene insertion are calculated by the following equations.

[0035]

(Equation 2)

The propylene polymer according to the present invention is substantially a homopolymer of propylene. However, as long as the conditions (A) and (B) regarding the propylene insertion form are satisfied, a small amount of α-olefin other than propylene (ethylene For example, 6.0 mol% based on propylene.
Copolymers with α-olefins such as ethylene, butene, hexene, and octene in amounts up to.

The terminal structure is represented by ¹³ C-NMR and ¹ H-N
Determined by MR. The propylene homopolymer may include the structures of general formulas [5] to [18], but the 1-propenyl terminal (general formula [15]) has a characteristic ¹³ C-NMR signal, δ115.5 (position 1). ), Δ137.5 (second place), δ
The presence or absence can be determined by 41.5 (third place).

The structure of each terminal is defined as follows.

Dimethyl terminal

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Ethyl terminal

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Propyl terminal

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Butyl terminal

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Isobutenyl terminal

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1-propenyl terminal

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1-butenyl terminal

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2-butenyl terminal

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Long chain vinyl terminal

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At this time, the assignment of signals at various terminals in the ¹³ C-NMR spectrum is based on the 1-propenyl terminal (general formula [1]
5]), δ115.5 (first place), δ1
37.5 (2nd), δ41.5 (3rd), δ30.9
(Position 4) and an isobutenyl terminal (general formula [14])
Are characteristic signals δ111.5 (1st), δ144.
7 (2nd position), δ22.5 (2nd methyl), and a propyl terminal (a signal characteristic of general formula [12] is δ14.4
(1st place), δ20.2 (2nd place), δ39.8 (3rd place),
δ 30.7 (4th position) and a dimethyl terminal (general formula [1
0]), δ22.6 (1st), δ2
3.7 (1st place) and δ25.9 (2nd place).

The assignment of a signal characteristic to an isobutenyl terminal (general formula [14]) is described in Reference 5, and the assignment of a signal characteristic to a propyl terminal (general formula [12]) is described in Reference 5 from a dimethyl terminal (general formula [14]). Assignment of a signal characteristic of [10]) was performed from Reference 6.

The characteristic signal at the 1-propenyl terminal (general formula [15]) is assigned to the terminal signal δ11 of the analogous compound 4-methyl-1-hexene assigned to Reference 1.
5.4 (1st place), δ137.8 (2nd place), δ41.3
(3rd place).

The distinction between the 1-propenyl terminal (general formula [15]), the 1-butenyl terminal having a similar structure (general formula [16]) and the long-chain vinyl terminal (general formula [18]) is based on the general formula [18]. 16]) and the chemical shift of the signal characteristic to (general formula [18]) was estimated from the chemical shift of a compound having a similar structure assigned in Reference 1.

The signals characteristic of the 1-butenyl terminal (general formula [16]) are δ114.1 (1st position) and δ139.3 (2
Position), δ31.9 (position 3), and a signal δ114.2 characteristic of a long-chain vinyl terminal (general formula [18]).
(1st place), δ139.1 (2nd place), δ34.0 (3rd place)
It was estimated.

On the other hand, in the ¹ H-NMR spectrum, the double bond hydrogen signal (δ 5.84 to 5.74, δ 5.02 to 4.96) at the 1-propenyl terminal (general formula [15]) and the isobutenyl terminal (general formula [15]) The double bond hydrogen signal (δ 4.78 to 4.66) of the formula [14] is observed separately from the other saturated hydrogen signals (δ 2.60 to 0.40).
The assignment of the double bond hydrogen signal was performed from the spectra of the analogous compounds 1-decene and 2-methyl-1- assigned in Reference 7.

The mol% of the 1-propenyl terminal (general formula [15]) and the isobutenyl terminal (general formula [14]) in the propylene unit, [1-Pr-Δ] and [i-Bu-
Δ] was determined from the following equation based on the ¹ H-NMR integrated value.

[1−Pr−Δ] = B / {(1/6) (B + B + B + B)} Equation 6 [i−Bu−Δ] = (1/2) B / {(1/6) (B + B + B + B)} Formula 7 In this formula, B is derived from 2.60 to saturated hydrogen.
The integrated value of the signal of 0.40 ppm, B is 5.84
-5.74 ppm, where B is 5.0
The integrated value of the signal of 2 to 4.96 ppm, and B is 4.
It is an integrated value of a signal of 78 to 4.66 ppm.

The mol% of the 1-propenyl terminal (general formula [15]) and the isobutenyl terminal (general formula [14]) in the olefin structural unit, [1-Pr-Δ] _db and [i-
[Bu-Δ] _db was determined from the following formula based on the ¹ H-NMR integrated value.

[1−Pr−Δ] _db = B / {B + (）) (B + B)} Equation 8 [i−Bu−Δ] _db = (１ ／) B / ｛B + (１ ／) (B + B)｝ Formula 9 References relating to NMR assignment are listed below.

1) Lindeman, L .; P. Ada
ms, J.M. Q. Anal. Chem. 43 (1971)
1245 2) Cooperus, P .; A. Clague, A .;
D. H. Van Dongen, J .; P. C. M. O
rg. Magn. Reson. 8 (1976) 426 3) Zambelli, A .; Locatgelli,
P. Et al. Macromol. 13 (198
0) 267-270 (2, 1) 4) Grassi, A .; Zambelli, A .; Ma
cromol. 21 (1988) 617-622 (1,
3) 5) Zambelli, A .; Macromol. 12
(1979) 154n-propyl, 2-methyl
line-propenyl (vinylidene) 6) Zambelli, A .; et al. Macromo
l. 15 (1982) 211-212 dimethyl
(I-propyl) 7) Aldrich NMR data collection The desired propylene polymer can be obtained by copolymerizing the above-obtained stereoregular polypropylene macromer having a terminal vinyl group with propylene. The branch of the target propylene polymer is quantified by 13C-NMR based on the ratio of the methylene peak at the α-position of the branch existing at 46.2 ppm to the entire methylene peak (46.6 ppm).

(B) Long Chain Branching The propylene polymer of the present invention has 0.02 to 2, preferably 0 to 2, long chain branches per 1000 carbon atoms in the propylene polymer main chain (including the branched main chain). .04 to 1.6. In the present invention, a long chain branch means a branch formed in a polymer main chain by polymerization of a monomer, and a short chain derived from a monomer forming a main chain like a methyl group in a propylene polymer. Does not include branches. Usually, the long-chain branch has a structure represented by the general formula [1]. When the number of long-chain branches is less than 0.02, the effect of improving the formability is small, and when the number of long-chain branches exceeds two, crystallization is reduced and rigidity is reduced, which is not preferable.

(C) Molecular Weight The propylene polymer of the present invention has a molecular weight of 50,000 to 1,000,000, preferably 100,000 to 800,000 as measured by GPC. Molecular weight 5000
If it is lower than 0, the melt viscosity is low and molding becomes difficult, and 1
If it exceeds 000000, the melt viscosity is too high and molding cannot be performed.

<Production of Propylene Polymer> The method for producing a propylene polymer according to the present invention is characterized in that a propylene homopolymer which satisfies the above-mentioned physical properties or a copolymer with 6 mol% or less of ethylene or an α-olefin other than propylene is used. There is no particular limitation as long as it gives a polymer.

Among them, a catalyst system suitable for producing the polymer of the present invention is a metallocene catalyst. For example, at least one component selected from the following catalyst component (A): a transition metal compound described below. Species metallocene compounds;
Catalyst component (B): [B1] aluminum oxy compound,
[B2] an ionic compound or Lewis acid capable of converting the catalyst component (A) into a cation by reacting with the catalyst component (A), [B3]: an ion-exchange layered compound other than silicate or an inorganic silicate , And optional component (C): fine particle carrier,
And / or optional component (D): a catalyst system composed of an organoaluminum compound, synthesizes a polypropylene macromer having propenyl at the terminal of the precursor, and then has an isotactic rule having excellent copolymerizability represented by catalyst component (E). It is produced by copolymerizing with propylene using a complex having high affinity.

<Catalyst Component (A)> First, examples of the transition metal compound of the catalyst component (A) capable of providing the polymer of the present invention will be described. Incidentally, as long as the polymer of the present invention is obtained,
It goes without saying that the catalyst component (A) is not limited to this example and is optional.

A typical example of the catalyst component (A) is a transition metal compound represented by the following general formula [3].

[0065]

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(Wherein R ¹ and R ⁴ each independently represent 3 to
A hydrocarbon group having 10 or a silicon-containing hydrocarbon group having 2 to 18 carbon atoms, and R ² and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms or a carbon group having 1 to 1 carbon atoms.
8 is a silicon-containing hydrocarbon group, and R ³ and R ⁶ are each independently a divalent saturated or unsaturated hydrocarbon having 3 to 10 carbon atoms which forms a condensed ring with the 5-membered ring to which it is bonded. Represents a group. Preferably, at least one of R ³ and R ⁶ has 5 to 10 carbon atoms. Of these, the groups R ¹ and R ⁴ are preferably branched hydrocarbons, and more preferably an isopropyl group. R ⁷ and R ⁸ each independently have 1 to 2 carbon atoms.
A hydrocarbon group of 0 or a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon, a nitrogen-containing hydrocarbon, and a phosphorus-containing hydrocarbon. m and n each independently represent an integer of 0 to 20. Q is a bond of two 5-membered rings, at least one of a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and phosphorus An alkylene group having a containing hydrocarbon group, or at least one hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing A silylene group having a hydrocarbon group or at least one of 1 to 1 carbon atoms
A germylene group having 20 hydrocarbon groups, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group. X and Y each independently 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, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and M is 3 shows transition metals of Groups 3 to 6 of the periodic table. The transition metal compound represented by the general formula [3] according to the present invention includes a five-membered ring ligand having substituents R ¹ , R ² , and R ³ , and substituents R ⁴ , R ⁵ , and R Included are compounds in which the five-membered ring ligand having ⁶ is asymmetric with respect to the plane containing M, X, and Y in terms of relative position via the group Q, and compounds that are symmetric. However, in order to produce an α-olefin polymer having a high activity, a high molecular weight and a high melting point, a five-membered ring ligand having substituents R ¹ , R ² and R ³ and a substituent R ⁴ , The five-membered ring ligand having R ⁵ and R ⁶ is a group Q
Is asymmetric with respect to the plane containing M, X, and Y in terms of relative position, in other words, M, X, and Y
A compound in which two five-membered ring ligands opposed to each other across a plane including the plane do not have a mirror image of the entity with respect to the plane is used.

R ¹ and R ⁴ are each independently a hydrocarbon group having 3 to 10 carbon atoms or a silicon-containing hydrocarbon group having 2 to 18 carbon atoms as described above, and R ² and R ⁵ are each independently
It is a hydrogen atom, a C1-C10 hydrocarbon group, or a C1-C18 silicon-containing hydrocarbon group.

More specifically, R ¹ , R ² , R ⁴ and R ⁵ are
(A) hydrogen atom, (b) carbon number 1 to 1
0 hydrocarbon groups such as methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, Alkyl groups such as methylcyclohexyl; alkenyl groups such as vinyl, propenyl and cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl;
arylalkenyl groups such as ansstyryl, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-naphthyl and the like; (c) silicon-containing hydrocarbon groups having 1 to 18 carbon atoms, for example, trimethylsilyl; Triethylsilyl, t
A trialkylsilyl group such as -butyldimethylsilyl; a triarylsilyl group such as triphenylsilyl; an (alkyl) (aryl) silyl group such as dimethylphenylsilyl; and an alkylsilylalkyl group such as bis (trimethylsilyl) methyl. Among these, as R ¹ and R ⁴ , hydrocarbon groups having 3 to 10 carbon atoms such as isopropyl, tertbutyl, cyclopropyl, phenyl, cyclopentyl and the like, and carbon atoms having 2 to 18 carbon atoms such as dimethylsilyl, trimethylsilyl and getylsilyl are preferred. Are used.

R ³ and R ⁶ each independently represent a divalent carbon atom having 3 to 1 carbon atoms which forms a condensed ring with respect to the five-membered ring to which it is bonded.
0 represents a saturated or unsaturated hydrocarbon group. Therefore, the condensed ring is a 5- to 12-membered ring. Preferably R ³ and R ⁶
At least one forms a condensed ring consisting of a 7-12 membered ring. At this time, at least one of the condensed rings is 7 to 10
It is preferable that both of the condensed rings are 7 to 1
More preferably, it is a zero-membered ring.

Specific examples of such R ³ and R ⁶ are as follows. Divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, etc., propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene, 2
-Pentenylene, 1,3-pentadienylene, 1,4-
Pentadienylene, 1-hexanylene, 2-hexanylene, 3-hexanylene, 1,3-hexadienylene,
Examples thereof include divalent unsaturated hydrocarbon groups such as 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, and 1,3,5-hexatrylene. Of these, pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene, and 1,3,5-hexatrienylene are preferred,
3-Pentadienylene and 1,4-pentadienylene are particularly preferred.

R ⁷ and R ⁸ each independently have 1 to 20 carbon atoms.
Or a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group,
Shows a phosphorus-containing hydrocarbon group. More specifically, (a) a hydrocarbon group having 1 to 20 carbon atoms, for example, methyl, ethyl, n-
Propyl, i-propyl, n-butyl, i-butyl, s
-Butyl, t-butyl, n-pentyl, n-hexyl,
Cyclopropyl, cyclopentyl, cyclohexyl, alkyl groups such as methylcyclohexyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl such as phenylpropyl, and trans-styryl such as arylalkenyl groups;
And aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-naphthyl, acenaphthylenyl, phenanthrenyl, and anthracenyl. Of these, methyl, ethyl, n-propyl, i-propyl,
Alkyl groups having 1 to 4 carbon atoms, such as n-butyl, i-butyl, s-butyl, t-butyl, cyclopropyl, etc., and carbon number of phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-naphthyl, etc. 6-20 aryl groups are preferred.

Other examples of R ⁷ and R ⁸ include (ii) halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups, and phosphorus-containing hydrocarbon groups. Can be Examples of the halogen atom constituting the halogenated hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the halogenated hydrocarbon group having 1 to 20 carbon atoms, for example, when a fluorine atom is taken as an example of a halogen atom, a compound in which a fluorine atom is substituted at any position of the above hydrocarbon group having 1 to 20 carbon atoms. It is. Specifically, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1
-Difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, o- or m- or p-fluorophenyl, o- or m- or p-chlorophenyl, o- or m- or p-bromo Phenyl, 2,
4- or 3,5- or 2,6- or 2,5-
Difluorophenyl, 2,4- or 3,5- or 2,6- or 2,5-dichlorophenyl, 2,
4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl,
2,4-difluoronaphthyl, heptafluoro-α-naphthyl, heptachloro-α-naphthyl, o- or m
-Or p-trifluoromethylphenyl, o- or m- or p-trichloromethylphenyl, 2,4
-Or 3,5- or 2,6- or 2,5-di-trifluoromethylphenyl, 2,4- or 3,
5- or 2,6- or 2,5-di-trichloromethylphenyl, 2,4,6-tri-trifluoromethylphenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2,4-di -Trifluoromethylnaphthyl group and the like.

Of these, a fluorinated hydrocarbon group or a chlorinated hydrocarbon group is preferable, and o-, m- or p-fluorophenyl, or o-, m- or p-chlorophenyl, or o- Or m-
Or a p-trifluoromethylphenyl group is particularly preferred.

As the oxygen-containing hydrocarbon group, methoxy,
Ethoxy, propoxy, phenoxy, ethoxyethyl,
Examples thereof include a furyl, methoxyphenyl, and methyl cellosolve group. Examples of the nitrogen-containing hydrocarbon group include dimethylamino, diethylamino, pyridyl, indolyl, carbazolyl, dimethylaminophenyl, and quinolyl groups. Examples of the phosphorus-containing hydrocarbon group include dimethylphosphino, diphenylphosphino, and dimethylphosphinoethyl groups.

M and n each independently represent an integer of 0 to 20. Preferably, m and n are 0-5. Here, when m or n, or both m and n are integers of 2 to 20, a plurality of groups R ⁷ (R ⁸ ) may be the same or different. When m, n, is 2 or more, these groups may be linked to form a new ring structure.

Q represents at least one hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, and a nitrogen-containing hydrocarbon which bond two 5-membered rings. Group, an alkylene group having a phosphorus-containing hydrocarbon group, or at least one hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group A silylene group having a phosphorus-containing hydrocarbon group or at least one
A germylene group having 20 hydrocarbon groups, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group.

Examples of the crosslinking group containing a hydrocarbon group include Q
Specific examples of methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene and the like Alkylene groups; arylalkylene groups such as (methyl) (phenyl) methylene and diphenylmethylene; silylene groups; methylsilylene;
Alkylsilylene groups such as dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, and (alkyl) (alkyl) such as methyl (phenyl) silylene and methyl (tolyl) silylene Aryl) silylene group; arylsilylene group such as diphenylsilylene; alkyl oligosilylene group such as tetramethyldisilylene; germylene group; silicon of the above-mentioned silylene group having a divalent hydrocarbon group having 1 to 20 carbon atoms is converted into germanium Substituted alkylgermylene groups; (alkyl) (aryl) germylene groups; arylgermylene groups, and the like. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms,
Alternatively, a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group, (alkyl)
An (aryl) silylene group or an arylsilylene group is particularly preferred.

Examples of the halogen atom constituting the halogenated hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specifically, (fluoromethyl)
Methylmethylene, (difluoromethyl) methylmethylene, (trifluoromethyl) methylmethylene, (4-fluorophenyl) methylmethylene, ditrifluoromethylmethylene, 1,2-ditrifluoromethylethylene,
(Fluoromethyl) methylsilylene, (chloromethyl)
Methylsilylene, di (chloromethyl) silylene, di (trifluoromethyl) silylene, (1,1,1-trifluoropropyl) methylsilylene, (2-fluorophenyl) methylsilylene, (3-fluorophenyl) methylsilylene, (4-fluorophenyl) methylsilylene,
(2-chlorophenyl) methylsilylene, (3-chlorophenyl) methylsilylene, (4-chlorophenyl) methylsilylene, (2-trifluoromethylphenyl) methylsilylene, (3-trifluoromethylphenyl) methylsilylene, (3-triphenyl (Fluoromethylphenyl) methylsilylene, (4-trifluoromethylphenyl) methylsilylene, (3,5-difluorophenyl) methylsilylene, (2,4,6-trifluorophenyl) methylsilylene, (4-fluorophenyl) ethyl Silylene, (4-chlorophenyl) ethylsilylene, (4-fluorophenyl) (chloromethyl) silylene, di (4-
Examples thereof include (fluorophenyl) silylene, di (4-chlorophenyl) silylene, and a germylene group in which silicon of the silylene group is replaced with germanium.

Examples of the crosslinking group having an oxygen-containing hydrocarbon group include phenoxymethylsilylene, methoxyphenylmethylsilylene, ethoxyethylmethylsilylene, dimethoxyphenylsilylene, diethoxyethylsilylene, and the like.
Various substituted germylene groups are exemplified. Examples of the nitrogen-containing hydrocarbon group-containing crosslinking group include diethylaminoethylmethylsilylene, dimethylaminophenylmethylsilylene, dipyridylsilylene, and the like. Examples of the phosphorus-containing hydrocarbon group-containing cross-linking group include diphenylphosphinoethylmethylsilylene and bis (dimethylphosphinomethyl) silylene.

X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group of 20; an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms; an amino group; a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, specifically, a hydrogen atom; a fluorine atom, a chlorine atom, A halogen atom such as a bromine atom or an iodine atom; a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group similar to those described above for R ⁷ and R ⁸ ; an alkoxy group such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy; Allyloxy groups such as phenoxy, methylphenoxy, dimethylphenoxy, and naphthoxy, and phenylmethoxy and arylalkoxy groups such as naphthylmethoxy have 1 to 1 carbon atoms.
20 oxygen-containing hydrocarbon groups; amino groups; methylamino;
Alkylamino groups such as dimethylamino, ethylamino and diethylamino; arylamino groups such as phenylamino and diphenylamino; and (alkyl) (aryl) amino groups such as (methyl) (phenyl) amino have 1 to 1 carbon atoms.
20 nitrogen-containing hydrocarbon groups. Among these, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms are preferable, and a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, A nitrogen-containing hydrocarbon group of the formulas 1 to 20 is preferable, and a chlorine atom, a methyl group, an i-butyl group, a phenyl group, a dimethylamino group, and a diethylamino group are particularly preferable.

M represents a transition metal of Groups 3 to 6 of the periodic table, preferably a transition metal of Group 4 of titanium, zirconium and hafnium, more preferably zirconium and hafnium. The transition metal compound represented by the general formula [3] according to the present invention can be synthesized by any method suitable for forming a substituent or a bond.

A typical synthetic route is as follows. Note that H ₂ Ra and H ₂ Rb each have the following structure.

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H ₂ Ra + n−C ₄ H ₉ Li → HRaLi + C ₄ H ₁₀ [21] H ₂ Rb + n−C ₄ H ₉ Li → HRbLi + C ₄ H ₁₀ [22] HRaLi + HRbLi + QCl ₂ → HRa-Q-HRb + 2LiCl [23] HRa− _{Q-HRb + 2n-C 4} H 9 Li → LiRa-Q-LiRb + 2C 4 H 10 [24] LiRa-Q-LiRb + ZrCl 4 → (Ra-Q-Rb) ZrCl 2 + 2LiC l 2 [25] also, the HRaLi, the HRbLi Such a metal salt of a cyclopentadienyl compound may be synthesized by a method involving an addition reaction of an alkyl group, an aryl group, or the like as described in, for example, European Patent No. 679418. Specifically, an alkyllithium compound, an aryllithium compound and an azulene compound are reacted in an inert solvent to generate a lithium salt of a dihydroazulenyl compound. Methyllithium, i-propyllithium, n-butyllithium, t-butyllithium, etc. are used as alkyllithium compounds, and phenyllithium, p-chlorophenyllithium, p-fluorophenyllithium, p-trilithium are used as aryllithium compounds. Fluoromethylphenyllithium, naphthyllithium and the like are used. As the inert solvent, hexane, benzene, toluene, diethyl ether, tetrahydrofuran, a mixed solvent thereof or the like is used.

The following are non-limiting examples of the transition metal compound represented by the general formula [3] according to the present invention. Although these compounds are simply referred to by their chemical names only, their steric structures mean both the compounds having asymmetry and the compounds having symmetry according to the present invention. (1) dichlorodimethylsilylenebis (2-isopropyl-4-phenyl-4H-azulenyl) zirconium (2) dichlorophenylmethylsilylenebis (2-isopropyl-4-phenyl-4H-azulenyl) zirconium (3) dichloro (4-chlorophenyl) methylsilylenebis (2-isopropylpropyl-4-phenyl- 4H-azulenyl) zirconium (4) dichlorodi (chloromethyl) silylenebis (2-isopropyl-4-phenyl-4H-azulenyl) zirconium dichloride (5) dichlorodimethylsilylenebis (2-cyclopentyl-4-phenyl-4Hazurenyl) zirconium (6) (4-fluorophenyl) Methylsilylenebis (2-cyclopentyl-4-phenyl-4H-azulenyl) zirconium (7) Lodimethylsilylenebis (2-isopropyl-4naphthyl-4H-azulenyl) zirconium (8) dichloro (chloromethyl) methylsilylenebis (2-isopropyl-4naphthyl-4H-azulenyl) zirconium (9) dichloro (4-fluorophenyl) methylsilylenebis (2 -Isopropyl-4naphthyl-4H-azulenyl) zirconium (10) dichloro (4-chlorophenyl) methylsilylenebis (2, isopropyl, 8-methyl-4-phenyl-4H-azulenyl) zirconium (11) dichlorodimethylsilylenebis (2-cyclopropyl, 4-phenyl-4H-azulenyl) ) Zirconium (12) Dichlorodimethylsilylene bis (2-cyclobutyl, 4-phenyl, 4H-azulenyl) zirconium (13) Chlorodimethylsilylenebis (2-isopropyl, 4-naphthyl, 4H-azulenyl) zirconium (14) dichlorodimethylsilylenebis (2-isopropyl, 4-anthracenyl, 4H-azulenyl) zirconium (15) dichlorodiethylsilylenebis (2-isopropyl, 4-phenyl, 4H-azulenyl) zirconium (16) dichlorophenylmethylsilylenebis (2-isopropyl, 4-phenyl, 4H-azulenyl) zirconium (17) dichloro, 1,2-ethylenebis (2-isopropyl-4-phenyl, 4H-azulenyl) zirconium (18) dichloro 2,2-butylenebis (2-isopropyl, 4-phenyl, 4H-azulenyl) zirconium (19) dichloroisopropylidenebis (2-isopropyl, 4-phenyl, 4H azulenyl) zirconium (20) dimethyl, dimethylsilylenebis (2-cyclopropyl, 4-phenyl, 4H-azulenyl) zirconium (21) dibenzyl, dimethylsilylenebis (2-cyclopropyl, 4-phenyl, 4H-azulenyl) zirconium Wherein one or both of the dichlorides forming the X and Y moieties in the above general formula [3] are a hydrogen atom, a bromine atom, an iodine atom, a methyl group, a phenyl group, a fluorophenyl group, a benzyl group, a methoxy group. And a compound substituted for a dimethylamino group or a diethylamino group. Further, compounds in which the central metal of the compounds exemplified above is changed to yttrium, lanthanum, scandium, titanium, hafnium, tantalum, niobium, vanadium, tungsten, and molybdenum instead of zirconium can also be exemplified.

Catalyst component (E)

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Wherein A and A ′ are conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q is two conjugated five-membered ring ligands. Represents a bonding group that crosslinks a child at an arbitrary position, and M represents a periodic table 4 to
X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group. A and A 'are conjugated five-membered ring ligands, which may be the same or different in the same compound, as described above. This conjugated five-membered ring ligand (A and A ')
Specific examples include a conjugated carbon 5-membered ring ligand, that is, a cyclopentadienyl group.

A cyclopentadienyl group having four hydrogen atoms (all bonding sites except for a bridge portion) [C ₅ H
₄ -] is an even better, also, its derivatives, i.e. some of its hydrogen atoms may be those which are substituted with a substituent. Examples of the substituent include C1 to C2.
0, preferably 1 to 12 hydrocarbon groups. Even if this hydrocarbon group is bonded to a cyclopentadienyl group as a monovalent group, when two or more of them are present, two of them are bonded at the other end (ω-end) to form cyclopentadienyl. A ring may be formed together with a part of the group.

As an example of the latter, two substituents are bonded at each ω-terminal to form a fused six-membered ring by sharing two adjacent carbon atoms in the cyclopentadienyl group. That is, an indenyl group, a tetrahydroindenyl group or a fluorenyl group. Two substituents bonded at each ω-terminal to share two adjacent carbon atoms in the cyclopentadienyl group to form a fused seven-membered ring, ie, azulenyl And a tetrahydroazulenyl group.

That is, specific examples of the conjugated five-membered ring ligand represented by A and A 'include a substituted or unsubstituted cyclopentadienyl group, an indenyl group, a fluorenyl group, an azulenyl group and the like. Preferably, it is a substituted or unsubstituted azulenyl group.

Examples of the substituent on the cyclopentadienyl group and the like include the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, halogen atom groups such as fluorine, chlorine and bromine, and C _1. alkoxy group -C _12, for example, -Si
A silicon-containing hydrocarbon group having 1 to 24 carbon atoms represented by (R ¹ ) (R ² ) (R ³ ); a phosphorus-containing hydrocarbon having 1 to 18 carbon atoms represented by —P (R ¹ ) (R ² ) Group, —N (R ¹ )
(R ²⁾ nitrogen-containing hydrocarbon group having 1 to 18 carbon atoms represented by, or -B (R ¹⁾ from 1 to 18 carbon atoms represented by (R ²⁾
A boron-containing hydrocarbon group, or halogen, oxygen, nitrogen, phosphorus, sulfur, boron, silicon-containing 1 to 20 carbon atoms,
Preferably, there are 1 to 12 hydrocarbon groups. When there are a plurality of these substituents, each substituent may be the same or different.

The above R¹~ R^ThreeAre the same but different
Hydrogen atom or C ₁~ C₂₀The alkyl of
Group, alkenyl group, aryl group and the like. Also linked
May form a cyclic substituent.

Q represents a bonding group bridging at any position between two conjugated five-membered ligands.

Specific examples of Q include (a) a methylene group,
An alkylene group having 1 to 20 carbon atoms such as an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group, a (b) silylene group,
Silylene groups such as dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group, tetramethyldisilylene group, (c) germanium, phosphorus,
Hydrocarbon groups containing nitrogen, boron or aluminum,
More specifically, (CH ₃ ) ₂ Ge, (C ₆ H ₅ ) ₂ G
e, (CH ₃ ) P, (C ₆ H ₅ ) P, (C ₄ H ₉ ) N, (C _{6
H 5) N, (CH 3} ) B, (C 4 H 9) B, (C 6 H 5) B,
And a group represented by (C ₆ H ₅ ) Al and (CH ₃ O) Al. Preferred are alkylene groups, silylene groups,
And germylene groups.

M is a metal atom selected from Groups 4 to 6 of the periodic table, preferably a metal atom of Group 4 of the periodic table, specifically, titanium, zirconium, hafnium and the like. Particularly, zirconium and hafnium are preferable.

X and Y each represent hydrogen, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, A nitrogen-containing hydrocarbon group containing 1 to 20, preferably 1 to 10, a phosphorus-containing hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms such as a diphenylphosphine group, or a trimethylsilyl group, bis (trimethylsilyl) methyl Group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms
Is a silicon-containing hydrocarbon group. X and Y may be the same or different. Of these, halogen atoms and carbon numbers 1 to 1
A hydrocarbon group having 8 and a nitrogen-containing hydrocarbon group having 1 to 12 carbon atoms are preferred.

In the olefin polymerization catalyst according to the present invention, among the compounds represented by the general formula [4] as the component (E), those having the following substituents are preferred.

A, A '= cyclopentadienyl, n-butyl-cyclopentadienyl, indenyl, 2-methyl-indenyl, 2-methyl-4-phenylindenyl,
Tetrahydroindenyl, 2-methyl-tetrahydroindenyl, 2-methylbenzoindenyl, 2,4-dimethylazulenyl, 2-methyl-4-phenylazulenyl, 2-methyl-4-naphthylazulenyl, 2-ethyl -4-naphthylazulenyl, 2-ethyl-4-phenylazulenyl, 2-methyl-4- (4-chlorophenyl)
Azulenyl, Q = ethylene, dimethylsilylene, isopropylidene, M = group 4 transition metal, X, Y = chlorine, methyl, phenyl, benzyl, diethylamino, particularly preferably A, A ′ = 2,4-dimethylazulenyl 2-methyl-4-phenylazulenyl, 2-methyl-4-naphthylazulenyl, 2-ethyl-4-naphthylazulenyl, 2-ethyl-4-phenylazulenyl,
It has 2-isopropyl-4-naphthylazulenyl and 2-methyl-4- (4-chlorophenyl) azulenyl.

The following are specific examples of the transition metal compound. Q = alkylene group includes, for example, (1) methylenebis (2-methyl, 4-phenyl,
4-hydroazulenyl) zirconium dichloride,
(2) ethylene bis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium dichloride, (3) ethylene bis (2-methyl, 4-phenyl, 4-hydroazulenyl) diloconium hydride monochloride,
(4) ethylenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) methylzirconium monochloride,
(5) ethylene bis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium monomethoxide monochloride, (6) ethylene bis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium diethoxy (7) ethylenebis (2-methyl, 4-phenyl,
4-hydroazulenyl) zirconium dimethyl, (8)
Ethylene bis (2-methylindenyl) zirconium dichloride, (9) ethylene bis (2-methyl, 4,5,
6,7-tetrahydroindenyl) zirconium dichloride, (10) ethylenebis (2-ethylindenyl)
Zirconium dichloride, (11) ethylenebis (2,
4-dimethylindenyl) zirconium dichloride,
(12) Ethylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl)
Zirconium dichloride, (13) ethylene (2-methyl-4-tert-butylcyclopentadienyl)
(3'-tert-butyl-5'-methylcyclopentadienyl) zirconium dichloride, (14) ethylene (2,3,5-trimethylcyclopentadienyl)
(2 ', 4', 5'-trimethylcyclopentadienyl) zirconium dichloride, (15) ethylene-1,
2-bis (4-indenyl) zirconium dichloride,
(16) ethylene-1,2-bis [4- (2,7-dimethylindenyl)] zirconium dichloride, (17)
Ethylenebis (4-phenylindenyl) zirconium dichloride, (18) ethylenebis [1,1 ′-(4-
Hydroazulenyl)] zirconium dichloride (19) ethylenebis [1,1 '-(2-ethyl, 4-
Phenyl, 4-hydroazulenyl)] zirconium dichloride (20) ethylenebis [1,1 ′-(2-methyl, 4-
(4-chlorophenyl), 4-hydroazulenyl)] zirconium dichloride (21) ethylenebis (9-bicyclo [8.3.0] trideca-2-methylpentaenyl) zirconium dichloride (22) ethylene (1-indenyl) [1- (4-Hydroazulenyl)] zirconium dichloride (23) isopropylidenebis (2-methyl, 4-phenyl, 4-hydroazulenyl) zirconium dichloride, (24) isopropylidene (2,4-dimethylcyclopentadienyl) ) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (25) isopropylidene (2-methyl-4-tert-butylcyclopentadienyl) (3'-tert-butyl-5-methylcyclopentane) Dienyl) zirconium dichloride and the like. It is.

Examples of the compound having Q = silylene group include (1) dimethylsilylenebis (2-methylindenyl) zirconium dichloride and (2) dimethylsilylenebis (2-methyl-4,5,6,7- (Tetrahydroindenyl) zirconium dichloride, (3) dimethylsilylenebis (2-methyl-4,5-benzoindenyl) zirconium dichloride, (4) dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, 5) dimethylsilylenebis (2,4-dimethylazulenyl) zirconium dichloride, (6) dimethylsilylenebis (2-methyl-4-phenyl-4,
(6,7,8-pentahydroazulenyl) zirconium dichloride, (7) dimethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, )
Dimethylsilylenebis (2-ethyl-4-phenyl-4
-Hydroazulenyl) zirconium dichloride, (9)
Dimethylsilylenebis (2-methyl-4,4-dimethyl-4,5,6,7-tetrahydro-4-silindenyl) zirconium dichloride, (10) dimethylsilylenebis [4- (2-phenylindenyl)] zirconium dichloride , (11) dimethylsilylenebis [4-
(2-tert-butylindenyl)] zirconium dichloride, (12) dimethylsilylenebis [4- (1-
Phenyl-3-methylindenyl)] zirconium dichloride, (13) dimethylsilylenebis [4- (2-phenyl-3-methylindenyl)] zirconium dichloride, (14) phenylmethylsilylenebis (2-methyl4-phenyl -4-hydroazulenyl) zirconium dichloride, (15) phenylmethylsilylenebis (2
-Methyl-4-phenyl-4,5,6,7,8-pentahydroazulenyl) zirconium dichloride, (16)
Phenylmethylsilylene (2,4-dimethylcyclopentadienyl) (3 ', 5'-dimethylcyclopentadienyl) zirconium dichloride, (17) diphenylsilylenebis (2-methyl4-phenyl-4-hydroazulenyl) zirconium dichloride , (18) tetramethyldisilylenebis (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride, (19) dimethylsilylenebis [1,1 '-(2-ethyl-4-naphthyl-4-hydroazulenyl) ] Zirconium dichloride (20) dimethylsilylene bis [1,1 '-{2-
Methyl-4- (4-chlorophenyl) -4-hydroazulenyl {] zirconium dichloride (21) dimethylsilylenebis (9-bicyclo [8.
3.0] Trideca-2-methylpentaenyl) zirconium dichloride (22) (methyl) (phenyl) silylenebis {1,1
'-(2-methyl-4-hydroazulenyl) zirconium dichloride and the like.

Q = As a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum,
For example, (1) dimethylgermanium bis (2-methyl-
4-phenyl-4-hydroazulenyl) zirconium dichloride, (2) methylaluminum bis (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride, (3) phenylaluminum bis (2-methyl-4-phenylazulenyl) Zirconium dichloride, (4) phenylphosphinobis (2-methyl-4-
Phenyl-4-hydroazulenyl) zirconium dichloride, (5) ethylboranobis (2-methyl-4-phenylazulenyl) zirconium dichloride, (6) phenylaminobis (2-methyl-4-phenyl-4-hydroazulenyl) zirconium dichloride and the like. No.

Further, those obtained by replacing chlorine in the above-mentioned compounds with bromine, iodine, hydride, methyl, phenyl and the like can also be used.

Further, in the present invention, the center metal of the zirconium compound exemplified above as the component (E) is titanium,
Compounds replaced with hafnium, niobium, molybdenum, tungsten, or the like can also be used.

Among these, preferred are zirconium compounds, hafnium compounds and titanium compounds. More preferred are zirconium compounds and hafnium compounds. These (E) components may be used in combination of two or more.

Catalyst component (B) The catalyst component (B) is [B
1] an aluminum oxy compound, [B2] an ionic compound or a Lewis acid capable of converting the catalyst component (A) into a cation by reacting with the catalyst component (A), [B3]
It is an ion-exchange layered compound or inorganic silicate except silicate.

Some Lewis acids can be regarded as ionic compounds capable of reacting with the catalyst component (A) to convert the catalyst component (A) into cations. Therefore, a compound belonging to both the Lewis acid and an ionic compound capable of converting the catalyst component (A) into a cation by reacting with the catalyst component (A) is understood to belong to either one. It shall be.

Specific examples of the aluminum oxy compound include the following general formulas [26], [27] and [28]
The compound represented by these is mentioned.

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In the above general formulas, R ³⁸ represents a hydrogen atom or a hydrocarbon residue, preferably a C 1-10, particularly preferably a C 1-6 hydrocarbon residue. The plurality of R ³⁸ may be the same or different. p is 0 to 40,
It preferably represents an integer of 2 to 30.

The compounds of the general formulas [26] and [27] are also called alumoxanes and are obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water.

Specifically, (a) methylalumoxane, ethylalumoxane, propylalumoxane, butylalumoxane, isobutylalumoxane obtained from one type of trialkylaluminum and water, and (b) two types of trialkylalumoxane Examples thereof include methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from aluminum and water. Among these,
Methylalumoxane and methylisobutylalumoxane are preferred.

The above-mentioned alumoxanes can be used in combination of two or more in each group and between each group.

The above alumoxane can be prepared under various known conditions. Specifically, the following method can be exemplified. (A) A method of directly reacting trialkylaluminum with water using a suitable organic solvent such as toluene, benzene or ether. (B) Salt hydrate having trialkylaluminum and water of crystallization, for example, water of copper sulfate or aluminum sulfate (C) Method of reacting trialkylaluminum with water impregnated in silica gel, etc. (d) Mixing trimethylaluminum and triisobutylaluminum and adding an appropriate organic solvent such as toluene, benzene, ether, etc. (E) A method in which trimethylaluminum and triisobutylaluminum are mixed and heated and reacted with a salt hydrate having water of crystallization, for example, copper sulfate, aluminum sulfate and a hydrate (f) Silica gel, etc. Impregnated with water and treated with triisobutylaluminum Then, a method of additional treatment with trimethylaluminum (g) A method of synthesizing methylalumoxane and isobutylalumoxane by a known method, mixing these two components in a predetermined amount, and causing a heat reaction (h) Aromatic substances such as benzene and toluene A salt having water of crystallization such as copper sulfate pentahydrate is added to a hydrocarbon solvent,
Method for reacting with trimethylaluminum under a temperature condition of about 40 ° C. The amount of water used in the reaction is usually 0.5 to 1.5 in molar ratio to trimethylaluminum. The methylalumoxane obtained by the above method is a linear or cyclic organoaluminum polymer.

The compound represented by the general formula [28] is
It can be obtained by a 10: 1 to 1: 1 (molar ratio) reaction between one kind of trialkylaluminum or two or more kinds of trialkylaluminums and an alkylboronic acid represented by the following general formula [29]. . General formula [29]
In the formula, R ¹⁰ represents a hydrocarbon residue having 1 to 10, preferably 1 to 6 carbon atoms or a halogenated hydrocarbon group. R ¹⁰ B (OH) ₂ [29] Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) Triisobutylaluminum and methylboronic acid 2: 1 reactant (c) Trimethylaluminum, triisobutylaluminum and methylboronic acid (d) Trimethylaluminum and ethylboronic acid 2:
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1. Reactant The ionic compound capable of converting the catalyst component (A) into a cation by reacting the catalyst component (A) includes a compound represented by the general formula [30]. [K] ^{e +} [Z] ^e− [30] In the general formula [30], K is an ionic cation component such as a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, Phonium cations and the like. In addition, cations of metals which are easily reduced by themselves, cations of organic metals, and the like can also be mentioned.

Specific examples of the above-mentioned cations include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N-dimethylanilinium, dipropylammonium, Dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium, and silver ion, gold ion, platinum ion, copper Ion, palladium ion, mercury ion, ferrocenium ion and the like.

Z in the above general formula [30] is an ionic anion component, which is a component (generally a non-coordinating component) that becomes a counter anion to the converted cation species in component (A). . Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic arsenic compound anion, an organic antimony compound anion, and the like, and specific examples include the following compounds. . (A) tetraphenylboron, tetrakis (3,4,5
-Trifluorophenyl) boron, tetrakis (3,5
-Di (trifluoromethyl) phenyl) boron, tetrakis (3,5-di (t-butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, etc. (b) tetraphenylaluminum, tetrakis (3
4,5-trifluorophenyl) aluminum, tetrakis (3,5-di (trifluoromethyl) phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, etc. (C) tetraphenylgallium, tetrakis (3,4,
5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl)
Gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenylphosphorous, tetrakis (pentafluorophenyl) phosphorous, etc. (e) tetraphenylarsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) tetraphenylantimony, tetrakis (penta) (G) decaborate, undecaborate, carbadodecaborate, decachlorodecaborate, etc. Lewis acids, especially Lewis acids capable of converting the catalyst component (A) into cations, include various organic borons. Compound,
Examples thereof include metal halide compounds and solid acids, and specific examples thereof include the following compounds. (A) Organic boron compounds such as triphenylboron, tris (3,5-difluorophenyl) boron and tris (pentafluorophenyl) boron (b) Aluminum chloride, aluminum bromide, aluminum iodide, magnesium chloride, magnesium bromide Metal halide compounds such as, magnesium iodide, magnesium chlorobromide, magnesium chloroiodide, magnesium bromoiodide, magnesium hydride, magnesium hydride, magnesium hydride, magnesium alkoxide, magnesium alkoxide, etc. c) As the ion-exchange layered compound excluding solid acids such as silica-alumina and alumina, and silicates, hexagonal close-packed type, antimony type, CdCl ₂ type, CdI
An ionic crystalline compound having a layered crystal structure such as type ₂ is exemplified. Specific examples thereof include α-Zr (HAsO
₄ ) ₂ · H ₂ O, α-Zr (HPO ₄ ) ₂ , α-Zr
(KPO ₄ ) ₂ .3H ₂ O, α-Ti (HPO ₄ ) ₂ ,
α-Ti (HAsO ₄ ) ₂ · H ₂ O, α-Sn (HPO
₄ ) ₂ · H ₂ O, γ-Zr (HPO ₄ ) ₂ , γ-Ti (H
_{PO 4) 2, γ-Ti} (NH 4 PO 4) polyvalent metal crystalline acid salts of such ₂ · H ₂ O and the like.

The above ionic exchangeable layered compound may be used after being subjected to a salt treatment and / or an acid treatment, if necessary. In a state where neither salt treatment nor acid treatment has been applied,
An ion-exchangeable layered compound other than silicate is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and contained ions can be exchanged.

Examples of the above inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. These may use synthetic products, or may use naturally occurring minerals.

Specific examples of clays and clay minerals include allophane group such as allophane, kaolin group such as dickite, nacrite, kaolinite, and anoxite; halloysite group such as metahaloisite and halloysite; chrysotile, lizardite, and antigolite. Serpentinite, montmorillonite, zaukonite, beidellite, nontronite, saponite, hectorite, etc., smectite, vermiculite, etc., vermiculite minerals, illite, sericite, marine green stone, etc., mica minerals, attapulgite, sepiolite, paigorskite, bentonite , Kibushi clay, gairome clay, hisingelite, pyrophyllite, ryokudeite group and the like. These may form a mixed layer. Examples of the artificially synthesized product include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Among the above inorganic silicates, kaolins such as deckite, nacrite, kaolinite and anoxite, halosites such as metahalosite and halosite, serpentine such as chrysotile, lizardite and antigolite Tribe, montmorillonite, zaukonite, beidellite, nontronite, smectites such as saponite, hectorite, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic Teniolite is preferred, smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic tenilite. Light is more preferable. These may be used as they are without any special treatment,
It may be used after processing such as ball milling and sieving. Further, they may be used alone or as a mixture of two or more.

The above-mentioned ion-exchange layered compound and inorganic silicate can change the solid acid strength by salt treatment and / or acid treatment. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

The exchangeable metal cation contained in the compound which has not been subjected to the above pretreatment is subjected to ion exchange with at least 40%, preferably at least 60%, of the cations dissociated from the following salts and / or acids. Is preferred.

The salts used for the above ion exchange are 1 to
At least one element selected from the group consisting of Group 14 atoms
A compound containing a cation containing a proton, preferably
At least one member selected from the group consisting of atoms of groups 1 to 14
A cation containing an atom of a halogen atom, an inorganic acid and
At least one anion selected from the group consisting of organic acids
And more preferably a group 2-14 group
Contains at least one atom selected from the group consisting of atoms.
Cations, Cl, Br, I, F, PO_Four, SO_Four, N
O_Three, CO_Three, C_TwoO_Four, ClO_Four, OOCCH_Three, CH_ThreeC
OCHCOCH _Three, OCI_Two, O (NO_Three)_Two, O (ClO
_Four)_Two, O (SO_Four), OH, O_TwoCl_Two, OCI_Three, OOC
H, OOCCH_TwoCH_Three, C_TwoH_FourO_FourAnd C₆H_FiveO₇From
From at least one anion selected from the group consisting of
Compound. Also, two or more of these salts may be used simultaneously.
May be used.

The acid used for the above ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid.
Two or more kinds may be used simultaneously. As a method of combining the salt treatment and the acid treatment, there are a method of performing the salt treatment and then the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment. In addition,
The acid treatment removes impurities on the surface, and has a crystal structure of Al,
This has the effect of eluting some cations such as Fe, Mg, and Li.

The conditions for the treatment with salts and acids are not particularly limited, but the salt and acid concentrations are usually 0.1 to 30.
It is preferable that the treatment is carried out under the conditions that the weight%, the treatment temperature is from room temperature to the boiling point of the solvent used, the treatment time is from 5 minutes to 24 hours, and at least a part of the compound to be treated is eluted. Also,
Salts and acids are generally used in aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. The ion-exchangeable layered compound and the inorganic silicate thus obtained have a pore volume of 0.1 mm or more as measured by a mercury intrusion method with a pore volume of 0.1 mm or more.
It is preferably at least cc / g, particularly preferably 0.3 to 5 cc / g. Such an ion-exchange layered compound and an inorganic silicate usually contain adsorbed water and interlayer water. Here, the adsorbed water is the water adsorbed on the surface of the ion-exchangeable layered compound or the inorganic silicate other than the silicate, or on the crystal fracture surface.
Interlayer water is water present between the layers of the crystal.

In the present invention, the ion-exchange layered compound and the inorganic silicate are preferably used after removing the above-mentioned adsorbed water and interlayer water. The dehydration method is not particularly limited, and methods such as thermal dehydration, thermal dehydration under a gas flow, thermal dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is in a temperature range where no interlayer water remains, and is usually 100 ° C. or higher, preferably 150 ° C. or higher. However, high temperature conditions that cause structural destruction are not preferable. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the component [(B) after dehydration and drying]
-3] at a temperature of 200 ° C. and a pressure of 1 mmHg.
0% by weight when dehydrated for 2 hours under the condition
It is preferable that the content be 3% by weight or less. In the present invention, when the component [(B) -3] which has been dehydrated and adjusted to have a water content of 3% by weight or less is used, when the component (A) and the optional component (D) described below are brought into contact with each other. Also, it is important to be treated so as to maintain the same moisture content.

Optional Component (C) The fine particle carrier as the optional component (C) is composed of an inorganic or organic compound, and is usually 5 μm to 5 mm, preferably 1 μm to 5 mm.
It is a granular or fine particle carrier having a particle size of 0 to 2 mm.

Examples of the inorganic carrier include, for example, SiO 2
₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ , B ₂ O ₃ , Zn
Oxides such as O, SiO ₂ —MgO, SiO ₂ —Al
₂ O ₃ , SiO ₂ —TiO ₂ , SiO ₂ —Cr ₂ O ₃ , SiO ₂
And complex oxides such as —Al ₂ O ₃ —MgO.

Examples of the above organic carriers include (co) polymers of α-olefins having 2 to 14 carbon atoms, such as ethylene, propylene 1-butene, 4-methyl-1-pentene, and styrene and divinylbenzene. A fine particle carrier of a porous polymer composed of a (co) polymer of an aromatic unsaturated hydrocarbon is exemplified. Their specific surface areas are between 20 and 1000
m ² / g, preferably 50~700m ² / g, a pore volume of 0.1 cm ² / g or more, preferably 0.3 cm ² /
g, more preferably 0.8 cm ² / g or more.

Optional Component (D) An example of the organoaluminum compound as the optional component (D) is represented by the following general formula (31).

AlR _a P _3-a [31] In the general formula [31], R represents a hydrocarbon group having 1 to 20 carbon atoms, P represents hydrogen, a halogen, an alkoxy group, and a represents 0
An integer greater than or equal to 3 is shown. Specific examples of the organoaluminum compound represented by the general formula [29] include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum; halogens such as diethylaluminum monochloride and diethylaluminum monomethoxide. Or an alkoxy-containing alkyl aluminum. Of these, trialkylaluminum is preferred. In the catalyst (2) of the present invention, an aluminoxane such as methylaluminoxane may be used as the component (D).

The olefin polymerization catalyst of the present invention is
Optional components other than the fine particle carrier include, for example, active hydrogen-containing compounds such as H ₂ O, methanol, ethanol, and butanol; electron-donating compounds such as ethers, esters, and amines; phenyl borate; dimethylmethoxyaluminum;
It can contain an alkoxy-containing compound such as phenyl phosphite, tetraethoxysilane, diphenyldimethoxysilane, and the like.

In the olefin polymerization catalyst of the present invention, it is possible to convert the catalyst component (A) or the catalyst component (E) into a cation by reacting with the aluminum oxy compound, the catalyst component (A) or the catalyst component (E). A nonionic compound, an ion-exchange layered compound other than a Lewis acid and a silicate, or an inorganic silicate can be used alone as the catalyst component (B), or can be used in an appropriate combination of these three components.

Further, the lower alkyl aluminum described above,
Halogen-containing alkyl aluminum, alkyl aluminum hydride, alkoxy-containing alkyl aluminum,
One or more of the aryloxy-containing alkylaluminums are optional components, but are preferably contained in the olefin polymerization catalyst in combination with an aluminumoxy compound, an ionic compound or a Lewis acid.

The olefin polymerization catalyst of the present invention is prepared by bringing the above-mentioned component (A) or component (E) and component (B) into contact with each other inside or outside the polymerization tank in the presence or absence of the monomer to be polymerized. Can be prepared. That is, the component (A) or the component (E), and the component (B) and, if necessary, the component (D) or the like may be separately introduced into the polymerization tank, or the component (A) or the component (E), After bringing the component and the component (B) into contact with each other in advance, they may be introduced into the polymerization tank. Alternatively, the mixture of the component (A) or the component (E) and the component (B) may be impregnated into the component (C) and then introduced into the polymerization tank. Further, the components (A), (B) and (D) may be used after being brought into contact with each other, or the components may be sequentially reacted.

The above components may be contacted in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, preferably between 0 ° C and the boiling point of the solvent. The catalyst thus prepared may be used without washing after preparation,
It may be used after washing. Further, new components may be used in combination as needed after preparation. It is also possible to use the components (A) and (E) together.

Further, component (A) or component (E)
When the component (B) and the component (C) or the component (D) are brought into contact in advance, the monomer to be polymerized is present and α
A so-called preliminary polymerization in which a part of the olefin is polymerized can also be performed. That is, before polymerization, ethylene, propylene, 1-butene, 1-hexene, 1-octene,
4-methyl-1-pentene, 3-methyl-1-butene,
An olefin such as vinylcycloalkane or styrene is preliminarily polymerized, and if necessary, a prepolymerized product washed may be used as a catalyst.

This preliminary polymerization is preferably carried out in an inert solvent under mild conditions.
It is desirable to carry out the reaction so as to produce from 01 to 1000 g, preferably from 0.1 to 100 g, of the polymer.

The amounts of component (A) or component (E) and component (B) used are arbitrary. For example, in the case of solvent polymerization, the amount of component (A) used is 10 ^-7 to
It is preferably in the range of 10 ² mmol / l, more preferably 10 ^-4 to 1 mmol / l. In the case of an aluminum oxy compound, the molar ratio of Al / transition metal is usually 10 to 1
It is in the range of 00,000, preferably 100 to 20,000, more preferably 100 to 10,000. On the other hand, when an ionic compound or Lewis acid is used as the component (B), the molar ratio thereof to the transition metal is usually 0.1 to 1,000, preferably 0.5 to 100, and more preferably 1 to 50. Range.

Further, when an ion-exchangeable layered compound or inorganic silicate other than silicate and an organic aluminum compound as an optional component (D) are used, it can be handled in the same manner as the other component (B). The contact method is not particularly limited,
The following method can be exemplified.

A) The component (A) is brought into contact with the component [B3]. b) After the component (A) is brought into contact with the component [B3], the component (D) is added. c) After contacting the component (A) with the component (D), the component [B
3] is added. d) The component (A) is added after the component [B3] is brought into contact with the component (D). In addition, the three components may be contacted simultaneously.

At the time of contacting each of the above components, a fine particle carrier which is an optional component (C) may coexist, or after the above each component is contacted, it may be contacted with the fine particle carrier.

The amount of each of the above components is determined by the amount of component [B3] 1
Component (A) per g is usually 0.0001 to 10 mmol
1, preferably 0.001 to 5 mmol, and the component (D) is 0.01 to 10000 mmol, preferably 0.1 to 100 mmol.

The atomic ratio of the transition metal in the component (A) to the aluminum in the component (D) is usually 1: 0.01.
１０００1,000,000, preferably 1: 0.1 to 10,000
0. The catalyst thus prepared may be used without washing after preparation, or may be used after washing. Further, if necessary, the component (D) may be newly used in combination. The amount of the component (D) used at this time is selected so that the atomic ratio of aluminum in the component (D) to transition metal in the component (A) is 1: 0 to 10,000. The contact can be exemplified by reading the above component (A) for the component (E).

Before the polymerization, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 4-methyl-1
An olefin such as -pentene, 3-methyl-1-butene, vinylcycloalkane, styrene or the like is preliminarily polymerized and, if necessary, washed, can be used as a catalyst.

This preliminary polymerization is preferably carried out in an inert solvent under mild conditions.
It is desirable to carry out the reaction so as to produce from 01 to 1000 g, preferably from 0.1 to 100 g, of the polymer.

Next, a method for producing a propylene polymer according to the present invention will be described. In the present invention, polymerization or copolymerization is carried out by bringing the aforementioned catalyst into contact with an α-olefin. The catalyst in the present invention is applied not only to solvent polymerization using a solvent but also to liquid phase solventless polymerization, gas phase polymerization, and melt polymerization substantially using no solvent. Further, the polymerization system may be either continuous polymerization or batch polymerization.

Solvents for the solvent polymerization include hexane, heptane, pentane, cyclohexane, benzene,
Inert saturated fatty acids or aromatic hydrocarbons, such as toluene, alone or in mixtures are used. The polymerization temperature is usually -78 to 250C, preferably -20 to 100C. There is no limitation on the polymerization method as long as a polymer having the characteristics of the present invention can be obtained. The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 2000 kg.
f / cm ² , more preferably from normal pressure to 50 kg / cm ^2.
G range. Further, for example, the molecular weight can be adjusted by known means such as selection of temperature and pressure or introduction of hydrogen.

[0152]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, the catalyst synthesis step and the polymerization step were all performed under a purified nitrogen atmosphere, and the solvent was dehydrated with MS-4A, and then deaerated by bubbling with purified nitrogen before use.

(1) Measurement of MFR: 6 g of an acetone solution (0.6% by weight) of a heat stabilizer (BHT) was added to 6 g of the polymer. Next, after drying the polymer, it was charged into a melt indexer (230 ° C.) and left under a load of 2.16 kg for 5 minutes. Thereafter, the amount of the polymer extruded was measured, converted into the amount per 10 minutes, and used as the MFR value.

(2) Measurement of molecular weight distribution: weight average molecular weight (Mw) and number average molecular weight (Mn) obtained by GPC
(All values in terms of polypropylene) were determined by the ratio (Q value). The GPC device is “150CV” manufactured by Waters.
Type "was used. Ortho-dichlorobenzene was used as the solvent, and the measurement temperature was 135 ° C.

(3) Measurement of melting point: DSC (“TA2000” manufactured by DuPont) was used at 20 ° C./min at 10 ° C./min.
The temperature was determined by measuring the temperature at the second time after the temperature was raised and lowered to 00 ° C. once.

(4) ¹³ C-NMR of polymer, ¹ H-N
Measurement of MR The ¹³ C-NMR spectrum of the polymer (MK-3-93) was 100 m in a 10 mmΦ NMR measurement sample tube.
g sample was completely dissolved in a solvent obtained by adding about 0.5 ml of deuterated benzene as a lock solvent to about 2.0 ml of o-dichlorobenzene, and measured at 130 ° C. by a proton complete decoupling method. As the measurement conditions, a flip angle of 65 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value among the spin lattice relaxation times of the methyl group) were selected. Since T ₁ of the methylene group and the methine group is shorter than the methyl group in the propylene polymer, the recovery of the magnetization of all carbons is 99% or more under these measurement conditions. ¹ H-NMR was also measured using a sample prepared in the same manner.

The ¹³ C-NMR chemical shift was set at 21.8 ppm for the methyl group in the third unit of the five-chain propylene unit in which head-to-tail bonds and the direction of branching of the methyl group were the same, and 21.8 ppm of the other carbon peaks were obtained. The chemical shift was based on this.
The chemical shift based on this standard almost coincides with the value based on the standard based on the signal of tetramethylsilane being 0.0 ppm and the standard based on the standard based on 2.0 ppm for hexamethyldisiloxane. ^{The 1} H-NMR chemical shift was set such that the signal on the high magnetic field side of o-dichlorobenzene was 6.94 ppm, and the chemical shifts of the other hydrogen peaks were based on this.

Example-1 (1) Polymerization Toluene 30 was placed in a stirred autoclave having an inner volume of 1 L.
0 ml was introduced, the temperature was raised to 40 ° C., and methyl alumoxane (MMAO, manufactured by Tosoh Akzo Co., Ltd.) 38 mmol (Al
Subsequently, after introducing propylene, the temperature was raised to 50 ° C., and the propylene pressure was maintained at 1 kg / cm ² . On the other hand, 6 mg of dichlorodimethylsilanediylbis (2-isopropyl, 4-phenyl-4Hazulenyl) hafnium diluted with toluene was introduced into a catalyst feeder with a rupture disk,
The rupture disk was cut, and a polymerization operation was performed for 4 hours while maintaining the pressure. After the completion of the polymerization, propylene was purged, and 40 ml of a toluene slurry was extracted. As a result, 2.2 g of a polymer was obtained. The melting point of the obtained polymer was 114.2.
° C., Mw was <5.6 × 10 ³ . [Mrm] =
7.0 mol%. 2,1- and 1,3-linkages were not detected.

[1-Pr-Δ] = 0.52 mol% [i-Bu-Δ] = 0.89 mol% [1-Pr-Δ] _db = 24.5 mol% [i-Bu-Δ] _db = 42.2 mol% [1-Pr-Δ] / [i-Bu-Δ] = 36.7 / 6
3.3 Next, 100 ml of toluene and 0.74 mg of dichlorodimethylsilanediylbis (2-methyl, 4-phenyl4Hazulenyl) hafnium were added to the polymerization tank, and polymerization was performed at 70 ° C. under a propylene pressure of 7 kg / cm ³ for 2 hours. . After completion of the polymerization, the polymer was filtered and dried. As a result, 28 g of the polymer was recovered. As a result of extracting 5 g of the obtained polymer with heptane, 3.5 g of the polymer was recovered. As a result of measuring the melting point of this polymer, two peaks were obtained at 114 ° C. and 152 ° C. The strength was about 1: 8. The weight average molecular weight was 453000, and the Q value was 3.4. ¹³ C-
As a result of NMR measurement, [mmmm] was 99%, [mrr
m] is 0.25%, 2,1-linkage is 0.36 mol%,
The 1,3-linkage was 0.34 mol%. The number of branches was 0.5 per 1000 carbons of the main chain. The ME of the obtained propylene polymer was 1.3.

Example-2 (1) Chemical treatment of clay mineral 10 g of montmorillonite ("Kunipia F" manufactured by Kunimine Industries) was added to dilute sulfuric acid composed of 10 g of sulfuric acid and 90 ml of demineralized water.
Was dispersed, heated to the boiling point, and then stirred for 6 hours. Thereafter, the collected montmorillonite was sufficiently washed with demineralized water, preliminarily dried, and then dried at 200 ° C. for 2 hours to obtain a chemically treated clay mineral.

The chemically treated montmorillonite 20
To 0 mg, 0.8 ml of a toluene solution of triethylaluminum having a concentration of 0.4 mol / ml was added, and the mixture was stirred at room temperature for 1 hour. Thereafter, the slurry was washed with toluene to obtain a slurry of 33 mg clay mineral / ml toluene.

(2) Polymerization of propylene 0.25 mmol of triisobutylaluminum (manufactured by Tosoh Akzo) was placed in a 1 L stirred autoclave.
(In terms of Al atoms) was introduced. On the other hand, 1.4 mg of dichlorodimethylsilanediylbis (2-isopropyl, 4-phenyl4Hazulenyl) zirconium and 0.74 mg of hafnium dichlorodimethylsilanediylbis (2-methyl, 4-phenyl4Hazulenyl) were added to a catalyst feeder with a rupturable plate in toluene. Then, 50 mg of the triethylaluminum-treated montmorillonite obtained in the above (1) and 0.015 mmol of triisobutylaluminum (in terms of Al atom) were introduced. Thereafter, 700 ml of propylene was introduced into the autoclave, the rupture plate was cut at room temperature, and the temperature was raised to 80 ° C., followed by polymerization for 1 hour.

As a result, 40.5 g of a polymer was obtained. The catalytic activity was 0.8 × 10 ³ g-polymer / g-catalyst. The MFR of the polymer is 1.2 (g / 10
Min) and the melting point was 154.0 ° C. [M
[mmm] is 99%, [mrm] is 0.10%, 2,1
-The bond was 0.38 mol% and the 1,3-bond was 0.38 mol%. The amount of branching is 0.0
There were six. The weight average molecular weight was 410000 and the Q value was 5.3, indicating a two-peak distribution. The ME of the obtained polymer showed 1.4.

Comparative Example 1 In Example 2, dichlorodimethylsilanediylbis (2-isopropyl, 4-phenyl4Hazulenyl) zirconium was not used as the complex, and instead, dichlorodimethylsilanediylbis (2-methyl, 4-phenyl4H) was used. Polymerization was carried out under the same conditions as in Example 2 except that 1.48 mg of (azulenyl) hafnium alone was used.

As a result, 120 g of the polymer was recovered. The catalytic activity was 2400 g polymer / g-catalyst. MFR = 0.8, melting point: 152.8 ° C., Mw = 44
0000, Q value was 3.1, and ME was 1.1. [Mmmm] of the polymer was 99%, the number of the heterogeneous bonds was 2,1-bonds, 0.46 mol%, and the number of 1,3-bonds was 0.42 mol%. The number of branches was below the detection limit.

[0166]

According to the present invention described above, there is provided a propylene polymer having a high isotactic triad fraction and having a polypropylene branch having a specific structure. A propylene polymer having such characteristics is rigid,
Despite excellence in heat resistance, moldability, and gloss, moldability is excellent.

[Brief description of the drawings]

FIG. 1 is a flowchart for assisting understanding of the present invention.

 ────────────────────────────────────────────────── ─── Continued on the front page F-term (reference) 4J028 AA02A AB00A AB01A AB02A AC01A AC19A AC27A AC31A AC38A AC41A AC45A BA00A BA01A BB00A BB01A BC12A BC14A BC15B BC16B BC25A BC39A BC40A CA14A CA15A CA19A CAA CAA CAACA CAA DA04 DA05 DA06 DA08 EA02 EB04 EC01 ED02 EF02 FA01 FA02 FA04 GA06 GA07 GA16 GA19 4J100 AA03P CA01 CA11 DA01 DA19 FA10 FA34 FA43

Claims (6)

[Claims] 1. A propylene polymer which satisfies the following conditions (A), (B) and (C). (A) the ratio of the meso-racemic-racemic-meso chain of 5 propylene units comprising head-to-tail bonds measured by ¹³ C-NMR is 9 mol% or less; (B) in the polymer main chain Per 1000 carbon atoms,
(C) the weight average molecular weight Mw measured by gel permeation chromatography is from 50,000 to 1,000,000
Range. 2. The propylene polymer according to claim 1, wherein the long branched chain and the branched portion in the condition (B) have a structure represented by the following general formula [1], and n is 10 to 2,000. Embedded image 3. Propylene is polymerized in the presence of the following essential catalyst components (A) and (B) and, if necessary, an optional component (C) and / or an optional component (D). Is produced, and the precursor is polymerized in the presence of the following catalyst components (E) and (B) and, if necessary, an optional component (C) and / or an optional component (D). A method for producing a propylene polymer, comprising producing the propylene polymer according to claim 1. Embedded image Catalyst component (A): transition metal compound represented by the following general formula [3] (In the general formula [3], R ¹ and R ⁴ are each independently a hydrocarbon group having 3 to 10 carbon atoms or a silicon-containing hydrocarbon group having 2 to 18 carbon atoms, and R ² and R ⁵ are each independently A hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, and R ³ and R ⁶ are each independently fused to a five-membered ring to which it is bonded. R ⁷ and R ⁸ each independently represent a divalent saturated or unsaturated hydrocarbon group having 3 to 10 carbon atoms which forms a ring;
A hydrocarbon group of 0 or a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon, a nitrogen-containing hydrocarbon, and a phosphorus-containing hydrocarbon. m and n each independently represent an integer of 0 to 20. Q represents at least one hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, Alkylene group having a hydrogen group, or at least one hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon group, nitrogen-containing hydrocarbon group, phosphorus-containing hydrocarbon A silylene group having a group, or at least one of 1 to 20 carbon atoms
, A halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a germylene group having a phosphorus-containing hydrocarbon group. X and Y each independently represent a hydrogen atom, a halogen atom,
0 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms, amino groups,
It represents a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and M represents a transition metal belonging to Groups 3 to 6 of the periodic table. Catalyst component (B): an aluminum oxy compound, an ionic compound capable of converting component (A) into a cation by reacting with component (A), an ion-exchange layered compound excluding Lewis acids and silicates, and One or more substances selected from the group consisting of inorganic silicates Optional component (C): fine particle carrier Optional component (D): organoaluminum compound Catalyst component (E): transition metal compound represented by the following general formula [4] Formula 4 (Wherein A and A ′ represent conjugated five-membered ring ligands (A and A ′ may be the same or different in the same compound), and Q represents any two conjugated five-membered ring ligands. And M represents a metal atom selected from Groups 4 to 6 of the periodic table, and X and Y represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, and a phosphorus-containing group. Shows a hydrocarbon group or a silicon-containing hydrocarbon group, except for those included in general formula [3]. 4. ¹³ C-NMR of branched polypropylene precursor
4. The process for producing a propylene polymer according to claim 3, wherein the proportion of the meso-racemic-racemic-meso-chain in the 5-chain portion of the monomer unit composed of head-to-tail bonds is 9 mol% or less. 5. The process for producing a propylene polymer according to claim 3, wherein the meso-meso chain of the monomer of the branched polypropylene precursor is 60 mol% or more. 6. A branched polypropylene precursor is produced in the first stage in the presence of the catalyst components (A) and (B) and, if necessary, the optional component (C) and / or the optional component (D). The method for producing a propylene polymer according to claim 3, wherein the component (E) is added to polymerize the precursor.